Nucleation of Organic Molecules via a Hot Precursor State: Pentacene on Amorphous Mica

PubMed Central

2013-01-01

Organic thin films have attracted considerable interest due to their applicability in organic electronics. The classical scenario for thin film nucleation is the diffusion-limited aggregation (DLA). Recently, it has been shown that organic thin film growth is better described by attachment-limited aggregation (ALA). However, in both cases, an unusual relationship between the island density and the substrate temperature was observed. Here, we present an aggregation model that goes beyond the classical DLA or ALA models to explain this behavior. We propose that the (hot) molecules impinging on the surface cannot immediately equilibrate to the substrate temperature but remain in a hot precursor state. In this state, the molecules can migrate considerable distances before attaching to a stable or unstable island. This results in a significantly smaller island density than expected by assuming fast equilibration and random diffusion. We have applied our model to pentacene film growth on amorphous Muscovite mica. PMID:24340130

Molecules with polymerizable ligands as precursors to porous doped materials

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

Hubert-Pfalzgraf, L.G.; Pajot, N.; Papiernik, R.

1996-12-31

Titanium and aluminum alkoxide derivatives with polymerizable ligands such as 2-(methacryloyloxy)ethylacetoacetate (HAAEMA), oleic acid and geraniol (HOGE) have been obtained. The various compounds have been characterized by FT-IR and NMR {sup 1}H. Copolymerization with styrene and divinylbenzene affords porous doped organic materials which have been characterized by scanning electron microscopy (SEM), elemental analysis, density measurements.

Radiative precursors driven by converging blast waves in noble gases

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

Burdiak, G. C.; Lebedev, S. V.; Harvey-Thompson, A. J.

2014-03-15

A detailed study of the radiative precursor that develops ahead of converging blast waves in gas-filled cylindrical liner z-pinch experiments is presented. The experiment is capable of magnetically driving 20 km s{sup −1} blast waves through gases of densities of the order 10{sup −5} g cm{sup −3} (see Burdiak et al. [High Energy Density Phys. 9(1), 52–62 (2013)] for a thorough description). Data were collected for Ne, Ar, and Xe gas-fills. The geometry of the setup allows a determination of the plasma parameters both in the precursor and across the shock, along a nominally uniform line of sight that is perpendicularmore » to the propagation of the shock waves. Radiation from the shock was able to excite NeI, ArII, and XeII/XeIII precursor spectral features. It is shown that the combination of interferometry and optical spectroscopy data is inconsistent with upstream plasmas being in LTE. Specifically, electron density gradients do not correspond to any apparent temperature change in the emission spectra. Experimental data are compared to 1D radiation hydrodynamics HELIOS-CR simulations and to PrismSPECT atomic physics calculations to assist in a physical interpretation of the observations. We show that upstream plasma is likely in the process of being radiatively heated and that the emission from a small percentage of ionised atoms within a cool background plasma dominates the emission spectra. Experiments were carried out on the MAGPIE and COBRA pulsed-power facilities at Imperial College London and Cornell University, respectively.« less

Growth of gallium nitride and indium nitride nanowires on conductive and flexible carbon cloth substrates.

PubMed

Yang, Yi; Ling, Yichuan; Wang, Gongming; Lu, Xihong; Tong, Yexiang; Li, Yat

2013-03-07

We report a general strategy for synthesis of gallium nitride (GaN) and indium nitride (InN) nanowires on conductive and flexible carbon cloth substrates. GaN and InN nanowires were prepared via a nanocluster-mediated growth method using a home built chemical vapor deposition (CVD) system with Ga and In metals as group III precursors and ammonia as a group V precursor. Electron microscopy studies reveal that the group III-nitride nanowires are single crystalline wurtzite structures. The morphology, density and growth mechanism of these nanowires are determined by the growth temperature. Importantly, a photoelectrode fabricated by contacting the GaN nanowires through a carbon cloth substrate shows pronounced photoactivity for photoelectrochemical water oxidation. The ability to synthesize group III-nitride nanowires on conductive and flexible substrates should open up new opportunities for nanoscale photonic, electronic and electrochemical devices.

Preparation of Pt Nanocatalyst on Carbon Materials via a Reduction Reaction of a Pt Precursor in a Drying Process.

PubMed

Lee, Jae-Young; Lee, Woo-Kum; Rim, Hyung-Ryul; Joung, Gyu-Bum; Weidner, John W; Lee, Hong-Ki

2016-06-01

Platinum (Pt) nanocatalyst for a proton-exchange membrane fuel cell (PEMFC) was prepared on a carbon black particle or a graphite particle coated with a nafion polymer via a reduction of platinum(II) bis(acetylacetonate) denoted as Pt(acac)2 as a Pt precursor in a drying process. Sublimed Pt(acac)2 adsorbed on the nafion-coated carbon materials was reduced to Pt nanoparticles in a glass reactor at 180 degrees C of N2 atmosphere. The morphology of Pt nanoparticles on carbon materials was observed by scanning electron microscopy (SEM) and the distribution of Pt nanoparticles was done by transmission electron microscopy (TEM). The particle size was estimated by analyzing the TEM image using an image analyzer. It was found that nano-sized Pt particles were deposited on the surface of carbon materials, and the number density and the average particle size increased with increasing reduction time.

Spatial analyses on seismo-ionospheric precursors observed by GIM TEC and DEMETER during the 2008 M8.0 Wenchuan earthquake

NASA Astrophysics Data System (ADS)

Liu, Jann-Yenq; Chen, Yuh-Ing; Huang, Ching-Chi; Parrot, Michel; Pulinets, Sergey; Ouzounov, Dimitar

2015-04-01

This paper examines seismo-ionospheric precursors (SIPs) in the total electron content (TEC) of the global ionosphere map (GIM) and observations in the French satellite DEMETER (Detection of Electro-Magnetic Emissions Transmitted from Earthquake Regions) during the 12 May 2008 M8.0 Wenchuan earthquake. The temporal and spatial analyses on the GIM TEC are used to search SIPs of the Wenchuan earthquake. Meanwhile, both daytime and nighttime electron density (Ne), electron temperature (Te), ion density (Ni) and ion temperature (Ti) probed by DEMETER are investigated. A statistical analysis of the box-and-whisker method is utilized to see if the four DEMETER data sets 1-6 days before and after the earthquake are significantly different. The analysis is employed to investigate the epicenter and three reference areas along the same magnetic latitude discriminating the SIPs from global effects. Results show that the nighttime Ne and Ni (daytime Ti) over the epicenter significantly decrease (increase) 1-6 days before the earthquake. The intersections of the global distribution of the significant differences (or anomalous changes) in the nighttime Ne, the nighttime Ni, and the daytime Ti 1-6 days before and after the earthquake specifically appear over the epicenter. The spatial analyses confirm that SIPs of GIM TEC and DEMETER observations appearing 2-6 days before are related to the 2008 M8.0 Wenchuan earthquake.

Multi precursors analysis associated with the powerful Ecuador (MW = 7.8) earthquake of 16 April 2016 using Swarm satellites data in conjunction with other multi-platform satellite and ground data

NASA Astrophysics Data System (ADS)

Akhoondzadeh, Mehdi; De Santis, Angelo; Marchetti, Dedalo; Piscini, Alessandro; Cianchini, Gianfranco

2018-01-01

After DEMETER satellite mission (2004-2010), the launch of the Swarm satellites (Alpha (A), Bravo (B) and Charlie (C)) has created a new opportunity in the study of earthquake ionospheric precursors. Nowadays, there is no doubt that multi precursors analysis is a necessary phase to better understand the LAIC (Lithosphere Atmosphere Ionosphere Coupling) mechanism before large earthquakes. In this study, using absolute scalar magnetometer, vector field magnetometer and electric field instrument on board Swarm satellites, GPS (Global Positioning System) measurements, MODIS-Aqua satellite and ECMWF (European Centre for Medium-Range Weather Forecasts) data, the variations of the electron density and temperature, magnetic field, TEC (Total Electron Content), LST (Land Surface Temperature), AOD (Aerosol Optical Depth) and SKT (SKin Temperature) have been surveyed to find the potential seismic anomalies around the strong Ecuador (Mw = 7.8) earthquake of 16 April 2016. The four solar and geomagnetic indices: F10.7, Dst, Kp and ap were investigated to distinguish whether the preliminary detected anomalies might be associated with the solar-geomagnetic activities instead of the seismo-ionospheric anomalies. The Swarm satellites (A, B and C) data analysis indicate the anomalies in time series of electron density variations on 7, 11 and 12 days before the event; the unusual variations in time series of electron temperature on 8 days preceding the earthquake; the analysis of the magnetic field scalar and vectors data show the considerable anomalies 52, 48, 23, 16, 11, 9 and 7 days before the main shock. A striking anomaly is detected in TEC variations on 1 day before earthquake at 9:00 UTC. The analysis of MODIS-Aqua night-time images shows that LST increase unusually on 11 days prior to main shock. In addition, the AOD variations obtained from MODIS measurements reach the maximum value on 10 days before the earthquake. The SKT around epicentral region presents anomalous higher value about 40 days before the earthquake. It should be noted that the different lead times of the observed anomalies could be acknowledged based on a reasonable LAIC earthquake mechanism. Our results emphasize that the Swarm satellites measurements play an undeniable role in progress the studies of the ionospheric precursors.

Electronic and elastic mode locking in charge density wave conductors

NASA Astrophysics Data System (ADS)

Zettl, A.

1986-12-01

Mode locking phenomena are investigated in the charge density wave (CDW) materials NbSe 3 and TaS 3. The joint application of ac and dc electric fields results in free running and mode locked solutions for the CDW drift velocity, with associated ac-induced dynamic coherence lengths ξ D(ac) on the order of several hundred microns. The electronic response couples directly to the elastic properties of the crystal, with corresponding free running and mode locked solutions for the velocity of sound. Phase slip center-induced discontinuities in the CDW phase velocity lead to mode locked solutions with period doubling routes to chaos, and noisy precursor effects at bifurcation points. These results are discussed in terms of simple models of CDW domain synchronization, and internal CDW dynamics.

The role of low-energy electrons in focused electron beam induced deposition: four case studies of representative precursors

PubMed Central

Thorman, Rachel M; Kumar T. P., Ragesh; Fairbrother, D Howard

2015-01-01

Summary Focused electron beam induced deposition (FEBID) is a single-step, direct-write nanofabrication technique capable of writing three-dimensional metal-containing nanoscale structures on surfaces using electron-induced reactions of organometallic precursors. Currently FEBID is, however, limited in resolution due to deposition outside the area of the primary electron beam and in metal purity due to incomplete precursor decomposition. Both limitations are likely in part caused by reactions of precursor molecules with low-energy (<100 eV) secondary electrons generated by interactions of the primary beam with the substrate. These low-energy electrons are abundant both inside and outside the area of the primary electron beam and are associated with reactions causing incomplete ligand dissociation from FEBID precursors. As it is not possible to directly study the effects of secondary electrons in situ in FEBID, other means must be used to elucidate their role. In this context, gas phase studies can obtain well-resolved information on low-energy electron-induced reactions with FEBID precursors by studying isolated molecules interacting with single electrons of well-defined energy. In contrast, ultra-high vacuum surface studies on adsorbed precursor molecules can provide information on surface speciation and identify species desorbing from a substrate during electron irradiation under conditions more representative of FEBID. Comparing gas phase and surface science studies allows for insight into the primary deposition mechanisms for individual precursors; ideally, this information can be used to design future FEBID precursors and optimize deposition conditions. In this review, we give a summary of different low-energy electron-induced fragmentation processes that can be initiated by the secondary electrons generated in FEBID, specifically, dissociative electron attachment, dissociative ionization, neutral dissociation, and dipolar dissociation, emphasizing the different nature and energy dependence of each process. We then explore the value of studying these processes through comparative gas phase and surface studies for four commonly-used FEBID precursors: MeCpPtMe3, Pt(PF3)4, Co(CO)3NO, and W(CO)6. Through these case studies, it is evident that this combination of studies can provide valuable insight into potential mechanisms governing deposit formation in FEBID. Although further experiments and new approaches are needed, these studies are an important stepping-stone toward better understanding the fundamental physics behind the deposition process and establishing design criteria for optimized FEBID precursors. PMID:26665061

The role of low-energy electrons in focused electron beam induced deposition: four case studies of representative precursors.

PubMed

Thorman, Rachel M; Kumar T P, Ragesh; Fairbrother, D Howard; Ingólfsson, Oddur

2015-01-01

Focused electron beam induced deposition (FEBID) is a single-step, direct-write nanofabrication technique capable of writing three-dimensional metal-containing nanoscale structures on surfaces using electron-induced reactions of organometallic precursors. Currently FEBID is, however, limited in resolution due to deposition outside the area of the primary electron beam and in metal purity due to incomplete precursor decomposition. Both limitations are likely in part caused by reactions of precursor molecules with low-energy (<100 eV) secondary electrons generated by interactions of the primary beam with the substrate. These low-energy electrons are abundant both inside and outside the area of the primary electron beam and are associated with reactions causing incomplete ligand dissociation from FEBID precursors. As it is not possible to directly study the effects of secondary electrons in situ in FEBID, other means must be used to elucidate their role. In this context, gas phase studies can obtain well-resolved information on low-energy electron-induced reactions with FEBID precursors by studying isolated molecules interacting with single electrons of well-defined energy. In contrast, ultra-high vacuum surface studies on adsorbed precursor molecules can provide information on surface speciation and identify species desorbing from a substrate during electron irradiation under conditions more representative of FEBID. Comparing gas phase and surface science studies allows for insight into the primary deposition mechanisms for individual precursors; ideally, this information can be used to design future FEBID precursors and optimize deposition conditions. In this review, we give a summary of different low-energy electron-induced fragmentation processes that can be initiated by the secondary electrons generated in FEBID, specifically, dissociative electron attachment, dissociative ionization, neutral dissociation, and dipolar dissociation, emphasizing the different nature and energy dependence of each process. We then explore the value of studying these processes through comparative gas phase and surface studies for four commonly-used FEBID precursors: MeCpPtMe3, Pt(PF3)4, Co(CO)3NO, and W(CO)6. Through these case studies, it is evident that this combination of studies can provide valuable insight into potential mechanisms governing deposit formation in FEBID. Although further experiments and new approaches are needed, these studies are an important stepping-stone toward better understanding the fundamental physics behind the deposition process and establishing design criteria for optimized FEBID precursors.

Method of making a layered composite electrode/electrolyte

DOEpatents

Visco, Steven J.; Jacobson, Craig P.; DeJonghe, Lutgard C.

2005-01-25

An electrode/electrolyte structure is prepared by a plurality of methods. An unsintered (possibly bisque fired) moderately catalytic electronically-conductive or homogeneous mixed ionic electronic conductive electrode material is deposited on a layer composed of a sintered or unsintered ionically-conductive electrolyte material prior to being sintered. A layer of particulate electrode material is deposited on an unsintered ("green") layer of electrolyte material and the electrode and electrolyte layers are sintered simultaneously, sometimes referred to as "co-firing," under conditions suitable to fully densify the electrolyte while the electrode retains porosity. Or, the layer of particulate electrode material is deposited on a previously sintered layer of electrolyte, and then sintered. Subsequently, a catalytic material is added to the electrode structure by infiltration of an electrolcatalyst precursor (e.g., a metal salt such as a transition metal nitrate). This may be followed by low temperature firing to convert the precursor to catalyst. The invention allows for an electrode with high electronic conductivity and sufficient catalytic activity to achieve high power density in an ionic (electrochemical) device such as fuel cells and electrolytic gas separation systems.

One-dimensional α-MoO3 nanorods for high energy density pseudocapacitor

NASA Astrophysics Data System (ADS)

Dutta, Shibsankar; Pal, Shreyasi; De, Sukanta

2018-04-01

Ultralong α-MoO3 nanorods having length of 500 nm to 1 µm and uniform width of around ˜50 nm have been synthesized by a simple one step hydrothermal route using a molybdenum organic salt precursor. An evaluation of the electrochemical properties of the nanorods was done by cyclic voltammetry (CV), and galvanometric charging- discharging (GCD) test. Because of the high active sites and rapid ion diffusion and electron transport of the electrodes using as prepared nanorods reveals energy density of 65 Wh/kg at a power density of 940 W/ kg and a maximum specific capacitance of 474 F/g. It also shows excellent cycling stability.

Ca-P spots modified zirconia by liquid precursor infiltration and the effect on osteoblast-like cell responses.

PubMed

Li, Yongmei; Liu, Yan; Zhang, Zutai; Zhuge, Ruishen; Ding, Ning; Tian, Yueming

2018-01-26

Ca-P spots modified zirconia by liquid precursor infiltration and the cell responses were investigated. Pre-sintered zirconia specimens were immersed in Ca-P precursor solution. After dense sintering, scanning electron microscopy showed Ca-P spots were formed on the zirconia and anchored with zirconia substrates. The distribution density was increased with the extension of immersion time. Energy dispersive spectrometer confirmed the stoichiometric Ca/P ratio was about 1.67. After hydrothermal treatment, Ca-P spots turned into rod crystals where diffraction peaks of tricalcium phosphate and hydroxyapatite were detected by X-ray diffraction, and Ca 2+ and PO 4 3- release decreased slightly (p>0.05). There was no significant decrease on three-point bending strength (p>0.05). Osteoblast-like MC3T3-E1 cells attached and spread well and showed higher proliferation on Ca-P spots modified zirconia (p<0.05), though its initial alkaline phosphatase activity was not significant high (p>0.05). In conclusion, Ca-P liquid precursor infiltration is a potential method to modify the zirconia ceramics for improving bioactivity.

Plasma-Assisted Atomic Layer Deposition of High-Density Ni Nanoparticles for Amorphous In-Ga-Zn-O Thin Film Transistor Memory

NASA Astrophysics Data System (ADS)

Qian, Shi-Bing; Wang, Yong-Ping; Shao, Yan; Liu, Wen-Jun; Ding, Shi-Jin

2017-02-01

For the first time, the growth of Ni nanoparticles (NPs) was explored by plasma-assisted atomic layer deposition (ALD) technique using NiCp2 and NH3 precursors. Influences of substrate temperature and deposition cycles on ALD Ni NPs were studied by field emission scanning electron microscope and X-ray photoelectron spectroscopy. By optimizing the process parameters, high-density and uniform Ni NPs were achieved in the case of 280 °C substrate temperature and 50 deposition cycles, exhibiting a density of 1.5 × 1012 cm-2 and a small size of 3 4 nm. Further, the above Ni NPs were used as charge storage medium of amorphous indium-gallium-zinc oxide (a-IGZO) thin film transistor (TFT) memory, demonstrating a high storage capacity for electrons. In particular, the nonvolatile memory exhibited an excellent programming characteristic, e.g., a large threshold voltage shift of 8.03 V was obtained after being programmed at 17 V for 5 ms.

Characterization of argon dielectric barrier discharges applied to ethyl lactate plasma polymerization

NASA Astrophysics Data System (ADS)

Laurent, Morgane; Desjardins, Edouard; Meichelboeck, Maximilian; Naudé, Nicolas; Stafford, Luc; Gherardi, Nicolas; Laroche, Gaétan

2017-11-01

The influence of the input voltage frequency (35 and 150 kHz), interelectrode gap (1 and 2 mm) and precursor concentration (250, 350, and 450 ppm) on the electron temperature (T e), number density of metastable Ar atoms (n(Ar m )), and discharge current density (proportional to the electron density ne) is studied in an argon-ethyl lactate dielectric barrier discharge (DBD). An argon-ammonia Penning mixture is also considered as reference. These results are correlated to the chemistry (XPS, IR) and topography (AFM) of the ethyl-lactate-based plasma polymer coatings. Low T e values from 0.3 to 0.5 eV were obtained for all discharges. This observation, in addition to resemblances with the Ar-NH3 mixture, suggested that the ionization kinetics of ethyl lactate-based discharges is driven by Penning reactions. Among the investigated parameters, the dissipated power obtained through changes of the excitation frequency had the largest impact on both the coatings properties and the discharge behavior.

Thermal Conductivity and Thermopower near the 2D Metal-Insulator transition, Final Technical Report

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

Sarachik, Myriam P.

2015-02-20

STUDIES OF STRONGLY-INTERACTING 2D ELECTRON SYSTEMS – There is a great deal of current interest in the properties of systems in which the interaction between electrons (their potential energy) is large compared to their kinetic energy. We have investigated an apparent, unexpected metal-insulator transition inferred from the behavior of the temperature-dependence of the resistivity; moreover, detailed analysis of the behavior of the magnetoresistance suggests that the electrons’ effective mass diverges, supporting this scenario. Whether this is a true phase transition or crossover behavior has been strenuously debated over the past 20 years. Our measurements have now shown that the thermoelectricmore » power of these 2D materials diverges at a finite density, providing clear evidence that this is, in fact, a phase transition to a new low-density phase which may be a precursor or a direct transition to the long sought-after electronic crystal predicted by Eugene Wigner in 1934.« less

Strong influence of coadsorbate interaction on CO desorption dynamics on Ru(0001) probed by ultrafast x-ray spectroscopy and ab initio simulations

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

Xin, H.; LaRue, J.; Oberg, H.

2015-04-16

We show that coadsorbed oxygen atoms have a dramatic influence on the CO desorption dynamics from Ru(0001). In contrast to the precursor-mediated desorption mechanism on Ru(0001), the presence of surface oxygen modifies the electronic structure of Ru atoms such that CO desorption occurs predominantly via the direct pathway. This phenomenon is directly observed in an ultrafast pump-probe experiment using a soft x-ray free-electron laser to monitor the dynamic evolution of the valence electronic structure of the surface species. This is supported with the potential of mean force along the CO desorption path obtained from density-functional theory calculations. Charge density distributionmore » and frozen-orbital analysis suggest that the oxygen-induced reduction of the Pauli repulsion, and consequent increase of the dative interaction between the CO 5σ and the charged Ru atom, is the electronic origin of the distinct desorption dynamics. Ab initio molecular dynamics simulations of CO desorption from Ru(0001) and oxygen-coadsorbed Ru(0001) provide further insights into the surface bond-breaking process.« less

Synthesis of metal nanoparticle and patterning in polymeric films induced by electron beam

NASA Astrophysics Data System (ADS)

Yamamoto, Hiroki; Kozawa, Takahiro; Tagawa, Seiichi; Marignier, Jean-Louis; Mostafavi, Mehran; Belloni, Jacqueline

2018-03-01

Using an electron beam, thin polymeric films loaded with metal nanoparticles of silver were prepared by a one-step irradiation-induced reduction of the metal ions embedded in the polymer. The metal nanoparticles were observed by either optical absorption or microscopy. The mechanism of the reduction of metal ions and of the polymer crosslinking were deduced from the average absorbance measurements. In view of realizing specific patterns of high resolution using the electron beam, electron beam produces 200 nm wide lines that can be separated by unexposed spaces of adjustable width, where precursors were dissolved. The resolution of the electron beam has been exploited to demonstrate the achievement of nanopatterning on polymer films using a direct-writing process. This method supplies interesting applications such as masks, replicas, or imprint molds of improved density and contrast.

Structural transitions in electron beam deposited Co-carbonyl suspended nanowires at high electrical current densities.

PubMed

Gazzadi, Gian Carlo; Frabboni, Stefano

2015-01-01

Suspended nanowires (SNWs) have been deposited from Co-carbonyl precursor (Co2(CO)8) by focused electron beam induced deposition (FEBID). The SNWs dimensions are about 30-50 nm in diameter and 600-850 nm in length. The as-deposited material has a nanogranular structure of mixed face-centered cubic (FCC) and hexagonal close-packed (HCP) Co phases, and a composition of 80 atom % Co, 15 atom % O and 5 atom % C, as revealed by transmission electron microscopy (TEM) analysis and by energy-dispersive X-ray (EDX) spectroscopy, respectively. Current (I)-voltage (V) measurements with current densities up to 10(7) A/cm(2) determine different structural transitions in the SNWs, depending on the I-V history. A single measurement with a sudden current burst leads to a polycrystalline FCC Co structure extended over the whole wire. Repeated measurements at increasing currents produce wires with a split structure: one half is polycrystalline FCC Co and the other half is graphitized C. The breakdown current density is found at 2.1 × 10(7) A/cm(2). The role played by resistive heating and electromigration in these transitions is discussed.

Development of inorganic resists for electron beam lithography: Novel materials and simulations

NASA Astrophysics Data System (ADS)

Jeyakumar, Augustin

Electron beam lithography is gaining widespread utilization as the semiconductor industry progresses towards both advanced optical and non-optical lithographic technologies for high resolution patterning. The current resist technologies are based on organic systems that are imaged most commonly through chain scission, networking, or a chemically amplified polarity change in the material. Alternative resists based on inorganic systems were developed and characterized in this research for high resolution electron beam lithography and their interactions with incident electrons were investigated using Monte Carlo simulations. A novel inorganic resist imaging scheme was developed using metal-organic precursors which decompose to form metal oxides upon electron beam irradiation that can serve as inorganic hard masks for hybrid bilayer inorganic-organic imaging systems and also as directly patternable high resolution metal oxide structures. The electron beam imaging properties of these metal-organic materials were correlated to the precursor structure by studying effects such as interactions between high atomic number species and the incident electrons. Optimal single and multicomponent precursors were designed for utilization as viable inorganic resist materials for sub-50nm patterning in electron beam lithography. The electron beam imaging characteristics of the most widely used inorganic resist material, hydrogen silsesquioxane (HSQ), was also enhanced using a dual processing imaging approach with thermal curing as well as a sensitizer catalyzed imaging approach. The interaction between incident electrons and the high atomic number species contained in these inorganic resists was also studied using Monte Carlo simulations. The resolution attainable using inorganic systems as compared to organic systems can be greater for accelerating voltages greater than 50 keV due to minimized lateral scattering in the high density inorganic systems. The effects of loading nanoparticles in an electron beam resist was also investigated using a newly developed hybrid Monte Carlo approach that accounts for multiple components in a solid film. The resolution of the nanocomposite resist process was found to degrade with increasing nanoparticle loading. Finally, the electron beam patterning of self-assembled monolayers, which were found to primarily utilize backscattered electrons from the high atomic number substrate materials to form images, was also investigated and characterized. It was found that backscattered electrons limit the resolution attainable at low incident electron energies.

Thermal selectivity of intermolecular versus intramolecular reactions on surfaces

PubMed Central

Cirera, Borja; Giménez-Agulló, Nelson; Björk, Jonas; Martínez-Peña, Francisco; Martin-Jimenez, Alberto; Rodriguez-Fernandez, Jonathan; Pizarro, Ana M.; Otero, Roberto; Gallego, José M.; Ballester, Pablo; Galan-Mascaros, José R.; Ecija, David

2016-01-01

On-surface synthesis is a promising strategy for engineering heteroatomic covalent nanoarchitectures with prospects in electronics, optoelectronics and photovoltaics. Here we report the thermal tunability of reaction pathways of a molecular precursor in order to select intramolecular versus intermolecular reactions, yielding monomeric or polymeric phthalocyanine derivatives, respectively. Deposition of tetra-aza-porphyrin species bearing ethyl termini on Au(111) held at room temperature results in a close-packed assembly. Upon annealing from room temperature to 275 °C, the molecular precursors undergo a series of covalent reactions via their ethyl termini, giving rise to phthalocyanine tapes. However, deposition of the tetra-aza-porphyrin derivatives on Au(111) held at 300 °C results in the formation and self-assembly of monomeric phthalocyanines. A systematic scanning tunnelling microscopy study of reaction intermediates, combined with density functional calculations, suggests a [2+2] cycloaddition as responsible for the initial linkage between molecular precursors, whereas the monomeric reaction is rationalized as an electrocyclic ring closure. PMID:26964764

Counterpropagating Radiative Shock Experiments on the Orion Laser

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

Suzuki-Vidal, F.; Clayson, T.; Stehlé, C.

We present new experiments to study the formation of radiative shocks and the interaction between two counterpropagating radiative shocks. The experiments are performed at the Orion laser facility, which is used to drive shocks in xenon inside large aspect ratio gas cells. The collision between the two shocks and their respective radiative precursors, combined with the formation of inherently three-dimensional shocks, provides a novel platform particularly suited for the benchmarking of numerical codes. The dynamics of the shocks before and after the collision are investigated using point-projection x-ray backlighting while, simultaneously, the electron density in the radiative precursor was measuredmore » via optical laser interferometry. Modeling of the experiments using the 2D radiation hydrodynamic codes nym and petra shows very good agreement with the experimental results.« less

Counterpropagating Radiative Shock Experiments on the Orion Laser.

PubMed

Suzuki-Vidal, F; Clayson, T; Stehlé, C; Swadling, G F; Foster, J M; Skidmore, J; Graham, P; Burdiak, G C; Lebedev, S V; Chaulagain, U; Singh, R L; Gumbrell, E T; Patankar, S; Spindloe, C; Larour, J; Kozlova, M; Rodriguez, R; Gil, J M; Espinosa, G; Velarde, P; Danson, C

2017-08-04

We present new experiments to study the formation of radiative shocks and the interaction between two counterpropagating radiative shocks. The experiments are performed at the Orion laser facility, which is used to drive shocks in xenon inside large aspect ratio gas cells. The collision between the two shocks and their respective radiative precursors, combined with the formation of inherently three-dimensional shocks, provides a novel platform particularly suited for the benchmarking of numerical codes. The dynamics of the shocks before and after the collision are investigated using point-projection x-ray backlighting while, simultaneously, the electron density in the radiative precursor was measured via optical laser interferometry. Modeling of the experiments using the 2D radiation hydrodynamic codes nym and petra shows very good agreement with the experimental results.

Counterpropagating Radiative Shock Experiments on the Orion Laser

DOE PAGES

Suzuki-Vidal, F.; Clayson, T.; Stehlé, C.; ...

2017-08-02

We present new experiments to study the formation of radiative shocks and the interaction between two counterpropagating radiative shocks. The experiments are performed at the Orion laser facility, which is used to drive shocks in xenon inside large aspect ratio gas cells. The collision between the two shocks and their respective radiative precursors, combined with the formation of inherently three-dimensional shocks, provides a novel platform particularly suited for the benchmarking of numerical codes. The dynamics of the shocks before and after the collision are investigated using point-projection x-ray backlighting while, simultaneously, the electron density in the radiative precursor was measuredmore » via optical laser interferometry. Modeling of the experiments using the 2D radiation hydrodynamic codes nym and petra shows very good agreement with the experimental results.« less

Response under low-energy electron irradiation of a thin film of a potential copper precursor for focused electron beam induced deposition (FEBID)

PubMed Central

Sala, Leo; Szymańska, Iwona B; Dablemont, Céline; Lafosse, Anne

2018-01-01

Background: Focused electron beam induced deposition (FEBID) allows for the deposition of free standing material within nanometre sizes. The improvement of the technique needs a combination of new precursors and optimized irradiation strategies to achieve a controlled fragmentation of the precursor for leaving deposited material of desired composition. Here a new class of copper precursors is studied following an approach that probes some surface processes involved in the fragmentation of precursors. We use complexes of copper(II) with amines and perfluorinated carboxylate ligands that are solid and stable under ambient conditions. They are directly deposited on the surface for studying the fragmentation with surface science tools. Results: Infrared spectroscopy and high-resolution electron energy loss spectroscopy (HREELS) are combined to show that the precursor is able to spontaneously lose amine ligands under vacuum. This loss can be enhanced by mild heating. The combination of mass spectrometry and low-energy electron irradiation (0–15 eV) shows that full amine ligands can be released upon irradiation, and that fragmentation of the perfluorinated ligands is induced by electrons of energy as low as 1.5 eV. Finally, the cross section for this process is estimated from the temporal evolution in the experiments on electron-stimulated desorption (ESD). Conclusion: The release of full ligands under high vacuum and by electron irradiation, and the cross section measured here for ligands fragmentation allow one to envisage the use of the two precursors for FEBID studies. PMID:29379701

Coating and functionalization of high density ion track structures by atomic layer deposition

NASA Astrophysics Data System (ADS)

Mättö, Laura; Szilágyi, Imre M.; Laitinen, Mikko; Ritala, Mikko; Leskelä, Markku; Sajavaara, Timo

2016-10-01

In this study flexible TiO2 coated porous Kapton membranes are presented having electron multiplication properties. 800 nm crossing pores were fabricated into 50 μm thick Kapton membranes using ion track technology and chemical etching. Consecutively, 50 nm TiO2 films were deposited into the pores of the Kapton membranes by atomic layer deposition using Ti(iOPr)4 and water as precursors at 250 °C. The TiO2 films and coated membranes were studied by scanning electron microscopy (SEM), X-ray diffraction (XRD) and X-ray reflectometry (XRR). Au metal electrode fabrication onto both sides of the coated foils was achieved by electron beam evaporation. The electron multipliers were obtained by joining two coated membranes separated by a conductive spacer. The results show that electron multiplication can be achieved using ALD-coated flexible ion track polymer foils.

A critical literature review of focused electron beam induced deposition

NASA Astrophysics Data System (ADS)

van Dorp, W. F.; Hagen, C. W.

2008-10-01

An extensive review is given of the results from literature on electron beam induced deposition. Electron beam induced deposition is a complex process, where many and often mutually dependent factors are involved. The process has been studied by many over many years in many different experimental setups, so it is not surprising that there is a great variety of experimental results. To come to a better understanding of the process, it is important to see to which extent the experimental results are consistent with each other and with the existing model. All results from literature were categorized by sorting the data according to the specific parameter that was varied (current density, acceleration voltage, scan patterns, etc.). Each of these parameters can have an effect on the final deposit properties, such as the physical dimensions, the composition, the morphology, or the conductivity. For each parameter-property combination, the available data are discussed and (as far as possible) interpreted. By combining models for electron scattering in a solid, two different growth regimes, and electron beam induced heating, the majority of the experimental results were explained qualitatively. This indicates that the physical processes are well understood, although quantitatively speaking the models can still be improved. The review makes clear that several major issues remain. One issue encountered when interpreting results from literature is the lack of data. Often, important parameters (such as the local precursor pressure) are not reported, which can complicate interpretation of the results. Another issue is the fact that the cross section for electron induced dissociation is unknown. In a number of cases, a correlation between the vertical growth rate and the secondary electron yield was found, which suggests that the secondary electrons dominate the dissociation rather than the primary electrons. Conclusive evidence for this hypothesis has not been found. Finally, there is a limited understanding of the mechanism of electron induced precursor dissociation. In many cases, the deposit composition is not directly dependent on the stoichiometric composition of the precursor and the electron induced decomposition paths can be very different from those expected from calculations or thermal decomposition. The dissociation mechanism is one of the key factors determining the purity of the deposits and a better understanding of this process will help develop electron beam induced deposition into a viable nanofabrication technique.

Ab initio molecular dynamics of atomic-scale surface reactions: insights into metal organic chemical vapor deposition of AlN on graphene.

PubMed

Sangiovanni, D G; Gueorguiev, G K; Kakanakova-Georgieva, A

2018-06-19

Metal organic chemical vapor deposition (MOCVD) of group III nitrides on graphene heterostructures offers new opportunities for the development of flexible optoelectronic devices and for the stabilization of conceptually-new two-dimensional materials. However, the MOCVD of group III nitrides is regulated by an intricate interplay of gas-phase and surface reactions that are beyond the resolution of experimental techniques. We use density-functional ab initio molecular dynamics (AIMD) with van der Waals corrections to identify atomistic pathways and associated electronic mechanisms driving precursor/surface reactions during metal organic vapor phase epitaxy at elevated temperatures of aluminum nitride on graphene, considered here as model case study. The results presented provide plausible interpretations of atomistic and electronic processes responsible for delivery of Al, C adatoms, and C-Al, CHx, AlNH2 admolecules on pristine graphene via precursor/surface reactions. In addition, the simulations reveal C adatom permeation across defect-free graphene, as well as exchange of C monomers with graphene carbon atoms, for which we obtain rates of ∼0.3 THz at typical experimental temperatures (1500 K), and extract activation energies Eexca = 0.28 ± 0.13 eV and attempt frequencies Aexc = 2.1 (×1.7±1) THz via Arrhenius linear regression. The results demonstrate that AIMD simulations enable understanding complex precursor/surface reaction mechanisms, and thus propose AIMD to become an indispensable routine prediction-tool toward more effective exploitation of chemical precursors and better control of MOCVD processes during synthesis of functional materials.

Ab initio study of the mechanism of bottom-up synthesis of graphene nanoribbons

NASA Astrophysics Data System (ADS)

Xiao, Zhongcan; Ma, Chuanxu; Zhang, Honghai; Liang, Liangbo; Huang, Jingsong; Lu, Wenchang; Hong, Kunlun; Li, An-Ping; Bernholc, Jerry

Graphene nanoribbons (GNRs) can be fabricated with atomic precision by using molecular precursors deposited on a metal substrate, and potentially form the basis for future molecular-scale electronics. The precursor molecules are first annealed to form a polymer, and further annealing at a higher temperature leads to the formation of a GNR. We systematically study the reaction pathways of this cyclodehydrogenation process, using density functional theory and the nudged elastic band method. We find that the Au substrate reduces the reaction barriers for key steps in the cyclodehydrogenation process: cyclization, hydrogen migration and desorption. Furthermore, our calculations explain recent experiments showing that an STM-tip can induce local polymer-to-GNR transition, which can be used to fabricate atomically precise heterojunctions: at a negative bias, the STM tip injects excess holes into the polymer HOMO state, lowering the energy barrier in agreement with Woodward-Hoffmann rules. At a positive bias, when excess electrons are injected into the LUMO state, the energy barrier is not significantly lowered and the transition is not observed.

Plasma-Assisted Atomic Layer Deposition of High-Density Ni Nanoparticles for Amorphous In-Ga-Zn-O Thin Film Transistor Memory.

PubMed

Qian, Shi-Bing; Wang, Yong-Ping; Shao, Yan; Liu, Wen-Jun; Ding, Shi-Jin

2017-12-01

For the first time, the growth of Ni nanoparticles (NPs) was explored by plasma-assisted atomic layer deposition (ALD) technique using NiCp 2 and NH 3 precursors. Influences of substrate temperature and deposition cycles on ALD Ni NPs were studied by field emission scanning electron microscope and X-ray photoelectron spectroscopy. By optimizing the process parameters, high-density and uniform Ni NPs were achieved in the case of 280 °C substrate temperature and 50 deposition cycles, exhibiting a density of ~1.5 × 10 12  cm -2 and a small size of 3~4 nm. Further, the above Ni NPs were used as charge storage medium of amorphous indium-gallium-zinc oxide (a-IGZO) thin film transistor (TFT) memory, demonstrating a high storage capacity for electrons. In particular, the nonvolatile memory exhibited an excellent programming characteristic, e.g., a large threshold voltage shift of 8.03 V was obtained after being programmed at 17 V for 5 ms.

Nanowire growth by an electron beam induced massive phase transformation

DOE PAGES

Sood, Shantanu; Kisslinger, Kim; Gouma, Perena

2014-11-15

Tungsten trioxide nanowires of a high aspect ratio have been synthesized in-situ in a TEM under an electron beam of current density 14A/cm² due to a massive polymorphic reaction. Sol-gel processed pseudocubic phase nanocrystals of tungsten trioxide were seen to rapidly transform to one dimensional monoclinic phase configurations, and this reaction was independent of the substrate on which the material was deposited. The mechanism of the self-catalyzed polymorphic transition and accompanying radical shape change is a typical characteristic of metastable to stable phase transformations in nanostructured polymorphic metal oxides. A heuristic model is used to confirm the metastable to stablemore » growth mechanism. The findings are important to the control electron beam deposition of nanowires for functional applications starting from colloidal precursors.« less

Patterned growth of p-type MoS 2 atomic layers using sol-gel as precursor

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

Zheng, Wei; Lin, Junhao; Feng, Wei

2D layered MoS 2 has drawn intense attention for its applications in flexible electronic, optoelectronic, and spintronic devices. Most of the MoS 2 atomic layers grown by conventional chemical vapor deposition techniques are n-type due to the abundant sulfur vacancies. Facile production of MoS 2 atomic layers with p-type behavior, however, remains challenging. Here, a novel one-step growth has been developed to attain p-type MoS 2 layers in large scale by using Mo-containing sol–gel, including 1% tungsten (W). Atomic-resolution electron microscopy characterization reveals that small tungsten oxide clusters are commonly present on the as-grown MoS 2 film due to themore » incomplete reduction of W precursor at the reaction temperature. These omnipresent small tungsten oxide clusters contribute to the p-type behavior, as verified by density functional theory calculations, while preserving the crystallinity of the MoS 2 atomic layers. The Mo containing sol–gel precursor is compatible with the soft-lithography techniques, which enables patterned growth of p-type MoS 2 atomic layers into regular arrays with different shapes, holding great promise for highly integrated device applications. Lastly, an atomically thin p–n junction is fabricated by the as-prepared MoS 2, which shows strong rectifying behavior.« less

Coinfection with recombinant vaccinia viruses expressing poliovirus P1 and P3 proteins results in polyprotein processing and formation of empty capsid structures.

PubMed

Ansardi, D C; Porter, D C; Morrow, C D

1991-04-01

The assembly process of poliovirus occurs via an ordered proteolytic processing of the capsid precursor protein, P1, by the virus-encoded proteinase 3CD. To further delineate this process, we have isolated a recombinant vaccinia virus which expresses, upon infection, the poliovirus P1 capsid precursor polyprotein with an authentic carboxy terminus. Coinfection of HeLa cells with the P1-expressing vaccinia virus and with a second recombinant vaccinia virus which expresses the poliovirus proteinase 3CD resulted in the correct processing of P1 to yield the three individual capsid proteins VP0, VP3, and VP1. When extracts from coinfected cells were fractionated on sucrose density gradients, the VP0, VP3, and VP1 capsid proteins were immunoprecipitated with type 1 poliovirus antisera from fractions corresponding to a sedimentation consistent for poliovirus 75S procapsids. Examination of these fractions by electron microscopy revealed structures which lacked electron-dense cores and which corresponded in size and shape to those expected for poliovirus empty capsids. We conclude that the expression of the two poliovirus proteins P1 and 3CD in coinfected cells is sufficient for the correct processing of the capsid precursor to VP0, VP3, and VP1 as well as for the assembly of poliovirus empty capsid-like structures.

Patterned growth of p-type MoS 2 atomic layers using sol-gel as precursor

DOE PAGES

Zheng, Wei; Lin, Junhao; Feng, Wei; ...

2016-07-19

2D layered MoS 2 has drawn intense attention for its applications in flexible electronic, optoelectronic, and spintronic devices. Most of the MoS 2 atomic layers grown by conventional chemical vapor deposition techniques are n-type due to the abundant sulfur vacancies. Facile production of MoS 2 atomic layers with p-type behavior, however, remains challenging. Here, a novel one-step growth has been developed to attain p-type MoS 2 layers in large scale by using Mo-containing sol–gel, including 1% tungsten (W). Atomic-resolution electron microscopy characterization reveals that small tungsten oxide clusters are commonly present on the as-grown MoS 2 film due to themore » incomplete reduction of W precursor at the reaction temperature. These omnipresent small tungsten oxide clusters contribute to the p-type behavior, as verified by density functional theory calculations, while preserving the crystallinity of the MoS 2 atomic layers. The Mo containing sol–gel precursor is compatible with the soft-lithography techniques, which enables patterned growth of p-type MoS 2 atomic layers into regular arrays with different shapes, holding great promise for highly integrated device applications. Lastly, an atomically thin p–n junction is fabricated by the as-prepared MoS 2, which shows strong rectifying behavior.« less

Self-Assembly of Antisite Defectless nano-LiFePO4 @C/Reduced Graphene Oxide Microspheres for High-Performance Lithium-Ion Batteries.

PubMed

Wang, Hongbin; Liu, Lijia; Wang, Runwei; Yan, Xiao; Wang, Ziqi; Hu, Jiangtao; Chen, Haibiao; Jiang, Shang; Ni, Ling; Qiu, Hailong; Tang, Haitong; Wei, Yingjin; Zhang, Zongtao; Qiu, Shilun; Pan, Feng

2018-05-18

LiFePO 4 @C/reduced graphene oxide (rGO) hierarchical microspheres with superior electrochemical activity and a high tap density were first synthesized by using a Fe 3+ -based single inorganic precursor (LiFePO 4 OH@RF/GO; RF=resorcinol-formaldehyde, GO=graphene oxide) obtained from a template-free self-assembly synthesis followed by direct calcination. The synthetic process requires no physical mixing step. The phase transformation pathway from tavorite LiFePO 4 OH to olivine LiFePO 4 upon calcination was determined by means of the in situ high-temperature XRD technique. Benefitting from the unique structure of the material, these microspheres can be densely packed together, giving a high tap density of 1.3 g cm -3 , and simultaneously, defectless LiFePO 4 primary nanocrystals modified with a highly conductive surface carbon layer and ultrathin rGO provide good electronic and ionic kinetics for fast electron/Li + ion transport. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

INTRACELLULAR FORMS OF POX VIRUSES AS SHOWN BY THE ELECTRON MICROSCOPE (VACCINIA, ECTROMELIA, MOLLUSCUM CONTAGIOSUM)

PubMed Central

Gaylord, William H.; Melnick, Joseph L.

1953-01-01

The intracellular development of three pox viruses has been studied with the electron microscope using thin sections of infected tissue. Cells infected with vaccinia, ectromelia, and molluscum contagiosum viruses all form developmental bodies preliminary to the production of mature virus. Developmental bodies, believed to be virus precursors, are round to oval, slightly larger than mature virus particles, less dense to electrons, and have a more varied morphology. It is suggested as a working hypothesis that the process of maturation of a virus particle takes place as follows. In the earliest form the developmental bodies appear as hollow spheres, imbedded in a very dense cytoplasmic mass constituting an inclusion body, or in a less dense matrix near the nucleus in cells without typical inclusion bodies. The spheres become filled with a homogeneous material of low electron density. A small, dense granule appears in each developmental body and grows in size at the expense of the low density material. Following growth of the granule, particles are found with the dimensions of mature virus and having complex internal structure resembling bars or dumbells. Mature virus is ovoid and very dense to electrons. An "empty" interior may be found within its thick walls. PMID:13069658

Insight into the kinetics and thermodynamics of the hydride transfer reactions between quinones and lumiflavin: a density functional theory study.

PubMed

Reinhardt, Clorice R; Jaglinski, Tanner C; Kastenschmidt, Ashly M; Song, Eun H; Gross, Adam K; Krause, Alyssa J; Gollmar, Jonathan M; Meise, Kristin J; Stenerson, Zachary S; Weibel, Tyler J; Dison, Andrew; Finnegan, Mackenzie R; Griesi, Daniel S; Heltne, Michael D; Hughes, Tom G; Hunt, Connor D; Jansen, Kayla A; Xiong, Adam H; Hati, Sanchita; Bhattacharyya, Sudeep

2016-09-01

The kinetics and equilibrium of the hydride transfer reaction between lumiflavin and a number of substituted quinones was studied using density functional theory. The impact of electron withdrawing/donating substituents on the redox potentials of quinones was studied. In addition, the role of these substituents on the kinetics of the hydride transfer reaction with lumiflavin was investigated in detail under the transition state (TS) theory assumption. The hydride transfer reactions were found to be more favorable for an electron-withdrawing substituent. The activation barrier exhibited a quadratic relationship with the driving force of these reactions as derived under the formalism of modified Marcus theory. The present study found a significant extent of electron delocalization in the TS that is stabilized by enhanced electrostatic, polarization, and exchange interactions. Analysis of geometry, bond-orders, and energetics revealed a predominant parallel (Leffler-Hammond) effect on the TS. Closer scrutiny reveals that electron-withdrawing substituents, although located on the acceptor ring, reduce the N-H bond order of the donor fragment in the precursor complex. Carried out in the gas-phase, this is the first ever report of a theoretical study of flavin's hydride transfer reactions with quinones, providing an unfiltered view of the electronic effect on the nuclear reorganization of donor-acceptor complexes.

Bottom-up synthesis of multifunctional nanoporous graphene

NASA Astrophysics Data System (ADS)

Moreno, César; Vilas-Varela, Manuel; Kretz, Bernhard; Garcia-Lekue, Aran; Costache, Marius V.; Paradinas, Markos; Panighel, Mirko; Ceballos, Gustavo; Valenzuela, Sergio O.; Peña, Diego; Mugarza, Aitor

2018-04-01

Nanosize pores can turn semimetallic graphene into a semiconductor and, from being impermeable, into the most efficient molecular-sieve membrane. However, scaling the pores down to the nanometer, while fulfilling the tight structural constraints imposed by applications, represents an enormous challenge for present top-down strategies. Here we report a bottom-up method to synthesize nanoporous graphene comprising an ordered array of pores separated by ribbons, which can be tuned down to the 1-nanometer range. The size, density, morphology, and chemical composition of the pores are defined with atomic precision by the design of the molecular precursors. Our electronic characterization further reveals a highly anisotropic electronic structure, where orthogonal one-dimensional electronic bands with an energy gap of ∼1 electron volt coexist with confined pore states, making the nanoporous graphene a highly versatile semiconductor for simultaneous sieving and electrical sensing of molecular species.

On the role of precursor powder composition in controlling microstructure, flux pinning, and the critical current density of Ag/Bi2Sr2CaCu2Ox conductors

NASA Astrophysics Data System (ADS)

Li, Pei; Naderi, Golsa; Schwartz, Justin; Shen, Tengming

2017-03-01

Precursor powder composition is known to strongly affect the critical current density (J c) of Ag/Bi2Sr2CaCu2Ox (Bi-2212) wires. However, reasons for such J c dependence have not yet been fully understood, compromising our ability to achieve further optimization. We systematically examined superconducting properties, microstructural evolution and phase transformation, and grain boundaries of Bi-2212 conductors fabricated from precursor powders with a range of compositions using a combination of transport-current measurements, a quench technique to freeze microstructures at high temperatures during heat treatment, and scanning transmission electron microscopy (STEM). Samples include both dip-coated tapes and round wires, among which a commercial round wire carries a high J c of 7600 A mm-2 at 4.2 K, self-field and 2600 A mm-2 at 4.2 K, 20 T, respectively. In the melt, this high-J c conductor, made using a composition of Bi2.17Sr1.94Ca0.89Cu2Ox, contains a uniform dispersion of fine alkaline-earth cuprate (AEC) and copper-free solid phases, whereas several low-J c conductors contain large AEC particles. Such significant differences in the phase morphologies in the melt are accompanied by a drastic difference in the formation kinetics of Bi-2212 during recrystallization cooling. STEM studies show that Bi-2212 grain colonies in the high-J c conductors have a high density of Bi2Sr2CuO y (Bi-2201) intergrowths, whereas a low-J c conductor, made using Bi2.14Sr1.66Ca1.24Cu1.96O x , is nearly free of them. STEM investigation shows grain boundaries in low-J c conductors are often insulated with a Bi-rich amorphous phase. High-J c conductors also show higher flux-pinning strength, which we ascribe to their higher Bi-2201 intergrowth density.

XPS study of thermal and electron-induced decomposition of Ni and Co acetylacetonate thin films for metal deposition

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

Weiss, Theodor; Warneke, Jonas; Zielasek, Volkmar, E-mail: zielasek@uni-bremen.de

2016-07-15

Optimizing thin metal film deposition techniques from metal-organic precursors such as atomic layer deposition, chemical vapor deposition (CVD), or electron beam-induced deposition (EBID) with the help of surface science analysis tools in ultrahigh vacuum requires a contamination-free precursor delivery technique, especially in the case of the less volatile precursors. For this purpose, the preparation of layers of undecomposed Ni(acac){sub 2} and Co(acac){sub 2} was tried via pulsed spray evaporation of a liquid solution of the precursors in ethanol into a flow of nitrogen on a CVD reactor. Solvent-free layers of intact precursor molecules were obtained when the substrate was heldmore » at a temperature of 115 °C. A qualitative comparison of thermally initiated and electron-induced precursor decomposition and metal center reduction was carried out. All deposited films were analyzed with respect to chemical composition quasi in situ by x-ray photoelectron spectroscopy. Thermally initiated decomposition yielded higher metal-to-metal oxide ratios in the deposit than the electron-induced process for which ratios of 60:40 and 20:80 were achieved for Ni and Co, resp. Compared to continuous EBID processes, all deposits showed low levels of carbon impurities of ∼10 at. %. Therefore, postdeposition irradiation of metal acetylacetonate layers by a focused electron beam and subsequent removal of intact precursor by dissolution in ethanol or by heating is proposed as electron beam lithography technique on the laboratory scale for the production of the metal nanostructures.« less

The hybrid nanostructure of MnCo2O4.5 nanoneedle/carbon aerogel for symmetric supercapacitors with high energy density

NASA Astrophysics Data System (ADS)

Hao, Pin; Zhao, Zhenhuan; Li, Liyi; Tuan, Chia-Chi; Li, Haidong; Sang, Yuanhua; Jiang, Huaidong; Wong, C. P.; Liu, Hong

2015-08-01

Current applications of carbon-based supercapacitors are limited by their low energy density. One promising strategy to enhance the energy density is to couple metal oxides with carbon materials. In this study, a porous MnCo2O4.5 nanoneedle/carbon aerogel hybrid nanostructure was synthesized by assembling MnCo2O4.5 nanoneedle arrays on the surface of channel walls of hierarchical porous carbon aerogels derived from chitosan for the supercapacitor application. The synthetic process of the hybrid nanostructure involves two steps, i.e. the growth of Mn-Co precursors on carbon aerogel by a hydrothermal process and the conversion of the precursor into MnCo2O4.5 nanoneedles by calcination. The carbon aerogel exhibits a high electrical conductivity, high specific surface area and porous structure, ensuring high electrochemical performance of the hybrid nanostructure when coupled with the porous MnCo2O4.5 nanoneedles. The symmetric supercapacitor using the MnCo2O4.5 nanoneedle/carbon aerogel hybrid nanostructure as the active electrode material exhibits a high energy density of about 84.3 Wh kg-1 at a power density of 600 W kg-1. The voltage window is as high as 1.5 V in neutral aqueous electrolytes. Due to the unique nanostructure of the electrodes, the capacitance retention reaches 86% over 5000 cycles.Current applications of carbon-based supercapacitors are limited by their low energy density. One promising strategy to enhance the energy density is to couple metal oxides with carbon materials. In this study, a porous MnCo2O4.5 nanoneedle/carbon aerogel hybrid nanostructure was synthesized by assembling MnCo2O4.5 nanoneedle arrays on the surface of channel walls of hierarchical porous carbon aerogels derived from chitosan for the supercapacitor application. The synthetic process of the hybrid nanostructure involves two steps, i.e. the growth of Mn-Co precursors on carbon aerogel by a hydrothermal process and the conversion of the precursor into MnCo2O4.5 nanoneedles by calcination. The carbon aerogel exhibits a high electrical conductivity, high specific surface area and porous structure, ensuring high electrochemical performance of the hybrid nanostructure when coupled with the porous MnCo2O4.5 nanoneedles. The symmetric supercapacitor using the MnCo2O4.5 nanoneedle/carbon aerogel hybrid nanostructure as the active electrode material exhibits a high energy density of about 84.3 Wh kg-1 at a power density of 600 W kg-1. The voltage window is as high as 1.5 V in neutral aqueous electrolytes. Due to the unique nanostructure of the electrodes, the capacitance retention reaches 86% over 5000 cycles. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr04421a

Is actinometry reliable for monitoring Si and silicone halides produced in silicon etching plasmas? A comparison with their absolute densities measured by UV broad band absorption

NASA Astrophysics Data System (ADS)

Kogelschatz, M.; Cunge, G.; Sadeghi, N.

2006-03-01

SiCl{x} radicals, the silicon etching by-products, are playing a major role in silicon gate etching processes because their redeposition on the wafer leads to the formation of a SiOCl{x} passivation layer on the feature sidewalls, which controls the final shape of the etching profile. These radicals are also the precursors to the formation of a similar layer on the reactor walls, leading to process drifts. As a result, the understanding and modelling of these processes rely on the knowledge of their densities in the plasma. Actinometry technique, based on optical emission, is often used to measure relative variations of the density of the above mentioned radicals, even if it is well known that the results obtained with this technique might not always be reliable. To determine the validity domain of actinometry in industrial silicon-etching high density plasmas, we measure the RF source power and pressure dependences of the absolute densities of SiCl{x} (x=0{-}2), SiF and SiBr radicals, deduced from UV broad band absorption spectroscopy. These results are compared to the evolution of the corresponding actinometry signals from these radicals. It is shown that actinometry predicts the global trends of the species density variations when the RF power is changed at constant pressure (that is to say when only the electron density changes) but it completely fails if the gas pressure, hence the electron temperature, changes.

High performance all-solid-state symmetric supercapacitor based on porous carbon made from a metal-organic framework compound

NASA Astrophysics Data System (ADS)

Yu, Feng; Wang, Teng; Wen, Zubiao; Wang, Hongxia

2017-10-01

In this work, we demonstrate the synthesis of porous carbon material with high specific surface area by using metal-organic framework (MOF) as precursor. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) have confirmed that the material was amorphous and consisted of nanoparticles (5-6 nm) and hierarchical distribution of pores. The characterization of the material by N2 adsorption/desorption isotherm measurement have shown that the material had a high specific surface area reaching to 2618.7 m2 g-1 and abundant porosity with pore size less than 10 nm. The investigation of the electrochemical properties of the material has shown the porous carbon electrode possessed excellent rate performance with high specific capacitances of 150.8 F g-1 at a current density of 5 A g-1, and 133.6 F g-1 at a current density of 50 A g-1, respectively. An all-solid-state symmetric supercapacitor assembled using the as-prepared porous carbon as electrodes and Na2SO4/PVA gel as an electrolyte delivered a high power density of 13 516.4 W kg-1 with an energy density of 8.26 Wh kg-1. A high energy density of 17.37 Wh kg-1 was obtained at discharge current density of 1 A g-1. In addition, the device exhibited superior cycling performance with 94.8% retention rate after 10 000 cycles at a current density of 10 A g-1.

Mesoporous Titania Powders: The Role of Precursors, Ligand Addition and Calcination Rate on Their Morphology, Crystalline Structure and Photocatalytic Activity

PubMed Central

Masolo, Elisabetta; Meloni, Manuela; Garroni, Sebastiano; Mulas, Gabriele; Enzo, Stefano; Baró, Maria Dolors; Rossinyol, Emma; Rzeszutek, Agnieszka; Herrmann-Geppert, Iris; Pilo, Maria

2014-01-01

We evaluate the influence of the use of different titania precursors, calcination rate, and ligand addition on the morphology, texture and phase content of synthesized mesoporous titania samples, parameters which, in turn, can play a key role in titania photocatalytic performances. The powders, obtained through the evaporation-induced self-assembly method, are characterized by means of ex situ X-Ray Powder Diffraction (XRPD) measurements, N2 physisorption isotherms and transmission electron microscopy. The precursors are selected basing on two different approaches: the acid-base pair, using TiCl4 and Ti(OBu)4, and a more classic route with Ti(OiPr)4 and HCl. For both precursors, different specimens were prepared by resorting to different calcination rates and with and without the addition of acetylacetone, that creates coordinated species with lower hydrolysis rates, and with different calcination rates. Each sample was employed as photoanode and tested in the water splitting reaction by recording I-V curves and comparing the results with commercial P25 powders. The complex data framework suggests that a narrow pore size distribution, due to the use of acetylacetone, plays a major role in the photoactivity, leading to a current density value higher than that of P25. PMID:28344237

Fe-Based Amorphous Coatings on AISI 4130 Structural Steel for Corrosion Resistance

NASA Astrophysics Data System (ADS)

Katakam, Shravana; Santhanakrishnan, S.; Dahotre, Narendra B.

2012-06-01

The current study focuses on synthesizing a novel functional coating for corrosion resistance applications, via laser surface alloying. The iron-based (Fe48Cr15Mo14Y2C15B) amorphous precursor powder is used for laser surface alloying on AISI 4130 steel substrate, with a continuous wave ytterbium Nd-YAG fiber laser. The corrosion resistance of the coatings is evaluated for different processing conditions. The microstructural evolution and the response of the microstructure to the corrosive environment is studied using x-ray diffraction, scanning electron microscopy, and transmission electron microscopy. Microstructural studies indicate the presence of face-centered cubic Fe-based dendrites intermixed within an amorphous matrix along with fine crystalline precipitates. The corrosion resistance of the coatings decrease with an increase in laser energy density, which is attributed to the precipitation and growth of chromium carbide. The enhanced corrosion resistance of the coatings processed with low energy density is attributed to the self-healing mechanism of this amorphous system.

Kinetic effects in InP nanowire growth and stacking fault formation: the role of interface roughening.

PubMed

Chiaramonte, Thalita; Tizei, Luiz H G; Ugarte, Daniel; Cotta, Mônica A

2011-05-11

InP nanowire polytypic growth was thoroughly studied using electron microscopy techniques as a function of the In precursor flow. The dominant InP crystal structure is wurtzite, and growth parameters determine the density of stacking faults (SF) and zinc blende segments along the nanowires (NWs). Our results show that SF formation in InP NWs cannot be univocally attributed to the droplet supersaturation, if we assume this variable to be proportional to the ex situ In atomic concentration at the catalyst particle. An imbalance between this concentration and the axial growth rate was detected for growth conditions associated with larger SF densities along the NWs, suggesting a different route of precursor incorporation at the triple phase line in that case. The formation of SFs can be further enhanced by varying the In supply during growth and is suppressed for small diameter NWs grown under the same conditions. We attribute the observed behaviors to kinetically driven roughening of the semiconductor/metal interface. The consequent deformation of the triple phase line increases the probability of a phase change at the growth interface in an effort to reach local minima of system interface and surface energy.

Low-temperature, high yield synthesis, and convenient isolation of the high-electron-density cluster compound Ta6Br14.8H2O for use in biomacromolecular crystallographic phase determination.

PubMed

Hay, Daniel N T; Messerle, Louis

2002-09-01

Reduction of TaBr(5) with Ga in the presence of KBr in a sealed borosilicate ampule at 400 degrees, followed by aqueous Soxhlet extraction and addition of stannous bromide and hydrobromic acid to the extract, yielded Ta(6)Br(14).8H(2)O in 80-84% yield. The new procedure provides a convenient, low temperature, high yield route to the synthesis of the title compound from inexpensive precursors.

Synthesis and spectroscopic characterization of gold nanoparticles via plasma-liquid interaction technique

NASA Astrophysics Data System (ADS)

Khatoon, N.; Yasin, H. M.; Younus, M.; Ahmed, W.; Rehman, N. U.; Zakaullah, M.; Iqbal, M. Zafar

2018-01-01

Fabrication of non-functionalized gold nanoparticles is interesting owing to their potential applications in sensing and biomedicine. We report on the synthesis of surfactant-free gold nanoparticles (AuNPs) by Plasma-Liquid Interaction (PLI) technique, using micro-atmospheric pressure D.C. plasma. The effects of discharge parameters, such as discharge current, precursor concentration and gas flow rates on the structure and morphology of AuNPs have been investigated. Optical Emission Spectroscopy (OES) was employed to estimate the UV radiation intensity and OH radical density. Scanning electron microscopy (SEM) and ultraviolet-visible (UV-Vis) optical spectroscopy were employed to study the morphology and structure of AuNPs. The normalized intensities of UV radiation and OH radical density found to increase with increase in discharge current. We observed that the particle size can be tuned by controlling any of the following parameters: intensity of the UV radiation, OH radical density, and concentration of the Au precursor. Interestingly, we found that addition of 1% Ar in the feedstock gas results in formation of relatively uniform size distribution of nanoparticles. The surfactant-free AuNPs, due to their bare-surface, exhibit excellent surface-enhanced Raman scattering (SERS) properties. The SERS study of Rhodamine 6G using AuNPs as substrates, shows significant Raman enhancement and fluorescence quenching, which makes our technique a potentially powerful route to detection of trace amounts of dangerous explosives and other materials.

The Flavivirus Precursor Membrane-Envelope Protein Complex: Structure and Maturation

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

Li, Long; Lok, Shee-Mei; Yu, I-Mei

2008-09-17

Many viruses go through a maturation step in the final stages of assembly before being transmitted to another host. The maturation process of flaviviruses is directed by the proteolytic cleavage of the precursor membrane protein (prM), turning inert virus into infectious particles. We have determined the 2.2 angstrom resolution crystal structure of a recombinant protein in which the dengue virus prM is linked to the envelope glycoprotein E. The structure represents the prM-E heterodimer and fits well into the cryo-electron microscopy density of immature virus at neutral pH. The pr peptide {beta}-barrel structure covers the fusion loop in E, preventingmore » fusion with host cell membranes. The structure provides a basis for identifying the stages of its pH-directed conformational metamorphosis during maturation, ending with release of pr when budding from the host.« less

Seismo-ionospheric anomalies in ionospheric TEC and plasma density before the 17 July 2006 M7.7 south of Java earthquake

NASA Astrophysics Data System (ADS)

Tao, Dan; Cao, Jinbin; Battiston, Roberto; Li, Liuyuan; Ma, Yuduan; Liu, Wenlong; Zhima, Zeren; Wang, Lanwei; Wray Dunlop, Malcolm

2017-04-01

In this paper, we report significant evidence for preseismic ionospheric anomalies in total electron content (TEC) of the global ionosphere map (GIM) and plasma density appearing on day 2 before the 17 July 2006 M7.7 south of Java earthquake. After distinguishing other anomalies related to the geomagnetic activities, we found a temporal precursor around the epicenter on day 2 before the earthquake (15 July 2006), which agrees well with the spatial variations in latitude-longitude-time (LLT) maps. Meanwhile, the sequences of latitude-time-TEC (LTT) plots reveal that the TECs on epicenter side anomalously decrease and lead to an anomalous asymmetric structure with respect to the magnetic equator in the daytime from day 2 before the earthquake. This anomalous asymmetric structure disappears after the earthquake. To further confirm these anomalies, we studied the plasma data from DEMETER satellite in the earthquake preparation zone (2046.4 km in radius) during the period from day 45 before to day 10 after the earthquake, and also found that the densities of both electron and total ion in the daytime significantly increase on day 2 before the earthquake. Very interestingly, O+ density increases significantly and H+ density decreases, while He+ remains relatively stable. These results indicate that there exists a distinct preseismic signal (preseismic ionospheric anomaly) over the epicenter.

Radio Tomography of Ionospheric Structures (probably) due to Underground-Surface-Atmosphere-Ionosphere Coupling

NASA Astrophysics Data System (ADS)

Kunitsyn, V.; Nesterov, I.; Andreeva, E.; Rekenthaler, D. A.

2012-12-01

Ionospheric radio-tomography (RT) utilizes radio signals transmitted from the global navigational satellite systems (GNSS), including low-orbiting (LO) navigational systems such as Transit, Tsikada, etc., and high-orbiting (HO) navigational systems such as GPS, GLONASS, Galileo, Beidou, etc. The signals that are transmitted from the LO navigational satellites and recorded by ground receiving chains can be inverted for almost instantaneous (5-8 min) 2D snapshots of electron density. The data from the networks of ground receivers that record the signals of the HO satellites are suitable for implementing high-orbital RT (HORT), i.e. reconstructing the 4D distributions of the ionospheric electron density (one 3D image every 20-30 min). In the regions densely covered by the GNSS receivers, it is currently possible to get a time step of 2-4 min. The LORT and HORT approaches have a common methodical basis: in both these techniques, the integrals of electron density along the ray between the satellite and the receiver are measured, and then the tomographic procedures are applied to reconstruct the distributions of electron density. We present several examples of the experiments on the ionospheric RT, which are related to the Underground-Surface-Atmosphere-Ionosphere (USAI) coupling. In particular, we demonstrate examples of RT images of the ionosphere after industrial explosions, rocket launches, and modification of the ionosphere by high-power radio waves. We also show RT cross sections reflecting ionospheric disturbances caused by the earthquakes (EQ) and tsunami waves. In these cases, there is an evident cause-and-effect relationship. The perturbations are transferred between the geospheres predominantly by acoustic gravity waves (AGW), whose amplitudes increase with increasing height. As far as EQ are concerned, the cause of the USAI coupling mechanism is not obvious. It is clear, however, that the regular RT studies can promote the solution of this challenging problem. The single-point measurements (by ionosondes or by isolated receivers) are not amenable to unambiguous interpretation; based on these data, it is impossible to distinguish the contribution of USAI coupling from the ionospheric effects induced by the "ordinary" impacts (the Sun, the solar wind, geomagnetic perturbations, galactic cosmic rays, etc.). In order to localize sources of the ionospheric disturbances, the geophysicist needs information on the spatial structure and dynamics of the ionospheric perturbations. This information (2D-4D RT images) is optimally provided by RT methods. We present examples of the ionospheric disturbances caused by EQs as well as the ionospheric precursors of these EQs in the form of specific ionospheric irregularities: AGW- and soliton-like wave disturbances, which we identified using RT methods. Based on the results of the RT studies in the Alaska and Taiwan regions, we have detected several dozen AGW-related precursors of EQs. These data allow us to attempt to locate the source of these perturbations. We discuss the possibilities and prospects of further research aimed at identifying and analyzing precursors of EQs and establishing the mechanisms of USAI coupling. We are grateful to Northwest Research Associates, Inc., and Dr. L.-C.Tsai for providing raw RT data for Alaska and Taiwan.

Spectroscopic studies of MW plasmas containing HMDSO, O2 and N2

NASA Astrophysics Data System (ADS)

Nave, Andy; Roepcke, Juergen; Mitschker, Felix; Awakowicz, Peter

2015-09-01

The deposition of SiOx layers based on organosilicon plasmas is used to implement advantageous mechanical, electrical, and/or optical properties on various substrates. The development of such coating processes resulting in a wide range of chemical and physical film properties, using hexamethyldisiloxane (HMDSO) as a precursor, has been in the center of interest of various studies. In plasma, the dissociation of HMDSO into a large amount of fragments is a complex chemical phenomenon. The monitoring of the precursor and of formed species is very valuable to understand the plasma chemistry. Infrared absorption spectroscopy based on lead salt lasers and EC Quantum Cascade Laser have been used to monitor the concentrations of HMDSO, and of the reaction products CH4, C2H2, C2H4,C2H6, CO, CO2 and CH3 as a function of the HMDSO/O2 mixture ratio, and the power at various pressures in a MW plasma deposition reactor. Optical emission spectroscopy has been applied as complementary diagnostics to evaluate electron density and electron temperature. Supported by the German Research Foundation within SFB-TR24 and SFB-TR87.

Precursor Selection for Property Optimization in Biomorphic SiC Ceramics

NASA Technical Reports Server (NTRS)

Varela-Feria, F. M.; Lopez-Robledo, M. J.; Martinez-Fernandez, J.; deArellano-Lopez, A. R.; Singh, M.; Gray, Hugh R. (Technical Monitor)

2002-01-01

Biomorphic SiC ceramics have been fabricated using different wood precursors. The evolution of volume, density and microstructure of the woods, carbon performs, and final SiC products are systematically studied in order to establish experimental guidelines that allow materials selection. The wood density is a critical characteristic, which results in a particular final SiC density, and the level of anisotropy in mechanical properties in directions parallel (axial) and perpendicular (radial) to the growth of the wood. The purpose of this work is to explore experimental laws that can help choose a type of wood as precursor for a final SiC product, with a given microstructure, density and level of anisotropy. Preliminary studies of physical properties suggest that not only mechanical properties are strongly anisotropic, but also electrical conductivity and gas permeability, which have great technological importance.

A sintering study on the β-spodumene-based glass ceramics prepared from gel-derived precursor powders with LiF additive

NASA Astrophysics Data System (ADS)

Wang, Moo-Chin; Wu, Nan-Chung; Yang, Sheng; Wen, Shaw-Bing

2002-01-01

Beta-spodumene (Li2O·Al2O3·4SiO2, LAS) powders were prepared by a sol-gel process using Si(OC2H5)4, Al(OC4H9)3, and LiNO3 as precursors and LiF as a sintering aid agent. Dilatometry, X-ray diffraction (XRD), scanning electron microscopy (SEM), scanning transmission electron microscopy (STEM), and electron diffraction (ED) were utilized to study the sintering, phase transformation, microstructure, and properties of the β-spodumene glass-ceramics prepared from the gel-derived precursor powders with and without LiF additives. For the LAS precursor powders containing no LiF, the only crystalline phase obtained was β-spodumene. For the pellets containing less than 4 wt pct LiF and sintered at 1050 °C for 5 hours the crystalline phases were β-spodumene and β-eucryptite (Li2O·Al2O3·2SiO2). When the LiF content was 5 wt pct and the sintering process was carried out at 1050 °C for 5 hours, the crystalline phases were β-spodumene, β-eucryptite (triclinic), and eucryptite (rhombohedral (hex.)) phases. With the LiF additive increased from 0.5 to 4 wt pct and sintering at 1050 °C for 5 hours, the open porosity of the sintered bodies decrease from 30 to 2.1 pct. The grains size is about to 4 to 5 µm when pellect LAS compact contains LiF 3 wt pct as sintered at 1050 °C for 5 hours. The grains size grew to 8 to 25 µm with a remarkable discontinuous grain growth for pellet LAS compact contain LiF 5 wt pct sintered at 1050 °C for 5 hours. Relative densities greater than 90 pct could be obtained for the LAS precursor powders with LiF > 2 wt pct when sintered at 1050 °C for 5 hours. The coefficient of thermal expansion of the sintered bodies decreased from 8.3 × 10-7 to 5.2 × 10-7/°C (25 °C to 900 °C) as the LiF addition increased from 0 to 5 wt pct.

Seismo-ionospheric Precursors of the Total Electron Content Associated with Global Large Earthquakes Examined by Using Ground-based and Space-based Radio Occultation GNSS Observations

NASA Astrophysics Data System (ADS)

Liu, J. Y. G.

2017-12-01

To verify seismo-ionospheric precursors (SIPs), statistical analyses are implemented on the relationship between the total electron content (TEC) in the global ionosphere map (GIM) derived from measurements of ground-based GNSS (global navigation satellite system) receivers and worldwide M≥7.0 earthquakes during 2000-2016. A median-based method is employed to determine the characteristic of TEC anomalies related to the earthquakes. It is found that the polarity of both negative (decrease) and positive (increase) in the GIM TEC, which varies location-by location, can be observed few days before the earthquakes. In general, PEIAs with the negative polarity associated with the earthquakes are more frequently detected. Meanwhile, FORMOSAT-3/COSMIC (Constellation Observing System for Meteorology, Ionosphere, and Climate) or F3/C in was launched into a circular low-Earth orbit on 15 April 2006. Six F3/C microsatellites with 72-degree inclination angle and 30-degree separation in longitude orbit at 800 km altitude, and conduct the ionospheric radio occultation (RO) observations by receiving signals from GNSS satellites and globally observing about 2500 vertical electron density profiles per day. Both ground-based and space-based RO GNSS observations are used to three dimensionally study SIPs related to the 11 March 2011 M9.0 Tohoku earthquake.

Density Functional Theory Study of the Reaction between d0 Tungsten Alkylidyne Complexes and H2O: Addition versus Hydrolysis.

PubMed

Chen, Ping; Zhang, Linxing; Xue, Zi-Ling; Wu, Yun-Dong; Zhang, Xinhao

2017-06-19

The reactions of early-transition-metal complexes with H 2 O have been investigated. An understanding of these elementary steps promotes the design of precursors for the preparation of metal oxide materials or supported heterogeneous catalysts. Density functional theory (DFT) calculations have been conducted to investigate two elementary steps of the reactions between tungsten alkylidyne complexes and H 2 O, i.e., the addition of H 2 O to the W≡C bond and ligand hydrolysis. Four tungsten alkylidyne complexes, W(≡CSiMe 3 )(CH 2 SiMe 3 ) 3 (A-1), W(≡CSiMe 3 )(CH 2 t Bu) 3 (B-1), W(≡C t Bu)(CH 2 t Bu) 3 (C-1), and W(≡C t Bu)(O t Bu) 3 (D-1), have been compared. The DFT studies provide an energy profile of the two competing pathways. An additional H 2 O molecule can serve as a proton shuttle, accelerating the H 2 O addition reaction. The effect of atoms at the α and β positions has also been examined. Because the lone-pair electrons of an O atom at the α position can interact with the orbital of the proton, the barrier of the ligand-hydrolysis reaction for D-1 is dramatically reduced. Both the electronic and steric effects of the silyl group at the β position lower the barriers of both the H 2 O addition and ligand-hydrolysis reactions. These new mechanistic findings may lead to the further development of metal complex precursors.

Simultaneous constraint and phase conversion processing of oxide superconductors

DOEpatents

Li, Qi; Thompson, Elliott D.; Riley, Jr., Gilbert N.; Hellstrom, Eric E.; Larbalestier, David C.; DeMoranville, Kenneth L.; Parrell, Jeffrey A.; Reeves, Jodi L.

2003-04-29

A method of making an oxide superconductor article includes subjecting an oxide superconductor precursor to a texturing operation to orient grains of the oxide superconductor precursor to obtain a highly textured precursor; and converting the textured oxide superconducting precursor into an oxide superconductor, while simultaneously applying a force to the precursor which at least matches the expansion force experienced by the precursor during phase conversion to the oxide superconductor. The density and the degree of texture of the oxide superconductor precursor are retained during phase conversion. The constraining force may be applied isostatically.

Structures with high number density of carbon nanotubes and 3-dimensional distribution

NASA Technical Reports Server (NTRS)

Chen, Zheng (Inventor); Tzeng, Yonhua (Inventor)

2002-01-01

A composite is described having a three dimensional distribution of carbon nanotubes. The critical aspect of such composites is a nonwoven network of randomly oriented fibers connected at their junctions to afford macropores in the spaces between the fibers. A variety of fibers may be employed, including metallic fibers, and especially nickel fibers. The composite has quite desirable properties for cold field electron emission applications, such as a relatively low turn-on electric field, high electric field enhancement factors, and high current densities. The composites of this invention also show favorable properties for other an electrode applications. Several methods, which also have general application in carbon nanotube production, of preparing these composites are described and employ a liquid feedstock of oxyhydrocarbons as carbon nanotube precursors.

Spheroidization of molybdenum powder by radio frequency thermal plasma

NASA Astrophysics Data System (ADS)

Liu, Xiao-ping; Wang, Kuai-she; Hu, Ping; Chen, Qiang; Volinsky, Alex A.

2015-11-01

To control the morphology and particle size of dense spherical molybdenum powder prepared by radio frequency (RF) plasma from irregular molybdenum powder as a precursor, plasma process parameters were optimized in this paper. The effects of the carrier gas flow rate and molybdenum powder feeding rate on the shape and size of the final products were studied. The molybdenum powder morphology was examined using high-resolution scanning electron microscopy. The powder phases were analyzed by X-ray diffraction. The tap density and apparent density of the molybdenum powder were investigated using a Hall flow meter and a Scott volumeter. The optimal process parameters for the spherical molybdenum powder preparation are 50 g/min powder feeding rate and 0.6 m3/h carrier gas rate. In addition, pure spherical molybdenum powder can be obtained from irregular powder, and the tap density is enhanced after plasma processing. The average size is reduced from 72 to 62 µm, and the tap density is increased from 2.7 to 6.2 g/cm3. Therefore, RF plasma is a promising method for the preparation of high-density and high-purity spherical powders.

Vibrational Properties of Hydrogen-Bonded Systems Using the Multireference Generalization to the "On-the-Fly" Electronic Structure within Quantum Wavepacket ab Initio Molecular Dynamics (QWAIMD).

PubMed

Li, Junjie; Li, Xiaohu; Iyengar, Srinivasan S

2014-06-10

We discuss a multiconfigurational treatment of the "on-the-fly" electronic structure within the quantum wavepacket ab initio molecular dynamics (QWAIMD) method for coupled treatment of quantum nuclear effects with electronic structural effects. Here, multiple single-particle electronic density matrices are simultaneously propagated with a quantum nuclear wavepacket and other classical nuclear degrees of freedom. The multiple density matrices are coupled through a nonorthogonal configuration interaction (NOCI) procedure to construct the instantaneous potential surface. An adaptive-mesh-guided set of basis functions composed of Gaussian primitives are used to simplify the electronic structure calculations. Specifically, with the replacement of the atom-centered basis functions positioned on the centers of the quantum-mechanically treated nuclei by a mesh-guided band of basis functions, the two-electron integrals used to compute the electronic structure potential surface become independent of the quantum nuclear variable and hence reusable along the entire Cartesian grid representing the quantum nuclear coordinates. This reduces the computational complexity involved in obtaining a potential surface and facilitates the interpretation of the individual density matrices as representative diabatic states. The parametric nuclear position dependence of the diabatic states is evaluated at the initial time-step using a Shannon-entropy-based sampling function that depends on an approximation to the quantum nuclear wavepacket and the potential surface. This development is meant as a precursor to an on-the-fly fully multireference electronic structure procedure embedded, on-the-fly, within a quantum nuclear dynamics formalism. We benchmark the current development by computing structural, dynamic, and spectroscopic features for a series of bihalide hydrogen-bonded systems: FHF(-), ClHCl(-), BrHBr(-), and BrHCl(-). We find that the donor-acceptor structural features are in good agreement with experiments. Spectroscopic features are computed using a unified velocity/flux autocorrelation function and include vibrational fundamentals and combination bands. These agree well with experiments and other theories.

Atomically resolved calcium phosphate coating on a gold substrate.

PubMed

Metoki, Noah; Baik, Sung-Il; Isheim, Dieter; Mandler, Daniel; Seidman, David N; Eliaz, Noam

2018-05-10

Some articles have revealed that the electrodeposition of calcium phosphate (CaP) coatings entails a precursor phase, similarly to biomineralization in vivo. The chemical composition of the initial layer and its thickness are, however, still arguable, to the best of our knowledge. Moreover, while CaP and electrodeposition of metal coatings have been studied utilizing atom-probe tomography (APT), the electrodeposition of CaP ceramics has not been heretofore studied. Herein, we present an investigation of the CaP deposition on a gold substrate. Using APT and transmission electron microscopy (TEM) it is found that a mixture of phases, which could serve as transient precursor phases to hydroxyapatite (HAp), can be detected. The thickness of these phases is tens of nanometers, and they consist of amorphous CaP (ACP), dibasic calcium phosphate dihydrate (DCPD), and octacalcium phosphate (OCP). This demonstrates the value of using atomic-resolved characterization techniques for identifying the precursor phases. It also indicates that the kinetics of their transformation into the more stable HAp is not too fast to enable their observation. The coating gradually displays higher Ca/P atomic ratios, a porous nature, and concomitantly a change in its density.

The Biermann Catastrophe in Numerical Magnetohydrodynamics

NASA Astrophysics Data System (ADS)

Graziani, Carlo; Tzeferacos, Petros; Lee, Dongwook; Lamb, Donald Q.; Weide, Klaus; Fatenejad, Milad; Miller, Joshua

2015-03-01

The Biermann battery effect is frequently invoked in cosmic magnetogenesis and studied in high-energy density laboratory physics experiments. Generation of magnetic fields by the Biermann effect due to misaligned density and temperature gradients in smooth flow behind shocks is well known. We show that a Biermann-effect magnetic field is also generated within shocks. Direct implementation of the Biermann effect in MHD codes does not capture this physical process, and worse, it produces unphysical magnetic fields at shocks whose value does not converge with resolution. We show that this convergence breakdown is due to naive discretization, which fails to account for the fact that discretized irrotational vector fields have spurious solenoidal components that grow without bound near a discontinuity. We show that careful consideration of the kinetics of ion viscous shocks leads to a formulation of the Biermann effect that gives rise to a convergent algorithm. We note two novel physical effects: a resistive magnetic precursor, in which a Biermann-generated field in the shock “leaks” resistively upstream, and a thermal magnetic precursor, in which a field is generated by the Biermann effect ahead of the shock front owing to gradients created by the shock’s electron thermal conduction precursor. Both effects appear to be potentially observable in experiments at laser facilities. We reexamine published studies of magnetogenesis in galaxy cluster formation and conclude that the simulations in question had inadequate resolution to reliably estimate the field generation rate. Corrected estimates suggest primordial field values in the range B˜ {{10}-22}-10-19 G by z = 3.

Tunable optical properties of some rare earth elements-doped mayenite Ca12Al14O33 nanopowders elaborated by oxalate precursor route

NASA Astrophysics Data System (ADS)

Rashad, Mohamed M.; Mostafa, Ahmed G.; Mwakikunga, Bonex W.; Rayan, Diaa A.

2017-01-01

Rare earth (RE) ions-doped mayenite Ca12Al14- x RE x O33 nanopowders (where RE = La and Gd and x = 0-1.0) were synthesized using the oxalate precursor technique. The as-prepared precursors were calcined at 800 °C for 2 h. Obviously, all RE-doped Ca12Al14- x RE x O33 possessed a well-crystalline cubic mayenite phase till RE content of 0.8. The crystallo-chemical aspects including crystallite size, lattice parameters, theoretical X-ray density and bulk density were robustly on RE nature and ratio. The microstructure and the average grain size were significantly influenced by the RE kind and content. The high transparency of Ca12Al14- x RE x O33 over 80% was found to be evinced in the visible wavelength range of 400-800 nm. Besides, the incorporation of RE cation minimized the direct band gap energy from 4.42 eV for pure mayenite to 3.85 and 3.59 eV with x value 1.0 of La3+ and Gd3+ ions. The photoluminescence spectra of pure mayenite nanoparticles showed that the band edge emission ( λ exc = 248 nm) with an intense visible emission band at 360 nm was detected. Otherwise, the band edge emission showed a slight shift toward short wavelength due to the substitution Al3+ by RE3+ ions. Such results open a new avenue for application of mayenite as a good candidate for transparent low-temperature electron conductor for optoelectronics applications.

Focused electron beam based direct-write fabrication of graphene and amorphous carbon from oxo-functionalized graphene on silicon dioxide.

PubMed

Schindler, Severin; Vollnhals, Florian; Halbig, Christian E; Marbach, Hubertus; Steinrück, Hans-Peter; Papp, Christian; Eigler, Siegfried

2017-01-25

Controlled patterning of graphene is an important task towards device fabrication and thus is the focus of current research activities. Graphene oxide (GO) is a solution-processible precursor of graphene. It can be patterned by thermal processing. However, thermal processing of GO leads to decomposition and CO 2 formation. Alternatively, focused electron beam induced processing (FEBIP) techniques can be used to pattern graphene with high spatial resolution. Based on this approach, we explore FEBIP of GO deposited on SiO 2 . Using oxo-functionalized graphene (oxo-G) with an in-plane lattice defect density of 1% we are able to image the electron beam-induced effects by scanning Raman microscopy for the first time. Depending on electron energy (2-30 keV) and doses (50-800 mC m -2 ) either reduction of GO or formation of permanent lattice defects occurs. This result reflects a step towards controlled FEBIP processing of oxo-G.

Realizing Large-Scale, Electronic-Grade Two-Dimensional Semiconductors.

PubMed

Lin, Yu-Chuan; Jariwala, Bhakti; Bersch, Brian M; Xu, Ke; Nie, Yifan; Wang, Baoming; Eichfeld, Sarah M; Zhang, Xiaotian; Choudhury, Tanushree H; Pan, Yi; Addou, Rafik; Smyth, Christopher M; Li, Jun; Zhang, Kehao; Haque, M Aman; Fölsch, Stefan; Feenstra, Randall M; Wallace, Robert M; Cho, Kyeongjae; Fullerton-Shirey, Susan K; Redwing, Joan M; Robinson, Joshua A

2018-02-27

Atomically thin transition metal dichalcogenides (TMDs) are of interest for next-generation electronics and optoelectronics. Here, we demonstrate device-ready synthetic tungsten diselenide (WSe 2 ) via metal-organic chemical vapor deposition and provide key insights into the phenomena that control the properties of large-area, epitaxial TMDs. When epitaxy is achieved, the sapphire surface reconstructs, leading to strong 2D/3D (i.e., TMD/substrate) interactions that impact carrier transport. Furthermore, we demonstrate that substrate step edges are a major source of carrier doping and scattering. Even with 2D/3D coupling, transistors utilizing transfer-free epitaxial WSe 2 /sapphire exhibit ambipolar behavior with excellent on/off ratios (∼10 7 ), high current density (1-10 μA·μm -1 ), and good field-effect transistor mobility (∼30 cm 2 ·V -1 ·s -1 ) at room temperature. This work establishes that realization of electronic-grade epitaxial TMDs must consider the impact of the TMD precursors, substrate, and the 2D/3D interface as leading factors in electronic performance.

Fractal growth mechanism of sp3-bonded 5H-BN microcones by plasma-assisted pulsed-laser chemical vapor deposition

NASA Astrophysics Data System (ADS)

Komatsu, Shojiro; Kazami, Daisuke; Tanaka, Hironori; Moriyoshi, Yusuke; Shiratani, Masaharu; Okada, Katsuyuki

2006-08-01

Here we propose a repetitive photochemical reaction and diffusion model for the fractal pattern formation of sp3-bonded 5H-BN microcones in laser-assisted plasma chemical vapor deposition, which was observed experimentally and reported previously. This model describing the behavior of the surface density of precursor species gave explanations to (1) the "line-drawing" nature of the patterns, (2) the origin of the scale-invariant self-similarity (fractality) of the pattern, and (3) the temperature-dependent uniform to fractal transition. The results have implications for controlling the self-organized arrangements of electron-emitter cones at the micro-and nanoscale by adjusting macroscopically the boundary condition (LX,LY) for the deposition, which will be very effective in improving the electron field emission properties.

Galvanic displacement assembly of ultrathin Co3O4 nanosheet arrays on nickel foam for a high-performance supercapacitor

NASA Astrophysics Data System (ADS)

You, Yuxiu; Zheng, Maojun; Ma, Liguo; Yuan, Xiaoliang; Zhang, Bin; Li, Qiang; Wang, Faze; Song, Jingnan; Jiang, Dongkai; Liu, Pengjie; Ma, Li; Shen, Wenzhong

2017-03-01

High-performance supercapacitors are very desirable for many portable electronic devices, electric vehicles and high-power electronic devices. Herein, a facile and binder-free synthesis method, galvanic displacement of the precursor followed by heat treatment, is used to fabricate ultrathin Co3O4 nanosheet arrays on nickel foam substrate. When used as a supercapacitor electrode the prepared Co3O4 on nickel foam exhibits a maximum specific capacitance of 1095 F g-1 at a current density of 1 A g-1 and good cycling stability of 71% retention after 2000 cycling tests. This excellent electrochemical performance can be ascribed to the high specific surface area of each Co3O4 nanosheet that comprises numerous nanoparticles.

Extracting the distribution of laser damage precursors on fused silica surfaces for 351 nm, 3 ns laser pulses at high fluences (20-150 J/cm2).

PubMed

Laurence, Ted A; Bude, Jeff D; Ly, Sonny; Shen, Nan; Feit, Michael D

2012-05-07

Surface laser damage limits the lifetime of optics for systems guiding high fluence pulses, particularly damage in silica optics used for inertial confinement fusion-class lasers (nanosecond-scale high energy pulses at 355 nm/3.5 eV). The density of damage precursors at low fluence has been measured using large beams (1-3 cm); higher fluences cannot be measured easily since the high density of resulting damage initiation sites results in clustering. We developed automated experiments and analysis that allow us to damage test thousands of sites with small beams (10-30 µm), and automatically image the test sites to determine if laser damage occurred. We developed an analysis method that provides a rigorous connection between these small beam damage test results of damage probability versus laser pulse energy and the large beam damage results of damage precursor densities versus fluence. We find that for uncoated and coated fused silica samples, the distribution of precursors nearly flattens at very high fluences, up to 150 J/cm2, providing important constraints on the physical distribution and nature of these precursors.

Highly conductive electrospun carbon nanofiber/MnO2 coaxial nano-cables for high energy and power density supercapacitors

NASA Astrophysics Data System (ADS)

Zhi, Mingjia; Manivannan, Ayyakkannu; Meng, Fanke; Wu, Nianqiang

2012-06-01

This paper presents highly conductive carbon nanofiber/MnO2 coaxial cables in which individual electrospun carbon nanofibers are coated with an ultrathin hierarchical MnO2 layer. In the hierarchical MnO2 structure, an around 4 nm thick sheath surrounds the carbon nanofiber (CNF) in a diameter of 200 nm, and nano-whiskers grow radically outward from the sheath in view of the cross-section of the coaxial cables, giving a high specific surface area of MnO2. The CNFs are synthesized by electrospinning a precursor containing iron acetylacetonate (AAI). The addition of AAI not only enlarges the specific surface area of the CNF but also greatly enhances their electronic conductivity, which leads to a dramatic improvement in the specific capacitance and the rate capability of the CNF/MnO2 electrode. The AAI-CNF/MnO2 electrode shows a specific capacitance of 311 F g-1 for the whole electrode and 900 F g-1 for the MnO2 shell at a scan rate of 2 mV s-1. Good cycling stability, high energy density (80.2 Wh kg-1) and high power density (57.7 kW kg-1) are achieved. This work indicates that high electronic conductivity of the electrode material is crucial to achieving high power and energy density for pseudo-supercapacitors.

On the role of precursor powder composition in controlling microstructure, flux pinning, and the critical current density of Ag/Bi$$_2$$Sr$$_2$$CaCu$$_2$$O$$_x$$ conductors

DOE PAGES

Li, Pei; Naderi, Golsa; Schwartz, Justin; ...

2017-01-04

Precursor powder composition is known to strongly affect the critical current density (J c) of Ag/Bimore » $$_2$$Sr$$_2$$CaCu$$_2$$O$$_x$$ (Bi-2212) wires. However, reasons for such J c dependence have not yet been fully understood, compromising our ability to achieve further optimization. In this paper, we systematically examined superconducting properties, microstructural evolution and phase transformation, and grain boundaries of Bi-2212 conductors fabricated from precursor powders with a range of compositions using a combination of transport-current measurements, a quench technique to freeze microstructures at high temperatures during heat treatment, and scanning transmission electron microscopy (STEM). Samples include both dip-coated tapes and round wires, among which a commercial round wire carries a high J c of 7600 A mm -2 at 4.2 K, self-field and 2600 A mm -2 at 4.2 K, 20 T, respectively. In the melt, this high-J c conductor, made using a composition of Bi 2.17Sr 1.94Ca 0.89Cu 2O x, contains a uniform dispersion of fine alkaline-earth cuprate (AEC) and copper-free solid phases, whereas several low-J c conductors contain large AEC particles. Such significant differences in the phase morphologies in the melt are accompanied by a drastic difference in the formation kinetics of Bi-2212 during recrystallization cooling. STEM studies show that Bi-2212 grain colonies in the high-J c conductors have a high density of Bi 2Sr 2CuO y (Bi-2201) intergrowths, whereas a low-J c conductor, made using Bi 2.14Sr 1.66Ca 1.24Cu 1.96O x , is nearly free of them. STEM investigation shows grain boundaries in low-J c conductors are often insulated with a Bi-rich amorphous phase. Finally, high-J c conductors also show higher flux-pinning strength, which we ascribe to their higher Bi-2201 intergrowth density.« less

On the role of precursor powder composition in controlling microstructure, flux pinning, and the critical current density of Ag/Bi$$_2$$Sr$$_2$$CaCu$$_2$$O$$_x$$ conductors

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

Li, Pei; Naderi, Golsa; Schwartz, Justin

Precursor powder composition is known to strongly affect the critical current density (J c) of Ag/Bimore » $$_2$$Sr$$_2$$CaCu$$_2$$O$$_x$$ (Bi-2212) wires. However, reasons for such J c dependence have not yet been fully understood, compromising our ability to achieve further optimization. In this paper, we systematically examined superconducting properties, microstructural evolution and phase transformation, and grain boundaries of Bi-2212 conductors fabricated from precursor powders with a range of compositions using a combination of transport-current measurements, a quench technique to freeze microstructures at high temperatures during heat treatment, and scanning transmission electron microscopy (STEM). Samples include both dip-coated tapes and round wires, among which a commercial round wire carries a high J c of 7600 A mm -2 at 4.2 K, self-field and 2600 A mm -2 at 4.2 K, 20 T, respectively. In the melt, this high-J c conductor, made using a composition of Bi 2.17Sr 1.94Ca 0.89Cu 2O x, contains a uniform dispersion of fine alkaline-earth cuprate (AEC) and copper-free solid phases, whereas several low-J c conductors contain large AEC particles. Such significant differences in the phase morphologies in the melt are accompanied by a drastic difference in the formation kinetics of Bi-2212 during recrystallization cooling. STEM studies show that Bi-2212 grain colonies in the high-J c conductors have a high density of Bi 2Sr 2CuO y (Bi-2201) intergrowths, whereas a low-J c conductor, made using Bi 2.14Sr 1.66Ca 1.24Cu 1.96O x , is nearly free of them. STEM investigation shows grain boundaries in low-J c conductors are often insulated with a Bi-rich amorphous phase. Finally, high-J c conductors also show higher flux-pinning strength, which we ascribe to their higher Bi-2201 intergrowth density.« less

Enhanced ionic conductivity in planar sodium-β"-alumina electrolyte for electrochemical energy storage applications.

PubMed

La Rosa, Daniela; Monforte, Giuseppe; D'Urso, Claudia; Baglio, Vincenzo; Antonucci, Vincenzo; Aricò, Antonino S

2010-12-17

Solid Na-β"-Al₂O₃ electrolyte is prepared by a simple chemical route involving a pseudo-boehmite precursor and thermal treatment. Boehmite powder is used for manufacturing the planar electrolyte with appropriate bulk density after firing at 1500 °C. The structure, morphology, and surface properties of precursor powders and sintered electrolytes are investigated by X-ray diffraction (XRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM), and X-ray photoelectron spectroscopy (XPS). As shown by XRD and TEM analyses, nanometer-sized particles are obtained for the boehmite precursor and a pure crystallographic phase is achieved for the sintered electrolyte. SEM analysis of the cross-section indicates good sintering characteristics. XPS shows a higher Na/Al atomic ratio on the surface for the planar electrolyte compared to a commercial tubular electrolyte (0.57 vs. 0.46). Energy-dispersive X-ray microanalysis (EDX) shows an Na/Al ratio in the bulk of 0.16, similar in the two samples. The ionic conductivity of the planar electrolyte is larger than that measured on a commercial tube of sodium-β"-alumina in a wide temperature range. At 350 °C, conductivity values of 0.5 S cm⁻¹ and 0.26 S cm⁻¹ are obtained for the planar electrolyte and the commercial tube, respectively. AC-impedance spectra show smaller grain boundary effects in the planar electrolyte than in the tubular electrolyte. These favorable properties may increase the perspectives for applying planar Na-β"-Al₂O₃ electrolytes in high-temperature batteries.

Nearly full-dense and fine-grained AZO:Y ceramics sintered from the corresponding nanoparticles

PubMed Central

2012-01-01

Aluminum-doped zinc oxide ceramics with yttria doping (AZO:Y) ranging from 0 to 0.2 wt.% were fabricated by pressureless sintering yttria-modified nanoparticles in air at 1,300°C. Scanning electron microscopy, energy-dispersive X-ray spectroscopy, X-ray diffraction analysis, a physical property measurement system, and a densimeter were employed to characterize the precursor nanoparticles and the sintered AZO ceramics. It was shown that a small amount of yttria doping can remarkably retard the growth of the as-received precursor nanoparticles, further improve the microstructure, refine the grain size, and enhance the density for the sintered ceramic. Increasing the yttria doping to 0.2 wt.%, the AZO:Y nanoparticles synthetized by a coprecipitation process have a nearly sphere-shaped morphology and a mean particle diameter of 15.1 nm. Using the same amount of yttria, a fully dense AZO ceramic (99.98% of theoretical density) with a grain size of 2.2 μm and a bulk resistivity of 4.6 × 10−3 Ω·cm can be achieved. This kind of AZO:Y ceramic has a potential to be used as a high-quality sputtering target to deposit ZnO-based transparent conductive films with better optical and electrical properties. PMID:22929049

Optical and vibrational properties of PbSe nanoparticles synthesized in clinoptilolite

NASA Astrophysics Data System (ADS)

Flores-Valenzuela, J.; Cortez-Valadez, M.; Ramírez-Bon, R.; Arizpe-Chavez, H.; Román-Zamorano, J. F.; Flores-Acosta, M.

2015-08-01

In this work, the optical and vibrational properties of composites based on PbSe semiconductor immersed in a zeolite matrix are reported. The natural zeolite, (clinoptilolite) was used as the host material of PbSe nanoparticles. The method for obtaining these particles is also reported here, which is based on ion exchange processes inside the natural zeolite in alkaline aqueous solution that contains the precursor ions Pb2+ and Se2-. The process of synthesis was conducted temperature, volume, concentration and reaction time of the precursors. The samples were studied by powder X-ray diffraction, TEM (transmission electron microscopy), diffuse reflectance and Raman spectroscopy. The experimental results demonstrate that with this method, the particles with nanometric PbSe sizes were synthesized in the zeolite matrix. Vibrational Raman bands at low wave numbers were detected in these particles by the presence of a shoulder located at 135 cm-1 and a band at around 149 cm-1. The vibrational calculations for small clusters of PbSe at LSDA (Local Spin Density Approximation) level combined with the basis set LANDL2DZ (Los Alamos National Laboratory 2 double ζ), were considered through DFT (Density Functionl Theory). The "breathing" Raman modes located at 119-152 cm-1 were detected for this level of theory.

The effects of shock wave precursors ahead of hypersonic entry vehicles

NASA Technical Reports Server (NTRS)

Stanley, Scott A.; Carlson, Leland A.

1991-01-01

A model has been developed to predict the magnitude and characteristics of the shock wave precursor ahead of a hypervelocity vehicle. This model includes both chemical and thermal nonequilibrium, utilizes detailed mass production rates for the photodissociation and photoionization reactions, and accounts for the effects of radiative absorption and emission on the individual internal energy modes of both atomic and diatomic species. Comparison of the present results with shock tube data indicates that the model is reasonably accurate. A series of test cases representing earth aerocapture return from Mars indicate that there is significant production of atoms, ions and electrons ahead of the shock front due to radiative absorption and that the precursor is characterized by an enhanced electron/electronic temperature and molecular ionization. However, the precursor has a negligible effect on the shock layer flow field.

Electron-Beam-Induced Deposition as a Technique for Analysis of Precursor Molecule Diffusion Barriers and Prefactors.

PubMed

Cullen, Jared; Lobo, Charlene J; Ford, Michael J; Toth, Milos

2015-09-30

Electron-beam-induced deposition (EBID) is a direct-write chemical vapor deposition technique in which an electron beam is used for precursor dissociation. Here we show that Arrhenius analysis of the deposition rates of nanostructures grown by EBID can be used to deduce the diffusion energies and corresponding preexponential factors of EBID precursor molecules. We explain the limitations of this approach, define growth conditions needed to minimize errors, and explain why the errors increase systematically as EBID parameters diverge from ideal growth conditions. Under suitable deposition conditions, EBID can be used as a localized technique for analysis of adsorption barriers and prefactors.

Propositional density and cognitive function in later life: findings from the Precursors Study.

PubMed

Engelman, Michal; Agree, Emily M; Meoni, Lucy A; Klag, Michael J

2010-11-01

We used longitudinal data from the Johns Hopkins Precursors Study to test the hypothesis that written propositional density measured early in life is lower for people who develop dementia categorized as Alzheimer's disease (AD). This association was reported in 1996 for the Nun Study, and the Precursors Study offered an unprecedented chance to reexamine it among respondents with different gender, education, and occupation profiles. Eighteen individuals classified as AD patients (average age at diagnosis: 74) were assigned 2 sex-and-age matched controls, and propositional density in medical school admission essays (average age at writing: 22) was assessed via Computerized Propositional Idea Density Rater 3 linguistic analysis software. Adjusted odds ratios (ORs) for the matched case-control study were calculated using conditional (fixed-effects) logistic regression. Mean propositional density is lower for cases than for controls (4.70 vs. 4.99 propositions per 10 words, 1-sided p = .01). Higher propositional density substantially lowers the odds of AD (OR = 0.16, 95% confidence interval = 0.03-0.90, 1-sided p = .02). Propositional density scores in writing samples from early adulthood appear to predict AD in later life for men as well as women. Studies of cognition across the life course might beneficially incorporate propositional density as a potential marker of cognitive reserve.

Methane chemistry involved in a low-pressure electron cyclotron wave resonant plasma discharge

NASA Astrophysics Data System (ADS)

Morrison, N. A.; William, C.; Milne, W. I.

2003-12-01

Radio frequency (rf) generated methane plasmas are commonly employed in the deposition of hydrogenated amorphous carbon (a-C:H) thin films. However, very little is known about the rf discharge chemistry and how it relates to the deposition process. Consequently, we have characterized a low-pressure methane plasma and compared the results with those obtained theoretically by considering the steady-state kinetics of the chemical processes present in a low-pressure plasma reactor, in order to elucidate the dominant reaction channels responsible for the generation of the active precursors required for film growth. Mass spectrometry measurements of the gas phase indicated little variation in the plasma chemistry with increasing electron temperature. This was later attributed to the partial saturation of the electron-impact dissociation and ionization rate constants at electron temperatures in excess of ˜4 eV. The ion densities in the plasma were also found to be strongly dependent upon the parent neutral concentration in the gas phase, indicating that direct electron-impact reactions exerted greater influence on the plasma chemistry than secondary ion-neutral reactions.

Physical Properties of 3D Interconnected Graphite Networks - Aerographite

DTIC Science & Technology

2015-10-30

Figure 1.2: Influence of toluene injection rate per time on Aerographite density...................... 6 Figure 1.3: Influence of toluene injection ...densities ........................... 20 Figure 3.15: Capacitance as a function of carbon precursor injection rate .............................. 20...At a constant temperature profile of 200° C in the injection zone and 760° C in main zone, a carbon precursor (toluene) is injected with a

Gold nanoparticles deposited on linker-free silicon substrate and embedded in aluminum Schottky contact.

PubMed

Gorji, Mohammad Saleh; Razak, Khairunisak Abdul; Cheong, Kuan Yew

2013-10-15

Given the enormous importance of Au nanoparticles (NPs) deposition on Si substrates as the precursor for various applications, we present an alternative approach to deposit Au NPs on linker-free n- and p-type Si substrates. It is demonstrated that, all conditions being similar, there is a significant difference between densities of the deposited NPs on both substrates. The Zeta-potential and polarity of charges surrounding the hydroxylamine reduced seeded growth Au NPs, are determined by a Zetasizer. To investigate the surface properties of Si substrates, contact angle measurement is performed. Field-emission scanning electron microscope is then utilized to distinguish the NPs density on the substrates. Finally, Al/Si Schottky barrier diodes with embedded Au NPs are fabricated, and their structural and electrical characteristics are further evaluated using an energy-filtered transmission electron microscope and current-voltage measurements, respectively. The results reveal that the density of NPs is significantly higher on n-type Si substrate and consequently has more pronounced effects on the electrical characteristics of the diode. It is concluded that protonation of Si-OH group on Si surface in low pH is responsible for the immobilization of Au NPs, which eventually contributes to the lowering of barrier height and enhances the electrical characteristics. Copyright © 2013 Elsevier Inc. All rights reserved.

Enhanced optoelectronic quality of perovskite thin films with hypophosphorous acid for planar heterojunction solar cells

PubMed Central

Zhang, Wei; Pathak, Sandeep; Sakai, Nobuya; Stergiopoulos, Thomas; Nayak, Pabitra K.; Noel, Nakita K.; Haghighirad, Amir A.; Burlakov, Victor M.; deQuilettes, Dane W.; Sadhanala, Aditya; Li, Wenzhe; Wang, Liduo; Ginger, David S.; Friend, Richard H.; Snaith, Henry J.

2015-01-01

Solution-processed metal halide perovskite semiconductors, such as CH3NH3PbI3, have exhibited remarkable performance in solar cells, despite having non-negligible density of defect states. A likely candidate is halide vacancies within the perovskite crystals, or the presence of metallic lead, both generated due to the imbalanced I/Pb stoichiometry which could evolve during crystallization. Herein, we show that the addition of hypophosphorous acid (HPA) in the precursor solution can significantly improve the film quality, both electronically and topologically, and enhance the photoluminescence intensity, which leads to more efficient and reproducible photovoltaic devices. We demonstrate that the HPA can reduce the oxidized I2 back into I−, and our results indicate that this facilitates an improved stoichiometry in the perovskite crystal and a reduced density of metallic lead. PMID:26615763

Generation of avian cells resembling osteoclasts from mononuclear phagocytes

NASA Technical Reports Server (NTRS)

Alvarez, J. I.; Teitelbaum, S. L.; Blair, H. C.; Greenfield, E. M.; Athanasou, N. A.; Ross, F. P.

1991-01-01

Several lines of indirect evidence suggest that a monocyte family precursor gives rise to the osteoclast, although this hypothesis is controversial. Starting with a uniform population of nonspecific esterase positive, tartrate-sensitive, acid phosphatase-producing, mannose receptor-bearing mononuclear cells, prepared from dispersed marrow of calcium-deprived laying hens by cell density separation and selective cellular adherence, we generated multinucleated cells in vitro. When cultured with devitalized bone, these cells show, by electron microscopy, the characteristic osteoclast morphology in that they are mitochondria-rich, multinucleated, and, most importantly, develop characteristic ruffled membranes at the matrix attachment site. Moreover, as documented by scanning electron microscopy, these cells pit bone slices in a manner identical to freshly isolated osteoclasts. In addition, isoenzymes of acid phosphatase from generated osteoclasts, separated by 7.5% polyacrylamide gel electrophoresis at pH 4, are identical to those of mature osteoclasts in migration pattern and tartrate resistance, although the precursor cells from which the osteoclasts are generated produce an entirely different isoenzyme, which is tartrate-sensitive and migrates less rapidly at pH 4. The fused cells also exhibit a cAMP response to prostaglandin E2. Therefore, osteoclast-like cells can be derived by in vitro culture of a marrow-derived monocyte cell population.

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

Kleinlein, Claudia; Zheng, Shao-Liang; Betley, Theodore A.

Three ferric dipyrromethene complexes featuring different ancillary ligands were synthesized by one electron oxidation of ferrous precursors. Four-coordinate iron complexes of the type ( ArL)FeX 2 [ ArL = 1,9-(2,4,6-Ph 3C 6H 2) 2-5-mesityldipyrromethene] with X = Cl or tBuO were prepared and found to be high-spin (S = 5/2), as determined by superconducting quantum interference device magnetometry, electron paramagnetic resonance, and 57Fe Mössbauer spectroscopy. The ancillary ligand substitution was found to affect both ground state and excited properties of the ferric complexes examined. While each ferric complex displays reversible reduction and oxidation events, each alkoxide for chloride substitution resultsmore » in a nearly 600 mV cathodic shift of the Fe III/II couple. The oxidation event remains largely unaffected by the ancillary ligand substitution and is likely dipyrrin-centered. While the alkoxide substituted ferric species largely retain the color of their ferrous precursors, characteristic of dipyrrin-based ligand-to-ligand charge transfer (LLCT), the dichloride ferric complex loses the prominent dipyrrin chromophore, taking on a deep green color. Time-dependent density functional theory analyses indicate the weaker-field chloride ligands allow substantial configuration mixing of ligand-to-metal charge transfer into the LLCT bands, giving rise to the color changes observed. Furthermore, the higher degree of covalency between the alkoxide ferric centers is manifest in the observed reactivity. Delocalization of spin density onto the tert-butoxide ligand in ( ArL)FeCl(O tBu) is evidenced by hydrogen atom abstraction to yield ( ArL)FeCl and HOtBu in the presence of substrates containing weak C–H bonds, whereas the chloride ( ArL)FeCl 2 analogue does not react under these conditions.« less

Hydrothermal Synthesis and Electrochemical Properties of Spherical α-MnO2 for Supercapacitors.

PubMed

Chen, Ya; Qin, Wenqing; Fan, Ruijuan; Wang, Jiawei; Chen, Baizhen

2015-12-01

In the present work, spherical α-MnO2 with a high specific capacitance was synthesized by a two-step hydrothermal route. MnCO3 precursors were first prepared by a common hydrothermal method, and then converted to α-MnO2 via a hydrothermal reaction between the precursors and KMnO4 solutions. The effects of hydrothermal temperature on the morphology, crystal structure and specific area of the MnO2 were investigated by scanning electron microscopy (SEM), X-ray diffraction (XRD) and BET measurements. The electrochemical capacitive properties of the manganese dioxides with different morphologies and structures were evaluated by cyclic voltammetry and galvonostatic charge-discharge tests. The results showed that the temperature in the second hydrothermal step had prominent impact on the capacitive properties of a-MnO2. The MnO2 synthesized at 150 *C exhibited a highest specific capacitance of 328.4 Fx g(-1) at a charge-discharge current density of 100 mA x g(-1).

Mechanical performance and thermal stability of glass fiber reinforced silica aerogel composites based on co-precursor method by freeze drying

NASA Astrophysics Data System (ADS)

Zhou, Ting; Cheng, Xudong; Pan, Yuelei; Li, Congcong; Gong, Lunlun; Zhang, Heping

2018-04-01

In order to maintain the integrity, glass fiber (GF) reinforced silica aerogel composites were synthesized using methltrimethoxysilane (MTMS) and water glass co-precursor by freeze drying method. The composites were characterized by scanning electron microscopy, Brunauer-Emmett-Teller analysis, uniaxial compressive test, three-point bending test, thermal conductivity analysis, contact angle test, TG-DSC analysis. It was found that the molar ratio of MTMS/water glass could significantly affect the properties of composites. The bulk density and thermal conductivity first decreased and then increased with the increasing molar ratio. The composites showed remarkable mechanical strength and flexibility compared with pure silica aerogel. Moreover, when the molar ratio is 1.8, the composites showed high specific surface area (870.9 m2/g), high contact angle (150°), great thermal stability (560 °C) and low thermal conductivity (0.0248 W/m·K). These outstanding properties indicate that GF/aerogels have broad prospects in the field of thermal insulation.

Photoionization in the Precursor of Laser Supported Detonation by Ultraviolet Radiation

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

Shimamura, Kohei; Michigami, Keisuke; Wang, Bin

The propagation mechanism of laser-supported detonation (LSD) is important for designing laser propulsion for a detonation type thruster. The purpose of this work to was to confirm that photo-ionization in precursor is the predominant LSD sustainment mechanism. First of all, we tried to investigate the dependency of LSD duration on ambient gas species, air and argon. We took a series of high-speed images using the laser shadow-graphy. Besides, to estimate the UV photons emitted from the plasma, we used plasma emission spectroscopy and determined the electron temperature and density. As a result, the LSD duration of argon plasma and airmore » plasma are 0.7 {mu}s and 0.3 {mu}s, resp. Besides, argon plasma emitted 10{sup 10} to 10{sup 14} photons/seconds, which was higher than air plasma. These results reveal that LSD propagation depends on the photon-contributing photoionization. The threshold photon-emission rate of LSD termination gives the elucidation of the LSD termination condition.« less

Doped silicon nanocrystals from organic dopant precursor by a SiCl4-based high frequency nonthermal plasma

NASA Astrophysics Data System (ADS)

Zhou, Shu; Ding, Yi; Pi, Xiaodong; Nozaki, Tomohiro

2014-11-01

Doped silicon nanocrystals (Si NCs) are of great interest in demanding low-cost nanodevices because of the abundance and nontoxicity of Si. Here, we demonstrate a cost-effective gas phase approach to synthesize phosphorous (P)-doped Si NCs in which the precursors used, i.e., SiCl4, trimethyl phosphite (TMP), are both safe and economical. It is found that the TMP-enabled P-doping does not change the crystalline structure of Si NCs. The surface of P-doped Si NCs is terminated by both Cl and H. The Si-H bond density at the surface of P-doped Si NCs is found to be much higher than that of undoped Si NCs. The X-ray photoelectron spectroscopy and electron spin resonance results indicate that P atoms are doped into the substitutional sites of the Si-NC core and electrically active in Si NCs. Unintentional impurities, such as carbon contained in TMP, are not introduced into Si NCs.

Electrical response of Pt/Ru/PbZr0.52Ti0.48O3/Pt capacitor as function of lead precursor excess

NASA Astrophysics Data System (ADS)

Gueye, Ibrahima; Le Rhun, Gwenael; Renault, Olivier; Defay, Emmanuel; Barrett, Nicholas

2017-11-01

We investigated the influence of the surface microstructure and chemistry of sol-gel grown PbZr0.52Ti0.48O3 (PZT) on the electrical performance of PZT-based metal-insulator-metal (MIM) capacitors as a function of Pb precursor excess. Using surface-sensitive, quantitative X-ray photoelectron spectroscopy and scanning electron microscopy, we confirm the presence of ZrOx surface phase. Low Pb excess gives rise to a discontinuous layer of ZrOx on a (100) textured PZT film with a wide band gap reducing the capacitance of PZT-based MIMs whereas the breakdown field is enhanced. At high Pb excess, the nanostructures disappear while the PZT grain size increases and the film texture becomes (111). Concomitantly, the capacitance density is enhanced by 8.7%, and both the loss tangent and breakdown field are reduced by 20 and 25%, respectively. The role of the low permittivity, dielectric interface layer on capacitance and breakdown is discussed.

The optimum titanium precursor of fabricating TiO2 compact layer for perovskite solar cells.

PubMed

Qin, Jianqiang; Zhang, Zhenlong; Shi, Wenjia; Liu, Yuefeng; Gao, Huiping; Mao, Yanli

2017-12-29

Perovskite solar cells (PSCs) have attracted tremendous attentions due to its high performance and rapid efficiency promotion. Compact layer plays a crucial role in transferring electrons and blocking charge recombination between the perovskite layer and fluorine-doped tin oxide (FTO) in PSCs. In this study, compact TiO 2 layers were synthesized by spin-coating method with three different titanium precursors, titanium diisopropoxide bis (acetylacetonate) (c-TTDB), titanium isopropoxide (c-TTIP), and tetrabutyl titanate (c-TBOT), respectively. Compared with the PSCs based on the widely used c-TTDB and c-TTIP, the device based on c-TBOT has significantly enhanced performance, including open-circuit voltage, short-circuit current density, fill factor, and hysteresis. The significant enhancement is ascribed to its excellent morphology, high conductivity and optical properties, fast charge transfer, and large recombination resistance. Thus, a power conversion efficiency (PCE) of 17.03% has been achieved for the solar cells based on c-TBOT.

The optimum titanium precursor of fabricating TiO2 compact layer for perovskite solar cells

NASA Astrophysics Data System (ADS)

Qin, Jianqiang; Zhang, Zhenlong; Shi, Wenjia; Liu, Yuefeng; Gao, Huiping; Mao, Yanli

2017-12-01

Perovskite solar cells (PSCs) have attracted tremendous attentions due to its high performance and rapid efficiency promotion. Compact layer plays a crucial role in transferring electrons and blocking charge recombination between the perovskite layer and fluorine-doped tin oxide (FTO) in PSCs. In this study, compact TiO2 layers were synthesized by spin-coating method with three different titanium precursors, titanium diisopropoxide bis (acetylacetonate) (c-TTDB), titanium isopropoxide (c-TTIP), and tetrabutyl titanate (c-TBOT), respectively. Compared with the PSCs based on the widely used c-TTDB and c-TTIP, the device based on c-TBOT has significantly enhanced performance, including open-circuit voltage, short-circuit current density, fill factor, and hysteresis. The significant enhancement is ascribed to its excellent morphology, high conductivity and optical properties, fast charge transfer, and large recombination resistance. Thus, a power conversion efficiency (PCE) of 17.03% has been achieved for the solar cells based on c-TBOT.

Transition Metal Dichalcogenide Growth via Close Proximity Precursor Supply

NASA Astrophysics Data System (ADS)

O'Brien, Maria; McEvoy, Niall; Hallam, Toby; Kim, Hye-Young; Berner, Nina C.; Hanlon, Damien; Lee, Kangho; Coleman, Jonathan N.; Duesberg, Georg S.

2014-12-01

Reliable chemical vapour deposition (CVD) of transition metal dichalcogenides (TMDs) is currently a highly pressing research field, as numerous potential applications rely on the production of high quality films on a macroscopic scale. Here, we show the use of liquid phase exfoliated nanosheets and patterned sputter deposited layers as solid precursors for chemical vapour deposition. TMD monolayers were realized using a close proximity precursor supply in a CVD microreactor setup. A model describing the growth mechanism, which is capable of producing TMD monolayers on arbitrary substrates, is presented. Raman spectroscopy, photoluminescence, X-ray photoelectron spectroscopy, atomic force microscopy, transmission electron microscopy, scanning electron microscopy and electrical transport measurements reveal the high quality of the TMD samples produced. Furthermore, through patterning of the precursor supply, we achieve patterned growth of monolayer TMDs in defined locations, which could be adapted for the facile production of electronic device components.

Femtosecond-laser induced dynamics of CO on Ru(0001): Deep insights from a hot-electron friction model including surface motion

NASA Astrophysics Data System (ADS)

Scholz, Robert; Floß, Gereon; Saalfrank, Peter; Füchsel, Gernot; Lončarić, Ivor; Juaristi, J. I.

2016-10-01

A Langevin model accounting for all six molecular degrees of freedom is applied to femtosecond-laser induced, hot-electron driven dynamics of Ru(0001)(2 ×2 ):CO. In our molecular dynamics with electronic friction approach, a recently developed potential energy surface based on gradient-corrected density functional theory accounting for van der Waals interactions is adopted. Electronic friction due to the coupling of molecular degrees of freedom to electron-hole pairs in the metal are included via a local density friction approximation, and surface phonons by a generalized Langevin oscillator model. The action of ultrashort laser pulses enters through a substrate-mediated, hot-electron mechanism via a time-dependent electronic temperature (derived from a two-temperature model), causing random forces acting on the molecule. The model is applied to laser induced lateral diffusion of CO on the surface, "hot adsorbate" formation, and laser induced desorption. Reaction probabilities are strongly enhanced compared to purely thermal processes, both for diffusion and desorption. Reaction yields depend in a characteristic (nonlinear) fashion on the applied laser fluence, as well as branching ratios for various reaction channels. Computed two-pulse correlation traces for desorption and other indicators suggest that aside from electron-hole pairs, phonons play a non-negligible role for laser induced dynamics in this system, acting on a surprisingly short time scale. Our simulations on precomputed potentials allow for good statistics and the treatment of long-time dynamics (300 ps), giving insight into this system which hitherto has not been reached. We find generally good agreement with experimental data where available and make predictions in addition. A recently proposed laser induced population of physisorbed precursor states could not be observed with the present low-coverage model.

Microwave synthesis of molybdenum doped LiFePO4/C and its electrochemical studies.

PubMed

Naik, Amol; P, Sajan C

2016-05-10

A Mo-doped LiFePO4 composite was prepared successfully from an iron carbonyl complex by adopting a facile and rapid microwave assisted solid state method. The evolution of gases from the iron precursor produces a highly porous product. The formation and substitution of Mo in LiFePO4 were confirmed by X-ray diffraction; surface analysis was carried out by scanning electron microscopy, field emission scanning electron microscopy, and transmission electron microscopy. The electrochemical properties of the substituted LiFePO4 were examined by cyclic voltammetry, electrochemical impedance spectroscopy and by recording charge-discharge cycles. It was observed that the as prepared composites consisted of a single phase orthorhombic olivine-type structure, where Mo(6+) was successfully introduced into the M2(Fe) sites. Incorporation of supervalent Mo(6+) introduced Li(+) ion vacancies in LiFePO4. The synthesized material facilitated lithium ion diffusion during charging/discharging due to the charge compensation effect and porosity. The battery performance studies showed that LiMo0.05Fe0.095PO4 exhibited a maximum capacity of 169.7 mA h g(-1) at 0.1 C current density, with admirable stability retention. Even at higher current densities, the retention of the specific capacity was exceptional.

Fine uniform filament superconductors

DOEpatents

Riley, Jr., Gilbert N.; Li, Qi; Roberts, Peter R.; Antaya, Peter D.; Seuntjens, Jeffrey M.; Hancock, Steven; DeMoranville, Kenneth L.; Christopherson, Craig J.; Garrant, Jennifer H.; Craven, Christopher A.

2002-01-01

A multifilamentary superconductor composite having a high fill factor is formed from a plurality of stacked monofilament precursor elements, each of which includes a low density superconductor precursor monofilament. The precursor elements all have substantially the same dimensions and characteristics, and are stacked in a rectilinear configuration and consolidated to provide a multifilamentary precursor composite. The composite is thereafter thermomechanically processed to provide a superconductor composite in which each monofilament is less than about 50 microns thick.

Study on GaN nanostructures: Growth and the suppression of the yellow emission

NASA Astrophysics Data System (ADS)

Wang, Ting; Chen, Fei; Ji, Xiaohong; Zhang, Qinyuan

2018-07-01

GaN nanostructures were synthesized via a simple chemical vapor deposition using Ga2O3 and NH3 as precursors. Structural and morphological properties were systematically characterized by field emission scanning electron microscopy, X-ray diffractometer, transmission electron microscopy, and Raman spectroscopy. The configuration of GaN nanostructures was found to be strongly dependent on the growth temperature and the NH3 flow rate. Photoluminescence analysis revealed that all the fabricated GaN NSs exhibited a strong ultra-violet emission (∼364 nm), and the yellow emission of GaN nanorods can be suppressed at appropriate III/V ratio. The suppression of the yellow emission was attributed to the low density of surface or the VGa defect. The work demonstrates that the GaN nanostructures have potential applications in the optoelectronic and nanoelectronic devices.

Nitrogen-containing species in the structure of the synthesized nano-hydroxyapatite

NASA Astrophysics Data System (ADS)

Gafurov, M.; Biktagirov, T.; Yavkin, B.; Mamin, G.; Filippov, Y.; Klimashina, E.; Putlayev, V.; Orlinskii, S.

2014-04-01

Synthesized by the wet chemical precipitation technique, hydroxyapatite (HAp) powders with the sizes of the crystallites of 20-50 nm and 1 μm were analyzed by different analytical methods. By means of electron paramagnetic resonance (EPR) it is shown that during the synthesis process nitrate anions from the reagents (byproducts) could incorporate into the HAp structure. The relaxation times and EPR parameters of the stable axially symmetric NO{3/2-} paramagnetic centers detected after X-ray irradiation are measured with high accuracy. Analyses of high-frequency (95 GHz) electron-nuclear double resonance spectra from 1H and 31P nuclei and ab initio density functional theory calculations allow suggesting that the paramagnetic centers and nitrate anions as the precursors of NO{3/2-} radicals preferably occupy PO{4/3-} site in the HAp structure.

Influence of aminosilane precursor concentration on physicochemical properties of composite Nafion membranes for vanadium redox flow battery applications

NASA Astrophysics Data System (ADS)

Kondratenko, Mikhail S.; Karpushkin, Evgeny A.; Gvozdik, Nataliya A.; Gallyamov, Marat O.; Stevenson, Keith J.; Sergeyev, Vladimir G.

2017-02-01

A series of composite proton-exchange membranes have been prepared via sol-gel modification of commercial Nafion membranes with [N-(2-aminoethyl)-3-aminopropyl]trimethoxysilane. The structure and physico-chemical properties (water uptake, ion-exchange capacity, vanadyl ion permeability, and proton conductivity) of the prepared composite membranes have been studied as a function of the precursor loading (degree of the membrane modification). If the amount of the precursor is below 0.4/1 M ratio of the amino groups of the precursor to the sulfonic groups of Nafion, the composite membranes exhibit decreased vanadium ion permeability while having relatively high proton conductivity. With respect to the use of a non-modified Nafion membrane, the performance of the composite membrane with an optimum precursor loading in a single-cell vanadium redox flow battery demonstrates enhanced energy efficiency in 20-80 mA cm-2 current density range. The maximum efficiency increase of 8% is observed at low current densities.

Thin HTSC films produced by a polymer metal precursor technique

NASA Astrophysics Data System (ADS)

Lampe, L. v.; Zygalsky, F.; Hinrichsen, G.

In precursors the metal ions are combined with acid groups of polymethacrylic acid (PMAA), polyacrylic acid (PAA) or novolac. Compared to thermal degradation temperature of pure polymers those of precursors are low. Precursors films were patterned by UV lithography. Diffractometric investigations showed that the c-axis oriented epitaxial films of YBa 2Cu 3O x and Bi 2Sr 2CaCu 2O x originated from amorphous metal oxide films, which were received after thermal degradation of the precursor. Transition temperatures and current densities were determined by electric resistivity measurements.

Propositional Density and Cognitive Function in Later Life: Findings From the Precursors Study

PubMed Central

Agree, Emily M.; Meoni, Lucy A.; Klag, Michael J.

2010-01-01

Objectives. We used longitudinal data from the Johns Hopkins Precursors Study to test the hypothesis that written propositional density measured early in life is lower for people who develop dementia categorized as Alzheimer's disease (AD). This association was reported in 1996 for the Nun Study, and the Precursors Study offered an unprecedented chance to reexamine it among respondents with different gender, education, and occupation profiles. Methods. Eighteen individuals classified as AD patients (average age at diagnosis: 74) were assigned 2 sex-and-age matched controls, and propositional density in medical school admission essays (average age at writing: 22) was assessed via Computerized Propositional Idea Density Rater 3 linguistic analysis software. Adjusted odds ratios (ORs) for the matched case-control study were calculated using conditional (fixed-effects) logistic regression. Results. Mean propositional density is lower for cases than for controls (4.70 vs. 4.99 propositions per 10 words, 1-sided p = .01). Higher propositional density substantially lowers the odds of AD (OR = 0.16, 95% confidence interval = 0.03-0.90, 1-sided p = .02). Discussion. Propositional density scores in writing samples from early adulthood appear to predict AD in later life for men as well as women. Studies of cognition across the life course might beneficially incorporate propositional density as a potential marker of cognitive reserve. PMID:20837676

Application of Chan-Lam cross coupling for the synthesis of N-heterocyclic carbene precursors bearing strong electron donating or withdrawing groups

NASA Astrophysics Data System (ADS)

Huang, Liliang; He, Chengxiang; Sun, Zhihua

2015-07-01

Chan-Lam cross coupling allowed efficient synthesis of N,N’-disubstituted ortho-phenylene diamines bearing strong electron donating or withdrawing groups, such as nitro or methoxy groups, with moderate to high yields. These diamines can then be turned into N-heterocyclic carbene precursors after condensation with trimethyl orthoformate. The same strategy can also be utilized for the synthesis of N-monosubstituted aniline derivatives containing a functionalized ortho-aminomethyl group as intermediates for chiral 6-membered ring carbene precursors.

Role of defects in laser-induced modifications of silica coatings and fused silica using picosecond pulses at 1053 nm: II Scaling laws and the density of precursors

DOE PAGES

Laurence, T. A.; Negres, R. A.; Ly, S.; ...

2017-06-22

Here, we investigate the role of defects in laser-induced damage of fused silica and of silica coatings produced by e-beam and PIAD processes which are used in damage resistant, multi-layer dielectric, reflective optics. We perform experiments using 1053 nm, 1–60 ps laser pulses with varying beam size, number of shots, and pulse widths in order to understand the characteristics of defects leading to laser-induced damage. This pulse width range spans a transition in mechanisms from intrinsic material ablation for short pulses to defect-dominated damage for longer pulses. We show that for pulse widths as short as 10 ps, laser-induced damagemore » properties of fused silica and silica films are dominated by isolated absorbers. The density of these precursors and their fluence dependence of damage initiation suggest a single photon process for initial energy absorption in these precursors. Higher density precursors that initiate close to the ablation threshold at shorter pulse widths are also observed in fused silica, whose fluence and pulse width scaling suggest a multiphoton initiation process. We also show that these initiated damage sites grow with subsequent laser pulses. We show that scaling laws obtained in more conventional ways depend on the beam size and on the definition of damage for ps pulses. For this reason, coupling scaling laws with the density of precursors are critical to understanding the damage limitations of optics in the ps regime.« less

Role of defects in laser-induced modifications of silica coatings and fused silica using picosecond pulses at 1053 nm: II Scaling laws and the density of precursors

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

Laurence, T. A.; Negres, R. A.; Ly, S.

Here, we investigate the role of defects in laser-induced damage of fused silica and of silica coatings produced by e-beam and PIAD processes which are used in damage resistant, multi-layer dielectric, reflective optics. We perform experiments using 1053 nm, 1–60 ps laser pulses with varying beam size, number of shots, and pulse widths in order to understand the characteristics of defects leading to laser-induced damage. This pulse width range spans a transition in mechanisms from intrinsic material ablation for short pulses to defect-dominated damage for longer pulses. We show that for pulse widths as short as 10 ps, laser-induced damagemore » properties of fused silica and silica films are dominated by isolated absorbers. The density of these precursors and their fluence dependence of damage initiation suggest a single photon process for initial energy absorption in these precursors. Higher density precursors that initiate close to the ablation threshold at shorter pulse widths are also observed in fused silica, whose fluence and pulse width scaling suggest a multiphoton initiation process. We also show that these initiated damage sites grow with subsequent laser pulses. We show that scaling laws obtained in more conventional ways depend on the beam size and on the definition of damage for ps pulses. For this reason, coupling scaling laws with the density of precursors are critical to understanding the damage limitations of optics in the ps regime.« less

Synthesis of carbon nanotubes via Fe-catalyzed pyrolysis of phenolic resin

NASA Astrophysics Data System (ADS)

Wang, Junkai; Deng, Xiangong; Zhang, Haijun; Zhang, Yuanzhuo; Duan, Hongjuan; Lu, Lilin; Song, Jianbo; Tian, Liang; Song, Shupeng; Zhang, Shaowei

2017-02-01

Carbon nanotubes (CNTs) with 40-100 nm in diameter and tens of micrometers in length were prepared via catalytic pyrolysis of phenol resin in Ar at 673-1273 K using ferric nitrate as a catalyst precursor. Structure and morphology of pyrolyzed resin were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and Raman spectroscopy. Ferric nitrate was transformed to Fe3O4 at 673 K, and to metallic Fe and FexC carbide at 873-1273 K. The optimal weight ratio of Fe catalyst to phenol resin for growing CNTs was 1.00 wt%, and the optimal temperature was 1073 K. In addition, use of a high pressure increased the yield of CNTs. Density functional theory (DFT) calculations suggest that Fe catalysts facilitate the CNTs growth by increasing the bond length and weakening the bond strength in C2H4 via donating electrons to the C atoms in it.

Ru-N-C Hybrid Nanocomposite for Ammonia Dehydrogenation: Influence of N-doping on Catalytic Activity

PubMed Central

Hien, Nguyen Thi Bich; Kim, Hyo Young; Jeon, Mina; Lee, Jin Hee; Ridwan, Muhammad; Tamarany, Rizcky; Yoon, Chang Won

2015-01-01

For application to ammonia dehydrogenation, novel Ru-based heterogeneous catalysts, Ru-N-C and Ru-C, were synthesized via simple pyrolysis of a mixture of RuCl3·6H2O and carbon black with or without dicyandiamide as a nitrogen-containing precursor at 550 °C. Characterization of the prepared Ru-N-C and Ru-C catalysts via scanning transmission electron microscopy, in conjunction with energy dispersive X-ray spectroscopy, indicated the formation of hollow nanocomposites in which the average sizes of the Ru nanoparticles were 1.3 nm and 5.1 nm, respectively. Compared to Ru-C, the Ru-N-C nanocomposites not only proved to be highly active for ammonia dehydrogenation, giving rise to a NH3 conversion of >99% at 550 °C, but also exhibited high durability. X-ray photoelectron spectroscopy revealed that the Ru active sites in Ru-N-C were electronically perturbed by the incorporated nitrogen atoms, which increased the Ru electron density and ultimately enhanced the catalyst activity.

Jupiter's Magnetosphere: Plasma Description from the Ulysses Flyby.

PubMed

Bame, S J; Barraclough, B L; Feldman, W C; Gisler, G R; Gosling, J T; McComas, D J; Phillips, J L; Thomsen, M F; Goldstein, B E; Neugebauer, M

1992-09-11

Plasma observations at Jupiter show that the outer regions of the Jovian magnetosphere are remarkably similar to those of Earth. Bow-shock precursor electrons and ions were detected in the upstream solar wind, as at Earth. Plasma changes across the bow shock and properties of the magnetosheath electrons were much like those at Earth, indicating that similar processes are operating. A boundary layer populated by a varying mixture of solar wind and magnetospheric plasmas was found inside the magnetopause, again as at Earth. In the middle magnetosphere, large electron density excursions were detected with a 10-hour periodicity as planetary rotation carried the tilted plasma sheet past Ulysses. Deep in the magnetosphere, Ulysses crossed a region, tentatively described as magnetically connected to the Jovian polar cap on one end and to the interplanetary magnetic field on the other. In the inner magnetosphere and lo torus, where corotation plays a dominant role, measurements could not be made because of extreme background rates from penetrating radiation belt particles.

Fabrication of low density ceramic material

DOEpatents

Meek, T.T.; Blake, R.D.; Sheinberg, H.

1985-01-01

A precursor mixture and a method of making a low-density ceramic structural material are disclosed. The precursor mixture includes hollow microballoons, typically made of glass, together with a cementing agent capable of being cured by microwave irradiation. A preferred cementing agent is liquid hydrated potassium silicate, which is mixed with the glass microballoons to form a slurry. Upon irradiation the potassium silicate is dehydrated to form a solid porous matrix in which the microballoons are evenly distributed. Ground glass or other filling agents may be included in the slurry to enhance the properties of the final product. Low-density structural ceramics having densities on the order of 0.1 to 0.3 are obtained.

Biosynthesis and characterization of silver nanoparticles prepared from two novel natural precursors by facile thermal decomposition methods

NASA Astrophysics Data System (ADS)

Goudarzi, Mojgan; Mir, Noshin; Mousavi-Kamazani, Mehdi; Bagheri, Samira; Salavati-Niasari, Masoud

2016-09-01

In this work, two natural sources, including pomegranate peel extract and cochineal dye were employed for the synthesis of silver nanoparticles. The natural silver complex from pomegranate peel extract resulted in nano-sized structures through solution-phase method, but this method was not efficient for cochineal dye-silver precursor and the as-formed products were highly agglomerated. Therefore, an alternative facile solid-state approach was investigated as for both natural precursors and the results showed successful production of well-dispersed nanoparticles with narrow size distribution for cochineal dye-silver precursor. The products were characterized by X-ray diffraction (XRD), Scanning Electron Microscopy (SEM), Energy dispersive X-ray microanalysis (EDX), and Transmission Electron Microscopy (TEM).

Enhanced optoelectronic quality of perovskite thin films with hypophosphorous acid for planar heterojunction solar cells

DOE PAGES

Zhang, Wei; Pathak, Sandeep; Sakai, Nobuya; ...

2015-11-30

Solution-processed metal halide perovskite semiconductors, such as CH 3NH 3PbI 3, have exhibited remarkable performance in solar cells, despite having non-negligible density of defect states. A likely candidate is halide vacancies within the perovskite crystals, or the presence of metallic lead, both generated due to the imbalanced I/Pb stoichiometry which could evolve during crystallization. Herein, we show that the addition of hypophosphorous acid (HPA) in the precursor solution can significantly improve the film quality, both electronically and topologically, and enhance the photoluminescence intensity, which leads to more efficient and reproducible photovoltaic devices. We demonstrate that the HPA can reduce themore » oxidized I2 back into I-, and our results indicate that this facilitates an improved stoichiometry in the perovskite crystal and a reduced density of metallic lead.« less

Infrared spectroscopy and density functional calculations on titanium-dinitrogen complexes

NASA Astrophysics Data System (ADS)

Yoo, Hae-Wook; Choi, Changhyeok; Cho, Soo Gyeong; Jung, Yousung; Choi, Myong Yong

2018-04-01

Titanium-nitrogen complexes were generated by laser ablated titanium (Ti) atoms and N2 gas molecules in this study. These complexes were isolated on the pre-deposited solid Ar matrix on the pre-cooled KBr window (T ∼ 5.4 K), allowing infrared spectra to be measured. Laser ablation experiments with 15N2 isotope provided distinct isotopic shifts in the infrared spectra that strongly implicated the formation of titanium-nitrogen complexes, Ti(NN)x. Density functional theory (DFT) calculations were employed to investigate the molecular structures, electronic ground state, relative energies, and IR frequencies of the anticipated Ti(NN)x complexes. Based on laser ablation experiments and DFT calculations, we were able to assign multiple Ti(NN)x (x = 1-6) species. Particularly, Ti(NN)5 and Ti(NN)6, which have high nitrogen content, may serve as good precursors in preparing polynitrogens.

Cobalt Nanoparticle-Embedded Porous Carbon Nanofibers with Inherent N- and F-Doping as Binder-Free Bifunctional Catalysts for Oxygen Reduction and Evolution Reactions.

PubMed

Singhal, Richa; Kalra, Vibha

2017-01-18

Efficient, low-cost, non-precious metal-based, and stable bifunctional electrocatalysts are key to various energy storage and conversion devices such as regenerative fuel cells and metal-air batteries. In this work, we report cobalt nanoparticle-embedded porous carbon nanofibers with inherent N- and F-doping as binder-free bifunctional electrocatalysts with excellent activity for both the oxygen reduction and oxygen evolution reaction (ORR/OER) in an alkaline medium. Single-step electrospinning of a solution of the polymer mixture (carbon precursor) and the cobalt precursor followed by controlled pyrolysis with an intermediate reduction step in H 2 (to reduce cobalt oxides to cobalt) was utilized to synthesize an integrated freestanding catalyst. The fabricated catalyst with effective structural and electronic interaction between the cobalt metal nanoparticles and the N- and F-doped carbon defect sites showed enhanced catalytic properties compared to the benchmark catalysts for ORR and OER (Pt, Ir, and Ru). The ORR potential at the current density of -3 mA cm -2 was 0.81 V RHE and the OER potential at a current density of 10 mA cm -2 was 1.595 V RHE , resulting in a ΔE of only 0.785 V. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Development of molecular precursors for deposition of indium sulphide thin film electrodes for photoelectrochemical applications.

PubMed

Ehsan, Muhammad Ali; Peiris, T A Nirmal; Wijayantha, K G Upul; Olmstead, Marilyn M; Arifin, Zainudin; Mazhar, Muhammad; Lo, K M; McKee, Vickie

2013-08-14

Symmetrical and unsymmetrical dithiocarbamato pyridine solvated and non-solvated complexes of indium(III) with the general formula [In(S2CNRR')3]·n(py) [where py = pyridine; R,R' = Cy, n = 2 (1); R,R' = (i)Pr, n = 1.5 (2); NRR' = Pip, n = 0.5 (3) and R = Bz, R' = Me, n = 0 (4)] have been synthesized. The compositions, structures and properties of these complexes have been studied by means of microanalysis, IR and (1)H-NMR spectroscopy, X-ray single crystal and thermogravimetric (TG/DTG) analyses. The applicability of these complexes as single source precursors (SSPs) for the deposition of β-In2S3 thin films on fluorine-doped SnO2 (FTO) coated conducting glass substrates by aerosol-assisted chemical vapour deposition (AACVD) at temperatures of 300, 350 and 400 °C is studied. All films have been characterized by powder X-ray diffraction (PXRD) and energy dispersive X-ray analysis (EDX) for the detection of phase and stoichiometry of the deposit. Scanning electron microscopy (SEM) studies reveal that precursors (1)-(4), irrespective of different metal ligand design, generate comparable morphologies of β-In2S3 thin films at different temperatures. Direct band gap energies of 2.2 eV have been estimated from the UV-vis spectroscopy for the β-In2S3 films fabricated from precursors (1) and (4). The photoelectrochemical (PEC) properties of β-In2S3 were confirmed by recording the current-voltage plots under light and dark conditions. The plots showed anodic photocurrent densities of 1.25 and 0.65 mA cm(-2) at 0.23 V vs. Ag/AgCl for the β-In2S3 films made at 400 and 350 °C from the precursors (1) and (4), respectively. The photoelectrochemical performance indicates that the newly synthesised precursors are highly useful in fabricating β-In2S3 electrodes for solar energy harvesting and optoelectronic application.

Shape-controlled synthesis of NiCo2S4 and their charge storage characteristics in supercapacitors.

PubMed

Zhang, Yufei; Ma, Mingze; Yang, Jun; Sun, Chencheng; Su, Haiquan; Huang, Wei; Dong, Xiaochen

2014-08-21

In this work, a facile hydrothermal approach for the shape-controlled synthesis of NiCo2S4 architectures is reported. Four different morphologies, urchin-, tube-, flower-, and cubic-like NiCo2S4 microstructures, have been successfully synthesized by employing various solvents. The obtained precursors and products have been characterized by X-ray diffraction, field-emission scanning electron microscopy and transmission electron microscopy. It is revealed that the supersaturation of nucleation and crystal growth is determined by the solvent polarity and solubility, which can precisely control the morphology of NiCo2S4 microstructures. The detailed electrochemical performances of the various NiCo2S4 microstructures are investigated by cyclic voltammetry and galvanostatic charge-discharge measurements. The results indicate that the tube-like NiCo2S4 exhibits promising capacitive properties with high capacitance and excellent retention. Its specific capacitance can reach 1048 F g(-1) at the current density of 3.0 A g(-1) and 75.9% of its initial capacitance is maintained at the current density of 10.0 A g(-1) after 5000 charge-discharge cycles.

Shape-controlled synthesis of NiCo2S4 and their charge storage characteristics in supercapacitors

NASA Astrophysics Data System (ADS)

Zhang, Yufei; Ma, Mingze; Yang, Jun; Sun, Chencheng; Su, Haiquan; Huang, Wei; Dong, Xiaochen

2014-07-01

In this work, a facile hydrothermal approach for the shape-controlled synthesis of NiCo2S4 architectures is reported. Four different morphologies, urchin-, tube-, flower-, and cubic-like NiCo2S4 microstructures, have been successfully synthesized by employing various solvents. The obtained precursors and products have been characterized by X-ray diffraction, field-emission scanning electron microscopy and transmission electron microscopy. It is revealed that the supersaturation of nucleation and crystal growth is determined by the solvent polarity and solubility, which can precisely control the morphology of NiCo2S4 microstructures. The detailed electrochemical performances of the various NiCo2S4 microstructures are investigated by cyclic voltammetry and galvanostatic charge-discharge measurements. The results indicate that the tube-like NiCo2S4 exhibits promising capacitive properties with high capacitance and excellent retention. Its specific capacitance can reach 1048 F g-1 at the current density of 3.0 A g-1 and 75.9% of its initial capacitance is maintained at the current density of 10.0 A g-1 after 5000 charge-discharge cycles.

Disruption mitigation and avoidance at ASDEX Upgrade

NASA Astrophysics Data System (ADS)

Maraschek, M.; Pautasso, G.; Esposito, B.; Granucci, G.; Stober, J.; Treutterer, W.

2009-11-01

Disruptions are a major concern for tokamaks and in particular for ITER. They cause high heat loads during the thermal quench and high mechanical forces during the subsequent current quench. The generation and loss of runaway electrons (highly accelerated electrons carrying large fractions of the plasma current) can produce damage to the vessel structures. Therefore, schemes are implemented in present tokamaks to mitigate or to even avoid them. Mitigation has been proven to be effective through the injection of noble gases causing a reduction of the thermal heat load by radiation and a reduction of the mechanical forces. In addition 25% of the required density for the collisional suppression of runaways in ITER has been reached. For the trigger of the noble gas injection a locked mode detector is routinely used at ASDEX Upgrade. An extension to more complex precursors is planed. A different approach has been used for disruption avoidance by injecting ECRH triggered by the loop voltage increase before the disruption. The avoidance of an ongoing density limit disruption has been achieved when the ECRH is deposited at resonant surfaces where MHD modes, such as the m=2/n=1, occur. Present schemes for the mitigation and eventually avoidance of disruptions will be discussed.

Persistence of Precursor Waves in Two-dimensional Relativistic Shocks

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

Iwamoto, Masanori; Amano, Takanobu; Hoshino, Masahiro

2017-05-01

We investigated the efficiency of coherent upstream large-amplitude electromagnetic wave emission via synchrotron maser instability in relativistic magnetized shocks using two-dimensional particle-in-cell simulations. We considered a purely perpendicular shock in an electron–positron plasma. The coherent wave emission efficiency was measured as a function of the magnetization parameter σ , which is defined as the ratio of the Poynting flux to the kinetic energy flux. The wave amplitude was systematically smaller than that observed in one-dimensional simulations. However, it continued to persist, even at a considerably low magnetization rate, where the Weibel instability dominated the shock transition. The emitted electromagnetic wavesmore » were sufficiently strong to disturb the upstream medium, and transverse filamentary density structures of substantial amplitude were produced. Based on this result, we discuss the possibility of the wakefield acceleration model to produce nonthermal electrons in a relativistic magnetized ion–electron shock.« less

Effect of fluorine doped TiO2 on the property of perovskite solar cell

NASA Astrophysics Data System (ADS)

Zhang, X. Q.; Wu, Y. P.; Huang, Y.; Zhou, Z. H.; Shen, S.

2017-03-01

Anatase TiO2 nanoparticles with different amounts of fluorine doping were synthesized by a hydrothermal method using hydrogen titanate nanotubes as a precursor and applied as mesoporous layer for preparing perovskite solar cell. The morphology and structures were characterized by scanning electron microscope (SEM) and X-ray diffraction (XRD), meanwhile, the properties and performances were tested by photoluminescence spectrum (PL) and current density and voltage (J-V) curve. It was found that doping fluorine into TiO2 made the photoelectric conversion efficiency (PCE) of perovskite solar cell (PSC) to be improved. The best PCE of PSC based on a F-doped TiO2 was 13.06% and increased by 51% compared to an un-doped TiO2. The study provided a direction for the exploration of high performance electron transport layer of perovskite solar cell.

Transformation, migration and outcome of residual bodies in the seminiferous tubules of the rat testis.

PubMed

Xiao, C-Y; Wang, Y-Q; Li, J-H; Tang, G-C; Xiao, S-S

2017-12-01

Experiments were performed to study the transformation, migration and outcome of residual bodies (RBs) in the seminiferous tubules of the rat testes. One part of the testes from adult Sprague-Dawley rats was used to generate paraffin sections to observe RBs and RB precursors through specific staining, and the other part of the testes was used to generate ultrathin sections to observe RBs under a transmission electron microscope. Deep blue particles of different sizes were observed in some seminiferous tubules through specific staining for RBs and RB precursors. These particles first appeared in the seminiferous tubules at stage I of the spermatogenic cycle, and after spermiation, the particles travelled rapidly towards the deeper region of the seminiferous epithelium and soon appeared close to the basement membrane of the seminiferous tubule. All of the particles in the tubules disappeared at stage IX. Using transmission electron microscopy, components of different electron densities were observed in the RBs on the surface of the seminiferous epithelium, all of which gradually formed in the cytoplasm of spermatozoon in later stages of spermiogenesis. After the spermatozoa were released, the RBs in the epithelium travelled quickly to the edge of the tube and were gradually transformed into lipid inclusions. These lipid inclusions ultimately became lipidlike particles. The lipidlike particles were discharged into the interstitial tissue. RBs initiate their own digestive process before their formation during spermiation in the rat testes. After spermiation, the RBs transform into lipid inclusions and finally into lipidlike particles. These lipidlike particles can be eliminated from the seminiferous tubules. © 2017 Blackwell Verlag GmbH.

The optimization functions of ICP discharge in preparation of Cu-Zn-Sn precursors and CZTS films by co-evaporation

NASA Astrophysics Data System (ADS)

Ye, Li; Junfang, Chen; Junhui, Ma; Lifen, Zhou

2016-02-01

Cu-Zn-Sn (CZT) precursors were successfully prepared on glass substrate with the introduction of the assistant technology ICP (inductively coupled plasma) based on the conventional co-evaporation process. The deposition was performed with the substrate temperature at 220 °C and the chamber pressure at 6.5 × 10-2 Pa. Argon plasma was investigated with a Langmuir probe. The plasma density and the electron temperature increased with the increasing of the discharge power. The impact of ICP discharge power on the structural and morphological properties of the CZT film were investigated with energy dispersive X-ray spectrometers (EDS), X-ray diffraction (XRD), and scanning electron microscopy (SEM). XRD and EDS were combined to investigate the structure of the film. The results show that Zn loss exists during the evaporation and the loss can be reduced by increasing the ICP discharge power. From the observation on the scanning electron microscope, the grain size becomes larger with argon plasma's assistance. The preparation of the Cu2ZnSnS4 (CZTS) film and the measured properties demonstrate that the ICP would optimize the growth of the film. Project supported by the Natural Science Foundation of Guangdong Province, China (No. S2013010012548), the Natural Science Foundation of Guangdong Province, China (No. 10151063101000048), the Key Program of the National Natural Science Foundation of China (No. 61072028), the Guangdong Provincial Natural Science Foundation of China (No. 2014A030313441), and the Guangdong Province and Chinese Ministry of Education Cooperation Project of Industry, Education and Academy (No. 2013B090600063).

Amorphous Metal Oxide Thin Films from Aqueous Precursors: New Routes to High-kappa Dielectrics, Impact of Annealing Atmosphere Humidity, and Elucidation of Non-Uniform Composition Profiles

NASA Astrophysics Data System (ADS)

Woods, Keenan N.

Metal oxide thin films serve as critical components in many modern technologies, including microelectronic devices. Industrial state-of-the-art production utilizes vapor-phase techniques to make high-quality (dense, smooth, uniform) thin film materials. However, vapor-phase techniques require large energy inputs and expensive equipment and precursors. Solution-phase routes to metal oxides have attracted great interest as cost-effective alternatives to vapor-phase methods and also offer the potential of large-area coverage, facile control of metal composition, and low-temperature processing. Solution deposition has previously been dominated by sol-gel routes, which utilize organic ligands, additives, and/or solvents. However, sol-gel films are often porous and contain residual carbon impurities, which can negatively impact device properties. All-inorganic aqueous routes produce dense, ultrasmooth films without carbon impurities, but the mechanisms involved in converting aqueous precursors to metal oxides are virtually unexplored. Understanding these mechanisms and the parameters that influence them is critical for widespread use of aqueous approaches to prepare microelectronic components. Additionally, understanding (and controlling) density and composition inhomogeneities is important for optimizing electronic properties. An overview of deposition approaches and the challenges facing aqueous routes are presented in Chapter I. A summary of thin film characterization techniques central to this work is given in Chapter II. This dissertation contributes to the field of solution-phase deposition by focusing on three areas. First, an all-inorganic aqueous route to high-kappa metal oxide dielectrics is developed for two ternary systems. Chapters III and IV detail the film formation chemistry and film properties of lanthanum zirconium oxide (LZO) and zirconium aluminum oxide (ZAO), respectively. The functionality of these dielectrics as device components is also demonstrated. Second, the impact of steam annealing on the evolution of aqueous-derived films is reported. Chapter V demonstrates that steam annealing lowers processing temperatures by effectively reducing residual counterion content, improving film stability with respect to water absorption, and enhancing dielectric properties of LZO films. Third, density and composition inhomogeneities in aqueous-derived films are investigated. Chapters VI and VII examine density inhomogeneities in single- and multi-metal component thin films, respectively, and show that these density inhomogeneities are related to inhomogeneous metal component distributions. This dissertation includes previously published coauthored material.

Fast electrochemical deposition of Ni(OH)2 precursor involving water electrolysis for fabrication of NiO thin films

NASA Astrophysics Data System (ADS)

Koyama, Miki; Ichimura, Masaya

2018-05-01

Ni(OH)2 precursor films were deposited by galvanostatic electrochemical deposition (ECD), and NiO thin films were fabricated by annealing in air. The effects of the deposition current densities were studied in a range that included current densities high enough to electrolyze water and generate hydrogen bubbles. The films fabricated by ECD involving water electrolysis had higher transparency and smoother surface morphology than those deposited with lower current densities. In addition, the annealed NiO films clearly had preferred (111) orientation when the deposition was accompanied by water electrolysis. p-type conduction was confirmed for the annealed films.

Hard metal composition

DOEpatents

Sheinberg, H.

1983-07-26

A composition of matter having a Rockwell A hardness of at least 85 is formed from a precursor mixture comprising between 3 and 10 wt % boron carbide and the remainder a metal mixture comprising from 70 to 90% tungsten or molybdenum, with the remainder of the metal mixture comprising nickel and iron or a mixture thereof. The composition has a relatively low density of between 7 and 14 g/cc. The precursor is preferably hot pressed to yield a composition having greater than 100% of theoretical density.

Hard metal composition

DOEpatents

Sheinberg, Haskell

1986-01-01

A composition of matter having a Rockwell A hardness of at least 85 is formed from a precursor mixture comprising between 3 and 10 weight percent boron carbide and the remainder a metal mixture comprising from 70 to 90 percent tungsten or molybdenum, with the remainder of the metal mixture comprising nickel and iron or a mixture thereof. The composition has a relatively low density of between 7 to 14 g/cc. The precursor is preferably hot pressed to yield a composition having greater than 100% of theoretical density.

Vertically aligned carbon nanotubes from natural precursors by spray pyrolysis method and their field electron emission properties

NASA Astrophysics Data System (ADS)

Ghosh, Pradip; Soga, T.; Tanemura, M.; Zamri, M.; Jimbo, T.; Katoh, R.; Sumiyama, K.

2009-01-01

Vertically aligned carbon nanotubes have been synthesized from botanical hydrocarbons: Turpentine oil and Eucalyptus oil on Si(100) substrate using Fe catalyst by simple spray pyrolysis method at 700°C and at atmospheric pressure. The as-grown carbon nanotubes were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), high-resolution TEM (HRTEM), thermogravimetric analysis (TGA), differential thermal analysis (DTA), and Raman spectroscopy. It was observed that nanotubes grown from turpentine oil have better degree of graphitization and field emission performance than eucalyptus oil grown carbon nanotubes. The turpentine oil and eucalyptus oil grown carbon nanotubes indicated that the turn-on field of about 1.7 and 1.93 V/μm, respectively, at 10 μA/cm2. The threshold field was observed to be about 2.13 and 2.9 V/μm at 1 mA/cm2 of nanotubes grown from turpentine oil and eucalyptus oil respectively. Moreover, turpentine oil grown carbon nanotubes show higher current density in relative to eucalyptus oil grown carbon nanotubes. The maximum current density of 15.3 mA/cm2 was obtained for ˜3 V/μm corresponding to the nanotubes grown from turpentine oil. The improved field emission performance was attributed to the enhanced crystallinity, fewer defects, and greater length of turpentine oil grown carbon nanotubes.

Study on deposition of Al2O3 films by plasma-assisted atomic layer with different plasma sources

NASA Astrophysics Data System (ADS)

Haiying, WEI; Hongge, GUO; Lijun, SANG; Xingcun, LI; Qiang, CHEN

2018-04-01

In this paper, Al2O3 thin films are deposited on a hydrogen-terminated Si substrate by using two home-built electron cyclotron resonance (ECR) and magnetic field enhanced radio frequency plasma-assisted atomic layer deposition (PA-ALD) devices with Al(CH3)3 (trimethylaluminum, TMA) and oxygen plasma used as precursor and oxidant, respectively. The thickness, chemical composition, surface morphology and group reactions are characterized by in situ spectroscopic ellipsometer, x-ray photoelectric spectroscopy, atomic force microscopy, scanning electron microscopy, a high-resolution transmission electron microscope and in situ mass spectrometry (MS), respectively. We obtain that both ECR PA-ALD and the magnetic field enhanced PA-ALD can deposit thin films with high density, high purity, and uniformity at a high deposition rate. MS analysis reveals that the Al2O3 deposition reactions are not simple reactions between TMA and oxygen plasma to produce alumina, water and carbon dioxide. In fact, acetylene, carbon monoxide and some other by-products also appear in the exhaustion gas. In addition, the presence of bias voltage has a certain effect on the deposition rate and surface morphology of films, which may be attributed to the presence of bias voltage controlling the plasma energy and density. We conclude that both plasma sources have a different deposition mechanism, which is much more complicated than expected.

Synthesis of two-dimensional titanium nitride Ti4N3 (MXene)

NASA Astrophysics Data System (ADS)

Urbankowski, Patrick; Anasori, Babak; Makaryan, Taron; Er, Dequan; Kota, Sankalp; Walsh, Patrick L.; Zhao, Mengqiang; Shenoy, Vivek B.; Barsoum, Michel W.; Gogotsi, Yury

2016-06-01

We report on the synthesis of the first two-dimensional transition metal nitride, Ti4N3-based MXene. In contrast to the previously reported MXene synthesis methods - in which selective etching of a MAX phase precursor occurred in aqueous acidic solutions - here a molten fluoride salt is used to etch Al from a Ti4AlN3 powder precursor at 550 °C under an argon atmosphere. We further delaminated the resulting MXene to produce few-layered nanosheets and monolayers of Ti4N3Tx, where T is a surface termination (F, O, or OH). Density functional theory calculations of bare, non-terminated Ti4N3 and terminated Ti4N3Tx were performed to determine the most energetically stable form of this MXene. Bare and functionalized Ti4N3 are predicted to be metallic. Bare Ti4N3 is expected to show magnetism, which is significantly reduced in the presence of functional groups.We report on the synthesis of the first two-dimensional transition metal nitride, Ti4N3-based MXene. In contrast to the previously reported MXene synthesis methods - in which selective etching of a MAX phase precursor occurred in aqueous acidic solutions - here a molten fluoride salt is used to etch Al from a Ti4AlN3 powder precursor at 550 °C under an argon atmosphere. We further delaminated the resulting MXene to produce few-layered nanosheets and monolayers of Ti4N3Tx, where T is a surface termination (F, O, or OH). Density functional theory calculations of bare, non-terminated Ti4N3 and terminated Ti4N3Tx were performed to determine the most energetically stable form of this MXene. Bare and functionalized Ti4N3 are predicted to be metallic. Bare Ti4N3 is expected to show magnetism, which is significantly reduced in the presence of functional groups. Electronic supplementary information (ESI) available. See DOI: 10.1039/c6nr02253g

Crystalline oxides on semiconductors: A structural transition of the interface phase

NASA Astrophysics Data System (ADS)

Walker, F. J.; Buongiorno-Nardelli, Marco; Billman, C. A.; McKee, R. A.

2004-03-01

The growth of crystalline oxides on silicon is facilitated by the preparation of a surface phase of alkaline earth silicide. We describe how the surface phase serves as a precursor of the final interface phase using reflection high energy electron diffraction (RHEED) and density functional theory (DFT). RHEED intensity oscillations of the growth of BaSrO show layer-by-layer build up of the oxide on the interface. The 2x1 symmetry of the surface precursor persists up to 3 ML BaSrO coverage at which point a 1x1 pattern characteristic of the rock-salt structure of BaSrO is observed. Prior to 3 ML growth of alkaline earth oxide, DFT calculations and RHEED show that the surface precursor persists as the interface phase and induces large displacements in the growing oxide layer away from the rock-salt structure and having a 2x1 symmetry. These distortions of the rock-salt structure are energetically unfavorable and become more unfavorable as the oxide thickness increases. At 3 ML, the stability of the rock-salt structure drives a structural transformation of the film and the interface phase to a structure that is distinct from the surface precursor. Research sponsored jointly by the Division of Materials Sciences and Engineering, Office of Basic Energy Sciences, U.S. Department of Energy at Oak Ridge National Laboratory under contract DE-AC05-00OR22725 with UT-Battelle, LLC and at the University of Tennessee under contract DE-FG02-01ER45937. Calculations have been performed on CCS supercomputers at Oak Ridge National Laboratory.

Electron pairing without superconductivity

NASA Astrophysics Data System (ADS)

Levy, Jeremy

Strontium titanate (SrTiO3) is the first and best known superconducting semiconductor. It exhibits an extremely low carrier density threshold for superconductivity, and possesses a phase diagram similar to that of high-temperature superconductors--two factors that suggest an unconventional pairing mechanism. Despite sustained interest for 50 years, direct experimental insight into the nature of electron pairing in SrTiO3 has remained elusive. Here we perform transport experiments with nanowire-based single-electron transistors at the interface between SrTiO3 and a thin layer of lanthanum aluminate, LaAlO3. Electrostatic gating reveals a series of two-electron conductance resonances--paired electron states--that bifurcate above a critical pairing field Bp of about 1-4 tesla, an order of magnitude larger than the superconducting critical magnetic field. For magnetic fields below Bp, these resonances are insensitive to the applied magnetic field; for fields in excess of Bp, the resonances exhibit a linear Zeeman-like energy splitting. Electron pairing is stable at temperatures as high as 900 millikelvin, well above the superconducting transition temperature (about 300 millikelvin). These experiments demonstrate the existence of a robust electronic phase in which electrons pair without forming a superconducting state. Key experimental signatures are captured by a model involving an attractive Hubbard interaction that describes real-space electron pairing as a precursor to superconductivity. Support from AFOSR, ONR, ARO, NSF, DOE and NSSEFF is gratefully acknowledged.

Tsunami related to solar and geomagnetic activity

NASA Astrophysics Data System (ADS)

Cataldi, Gabriele; Cataldi, Daniele; Straser, Valentino

2016-04-01

The authors of this study wanted to verify the existence of a correlation between earthquakes of high intensity capable of generating tsunami and variations of solar and Earth's geomagnetic activity. To confirming or not the presence of this kind of correlation, the authors analyzed the conditions of Spaceweather "near Earth" and the characteristics of the Earth's geomagnetic field in the hours that preceded the four earthquakes of high intensity that have generated tsunamis: 1) Japan M9 earthquake occurred on March 11, 2011 at 05:46 UTC; 2) Japan M7.1 earthquake occurred on October 25, 2013 at 17:10 UTC; 3) Chile M8.2 earthquake occurred on April 1, 2014 at 23:46 UTC; 4) Chile M8.3 earthquake occurred on September 16, 2015 at 22:54 UTC. The data relating to the four earthquakes were provided by the United States Geological Survey (USGS). The data on ion density used to realize the correlation study are represented by: solar wind ion density variation detected by ACE (Advanced Composition Explorer) Satellite, in orbit near the L1 Lagrange point, at 1.5 million of km from Earth, in direction of the Sun. The instrument used to perform the measurement of the solar wind ion density is the Electron, Proton, and Alpha Monitor (EPAM) instrument, equipped on the ACE Satellite. To conduct the study, the authors have taken in consideration the variation of the solar wind protons density of three different energy fractions: differential proton flux 1060-1900 keV (p/cm^2-sec-ster-MeV); differential proton flux 761-1220 keV (p/cm^2-sec-ster-MeV); differential proton flux 310-580 keV (p/cm^2-sec-ster-MeV). Geomagnetic activity data were provided by Tromsø Geomagnetic Observatory (TGO), Norway; by Scoresbysund Geomagnetic Observatory (SCO), Greenland, Denmark and by Space Weather Prediction Center of Pushkov Institute of terrestrial magnetism, ionosphere and radio wave propagation (IZMIRAN), Troitsk, Moscow Region. The results of the study, in agreement with what already ascertained by authors from 2012, have confirmed that the four strongest earthquakes (and then the four tsunami) were preceded by a clear increase of the solar wind proton density which subsequently generated perturbation of the Earth's geomagnetic field. The temporal characteristics of the proton increases and geomagnetic disturbances that preceded the four tsunami have a clear predictive significance especially in the face of recent studies on Seismic Solar Precursors (SSPs), on Interplanetary Seismic Precursors (ISPs) and on Seismic Geomagnetic Precursors (SGPs) presented by the authors in the last two years.

Dynamic Consolidation and Investigation of Nanostructural W-Cu / W-Y Cylindrical Billets

NASA Astrophysics Data System (ADS)

Godibadze, B.; Dgebuadze, A.; Chagelishvili, E.; Mamniashvili, G.; Peikrishvili, A.

2018-03-01

The main purpose of presented work is to obtain W-Cu & W-Y cylindrical bulk nanostructured billets by explosive consolidation technology (ECT) in hot condition, with low porosity near to theoretical densities and improved physical / mechanical properties. Nanocomposites were subjected to densification into cylindrical steel tube containers using hot explosive consolidation (HEC) technology to fabricate high dense cylindrical billets. The first stage : Preliminary explosive densification of the precursor powder blend is carried out at room temperature with a loading intensity up to 10GPa to increase the initial density and to activate the particle surfaces in the blend. The second stage investigation were carried out for the same already predensified billets, but consolidation were conducted in hot conditions, after heating of samples in between 940-11000C, the intensity of loading was equal to 10GPa. Consolidated different type of W-Cu composition containing 10-40% of nanoscale W, during investigation showed that the combination of high temperatures (above 940°C) and two-stage shock wave compression was beneficial to the consolidation of the incompatible pair W-Cu composites, resulting in high densities, good integrity and good electronic properties. The structure and property of the samples obtained, depended on the sizes of tungsten particles. It was established that in comparison with W-Cu composites with coarse tungsten the application of nanoscale W precursors and depending of content of W gives different result. Tungsten is a prime material candidate for the first wall of a future fusion reactor. In this study, the microstructure and microhardness of tungsten-yttrium (W-Y) composites were investigated as a function of Y doping content (0.5÷2 wt. %). It was found that the crystallite sizes and the powder particle sizes were increased as a result of the increase of Y content. Nearly fully dense materials were obtained for W-Y alloys when the Y content was higher than 0.5 wt. %. Investigation revealed that the Y rich phases were complex (W-Y) oxides formed during the sintering process. Also very interesting to use doping chromium with yttrium-containing alloys. e.g. (W - 10÷12 Cr -0.5÷2 Y) wt. %. The extent up to which yttrium acts as an active element improving the adherence and stability of the protective Cr 2 O 3 layer formed during oxidation is assessed. The structure and characteristics of the obtained samples depends on the phase content, distribution of phases and processing parameters during explosive synthesis and consolidation. Cu – (10-30%) W powder mixtures were formed into cylindrical rods using a hot shock wave consolidation (HSWC) process. Different type of Cu - W precursor composition containing 10, 20 and 30% of nanoscale W were consolidated near theoretical density under 900°C The loading intensity was under 10 GPa. The investigation showed that the combination of high temperatures (above 800°C) and two stage shock wave compression was beneficial to the consolidation of the W-Cu & W-Y composites, resulting in high densities, good integrity and good electronic properties.

Numerical studies of electron dynamics in oblique quasi-perpendicular collisionless shock waves

NASA Technical Reports Server (NTRS)

Liewer, P. C.; Decyk, V. K.; Dawson, J. M.; Lembege, B.

1991-01-01

Linear and nonlinear electron damping of the whistler precursor wave train to low Mach number quasi-perpendicular oblique shocks is studied using a one-dimensional electromagnetic plasma simulation code with particle electrons and ions. In some parameter regimes, electrons are observed to trap along the magnetic field lines in the potential of the whistler precursor wave train. This trapping can lead to significant electron heating in front of the shock for low beta(e). Use of a 64-processor hypercube concurrent computer has enabled long runs using realistic mass ratios in the full particle in-cell code and thus simulate shock parameter regimes and phenomena not previously studied numerically.

Enhanced Multiferroic Properties of YMnO3 Ceramics Fabricated by Spark Plasma Sintering Along with Low-Temperature Solid-State Reaction

PubMed Central

Wang, Meng; Wang, Ting; Song, Shenhua; Ravi, Muchakayala; Liu, Renchen; Ji, Shishan

2017-01-01

Based on precursor powders with a size of 200–300 nm prepared by the low-temperature solid-state reaction method, phase-pure YMnO3 ceramics are fabricated using spark plasma sintering (SPS). X-ray diffraction (XRD) and scanning electron microscopy (SEM) reveal that the high-purity YMnO3 ceramics can be prepared by SPS at 1000 °C for 5 minutes with annealing at 800 °C for 2 h. The relative density of the sample is as high as 97%, which is much higher than those of the samples sintered by other methods. The present dielectric and magnetic properties are much better than those of the samples fabricated by conventional methods and SPS with ball-milling precursors, and the ferroelectric loops at room temperature can be detected. These findings indicate that the YMnO3 ceramics prepared by the low temperature solid reaction method and SPS possess excellent dielectric lossy ferroelectric properties at room temperature, and magnetic properties at low temperature (10 K), making them suitable for potential multiferroic applications. PMID:28772832

Supercapacitance from Cellulose and Carbon Nanotube Nanocomposite Fibers

PubMed Central

2013-01-01

Multiwalled carbon nanotube (MWNT)/cellulose composite nanofibers have been prepared by electrospinning a MWNT/cellulose acetate blend solution followed by deacetylation. These composite nanofibers were then used as precursors for carbon nanofibers (CNFs). The effect of nanotubes on the stabilization of the precursor and microstructure of the resultant CNFs were investigated using thermogravimetric analysis, transmission electron microscopy and Raman spectroscopy. It is demonstrated that the incorporated MWNTs reduce the activation energy of the oxidative stabilization of cellulose nanofibers from ∼230 to ∼180 kJ mol–1. They also increase the crystallite size, structural order, and electrical conductivity of the activated CNFs (ACNFs). The surface area of the ACNFs increased upon addition of nanotubes which protrude from the fiber leading to a rougher surface. The ACNFs were used as the electrodes of a supercapacitor. The electrochemical capacitance of the ACNF derived from pure cellulose nanofibers is demonstrated to be 105 F g–1 at a current density of 10 A g–1, which increases to 145 F g–1 upon the addition of 6% of MWNTs. PMID:24070254

Scalable synthesis of aligned carbon nanotubes bundles using green natural precursor: neem oil

NASA Astrophysics Data System (ADS)

Kumar, Rajesh; Tiwari, Radhey Shyam; Srivastava, Onkar Nath

2011-12-01

Practical application of aligned carbon nanotubes (ACNTs) would have to be determined by a matter of its economical and large-scale preparation. In this study, neem oil (also named Margoaa oil, extracted from the seeds of the neem-- Azadirachta indica) was used as carbon source to fabricate the bundles of ACNTs. ACNTs have been synthesized by spray pyrolysis of neem oil and ferrocene mixture at 825°C. The major components of neem oil are hydrocarbon with less amount of oxygen, which provided the precursor species in spray pyrolysis growth of CNTs. The bundles of ACNTs have been grown directly inside the quartz tube. The as-grown ACNTs have been characterized through Raman spectroscopy, scanning and transmission electron microscopic (SEM/TEM) techniques. SEM images reveal that the bundles of ACNTs are densely packed and are of several microns in length. High-resolution TEM analysis reveals these nanotubes to be multi-walled CNTs. These multi-walled CNTs were found to have inner diameter between 15 and 30 nm. It was found that present technique gives high yield with high density of bundles of ACNTs.

Scalable synthesis of aligned carbon nanotubes bundles using green natural precursor: neem oil.

PubMed

Kumar, Rajesh; Tiwari, Radhey Shyam; Srivastava, Onkar Nath

2011-01-18

Practical application of aligned carbon nanotubes (ACNTs) would have to be determined by a matter of its economical and large-scale preparation. In this study, neem oil (also named Margoaa oil, extracted from the seeds of the neem--Azadirachta indica) was used as carbon source to fabricate the bundles of ACNTs. ACNTs have been synthesized by spray pyrolysis of neem oil and ferrocene mixture at 825°C. The major components of neem oil are hydrocarbon with less amount of oxygen, which provided the precursor species in spray pyrolysis growth of CNTs. The bundles of ACNTs have been grown directly inside the quartz tube. The as-grown ACNTs have been characterized through Raman spectroscopy, scanning and transmission electron microscopic (SEM/TEM) techniques. SEM images reveal that the bundles of ACNTs are densely packed and are of several microns in length. High-resolution TEM analysis reveals these nanotubes to be multi-walled CNTs. These multi-walled CNTs were found to have inner diameter between 15 and 30 nm. It was found that present technique gives high yield with high density of bundles of ACNTs.

Atmospheric-pressure plasma jet processed Pt/ZnO composites and its application as counter-electrodes for dye-sensitized solar cells

NASA Astrophysics Data System (ADS)

Lee, Chia-Chun; Wan, Ting-Hao; Hsu, Cheng-Che; Cheng, I.-Chun; Chen, Jian-Zhang

2018-04-01

Nitrogen dc-pulse atmospheric pressure plasma jet (APPJ) is used to fabricate Pt/ZnO composites as the counter electrodes (CEs) of dye-sensitized solar cells (DSSCs). Due to the synergetic effect of the reactive plasma species and heat in nitrogen APPJ, the spin-coated precursors including chloroplatinic acid and zinc acetate can be reduced on fluorine-doped tin oxide (FTO) glass substrates in a few seconds. X-ray photoelectron spectroscopy (XPS) and Auger electron spectroscopy (AES) analyses indicate that the precursors are reduced to Pt/ZnO under APPJ calcination. Electrochemical impedance spectroscopy (EIS) and Tafel measurement show the promising catalytic activities of Pt/ZnO CEs with low charge transfer resistance and high exchange current density. The efficiency of a DSSC with a 30-s APPJ-calcined Pt/ZnO CE is similar to that with a conventional furnace-annealed Pt CE for 15 min. The results indicate that nitrogen dc-pulse APPJ treatment is an efficient tool for rapidly fabricating Pt/ZnO composite CEs of DSSCs.

Enhancing the platinum atomic layer deposition infiltration depth inside anodic alumina nanoporous membrane

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

Vaish, Amit, E-mail: anv@udel.edu; Krueger, Susan; Dimitriou, Michael

Nanoporous platinum membranes can be straightforwardly fabricated by forming a Pt coating inside the nanopores of anodic alumina membranes (AAO) using atomic layer deposition (ALD). However, the high-aspect-ratio of AAO makes Pt ALD very challenging. By tuning the process deposition temperature and precursor exposure time, enhanced infiltration depth along with conformal coating was achieved for Pt ALD inside the AAO templates. Cross-sectional scanning electron microscopy/energy dispersive x-ray spectroscopy and small angle neutron scattering were employed to analyze the Pt coverage and thickness inside the AAO nanopores. Additionally, one application of platinum-coated membrane was demonstrated by creating a high-density protein-functionalized interface.

Hydrodeoxygenation of coal using organometallic catalyst precursors

NASA Astrophysics Data System (ADS)

Kirby, Stephen R.

2002-04-01

The objective of this dissertation was to determine the desirability of organometallic compounds for the hydrodeoxygenation (HDO) of coal during liquefaction. The primary focus of this study was the removal of phenol-like compounds from coal liquids for the production of a thermally stable jet fuel. Investigation of the HDO ability of an organometallic compound containing both cobalt and molybdenum (CoMo-T2) was achieved using a combination of model compound and coal experiments. Model compounds were chosen representing four oxygen functional groups present in a range of coals. Electron density and bond order calculations were performed for anthrone, dinaphthyl ether, xanthene, di-t-butylmethylphenol, and some of their derivatives to ascertain a potential order of hydrogenolysis and hydrogenation reactivity for these compounds. The four model compounds were then reacted with CoMo-T2, as well as ammonium tetrathiomolybdate (ATTM). Products of reaction were grouped as compounds that had undergone deoxygenation, those that had aromatic rings reduced, those that were products of both reaction pathways, and those produced through other routes. ATTM had an affinity for both reaction types. Its reaction order for the four model compounds with respect to deoxygenated compounds was the same as that estimated from electron density calculations for hydrogenolysis reactivity. CoMo-T2 appeared to show a preference toward hydrogenation, although deoxygenated products were still achieved in similar, or greater, yields, for almost all the model compounds. The reactivity order achieved for the four compounds with CoMo-T2 was similar to that estimated from bond order calculations for hydrogenation reactivity. Three coals were selected representing a range of coal ranks and oxygen contents. DECS-26 (Wyodak), DECS-24 (Illinois #6), and DECS-23 (Pittsburgh #8) were analyzed by CPMAS 13C NMR and pyrolysis-GC-MS to determine the functional groups comprising the oxygen content of these coals. Trends within the data were similar to those reported by other authors. Based on the conclusions from both the model compound studies and the coal analysis, predictions were made of the catalyst precursors' performance in the HDO of the three selected coals. It was concluded that CoMo-T2 is a desirable catalyst precursor for the HDO of coals (particularly low-rank coals), but that an optimum set of conditions must be determined to take full advantage of its HDO ability. (Abstract shortened by UMI.)

Growth of ZnO nanorods on glass substrate deposited using dip coating method

NASA Astrophysics Data System (ADS)

Rani, Rozina Abdul; Ghafar, Safiah Ab; Zoolfakar, Ahmad Sabirin; Rusop, M.

2018-05-01

ZnO unique properties make it attractive for electronics and optoelectronics application. There are varieties synthesis of ZnO nanostructure but one of the best ways is by using dip coating method due to its simplicity, low cost and reliability. This research investigated the effect of precursor concentration on the morphology of ZnO nanorods using dip coating technique. ZnO nanorods is synthesized by using zinc nitrate as precursor and glass slide as substrate. The morphology of ZnO is characterized using Field Emission Scanning Electron Microscope (FESEM). By using different concentration of precursor, each outcome demonstrated diverse morphologies.

Tailoring properties of reticulated vitreous carbon foams with tunable density

NASA Astrophysics Data System (ADS)

Smorygo, Oleg; Marukovich, Alexander; Mikutski, Vitali; Stathopoulos, Vassilis; Hryhoryeu, Siarhei; Sadykov, Vladislav

2016-06-01

Reticulated vitreous carbon (RVC) foams were manufactured by multiple replications of a polyurethane foam template structure using ethanolic solutions of phenolic resin. The aims were to create an algorithm of fine tuning the precursor foam density and ensure an open-cell reticulated porous structure in a wide density range. The precursor foams were pyrolyzed in inert atmospheres at 700°C, 1100°C and 2000°C, and RVC foams with fully open cells and tunable bulk densities within 0.09-0.42 g/cm3 were synthesized. The foams were characterized in terms of porous structure, carbon lattice parameters, mechanical properties, thermal conductivity, electric conductivity, and corrosive resistance. The reported manufacturing approach is suitable for designing the foam microstructure, including the strut design with a graded microstructure.

Synthesis and assembly of retrovirus Gag precursors into immature capsids in vitro.

PubMed Central

Sakalian, M; Parker, S D; Weldon, R A; Hunter, E

1996-01-01

The assembly of retroviral particles is mediated by the product of the gag gene; no other retroviral gene products are necessary for this process. While most retroviruses assemble their capsids at the plasma membrane, viruses of the type D class preassemble immature capsids within the cytoplasm of infected cells. This has allowed us to determine whether immature capsids of the prototypical type D retrovirus, Mason-Pfizer monkey virus (M-PMV), can assemble in a cell-free protein synthesis system. We report here that assembly of M-PMV Gag precursor proteins can occur in this in vitro system. Synthesized particles sediment in isopycnic gradients to the appropriate density and in thin-section electron micrographs have a size and appearance consistent with those of immature retrovirus capsids. The in vitro system described in this report appears to faithfully mimic the process of assembly which occurs in the host cell cytoplasm, since M-PMV gag mutants defective in in vivo assembly also fail to assemble in vitro. Likewise, the Gag precursor proteins of retroviruses that undergo type C morphogenesis, Rous sarcoma virus and human immunodeficiency virus, which do not preassemble capsids in vivo, fail to assemble particles in this system. Additionally, we demonstrate, with the use of anti-Gag antibodies, that this cell-free system can be utilized for analysis in vitro of potential inhibitors of retrovirus assembly. PMID:8648705

The E2 Domains of APP and APLP1 Share a Conserved Mode of Dimerization

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

S Lee; Y Xue; J Hulbert

2011-12-31

Amyloid precursor protein (APP) is genetically linked to Alzheimer's disease. APP is a type I membrane protein, and its oligomeric structure is potentially important because this property may play a role in its function or affect the processing of the precursor by the secretases to generate amyloid {beta}-peptide. Several independent studies have shown that APP can form dimers in the cell, but how it dimerizes remains controversial. At least three regions of the precursor, including a centrally located and conserved domain called E2, have been proposed to contribute to dimerization. Here we report two new crystal structures of E2, onemore » from APP and the other from APLP1, a mammalian APP homologue. Comparison with an earlier APP structure, which was determined in a different space group, shows that the E2 domains share a conserved and antiparallel mode of dimerization. Biophysical measurements in solution show that heparin binding induces E2 dimerization. The 2.1 {angstrom} resolution electron density map also reveals phosphate ions that are bound to the protein surface. Mutational analysis shows that protein residues interacting with the phosphate ions are also involved in heparin binding. The locations of two of these residues, Arg-369 and His-433, at the dimeric interface suggest a mechanism for heparin-induced protein dimerization.« less

Simulations of the synthesis of boron-nitride nanostructures in a hot, high pressure gas volume† †Electronic supplementary information (ESI) available. See DOI: 10.1039/c8sc00667a

PubMed Central

Han, Longtao; Irle, Stephan; Nakai, Hiromi

2018-01-01

We performed nanosecond timescale computer simulations of clusterization and agglomeration processes of boron nitride (BN) nanostructures in hot, high pressure gas, starting from eleven different atomic and molecular precursor systems containing boron, nitrogen and hydrogen at various temperatures from 1500 to 6000 K. The synthesized BN nanostructures self-assemble in the form of cages, flakes, and tubes as well as amorphous structures. The simulations facilitate the analysis of chemical dynamics and we are able to predict the optimal conditions concerning temperature and chemical precursor composition for controlling the synthesis process in a high temperature gas volume, at high pressure. We identify the optimal precursor/temperature choices that lead to the nanostructures of highest quality with the highest rate of synthesis, using a novel parameter of the quality of the synthesis (PQS). Two distinct mechanisms of BN nanotube growth were found, neither of them based on the root-growth process. The simulations were performed using quantum-classical molecular dynamics (QCMD) based on the density-functional tight-binding (DFTB) quantum mechanics in conjunction with a divide-and-conquer (DC) linear scaling algorithm, as implemented in the DC-DFTB-K code, enabling the study of systems as large as 1300 atoms in canonical NVT ensembles for 1 ns time. PMID:29780513

Preparation of boron nitride fiber by organic precursor method

NASA Astrophysics Data System (ADS)

Zhou, Yingying; Sun, Runjun; Zhang, Zhaohuan; Fan, Wei; Zhou, Dan; Sheng, Cuihong

In this paper, boron nitride polymer precursor was made by boric acid, melamine, twelve sodium alkyl sulfate as raw materials and pure water as medium which is heated to 70 °C. Boron nitride precursor polymer was soluble in formic acid solution. The boron nitride precursor can be electrostatically spun at the voltage in 23 kV and the distance between the positive and negative poles is 15 cm. The formed fiber is very uniform. The properties of the precursors were analyzed through electron microscope, infrared spectrum, X-ray and ultraviolet spectrum. The aim of the job is to got the precursor of BN and spun it.

Hydrothermal growth of ZnO nanowire arrays: fine tuning by precursor supersaturation

DOE PAGES

Yan, Danhua; Cen, Jiajie; Zhang, Wenrui; ...

2016-12-20

In this paper, we develop a technique that fine tunes the hydrothermal growth of ZnO nanowires to address the difficulties in controlling their growth in a conventional one-pot hydrothermal method. In our technique, precursors are separately and slowly supplied with the assistance of a syringe pump, through the entire course of the growth. Compared to the one-pot method, the significantly lowered supersaturation of precursors helps eliminating competitive homogeneous nucleation and improves the reproducibility. The supersaturation degree can be readily tuned by the precursor quantity and injection rate, thus forming ZnO nanowire arrays of various geometries and packing densities in amore » highly controllable fashion. The precise control of ZnO nanowire growth enables systematic studies on the correlation between the material's properties and its morphology. Finally, in this work, ZnO nanowire arrays of various morphologies are studied as photoelectrochemical (PEC) water splitting photoanodes, in which we establish clear correlations between the water splitting performance and the nanowires' size, shape, and packing density.« less

Atomistic kinetic Monte Carlo study of atomic layer deposition derived from density functional theory.

PubMed

Shirazi, Mahdi; Elliott, Simon D

2014-01-30

To describe the atomic layer deposition (ALD) reactions of HfO2 from Hf(N(CH3)2)4 and H2O, a three-dimensional on-lattice kinetic Monte-Carlo model is developed. In this model, all atomistic reaction pathways in density functional theory (DFT) are implemented as reaction events on the lattice. This contains all steps, from the early stage of adsorption of each ALD precursor, kinetics of the surface protons, interaction between the remaining precursors (steric effect), influence of remaining fragments on adsorption sites (blocking), densification of each ALD precursor, migration of each ALD precursors, and cooperation between the remaining precursors to adsorb H2O (cooperative effect). The essential chemistry of the ALD reactions depends on the local environment at the surface. The coordination number and a neighbor list are used to implement the dependencies. The validity and necessity of the proposed reaction pathways are statistically established at the mesoscale. The formation of one monolayer of precursor fragments is shown at the end of the metal pulse. Adsorption and dissociation of the H2O precursor onto that layer is described, leading to the delivery of oxygen and protons to the surface during the H2O pulse. Through these processes, the remaining precursor fragments desorb from the surface, leaving the surface with bulk-like and OH-terminated HfO2, ready for the next cycle. The migration of the low coordinated remaining precursor fragments is also proposed. This process introduces a slow reordering motion (crawling) at the mesoscale, leading to the smooth and conformal thin film that is characteristic of ALD. Copyright © 2013 Wiley Periodicals, Inc.

Spectroscopic Identification of Isomeric Trimethylbenzyl Radicals Generated in Corona Discharge of Tetramethylbenzene

NASA Astrophysics Data System (ADS)

Yoon, Young Wook; Lee, Sang Kuk; Lee, Gi Woo

2011-06-01

The visible vibronic emission spectra were recorded from the corona discharge of precursor tetramethylbenzene with a large amount of inert carrier gas helium using a pinhole-type glass nozzle coupled with corona excited supersonic expansion (CESE) well developed in this laboratory. The spectra showed a series of vibronic bands in the D_1 → D_0 electronic transition of jet-cooled benzyl-type radicals formed from the precursor in a corona excitation. The analysis confirmed that two isomeric radicals, 2,3,4- and 2,3,6-trimethylbenzyl radicals and three isomeric radicals, 3,4,5-, 2,3,5- and 2,4,6-trimethylbenzyl radicals were produced, respectively, from 1,2,3,4- and 1,2,3,5-tetramethylbenzenes as a result of removal of a hydrogen atom from the methyl group at different substitution position. For each isomeric trimethylbenzyl radical generated in the corona discharge of precursor, the electronic transition and a few vibrational mode frequencies were determined in the ground electronic state by comparing with those from both ab initio calculations and the known vibrational data of the precursor. The substitution effect that states the shift of electronic transition depends on the nature, the number, and the position of substituents on the ring has been qualitatively proved for the case of benzyl-type radicals.

Effect of precursor concentration and spray pyrolysis temperature upon hydroxyapatite particle size and density.

PubMed

Cho, Jung Sang; Lee, Jeong-Cheol; Rhee, Sang-Hoon

2016-02-01

In the synthesis of hydroxyapatite powders by spray pyrolysis, control of the particle size was investigated by varying the initial concentration of the precursor solution and the pyrolysis temperature. Calcium phosphate solutions (Ca/P ratio of 1.67) with a range of concentrations from 0.1 to 2.0 mol/L were prepared by dissolving calcium nitrate tetrahydrate and diammonium hydrogen phosphate in deionized water and subsequently adding nitric acid. Hydroxyapatite powders were then synthesized by spray pyrolysis at 900°C and at 1500°C, using these calcium phosphate precursor solutions, under the fixed carrier gas flow rate of 10 L/min. The particle size decreased as the precursor concentration decreased and the spray pyrolysis temperature increased. Sinterability tests conducted at 1100°C for 1 h showed that the smaller and denser the particles were, the higher the relative densities were of sintered hydroxyapatite disks formed from these particles. The practical implication of these results is that highly sinterable small and dense hydroxyapatite particles can be synthesized by means of spray pyrolysis using a low-concentration precursor solution and a high pyrolysis temperature under a fixed carrier gas flow rate. © 2015 Wiley Periodicals, Inc.

Nano-casted Metal Oxide Aerogels as Dual Purpose Structural Components for Space Exploration

NASA Technical Reports Server (NTRS)

Vassilaras, Plousia E.

2004-01-01

NASA missions and space exploration rely on strong, ultra lightweight materials. Such materials are needed for building up past and present space vehicles such as the Sojourner Rover (1997) or the two MERs (2003), but also for a number of components and/or systems including thermal insulators, Solar Sails, Rigid Aeroshells, and Ballutes. The purpose of my internship here at Glenn Research Center is to make dual purpose materials; materials that in addition to being lightweight have electronic, photophysical and magnetic properties and, therefore, act as electronic components and sensors as well as structural components. One type of ultra lightweight material of great interest is aerogels, which have densities ranging from 0.003 g/cc to 0.8 g/cc . However, aerogels are extremely fragile and, as a result, have limited practical applications. Recently, Glenn Research Center has developed a process of nano-casting polymers onto the inorganic network of silica-based aerogels increasing the strength 300 fold while only increasing the density 3 fold. By combining the process of nano-casting polymers with inorganic oxide networks other than silica, we are actively pursuing lightweight dual purpose materials. To date, thirty different inorganic oxide aerogels have been prepared using either standard sol-gel chemistry or a non-alkoxide method involving metal chloride precursors and an epoxide; epichlorohydrin, propylene oxide or trimethylene oxide, as proton scavengers. More importantly, preliminary investigations show that the residual surface hydroxyl groups on each of these inorganic oxide aerogels can be successfully crosslinked with urethane. In addition to characterizing physical and mechanical properties such as density, strength and flexibility, each of these metal oxide aerogels are being characterized for thermal and electronic conductivity and magnetic and optical properties.

Structural, Optical, and Electronic Characterization of Fe-Doped Alumina Nanoparticles

NASA Astrophysics Data System (ADS)

Heiba, Zein K.; Mohamed, Mohamed Bakr; Wahba, Adel Maher; Imam, N. G.

2018-01-01

The effects of iron doping on the structural, optical, and electronic properties of doped alumina have been studied. Single-phase iron-doped alumina Al2- x Fe x O3 ( x = 0.00 to 0.30) nanoparticles were synthesized via citrate-precursor method. Formation of single-phase hexagonal corundum structure with no other separate phases was demonstrated by x-ray diffraction (XRD) analysis and Fourier-transform infrared spectroscopy. The effects of iron doping on the α-Al2O3 structural parameters, viz. atomic coordinates, lattice parameters, crystallite size, and microstrain, were estimated from XRD data by applying the Rietveld profile fitting method. Transmission electron microscopy further confirmed the nanosize nature of the prepared samples with size ranging from 12 nm to 83 nm. The electronic band structure was investigated using density functional theory calculations to explain the decrease in the energy gap of Al2- x Fe x O3 as the amount of Fe was increased. The colored emission peaks in the visible region (blue, red, violet) of the electromagnetic spectrum obtained for the Fe-doped α-Al2O3 nanoparticles suggest their potential application as ceramic nanopigments.

First principles study of the structural, electronic, and transport properties of triarylamine-based nanowires

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

Akande, Akinlolu, E-mail: akandea@tcd.ie; Bhattacharya, Sandip; Cathcart, Thomas

2014-02-21

We investigate with state of the art density functional theory the structural, electronic, and transport properties of a class of recently synthesized nanostructures based on triarylamine derivatives. First, we consider the single molecule precursors in the gas phase and calculate their static properties, namely (i) the geometrical structure of the neutral and cationic ions, (ii) the electronic structure of the frontier molecular orbitals, and (iii) the ionization potential, hole extraction potential, and internal reorganization energy. This initial study does not evidence any direct correlation between the properties of the individual molecules and their tendency to self-assembly. Subsequently, we investigate themore » charge transport characteristics of the triarylamine derivatives nanowires, by using Marcus theory. For one derivative we further construct an effective Hamiltonian including intermolecular vibrations and evaluate the mobility from the Kubo formula implemented with Monte Carlo sampling. These two methods, valid respectively in the sequential hopping and polaronic band limit, give us values for the room-temperature mobility in the range 0.1–12 cm{sup 2}/Vs. Such estimate confirms the superior transport properties of triarylamine-based nanowires, and make them an attracting materials platform for organic electronics.« less

Interactions of hydrogen with amorphous hafnium oxide

NASA Astrophysics Data System (ADS)

Kaviani, Moloud; Afanas'ev, Valeri V.; Shluger, Alexander L.

2017-02-01

We used density functional theory (DFT) calculations to study the interaction of hydrogen with amorphous hafnia (a -HfO2 ) using a hybrid exchange-correlation functional. Injection of atomic hydrogen, its diffusion towards electrodes, and ionization can be seen as key processes underlying charge instability of high-permittivity amorphous hafnia layers in many applications. Hydrogen in many wide band gap crystalline oxides exhibits negative-U behavior (+1 and -1 charged states are thermodynamically more stable than the neutral state) . Our results show that in a -HfO2 hydrogen is also negative-U, with charged states being the most thermodynamically stable at all Fermi level positions. However, metastable atomic hydrogen can share an electron with intrinsic electron trapping precursor sites [Phys. Rev. B 94, 020103 (2016)., 10.1103/PhysRevB.94.020103] forming a [etr -+O -H ] center, which is lower in energy on average by about 0.2 eV. These electron trapping sites can affect both the dynamics and thermodynamics of the interaction of hydrogen with a -HfO2 and the electrical behavior of amorphous hafnia films in CMOS devices.

Characteristics of a large vacuum wave precursor on the SABRE voltage adder MITL and extraction ion diode

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

Cuneo, M.E.; Hanson, D.L.; Menge, P.R.

SABRE (Sandia Accelerator and Beam Research Experiment) is a ten-cavity linear induction magnetically insulated voltage adder (6 MV, 300 kA) operated in positive polarity to investigate issues relevant to ion beam production and propagation for inertial confinement fusion. The voltage adder section is coupled to an applied-B extraction ion diode via a long coaxial output transmission line. Observations indicate that the power propagates in a vacuum wave prior to electron emission. After the electron emission threshold is reached, power propagates in a magnetically insulated wave. The precursor is observed to have a dominant impact on he turn-on, impedance history, andmore » beam characteristics of applied-B ion diodes since the precursor voltage is large enough to cause electron emission at the diode from both the cathode feed and cathode tips. The amplitude of the precursor at the load (3--4.5 MV) is a significant fraction of the maximum load voltage (5--6 MV) because (1) the transmission line gaps ( {approx} 9 cm at output) and therefore impedances are relatively large, and hence the electric field threshold for electron emission (200 to 300 kV/cm) is not reached until well into the power pulse rise time; and (2) the rapidly falling forward wave and diode impedance reduces the ratio of main pulse voltage to precursor voltage. Experimental voltage and current data from the transmission line and the ion diode will be presented and compared with TWOQUICK (2-D electromagnetic PIC code) simulations and analytic models.« less

Observation of lower defect density in CH{sub 3}NH{sub 3}Pb(I,Cl){sub 3} solar cells by admittance spectroscopy

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

Jiang, Minlin; Lan, Fei; Tao, Quan

The introduction of Cl into CH{sub 3}NH{sub 3}PbI{sub 3} precursors is reported to enhance the performance of CH{sub 3}NH{sub 3}PbI{sub 3} solar cell, which is attributed to the significantly increased diffusion lengths of carriers in CH{sub 3}NH{sub 3}Pb(I,Cl){sub 3} solar cell. It has been assumed but never experimentally approved that the defect density in CH{sub 3}NH{sub 3}Pb(I,Cl){sub 3} solar cell should be reduced according to the higher carrier lifetime observed from photoluminescence (PL) measurement. We have fabricated CH{sub 3}NH{sub 3}Pb(I,Cl){sub 3} solar cell by adding a small amount of Cl source into CH{sub 3}NH{sub 3}PbI{sub 3} precursor. The performance ofmore » CH{sub 3}NH{sub 3}Pb(I,Cl){sub 3} solar cell is significantly improved from 15.39% to 18.60%. Results from scanning electron microscopy and X-ray diffraction indicate that the morphologies and crystal structures of CH{sub 3}NH{sub 3}PbI{sub 3} and CH{sub 3}NH{sub 3}Pb(I,Cl){sub 3} thin films remain unchanged. Open circuit voltage decay and admittance spectroscopy characterization jointly approve that Cl plays an extremely important role in suppressing the formation of defects in perovskite solar cells.« less

The Seismo-Generated Electric Field Probed by the Ionospheric Ion Velocity

NASA Astrophysics Data System (ADS)

(Tiger) Liu, Jann-Yenq

2017-04-01

The ion density, ion temperature, and the ion velocity probed by IPEI (ionospheric Plasma and Electrodynamics Instrument) onboard ROCSAT (i.e. FORMOSAT-1), and the global ionospheric map (GIM) of the total electron content (TEC) derived from measurements of ground-based GPS receivers are employed to study seismo-ionospheric precursors (SIPs) of the 31 March 2002 M6.8 Earthquake in Taiwan. The GIM TEC and ROCSAT/IPEI ion density significantly decrease specifically over the epicenter area 1-5 days before the earthquake, which suggests that the associated SIPs have observed. The ROCSAT/IPEI ion temperature reveals no significant changes before and after the earthquake, while the latitude-time-TEC plots extracted from the GIMs along the Taiwan longitude illustrate that the equatorial ionization anomaly significantly weakens and moves equatorward, which indicates that the daily dynamo electric field has been disturbed and cancelled by possible seismo-generated electric field on 2 days before (29 March) the earthquake. Here, for the first time a vector parameter of ion velocity is employed to study SIPs. It is found that ROCSAT/IPEI ion velocity becomes significantly downward, which confirms that a westward electric field of about 0.91mV/m generated during the earthquake preparation period being essential 1-5 days before the earthquake. Liu, J. Y., and C. K. Chao (2016), An observing system simulation experiment for FORMOSAT-5/AIP detecting seismo-ionospheric precursors, Terrestrial Atmospheric and Oceanic Sciences, DOI: 10.3319/TAO.2016.07.18.01(EOF5).

Effects of Low Level Radiation exposure on Neurogenesis and Cognitive Function: Mechanisms and Prevention

DTIC Science & Technology

2005-09-01

precursor cells in culture with uX-lipoic acid reverses the density dependent changes observed in culture; this compound may provide an effective means...inhibited growth of precursor cells in vitro; - Antioxidant treatment of neural precursor cells in culture with a-lipoic acid (ALA) reverses the...with a single lO-Gy dose, and tissues avidin-biotinylated pemxidase complex; GFAP, glial fibrillary acidic protein; DAB, 3,3’- were collected from 6 to

Hotspot ignition using a Z-pinch precursor plasma in a magneto-inertial ICF scheme

NASA Astrophysics Data System (ADS)

Chittenden, J. P.; Vincent, P.; Jennings, C. A.; Ciardi, A.

2006-01-01

Precursor plasma flow is a common feature of wire array Z-pinches. The precursor flow represents a fraction of the mass of the array which arrives on the axis early in time and remains confined at high density by the inertia of further material bombarding the axis. Later on, the main implosion of the Z-pinch then compresses this precursor to substantially higher density. We show that if the same system can be generated with a Deuterium-Tritium plasma then the precursor provides an ideal target for a cylindrical magneto-inertial ICF scheme. The implosion of the DT Z-pinch produces a dense, low temperature shell which compressively heats the precursor target to high temperatures and tamps its expansion. The azimuthal magnetic field in the hotspot is sufficient to reduce the Larmor radius for the alpha particles to much less than the hotspot size, which dramatically reduces the pR required for ignition. A computational analysis of this approach is presented, including a study of the thermonuclear burn wave propagation. The robustness of the scheme with respect to instabilities, confinement time and drive parameters is examined. The results indicate that a high energy gain can be achieved using Z-pinches with 50-100 MA currents and a few hundred nanosecond rise-times. This work was partially supported by the U.S. Department of Energy through cooperative agreement DE-FC03-02NA00057.

The rational design of a Au(I) precursor for focused electron beam induced deposition

PubMed Central

Marashdeh, Ali; Tiesma, Thiadrik; van Velzen, Niels J C; Harder, Sjoerd; Havenith, Remco W A; De Hosson, Jeff T M

2017-01-01

Au(I) complexes are studied as precursors for focused electron beam induced processing (FEBIP). FEBIP is an advanced direct-write technique for nanometer-scale chemical synthesis. The stability and volatility of the complexes are characterized to design an improved precursor for pure Au deposition. Aurophilic interactions are found to play a key role. The short lifetime of ClAuCO in vacuum is explained by strong, destabilizing Au–Au interactions in the solid phase. While aurophilic interactions do not affect the stability of ClAuPMe3, they leave the complex non-volatile. Comparison of crystal structures of ClAuPMe3 and MeAuPMe3 shows that Au–Au interactions are much weaker or partially even absent for the latter structure. This explains its high volatility. However, MeAuPMe3 dissociates unfavorably during FEBIP, making it an unsuitable precursor. The study shows that Me groups reduce aurophilic interactions, compared to Cl groups, which we attribute to electronic rather than steric effects. Therefore we propose MeAuCO as a potential FEBIP precursor. It is expected to have weak Au–Au interactions, making it volatile. It is stable enough to act as a volatile source for Au deposition, being stabilized by 6.5 kcal/mol. Finally, MeAuCO is likely to dissociate in a single step to pure Au. PMID:29354346

The rational design of a Au(I) precursor for focused electron beam induced deposition.

PubMed

Marashdeh, Ali; Tiesma, Thiadrik; van Velzen, Niels J C; Harder, Sjoerd; Havenith, Remco W A; De Hosson, Jeff T M; van Dorp, Willem F

2017-01-01

Au(I) complexes are studied as precursors for focused electron beam induced processing (FEBIP). FEBIP is an advanced direct-write technique for nanometer-scale chemical synthesis. The stability and volatility of the complexes are characterized to design an improved precursor for pure Au deposition. Aurophilic interactions are found to play a key role. The short lifetime of ClAuCO in vacuum is explained by strong, destabilizing Au-Au interactions in the solid phase. While aurophilic interactions do not affect the stability of ClAuPMe 3 , they leave the complex non-volatile. Comparison of crystal structures of ClAuPMe 3 and MeAuPMe 3 shows that Au-Au interactions are much weaker or partially even absent for the latter structure. This explains its high volatility. However, MeAuPMe 3 dissociates unfavorably during FEBIP, making it an unsuitable precursor. The study shows that Me groups reduce aurophilic interactions, compared to Cl groups, which we attribute to electronic rather than steric effects. Therefore we propose MeAuCO as a potential FEBIP precursor. It is expected to have weak Au-Au interactions, making it volatile. It is stable enough to act as a volatile source for Au deposition, being stabilized by 6.5 kcal/mol. Finally, MeAuCO is likely to dissociate in a single step to pure Au.

High-performance field emission device utilizing vertically aligned carbon nanotubes-based pillar architectures

NASA Astrophysics Data System (ADS)

Gupta, Bipin Kumar; Kedawat, Garima; Gangwar, Amit Kumar; Nagpal, Kanika; Kashyap, Pradeep Kumar; Srivastava, Shubhda; Singh, Satbir; Kumar, Pawan; Suryawanshi, Sachin R.; Seo, Deok Min; Tripathi, Prashant; More, Mahendra A.; Srivastava, O. N.; Hahm, Myung Gwan; Late, Dattatray J.

2018-01-01

The vertical aligned carbon nanotubes (CNTs)-based pillar architectures were created on laminated silicon oxide/silicon (SiO2/Si) wafer substrate at 775 °C by using water-assisted chemical vapor deposition under low pressure process condition. The lamination was carried out by aluminum (Al, 10.0 nm thickness) as a barrier layer and iron (Fe, 1.5 nm thickness) as a catalyst precursor layer sequentially on a silicon wafer substrate. Scanning electron microscope (SEM) images show that synthesized CNTs are vertically aligned and uniformly distributed with a high density. The CNTs have approximately 2-30 walls with an inner diameter of 3-8 nm. Raman spectrum analysis shows G-band at 1580 cm-1 and D-band at 1340 cm-1. The G-band is higher than D-band, which indicates that CNTs are highly graphitized. The field emission analysis of the CNTs revealed high field emission current density (4mA/cm2 at 1.2V/μm), low turn-on field (0.6 V/μm) and field enhancement factor (6917) with better stability and longer lifetime. Emitter morphology resulting in improved promising field emission performances, which is a crucial factor for the fabrication of pillared shaped vertical aligned CNTs bundles as practical electron sources.

Density functional theoretical modeling, electrostatic surface potential and surface enhanced Raman spectroscopic studies on biosynthesized silver nanoparticles: observation of 400 PM sensitivity to explosives.

PubMed

Sil, Sanchita; Chaturvedi, Deepika; Krishnappa, Keerthi B; Kumar, Srividya; Asthana, S N; Umapathy, Siva

2014-04-24

Interaction of adsorbate on charged surfaces, orientation of the analyte on the surface, and surface enhancement aspects have been studied. These aspects have been explored in details to explain the surface-enhanced Raman spectroscopic (SERS) spectra of 2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane (HNIW or CL-20), a well-known explosive, and 2,4,6-trinitrotoluene (TNT) using one-pot synthesis of silver nanoparticles via biosynthetic route using natural precursor extracts of clove and pepper. The biosynthesized silver nanoparticles (bio Ag Nps) have been characterized using UV-vis spectroscopy, scanning electron microscopy and atomic force microscopy. SERS studies conducted using bio Ag Nps on different water insoluble analytes, such as CL-20 and TNT, lead to SERS signals at concentration levels of 400 pM. The experimental findings have been corroborated with density functional computational results, electrostatic surface potential calculations, Fukui functions and ζ potential measurements.

A Direct Ultrasound Irradiation Method Synthesis of Monodisperse ZnO Microspheres for Varistors Ceramics Application

NASA Astrophysics Data System (ADS)

Chen, Tao; Wang, Mao-Hua; Zhang, Han-Ping; Liu, Jin-Ran; Yao, Da-Chuan

2016-08-01

Monodisperse and uniform ZnO microspheres were synthesized via an ultrasound irradiation method. The microstructure and morphology of the as-prepared sample were characterized by x-ray powder diffraction, Fourier transformation infrared spectra and scanning electron microscopy. The results indicate that the size of ZnO microspheres was strongly affected by the Zn(NO3)2·6H2O. As the amount of the precursor increased, the diameters of the ZnO microspheres can be turned from ˜500 nm to ˜2 μm. The electrical properties of the varistors ceramics prepared from the as-obtained ZnO powders were investigated. The results show that the varistors ceramics made from ZnO with a size of ˜500 nm and sintered in air at 1150°C for 2 h possess a density of 5.50 g/cm3 corresponding to 95.1% of the theoretical density, with breakdown voltage of 280.9 V/mm and nonlinear coefficient of ˜61.3.

Density Functional Theory Study of Spirodienone Stereoisomers in Lignin

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

Elder, Thomas; Berstis, Laura; Beckham, Gregg T.

The spirodienone structure in lignin is a relatively recent discovery, and it has been found to occur in lignin of various plant species at concentrations of ~3%, which is sufficiently high to be important for better understanding of its properties and reactivity. The cyclic structure, with a ..beta..-1 bond, has been proposed to be a precursor for acyclic ..beta..-1 linkages in lignin. Previous analytical work has revealed the presence, but not the absolute configuration, of two stereoisomeric forms of spirodienone. The objective of the current work was to determine if there are thermodynamic differences that could help identify the experimentallymore » observed stereoisomers. Results from density functional theory calculations reveal the presence of clusters of stereoisomers with varying stability that may be of use in narrowing the list of possible structures. Furthermore, the bond dissociation enthalpy of the cyclic ring exhibited a particularly high value for the C-O cleavage reaction relative to more conventional ether bonds in lignin, perhaps due to limited electron delocalization possibilities.« less

Density Functional Theory Study of Spirodienone Stereoisomers in Lignin

DOE PAGES

Elder, Thomas; Berstis, Laura; Beckham, Gregg T.; ...

2017-06-28

The spirodienone structure in lignin is a relatively recent discovery, and it has been found to occur in lignin of various plant species at concentrations of ~3%, which is sufficiently high to be important for better understanding of its properties and reactivity. The cyclic structure, with a ..beta..-1 bond, has been proposed to be a precursor for acyclic ..beta..-1 linkages in lignin. Previous analytical work has revealed the presence, but not the absolute configuration, of two stereoisomeric forms of spirodienone. The objective of the current work was to determine if there are thermodynamic differences that could help identify the experimentallymore » observed stereoisomers. Results from density functional theory calculations reveal the presence of clusters of stereoisomers with varying stability that may be of use in narrowing the list of possible structures. Furthermore, the bond dissociation enthalpy of the cyclic ring exhibited a particularly high value for the C-O cleavage reaction relative to more conventional ether bonds in lignin, perhaps due to limited electron delocalization possibilities.« less

Liquefaction of oak tree bark with different biomass/phenol mass ratios and utilizing bio-based polyols for carbon foam production

NASA Astrophysics Data System (ADS)

Ozbay, N.; Yargic, A. S.

2017-02-01

Carbon foam is sponge like carbonaceous material with low density, high conductivity and high strength; which is used in various applications such as catalyst supports, membrane separations, high thermally conductive heat sinks, energy absorption materials, high temperature thermal insulation. Coal or fossil oils are conventionally used to fabricate pitch, phenolic resin and polyurethane as carbon foam precursor. Biomass liquefaction is a developing technique to convert biomass resources into the industrial chemicals. In this study, oak tree bark was liquefied under mild conditions with different mass ratio of biomass/phenol; and the liquefaction product was used as polyol to produce porous resin foams. Obtained resin foams were carbonized at 400 °C, and then activated at 800 °C under nitrogen atmosphere. Structure evaluation of resin foams, carbonized foams and activated carbon foams from liquefied oak tree bark was investigated by using elemental analysis, x-ray diffraction, nitrogen adsorption/desorption isotherms, scanning electron microscopy, bulk density and compressive strength tests.

A study on ionospheric scintillation near the EIA crest in relation to equatorial electrodynamics

NASA Astrophysics Data System (ADS)

Chatterjee, S.; Chakraborty, S. K.; Veenadhari, B.; Banola, S.

2014-02-01

Equatorial electrojet (EEJ) data, which are considered as a proxy index of equatorial electric field, are analyzed in conjunction with equatorial ionosonde, total electron content (TEC) and scintillation data near the equatorial ionization anomaly (EIA) crest for the equinoctial months of high solar activity years (2011-2012) to identify any precursor index of postsunset evolution of equatorial electron density irregularities and subsequent occurrence of scintillation near the northern EIA crest. Only geomagnetically quiet and normal electrojet days are considered. The diurnal profiles of EEJ on the scintillation days exhibit a secondary enhancement in the afternoon to presunset hours following diurnal peaks. A series of electrodynamical processes conducive for generation of irregularities emerge following secondary enhancement of EEJ. Latitudinal profile of TEC exhibits resurgence in EIA structure around the postsunset period. Diurnal TEC profile near the EIA crest resembles postsunset secondary enhancement on the days with afternoon enhancement in EEJ. Occurrence of equatorial spread F and postsunset scintillation near the EIA crest seems to follow the secondary enhancement events in EEJ. Both the magnitude and duration of enhanced EEJ are found to be important for postsunset intensification of EIA structure and subsequent occurrence of equatorial irregularities. A critical value combining the two may be considered an important precursor for postsunset occurrence of scintillation near the EIA crest. The results are validated using archived data for the years 1989-1990 and explained in terms of modulation effects of enhanced equatorial fountain.

Characterization of High-Velocity Solution Precursor Flame-Sprayed Manganese Cobalt Oxide Spinel Coatings for Metallic SOFC Interconnectors

NASA Astrophysics Data System (ADS)

Puranen, Jouni; Laakso, Jarmo; Kylmälahti, Mikko; Vuoristo, Petri

2013-06-01

A modified high-velocity oxy-fuel spray (HVOF) thermal spray torch equipped with liquid feeding hardware was used to spray manganese-cobalt solutions on ferritic stainless steel grade Crofer 22 APU substrates. The HVOF torch was modified in such a way that the solution could be fed axially into the combustion chamber through 250- and 300-μm-diameter liquid injector nozzles. The solution used in this study was prepared by diluting nitrates of manganese and cobalt, i.e., Mn(NO3)2·4H2O and Co(NO3)2·6H2O, respectively, in deionized water. The as-sprayed coatings were characterized by X-ray diffraction and field-emission scanning electron microscopy operating in secondary electron mode. Chemical analyses were performed on an energy dispersive spectrometer. Coatings with remarkable density could be prepared by the novel high-velocity solution precursor flame spray (HVSPFS) process. Due to finely sized droplet formation in the HVSPFS process and the use of as delivered Crofer 22 APU substrate material having very low substrate roughness ( R a < 0.5 μm), thin and homogeneous coatings, with thicknesses lower than 10 μm could be prepared. The coatings were found to have a crystalline structure equivalent to MnCo2O4 spinel with addition of Co-oxide phases. Crystallographic structure was restored back to single-phase spinel structure by heat treatment.

Cd–cysteine precursor nanowire templated microwave-assisted transformation route to CdS nanotubes

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

Liu, Xiao-Lin, E-mail: liu_x_l@sina.cn; Zhu, Ying-Jie; Zhang, Qian

2012-12-15

Graphical abstract: Cadmium sulfide polycrystalline nanotubes have been successfully synthesized by microwave-assisted transformation method using Cd–cysteine precursor nanowires as the source material and template in ethylene glycol at 160 °C or ethanol at 60 °C. Display Omitted Highlights: ► Cd–cysteine precursor nanowires were successfully synthesized in alkaline solution. ► CdS nanotubes were prepared by templated microwave-assisted transformation method. ► CdS nanotubes can well duplicate the size and morphology of precursor nanowires. ► This method has the advantages of the simplicity and low cost. -- Abstract: We report the Cd–cysteine precursor nanowire templated microwave-assisted transformation route to CdS nanotubes. In thismore » method, the Cd–cysteine precursor nanowires are synthesized using CdCl{sub 2}·2.5H{sub 2}O, L-cysteine and ethanolamine in water at room temperature. The Cd–cysteine precursor nanowires are used as the source material and template for the subsequent preparation of CdS nanotubes by a microwave-assisted transformation method using ethylene glycol or ethanol as the solvent. This method has the advantages of the simplicity and low cost, and may be extended to the synthesis of nanotubes of other compounds. The products are characterized by X-ray powder diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM).« less

Acoustic levitation for high temperature containerless processing in space

NASA Technical Reports Server (NTRS)

Rey, C. A.; Sisler, R.; Merkley, D. R.; Danley, T. J.

1990-01-01

New facilities for high-temperature containerless processing in space are described, including the acoustic levitation furnace (ALF), the high-temperature acoustic levitator (HAL), and the high-pressure acoustic levitator (HPAL). In the current ALF development, the maximum temperature capabilities of the levitation furnaces are 1750 C, and in the HAL development with a cold wall furnace they will exceed 2000-2500 C. The HPAL demonstrated feasibility of precursor space flight experiments on the ground in a 1 g pressurized-gas environment. Testing of lower density materials up to 1300 C has also been accomplished. It is suggested that advances in acoustic levitation techniques will result in the production of new materials such as ceramics, alloys, and optical and electronic materials.

Density functional theory study of HfCl4, ZrCl4, and Al(CH3)3 decomposition on hydroxylated SiO2: Initial stage of high-k atomic layer deposition

NASA Astrophysics Data System (ADS)

Jeloaica, L.; Estève, A.; Djafari Rouhani, M.; Estève, D.

2003-07-01

The initial stage of atomic layer deposition of HfO2, ZrO2, and Al2O3 high-k films, i.e., the decomposition of HfCl4, ZrCl4, and Al(CH3)3 precursor molecules on an OH-terminated SiO2 surface, is investigated within density functional theory. The energy barriers are determined using artificial activation of vibrational normal modes. For all precursors, reaction proceeds through the formation of intermediate complexes that have equivalent formation energies (˜-0.45 eV), and results in HCl and CH4 formation with activation energies of 0.88, 0.91, and 1.04 eV for Hf, Zr, and Al based precursors, respectively. The reaction product of Al(CH3)3 decomposition is found to be more stable (by -1.45 eV) than the chemisorbed intermediate complex compared to the endothermic decomposition of HfCl4 and ZrCl4 chemisorbed precursors (0.26 and 0.29 eV, respectively).

Gelcasting polymeric precursors for producing net-shaped graphites

DOEpatents

Klett, James W.; Janney, Mark A.

2002-01-01

The present invention discloses a method for molding complex and intricately shaped high density monolithic carbon, carbon-carbon, graphite, and thermoplastic composites using gelcasting technology. The method comprising a polymeric carbon precursor, a solvent, a dispersant, an anti-foaming agent, a monomer system, and an initiator system. The components are combined to form a suspension which is poured into a mold and heat-treated to form a thermoplastic part. The thermoplastic part can then be further densified and heat-treated to produce a high density carbon or graphite composite. The present invention also discloses the products derived from this method.

Nitrogen-doped carbon spheres: A new high-energy-density and long-life pseudo-capacitive electrode material for electrochemical flow capacitor.

PubMed

Hou, Shujin; Wang, Miao; Xu, Xingtao; Li, Yandong; Li, Yanjiang; Lu, Ting; Pan, Likun

2017-04-01

One of the most challenging issues in developing electrochemical flow capacitor (EFC) technology is the design and synthesis of active electrode materials with high energy density and long cycle life. However, in practical cases, the energy density and cycle ability obtained currently cannot meet the practical need. In this work, we propose a new active material, nitrogen-doped carbon spheres (NCSs), as flowable electrodes for EFC application. The NCSs were prepared via one-pot hydrothermal synthesis in the presence of resorcinol/formaldehyde as carbon precursors and melamine as nitrogen precursor, followed by carbonization in nitrogen flow at various temperatures. The results of EFC experiments demonstrate that NCSs obtained at 800°C exhibit a high energy density of 13.5Whkg -1 and an excellent cycle ability, indicating the superiority of NCSs for EFC application. Copyright © 2016 Elsevier Inc. All rights reserved.

Grafting density effects, optoelectrical properties and nano-patterning of poly(para-phenylene) brushes

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

Chen, Jihua; Alonzo, Jose; Yu, Xiang

2013-09-24

Well-defined conjugated polymers in confined geometries are challenging to synthesize and characterize, yet they are potentially useful in a broad range of organic optoelectronic devices such as transistors, light emitting diodes, solar cells, sensors, and nanocircuits. We report a systematic study of optoelectrical properties, grafting density effects, and nanopatterning of a model, end-tethered conjugated polymer system. Specifically, poly(para-phenylene) (PPP) brushes of various grafting density are created in situ by aromatizing well-defined, end-tethered poly(1,3-cyclohexadiene) (PCHD) “precursor brushes”. Furthermore, this novel precursor brush approach provides a convenient way to make and systematically control the grafting density of high molecular weight conjugated polymermore » brushes that would otherwise be insoluble. Finally, this allows us to examine how grafting density impacts the effective conjugation length of the conjugated PPP brushes and to adapt the fabrication method to develop spatially patterned conjugated brush systems, which is important for practical applications of conjugated polymer brushes.« less

Observations of Electron-driven Evaporation in a Flare Precursor

NASA Astrophysics Data System (ADS)

Li, Dong; Li, Ying; Su, Wei; Huang, Yu; Ning, Zongjun

2018-02-01

We investigate the relationship between the blueshifts of a hot emission line and the nonthermal emissions in microwave and hard X-ray (HXR) wavelengths in the precursor of a solar flare on 2014 October 27. The flare precursor is identified as a small but well-developed peak in the soft X-ray and extreme-ultraviolet passbands before the GOES flare onset, which is accompanied by a pronounced burst in microwave 17 and 34 GHz and in HXR 25–50 keV. The slit of the Interface Region Imaging Spectrograph (IRIS) stays on one ribbon-like transient during the flare precursor phase, which shows visible nonthermal emissions in Nobeyama Radioheliograph and RHESSI images. The IRIS spectroscopic observations show that the hot line of Fe XXI 1354.09 Å (log T ∼ 7.05) displays blueshifts, while the cool line of Si IV 1402.77 Å (log T ∼ 4.8) exhibits redshifts. The blueshifts and redshifts are well correlated with each other, indicative of an explosive chromospheric evaporation during the flare precursor phase combining a high nonthermal energy flux with a short characteristic timescale. In addition, the blueshifts of Fe XXI 1354.09 Å are well correlated with the microwave and HXR emissions, implying that the explosive chromospheric evaporation during the flare precursor phase is driven by nonthermal electrons.

Electrodeposition of Rhodium Nanowires Arrays and Their Morphology-Dependent Hydrogen Evolution Activity

PubMed Central

Zhang, Liqiu; Liu, Lichun; Wang, Hongdan; Shen, Hongxia; Cheng, Qiong; Yan, Chao; Park, Sungho

2017-01-01

This work reports on the electrodeposition of rhodium (Rh) nanowires with a controlled surface morphology synthesized using an anodic aluminum oxide (AAO) template. Vertically aligned Rh nanowires with a smooth and coarse morphology were successfully deposited by adjusting the electrode potential and the concentration of precursor ions and by involving a complexing reagent in the electrolyte solution. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) analyses were used to follow the morphological evolution of Rh nanowires. As a heterogeneous electrocatalyst for hydrogen evolution reactions (HER), the coarse Rh nanowire array exhibited an enhanced catalytic performance respect to smooth ones due to the larger surface area to mass ratio and the higher density of catalytically active defects, as evidenced by voltammetric measurements and TEM. Results suggest that the morphology of metallic nanomaterials could be readily engineered by electrodeposition. The controlled electrodeposition offers great potential for the development of an effective synthesis tool for heterogeneous catalysts with a superior performance for wide applications. PMID:28467375

Characteristic Study of Boron Doped Carbon Nanowalls Films Deposited by Microwave Plasma Enhanced Chemical Vapor Deposition.

PubMed

Lu, Chunyuan; Dong, Qi; Tulugan, Kelimu; Park, Yeong Min; More, Mahendra A; Kim, Jaeho; Kim, Tae Gyu

2016-02-01

In this research, catalyst-free vertically aligned boron doped carbon nanowalls films were fabricated on silicon (100) substrates by MPECVD using feeding gases CH4, H2 and B2H6 (diluted with H2 to 5% vol) as precursors. The substrates were pre-seeded with nanodiamond colloid. The fabricated CNWs films were characterized by Scanning Electron Microscopy (SEM) and Raman Spectroscopy. The data obtained from SEM confirms that the CNWs films have different density and wall thickness. From Raman spectrum, a G peak around 1588 cm(-1) and a D band peak at 1362 cm(-1) were observed, which indicates a successful fabrication of CNWs films. The EDX spectrum of boron doped CNWs film shows the existence of boron and carbon. Furthermore, field emission properties of boron doped carbon nanowalls films were measured and field enhancement factor was calculated using Fowler-Nordheim plot. The result indicates that boron doped CNWs films could be potential electron emitting materials.

Radiation from Accelerated Particles in Shocks and Reconnections

NASA Technical Reports Server (NTRS)

Nishikawa, K. I.; Choi, E. J.; Min, K. W.; Niemiec, J.; Zhang, B.; Hardee, P.; Mizuno, Y.; Medvedev, M.; Nordlund, A.; Frederiksen, J.;

2-Aryl-2-nitroacetates as Central Precursors to Aryl Nitromethanes, α-Ketoesters, and α-Amino Acids

PubMed Central

Metz, Alison E.

2013-01-01

Nitroarylacetates are useful small molecular building blocks that act as precursors to α-ketoesters and aryl nitromethanes as well as α-amino acids. Methods were developed that produce each of these compound types in good yields. Two different conditions for decarboxylation are discussed for substrates with neutral and electron-poor aryl groups versus electron-rich aryl groups. For formation of the α-ketoesters, new mild conditions for the Nef disproportionation were identified. PMID:23245626

Highly Strong and Elastic Graphene Fibres Prepared from Universal Graphene Oxide Precursors

PubMed Central

Huang, Guoji; Hou, Chengyi; Shao, Yuanlong; Wang, Hongzhi; Zhang, Qinghong; Li, Yaogang; Zhu, Meifang

2014-01-01

Graphene fibres are continuously prepared from universal graphene oxide precursors by a novel hydrogel-assisted spinning method. With assistance of a rolling process, meters of ribbon-like GFs, or GRs with improved conductivity, tensile strength, and a long-range ordered compact layer structure are successfully obtained. Furthermore, we refined our spinning process to obtained elastic GRs with a mixing microstructure and exceptional elasticity, which may provide a platform for electronic skins and wearable electronics, sensors, and energy devices. PMID:24576869

Investigation of energy deposited by femtosecond electron transfer in collisions using hydrated ion nanocalorimetry.

PubMed

Holm, Anne I S; Donald, William A; Hvelplund, Preben; Larsen, Mikkel K; Nielsen, Steen Brøndsted; Williams, Evan R

2008-10-30

Ion nanocalorimetry is used to investigate the internal energy deposited into M (2+)(H 2O) n , M = Mg ( n = 3-11) and Ca ( n = 3-33), upon 100 keV collisions with a Cs or Ne atom target gas. Dissociation occurs by loss of water molecules from the precursor (charge retention) or by capture of an electron to form a reduced precursor (charge reduction) that can dissociate either by loss of a H atom accompanied by water molecule loss or by exclusively loss of water molecules. Formation of bare CaOH (+) and Ca (+) by these two respective dissociation pathways occurs for clusters with n up to 33 and 17, respectively. From the threshold dissociation energies for the loss of water molecules from the reduced clusters, obtained from binding energies calculated using a discrete implementation of the Thomson liquid drop model and from quantum chemistry, estimates of the internal energy deposition can be obtained. These values can be used to establish a lower limit to the maximum and average energy deposition. Not taking into account effects of a kinetic shift, over 16 eV can be deposited into Ca (2+)(H 2O) 33, the minimum energy necessary to form bare CaOH (+) from the reduced precursor. The electron capture efficiency is at least a factor of 40 greater for collisions of Ca (2+)(H 2O) 9 with Cs than with Ne, reflecting the lower ionization energy of Cs (3.9 eV) compared to Ne (21.6 eV). The branching ratio of the two electron capture dissociation pathways differs significantly for these two target gases, but the distributions of water molecules lost from the reduced precursors are similar. These results suggest that the ionization energy of the target gas has a large effect on the electron capture efficiency, but relatively little effect on the internal energy deposited into the ion. However, the different branching ratios suggest that different electronic excited states may be accessed in the reduced precursor upon collisions with these two different target gases.

1 D analysis of Radiative Shock damping by lateral radiative losses.

NASA Astrophysics Data System (ADS)

Busquet, Michel; Colombier, Jean-Philippe; Stehle, Chantal

2007-11-01

It has been shown theoretically and experimentally [1] that the radiative precursor in front of a strong shock in hi-Z material is slowed down by lateral radiative losses. The 2D simulation showed that the shock front and the precursor front remain planar, with an increase of density and a decrease of temperature close to the walls. The damping of the precursor is obviously sensitive to the fraction of self-emitted radiation reflected by the walls (the albedo). In order to perform parametric studies we include the albedo controlled lateral radiative losses in the 1D hydro-code MULTI (created by Ramis et al [2]) both in terms of energy balance and of spectral diagnostic. [1] Gonzales et al, Laser Part. Beams 24, 1-6 (2006) ; Busquet et al, High Energy Density Physics (2007), doi: 10.1016/j.hedp.2007.01.002 [2] Ramis et al, Comp. Phys. Comm., 49 (1988), 475

A global scale picture of ionospheric peak electron density changes during geomagnetic storms

NASA Astrophysics Data System (ADS)

Kumar, Vickal V.; Parkinson, Murray L.

2017-04-01

Changes in ionospheric plasma densities can affect society more than ever because of our increasing reliance on communication, surveillance, navigation, and timing technology. Models struggle to predict changes in ionospheric densities at nearly all temporal and spatial scales, especially during geomagnetic storms. Here we combine a 50 year (1965-2015) geomagnetic disturbance storm time (Dst) index with plasma density measurements from a worldwide network of 132 vertical incidence ionosondes to develop a picture of global scale changes in peak plasma density due to geomagnetic storms. Vertical incidence ionosondes provide measurements of the critical frequency of the ionospheric F2 layer (foF2), a direct measure of the peak electron density (NmF2) of the ionosphere. By dissecting the NmF2 perturbations with respect to the local time at storm onset, season, and storm intensity, it is found that (i) the storm-associated depletions (negative storm effects) and enhancements (positive storm effects) are driven by different but related physical mechanisms, and (ii) the depletion mechanism tends to dominate over the enhancement mechanism. The negative storm effects, which are detrimental to HF radio links, are found to start immediately after geomagnetic storm onset in the nightside high-latitude ionosphere. The depletions in the dayside high-latitude ionosphere are delayed by a few hours. The equatorward expansion of negative storm effects is found to be regulated by storm intensity (farthest equatorward and deepest during intense storms), season (largest in summer), and time of day (generally deeper on the nightside). In contrast, positive storm effects typically occur on the dayside midlatitude and low-latitude ionospheric regions when the storms are in the main phase, regardless of the season. Closer to the magnetic equator, moderate density enhancements last up to 40 h during the recovery phase of equinox storms, regardless of the local time. Strikingly, high-latitude plasma densities are moderately enhanced for up to 60 h prior to the actual onset of storms during the equinoxes and summer; a potential precursor of a geomagnetic storm.

Nanoporous active carbons at ambient conditions: a comparative study using X-ray scattering and diffraction, Raman spectroscopy and N2 adsorption

NASA Astrophysics Data System (ADS)

Shiryaev, A. A.; Voloshchuk, A. M.; Volkov, V. V.; Averin, A. A.; Artamonova, S. D.

2017-05-01

Furfural-derived sorbents and activated carbonaceous fibers were studied using Small- and Wide-angle X-ray scattering (SWAXS), X-ray diffraction and multiwavelength Raman spectroscopy after storage at ambient conditions. Correlations between structural features with degree of activation and with sorption parameters are observed for samples obtained from a common precursor and differing in duration of activation. However, the correlations are not necessarily applicable to the carbons obtained from different precursors. Using two independent approaches we show that treatment of SWAXS results should be performed with careful analysis of applicability of the Porod law to the sample under study. In general case of a pore with rough/corrugated surface deviations from the Porod law may became significant and reflect structure of the pore-carbon interface. Ignorance of these features may invalidate extraction of closed porosity values. In most cases the pore-matrix interface in the studied samples is not atomically sharp, but is characterized by 1D or 2D fluctuations of electronic density responsible for deviations from the Porod law. Intensity of the pores-related small-angle scattering correlates positively with SBET values obtained from N2 adsorption.

High-performance thin-film transistors with solution-processed ScInO channel layer based on environmental friendly precursor

NASA Astrophysics Data System (ADS)

Song, Wei; Lan, Linfeng; Li, Meiling; Wang, Lei; Lin, Zhenguo; Sun, Sheng; Li, Yuzhi; Song, Erlong; Gao, Peixiong; Li, Yan; Peng, Junbiao

2017-09-01

Thin-film transistors (TFTs) with solution-processed scandium (Sc) substituted indium oxide (Sc x In1-x O3, ScInO) thin films based on environmental friendly water-induced precursor were fabricated. As the Sc concentration increases from 0% to 10%, the mobility decreases from 23.7 cm2 V-1 s-1 to 6.4 cm2 V-1 s-1, which is attributed to the non-overlapping of the Sc3+ electron orbit. However, the off current decreases and the turn-ON voltage (V ON) shifts towards the positive direction as the Sc content increases, which indicates lower carrier density after incorporation of Sc into In2O3. More interestingly, the incorporation of Sc into In2O3 can effectively improve the electrical stability of the TFT devices under gate bias stress, which is attributed to the reduction of the number of oxygen vacancies due to the relatively low standard electrode potential (-2.36) of Sc and strong bonding strength of Sc-O (680 kJ mol-1). The reduction of oxygen vacancies is confirmed by the x-ray photoelectron spectroscopy (XPS) experiments.

Synthesis and optimization of the magnetic properties of aligned strontium ferrite nanowires

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

Ebrahimi, Fatemeh, E-mail: F.Ebrahimi@ma.iut.ac.ir; Bakhshi, Saeed Reza; Ashrafizadeh, Fakhreddin

Highlights: • Dip coating method was used to synthesize strontium ferrite nanowires in template. • Size of nanowires was controlled via anodization parameters. • Fe/Sr ratio was optimized in precursor. • Magnetic properties of nanowires and nanopowders were compared. - Abstract: High aspect ratio strontium hexaferrite nanowires were fabricated by dip coating in alumina template. Fe/Sr ratio was changed from 10 to 12 in precursor, and the samples were annealed at a range of temperatures 500–900 °C in order to optimize the magnetic properties of strontium ferrite in the form of nanowires. Field emission scanning electron microscope (FESEM) proved themore » formation of nanowires in the templates, while TEM images revealed a high degree of crystallinity. The ferrites were further characterized by X-ray diffraction (XRD) and energy dispersive X-ray spectrometer (EDS). Magnetic properties of the specimens were studied by a SQUID at 10–300 K. The results showed that the coercivity of packed density nanowires in the template was much less than that of the nanopowders. On the other hand, the coercivity of nanowires at ambient temperature was less than low temperature coercivity.« less

Synthesis and Characterization of Chalcopyrite (CuInS2 and CuhInSe2) Colloidal Nanoparticles for Optoelectronic Applications via Low-Temperature Pyrolysis of Single-Source Precursors

NASA Technical Reports Server (NTRS)

Castro, S. L.; Bailey, S. G.; Raffaelle, R. P.; Banger, K. K.; Fahey, Stephen; Hepp, A. F.

2003-01-01

Nanocrystalline (or quantum dot) materials hold potential as components of next-generation photovoltaic (PV) devices. The inclusion of quantum dots in PV devices has been proposed as a means to improve the efficiency of photon conversion (quantum dot solar cell), enable low-cost deposition of thin-films, provide sites for exciton dissociation, and pathways for electron transport. Quantum dots are also expected to be more resistant to degradation from electron, proton, and alpha particle radiation than the corresponding bulk material, a requirement for use in space solar sells. Chalcopyrite nanocrystals can be produced by low-temperature thermal decomposition of single-source precursors such as (PR3)2CuIn(ER')4 (R = Ph, R' = Et, E = S; R = R' = Ph, E = Se). Single-source precursors are molecules which contain all the necessary elements for synthesis of a desired material. Thermal decomposition of the precursor results in the formation of material with the correct stoichiometry as a nanocrystalline powder or a thin film, often at significantly lower temperatures than those typically employed for thin-film deposition by multi-source evaporation techniques, typically less than 500 C. We show that CuInSz and CuInSe2 nanocrystals can be synthesized from the precursors at temperatures as low as 250 C. The nanocrystals are characterized by optical spectroscopy, X-ray diffraction, and electron microscopy.

Nonequilibrium Phase Precursors during a Photoexcited Insulator-to-Metal Transition in V2O3

NASA Astrophysics Data System (ADS)

Singer, Andrej; Ramirez, Juan Gabriel; Valmianski, Ilya; Cela, Devin; Hua, Nelson; Kukreja, Roopali; Wingert, James; Kovalchuk, Olesya; Glownia, James M.; Sikorski, Marcin; Chollet, Matthieu; Holt, Martin; Schuller, Ivan K.; Shpyrko, Oleg G.

2018-05-01

Here, we photoinduce and directly observe with x-ray scattering an ultrafast enhancement of the structural long-range order in the archetypal Mott system V2O3 . Despite the ultrafast increase in crystal symmetry, the change of unit cell volume occurs an order of magnitude slower and coincides with the insulator-to-metal transition. The decoupling between the two structural responses in the time domain highlights the existence of a transient photoinduced precursor phase, which is distinct from the two structural phases present in equilibrium. X-ray nanoscopy reveals that acoustic phonons trapped in nanoscale twin domains govern the dynamics of the ultrafast transition into the precursor phase, while nucleation and growth of metallic domains dictate the duration of the slower transition into the metallic phase. The enhancement of the long-range order before completion of the electronic transition demonstrates the critical role the nonequilibrium structural phases play during electronic phase transitions in correlated electrons systems.

Atomically precise graphene nanoribbon heterojunctions from a single molecular precursor

NASA Astrophysics Data System (ADS)

Nguyen, Giang D.; Tsai, Hsin-Zon; Omrani, Arash A.; Marangoni, Tomas; Wu, Meng; Rizzo, Daniel J.; Rodgers, Griffin F.; Cloke, Ryan R.; Durr, Rebecca A.; Sakai, Yuki; Liou, Franklin; Aikawa, Andrew S.; Chelikowsky, James R.; Louie, Steven G.; Fischer, Felix R.; Crommie, Michael F.

2017-11-01

The rational bottom-up synthesis of atomically defined graphene nanoribbon (GNR) heterojunctions represents an enabling technology for the design of nanoscale electronic devices. Synthetic strategies used thus far have relied on the random copolymerization of two electronically distinct molecular precursors to yield GNR heterojunctions. Here we report the fabrication and electronic characterization of atomically precise GNR heterojunctions prepared through late-stage functionalization of chevron GNRs obtained from a single precursor. Post-growth excitation of fully cyclized GNRs induces cleavage of sacrificial carbonyl groups, resulting in atomically well-defined heterojunctions within a single GNR. The GNR heterojunction structure was characterized using bond-resolved scanning tunnelling microscopy, which enables chemical bond imaging at T = 4.5 K. Scanning tunnelling spectroscopy reveals that band alignment across the heterojunction interface yields a type II heterojunction, in agreement with first-principles calculations. GNR heterojunction band realignment proceeds over a distance less than 1 nm, leading to extremely large effective fields.

Metalorganic Chemical Vapor Deposition of Ruthenium-Doped Diamond like Carbon Films

NASA Technical Reports Server (NTRS)

Sunkara, M. K.; Ueno, M.; Lian, G.; Dickey, E. C.

2001-01-01

We investigated metalorganic precursor deposition using a Microwave Electron Cyclotron Resonance (ECR) plasma for depositing metal-doped diamondlike carbon films. Specifically, the deposition of ruthenium doped diamondlike carbon films was investigated using the decomposition of a novel ruthenium precursor, Bis(ethylcyclopentadienyl)-ruthenium (Ru(C5H4C2H5)2). The ruthenium precursor was introduced close to the substrate stage. The substrate was independently biased using an applied RF power. Films were characterized using Fourier Transform Infrared Spectroscopy (FTIR), Transmission Electron Microscopy (TEM) and Four Point Probe. The conductivity of the films deposited using ruthenium precursor showed strong dependency on the deposition parameters such as pressure. Ruthenium doped sample showed the presence of diamond crystallites with an average size of approx. 3 nm while un-doped diamondlike carbon sample showed the presence of diamond crystallites with an average size of 11 nm. TEM results showed that ruthenium was atomically dispersed within the amorphous carbon network in the films.

Stress-induced microcrack density evolution in β-eucryptite ceramics: Experimental observations and possible route to strain hardening

DOE PAGES

Müller, B. R.; Cooper, R. C.; Lange, A.; ...

2017-11-01

In order to investigate their microcracking behaviour, the microstructures of several β-eucryptite ceramics, obtained from glass precursor and cerammed to yield different grain sizes and microcrack densities, were characterized by laboratory and synchrotron x-ray refraction and tomography. Here, results were compared with those obtained from scanning electron microscopy (SEM). In SEM images, the characterized materials appeared fully dense but computed tomography showed the presence of pore clusters. Uniaxial tensile testing was performed on specimens while strain maps were recorded and analyzed by Digital Image Correlation (DIC). X-ray refraction techniques were applied on specimens before and after tensile testing to measuremore » the amount of the internal specific surface (i.e., area per unit volume). X-ray refraction revealed that (a) the small grain size (SGS) material contained a large specific surface, originating from the grain boundaries and the interfaces of TiO 2 precipitates; (b) the medium (MGS) and large grain size (LGS) materials possessed higher amounts of specific surface compared to SGS material due to microcracks, which decreased after tensile loading; (c) the precursor glass had negligible internal surface. The unexpected decrease in the internal surface of MGS and LGS after tensile testing is explained by the presence of compressive regions in the DIC strain maps and further by theoretical arguments. It is suggested that while some microcracks merge via propagation, more close mechanically, thereby explaining the observed X-ray refraction results. Lastly, the mechanisms proposed would allow the development of a strain hardening route in ceramics.« less

Stress-induced microcrack density evolution in β-eucryptite ceramics: Experimental observations and possible route to strain hardening

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

Müller, B. R.; Cooper, R. C.; Lange, A.

In order to investigate their microcracking behaviour, the microstructures of several β-eucryptite ceramics, obtained from glass precursor and cerammed to yield different grain sizes and microcrack densities, were characterized by laboratory and synchrotron x-ray refraction and tomography. Here, results were compared with those obtained from scanning electron microscopy (SEM). In SEM images, the characterized materials appeared fully dense but computed tomography showed the presence of pore clusters. Uniaxial tensile testing was performed on specimens while strain maps were recorded and analyzed by Digital Image Correlation (DIC). X-ray refraction techniques were applied on specimens before and after tensile testing to measuremore » the amount of the internal specific surface (i.e., area per unit volume). X-ray refraction revealed that (a) the small grain size (SGS) material contained a large specific surface, originating from the grain boundaries and the interfaces of TiO 2 precipitates; (b) the medium (MGS) and large grain size (LGS) materials possessed higher amounts of specific surface compared to SGS material due to microcracks, which decreased after tensile loading; (c) the precursor glass had negligible internal surface. The unexpected decrease in the internal surface of MGS and LGS after tensile testing is explained by the presence of compressive regions in the DIC strain maps and further by theoretical arguments. It is suggested that while some microcracks merge via propagation, more close mechanically, thereby explaining the observed X-ray refraction results. Lastly, the mechanisms proposed would allow the development of a strain hardening route in ceramics.« less

Porphyrin amino acids-amide coupling, redox and photophysical properties of bis(porphyrin) amides.

PubMed

Melomedov, Jascha; Wünsche von Leupoldt, Anica; Meister, Michael; Laquai, Frédéric; Heinze, Katja

2013-07-14

New trans-AB2C meso-substituted porphyrin amino acid esters with meso-substituents of tunable electron withdrawing power (B = mesityl, 4-C6H4F, 4-C6H4CF3, C6F5) were prepared as free amines 3a-3d, as N-acetylated derivatives Ac-3a-Ac-3d and corresponding zinc(II) complexes Zn-Ac-3a-Zn-Ac-3d. Several amide-linked bis(porphyrins) with a tunable electron density at each porphyrin site were obtained from the amino porphyrin precursors by condensation reactions (4a-4d) and mono- and bis(zinc(II)) complexes Zn(2)-4d and Zn(1)Zn(2)-4d were prepared. The electronic interaction between individual porphyrin units in bis(porphyrins) 4 is probed by electrochemical experiments (CV, EPR), electronic absorption spectroscopy, steady-state and time-resolved fluorescence spectroscopy in combination with DFT/PCM calculations on diamagnetic neutral bis(porphyrins) 4 and on respective charged mixed-valent radicals 4(+/-). The interaction via the -C6H4-NHCO-C6H4- bridge, the site of oxidation and reduction and the lowest excited singlet state S1, is tuned by the substituents on the individual porphyrins and the metalation state.

Crosslinked polymeric dielectric materials and electronic devices incorporating same

NASA Technical Reports Server (NTRS)

Facchetti, Antonio (Inventor); Suh, legal representative, Nae-Jeong (Inventor); Marks, Tobin J. (Inventor); Choi, Hyuk-Jin (Inventor); Wang, Zhiming (Inventor)

2012-01-01

Solution-processable dielectric materials are provided, along with precursor compositions and processes for preparing the same. Composites and electronic devices including the dielectric materials also are provided.

Lessons from isolable nickel(I) precursor complexes for small molecule activation.

PubMed

Yao, Shenglai; Driess, Matthias

2012-02-21

Small-molecule activation by transition metals is essential to numerous organic transformations, both biological and industrial. Creating useful metal-mediated activation systems often depends on stabilizing the metal with uncommon low oxidation states and low coordination numbers. This provides a redox-active metal center with vacant coordination sites well suited for interacting with small molecules. Monovalent nickel species, with their d(9) electronic configuration, are moderately strong one-electron reducing agents that are synthetically attractive if they can be isolated. They represent suitable reagents for closing the knowledge gap in nickel-mediated activation of small molecules. Recently, the first strikingly stable dinuclear β-diketiminate nickel(I) precursor complexes were synthesized, proving to be suitable promoters for small-molecule binding and activation. They have led to many unprecedented nickel complexes bearing activated small molecules in different reduction stages. In this Account, we describe selected achievements in the activation of nitrous oxide (N(2)O), O(2), the heavier chalcogens (S, Se, and Te), and white phosphorus (P(4)) through this β-diketiminatonickel(I) precursor species. We emphasize the reductive activation of O(2), owing to its promise in oxidation processes. The one-electron-reduced O(2) activation product, that is, the corresponding β-diketiminato-supported Ni-O(2) complex, is a genuine superoxonickel(II) complex, representing an important intermediate in the early stages of O(2) activation. It selectively acts as an oxygen-atom transfer agent, hydrogen-atom scavenger, or both towards exogenous organic substrates to yield oxidation products. The one-electron reduction of the superoxonickel(II) moiety was examined by using elemental potassium, β-diketiminatozinc(II) chloride, and β-diketiminatoiron(I) complexes, affording the first heterobimetallic complexes featuring a [NiO(2)M] subunit (M is K, Zn, or Fe). Through density functional theory (DFT) calculations, the geometric and electronic structures of these complexes were established and their distinctive reactivity, including the unprecedented monooxygenase-like activity of a bis(μ-oxo)nickel-iron complex, was studied. The studies have further led to other heterobimetallic complexes containing a [NiO(2)M] core, which are useful for understanding the influence of the heterometal on structure-reactivity relationships. The activation of N(2)O led directly to the hydrogen-atom abstraction product bis(μ-hydroxo)nickel(II) species and prevented isolation of any intermediate. In contrast, the activation of elemental S, Se, and Te with the same nickel(I) reagent furnished activation products with superchalcogenido E(2)(-) (E is S, Se, or Te) and dichalcogenido E(2)(2-) ligand in different activation stages. The isolable supersulfidonickel(II) subunit may serve as a versatile building block for the synthesis of heterobimetallic disulfidonickel(II) complexes with a [NiS(2)M] core. In the case of white phosphorus, the P(4) molecule has been coordinated to the nickel(I) center of dinuclear β-diketiminatonickel(I) precursor complexes; however, the whole P(4) subunit is a weaker electron acceptor than the dichalcogen ligands E(2), thus remaining unreduced. This P(4) binding mode is rare and could open new doors for subsequent functionalization of P(4). Our advances in understanding how these small molecules are bound to a nickel(I) center and are activated for further transformation offer promise for designing new catalysts. These nickel-containing complexes offer exceptional potential for nickel-mediated transformations of organic molecules and as model compounds for mimicking active sites of nickel-containing metalloenzymes.

Design and fabrication of highly open nickel cobalt sulfide nanosheets on Ni foam for asymmetric supercapacitors with high energy density and long cycle-life

NASA Astrophysics Data System (ADS)

Zha, Daosong; Fu, Yongsheng; Zhang, Lili; Zhu, Junwu; Wang, Xin

2018-02-01

Nickel cobalt sulfides (NiCo-S) are promising electrode materials for high-performance supercapacitors but normally show poor rate capability and unsatisfactory long-term endurance. To overcome these disadvantages, a properly constructed electrode architecture with abundant electron transport channels, excellent electronic conductivity and robust structural stability is required. Herein, considering that in situ transformation can mostly retain the specific structural advantages of the precursors, a two-step strategy is purposefully developed to construct a binder-free electrode composed of interconnected NiCo-S nanosheets on Ni foam (NiCo-S/NF), in which NiCo-S/NF is synthesized via the in situ sulfuration of networked acetate anion-intercalated nickel cobalt layered double hydroxide nanosheets loaded on Ni foam (A-NiCo-LDH/NF). Noticeably, the optimized Ni1Co1-S/NF exhibits an ultrahigh specific capacitance of 2553.9 F g-1 at 0.5 A g-1, excellent rate capability (1898.1 F g-1 at 50 A g-1) and superior cycling stability (nearly 90% capacitance retention after 10,000 cycles). Furthermore, the assembled asymmetric supercapacitor based on Ni1Co1-S/NF demonstrates a high energy density of 58.1 Wh kg-1 at a power density of 796 W kg-1 and impressive long-term durability even after a repeated charge/discharge process as long as 70,000 cycles (∼92% capacitance retention). The attractive properties endow the Ni1Co1-S/NF electrode with significant potential for high-performance energy storage devices.

Towards graphane field emitters

PubMed Central

Ding, Shuyi; Li, Chi; Zhou, Yanhuai; Collins, Clare M.; Kang, Moon H.; Parmee, Richard J.; Zhang, Xiaobing; Milne, William I.; Wang, Baoping

2015-01-01

We report on the improved field emission performance of graphene foam (GF) following transient exposure to hydrogen plasma. The enhanced field emission mechanism associated with hydrogenation has been investigated using Fourier transform infrared spectroscopy, plasma spectrophotometry, Raman spectroscopy, and scanning electron microscopy. The observed enhanced electron emissionhas been attributed to an increase in the areal density of lattice defects and the formation of a partially hydrogenated, graphane-like material. The treated GF emitter demonstrated a much reduced macroscopic turn-on field (2.5 V μm–1), with an increased maximum current density from 0.21 mA cm–2 (pristine) to 8.27 mA cm–2 (treated). The treated GFs vertically orientated protrusions, after plasma etching, effectively increased the local electric field resulting in a 2.2-fold reduction in the turn-on electric field. The observed enhancement is further attributed to hydrogenation and the subsequent formation of a partially hydrogenated structured 2D material, which advantageously shifts the emitter work function. Alongside augmentation of the nominal crystallite size of the graphitic superstructure, surface bound species are believed to play a key role in the enhanced emission. The hydrogen plasma treatment was also noted to increase the emission spatial uniformity, with an approximate four times reduction in the per unit area variation in emission current density. Our findings suggest that plasma treatments, and particularly hydrogen and hydrogen-containing precursors, may provide an efficient, simple, and low cost means of realizing enhanced nanocarbon-based field emission devices via the engineered degradation of the nascent lattice, and adjustment of the surface work function. PMID:28066543

Internal structure of laser supported detonation waves by two-wavelength Mach-Zehnder interferometer

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

Shimamura, Kohei; Kawamura, Koichi; Fukuda, Akio

Characteristics of the internal structure of the laser supported detonation (LSD) waves, such as the electron density n{sub e} and the electron temperature T{sub e} profiles behind the shock wave were measured using a two-wavelength Mach-Zehnder interferometer along with emission spectroscopy. A TEA CO{sub 2} laser with energy of 10 J/pulse produced explosive laser heating in atmospheric air. Results show that the peak values of n{sub e} and T{sub e} were, respectively, about 2 x 10{sup 24} m{sup -3} and 30 000 K, during the LSD regime. The temporal variation of the laser absorption coefficient profile estimated from the measuredmore » properties reveals that the laser energy was absorbed perfectly in a thin layer behind the shock wave during the LSD regime, as predicted by Raizer's LSD model. However, the absorption layer was much thinner than a plasma layer, the situation of which was not considered in Raizer's model. The measured n{sub e} at the shock front was not zero while the LSD was supported, which implies that the precursor electrons exist ahead of the shock wave.« less

Environment Conscious, Biomorphic Ceramics from Pine and Jelutong Wood Precursors

NASA Technical Reports Server (NTRS)

Singh, Mrityunjay; Yee, Bo-Moon; Gray, Hugh R. (Technical Monitor)

2002-01-01

Environment conscious, biomorphic ceramics have been fabricated from pine and jelutong wood precursors. A carbonaceous preform is produced through wood pyrolysis and subsequent infiltration with oxides (ZrO2 sols) and liquid silicon to form ceramics. These biomorphic ceramics show a wide variety of microstructures, densities, and hardness behavior that are determined by the type of wood and infiltrants selected.

A Simple Method for High-Performance, Solution-Processed, Amorphous ZrO2 Gate Insulator TFT with a High Concentration Precursor

PubMed Central

Cai, Wei; Zhu, Zhennan; Wei, Jinglin; Fang, Zhiqiang; Zheng, Zeke; Zhou, Shangxiong; Peng, Junbiao; Lu, Xubing

2017-01-01

Solution-processed high-k dielectric TFTs attract much attention since they cost relatively little and have a simple fabrication process. However, it is still a challenge to reduce the leakage of the current density of solution-processed dielectric TFTs. Here, a simple solution method is presented towards enhanced performance of ZrO2 films by intentionally increasing the concentration of precursor. The ZrO2 films not only exhibit a low leakage current density of 10−6 A/cm2 at 10 V and a breakdown field of 2.5 MV/cm, but also demonstrate a saturation mobility of 12.6 cm2·V−1·s−1 and a Ion/Ioff ratio of 106 in DC pulse sputtering IGZO-TFTs based on these films. Moreover, the underlying mechanism of influence of precursor concentration on film formation is presented. Higher concentration precursor results in a thicker film within same coating times with reduced ZrO2/IGZO interface defects and roughness. It shows the importance of thickness, roughness, and annealing temperature in solution-processed dielectric oxide TFT and provides an approach to precisely control solution-processed oxide films thickness. PMID:28825652

A Simple Method for High-Performance, Solution-Processed, Amorphous ZrO₂ Gate Insulator TFT with a High Concentration Precursor.

PubMed

Cai, Wei; Zhu, Zhennan; Wei, Jinglin; Fang, Zhiqiang; Ning, Honglong; Zheng, Zeke; Zhou, Shangxiong; Yao, Rihui; Peng, Junbiao; Lu, Xubing

2017-08-21

Solution-processed high-k dielectric TFTs attract much attention since they cost relatively little and have a simple fabrication process. However, it is still a challenge to reduce the leakage of the current density of solution-processed dielectric TFTs. Here, a simple solution method is presented towards enhanced performance of ZrO₂ films by intentionally increasing the concentration of precursor. The ZrO₂ films not only exhibit a low leakage current density of 10 -6 A/cm² at 10 V and a breakdown field of 2.5 MV/cm, but also demonstrate a saturation mobility of 12.6 cm²·V -1 ·s -1 and a I on /I off ratio of 10⁶ in DC pulse sputtering IGZO-TFTs based on these films. Moreover, the underlying mechanism of influence of precursor concentration on film formation is presented. Higher concentration precursor results in a thicker film within same coating times with reduced ZrO₂/IGZO interface defects and roughness. It shows the importance of thickness, roughness, and annealing temperature in solution-processed dielectric oxide TFT and provides an approach to precisely control solution-processed oxide films thickness.

Improved electron transfer and plasmonic effect in dye-sensitized solar cells with bi-functional Nb-doped TiO2/Ag ternary nanostructures.

PubMed

Park, Jung Tae; Chi, Won Seok; Jeon, Harim; Kim, Jong Hak

2014-03-07

TiO2 nanoparticles are surface-modified via atom transfer radical polymerization (ATRP) with a hydrophilic poly(oxyethylene)methacrylate (POEM), which can coordinate to the Ag precursor, i.e. silver trifluoromethanesulfonate (AgCF3SO3). Following the reduction of Ag ions, a Nb2O5 doping process and calcination at 450 °C, bi-functional Nb-doped TiO2/Ag ternary nanostructures are generated. The resulting nanostructures are characterized by energy-filtering transmission electron microscopy (EF-TEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and UV-visible spectroscopy. The dye-sensitized solar cell (DSSC) based on the Nb-doped TiO2/Ag nanostructure photoanode with a polymerized ionic liquid (PIL) as the solid polymer electrolyte shows an overall energy conversion efficiency (η) of 6.9%, which is much higher than those of neat TiO2 (4.7%) and Nb-doped TiO2 (5.4%). The enhancement of η is mostly due to the increase of current density, attributed to the improved electron transfer properties including electron injection, collection, and plasmonic effects without the negative effects of charge recombination or problems with corrosion. These properties are supported by intensity modulated photocurrent/voltage spectroscopy (IMPS/IMVS) and incident photon-to-electron conversion efficiency (IPCE) measurements.

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

Pulsed Laser-Assisted Focused Electron-Beam-Induced Etching of Titanium with XeF 2 : Enhanced Reaction Rate and Precursor Transport

DOE PAGES

Noh, J. H.; Fowlkes, J. D.; Timilsina, R.; ...

2015-01-28

We introduce a laser-assisted focused electron-beam-induced etching (LA-FEBIE) process which is a versatile, direct write nanofabrication method that allows nanoscale patterning and editing; we do this in order to enhance the etch rate of electron-beam-induced etching. The results demonstrate that the titanium electron stimulated etch rate via the XeF2 precursor can be enhanced up to a factor of 6 times with an intermittent pulsed laser assist. Moreover, the evolution of the etching process is correlated to in situ stage current measurements and scanning electron micrographs as a function of time. Finally, the increased etch rate is attributed to photothermally enhancedmore » Ti–F reaction and TiF4 desorption and in some regimes enhanced XeF2 surface diffusion to the reaction zone.« less

Accurate quantum yields by laser gain vs absorption spectroscopy - Investigation of Br/Br(asterisk) channels in photofragmentation of Br2 and IBr

NASA Technical Reports Server (NTRS)

Haugen, H. K.; Weitz, E.; Leone, S. R.

1985-01-01

Various techniques have been used to study photodissociation dynamics of the halogens and interhalogens. The quantum yields obtained by these techniques differ widely. The present investigation is concerned with a qualitatively new approach for obtaining highly accurate quantum yields for electronically excited states. This approach makes it possible to obtain an accuracy of 1 percent to 3 percent. It is shown that measurement of the initial transient gain/absorption vs the final absorption in a single time-resolved signal is a very accurate technique in the study of absolute branching fractions in photodissociation. The new technique is found to be insensitive to pulse and probe laser characteristics, molecular absorption cross sections, and absolute precursor density.

Synthesis and characterization of a nanocrystalline diamond aerogel

PubMed Central

Pauzauskie, Peter J.; Crowhurst, Jonathan C.; Worsley, Marcus A.; Laurence, Ted A.; Kilcoyne, A. L. David; Wang, Yinmin; Willey, Trevor M.; Visbeck, Kenneth S.; Fakra, Sirine C.; Evans, William J.; Zaug, Joseph M.; Satcher, Joe H.

2011-01-01

Aerogel materials have myriad scientific and technological applications due to their large intrinsic surface areas and ultralow densities. However, creating a nanodiamond aerogel matrix has remained an outstanding and intriguing challenge. Here we report the high-pressure, high-temperature synthesis of a diamond aerogel from an amorphous carbon aerogel precursor using a laser-heated diamond anvil cell. Neon is used as a chemically inert, near-hydrostatic pressure medium that prevents collapse of the aerogel under pressure by conformally filling the aerogel’s void volume. Electron and X-ray spectromicroscopy confirm the aerogel morphology and composition of the nanodiamond matrix. Time-resolved photoluminescence measurements of recovered material reveal the formation of both nitrogen- and silicon- vacancy point-defects, suggesting a broad range of applications for this nanocrystalline diamond aerogel. PMID:21555550

Synthesis and characterization of a nanocrystalline diamond aerogel

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

Pauzauskie, Peter J.; Crowhurst, Jonathan C.; Worsley, Marcus A.

2011-07-06

Aerogel materials have myriad scientific and technological applications due to their large intrinsic surface areas and ultralow densities. However, creating a nanodiamond aerogel matrix has remained an outstanding and intriguing challenge. Here we report the high-pressure, high-temperature synthesis of a diamond aerogel from an amorphous carbon aerogel precursor using a laser-heated diamond anvil cell. Neon is used as a chemically inert, near-hydrostatic pressure medium that prevents collapse of the aerogel under pressure by conformally filling the aerogel's void volume. Electron and X-ray spectromicroscopy confirm the aerogel morphology and composition of the nanodiamond matrix. Time-resolved photoluminescence measurements of recovered material revealmore » the formation of both nitrogen- and silicon- vacancy point-defects, suggesting a broad range of applications for this nanocrystalline diamond aerogel.« less

Precursor binding to an 880-kDa Toc complex as an early step during active import of protein into chloroplasts.

PubMed

Chen, Kuan-Yu; Li, Hsou-min

2007-01-01

The import of protein into chloroplasts is mediated by translocon components located in the chloroplast outer (the Toc proteins) and inner (the Tic proteins) envelope membranes. To identify intermediate steps during active import, we used sucrose density gradient centrifugation and blue-native polyacrylamide gel electrophoresis (BN-PAGE) to identify complexes of translocon components associated with precursor proteins under active import conditions instead of arrested binding conditions. Importing precursor proteins in solubilized chloroplast membranes formed a two-peak distribution in the sucrose density gradient. The heavier peak was in a similar position as the previously reported Tic/Toc supercomplex and was too large to be analyzed by BN-PAGE. The BN-PAGE analyses of the lighter peak revealed that precursors accumulated in at least two complexes. The first complex migrated at a position close to the ferritin dimer (approximately 880 kDa) and contained only the Toc components. Kinetic analyses suggested that this Toc complex represented an earlier step in the import process than the Tic/Toc supercomplex. The second complex in the lighter peak migrated at the position of the ferritin trimer (approximately 1320 kDa). It contained, in addition to the Toc components, Tic110, Hsp93, and an hsp70 homolog, but not Tic40. Two different precursor proteins were shown to associate with the same complexes. Processed mature proteins first appeared in the membranes at the same fractions as the Tic/Toc supercomplex, suggesting that processing of transit peptides occurs while precursors are still associated with the supercomplex.

Precursor binding to an 880-kDa Toc complex as an early step during active import of protein into chloroplasts

PubMed Central

Chen, Kuan-Yu; Li, Hsou-min

2007-01-01

The import of protein into chloroplasts is mediated by translocon components located in the chloroplast outer (the Toc proteins) and inner (the Tic proteins) envelope membranes. To identify intermediate steps during active import, we used sucrose density gradient centrifugation and blue-native polyacrylamide gel electrophoresis (BN-PAGE) to identify complexes of translocon components associated with precursor proteins under active import conditions instead of arrested binding conditions. Importing precursor proteins in solubilized chloroplast membranes formed a two-peak distribution in the sucrose density gradient. The heavier peak was in a similar position as the previously reported Tic/Toc supercomplex and was too large to be analyzed by BN-PAGE. The BN-PAGE analyses of the lighter peak revealed that precursors accumulated in at least two complexes. The first complex migrated at a position close to the ferritin dimer (approximately 880 kDa) and contained only the Toc components. Kinetic analyses suggested that this Toc complex represented an earlier step in the import process than the Tic/Toc supercomplex. The second complex in the lighter peak migrated at the position of the ferritin trimer (approximately 1320 kDa). It contained, in addition to the Toc components, Tic110, Hsp93, and an hsp70 homolog, but not Tic40. Two different precursor proteins were shown to associate with the same complexes. Processed mature proteins first appeared in the membranes at the same fractions as the Tic/Toc supercomplex, suggesting that processing of transit peptides occurs while precursors are still associated with the supercomplex. PMID:17144891

Multiscale analysis: a way to investigate laser damage precursors in materials for high power applications at nanosecond pulse duration

NASA Astrophysics Data System (ADS)

Natoli, J. Y.; Wagner, F.; Ciapponi, A.; Capoulade, J.; Gallais, L.; Commandré, M.

2010-11-01

The mechanism of laser induced damage in optical materials under high power nanosecond laser irradiation is commonly attributed to the presence of precursor centers. Depending on material and laser source, the precursors could have different origins. Some of them are clearly extrinsic, such as impurities or structural defects linked to the fabrication conditions. In most cases the center size ranging from sub-micrometer to nanometer scale does not permit an easy detection by optical techniques before irradiation. Most often, only a post mortem observation of optics permits to proof the local origin of breakdown. Multi-scale analyzes by changing irradiation beam size have been performed to investigate the density, size and nature of laser damage precursors. Destructive methods such as raster scan, laser damage probability plot and morphology studies permit to deduce the precursor densities. Another experimental way to get information on nature of precursors is to use non destructive methods such as photoluminescence and absorption measurements. The destructive and non destructive multiscale studies are also motivated for practical reasons. Indeed LIDT studies of large optics as those used in LMJ or NIF projects are commonly performed on small samples and with table top lasers whose characteristics change from one to another. In these conditions, it is necessary to know exactly the influence of the different experimental parameters and overall the spot size effect on the final data. In this paper, we present recent developments in multiscale characterization and results obtained on optical coatings (surface case) and KDP crystal (bulk case).

New five coordinated supramolecular structured cadmium complex as precursor for CdO nanoparticles: Synthesis, crystal structure, theoretical and 3D Hirshfeld surface analyses

NASA Astrophysics Data System (ADS)

Ghanbari Niyaky, S.; Montazerozohori, M.; Masoudiasl, A.; White, J. M.

2017-03-01

In this paper, a combined experimental and theoretical study on a new CdLBr2 complex (L = N1-(2-bromobenzylidene)-N2-(2-((E)-(2-bromobenzylidene) amino)ethyl) ethane-1,2-diamine) synthesized via template method, is described. The crystal structure analysis of the complex indicates that, the Cd(II) ion is centered in a distorted square pyramidal space constructed by three iminic nitrogens of the ligand as well as two bromide anions. More analysis of crystal packing proposed a supramolecular structure stabilized by some non-covalent interactions such as Br⋯Br and Xsbnd H⋯Br (X = N and C) in solid state. Furthermore, 3D Hirshfeld surface analyses and DFT studies were applied for theoretical investigation of the complexes. Theoretical achievements were found in a good agreement with respect to the experimental data. To evaluate the nature of bonding and the strength of the intra and inter-molecular interactions a natural bond orbital (NBO) analysis on the complex structure was performed. Time dependent density functional theory (TD-DFT) was also applied to predict the electronic spectral data of the complex as compared with the experimental ones. CdLBr2 complex as nano-structure compound was also prepared under ultrasonic conditions and characterized by scanning electron microscopy (SEM) and X-ray powder diffraction (XRPD). Finally, it was found that the cadmium complex can be used as a suitable precursor for preparation of CdO nanoparticles via calcination process at 600 °C under air atmosphere.

Pressure induced band inversion, electronic and structural phase transitions in InTe: A combined experimental and theoretical study

NASA Astrophysics Data System (ADS)

Rajaji, V.; Pal, Koushik; Sarma, Saurav Ch.; Joseph, B.; Peter, Sebastian C.; Waghmare, Umesh V.; Narayana, Chandrabhas

2018-04-01

We report high-pressure Raman scattering measurements on the tetragonal phase of InTe corroborated with the first-principles density functional theory and synchrotron x-ray diffraction measurements. Anomalous pressure-dependent linewidths of the A1 g and Eg phonon modes provide evidence of an isostructural electronic transition at ˜3.6 GPa . The first-principles theoretical analysis reveals that it is associated with a semiconductor-to-metal transition due to increased density of states near the Fermi level. Further, this pressure induced metallization acts as a precursor for structural phase transition to a face centered cubic phase (F m 3 ¯m ) at ˜6.0 GPa . Interestingly, theoretical results reveal a pressure induced band inversion at the Z and M points of the Brillouin zone corresponding to pressures ˜1.0 and ˜1.4 GPa , respectively. As the parity of bands undergoing inversions is the same, the topology of the electronic state remains unchanged, and hence InTe retains its trivial band topology (Z2=0 ) . The pressure dependent behavior of the A1 g and Eg modes can be understood based on the results from the synchrotron x-ray diffraction, which shows anisotropic compressibility of the lattice in the a and c directions. Our Raman measurements up to ˜19 GPa further confirms the pressure induced structural phase transition from a face-centered to primitive cubic (F m 3 ¯m to P m 3 ¯m ) at P ˜15 GPa .

Statistical density modification using local pattern matching

DOEpatents

Terwilliger, Thomas C.

2007-01-23

A computer implemented method modifies an experimental electron density map. A set of selected known experimental and model electron density maps is provided and standard templates of electron density are created from the selected experimental and model electron density maps by clustering and averaging values of electron density in a spherical region about each point in a grid that defines each selected known experimental and model electron density maps. Histograms are also created from the selected experimental and model electron density maps that relate the value of electron density at the center of each of the spherical regions to a correlation coefficient of a density surrounding each corresponding grid point in each one of the standard templates. The standard templates and the histograms are applied to grid points on the experimental electron density map to form new estimates of electron density at each grid point in the experimental electron density map.

Chemical factors that control lignin polymerization.

PubMed

Sangha, Amandeep K; Davison, Brian H; Standaert, Robert F; Davis, Mark F; Smith, Jeremy C; Parks, Jerry M

2014-01-09

Lignin is a complex, branched polymer that reinforces plant tissue. Understanding the factors that govern lignin structure is of central importance to the development of technologies for converting lignocellulosic biomass into fuels because lignin imparts resistance to chemical, enzymatic, and mechanical deconstruction. Lignin is formed by enzymatic oxidation of phenolic monomers (monolignols) of three main types, guaiacyl (G), syringyl (S), and p-hydroxyphenyl (H) subunits. It is known that increasing the relative abundance of H subunits results in lower molecular weight lignin polymers and hence more easily deconstructed biomass, but it is not known why. Here, we report an analysis of frontier molecular orbitals in mono-, di-, and trilignols, calculated using density functional theory, which points to a requirement of strong p-electron density on the reacting phenolic oxygen atom of the neutral precursor for enzymatic oxidation to occur. This model is consistent with a proton-coupled electron transfer (PCET) mechanism and for the first time explains why H subunits in certain linkages (β-β or β-5) react poorly and tend to "cap" the polymer. In general, β-5 linkages with either a G or H terminus are predicted to inhibit elongation. More broadly, the model correctly accounts for the reactivity of the phenolic groups in a diverse set of dilignols comprising H and G subunits. Thus, we provide a coherent framework for understanding the propensity toward growth or termination of different terminal subunits in lignin.

Reversing methanogenesis to capture methane for liquid biofuel precursors

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

Soo, Valerie W. C.; McAnulty, Michael J.; Tripathi, Arti

Energy from remote methane reserves is transformative; however, unintended release of this potent greenhouse gas makes it imperative to convert methane efficiently into more readily transported biofuels. No pure microbial culture that grows on methane anaerobically has been isolated, despite that methane capture through anaerobic processes is more efficient than aerobic ones. Here we engineered the archaeal methanogen Methanosarcina acetivorans to grow anaerobically on methane as a pure culture and to convert methane into the biofuel precursor acetate. To capture methane, we cloned the enzyme methyl-coenzyme M reductase (Mcr) from an unculturable organism, anaerobic methanotrophic archaeal population 1 (ANME-1) frommore » a Black Sea mat, into M. acetivorans to effectively run methanogenesis in reverse. Starting with low-density inocula, M. acetivorans cells producing ANME-1 Mcr consumed up to 9 ± 1 % of methane (corresponding to 109 ± 12 µmol of methane) after 6 weeks of anaerobic growth on methane and utilized 10 mM FeCl 3 as an electron acceptor. Accordingly, increases in cell density and total protein were observed as cells grew on methane in a biofilm on solid FeCl 3. When incubated on methane for 5 days, high-densities of ANME-1 Mcr-producing M. acetivorans cells consumed 15 ± 2 % methane (corresponding to 143 ± 16 µmol of methane), and produced 10.3 ± 0.8 mM acetate (corresponding to 52 ± 4 µmol of acetate). We further confirmed the growth on methane and acetate production using 13C isotopic labeling of methane and bicarbonate coupled with nuclear magnetic resonance and gas chromatography/mass spectroscopy, as well as RNA sequencing. Lastly, we anticipate that our metabolically-engineered strain will provide insights into how methane is cycled in the environment by Archaea as well as will possibly be utilized to convert remote sources of methane into more easily transported biofuels via acetate.« less

Reversing methanogenesis to capture methane for liquid biofuel precursors

DOE PAGES

Soo, Valerie W. C.; McAnulty, Michael J.; Tripathi, Arti; ...

2016-01-14

Energy from remote methane reserves is transformative; however, unintended release of this potent greenhouse gas makes it imperative to convert methane efficiently into more readily transported biofuels. No pure microbial culture that grows on methane anaerobically has been isolated, despite that methane capture through anaerobic processes is more efficient than aerobic ones. Here we engineered the archaeal methanogen Methanosarcina acetivorans to grow anaerobically on methane as a pure culture and to convert methane into the biofuel precursor acetate. To capture methane, we cloned the enzyme methyl-coenzyme M reductase (Mcr) from an unculturable organism, anaerobic methanotrophic archaeal population 1 (ANME-1) frommore » a Black Sea mat, into M. acetivorans to effectively run methanogenesis in reverse. Starting with low-density inocula, M. acetivorans cells producing ANME-1 Mcr consumed up to 9 ± 1 % of methane (corresponding to 109 ± 12 µmol of methane) after 6 weeks of anaerobic growth on methane and utilized 10 mM FeCl 3 as an electron acceptor. Accordingly, increases in cell density and total protein were observed as cells grew on methane in a biofilm on solid FeCl 3. When incubated on methane for 5 days, high-densities of ANME-1 Mcr-producing M. acetivorans cells consumed 15 ± 2 % methane (corresponding to 143 ± 16 µmol of methane), and produced 10.3 ± 0.8 mM acetate (corresponding to 52 ± 4 µmol of acetate). We further confirmed the growth on methane and acetate production using 13C isotopic labeling of methane and bicarbonate coupled with nuclear magnetic resonance and gas chromatography/mass spectroscopy, as well as RNA sequencing. Lastly, we anticipate that our metabolically-engineered strain will provide insights into how methane is cycled in the environment by Archaea as well as will possibly be utilized to convert remote sources of methane into more easily transported biofuels via acetate.« less

Electron interactions with the heteronuclear carbonyl precursor H2FeRu3(CO)13 and comparison with HFeCo3(CO)12: from fundamental gas phase and surface science studies to focused electron beam induced deposition.

PubMed

P, Ragesh Kumar T; Weirich, Paul; Hrachowina, Lukas; Hanefeld, Marc; Bjornsson, Ragnar; Hrodmarsson, Helgi Rafn; Barth, Sven; Fairbrother, D Howard; Huth, Michael; Ingólfsson, Oddur

2018-01-01

In the current contribution we present a comprehensive study on the heteronuclear carbonyl complex H 2 FeRu 3 (CO) 13 covering its low energy electron induced fragmentation in the gas phase through dissociative electron attachment (DEA) and dissociative ionization (DI), its decomposition when adsorbed on a surface under controlled ultrahigh vacuum (UHV) conditions and exposed to irradiation with 500 eV electrons, and its performance in focused electron beam induced deposition (FEBID) at room temperature under HV conditions. The performance of this precursor in FEBID is poor, resulting in maximum metal content of 26 atom % under optimized conditions. Furthermore, the Ru/Fe ratio in the FEBID deposit (≈3.5) is higher than the 3:1 ratio predicted. This is somewhat surprising as in recent FEBID studies on a structurally similar bimetallic precursor, HFeCo 3 (CO) 12 , metal contents of about 80 atom % is achievable on a routine basis and the deposits are found to maintain the initial Co/Fe ratio. Low temperature (≈213 K) surface science studies on thin films of H 2 FeRu 3 (CO) 13 demonstrate that electron stimulated decomposition leads to significant CO desorption (average of 8-9 CO groups per molecule) to form partially decarbonylated intermediates. However, once formed these intermediates are largely unaffected by either further electron irradiation or annealing to room temperature, with a predicted metal content similar to what is observed in FEBID. Furthermore, gas phase experiments indicate formation of Fe(CO) 4 from H 2 FeRu 3 (CO) 13 upon low energy electron interaction. This fragment could desorb at room temperature under high vacuum conditions, which may explain the slight increase in the Ru/Fe ratio of deposits in FEBID. With the combination of gas phase experiments, surface science studies and actual FEBID experiments, we can offer new insights into the low energy electron induced decomposition of this precursor and how this is reflected in the relatively poor performance of H 2 FeRu 3 (CO) 13 as compared to the structurally similar HFeCo 3 (CO) 12 .

Electron interactions with the heteronuclear carbonyl precursor H2FeRu3(CO)13 and comparison with HFeCo3(CO)12: from fundamental gas phase and surface science studies to focused electron beam induced deposition

PubMed Central

P, Ragesh Kumar T; Weirich, Paul; Hrachowina, Lukas; Hanefeld, Marc; Bjornsson, Ragnar; Hrodmarsson, Helgi Rafn; Barth, Sven; Fairbrother, D Howard; Huth, Michael

2018-01-01

In the current contribution we present a comprehensive study on the heteronuclear carbonyl complex H2FeRu3(CO)13 covering its low energy electron induced fragmentation in the gas phase through dissociative electron attachment (DEA) and dissociative ionization (DI), its decomposition when adsorbed on a surface under controlled ultrahigh vacuum (UHV) conditions and exposed to irradiation with 500 eV electrons, and its performance in focused electron beam induced deposition (FEBID) at room temperature under HV conditions. The performance of this precursor in FEBID is poor, resulting in maximum metal content of 26 atom % under optimized conditions. Furthermore, the Ru/Fe ratio in the FEBID deposit (≈3.5) is higher than the 3:1 ratio predicted. This is somewhat surprising as in recent FEBID studies on a structurally similar bimetallic precursor, HFeCo3(CO)12, metal contents of about 80 atom % is achievable on a routine basis and the deposits are found to maintain the initial Co/Fe ratio. Low temperature (≈213 K) surface science studies on thin films of H2FeRu3(CO)13 demonstrate that electron stimulated decomposition leads to significant CO desorption (average of 8–9 CO groups per molecule) to form partially decarbonylated intermediates. However, once formed these intermediates are largely unaffected by either further electron irradiation or annealing to room temperature, with a predicted metal content similar to what is observed in FEBID. Furthermore, gas phase experiments indicate formation of Fe(CO)4 from H2FeRu3(CO)13 upon low energy electron interaction. This fragment could desorb at room temperature under high vacuum conditions, which may explain the slight increase in the Ru/Fe ratio of deposits in FEBID. With the combination of gas phase experiments, surface science studies and actual FEBID experiments, we can offer new insights into the low energy electron induced decomposition of this precursor and how this is reflected in the relatively poor performance of H2FeRu3(CO)13 as compared to the structurally similar HFeCo3(CO)12. PMID:29527432

LiCoPO4 cathode from a CoHPO4·xH2O nanoplate precursor for high voltage Li-ion batteries

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

Choi, Daiwon; Li, Xiaolin; Henderson, Wesley A.

2016-02-01

Highly crystalline LiCoPO4/C cathode has been synthesized without any impurities via single step solid-state reaction using CoHPO4xH2O nanoplates as a precursor obtained by simple precipitation route. The electrochemical test shows specific capacity as high as 125mAh/g at charge/discharge rate of C/10. Synthesis approach for obtaining CoHPO4xH2O nanoplate precursor and final LiCoPO4/C cathode using single step solid-state reaction have been characterized using X-ray diffraction, thermos gravimetric analyses (TGA) – differential scanning calorimetry (DSC), transmission electron microscopy (TEM), and scanning electron microscopy (SEM). The electrochemical test and cycling stability using different electrolytes, additive and separator have been investigated.

Low-temperature MOCVD deposition of Bi2Te3 thin films using Et2BiTeEt as single source precursor

NASA Astrophysics Data System (ADS)

Bendt, Georg; Gassa, Sanae; Rieger, Felix; Jooss, Christian; Schulz, Stephan

2018-05-01

Et2BiTeEt was used as single source precursor for the deposition of Bi2Te3 thin films on Si(1 0 0) substrates by metal organic chemical vapor deposition (MOCVD) at very low substrate temperatures. Stoichiometric and crystalline Bi2Te3 films were grown at 230 °C, which is approximately 100 °C lower compared to conventional MOCVD processes using one metal organic precursors for each element. The Bi2Te3 films were characterized using scanning electron microscopy, high-resolution transmission electron microscopy and X-ray diffraction. The elemental composition of the films, which was determined by energy-dispersive X-ray spectroscopy and X-ray photoelectron spectroscopy, was found to be strongly dependent of the substrate temperature.

Human proinsulin C-peptide from a precursor overexpressed in Pichia pastoris.

PubMed

Huang, Yang-Bin; Li, Jiang; Gao, Xin; Sun, Jiu-Ru; Lu, Yi; Feng, Tao; Fei, Jian; Cui, Da-Fu; Xia, Qi-Chang; Ren, Jun; Zhang, You-Shang

2006-08-01

In this article we report the production of human proinsulin C-peptide with 31 amino acid residues from a precursor overexpressed in Pichia pastoris. A C-peptide precursor expression plasmid containing nine C-peptide genes in tandem was constructed and used to transform P. pastoris. Transformants with a high copy number of the C-peptide precursor gene integrated into the chromosome of P. pastoris were selected. In high-density fermentation in a 300 liter fermentor using a simple culture medium composed mainly of salt and methanol, the C-peptide precursor was overexpressed to a level of 2.28 g per liter. A simple procedure was established to purify the expression product from the culture medium. The purified C-peptide precursor was converted into C-peptide by trypsin and carboxypeptidase B joint digestion. The yield of C-peptide with a purity of 96% was 730 mg per liter of culture. The purified C-peptide was characterized by mass spectrometry, N- and C-terminal amino acid sequencing, and sodium dodecylsulfate-polyacrylamide gel electrophoresis.

Annealed Au-assisted epitaxial growth of si nanowires: control of alignment and density.

PubMed

Park, Yi-Seul; Jung, Da Hee; Kim, Hyun Ji; Lee, Jin Seok

2015-04-14

The epitaxial growth of 1D nanostructures is of particular interest for future nanoelectronic devices such as vertical field-effect transistors because it directly influences transistor densities and 3D logic or memory architectures. Silicon nanowires (SiNWs) are a particularly important 1D nanomaterial because they possess excellent electronic and optical properties. What is more, the scalable fabrication of vertically aligned SiNW arrays presents an opportunity for improved device applications if suitable properties can be achieved through controlling the alignment and density of SiNWs, yet this is something that has not been reported in the case of SiNWs synthesized from Au films. This work therefore explores the controllable synthesis of vertically aligned SiNWs through the introduction of an annealing process prior to growth via a Au-catalyzed vapor-liquid-solid mechanism. The epitaxial growth of SiNWs was demonstrated to be achievable using SiCl4 as the Si precursor in chemical vapor deposition, whereas the alignment and density of the SiNWs could be controlled by manipulating the annealing time during the formation of Au nanoparticles (AuNPs) from Au films. During the annealing process, gold silicide was observed to form on the interface of the liquid-phase AuNPs, depending on the size of the AuNPs and the annealing time. This work therefore makes a valuable contribution to improving nanowire-based engineering by controlling its alignment and density as well as providing greater insight into the epitaxial growth of 1D nanostructures.

Ion and aerosol precursor densities in Titan's ionosphere: A multi-instrument case study

NASA Astrophysics Data System (ADS)

Shebanits, O.; Wahlund, J.-E.; Edberg, N. J. T.; Crary, F. J.; Wellbrock, A.; Andrews, D. J.; Vigren, E.; Desai, R. T.; Coates, A. J.; Mandt, K. E.; Waite, J. H.

2016-10-01

The importance of the heavy ions and dust grains for the chemistry and aerosol formation in Titan's ionosphere has been well established in the recent years of the Cassini mission. In this study we combine independent in situ plasma (Radio Plasma and Wave Science Langmuir Probe (RPWS/LP)) and particle (Cassini Plasma Science Electron Spectrometer, Cassini Plasma Science Ion Beam Spectrometer, and Ion and Neutral Mass Spectrometer) measurements of Titan's ionosphere for selected flybys (T16, T29, T40, and T56) to produce altitude profiles of mean ion masses including heavy ions and develop a Titan-specific method for detailed analysis of the RPWS/LP measurements (applicable to all flybys) to further constrain ion charge densities and produce the first empirical estimate of the average charge of negative ions and/or dust grains. Our results reveal the presence of an ion-ion (dusty) plasma below 1100 km altitude, with charge densities exceeding the primary ionization peak densities by a factor ≥2 in the terminator and nightside ionosphere (ne/ni ≤ 0.1). We suggest that ion-ion (dusty) plasma may also be present in the dayside ionosphere below 900 km (ne/ni < 0.5 at 1000 km altitude). The average charge of the dust grains (≥1000 amu) is estimated to be between -2.5 and -1.5 elementary charges, increasing toward lower altitudes.

Effects of densification of precursor pellets on microstructures and critical current properties of YBCO melt-textured bulks

NASA Astrophysics Data System (ADS)

Setoyama, Yui; Shimoyama, Jun-ichi; Motoki, Takanori; Kishio, Kohji; Awaji, Satoshi; Kon, Koichi; Ichikawa, Naoki; Inamori, Satoshi; Naito, Kyogo

2016-12-01

Effects of densification of precursor disks on the density of residual voids and critical current properties for YBCO melt-textured bulk superconductors were systematically investigated. Six YBCO bulks were prepared from precursor pellets with different initial particle sizes of YBa2Cu3Oy (Y123) powder and applied pressures for pelletization. It was revealed that use of finer Y123 powder and consolidation using cold-isostatic-pressing (CIP) with higher pressures result in reduction of residual voids at inner regions of bulks and enhance Jc especially under low fields below the second peak.

Experimental and theoretical rationalization of the growth mechanism of silicon quantum dots in non-stoichiometric SiN x : role of chlorine in plasma enhanced chemical vapour deposition

NASA Astrophysics Data System (ADS)

Mon-Pérez, E.; Salazar, J.; Ramos, E.; Santoyo Salazar, J.; López Suárez, A.; Dutt, A.; Santana, G.; Marel Monroy, B.

2016-11-01

Silicon quantum dots (Si-QDs) embedded in an insulator matrix are important from a technological and application point of view. Thus, being able to synthesize them in situ during the matrix growth process is technologically advantageous. The use of SiH2Cl2 as the silicon precursor in the plasma enhanced chemical vapour deposition (PECVD) process allows us to obtain Si-QDs without post-thermal annealing. Foremost in this work, is a theoretical rationalization of the mechanism responsible for Si-QD generation in a film including an analysis of the energy released by the extraction of HCl and the insertion of silylene species into the terminal surface bonds. From the results obtained using density functional theory (DFT), we propose an explanation of the mechanism responsible for the formation of Si-QDs in non-stoichiometric SiN x starting from chlorinated precursors in a PECVD system. Micrograph images obtained through transmission electron microscopy confirmed the presence of Si-QDs, even in nitrogen-rich (N-rich) samples. The film stoichiometry was controlled by varying the growth parameters, in particular the NH3/SiH2Cl2 ratio and hydrogen dilution. Experimental and theoretical results together show that using a PECVD system, along with chlorinated precursors it is possible to obtain Si-QDs at a low substrate temperature without annealing treatment. The optical property studies carried out in the present work highlight the prospects of these thin films for down shifting and as an antireflection coating in silicon solar cells.

Synthesis and optical properties of Mg-Al layered double hydroxides precursor powders

NASA Astrophysics Data System (ADS)

Lin, Chia-Hsuan; Chu, Hsueh-Liang; Hwang, Weng-Sing; Wang, Moo-Chin; Ko, Horng-Huey

2017-12-01

The synthesis and optical properties of Mg-Al layered double hydroxide (LDH) precursor powders were investigated using X-ray diffraction (XRD), Fourier transform-infrared (FT-IR) spectroscopy, transmission electron microscopy (TEM), selected area electron diffraction (SAED), high-resolution TEM (HRTEM), UV-transmission spectrometer, and fluorescence spectrophotometer. The FT-IR results show that the intense absorption at around 1363-1377 cm-1 can be assigned to the antisymmetric ν3 mode of interlayer carbonate anions because the LDH phase contains some CO32-. The XRD results show that all of the Mg-Al LDH precursor powders contain only a single phase of [Mg0.833Al0.167(OH)2](CO3)0.083.(H2O)0.75 but have broad and weak intensities of peaks. All of Mg-Al LDHs precursor powders before calcination have the same photoluminescence (PL) spectra. Moreover, these spectra were excited at λex = 235 nm, and the broad emission band was in the range 325-650 nm. In the range, there were relatively strong intensity at around 360, 407 and 510 nm, respectively.

Mechanically activated synthesis of PZT and its electromechanical properties

NASA Astrophysics Data System (ADS)

Liu, X.; Akdogan, E. K.; Safari, A.; Riman, R. E.

2005-08-01

Mechanical activation was successfully used to synthesize nanostructured phase-pure Pb(Zr0.7Ti0.3)O3 (PZT) powders. Lead zirconium titanium (PbZrTi) hydrous oxide precursor, synthesized from chemical co-precipitation, was mechanically activated in a NaCl matrix. The synthesized PZT particles were characterized by using X-ray diffraction, field-emission scanning electron microscopy, transmission electron microscopy, laser-light diffraction, and nitrogen adsorption. Thermogravimetric analysis and differential thermal analysis were used to monitor dehydration and phase transformation of PbZrTi hydrous oxide precursor during mechanical activation. The best mechanical activation conditions corresponded to mechanically activating PbZrTi hydrous oxide precursor in a NaCl matrix with a NaCl/precursor weight ratio of 4:1 for 8 h. These conditions resulted in a dispersible phase-pure PZT powder with a median secondary-particle size of ˜110 nm. The properties of PZT 70/30 from mechanically activated powder, as measured on discs sintered at 1150 °C for 2 h, were found to be in close conformity to those obtained by a conventional mixed oxide solid state reaction route.

Spectroscopy Identification of Benzyl-Type Radicals Generated by Corona Discharge of Precursors of Mixed Substituents

NASA Astrophysics Data System (ADS)

Yoon, Young Wook; Huh, Chang Soon; Lee, Sang Kuk

2012-06-01

We generated vibronically excited but jet-cooled benzyl-type radicals from corona discharge of precursor of mixed substituents using a technique of corona excited supersonic expansion coupled with a pinhole-type glass nozzle, from which the visible vibronic emission spectra were recorded with a long-path monochromator. The spectra exhibit the intensity variation of each species with discharging voltage, indicating the radical species generated in corona discharge is highly sensitive to excitation. From the analysis of the spectra, we found the Cl substituent is replaced in preference to the F substituent by the hydrogen atoms liberated from the dissociation of the C-H bond of the methyl group of the precursor, from which we proposed the possible mechanism for the elimination reaction of substituent in terms of the bond dissociation energy. Additionally, we obtained an accurate electronic energy in the D_1 → D_0 transition and the vibrational mode frequencies of newly detected benzyl-type radicals in the ground electronic state by comparison with those of ab initio calculations and the known spectroscopic data of precursors for the first time.

Ion-induced conversion of polysiloxanes and polycarbosilanes into ceramics: Mechanisms and properties

NASA Astrophysics Data System (ADS)

Pivin, J. C.; Colombo, P.; Sendova-Vassileva, M.; Salomon, J.; Sagon, G.; Quaranta, A.

1998-05-01

Thin films of polysiloxanes and polycarbosilanes with various substituents were converted into SiOC and SiC ceramics by irradiation with ions of increasing masses. The transformation kinetics as a function of the ion dose was assessed by means of ion beam analyses (RBS, NRA, ERDA), compaction measurements, spectroscopies of infrared absorption and Raman scattering. The kinetics depends strongly on the linear density of electronic excitations. The formed radicals tend to react with the atmosphere after irradiations when this density is too low for permitting their combination into crosslinks. Part of the C atoms segregate into clusters with a noticeable degree of tetragonal hybridization, varying with the nature of side groups in the polymeric precursor. This precipitation affords to the films interesting properties: (1) a strong yellow photoluminescence, within a given range of ion doses where the quantum dots of C are not too coarse or too numerous; (2) at higher doses, a hardness reaching that of amorphous SiC and three times that of films converted by heat treatment at 1000-1200°C (as evidenced by nanoindentation tests); (3) a greatly improved thermochemical stability.

FORMATION OF INTRACYTOPLASMIC MEMBRANE SYSTEM OF MYCOBACTERIA RELATED TO CELL DIVISION

PubMed Central

Imaeda, Tamotsu; Ogura, Mituo

1963-01-01

Imaeda, Tamotsu (Instituto Venezolano de Investigaciones Científicas, Caracas, Venezuela) and Mitua Ogura. Formation of intracytoplasmic membrane system of mycobacteria related to cell division. J. Bacteriol. 85:150–163. 1963.—Mycobacterium leprae, M. lepraemurium, and a Mycobacterium sp. were observed with an electron microscope. In these bacilli, the three-dimensional structure of the intracytoplasmic membrane system consists of tubular infoldings of the invaginated plasma membrane. The moderately dense substance, presumably representing the cell-wall precursor, is found in the membranous system, especially in the rapid growth phase of mycobacteria. This system always shows an intimate relationship with cell division. A low-density zone, probably corresponding to the low-density substance which coats the cell wall, appears in the connecting regions of the system and in the longitudinal portion of the cell wall. These zones extend centripetally, and the separation of the cell wall occurs after the two zones meet. Based on these results, we hypothesize that the intracytoplasmic membrane system may produce cell-wall material during cell division of mycobacteria. Images PMID:13956365

Synthesis and electrochemical properties of layered structure Li[Ni{sub 0.5}Co{sub 0.25}Mn{sub 0.25}]O{sub 2} cathode material

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

Prathibha, G.; Rosaiah, P.; Reddy, B. Purusottam

Lithium ion (Li-ion) batteries are currently the energy source of choice for cell phones, laptops, and other mobile electronic devices due to their balance of high energy density with high power density compared to other electrochemical energy carriers. In the present study, mixed hydroxide method is used to prepare Li[Ni{sub 0.5}Co{sub 0.25}Mn{sub 0.25}]O{sub 2} from the precursors and analyze qualitatively and studied the electrochemical properties. The XRD spectrum exhibited predominant (003) orientation at 2θ =18.39{sup o} corresponding to hexagonal layered structure of R3m symmetry with evaluated lattice parameters are a= 2.84 Å, c= 14.43 Å. Raman measurements were performed tomore » understand the microstructure and vibrational modes of the prepared sample. From the electrochemical (EC) studies an initial discharge capacity of about 140 mAhg{sup −1} with good cyclic stability was observed for the prepared sample in the potential range 0.0 −1.0V in aqueous medium.« less

High surface area neodymium phosphate nano particles by modified aqueous sol-gel method

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

Sankar, Sasidharan; Warrier, Krishna Gopakumar, E-mail: wwarrierkgk@yahoo.co.in; Komban, Rajesh

2011-12-15

Graphical abstract: Synthesis of nano rod shaped neodymium phosphate particles with specific surface area as high as 107 m{sup 2} g{sup -1} and particles could be compacted and sintered at as low as 1300 Degree-Sign C to a density of 98.5% (theoretical) with an average grain size of {approx}1 {mu}m. Highlights: Black-Right-Pointing-Pointer Nano size neodymium phosphate is synthesized and characterized using a novel modified aqueous sol gel process. Black-Right-Pointing-Pointer Specific surface area above 100 m{sup 2} g{sup -1} achieved without the addition of any complexing agents. Black-Right-Pointing-Pointer High sintered density reported than the density obtained for powder synthesized through conventionalmore » solid state reaction. Black-Right-Pointing-Pointer The particles are nano sized and have rod shape morphology and are retained at higher temperatures. Black-Right-Pointing-Pointer An average grain size of {approx}1 {mu}m obtained for sintered NdPO{sub 4} after thermal etching at 1400 Degree-Sign C. -- Abstract: Synthesis of nano rod shaped neodymium phosphate (NdPO{sub 4}) particles with specific surface area as high as 107 m{sup 2}g{sup -1} and an average length of 50 nm with aspect ratio 5 was achieved using modified sol gel method. Crystallite size calculated from the X-ray diffraction data by applying Scherer equation was 5 nm for the precursor gel after calcination at 400 Degree-Sign C. NdPO{sub 4} was first precipitated from neodymium nitrate solution using phosphoric acid followed by peptization using dilute nitric acid and further gelation in ammonia atmosphere. The calcined gel powders were further characterized by surface area (Brunauer-Emmet-Teller nitrogen adsorption analysis), Transmission electron microscopy, scanning electron microscopy, UV-vis and FT-IR analysis. Transmission electron microscopy confirms the formation of rod like morphology from the sol, gel and the calcined particles in nano size range. These particles could be compacted and sintered at as low as 1300 Degree-Sign C to a density of 98.5% (theoretical) with an average grain size of {approx}1 {mu}m.« less

Confirmed Assignments of Isomeric Dimethylbenzyl Radicals Generated by Corona Discharge

NASA Astrophysics Data System (ADS)

Yoon, Young Wook; Lee, Sang Kuk

2012-06-01

Polymethylbenzyl radicals, multi-methyl-substituted benzyl radicals, have been believed to be an ideal model for understanding the torsional effect of methyl group and substitution effect on electronic transition. These radicals are mainly generated from polymethylbenzenes by electric discharge for spectroscopic observation. However, the existence of several methyl groups on the benzene ring may produce several isomeric polymethylbenzyl radicals by removing one of the C-H bonds of each methyl group at different substitution position, which makes the assignment of spectrum ambiguous. In this work, the controversial vibronic assignments of isomeric dimethylbenzyl radicals were clearly resolved by using different precursors. By using corresponding dimethylbenzyl chlorides as precursors, we identified the origins of the vibronic bands of the dimethylbenzyl radicals generated by corona discharge of precursors 1,2,3- and 1,2,4-trimethylbenzenes. From the analysis of the spectra observed from the dimethylbenzyl chlorides in a corona excited supersonic expansion using a pinhole-type glass nozzle, we revised previous assignments of the 2,6- and 2,3-dimethylbenzyl radicals as well as the 3,4-, 2,4-, and 2,5-dimethylbenzyl radicals. In addition, spectroscopic data of electronic transition and vibrational mode frequencies in the ground electronic state of each isomer were accurately determined by comparing them with those obtained by an ab initio calculation and with the known vibrational data of precursors.

A facile thermal decomposition route to synthesise CoFe2O4 nanostructures

NASA Astrophysics Data System (ADS)

Kalpanadevi, K.; Sinduja, C. R.; Manimekalai, R.

2014-01-01

The synthesis of CoFe2O4 nanoparticles has been achieved by a simple thermal decomposition method from an inorganic precursor, cobalt ferrous cinnamate hydrazinate (CoFe2(cin)3(N2H4)3) which was obtained by a novel precipitation method from the corresponding metal salts, cinnamic acid and hydrazine hydrate. The precursor was characterized by hydrazine and metal analyses, infrared spectral analysis and thermo gravimetric analysis. Under appropriate annealing, CoFe2(cin)3(N2H4)3 yielded CoFe2O4 nanoparticles, which were characterized for their size and structure using X-Ray diffraction (XRD), high resolution transmission electron microscopic (HRTEM), selected area electron diffraction (SAED) and scanning electron microscopic (SEM) techniques.

Electron induced surface reactions of (η5-C5H5)Fe(CO)2Mn(CO)5, a potential heterobimetallic precursor for focused electron beam induced deposition (FEBID).

PubMed

Unlu, Ilyas; Spencer, Julie A; Johnson, Kelsea R; Thorman, Rachel M; Ingólfsson, Oddur; McElwee-White, Lisa; Fairbrother, D Howard

2018-03-14

Electron-induced surface reactions of (η 5 -C 5 H 5 )Fe(CO) 2 Mn(CO) 5 were explored in situ under ultra-high vacuum conditions using X-ray photoelectron spectroscopy and mass spectrometry. The initial step involves electron-stimulated decomposition of adsorbed (η 5 -C 5 H 5 )Fe(CO) 2 Mn(CO) 5 molecules, accompanied by the desorption of an average of five CO ligands. A comparison with recent gas phase studies suggests that this precursor decomposition step occurs by a dissociative ionization (DI) process. Further electron irradiation decomposes the residual CO groups and (η 5 -C 5 H 5 , Cp) ligand, in the absence of any ligand desorption. The decomposition of CO ligands leads to Mn oxidation, while electron stimulated Cp decomposition causes all of the associated carbon atoms to be retained in the deposit. The lack of any Fe oxidation is ascribed to either the presence of a protective carbonaceous matrix around the Fe atoms created by the decomposition of the Cp ligand, or to desorption of both CO ligands bound to Fe in the initial decomposition step. The selective oxidation of Mn in the absence of any Fe oxidation suggests that the fate of metal atoms in mixed-metal precursors for focused electron beam induced deposition (FEBID) will be sensitive to the nature and number of ligands in the immediate coordination sphere. In related studies, the composition of deposits created from (η 5 -C 5 H 5 )Fe(CO) 2 Mn(CO) 5 under steady state deposition conditions, representative of those used to create nanostructures in electron microscopes, were measured and found to be qualitatively consistent with predictions from the UHV surface science studies.

Ultrafast Scavenging of the Precursor of H(•) Atom, (e(-), H3O(+)), in Aqueous Solutions.

PubMed

Balcerzyk, Anna; Schmidhammer, Uli; Wang, Furong; de la Lande, Aurélien; Mostafavi, Mehran

2016-09-01

Picosecond pulse radiolysis measurements have been performed in several highly concentrated HClO4 and H3PO4 aqueous solutions containing silver ions at different concentrations. Silver ion reduction is used to unravel the ultrafast reduction reactions observed at the end of a 7 ps electron pulse. Solvated electrons and silver atoms are observed by the pulse (electron beam)-probe (supercontinuum light) method. In highly acidic solutions, ultrafast reduction of silver ions is observed, a finding that is not compatible with a reaction between the H(•) atom and silver ions, which is known to be thermally activated. In addition, silver ion reduction is found to be even more efficient in phosphoric acid solution than that in neutral solution. In the acidic solutions investigated here, the species responsible for the reduction of silver atoms is considered to be the precursor of the H(•) atom. This precursor, denoted (e(-), H3O(+)), is a pair constituting an electron (not fully solvated) and H3O(+). Its structure differs from that of the pair of a solvated electron and a hydronium ion (es(-), H3O(+)), which absorbs in the visible region. The (e(-), H3O(+)) pair , called the pre-H(•) atom here, undergoes ultrafast electron transfer and can, like the presolvated electron, reduce silver ions much faster than the H(•) atom. Moreover, it is found that with the same concentration of H3O(+) the reduction reaction is favored in the phosphoric acid solution compared to that in the perchloric acid solution because of the less-efficient electron solvation process. The kinetics show that among the three reducing species, (e(-), H3O(+)), (es(-), H3O(+)), and H(•) atom, the first one is the most efficient.

A Novel and Facile Route to Synthesize Atomic-Layered MoS2 Film for Large-Area Electronics.

PubMed

Boandoh, Stephen; Choi, Soo Ho; Park, Ji-Hoon; Park, So Young; Bang, Seungho; Jeong, Mun Seok; Lee, Joo Song; Kim, Hyeong Jin; Yang, Woochul; Choi, Jae-Young; Kim, Soo Min; Kim, Ki Kang

2017-10-01

High-quality and large-area molybdenum disulfide (MoS 2 ) thin film is highly desirable for applications in large-area electronics. However, there remains a challenge in attaining MoS 2 film of reasonable crystallinity due to the absence of appropriate choice and control of precursors, as well as choice of suitable growth substrates. Herein, a novel and facile route is reported for synthesizing few-layered MoS 2 film with new precursors via chemical vapor deposition. Prior to growth, an aqueous solution of sodium molybdate as the molybdenum precursor is spun onto the growth substrate and dimethyl disulfide as the liquid sulfur precursor is supplied with a bubbling system during growth. To supplement the limiting effect of Mo (sodium molybdate), a supplementary Mo is supplied by dissolving molybdenum hexacarbonyl (Mo(CO) 6 ) in the liquid sulfur precursor delivered by the bubbler. By precisely controlling the amounts of precursors and hydrogen flow, full coverage of MoS 2 film is readily achievable in 20 min. Large-area MoS 2 field effect transistors (FETs) fabricated with a conventional photolithography have a carrier mobility as high as 18.9 cm 2 V -1 s -1 , which is the highest reported for bottom-gated MoS 2 -FETs fabricated via photolithography with an on/off ratio of ≈10 5 at room temperature. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Analysis of Precursor Properties of mixed Al/Alumel Cylindrical Wire Arrays*

NASA Astrophysics Data System (ADS)

Stafford, A.; Safronova, A. S.; Kantsyrev, V. L.; Esaulov, A. A.; Weller, M. E.; Shrestha, I.; Osborne, G. C.; Shlyaptseva, V. V.; Keim, S. F.; Coverdale, C. A.; Chuvatin, A. S.

2012-10-01

Previous studies of mid-Z (Cu and Ni) cylindrical wire arrays (CWAs) on Zebra have found precursors with high electron temperatures of >300 eV. However, past experiments with Al CWAs did not find the same high temperature precursors. New precursor experiments using mixed Al/Alumel (Ni 95%, Si 2%, and Al 2%) cylindrical wire arrays have been performed to understand how the properties of L-shell Ni precursor will change and whether Al precursor will be observed. Time gated spectra and pinholes are used to determine precursor plasma conditions for comparison with previous Alumel precursor experiments. A full diagnostic set which included more than ten different beam-lines was implemented. Future work in this direction is discussed. [4pt] *This work was supported by NNSA under DOE Cooperative Agreements DE-FC52-06NA27588, and in part by DE-FC52-06NA27586, and DE-FC52-06NA27616. Sandia is a multi-program laboratory operated by Sandia Corporation, a Lockheed Martin Company, for the United States Department of Energy under Contract DE-AC04-94AL85000.

Structural, optical and electrical properties of well-ordered ZnO nanowires grown on (1 1 1) oriented Si, GaAs and InP substrates by electrochemical deposition method

NASA Astrophysics Data System (ADS)

Pham, Huyen T.; Nguyen, Tam D.; Tran, Dat Q.; Akabori, Masashi

2017-05-01

ZnO semiconductors, especially in form of nanomaterials, possess many excellent properties and have been employed in many applications. In this article, we reported the selective area growth of ZnO nanowires on different (1 1 1) oriented Si, GaAs, and first time on InP substrates by electrochemical deposition method without any seed layers, using zinc nitrate hexahydrate precursor in the presence of hexamethylenetetramine. The position, density and orientation of such ZnO nanowires were controlled by the substrate patterning technique using electron-beam lithography. As-synthesized ZnO nanowires grown on patterned substrates show smaller diameter, higher density and better orientation, compared to the one grown on unpatterned substrates. In particular, the ZnO nanowires grown on GaAs patterned substrate indicate the best morphological property, with the average diameter, length and density of about 100 nm, 2.4 µm and 35 µm-2, respectively. The x-ray diffraction and Raman scattering also demonstrate high crystalline quality of our ZnO nanowires. Moreover, as-reported ZnO nanowires are also conductive, which would allow their use in field-effect transistor and other potential nanoscale device applications.

Patterned growth of carbon nanotubes obtained by high density plasma chemical vapor deposition

NASA Astrophysics Data System (ADS)

Mousinho, A. P.; Mansano, R. D.

2015-03-01

Patterned growth of carbon nanotubes by chemical vapor deposition represents an assembly approach to place and orient nanotubes at a stage as early as when they are synthesized. In this work, the carbon nanotubes were obtained at room temperature by High Density Plasmas Chemical Vapor Deposition (HDPCVD) system. This CVD system uses a new concept of plasma generation, where a planar coil coupled to an RF system for plasma generation was used with an electrostatic shield for plasma densification. In this mode, high density plasmas are obtained. We also report the patterned growth of carbon nanotubes on full 4-in Si wafers, using pure methane plasmas and iron as precursor material (seed). Photolithography processes were used to pattern the regions on the silicon wafers. The carbon nanotubes were characterized by micro-Raman spectroscopy, the spectra showed very single-walled carbon nanotubes axial vibration modes around 1590 cm-1 and radial breathing modes (RBM) around 120-400 cm-1, confirming that high quality of the carbon nanotubes obtained in this work. The carbon nanotubes were analyzed by atomic force microscopy and scanning electron microscopy too. The results showed that is possible obtain high-aligned carbon nanotubes with patterned growth on a silicon wafer with high reproducibility and control.

THE COUPLED EVOLUTION OF ELECTRONS AND IONS IN CORONAL MASS EJECTION-DRIVEN SHOCKS

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

Manchester IV, W. B.; Van der Holst, B.; Toth, G.

2012-09-01

We present simulations of coronal mass ejections (CMEs) performed with a new two-temperature coronal model developed at the University of Michigan, which is able to address the coupled thermodynamics of the electron and proton populations in the context of a single fluid. This model employs heat conduction for electrons, constant adiabatic index ({gamma} = 5/3), and includes Alfven wave pressure to accelerate the solar wind. The Wang-Sheeley-Arge empirical model is used to determine the Alfven wave pressure necessary to produce the observed bimodal solar wind speed. The Alfven waves are dissipated as they propagate from the Sun and heat protonsmore » on open magnetic field lines to temperatures above 2 MK. The model is driven by empirical boundary conditions that includes GONG magnetogram data to calculate the coronal field, and STEREO/EUVI observations to specify the density and temperature at the coronal boundary by the Differential Emission Measure Tomography method. With this model, we simulate the propagation of fast CMEs and study the thermodynamics of CME-driven shocks. Since the thermal speed of the electrons greatly exceeds the speed of the CME, only protons are directly heated by the shock. Coulomb collisions low in the corona couple the protons and electrons allowing heat exchange between the two species. However, the coupling is so brief that the electrons never achieve more than 10% of the maximum temperature of the protons. We find that heat is able to conduct on open magnetic field lines and rapidly propagates ahead of the CME to form a shock precursor of hot electrons.« less

Synthesis of LiCoO 2 thin films by sol/gel process

NASA Astrophysics Data System (ADS)

Porthault, H.; Le Cras, F.; Franger, S.

LiCoO 2 thin films were synthesized by sol/gel process using acrylic acid (AA) as chelating agent. The gel formulation was optimized by varying solvent (ethylene glycol or water) and precursors molar ratios (Li, Co, AA) in order to obtain a dense film for positive electrode of lithium batteries. The gel was deposited by spin-coating technique on an Au/TiO 2/SiN/SiO 2/Si substrate. Thin films were deposited by either single or multistep process to enhance the density of the thin film and then calcined during 5 h at 800 °C to obtain the R-3m phase (HT-LiCoO 2). A chemical characterization of the solution was realized by Fourier Transform Infrared (FTIR) spectroscopy. Thermal decomposition of precursors and gel was studied by Thermo Gravimetric Analyses (TGA). Further investigations were done to characterize rheologic behaviour of the gel and solvents affinity with the substrate. Crystallinity and morphology were analyzed respectively by X-ray diffraction (XRD) and Scanning Electron Microscopy (SEM). The formation of R-3m phase was confirmed by the electrochemical behaviour of the gel derived LiCoO 2. Cyclic voltammograms and galvanostatic cycling show typical curve shape of the HT-LiCoO 2.

Lanthanum aluminum oxide thin-film dielectrics from aqueous solution.

PubMed

Plassmeyer, Paul N; Archila, Kevin; Wager, John F; Page, Catherine J

2015-01-28

Amorphous LaAlO3 dielectric thin films were fabricated via solution processing from inorganic nitrate precursors. Precursor solutions contained soluble oligomeric metal-hydroxyl and/or -oxo species as evidenced by dynamic light scattering (DLS) and Raman spectroscopy. Thin-film formation was characterized as a function of annealing temperature using Fourier transform infrared (FTIR), X-ray diffraction (XRD), X-ray reflectivity (XRR), scanning electron microscopy (SEM), and an array of electrical measurements. Annealing temperatures ≥500 °C result in thin films with low leakage-current densities (∼1 × 10(-8) A·cm(-2)) and dielectric constants ranging from 11.0 to 11.5. When incorporated as the gate dielectric layer in a-IGZO thin-film transistors (TFTs), LaAlO3 thin films annealed at 600 °C in air yielded TFTs with relatively low average mobilities (∼4.5 cm(2)·V(-1)·s(-1)) and high turn-on voltages (∼26 V). Interestingly, reannealing the LaAlO3 in 5%H2/95%N2 at 300 °C before deposition of a-IGZO channel layers resulted in TFTs with increased average mobilities (11.1 cm(2)·V(-1)·s(-1)) and lower turn-on voltages (∼6 V).

Performance evaluation of GDC-SrMoO4-YSZ SOFCs prepared with different pore formers

NASA Astrophysics Data System (ADS)

Hongxin, You; Lian, Peng; Xiaojuan, Wang; Cong, Zhao; Yajun, Guan; Tao, Yu; Lijun, Xu; Abuliti

2018-04-01

The paper aims to evaluate the performance of anodes prepared with different pore formers. Anodic precursor material SrMoO4 was prepared by hard template method. Gd0.2Ce0.8O1.9 (GDC) was introduced to the precursor to prepare composite anode material GDC-SrMoO4-YSZ by wet impregnation method. Cotton-fibers, graphite powder, flour and activated carbon fibers (ACF) were added as pore formers to the anode to prepare the corresponding solid oxide fuel cell (SOFC), respectively. The electrical performance testing was conducted under the methane environment at 800°C. The result showed that the single cell with 5wt% cotton-fibers as anode pore-former performed best with the maximum power density (464.49 mW.cm2). The cross section samples of the test cells indicated that the anode was left with a plenty of continuous long channels because of the burning of cotton-fibers. Thus, the influence of the amount of cotton-fibers (2wt%, 4wt%, 5wt%, 7wt%, 10wt%) of the anode on the performance of SOFC was tested and further analyzed by the scanning electron microscope (SEM). It was indicated that the optimum adding amount of cotton-fibers was 5wt%.

High-purity Cu nanocrystal synthesis by a dynamic decomposition method.

PubMed

Jian, Xian; Cao, Yu; Chen, Guozhang; Wang, Chao; Tang, Hui; Yin, Liangjun; Luan, Chunhong; Liang, Yinglin; Jiang, Jing; Wu, Sixin; Zeng, Qing; Wang, Fei; Zhang, Chengui

2014-12-01

Cu nanocrystals are applied extensively in several fields, particularly in the microelectron, sensor, and catalysis. The catalytic behavior of Cu nanocrystals depends mainly on the structure and particle size. In this work, formation of high-purity Cu nanocrystals is studied using a common chemical vapor deposition precursor of cupric tartrate. This process is investigated through a combined experimental and computational approach. The decomposition kinetics is researched via differential scanning calorimetry and thermogravimetric analysis using Flynn-Wall-Ozawa, Kissinger, and Starink methods. The growth was found to be influenced by the factors of reaction temperature, protective gas, and time. And microstructural and thermal characterizations were performed by X-ray diffraction, scanning electron microscopy, transmission electron microscopy, and differential scanning calorimetry. Decomposition of cupric tartrate at different temperatures was simulated by density functional theory calculations under the generalized gradient approximation. High crystalline Cu nanocrystals without floccules were obtained from thermal decomposition of cupric tartrate at 271°C for 8 h under Ar. This general approach paves a way to controllable synthesis of Cu nanocrystals with high purity.

High-purity Cu nanocrystal synthesis by a dynamic decomposition method

NASA Astrophysics Data System (ADS)

Jian, Xian; Cao, Yu; Chen, Guozhang; Wang, Chao; Tang, Hui; Yin, Liangjun; Luan, Chunhong; Liang, Yinglin; Jiang, Jing; Wu, Sixin; Zeng, Qing; Wang, Fei; Zhang, Chengui

2014-12-01

Cu nanocrystals are applied extensively in several fields, particularly in the microelectron, sensor, and catalysis. The catalytic behavior of Cu nanocrystals depends mainly on the structure and particle size. In this work, formation of high-purity Cu nanocrystals is studied using a common chemical vapor deposition precursor of cupric tartrate. This process is investigated through a combined experimental and computational approach. The decomposition kinetics is researched via differential scanning calorimetry and thermogravimetric analysis using Flynn-Wall-Ozawa, Kissinger, and Starink methods. The growth was found to be influenced by the factors of reaction temperature, protective gas, and time. And microstructural and thermal characterizations were performed by X-ray diffraction, scanning electron microscopy, transmission electron microscopy, and differential scanning calorimetry. Decomposition of cupric tartrate at different temperatures was simulated by density functional theory calculations under the generalized gradient approximation. High crystalline Cu nanocrystals without floccules were obtained from thermal decomposition of cupric tartrate at 271°C for 8 h under Ar. This general approach paves a way to controllable synthesis of Cu nanocrystals with high purity.

Ratiometric Fluorescence Azide-Alkyne Cycloaddition for Live Mammalian Cell Imaging.

PubMed

Fu, Hongxia; Li, Yanru; Sun, Lingbo; He, Pan; Duan, Xinrui

2015-11-17

Click chemistry with metabolic labeling has been widely used for selectively imaging biomacromolecules in cells. The first example of azide-alkyne cycloaddition for ratiometric fluorescent imaging of live cells is reported. The precursor of the azido fluorophore (cresyl violet) has a fluorescence emission peak at 620 nm. The electron-rich nitrogen of the azido group blue-shifts the emission peak to 566 nm. When the click reaction occurs, an emission peak appears at 620 nm due to the lower electronic density of the newly formed triazole ring, which allows us to ratiometrically record fluorescence signals. This emission shift was applied to ratiometric imaging of propargylcholine- and dibenzocyclooctyne-labeled human breast cancer cells MCF-7 under laser confocal microscopy. Two typical triazole compounds were isolated for photophysical parameter measurements. The emission spectra presented a fluorescence emission peak around 620 nm for both click products. The results further confirmed the emission wavelength change was the result of azide-alkyne cycloaddition reaction. Since nearly all biomolecules can be metabolically labeled by reported alkyne-functionalized derivatives of native metabolites, our method can be readily applied to image these biomacromolecules.

From Bench Top to Market: Growth of Multi-Walled Carbon Nanotubes by Injection CVD Using Fe Organometallics - Production of a Commercial Reactor

NASA Technical Reports Server (NTRS)

Rowsell, J.; Hepp, A. F.; Harris, J. D.; Raffaelle, R. P.; Cowen, J. C.; Scheiman, D. A.; Flood, D. M.; Flood, D. J.

2009-01-01

Preferential oriented multiwalled carbon nanotubes were prepared by the injection chemical vapor deposition (CVD) method using either cyclopentadienyliron dicarbonyl dimer or cyclooctatetraene iron tricarbonyl as the iron catalyst source. The catalyst precursors were dissolved in toluene as the carrier solvent for the injections. The concentration of the catalyst was found to influence both the growth (i.e., MWNT orientation) of the nanotubes, as well as the amount of iron in the deposited material. As deposited, the multiwalled carbon nanotubes contained as little as 2.8% iron by weight. The material was deposited onto tantalum foil and fused silica substrates. The nanotubes were characterized by scanning electron microscopy, transmission electron microscopy, Raman spectroscopy and thermogravimetric analysis. This synthetic route provides a simple and scalable method to deposit MWNTs with a low defect density, low metal content and a preferred orientation. Subsequently, a small start-up was founded to commercialize the deposition equipment. The contrast between the research and entrepreneurial environments will be discussed.

A High Stability Optical Shadow Sensor With Applications for Precision Accelerometers

NASA Astrophysics Data System (ADS)

Bramsiepe, Steven G.; Loomes, David; Middlemiss, Richard P.; Paul, Douglas J.; Hammond, Giles D.

2018-05-01

Gravimeters are devices which measure changes in the value of the gravitational acceleration, \\textit{g}. This information is used to infer changes in density under the ground allowing the detection of subsurface voids; mineral, oil and gas reserves; and even the detection of the precursors of volcanic eruptions. A micro-electro mechanical system (MEMS) gravimeter has been fabricated completely in silicon allowing the possibility of cost e-effective, lightweight and small gravimeters. To obtain a measurement of gravity, a highly stable displacement measurement of the MEMS is required. This requires the development of a portable electronics system that has a displacement sensitivity of $\\leq 2.5$ nm over a period of a day or more. The portable electronics system presented here has a displacement sensitivity $\\leq 10$ nm$/\\sqrt{\\textrm{Hz}}$ ($\\leq 0.6$ nm at $1000$ s). The battery power system used a modulated LED for measurements and required temperature control of the system to $\\pm$ 2 mK, monitoring of the tilt to $\\pm$ 2 $\\mu$radians, the storage of measured data and the transmission of the data to an external server.

Magnetization and transport properties of silver-sheathed (Hg, Re)Ba2Ca2Cu3O8+delta tapes

NASA Astrophysics Data System (ADS)

Su, J. H.; Sastry, P. V. P. S. S.; Schwartz, J.

2003-10-01

(Hg, Re)Ba2Ca2Cu3O8+delta ((Hg, Re)-1223) samples have been fabricated by wrapping Re0.2Ba2Ca2Cu3Oy precursor powder within Ag foil and pressing or rolling. The Ag/precursor composite is then reacted with CaHgO2 in sealed reaction tubes. X-ray diffraction (XRD) patterns showed only one superconducting phase, (Hg, Re)-1223, in agreement with magnetization measurements showing an onset critical temperature (Tc) of 132 K. The magnetization properties were studied by dc magnetic measurements. The irreversibility line (Hirr), deduced from magnetization hysteresis loops, is approximated by a power law, Hirr ~ (1 - T/Tc)n, with n ~ 2.5, indicating moderate coupling between CuO2 layers compared to YBa2Cu3O7 (n ~ 1.5) and Bi/Tl-based superconductors (n ~ 5.5). The temperature dependence of the magnetization hysteresis loop width DeltaM showed three regimes, dominated by weak links at low temperature (regime I), thermally activated depinning of vortices at intermediate temperature (regime II) and giant flux creep at high temperature (regime III), respectively. Two field dependences were found in the intragrain critical current density (Jmagc) versus applied field at various temperatures: a weak one at lower temperature (leq50 K) and a stronger one at high temperature (geq65 K), indicating a transition from vortex lattice to vortex liquid in the tapes. The transport critical current density (Jtranc) of ~3 × 103 A cm-2 at 4.2 K and self-field was comparable to those for bulk Hg-based superconductors, indicating granular nature of the samples, which was confirmed further by XRD, scanning electron microscopy (SEM) and magneto-optical imaging (MOI).

Thermally switchable dielectrics

DOEpatents

Dirk, Shawn M.; Johnson, Ross S.

2013-04-30

Precursor polymers to conjugated polymers, such as poly(phenylene vinylene), poly(poly(thiophene vinylene), poly(aniline vinylene), and poly(pyrrole vinylene), can be used as thermally switchable capacitor dielectrics that fail at a specific temperature due to the non-conjugated precursor polymer irreversibly switching from an insulator to the conjugated polymer, which serves as a bleed resistor. The precursor polymer is a good dielectric until it reaches a specific temperature determined by the stability of the leaving groups. Conjugation of the polymer backbone at high temperature effectively disables the capacitor, providing a `built-in` safety mechanism for electronic devices.

High power beta electron device - Beyond betavoltaics

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

Ayers, William M.; Gentile, Charles A.

Developing watt level power sources with beta emitting radioisotopes has been limited by the inability to utilize high energy (> 100 KeV) beta emitters at high radioisotope loadings without damaging the energy conversion materials. A new type of beta electron power source is described that removes those restrictions. This approach contains the radioisotope in a beta transparent titanium tube and confines beta electrons emitted through the tube wall to spiral trajectories around the tube with an axial magnetic field. The confined beta electrons dissipate energy though multiple interactions with surrounding excimer precursor gas atoms to efficiently generate photons. Photovoltaic cellsmore » convert the photons to electrical power. Since the beta electrons dissipate energy in the excimer precursor gas, the device can be loaded with more than 10 13 Bq of radioisotope to generate 100 milliwatt to watt levels of electrical power without damaging the device materials or degrading its performance. Furthermore, the power source can use a variety of beta radioisotopes and scales by stacking the devices.« less

High power beta electron device - Beyond betavoltaics

DOE PAGES

Ayers, William M.; Gentile, Charles A.

2017-11-10

Developing watt level power sources with beta emitting radioisotopes has been limited by the inability to utilize high energy (> 100 KeV) beta emitters at high radioisotope loadings without damaging the energy conversion materials. A new type of beta electron power source is described that removes those restrictions. This approach contains the radioisotope in a beta transparent titanium tube and confines beta electrons emitted through the tube wall to spiral trajectories around the tube with an axial magnetic field. The confined beta electrons dissipate energy though multiple interactions with surrounding excimer precursor gas atoms to efficiently generate photons. Photovoltaic cellsmore » convert the photons to electrical power. Since the beta electrons dissipate energy in the excimer precursor gas, the device can be loaded with more than 10 13 Bq of radioisotope to generate 100 milliwatt to watt levels of electrical power without damaging the device materials or degrading its performance. Furthermore, the power source can use a variety of beta radioisotopes and scales by stacking the devices.« less

High power beta electron device - Beyond betavoltaics.

PubMed

Ayers, William M; Gentile, Charles A

2018-01-01

Developing watt level power sources with beta emitting radioisotopes has been limited by the inability to utilize high energy (> 100KeV) beta emitters at high radioisotope loadings without damaging the energy conversion materials. A new type of beta electron power source is described that removes those restrictions. The approach contains the radioisotope in a beta transparent titanium tube and confines beta electrons emitted through the tube wall to spiral trajectories around the tube with an axial magnetic field. The confined beta electrons dissipate energy though multiple interactions with surrounding excimer precursor gas atoms to efficiently generate photons. Photovoltaic cells convert the photons to electrical power. Since the beta electrons dissipate energy in the excimer precursor gas, the device can be loaded with more than 10 13 Bq of radioisotope to generate 100 milliwatt to watt levels of electrical power without damaging the device materials or degrading its performance. The power source can use a variety of beta radioisotopes and scales by stacking the devices. Copyright © 2017. Published by Elsevier Ltd.

Gas chromatography-mass spectrometric studies of O-alkyl O-2-(N,N-dialkylamino) ethyl alkylphosphonites(phosphonates) for chemical weapons convention verification.

PubMed

Saeidian, Hamid; Babri, Mehran; Ramezani, Atefeh; Ashrafi, Davood; Sarabadani, Mansour; Naseri, Mohammad Taghi

2013-01-01

The electron ionization (EI) mass spectra of a series of O-alkyl O-2-(N,N-dialkylaminolethyl alkylphosphonites(phosphonates), which are precursors of nerve agents, were studied for Chemical Weapons Convention (CWC) verification. General El fragmentation pathways were constructed and discussed. Proposed fragment structures were confirmed through analyzing fragment ions of deuterated analogs and density functional theory (DFT) calculations. The observed fragment ions are due to different fragmentation pathways such as hydrogen and McLafferty+1 rearrangements, alkene, amine and alkoxy elimination by alpha- or beta-cleavage process. Fragment ions distinctly allow unequivocal identification of the interested compounds including those of isomeric compounds. The presence and abundance of fragment ions were found to depend on the size and structure of the alkyl group attached to nitrogen, phosphorus and oxygen atoms.

Effect of growth temperature on the epitaxial growth of ZnO on GaN by ALD

NASA Astrophysics Data System (ADS)

Särkijärvi, Suvi; Sintonen, Sakari; Tuomisto, Filip; Bosund, Markus; Suihkonen, Sami; Lipsanen, Harri

2014-07-01

We report on the epitaxial growth of ZnO on GaN template by atomic layer deposition (ALD). Diethylzinc (DEZn) and water vapour (H2O) were used as precursors. The structure and the quality of the grown ZnO layers were studied with scanning electron microscope (SEM), X-ray diffraction (XRD), photoluminescence (PL) measurements and positron annihilation spectroscopy. The ZnO films were confirmed epitaxial, and the film quality was found to improve with increasing deposition temperature in the vicinity of the threshold temperature of two dimensional growth. We conclude that high quality ZnO thin films can be grown by ALD. Interestingly only separate Zn-vacancies were observed in the films, although ZnO thin films typically contain fairly high density of surface pits and vacancy clusters.

Electrodeposition and characterisation of Al-W alloy films from ionic liquid

NASA Astrophysics Data System (ADS)

Höhlich, D.; Wachner, D.; Müller, M.; Scharf, I.; Lampke, T.

2018-06-01

Al–W alloy films were prepared by electrodeposition using anhydrous 1-ethyl-3-methylimidazolium chloride (EMIMCl) ionic-liquid solution with aluminium chloride in a ratio of 1:1.5. As a commercially available tungsten precursor, tungsten hexachloride was used. The metal is dissolved in the ionic liquid at concentrations up to 0.06 mol/l. The deposition took place outside the glove box with a continuous argon stream over the electrolyte at a temperature of 60 °C with a current density of 1 A/m2. Resulting alloys show a tungsten content higher than 20 wt% (3.5 at%). The phase composition of Al-W alloys was observed by X-ray diffraction (XRD), and the chemical composition was characterised by scanning electron microscopy (SEM) and inductively-coupled plasma optical emission spectroscopy (ICP-OES).

Comprehensive investigation of the electronic excitation of W(CO)6 by photoabsorption and theoretical analysis in the energy region from 3.9 to 10.8 eV.

PubMed

Mendes, Mónica; Regeta, Khrystyna; Ferreira da Silva, Filipe; Jones, Nykola C; Hoffmann, Søren Vrønning; García, Gustavo; Daniel, Chantal; Limão-Vieira, Paulo

2017-01-01

High-resolution vacuum ultraviolet photoabsorption measurements in the wavelength range of 115-320 nm (10.8-3.9 eV) have been performed together with comprehensive relativistic time-dependent density functional calculations (TDDFT) on the low-lying excited sates of tungsten hexacarbonyl, W(CO) 6 . The higher resolution obtained reveals previously unresolved spectral features of W(CO) 6 . The spectrum shows two higher-energy bands (in the energy ranges of 7.22-8.12 eV and 8.15-9.05 eV), one of them with clear vibrational structure, and a few lower-energy shoulders in addition to a couple of lower-energy metal-to-ligand charge-transfer (MLCT) bands reported in the literature before. Absolute photoabsorption cross sections are reported and, where possible, compared to previously published results. On the basis of this combined experimental/theoretical study the absorption spectrum of the complex has been totally re-assigned between 3.9 and 10.8 eV under the light of spin-orbit coupling (SOC) effects. The present comprehensive knowledge of the nature of the electronically excited states may be of relevance to estimate neutral dissociation cross sections of W(CO) 6 , a precursor molecule in focused electron beam induced deposition (FEBID) processes, from electron scattering measurements.

Comprehensive investigation of the electronic excitation of W(CO)6 by photoabsorption and theoretical analysis in the energy region from 3.9 to 10.8 eV

PubMed Central

Mendes, Mónica; Regeta, Khrystyna; Ferreira da Silva, Filipe; Jones, Nykola C; Hoffmann, Søren Vrønning; García, Gustavo

2017-01-01

High-resolution vacuum ultraviolet photoabsorption measurements in the wavelength range of 115–320 nm (10.8–3.9 eV) have been performed together with comprehensive relativistic time-dependent density functional calculations (TDDFT) on the low-lying excited sates of tungsten hexacarbonyl, W(CO)6. The higher resolution obtained reveals previously unresolved spectral features of W(CO)6. The spectrum shows two higher-energy bands (in the energy ranges of 7.22–8.12 eV and 8.15–9.05 eV), one of them with clear vibrational structure, and a few lower-energy shoulders in addition to a couple of lower-energy metal-to-ligand charge-transfer (MLCT) bands reported in the literature before. Absolute photoabsorption cross sections are reported and, where possible, compared to previously published results. On the basis of this combined experimental/theoretical study the absorption spectrum of the complex has been totally re-assigned between 3.9 and 10.8 eV under the light of spin–orbit coupling (SOC) effects. The present comprehensive knowledge of the nature of the electronically excited states may be of relevance to estimate neutral dissociation cross sections of W(CO)6, a precursor molecule in focused electron beam induced deposition (FEBID) processes, from electron scattering measurements. PMID:29114447

Tetraphenylporphyrin electronic properties: a combined theoretical and experimental study of thin films deposited by SuMBD.

PubMed

Nardi, Marco; Verucchi, Roberto; Corradi, Claudio; Pola, Marco; Casarin, Maurizio; Vittadini, Andrea; Iannotta, Salvatore

2010-01-28

Porphyrins and their metal complexes are particularly well suitable for applications in photoelectronics, sensing, energy production, because of their chemical, electronic and optical properties. The understanding of the electronic properties of the pristine molecule is of great relevance for the study and application of the wide class of these compounds. This is notably important for the recently achieved in-vacuo synthesis of organo-metallic thin films directly from the pure free base organic-inorganic precursors in the vapor phase, and its interpretation by means of surface electron spectroscopies. We report on a combined experimental and theoretical study of the physical/chemical properties of tetraphenylporphyrin, H(2)TPP, deposited on the SiO(2)/Si(100) native oxide surface by supersonic molecular beam deposition (SuMBD). Valence states and 1s core level emissions of carbon and nitrogen have been investigated with surface photoelectron spectroscopies by using synchrotron radiation light. The interpretation of the spectra has been guided by density functional numerical experiments on the gas-phase molecule. Non-relativistic calculations were carried out for the valence states, whereas a two component relativistic approach in the zeroth-order regular approximation was used to investigate the core levels. The good agreement between theoretical and experimental analysis results in a comprehensive overview of the chemical properties of the H(2)TPP molecule, highly improving reliability in the interpretation of experimental photoemission spectra.

Y2O3-MgO Nano-Composite Synthesized by Plasma Spraying and Thermal Decomposition of Solution Precursors

NASA Astrophysics Data System (ADS)

Muoto, Chigozie Kenechukwu

This research aims to identify the key feedstock characteristics and processing conditions to produce Y2O3-MgO composite coatings with high density and hardness using solution precursor plasma spray (SPPS) and suspension plasma spray (SPS) processes, and also, to explore the phenomena involved in the production of homogenized nano-composite powders of this material system by thermal decomposition of solution precursor mixtures. The material system would find potential application in the fabrication of components for optical applications such as transparent windows. It was shown that a lack of major endothermic events during precursor decomposition and the resultant formation of highly dense particles upon pyrolysis are critical precursor characteristics for the deposition of dense and hard Y2O3-MgO coatings by SPPS. Using these principles, a new Y2O3-MgO precursor solution was developed, which yielded a coating with Vickers hardness of 560 Hv. This was a considerable improvement over the hardness of the coatings obtained using conventional solution precursors, which was as low as 110 Hv. In the thermal decomposition synthesis process, binary solution precursor mixtures of: yttrium nitrate (Y[n]) or yttrium acetate (Y[a]), with magnesium nitrate (Mg[n]) or magnesium acetate (Mg[a]) were used in order to study the effects of precursor chemistry on the structural characteristics of the resultant Y2O3-MgO powders. The phase domains were coarse and distributed rather inhomogeneously in the materials obtained from the Y[n]Mg[n] and Y[a]Mg[a] mixtures; finer and more homogeneously-distributed phase domains were obtained for ceramics produced from the Y[a]Mg[n] and Y[n]Mg[a] mixtures. It was established that these phenomena were related to the thermal characteristics for the decomposition of the precursors and their effect on phase separation during oxide crystallization. Addition of ammonium acetate to the Y[n[Mg[n] mixture changed the endothermic process to exothermic and improved the dispersion of the component phases. Two suspension types, made with powders synthesized from the Y[n]Mg[n] and Y[n]Mg[a] precursor mixtures were sprayed by SPS. The densities and hardnesses of the coatings deposited using the two powder types were similar. However, the microstructure of coatings deposited using the Y[n]Mg[a]-synthesized powder exhibited some eutectic configuration which was not observed in the coatings deposited using the Y[n]Mg[n]-synthesized powder.

Studies on photoinduced H-atom and electron transfer reactions of o-naphthoquinones by laser flash photolysis.

PubMed

Pan, Yang; Fu, Yao; Liu, Shaoxiong; Yu, Haizhu; Gao, Yuhe; Guo, Qingxiang; Yu, Shuqin

2006-06-15

The quenching of the triplets of 1,2-naphthoquinone (NQ) and 1,2-naphthoquinone-4-sulfonic acid sodium salt (NQS) by various electron and H-atom donors was investigated by laser flash photolysis measurement in acetonitrile and benzene. The results showed that the reactivities and configurations of 3NQ* (3NQS*) are governed by solvent polarity. All the quenching rate constants (kq) measured in benzene are larger than those in acetonitrile. The SO3Na substituent at the C-4 position of NQS makes 3NQS* more reactive than 3NQ* in electron/H-atom transfer reactions. Large differences of kq values were discovered in H-atom transfer reactions for alcohols and phenols, which can be explained by different H-abstraction mechanisms. Detection of radical cations of amines/anilines in time-resolved transient absorption spectra confirms an electron transfer mechanism. Triplets are identified as precursors of formed radical anions of NQ and NQS in photoinduced reactions. The dependence of electron transfer rate constants on the free energy changes (DeltaG) was treated by using the Rehm-Weller equation. For the four anilines with different substituents on the para or meta position of amidocyanogen, good correlation between log kq values with Hammett sigma constants testifies the correctness of empirical Hammett equation. Charge density distributions, adiabatic ionization/affinity potentials and redox potentials of NQ (NQS) and some quenchers were studied by quantum chemistry calculation.

Plasma Spray Synthesis Of Nanostructured V2O5 Films For Electrical Energy Storage

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

Nanda, Jagjit

We demonstrate for the first time, the synthesis of nanostructured vanadium pentoxide (V2O5) films and coatings using plasma spray technique. V2O5 has been used in several applications such as catalysts, super-capacitors and also as an electrode material in lithium ion batteries. In the present studies, V2O5 films were synthesized using liquid precursors (vanadium oxychloride and ammonium metavanadate) and powder suspension. In our approach, the precursors were atomized and injected radially into the plasma gun for deposition on the substrates. During the flight towards the substrate, the high temperature of the plasma plume pyrolyzes the precursor particles resulting into the desiredmore » film coatings. These coatings were then characterized using X-ray diffraction (XRD), scanning electron microscopy (SEM), Transmission electron microscopy (TEM) and Differential Scanning Calorimetry (DSC). Among the precursors, vanadium oxychloride gave the best results in terms of nanocrystalline and monophasic films. Spraying of commercial powder suspension yielded multi-phasic mixture in the films. Our approach enables deposition of large area coatings of high quality nanocrystalline films of V2O5 with controllable particle morphology. This has been optimized by means of control over precursor composition and plasma spray conditions. Initial electrochemical studies of V2O5 film electrodes show potential for energy storage studies.« less

Mulliken Hush elucidation of the encounter (precursor) complex in intermolecular electron transfer via self-exchange of tetracyanoethylene anion-radical

NASA Astrophysics Data System (ADS)

Rosokha, S. V.; Newton, M. D.; Head-Gordon, M.; Kochi, J. K.

2006-05-01

The paramagnetic [1:1] encounter complex (TCNE)2-rad is established as the important precursor in the kinetics and mechanism of electron-transfer for the self-exchange between tetracyanoethylene acceptor ( TCNE) and its radical-anion as the donor. Spectroscopic observation of the dimeric complex (TCNE)2-rad by its intervalence absorption band at the solvent-dependent wavelength of λIV ˜ 1500 nm facilitates the application of Mulliken-Hush theory which reveals the significant electronic interaction extant between the pair of cofacial TCNE moieties with the sizable coupling of HDA = 1000 cm -1. The transient existence of such an encounter complex provides the critical link in the electron-transfer kinetics by lowering the classical Marcus reorganization barrier by the amount of HDA in this strongly adiabatic system. Ab initio quantum-mechanical methods as applied to independent theoretical computations of both the reorganization energy ( λ) and the electronic coupling element ( HDA) confirm the essential correctness of the Mulliken-Hush formalism for fast electron transfer via strongly coupled donor/acceptor encounter complexes.

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

Kruska, Karen; Zhai, Ziqing; Bruemmer, Stephen M.

Due to its superior resistance to corrosion and stress corrosion cracking (SCC), high Cr, Ni-base Alloy 690 is now commonly used in pressurized water reactors (PWRs). Even though highly cold-worked (CW) Alloy 690 has been shown to be susceptible to SCC crack growth in PWR primary water environments, an open question remains whether SCC initiation was possible for these materials under constant load test conditions. Testing has been performed on a series of CW alloy 690 CRDM tubing specimens at constant load for up to 9,220 hours in 360°C simulated PWR primary water. A companion paper will discuss the overallmore » testing approach and describe results on different alloy 690 heats and cold work levels. The focus of the current paper is to illustrate the use of focused ion beam (FIB), scanning electron microscopy (SEM) and transmission electron microscopy (TEM) for the high-resolution investigation of precursor damage and intergranular (IG) crack nucleation in these specimens. Three-dimensional (3D) FIB/SEM imaging has been conducted on a series of grain boundary (GB) damage precursors, such as IG small cavities, local corrosion and even shallow cracks observed at the specimen surface. Contrast variations and EDS mapping were used to distinguish oxides, carbides and cavities from the matrix material. Nanometer-sized cavities were observed associated with GB carbides in the highly CW specimens. Shallow IG cracks were present in the 30%CW specimens and exhibited oxidized crack flanks and a higher density of cavities ahead of the oxide front in all cases. The shape and distribution of carbides and cavities in the plane of the cracked GBs was analyzed in 3D to gain a mechanistic understanding of the processes that may be leading to crack initiation in highly CW alloy 690.« less

Fabrication and Synthesis of Highly Ordered Nickel Cobalt Sulfide Nanowire-Grown Woven Kevlar Fiber/Reduced Graphene Oxide/Polyester Composites.

PubMed

Hazarika, Ankita; Deka, Biplab K; Kim, DoYoung; Roh, Hyung Doh; Park, Young-Bin; Park, Hyung Wook

2017-10-18

Well-aligned NiCo 2 S 4 nanowires, synthesized hydrothermally on the surface of woven Kevlar fiber (WKF), were used to fabricate composites with reduced graphene oxide (rGO) dispersed in polyester resin (PES) by means of vacuum-assisted resin transfer molding. The NiCo 2 S 4 nanowires were synthesized with three precursor concentrations. Nanowire growth was characterized using scanning electron microscopy, transmission electron microscopy, X-ray diffraction, and X-ray photoelectron spectroscopy. Hierarchical and high growth density of the nanowires led to exceptional mechanical properties of the composites. Compared with bare WKF/PES, the tensile strength and absorbed impact energy were enhanced by 96.2% and 92.3%, respectively, for WKF/NiCo 2 S 4 /rGO (1.5%)/PES. The synergistic effect of NiCo 2 S 4 nanowires and rGO in the fabricated composites improved the electrical conductivity of insulating WKF/PES composites, reducing the resistance to ∼10 3 Ω. Joule heating performance depended strongly on the precursor concentration of the nanowires and the presence of rGO in the composite. A maximum surface temperature of 163 °C was obtained under low-voltage (5 V) application. The Joule heating performance of the composites was demonstrated in a surface deicing experiment; we observed that 17 g of ice melted from the surface of the composite in 14 min under an applied voltage of 5 V at -28 °C. The excellent performance of WKF/NiCo 2 S 4 /rGO/PES composites shows great potential for aerospace structural applications requiring outstanding mechanical properties and Joule heating capability for deicing of surfaces.

Synthesis of Al₂Ca Dispersoids by Powder Metallurgy Using a Mg-Al Alloy and CaO Particles.

PubMed

Fujita, Junji; Umeda, Junko; Kondoh, Katsuyoshi

2017-06-28

The elemental mixture of Mg-6 wt %Al-1 wt %Zn-0.3 wt %Mn (AZ61B) alloy powder and CaO particles was consolidated by an equal-channel angular bulk mechanical alloying (ECABMA) process to form a composite precursor. Subsequently, the precursor was subjected to a heat treatment to synthesize fine Al₂Ca particles via a solid-state reaction between the Mg-Al matrix and CaO additives. Scanning electron microscopy-energy-dispersive spectroscopy (SEM-EDS) and electron probe micro-analysis on the precursor indicated that 4.7-at % Al atoms formed a supersaturated solid solution in the α-Mg matrix. Transmission electron microscopy-EDS and X-ray diffraction analyses on the AZ61B composite precursor with 10-vol % CaO particles obtained by heat treatment confirmed that CaO additives were thermally decomposed in the Mg-Al alloy, and the solid-soluted Ca atoms diffused along the α-Mg grain boundaries. Al atoms also diffused to the grain boundaries because of attraction to the Ca atoms resulting from a strong reactivity between Al and Ca. As a result, needle-like (Mg,Al)₂Ca intermetallics were formed as intermediate precipitates in the initial reaction stage during the heat treatment. Finally, the precipitates were transformed into spherical Al₂Ca particles by the substitution of Al atoms for Mg atoms in (Mg,Al)₂Ca after a long heat treatment.

Nonrelativistic grey S n -transport radiative-shock solutions

DOE PAGES

Ferguson, J. M.; Morel, J. E.; Lowrie, R. B.

2017-06-01

We present semi-analytic radiative-shock solutions in which grey Sn-transport is used to model the radiation, and we include both constant cross sections and cross sections that depend on temperature and density. These new solutions solve for a variable Eddington factor (VEF) across the shock domain, which allows for interesting physics not seen before in radiative-shock solutions. Comparisons are made with the grey nonequilibrium-diffusion radiative-shock solutions of Lowrie and Edwards [1], which assumed that the Eddington factor is constant across the shock domain. It is our experience that the local Mach number is monotonic when producing nonequilibrium-diffusion solutions, but that thismore » monotonicity may disappear while integrating the precursor region to produce Sn-transport solutions. For temperature- and density-dependent cross sections we show evidence of a spike in the VEF in the far upstream portion of the radiative-shock precursor. We show evidence of an adaptation zone in the precursor region, adjacent to the embedded hydrodynamic shock, as conjectured by Drake [2, 3], and also confirm his expectation that the precursor temperatures adjacent to the Zel’dovich spike take values that are greater than the downstream post-shock equilibrium temperature. We also show evidence that the radiation energy density can be nonmonotonic under the Zel’dovich spike, which is indicative of anti-diffusive radiation flow as predicted by McClarren and Drake [4]. We compare the angle dependence of the radiation flow for the Sn-transport and nonequilibriumdiffusion radiation solutions, and show that there are considerable differences in the radiation flow between these models across the shock structure. Lastly, we analyze the radiation flow to understand the cause of the adaptation zone, as well as the structure of the Sn-transport radiation-intensity solutions across the shock structure.« less

Nonrelativistic grey S n -transport radiative-shock solutions

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

Ferguson, J. M.; Morel, J. E.; Lowrie, R. B.

We present semi-analytic radiative-shock solutions in which grey Sn-transport is used to model the radiation, and we include both constant cross sections and cross sections that depend on temperature and density. These new solutions solve for a variable Eddington factor (VEF) across the shock domain, which allows for interesting physics not seen before in radiative-shock solutions. Comparisons are made with the grey nonequilibrium-diffusion radiative-shock solutions of Lowrie and Edwards [1], which assumed that the Eddington factor is constant across the shock domain. It is our experience that the local Mach number is monotonic when producing nonequilibrium-diffusion solutions, but that thismore » monotonicity may disappear while integrating the precursor region to produce Sn-transport solutions. For temperature- and density-dependent cross sections we show evidence of a spike in the VEF in the far upstream portion of the radiative-shock precursor. We show evidence of an adaptation zone in the precursor region, adjacent to the embedded hydrodynamic shock, as conjectured by Drake [2, 3], and also confirm his expectation that the precursor temperatures adjacent to the Zel’dovich spike take values that are greater than the downstream post-shock equilibrium temperature. We also show evidence that the radiation energy density can be nonmonotonic under the Zel’dovich spike, which is indicative of anti-diffusive radiation flow as predicted by McClarren and Drake [4]. We compare the angle dependence of the radiation flow for the Sn-transport and nonequilibriumdiffusion radiation solutions, and show that there are considerable differences in the radiation flow between these models across the shock structure. Lastly, we analyze the radiation flow to understand the cause of the adaptation zone, as well as the structure of the Sn-transport radiation-intensity solutions across the shock structure.« less

Model of electron pairs in electron-doped cuprates

NASA Astrophysics Data System (ADS)

Singh, R. J.; Khan, Shakeel

2016-07-01

In the order parameter of hole-doped cuprate superconductors in the pseudogap phase, two holes enter the order parameter from opposite sides and pass through various CuO2 cells jumping from one O2- to the other under the influence of magnetic field offered by the Cu2+ ions in that CuO2 cell and thus forming hole pairs. In the pseudogap phase of electron-doped cuprates, two electrons enter the order parameter at Cu2+ sites from opposite ends and pass from one Cu2+ site to the diagonally opposite Cu2+ site. Following this type of path, they are subjected to high magnetic fields from various Cu2+ ions in that cell. They do not travel from one Cu2+ site to the other along straight path but by helical path. As they pass through the diagonal, they face high to low to very high magnetic field. Therefore, frequency of helical motion and pitch goes on changing with the magnetic field. Just before reaching the Cu2+ ions at the exit points of all the cells, the pitch of the helical motion is enormously decreased and thus charge density at these sites is increased. So the velocity of electrons along the diagonal path is decreased. Consequently, transition temperature of electron-doped cuprates becomes less than that of hole-doped cuprates. Symmetry of the order parameter of the electron-doped cuprates has been found to be of 3dx2-y2 + iS type. It has been inferred that internal magnetic field inside the order parameter reconstructs the Fermi surface, which is requisite for superconductivity to take place. Electron pairs formed in the pseudogap phase are the precursors of superconducting order parameter when cooled below Tc.

Structure and dynamics in self-organized C60 fullerenes.

PubMed

Patnaik, Archita

2007-01-01

This manuscript on 'structure and dynamics in self-organized C60 fullerenes' has three sections dealing with: (A) pristine C60 aggregate structure and geometry in solvents of varying dielectric constant. Here, using positronium (Ps) as a fundamental probe which maps changes in the local electron density of the microenvironment, the onset concentration for stable C60 aggregate formation and its phase behavior is deduced from the specific interactions of the Ps atom with the surrounding. (B) A novel methanofullerene dyad, based on a hydrophobic (acceptor C60 moiety)-hydrophilic (bridge with benzene and ester functionalities)-hydrophobic (donor didodecyloxybenzene) network is chosen for investigation of characteristic self-assembly it undergoes leading to supramolecular aggregates. The pi-electronic amphiphile, necessitating a critical dielectric constant epsilon > or = 30 in binary THF-water mixtures, dictated the formation of bilayer vesicles as precursors for spherical fractal aggregates upon complete dyad extraction into a more polar water phase. (C) While the molecular orientation is dependent on the packing density, the ordering of the molecular arrangement, indispensable for self-assembly depends on the balance between the structures demanded by inter-molecular and molecule-substrate interactions. The molecular orientation in a monolayer affects the orientation in a multilayer, formed on the monolayer, suggesting the possibility of the latter to act as a template for controlling the structure of the three dimensionally grown self-assembled molecular aggregation. A systematic study on the electronic structure and orientation associated with C60 functionalized aminothiol self-assembled monolayers on Au(111) surface is presented using surface sensitive Ultra-Violet Photoelectron Spectroscopy (UPS) and C-K edge Near-Edge X-ray Absorption Fine Structure (NEXAFS) spectroscopy. The results revealed drastic modifications to d-band structure of Au(111) and the electronic structure was found sensitive towards the S-Au interface and the C60 end functional moiety with formation of localized sigma-(S-Au) and sigma(N-C) bonds, respectively. Upon binding C60 to the amine-terminated alkanethiol SAM, a drastically reduced HOMO-LUMO gap of 2.7 eV as compared to a large electronic gap of approximately 8 eV in alkanethiols enables the SAM to be a potential electron transport medium.

Preparation of activated carbon monolith by application of phenolic resins as carbon precursors

NASA Astrophysics Data System (ADS)

Sajad, Mehran; Kazemzad, Mahmood; Hosseinnia, Azarmidokht

2014-04-01

In the current work, activated carbon monoliths have been prepared by application of different phenolic hydrocarbons namely catechol and resorcinol as carbon precursors. For synthesis of carbon monolith, the precursors have been mixed with Genapol PF-10 as template and then polymerized in the presence of lysine as catalyst. Then the polymerized monolith carbonized in inert atmosphere at 700°C and activated by water steam at 550°C. It was found that resorcinol polymerization is easier than catechol and occurred at 90°C while for polymerization of catechol elevated temperature of 120°C at hydrothermal condition is necessary. The prepared activated carbon samples have been characterized by various analysis methods including scanning electron microscopy (SEM), surface area measurement, and transmission electron microscopy (TEM). The adsorptions of three different aromatic hydrocarbons by the prepared activated carbon samples have also been investigated by high performance liquid chromatography (HPLC) and UV-Vis spectroscopy. It was found that carbon monolith prepared by catechol as carbon precursor has higher adsorpability and strength in comparison with the other sample. The higher performance of carbon monolith prepared by catechol can be associated with its higher active sites in comparison with resorcinol.

Limitations of Cs3Bi2I9 as lead-free photovoltaic absorber materials.

PubMed

Ghosh, Biplab; Wu, Bo; Mulmudi, Hemant Kumar; Guet, Claude; Weber, Klaus; Sum, Tze Chien; Mhaisalkar, Subodh G; Mathews, Nripan

2018-01-17

Lead (Pb) halide perovskites have attracted tremendous attention in recent years due to their rich optoelectronic properties, which have resulted in more than 22% power conversion efficient photovoltaics. Nevertheless, Pb-metal toxicity remains a huge hurdle for extensive applications of these compounds. Thus, alternative compounds with similar optoelectronic properties need to be developed. Bismuth possesses similar electronic structure as that of lead with the presence of ns2 electrons that exhibit rich structural variety as well as interesting optical and electronic properties. Herein, we critically assess Cs3Bi2I9 as a candidate for thin-film solar cell absorber. Despite a reasonable optical bandgap (~2eV) and absorption coefficient, the power conversion efficiency of the Cs3Bi2I9 mesoscopic solar cells was found to be severely lacking, limited by poor photocurrent density. The efficiency of the Cs3Bi2I9 solar cell can be slightly improved by changing the stoichiometry of the precursor solutions. We have investigated the possible reasons behind the poor performance of Cs3Bi2I9 by transient absorption and luminescence spectroscopy. Comparison between thin-films and single crystals highlights the presence of intrinsic defects in thin-films which act as nonradiative recombination centers.

Three-dimensional morphology of GaP-GaAs nanowires revealed by transmission electron microscopy tomography.

PubMed

Verheijen, Marcel A; Algra, Rienk E; Borgström, Magnus T; Immink, George; Sourty, Erwan; Enckevort, Willem J P van; Vlieg, Elias; Bakkers, Erik P A M

2007-10-01

We have investigated the morphology of heterostructured GaP-GaAs nanowires grown by metal-organic vapor-phase epitaxy as a function of growth temperature and V/III precursor ratio. The study of heterostructured nanowires with transmission electron microscopy tomography allowed the three-dimensional morphology to be resolved, and discrimination between the effect of axial (core) and radial (shell) growth on the morphology. A temperature- and precursor-dependent structure diagram for the GaP nanowire core morphology and the evolution of the different types of side facets during GaAs and GaP shell growth were constituted.

Production of jet fuel precursor monoterpenoids from engineered Escherichia coli: Production of Jet Fuel Precursor Monoterpenoids

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

Mendez-Perez, Daniel; Alonso-Gutierrez, Jorge; Hu, Qijun

Monoterpenes (C 10 isoprenoids) are the main components of essential oils and are possible precursors for many commodity chemicals and high energy density fuels. Monoterpenes are synthesized from geranyl diphosphate (GPP), which is also the precursor for the biosynthesis of farnesyl diphosphate (FPP). FPP biosynthesis diverts the carbon flux from monoterpene production to C 15 products and quinone biosynthesis. In this study, we tested a chromosomal mutation of Escherichia coli's native FPP synthase (IspA) to improve GPP availability for the production of monoterpenes using a heterologous mevalonate pathway. Monoterpene production at high levels required not only optimization of GPP productionmore » but also a basal level of FPP to maintain growth. The optimized strains produced two jet fuel precursor monoterpenoids 1,8-cineole and linalool at the titer of 653 mg/L and 505 mg/L, respectively, in batch cultures with 1% glucose. The engineered strains developed in this work provide useful resources for the production of high-value monoterpenes.« less

Production of jet fuel precursor monoterpenoids from engineered Escherichia coli: Production of Jet Fuel Precursor Monoterpenoids

DOE PAGES

Mendez-Perez, Daniel; Alonso-Gutierrez, Jorge; Hu, Qijun; ...

2017-05-18

Monoterpenes (C 10 isoprenoids) are the main components of essential oils and are possible precursors for many commodity chemicals and high energy density fuels. Monoterpenes are synthesized from geranyl diphosphate (GPP), which is also the precursor for the biosynthesis of farnesyl diphosphate (FPP). FPP biosynthesis diverts the carbon flux from monoterpene production to C 15 products and quinone biosynthesis. In this study, we tested a chromosomal mutation of Escherichia coli's native FPP synthase (IspA) to improve GPP availability for the production of monoterpenes using a heterologous mevalonate pathway. Monoterpene production at high levels required not only optimization of GPP productionmore » but also a basal level of FPP to maintain growth. The optimized strains produced two jet fuel precursor monoterpenoids 1,8-cineole and linalool at the titer of 653 mg/L and 505 mg/L, respectively, in batch cultures with 1% glucose. The engineered strains developed in this work provide useful resources for the production of high-value monoterpenes.« less

Influence of calcium precursors on the morphology and crystallinity of sol gel-derived hydroxyapatite nanoparticles

NASA Astrophysics Data System (ADS)

Vijayalakshmi Natarajan, U.; Rajeswari, S.

2008-10-01

Nanosized hydroxyapatite (HAP) particles were prepared by sol-gel method from the water-based solution of calcium and phosphorus precursor. In this study, two calcium precursors such as calcium nitrate tetrahydrate and calcium acetate were chosen as calcium precursors. The influence of aging period, pH, viscosity and sintering temperature on crystallinity and morphology of the HAP particles were investigated for the two calcium precursors with triethyl phosphate precursor. The morphology of nano-HAP towards phosphorous precursor was dependent on the type of calcium precursor used. The HAP prepared from calcium nitrate and triethyl phosphate was spherically shaped whereas the one from calcium acetate was found to be fibrous in structure. Both HAPs were stable up to 1200 °C and their crystallinity increased with respect to the sintering temperature. The obtained sample was characterized through X-ray diffraction (XRD), P 31 nuclear magnetic resonance (NMR), scanning electronic microscopy (SEM) and TEM analysis. The sol derived from the optimized aging period for the two different calcium precursors was coated on 316L stainless-steel (SS) implant and its corrosion resistivity during long-term implantation was studied by cyclic polarization in Ringer's solution. Both HAPs have their own desirable qualities and were found to be corrosion resistive.

Multicomponent density functional theory embedding formulation.

PubMed

Culpitt, Tanner; Brorsen, Kurt R; Pak, Michael V; Hammes-Schiffer, Sharon

2016-07-28

Multicomponent density functional theory (DFT) methods have been developed to treat two types of particles, such as electrons and nuclei, quantum mechanically at the same level. In the nuclear-electronic orbital (NEO) approach, all electrons and select nuclei, typically key protons, are treated quantum mechanically. For multicomponent DFT methods developed within the NEO framework, electron-proton correlation functionals based on explicitly correlated wavefunctions have been designed and used in conjunction with well-established electronic exchange-correlation functionals. Herein a general theory for multicomponent embedded DFT is developed to enable the accurate treatment of larger systems. In the general theory, the total electronic density is separated into two subsystem densities, denoted as regular and special, and different electron-proton correlation functionals are used for these two electronic densities. In the specific implementation, the special electron density is defined in terms of spatially localized Kohn-Sham electronic orbitals, and electron-proton correlation is included only for the special electron density. The electron-proton correlation functional depends on only the special electron density and the proton density, whereas the electronic exchange-correlation functional depends on the total electronic density. This scheme includes the essential electron-proton correlation, which is a relatively local effect, as well as the electronic exchange-correlation for the entire system. This multicomponent DFT-in-DFT embedding theory is applied to the HCN and FHF(-) molecules in conjunction with two different electron-proton correlation functionals and three different electronic exchange-correlation functionals. The results illustrate that this approach provides qualitatively accurate nuclear densities in a computationally tractable manner. The general theory is also easily extended to other types of partitioning schemes for multicomponent systems.

Multicomponent density functional theory embedding formulation

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

Culpitt, Tanner; Brorsen, Kurt R.; Pak, Michael V.

Multicomponent density functional theory (DFT) methods have been developed to treat two types of particles, such as electrons and nuclei, quantum mechanically at the same level. In the nuclear-electronic orbital (NEO) approach, all electrons and select nuclei, typically key protons, are treated quantum mechanically. For multicomponent DFT methods developed within the NEO framework, electron-proton correlation functionals based on explicitly correlated wavefunctions have been designed and used in conjunction with well-established electronic exchange-correlation functionals. Herein a general theory for multicomponent embedded DFT is developed to enable the accurate treatment of larger systems. In the general theory, the total electronic density ismore » separated into two subsystem densities, denoted as regular and special, and different electron-proton correlation functionals are used for these two electronic densities. In the specific implementation, the special electron density is defined in terms of spatially localized Kohn-Sham electronic orbitals, and electron-proton correlation is included only for the special electron density. The electron-proton correlation functional depends on only the special electron density and the proton density, whereas the electronic exchange-correlation functional depends on the total electronic density. This scheme includes the essential electron-proton correlation, which is a relatively local effect, as well as the electronic exchange-correlation for the entire system. This multicomponent DFT-in-DFT embedding theory is applied to the HCN and FHF{sup −} molecules in conjunction with two different electron-proton correlation functionals and three different electronic exchange-correlation functionals. The results illustrate that this approach provides qualitatively accurate nuclear densities in a computationally tractable manner. The general theory is also easily extended to other types of partitioning schemes for multicomponent systems.« less

Surface defects on the Gd{sub 2}Zr{sub 2}O{sub 7} oxide films grown on textured NiW technical substrates by chemical solution method

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

Zhao, Y., E-mail: yuezhao@sjtu.edu.cn

2017-02-15

Epitaxial growth of oxide thin films has attracted much interest because of their broad applications in various fields. In this study, we investigated the microstructure of textured Gd{sub 2}Zr{sub 2}O{sub 7} films grown on (001)〈100〉 orientated NiW alloy substrates by a chemical solution deposition (CSD) method. The aging effect of precursor solution on defect formation was thoroughly investigated. A slight difference was observed between the as-obtained and aged precursor solutions with respect to the phase purity and global texture of films prepared using these solutions. However, the surface morphologies are different, i.e., some regular-shaped regions (mainly hexagonal or dodecagonal) weremore » observed on the film prepared using the as-obtained precursor, whereas the film prepared using the aged precursor exhibits a homogeneous structure. Electron backscatter diffraction and scanning electron microscopy analyses showed that the Gd{sub 2}Zr{sub 2}O{sub 7} grains present within the regular-shaped regions are polycrystalline, whereas those present in the surrounding are epitaxial. Some polycrystalline regions ranging from several micrometers to several tens of micrometers grew across the NiW grain boundaries underneath. To understand this phenomenon, the properties of the precursors and corresponding xerogel were studied by Fourier transform infrared spectroscopy and coupled thermogravimetry/differential thermal analysis. The results showed that both the solutions mainly contain small Gd−Zr−O clusters obtained by the reaction of zirconium acetylacetonate with propionic acid during the precursor synthesis. The regular-shaped regions were probably formed by large Gd−Zr−O frameworks with a metastable structure in the solution with limited aging time. This study demonstrates the importance of the precise control of chemical reaction path to enhance the stability and homogeneity of the precursors of the CSD route. - Highlights: •We investigate microstructure of Gd{sub 2}Zr{sub 2}O{sub 7} films grown by a chemical solution route. •The aging effect of precursor solution on formation of surface defect was thoroughly studied. •Gd−Zr−O clusters are present in the precursor solutions.« less

Normal and abnormal evolution of argon metastable density in high-density plasmas

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

Seo, B. H.; Kim, J. H., E-mail: jhkim86@kriss.re.kr; You, S. J., E-mail: sjyou@cnu.ac.kr

2015-05-15

A controversial problem on the evolution of Ar metastable density as a function of electron density (increasing trend versus decreasing trend) was resolved by discovering the anomalous evolution of the argon metastable density with increasing electron density (discharge power), including both trends of the metastable density [Daltrini et al., Appl. Phys. Lett. 92, 061504 (2008)]. Later, by virtue of an adequate physical explanation based on a simple global model, both evolutions of the metastable density were comprehensively understood as part of the abnormal evolution occurring at low- and high-density regimes, respectively, and thus the physics behind the metastable evolution hasmore » seemed to be clearly disclosed. In this study, however, a remarkable result for the metastable density behavior with increasing electron density was observed: even in the same electron density regime, there are both normal and abnormal evolutions of metastable-state density with electron density depending on the measurement position: The metastable density increases with increasing electron density at a position far from the inductively coupled plasma antenna but decreases at a position close to the antenna. The effect of electron temperature, which is spatially nonuniform in the plasma, on the electron population and depopulation processes of Argon metastable atoms with increasing electron density is a clue to understanding the results. The calculated results of the global model, including multistep ionization for the argon metastable state and measured electron temperature, are in a good agreement with the experimental results.« less

Experimental and theoretical rationalization of the growth mechanism of silicon quantum dots in non-stoichiometric SiN x : role of chlorine in plasma enhanced chemical vapour deposition.

PubMed

Mon-Pérez, E; Salazar, J; Ramos, E; Salazar, J Santoyo; Suárez, A López; Dutt, A; Santana, G; Monroy, B Marel

2016-11-11

Silicon quantum dots (Si-QDs) embedded in an insulator matrix are important from a technological and application point of view. Thus, being able to synthesize them in situ during the matrix growth process is technologically advantageous. The use of SiH 2 Cl 2 as the silicon precursor in the plasma enhanced chemical vapour deposition (PECVD) process allows us to obtain Si-QDs without post-thermal annealing. Foremost in this work, is a theoretical rationalization of the mechanism responsible for Si-QD generation in a film including an analysis of the energy released by the extraction of HCl and the insertion of silylene species into the terminal surface bonds. From the results obtained using density functional theory (DFT), we propose an explanation of the mechanism responsible for the formation of Si-QDs in non-stoichiometric SiN x starting from chlorinated precursors in a PECVD system. Micrograph images obtained through transmission electron microscopy confirmed the presence of Si-QDs, even in nitrogen-rich (N-rich) samples. The film stoichiometry was controlled by varying the growth parameters, in particular the NH 3 /SiH 2 Cl 2 ratio and hydrogen dilution. Experimental and theoretical results together show that using a PECVD system, along with chlorinated precursors it is possible to obtain Si-QDs at a low substrate temperature without annealing treatment. The optical property studies carried out in the present work highlight the prospects of these thin films for down shifting and as an antireflection coating in silicon solar cells.

TOPICAL REVIEW: Review of a chemical approach to YBa2Cu3O7-x-coated superconductors—metalorganic deposition using trifluoroacetates

NASA Astrophysics Data System (ADS)

Araki, Takeshi; Hirabayashi, Izumi

2003-11-01

Large-area, uniform, high critical current density (Jc) YBa2Cu3O7-x (YBCO) superconductor films are now routinely obtained by metalorganic deposition using trifluoroacetates (TFA-MOD). This method does not require any expensive vacuum apparatus at any time during the whole process. Thus, TFA-MOD is regarded as one of the most suitable candidates for fabricating a YBCO tape for many high-power applications. This method originated from an electron beam process using BaF2 developed by Mankiewich et al. Afterwards, Gupta et al reported using TFA-MOD to prepare a similar precursor film. These two ex situ processes used fluorides instead of BaCO3 to avoid the fatal deterioration in Jc, which is caused in the resulting films through metal carboxylic groups. Fluorides not only avoid such deterioration but also lead to perfectly c-axis-oriented epitaxial crystal growth. In conventional metalorganic deposition, nucleation in the precursor film causes random orientation in the resulting film. However, in TFA-MOD, nanocrystallites in the precursor film never cause such disorder. Furthermore, during the firing process of TFA-MOD, water and HF gas diffuse quickly between the film surface and growth front of the YBCO layer. This diffusion never limits the growth rate of YBCO. What distinguishes TFA-MOD from conventional metalorganic deposition? What happens during heat treatment? In this paper, we discuss all the TFA-MOD processes and the peculiar growth scheme of the YBCO layer in TFA-MOD using the model of a quasi-liquid network. In addition, we review the history of TFA-MOD and recent results and discuss the prospects of future applications.

Preparation of TiO2-SiO2 via sol-gel method: Effect of Silica precursor on Catalytic and Photocatalytic properties

NASA Astrophysics Data System (ADS)

Fatimah, I.

2017-02-01

TiO2-SiO2have been synthesized by the sol-gel method from titanium isopropoxide and varied silica precursors: tetraethyl orthosilicate and tetra methyl ortho silicate. To study the effect of the precursor, prepared materials were characterized by X-ray diffraction, scanning electron microscopy, Diffuse Reflectance UV-vis optical absorption, and also gas sorption analysis. XRD patterns showed the formation of TiO2 anatase in the TiO2-SiO2 composite with different crystallite size from different silica precursor as well as the different surface morphology. The DRUV-vis absorption spectra exhibit similar band gap energy correspond to 3.21eV value while the surface area, pore volume and pore radius of the materials seems to be affected by the precursor. The higher specific surface area contributes to give the enhanced activity in phenol hydroxylation and methylene blue photodegradation.

Synthesis and Characterization of the First Liquid Single Source Precursors for the Deposition of Ternary Chalcopyrite (CuInS2) Thin Film Materials

NASA Technical Reports Server (NTRS)

Banger, Kulbinder K.; Cowen, Jonathan; Hepp, Aloysius

2002-01-01

Molecular engineering of ternary single source precursors based on the [{PBu3}2Cu(SR')2In(SR')2] architecture have afforded the first liquid CIS ternary single source precursors (when R = Et, n-Pr), which are suitable for low temperature deposition (< 350 C). Thermogravimetric analyses (TGA) and modulated-differential scanning calorimetry (DSC) confirm their liquid phase and reduced stability. X-ray diffraction studies, energy dispersive analyzer (EDS), and scanning electron microscopy (SEM) support the formation of the single-phase chalcopyrite CuInS2 at low temperatures.

α-Fe2O3 nanosheet-assembled hierarchical hollow mesoporous microspheres: Microwave-assisted solvothermal synthesis and application in photocatalysis.

PubMed

Sun, Tuan-Wei; Zhu, Ying-Jie; Qi, Chao; Ding, Guan-Jun; Chen, Feng; Wu, Jin

2016-02-01

α-Fe2O3 nanosheet-assembled hierarchical hollow mesoporous microspheres (HHMSs) were prepared by thermal transformation of nanosheet-assembled hierarchical hollow mesoporous microspheres of a precursor. The precursor was rapidly synthesized using FeCl3·6H2O as the iron source, ethanolamine (EA) as the alkali source, and ethylene glycol (EG) as the solvent by the microwave-assisted solvothermal method. The samples were characterized by X-ray powder diffraction (XRD), thermogravimetric (TG) analysis, Fourier transform infrared (FTIR) spectroscopy, scanning electron microscopy (SEM), transmission electron microscopy (TEM) and nitrogen adsorption-desorption isotherm. The effects of the microwave solvothermal temperature and EA amount on the morphology of the precursor were investigated. The as-prepared α-Fe2O3 HHMSs exhibit a good photocatalytic activity for the degradation of salicylic acid, and are promising for the application in wastewater treatment. Copyright © 2015 Elsevier Inc. All rights reserved.

Selective ultrafast probing of transient hot chemisorbed and precursor states of CO on Ru(0001).

PubMed

Beye, M; Anniyev, T; Coffee, R; Dell'Angela, M; Föhlisch, A; Gladh, J; Katayama, T; Kaya, S; Krupin, O; Møgelhøj, A; Nilsson, A; Nordlund, D; Nørskov, J K; Öberg, H; Ogasawara, H; Pettersson, L G M; Schlotter, W F; Sellberg, J A; Sorgenfrei, F; Turner, J J; Wolf, M; Wurth, W; Oström, H

2013-05-03

We have studied the femtosecond dynamics following optical laser excitation of CO adsorbed on a Ru surface by monitoring changes in the occupied and unoccupied electronic structure using ultrafast soft x-ray absorption and emission. We recently reported [M. Dell'Angela et al. Science 339, 1302 (2013)] a phonon-mediated transition into a weakly adsorbed precursor state occurring on a time scale of >2 ps prior to desorption. Here we focus on processes within the first picosecond after laser excitation and show that the metal-adsorbate coordination is initially increased due to hot-electron-driven vibrational excitations. This process is faster than, but occurs in parallel with, the transition into the precursor state. With resonant x-ray emission spectroscopy, we probe each of these states selectively and determine the respective transient populations depending on optical laser fluence. Ab initio molecular dynamics simulations of CO adsorbed on Ru(0001) were performed at 1500 and 3000 K providing insight into the desorption process.

Copolymer semiconductors comprising thiazolothiazole or benzobisthiazole, or benzobisoxazole electron acceptor subunits, and electron donor subunits, and their uses in transistors and solar cells

DOEpatents

Jenekhe, Samson A; Subramaniyan, Selvam; Ahmed, Eilaf; Xin, Hao; Kim, Felix Sunjoo

2014-10-28

The inventions disclosed, described, and/or claimed herein relate to copolymers comprising copolymers comprising electron accepting A subunits that comprise thiazolothiazole, benzobisthiazole, or benzobisoxazoles rings, and electron donating subunits that comprise certain heterocyclic groups. The copolymers are useful for manufacturing organic electronic devices, including transistors and solar cells. The invention also relates to certain synthetic precursors of the copolymers. Methods for making the copolymers and the derivative electronic devices are also described.

Treatment of surfaces with low-energy electrons

NASA Astrophysics Data System (ADS)

Frank, L.; Mikmeková, E.; Lejeune, M.

2017-06-01

Electron-beam-induced deposition of various materials from suitable precursors has represented an established branch of nanotechnology for more than a decade. A specific alternative is carbon deposition on the basis of hydrocarbons as precursors that has been applied to grow various nanostructures including masks for subsequent technological steps. Our area of study was unintentional electron-beam-induced carbon deposition from spontaneously adsorbed hydrocarbon molecules. This process traditionally constitutes a challenge for scanning electron microscopy practice preventing one from performing any true surface studies outside an ultrahigh vacuum and without in-situ cleaning of samples, and also jeopardising other electron-optical devices such as electron beam lithographs. Here we show that when reducing the energy of irradiating electrons sufficiently, the e-beam-induced deposition can be converted to e-beam-induced release causing desorption of hydrocarbons and ultimate cleaning of surfaces in both an ultrahigh and a standard high vacuum. Using series of experiments with graphene samples, we demonstrate fundamental features of e-beam-induced desorption and present results of checks for possible radiation damage using Raman spectroscopy that led to optimisation of the electron energy for damage-free cleaning. The method of preventing carbon contamination described here paves the way for greatly enhanced surface sensitivity of imaging and substantially reduced demands on vacuum systems for nanotechnological applications.

Synthesis of nano-sized lithium cobalt oxide via a sol-gel method

NASA Astrophysics Data System (ADS)

Li, Guangfen; Zhang, Jing

2012-07-01

In this study, nano-structured LiCoO2 thin film were synthesized by coupling a sol-gel process with a spin-coating method using polyacrylic acid (PAA) as chelating agent. The optimized conditions for obtaining a better gel formulation and subsequent homogenous dense film were investigated by varying the calcination temperature, the molar mass of PAA, and the precursor's molar ratios of PAA, lithium, and cobalt ions. The gel films on the silicon substrate surfaces were deposited by multi-step spin-coating process for either increasing the density of the gel film or adjusting the quantity of PAA in the film. The gel film was calcined by an optimized two-step heating procedure in order to obtain regular nano-structured LiCoO2 materials. Both atomic force microscopy (AFM) and scanning electron microscopy (SEM) were utilized to analyze the crystalline and the morphology of the films, respectively.

Beam-plasma instabilities and the beam-plasma discharge

NASA Technical Reports Server (NTRS)

Kellogg, P. J.; Boswell, R. W.

1986-01-01

Using a new waves on magnetized beams and turbulence (WOMBAT) 0-450 eV electron gun, measurements bearing on the generation of beam-plasma discharge (BPD) are made. The new gun has a narrower divergence angle than the old, and the BPD ignition current is found to be proportional to the cross-sectional area of the plasma. The high-frequency instabilities are identified with the two Trivelpiece-Gould modes, (1959). The upper frequency is identified as a Cerenkov resonance with the upper Trivelpiece-Gould mode, and the lower frequency with a cyclotron resonance with the lower mode, in agreement with theoretical expectations. Convective growth rates are found to be small. A mechanism involving the conversion of a convective instability to an absolute one by trapping of the unstable waves in the density perturbations of the low-frequency waves, is suggested for the low-frequency wave control of the onset of the high frequency precursors to the BPD.

Green Synthesis of Ag-Cu Nanoalloys Using Opuntia ficus- indica

NASA Astrophysics Data System (ADS)

Rocha-Rocha, O.; Cortez-Valadez, M.; Hernández-Martínez, A. R.; Gámez-Corrales, R.; Alvarez, Ramón A. B.; Britto-Hurtado, R.; Delgado-Beleño, Y.; Martinez-Nuñez, C. E.; Pérez-Rodríguez, A.; Arizpe-Chávez, H.; Flores-Acosta, M.

2017-02-01

Bimetallic Ag/Cu nanoparticles have been obtained by green synthesis using Opuntia ficus- indica plant extract. Two synthesis methods were applied to obtain nanoparticles with core-shell and Janus morphologies by reversing the order of precursors. Transmission electronic microscopy revealed size of 10 nm and 20 nm for the core-shell and Janus nanoparticles, respectively. Other small particles with size of up to 2 nm were also observed. Absorption bands attributed to surface plasmon resonance were detected at 440 nm and 500 nm for the core-shell and Janus nanoparticles, respectively. Density functional theory predicted a breathing mode type (BMT) located at low wavenumber due to small, low-energy clusters of (AgCu) n with n = 2 to 9, showing a certain correlation with the experimental one (at 220 cm-1). The dependence of the BMT on the number of atoms constituting the cluster is also studied.

Synthesis And Characterization Of Reduced Size Ferrite Reinforced Polymer Composites

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

Borah, Subasit; Bhattacharyya, Nidhi S.

2008-04-24

Small sized Co{sub 1-x}Ni{sub x}Fe{sub 2}O{sub 4} ferrite particles are synthesized by chemical route. The precursor materials are annealed at 400, 600 and 800 C. The crystallographic structure and phases of the samples are characterized by X-ray diffraction (XRD). The annealed ferrite samples crystallized into cubic spinel structure. Transmission Electron Microscopy (TEM) micrographs show that the average particle size of the samples are <20 nm. Particulate magneto-polymer composite materials are fabricated by reinforcing low density polyethylene (LDPE) matrix with the ferrite samples. The B-H loop study conducted at 10 kHz on the toroid shaped composite samples shows reduction in magneticmore » losses with decrease in size of the filler sample. Magnetic losses are detrimental for applications of ferrite at high powers. The reduction in magnetic loss shows a possible application of Co-Ni ferrites at high microwave power levels.« less

Comparison of photovoltaic properties of TiO2 electrodes prepared with nanoparticles and nanorods.

PubMed

Nam, Sang-Hun; Ju, Dong-Woo; Boo, Jin-Hyo

2014-12-01

In this report, single crystalline rutile TiO2 nanoparticles and nanorods were synthesized via the hydrothermal method using titanium tetra-isopropoxide as a precursor then, these were coated on top of a fluorine-doped tin oxide (FTO) substrate by using a doctor blade and direct deposition, respectively. Consequently, TiO2 nanorods-based dye-sensitized solar cells (DSSC) exhibit a J(sc) of 3.37 mA/cm2, a V(oc) of 0.82 V and fill factor of 60.1% with an overall conversion efficiency of 1.66%. This result shows an increase of around 38% for current density and 35% for conversion efficiency. Also, with respect to the impedance data, TiO2 nanorods-based DSSCs had smaller semicircles than did the nanoparticles-based DSSCs. These results demonstrate that the nanorod structure can have fast electron transport and reduced charge recombination.

Fabrication of superconducting nanowires from ultrathin MgB2 films via focused ion beam milling

NASA Astrophysics Data System (ADS)

Zhang, Chen; Wang, Da; Liu, Zheng-Hao; Zhang, Yan; Ma, Ping; Feng, Qing-Rong; Wang, Yue; Gan, Zi-Zhao

2015-02-01

High quality superconducting nanowires were fabricated from ultrathin MgB2 films by a focused ion beam milling technique. The precursor MgB2 films in 10 nm thick were grown on MgO substrates by using a hybrid physical-chemical vapor deposition method. The nanowires, in widths of about 300-600 nm and lengths of 1 or 10 μm, showed high superconducting critical temperatures (Tc's) above 34 K and narrow superconducting transition widths (ΔTc's) of 1-3 K. The superconducting critical current density Jc of the nanowires was above 5 × 107 A/cm2 at 20 K. The high Tc, narrow ΔTc, and high Jc of the nanowires offered the possibility of making MgB2-based nano-devices such as hot-electron bolometers and superconducting nanowire single-photon detectors with high operating temperatures at 15-20 K.

Growth of tungsten oxide nanostructures by chemical solution deposition

NASA Astrophysics Data System (ADS)

Jin, L. H.; Bai, Y.; Li, C. S.; Wang, Y.; Feng, J. Q.; Lei, L.; Zhao, G. Y.; Zhang, P. X.

2018-05-01

Tungsten oxide nanostructures were fabricated on LaAlO3 (00l) substrates by a simple chemical solution deposition. The decomposition behavior and phase formation of ammonium tungstate precursor were characterized by thermal analysis and X-ray diffraction. Moreover, the morphology and chemical state of nanostructures were analyzed by scanning electron microscopy, atomic force microscopy and X-ray photoelectron spectra. The effects of crystallization temperature on the formation of nanodots and nanowires were investigated. The results indicated that the change of nanostructures had close relationship with the crystallization temperature during the chemical solution deposition process. Under higher crystallization temperature, the square-like dots transformed into the dome-like nanodots and nanowires. Moreover high density well-ordered nanodots could be obtained on the substrate with the further increase of crystallization temperature. It also suggested that this simple chemical solution process could be used to adjust the nanostructures of tungsten oxide compounds on substrate.

Low Temperature Metal Free Growth of Graphene on Insulating Substrates by Plasma Assisted Chemical Vapor Deposition

PubMed Central

Muñoz, R.; Munuera, C.; Martínez, J. I.; Azpeitia, J.; Gómez-Aleixandre, C.; García-Hernández, M.

2016-01-01

Direct growth of graphene films on dielectric substrates (quartz and silica) is reported, by means of remote electron cyclotron resonance plasma assisted chemical vapor deposition r-(ECR-CVD) at low temperature (650°C). Using a two step deposition process- nucleation and growth- by changing the partial pressure of the gas precursors at constant temperature, mostly monolayer continuous films, with grain sizes up to 500 nm are grown, exhibiting transmittance larger than 92% and sheet resistance as low as 900 Ω·sq-1. The grain size and nucleation density of the resulting graphene sheets can be controlled varying the deposition time and pressure. In additon, first-principles DFT-based calculations have been carried out in order to rationalize the oxygen reduction in the quartz surface experimentally observed. This method is easily scalable and avoids damaging and expensive transfer steps of graphene films, improving compatibility with current fabrication technologies. PMID:28070341

Three-dimensional polypyrrole-derived carbon nanotube framework for dye adsorption and electrochemical supercapacitor

NASA Astrophysics Data System (ADS)

Xin, Shengchang; Yang, Na; Gao, Fei; Zhao, Jing; Li, Liang; Teng, Chao

2017-08-01

Three-dimensional carbon nanotube frameworks have been prepared via pyrolysis of polypyrrole nanotube aerogels that are synthesized by the simultaneous self-degraded template synthesis and hydrogel assembly followed by freeze-drying. The microstructure and composition of the materials are investigated by thermal gravimetric analysis, Raman spectrum, X-ray photoelectron spectroscopy, transmission electron microscopy, and specific surface analyzer. The results confirm the formation of three-dimensional carbon nanotube frameworks with low density, high mechanical properties, and high specific surface area. Compared with PPy aerogel precursor, the as-prepared three-dimensional carbon nanotube frameworks exhibit outstanding adsorption capacity towards organic dyes. Moreover, electrochemical tests show that the products possess high specific capacitance, good rate capability and excellent cycling performance with no capacitance loss over 1000 cycles. These characteristics collectively indicate the potential of three-dimensional polypyrrole-derived carbon nanotube framework as a promising macroscopic device for the applications in environmental and energy storages.

Electron temperatures within magnetic clouds between 2 and 4 AU: Voyager 2 observations

NASA Astrophysics Data System (ADS)

Sittler, E. C.; Burlaga, L. F.

1998-08-01

We have performed an analysis of Voyager 2 plasma electron observations within magnetic clouds between 2 and 4 AU identified by Burlaga and Behannon [1982]. The analysis has been confined to three of the magnetic clouds identified by Burlaga and Behannon that had high-quality data. The general properties of the plasma electrons within a magnetic cloud are that (1) the moment electron temperature anticorrelates with the electron density within the cloud, (2) the ratio Te/Tp tends to be >1, and (3) on average, Te/Tp~7.0. All three results are consistent with previous electron observations within magnetic clouds. Detailed analyses of the core and halo populations within the magnetic clouds show no evidence of either an anticorrelation between the core temperature TC and the electron density Ne or an anticorrelation between the halo temperature TH and the electron density. Within the magnetic clouds the halo component can contribute more than 50% of the electron pressure. The anticorrelation of Te relative to Ne can be traced to the density of the halo component relative to the density of the core component. The core electrons dominate the electron density. When the density goes up, the halo electrons contribute less to the electron pressure, so we get a lower Te. When the electron density goes down, the halo electrons contribute more to the electron pressure, and Te goes up. We find a relation between the electron pressure and density of the form Pe=αNeγ with γ~0.5.

Catalysts based on PdO_ZrO2 in the hydrodechlorination reaction of chlorobenzene

NASA Astrophysics Data System (ADS)

Otroshchenko, T. P.; Turakulova, A. O.; Lokteva, E. S.; Golubina, E. V.; Lunin, V. V.

2015-07-01

The possibility of using mixed oxides of palladium and zirconium obtained with biotemplates (cellulose and wood pulp) as the precursor of catalysts for the hydrodechlorination of chlorobenzene is analyzed. The properties of the samples are studied by means of scanning electron microscopy (SEM), transmission electron microscopy (TEM), the Brunauer-Emmet-Teller (BET) method, and temperature-programmed reduction (TPR). They are then compared to the properties of a supported analogue. The biomorphic precursors are characterized by high porosity and include micropores, mesopores, and macropores; the results from TPR reveal the presence in the precursors of several forms of PdO that differ by reduction temperature. It is shown that the distribution of palladium in the catalysts obtained by reducing the precursors with hydrogen depends on the method used in synthesizing the precursor. It is shown that the studied catalysts ensure 100% conversion of chlorobenzene at temperatures of 100 to 250°C. It is established that cyclohexane is the principal product in the presence of the supported catalyst across the range of temperatures, while cyclohexane and benzene are detected among the products in the presence of biomorphous samples at temperatures above 130°C. The effect the presence of an admixture of alkaline and alkaline-earth metals in the catalyst has on the selectivity of the process is noted. It is established that the catalysts operate in a stable manner for at least 27 h of use under experimental conditions.

Elastic precursor wave decay in shock-compressed aluminum over a wide range of temperature

NASA Astrophysics Data System (ADS)

Austin, Ryan A.

2018-01-01

The effect of temperature on the dynamic flow behavior of aluminum is considered in the context of precursor wave decay measurements and simulations. In this regard, a dislocation-based model of high-rate metal plasticity is brought into agreement with previous measurements of evolving wave profiles at 300 to 933 K, wherein the amplification of the precursor structure with temperature arises naturally from the dislocation mechanics treatment. The model suggests that the kinetics of inelastic flow and stress relaxation are governed primarily by phonon scattering and radiative damping (sound wave emission from dislocation cores), both of which intensify with temperature. The manifestation of these drag effects is linked to low dislocation density ahead of the precursor wave and the high mobility of dislocations in the face-centered cubic lattice. Simulations performed using other typical models of shock wave plasticity do not reproduce the observed temperature-dependence of elastic/plastic wave structure.

Mixed-ligand approach to design of heterometallic single-source precursors with discrete molecular structure.

PubMed

Lieberman, Craig M; Navulla, Anantharamulu; Zhang, Haitao; Filatov, Alexander S; Dikarev, Evgeny V

2014-05-05

Heterometallic single-source precursors for the Pb/Fe = 1:1 oxide materials, PbFe(β-dik)4 (β-dik = hexafluoroacetylacetonate (hfac, 1), acetylacetonate (acac, 2), and trifluoroacetylacetonate (tfac, 4)), have been isolated by three different solid-state synthetic methods. The crystal structures of heterometallic diketonates 1, 2, and 4 were found to contain polymeric chains built on alternating [Fe(β-dik)2] and [Pb(β-dik)2] units that are held together by bridging M-O interactions. Heterometallic precursors are highly volatile, but soluble only in coordinating solvents, in which they dissociate into solvated homometallic fragments. In order to design the heterometallic precursor with a proper metal/metal ratio and with a discrete molecular structure, we used a combination of two different diketonate ligands. Heteroleptic complex Pb2Fe2(hfac)6(acac)2 (5) has been obtained by optimized stoichiometric reaction of an addition of homo-Fe(acac)2 to heterometallic Pb2Fe(hfac)6 (3) diketonate that can be run in solution on a high scale. The combination of two ligands with electron-withdrawing and electron-donating groups allows changing the connectivity pattern within the heterometallic assembly and yields the precursor with a discrete tetranuclear structure. In accord with its molecular structure, heteroleptic complex 5 is soluble even in noncoordinating solvents and was found to retain its heterometallic structure in solution. Thermal decomposition of heterometallic precursors in air at 750 °C resulted in the target Pb2Fe2O5 oxide, a prospective multiferroic material. Prolonging the annealing time or increasing the decomposition temperature leads to another phase-pure lead-iron oxide PbFe12O19 that is a representative of the important family of magnetic hexaferrites.

Non-noble electrocatalysts for alkaline fuel cells

NASA Technical Reports Server (NTRS)

Sarangapani, S.; Lessner, P.; Manoukian, M.; Giner, J.

1989-01-01

Carbons activated with macrocyclics have attracted increasing attention as alternative electrocatalysts for oxygen reduction. Initial activity of these catalysts is good, but performance declines rapidly. Pyrolyzing the macrocyclic on the carbon support leads to enhanced stability and the catalysts retain good activity. The approach described is designed to develop bulk doped catalysts with similar structures to pyrolyzed macrocyclic catalysts. The transition metal and coordinated ligands are dispersed throughout the bulk of the conductive carbon skeleton. Two approaches to realizing this concept are being pursued, both involving the doping of carbon precursors. In one approach, the precursor is a solid phase carbon-containing ion-exchange resin. The precursor is doped with a transition metal and/or nitrogen, and the resulting mixture is pyrolyzed. In the other approach, the precursor is a gas-phase hydrocarbon. This is introduced with a transition metal species and nitrogen species into a reactor and pyrolyzed. Several studies have been conducted to determine if there is a synergistic effect between the transition metal and nitrogen and the effect of different methods of introducing the metal-nitrogen (M-N) coordination on performance. One approach was to introduce the metal and nitrogen separately, for example, by sequentially doping FeCl3 and NH4OH into the resin. Catalysts were prepared from an undoped ion-exchange resin, a resin doped only with N, a resin doped only with Fe, and a resin doped with both Fe and N. Introduction of nitrogen alone has no beneficial effect on the performance of the catalysts. The introduction of the Fe alone significantly improves the performance in both the high and low current density regions. When both Fe and N are introduced, the performance at lower current densities (catalytic activity) is increased beyond that of the Fe-doped carbon, but the performance at higher current densities is similar to the carbon containing only Fe. Catalysts prepared from resins-Fe(bipy)3SO4 precursors have performance that is only slightly less then CoTMPP adsorbed and pyroloyzed on Vulcan XC-72. Their performance is much better than carbons which have had the N and Fe introduced separately.

Structural and Luminescence Properties of Lu2O3:Eu3+ F127 Tri-Block Copolymer Modified Thin Films Prepared by Sol-Gel Method

PubMed Central

de Jesus Morales Ramírez, Angel; Hernández, Margarita García; Murillo, Antonieta García; de Jesús Carrillo Romo, Felipe; Palmerin, Joel Moreno; Velazquez, Dulce Yolotzin Medina; Jota, María Luz Carrera

2013-01-01

Lu2O3:Eu3+ transparent, high density, and optical quality thin films were prepared using the sol-gel dip-coating technique, starting with lutetium and europium nitrates as precursors and followed by hydrolysis in an ethanol-ethylene glycol solution. Acetic acid and acetylacetonate were incorporated in order to adjust pH and as a sol stabilizer. In order to increment the thickness of the films and orient the structure, F127 Pluronic acid was incorporated during the sol formation. Structural, morphological, and optical properties of the films were investigated for different F127/Lu molar ratios (0–5) in order to obtain high optical quality films with enhanced thickness compared with the traditional method. X-ray diffraction (XRD) shows that the films present a highly oriented cubic structure <111> beyond 1073 K for a 3-layer film, on silica glass substrates. The thickness, density, porosity, and refractive index evolution of the films were investigated by means of m-lines microscopy along with the morphology by scanning electron microscope (SEM) and luminescent properties. PMID:28809336

Amyloid-β Production Via Cleavage of Amyloid-β Protein Precursor is Modulated by Cell Density

PubMed Central

Zhang, Can; Browne, Andrew; DiVito, Jason R.; Stevenson, Jesse A.; Romano, Donna; Dong, Yuanlin; Xie, Zhongcong; Tanzi, Rudolph E.

2012-01-01

Mounting evidence suggests that Alzheimer disease (AD) is caused by the accumulation of the small peptide, Aβ, a proteolytic cleavage product of amyloid-β protein precursor (AβPP; or APP). Aβ is generated through a serial cleavage of APP by β- and γ-secretase. Aβ40 and Aβ42 are the two main components of amyloid plaques in AD brains, with Aβ42 being more prone to aggregation. APP can also be processed by α-secretase, which cleaves APP within the Aβ sequence, thereby preventing the generation of Aβ. Little is currently known regarding the effects of cell density on APP processing and Aβ generation. Here we assessed the effects of cell density on APP processing in neuronal and non-neuronal cell lines, as well as mouse primary cortical neurons. We found that decreased cell density significantly increases levels of Aβ40, Aβ42, total Aβ, and the ratio of Aβ42:Aβ40. These results also indicate that cell density is a significant modulator of APP processing. Overall, these findings carry profound implications for both previous and forthcoming studies aiming to assess the effects of various conditions and genetic/chemical factors, e.g. novel drugs on APP processing and Aβ generation in cell-based systems. Moreover, it is interesting to speculate whether cell density changes in vivo may also affect APP processing and Aβ levels in the AD brain. PMID:20847415

Influence of hot isostatic pressing on ZrO2-CaO dental ceramics properties.

PubMed

Gionea, Alin; Andronescu, Ecaterina; Voicu, Georgeta; Bleotu, Coralia; Surdu, Vasile-Adrian

2016-08-30

Different hot isostatic pressing conditions were used to obtain zirconia ceramics, in order to assess the influence of HIP on phase transformation, compressive strength, Young's modulus and density. First, CaO stabilized zirconia powder was synthesized through sol-gel method, using zirconium propoxide, calcium isopropoxide and 2-metoxiethanol as precursors, then HIP treatment was applied to obtain final dense ceramics. Ceramics were morphologically and structurally characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM). Density measurements, compressive strength and Young's modulus tests were also performed in order to evaluate the effect of HIP treatment. The zirconia powders heat treated at 500°C for 2h showed a pure cubic phase with average particle dimension about 70nm. The samples that were hot isostatic pressed presented a mixture of monoclinic-tetragonal or monoclinic-cubic phases, while for pre-sintered samples, cubic zirconia was the single crystalline form. Final dense ceramics were obtained after HIP treatment, with relative density values higher than 94%. ZrO2-CaO ceramics presented high compressive strength, with values in the range of 500-708.9MPa and elastic behavior with Young's modulus between 1739MPa and 4372MPa. Finally zirconia ceramics were tested for biocompatibility allowing the normal development of MG63 cells in vitro. Copyright © 2015 Elsevier B.V. All rights reserved.

Methods and systems for fabricating high quality superconducting tapes

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

Majkic, Goran; Selvamanickam, Venkat

An MOCVD system fabricates high quality superconductor tapes with variable thicknesses. The MOCVD system can include a gas flow chamber between two parallel channels in a housing. A substrate tape is heated and then passed through the MOCVD housing such that the gas flow is perpendicular to the tape's surface. Precursors are injected into the gas flow for deposition on the substrate tape. In this way, superconductor tapes can be fabricated with variable thicknesses, uniform precursor deposition, and high critical current densities.

Automated electrochemical assembly of the protected potential TMG-chitotriomycin precursor based on rational optimization of the carbohydrate building block.

PubMed

Nokami, Toshiki; Isoda, Yuta; Sasaki, Norihiko; Takaiso, Aki; Hayase, Shuichi; Itoh, Toshiyuki; Hayashi, Ryutaro; Shimizu, Akihiro; Yoshida, Jun-ichi

2015-03-20

The anomeric arylthio group and the hydroxyl-protecting groups of thioglycosides were optimized to construct carbohydrate building blocks for automated electrochemical solution-phase synthesis of oligoglucosamines having 1,4-β-glycosidic linkages. The optimization study included density functional theory calculations, measurements of the oxidation potentials, and the trial synthesis of the chitotriose trisaccharide. The automated synthesis of the protected potential N,N,N-trimethyl-d-glucosaminylchitotriomycin precursor was accomplished by using the optimized building block.

Development of polyimide foams with blowing agents

NASA Technical Reports Server (NTRS)

Gagliani, John (Inventor); Sorathia, Usman A. K. (Inventor); Lee, Raymond (Inventor)

1985-01-01

A method of preparing a polyimide foam which includes the steps of: preparing, foaming, and curing a precursor containing at least one alkyl ester of 3,3'4,4'-benzophenonetetracarboxylic acid; a meta- or para-substituted aromatic diamine; a heterocyclic diamine; an aliphatic diamine; and a solid blowing agent. The blowing agent is added to said precursor in a concentration which is sufficient to effect at least one of the following attributes of the foam: cell size, proportion of open cells, cell density, and indentation load deflection.

Fingerprint-Based Structure Retrieval Using Electron Density

PubMed Central

Yin, Shuangye; Dokholyan, Nikolay V.

2010-01-01

We present a computational approach that can quickly search a large protein structural database to identify structures that fit a given electron density, such as determined by cryo-electron microscopy. We use geometric invariants (fingerprints) constructed using 3D Zernike moments to describe the electron density, and reduce the problem of fitting of the structure to the electron density to simple fingerprint comparison. Using this approach, we are able to screen the entire Protein Data Bank and identify structures that fit two experimental electron densities determined by cryo-electron microscopy. PMID:21287628

Fingerprint-based structure retrieval using electron density.

PubMed

Yin, Shuangye; Dokholyan, Nikolay V

2011-03-01

We present a computational approach that can quickly search a large protein structural database to identify structures that fit a given electron density, such as determined by cryo-electron microscopy. We use geometric invariants (fingerprints) constructed using 3D Zernike moments to describe the electron density, and reduce the problem of fitting of the structure to the electron density to simple fingerprint comparison. Using this approach, we are able to screen the entire Protein Data Bank and identify structures that fit two experimental electron densities determined by cryo-electron microscopy. Copyright © 2010 Wiley-Liss, Inc.

Stabilization of electron-scale turbulence by electron density gradient in national spherical torus experiment

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

Ruiz Ruiz, J.; White, A. E.; Ren, Y.

2015-12-15

Theory and experiments have shown that electron temperature gradient (ETG) turbulence on the electron gyro-scale, k{sub ⊥}ρ{sub e} ≲ 1, can be responsible for anomalous electron thermal transport in NSTX. Electron scale (high-k) turbulence is diagnosed in NSTX with a high-k microwave scattering system [D. R. Smith et al., Rev. Sci. Instrum. 79, 123501 (2008)]. Here we report on stabilization effects of the electron density gradient on electron-scale density fluctuations in a set of neutral beam injection heated H-mode plasmas. We found that the absence of high-k density fluctuations from measurements is correlated with large equilibrium density gradient, which ismore » shown to be consistent with linear stabilization of ETG modes due to the density gradient using the analytical ETG linear threshold in F. Jenko et al. [Phys. Plasmas 8, 4096 (2001)] and linear gyrokinetic simulations with GS2 [M. Kotschenreuther et al., Comput. Phys. Commun. 88, 128 (1995)]. We also found that the observed power of electron-scale turbulence (when it exists) is anti-correlated with the equilibrium density gradient, suggesting density gradient as a nonlinear stabilizing mechanism. Higher density gradients give rise to lower values of the plasma frame frequency, calculated based on the Doppler shift of the measured density fluctuations. Linear gyrokinetic simulations show that higher values of the electron density gradient reduce the value of the real frequency, in agreement with experimental observation. Nonlinear electron-scale gyrokinetic simulations show that high electron density gradient reduces electron heat flux and stiffness, and increases the ETG nonlinear threshold, consistent with experimental observations.« less

Vapor-liquid-solid epitaxial growth of Si 1-xGe x alloy nanowires. Composition dependence on precursor reactivity and morphology control for vertical forests

DOE PAGES

Choi, S. G.; Manandhar, P.; Picraux, S. T.

2015-07-07

The growth of high-density group IV alloy nanowire forests is critical for exploiting their unique functionalities in many applications. Here, the compositional dependence on precursor reactivity and optimized conditions for vertical growth are studied for Si 1- x Ge x alloy nanowires grown by the vapor-liquid-solid method. The nanowire composition versus gas partial-pressure ratio for germane-silane and germane-disilane precursor combinations is obtained at 350°C over a wide composition range (0.05 ≤ x ≤ 0.98) and a generalized model to predict composition for alloy nanowires is developed based on the relative precursor partial pressures and reactivity ratio. In combination with germane,more » silane provides more precise compositional control at high Ge concentrations (x > 0.7), whereas disilane greatly increases the Si concentration for a given gas ratio and enables more precise alloy compositional control at small Ge concentrations (x < 0.3). Vertically oriented, non-kinking nanowire forest growth on Si (111) substrates is then discussed for silane/germane over a wide range of compositions, with temperature and precursor partial pressure optimized by monitoring the nanowire growth front using in-situ optical reflectance. For high Ge compositions (x ≈ 0.9), a “two-step” growth approach with nucleation at higher temperatures results in nanowires with high-density and uniform vertical orientation. Furthermore, increasing Si content (x ≈ 0.8), the optimal growth window is shifted to higher temperatures, which minimizes nanowire kinking morphologies. For Si-rich Si 1- x Ge x alloys (x ≈ 0.25), vertical nanowire growth is enhanced by single-step, higher-temperature growth at reduced pressures.« less

Enhanced cyclic stability of SnS microplates with conformal carbon coating derived from ethanol vapor deposition for sodium-ion batteries

NASA Astrophysics Data System (ADS)

Li, Xiang; Liu, Jiangwen; Ouyang, Liuzhang; Yuan, Bin; Yang, Lichun; Zhu, Min

2018-04-01

Carbon coated SnS microplates (SnS@C MPs) were prepared via a facile chemical vapor deposition method using SnS2 nanoflakes as precursor and ethanol vapor as carbon source. The carbon coating restrains the growth of SnS during the heat treatment. Furthermore, it improves the electronic conductivity as well as accommodates volume variations of SnS during the sodiation and desodiation processes. Therefore, the rate capability and cycle performance of the SnS@C MPs as anode materials for sodium-ion batteries are remarkably enhanced compared with the bare SnS and the SnS2 precursor. At current densities of 0.1, 0.2, 0.5, 1 and 2 A g-1, the optimized SnS@C MPs exhibit stable capacities of 602.9, 532.1, 512.2, 465.9 and 427.2 mAh g-1, respectively. At 1 A g-1, they show a reversible capacity of 528.8 mAh g-1 in the first cycle, and maintain 444.7 mAh g-1 after 50 cycles, with capacity retention of 84.1%. The carbon coating through chemical vapor deposition using ethanol vapor as carbon sources is green, simple and cost-effective, which shows great promise to improve the reversible Na+ storage of electrode materials.

Analysis of channel confined selective area growth in evolutionary growth of GaN on SiO 2

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

Leung, Benjamin; Tsai, Miao-Chan; Song, Jie

2015-09-01

Here, we analyze the chemical vapor deposition of semiconductor crystals by selective area growth in a non-planar geometry. Specifically, the growth process in laterally and vertically confined masks forming single-crystal GaN on SiO2 by metal-organic chemical vapor deposition is considered in detail. A textured AlN seed is used to initiate growth of oriented GaN selectively through the mask, allowing the reduction of degrees of freedom by the evolutionary grain selection process. As shown by measurements of growth rates within the mask, the sub micron length scale of the channel opening is comparable to the mean free path of precursors inmore » the gas phase, resulting in transport characteristics that can be described by an intermediate flow regime between continuum and free-molecular. Mass transport is modeled through kinetic theory to explain the growth rate enhancements of more than a factor of two by changes in reactor pressure. The growth conditions that enable the modification of nucleation density within the channel are then discussed, and are measured by electron-back scatter diffraction of the nucleated grains on the AlN seed. Finally, the selectivity behavior using the low fill factor masks needed in these configurations has been optimized by control of precursor flow rates and the H2 enhanced etching of the polycrystalline GaN nuclei.« less

Cloning, overexpression, crystallization and preliminary X-ray crystallographic analysis of a slow-processing mutant of penicillin G acylase from Kluyvera citrophila.

PubMed

Varshney, Nishant Kumar; Ramasamy, Sureshkumar; Brannigan, James A; Wilkinson, Anthony J; Suresh, C G

2013-08-01

Kluyvera citrophila penicillin G acylase (KcPGA) has recently attracted increased attention relative to the well studied and commonly used Escherichia coli PGA (EcPGA) because KcPGA is more resilient to harsh conditions and is easier to immobilize for the industrial hydrolysis of natural penicillins to generate the 6-aminopenicillin (6-APA) nucleus, which is the starting material for semi-synthetic antibiotic production. Like other penicillin acylases, KcPGA is synthesized as a single-chain inactive pro-PGA, which upon autocatalytic processing becomes an active heterodimer of α and β chains. Here, the cloning of the pac gene encoding KcPGA and the preparation of a slow-processing mutant precursor are reported. The purification, crystallization and preliminary X-ray analysis of crystals of this precursor protein are described. The protein crystallized in two different space groups, P1, with unit-cell parameters a = 54.0, b = 124.6, c = 135.1 Å, α = 104.1, β = 101.4, γ = 96.5°, and C2, with unit-cell parameters a = 265.1, b = 54.0, c = 249.2 Å, β = 104.4°, using the sitting-drop vapour-diffusion method. Diffraction data were collected at 100 K and the phases were determined using the molecular-replacement method. The initial maps revealed electron density for the spacer peptide.

Synthesis and characterization of scandia ceria stabilized zirconia powders prepared by polymeric precursor method for integration into anode-supported solid oxide fuel cells

NASA Astrophysics Data System (ADS)

Tu, Hengyong; Liu, Xin; Yu, Qingchun

2011-03-01

Scandia ceria stabilized zirconia (10Sc1CeSZ) powders are synthesized by polymeric precursor method for use as the electrolyte of anode-supported solid oxide fuel cell (SOFC). The synthesized powders are characterized in terms of crystalline structure, particle shape and size distribution by X-ray diffraction (XRD), transmission electron microscopy (TEM) and photon correlation spectroscopy (PCS). 10Sc1CeSZ electrolyte films are deposited on green anode substrate by screen-printing method. Effects of 10Sc1CeSZ powder characteristics on sintered films are investigated regarding the integration process for application as the electrolytes in anode-supported SOFCs. It is found that the 10Sc1CeSZ films made from nano-sized powders with average size of 655 nm are very porous with many open pores. In comparison, the 10Sc1CeSZ films made from micron-sized powders with average size of 2.5 μm, which are obtained by calcination of nano-sized powders at higher temperatures, are much denser with a few closed pinholes. The cell performances are 911 mW cm-2 at the current density of 1.25 A cm-2 and 800 °C by application of Ce0.8Gd0.2O2 (CGO) barrier layer and La0.6Sr0.4CoO3 (LSC) cathode.

Green synthesis of boron doped graphene and its application as high performance anode material in Li ion battery

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

Sahoo, Madhumita; Sreena, K.P.; Vinayan, B.P.

2015-01-15

Graphical abstract: Boron doped graphene (B-G), synthesized by simple hydrogen induced reduction technique using boric acid as boron precursor, have more uneven surface as a result of smaller bonding distance of boron compared to carbon, showed high capacity and high rate capability compared to pristine graphene as an anode material for Li ion battery application. - Abstract: The present work demonstrates a facile route for the large-scale, catalyst free, and green synthesis approach of boron doped graphene (B-G) and its use as high performance anode material for Li ion battery (LIB) application. Boron atoms were doped into graphene framework withmore » an atomic percentage of 5.93% via hydrogen induced thermal reduction technique using graphite oxide and boric acid as precursors. Various characterization techniques were used to confirm the boron doping in graphene sheets. B-G as anode material shows a discharge capacity of 548 mAh g{sup −1} at 100 mA g{sup −1} after 30th cycles. At high current density value of 1 A g{sup −1}, B-G as anode material enhances the specific capacity by about 1.7 times compared to pristine graphene. The present study shows a simplistic way of boron doping in graphene leading to an enhanced Li ion adsorption due to the change in electronic states.« less

Biomass-derived nitrogen-doped porous carbons with tailored hierarchical porosity and high specific surface area for high energy and power density supercapacitors

NASA Astrophysics Data System (ADS)

Sun, Junting; Niu, Jin; Liu, Mengyue; Ji, Jing; Dou, Meiling; Wang, Feng

2018-01-01

Porous carbon materials with hierarchical structures attract intense interest for the development of high-performance supercapacitors. Herein, we demonstrate a facile and efficient strategy to synthesize nitrogen-doped hierarchically porous carbons with tailored porous structure combined with high specific surface area (SSA), which involves a pre-carbonization and a subsequent carbonization combined with KOH activation of silkworm cocoon precursors. Through adjusting the mass ratio of the activator (KOH) to pre-carbonized precursor in the activation process, the hierarchically porous carbon prepared at the mass ratio of 2 (referred to as NHPC-2) possesses a high defect density and a high SSA of 3386 m2 g-1 as well as the relatively high volumetric proportion of mesopores and macropores (45.5%). As a result, the energy density and power density of the symmetric supercapacitor based on NHPC-2 electrode are as high as 34.41 Wh kg-1 and 31.25 kW kg-1 in organic-solvent electrolyte, and are further improved to 112.1 Wh kg-1 and 23.91 kW kg-1 in ionic-liquid electrolyte.

Mechanical properties in crumple-formed paper derived materials subjected to compression.

PubMed

Hanaor, D A H; Flores Johnson, E A; Wang, S; Quach, S; Dela-Torre, K N; Gan, Y; Shen, L

2017-06-01

The crumpling of precursor materials to form dense three dimensional geometries offers an attractive route towards the utilisation of minor-value waste materials. Crumple-forming results in a mesostructured system in which mechanical properties of the material are governed by complex cross-scale deformation mechanisms. Here we investigate the physical and mechanical properties of dense compacted structures fabricated by the confined uniaxial compression of a cellulose tissue to yield crumpled mesostructuring. A total of 25 specimens of various densities were tested under compression. Crumple formed specimens exhibited densities in the range 0.8-1.3 g cm -3 , and showed high strength to weight characteristics, achieving ultimate compressive strength values of up to 200 MPa under both quasi-static and high strain rate loading conditions and deformation energy that compares well to engineering materials of similar density. The materials fabricated in this work and their mechanical attributes demonstrate the potential of crumple-forming approaches in the fabrication of novel energy-absorbing materials from low-cost precursors such as recycled paper. Stiffness and toughness of the materials exhibit density dependence suggesting this forming technique further allows controllable impact energy dissipation rates in dynamic applications.

Room temperature synthesis of Cu₂O nanospheres: optical properties and thermal behavior.

PubMed

Nunes, Daniela; Santos, Lídia; Duarte, Paulo; Pimentel, Ana; Pinto, Joana V; Barquinha, Pedro; Carvalho, Patrícia A; Fortunato, Elvira; Martins, Rodrigo

2015-02-01

The present work reports a simple and easy wet chemistry synthesis of cuprous oxide (Cu2O) nanospheres at room temperature without surfactants and using different precursors. Structural characterization was carried out by X-ray diffraction, transmission electron microscopy, and scanning electron microscopy coupled with focused ion beam and energy-dispersive X-ray spectroscopy. The optical band gaps were determined from diffuse reflectance spectroscopy. The photoluminescence behavior of the as-synthesized nanospheres showed significant differences depending on the precursors used. The Cu2O nanospheres were constituted by aggregates of nanocrystals, in which an on/off emission behavior of each individual nanocrystal was identified during transmission electron microscopy observations. The thermal behavior of the Cu2O nanospheres was investigated with in situ X-ray diffraction and differential scanning calorimetry experiments. Remarkable structural differences were observed for the nanospheres annealed in air, which turned into hollow spherical structures surrounded by outsized nanocrystals.

Polymethacrylic acid as a new precursor of CuO nanoparticles

NASA Astrophysics Data System (ADS)

Hosny, Nasser Mohammed; Zoromba, Mohamed Shafick

2012-11-01

Polymethacrylic acid and its copper complexes have been synthesized and characterized. These complexes have been used as precursors to produce CuO nanoparticles by thermal decomposition in air. The stages of decompositions and the calcination temperature of the precursors have been determined from thermal analyses (TGA). The obtained CuO nanoparticles have been characterized by X-ray diffraction (XRD), scanning tunneling microscopy (STM) and transmission electron microscopy (TEM). XRD showed a monoclinic structure with particle size 8-20 nm for the synthesized copper oxide nanoparticles. These nanoparticles are catalytically active in decomposing hydrogen peroxide and a mechanism of decomposition has been suggested.

Effect of Phosphine-Free Selenium Precursor Reactivity on The Optical and Vibrational properties of Colloidal CdSe Nanocrystals

NASA Astrophysics Data System (ADS)

Thi, L. A.; Lieu, N. T. T.; Hoa, N. M.; Tran, N.; Binh, N. T.; Quang, V. X.; Nghia, N. X.

2018-03-01

Phosphine-free selenium precursor solutions have been prepared by heating at temperatures ranging from 160 °C to 240 °C and studied by means of infrared absorption spectroscopy. The colloidal CdSe nanocrystals (NCs) synthesized from all those solutions by the wet chemical method. The influence of heating temperature on the chemical reactivity of selenium precursor and its role on the optical and vibrational properties of CdSe NCs are discussed in details. Their morphology, particle size, structural, optical and vibrational properties were investigated using transmission electron microscopy, X-ray diffraction, UV-Vis, fluorescence and Raman spectroscopy, respectively.

Preseismic Lithosphere-Atmosphere-Ionosphere Coupling

NASA Astrophysics Data System (ADS)

Kamogawa, Masashi

Preseismic atmospheric and ionospheric disturbances besides preseismic geo-electric potential anomalies and ultra-low-frequency (ULF) geomagnetic variations observed on the ground have been reported. Both the phenomena have been found since the 1980s and a number of papers have been published. Since most of the reported phenomena transiently appear with accompanying quiescence before the mainshock, this prevents us to intuitively recognize a correlation between the anomaly appearance and the earthquake occurrence. Some of them, however, showed that anomalies monotonically grew into the mainshock, of which a variation supports the concept of seismic nucleation process under the pre-earthquake state. For example, Heki [GRL, 2011] reported that ionospheric electron density monotonically enhanced tens of minutes prior to the subduction mega-earthquake. However, this preseismic enhancement is apparent variation attributed to tsunamigenic ionospheric hole [Kakinami and Kamogawa et al, GRL, 2012], namely wide and long-duration depression of ionospheric electron after tsunami-excited acoustic waves reach the ionosphere. Since the tsunamigenic ionospheric hole could be simulated [Shinagawa et al., GRL, 2013], the reported variations are high-possibly pseudo phenomena [Kamogawa and Kakinami, JGR, 2013]. Thus, there are barely a few reports which show the preseismic monotonic variation supported by the concept of the seismic nucleation process. As far as we discuss the preseismic geoelectromagnetical and atmospheric-ionospheric anomalies, preseismic transient events from a few weeks to a few hours prior to the mainshock are paid attention to for the precursor study. In order to identify precursors from a number of anomalies, one has to show a statistical significance of correlation between the earthquake and the anomalies, to elucidate the physical mechanism, or to conduct both statistical and physical approach. Since many speculation of the physical mechanism have been hardly verified so far, a statistical approach has been unique way to promote the research. After the 2000s, several papers showing robust statistical results have arisen. In this paper, we focus on publications satisfying the following identification criteria: 1) A candidate of precursor, namely anomaly, is quantitatively defied. 2) Two time-series of anomalies and earthquake are constructed within the fixed thresholds such as a minimum magnitude, a region, and a lead-time. 3) To obtain a statistical correlation, a statistical process which includes four relations considering all combination among earthquake - no earthquake versus anomaly and no anomalies is applied, e. g., phi correlation. 4) For correlations under various thresholds the results keep consistency. 5) Large anomalies appear before large earthquakes. One of papers based on the identification criteria, which concerns preseismic geoelectrically anomalies, is introduced as an educative example. VAN method in Greece, i. e., Geo-electric potential difference measurement for precursor study in Greece, has been often discussed in the point of view of success and failure performance for practical prediction [Varotsos et al, Springer, 2011] to show a correlation and then less number of papers shows the statistical correlation with satisfying the identification criteria [Geller (ed.), GRL, 1996], so that the phenomena had been controversial. However, recent related study in Kozu-Island, Japan which satisfied the criteria showed the robust correlation [Orihara and Kamogawa et al., PNAS, 2012]. Therefore, the preseismic geoelectric anomalies are expected to be a precursor. Preseismic lithosphere-atmosphere-ionosphere coupling has been intensively discussed [Kamogawa, Eos, 2006]. According to review based on the identification criteria with considering recent publications, plausible precursors have been found, which are tropospheric anomaly [Fujiwara and Kamogawa, GRL, 2004], daytime electron depletion in F region [Liu et al, JGR, 2006], nighttime decrease of background intensity of VLF electromagnetic waves possibly attributed to ionospheric disturbance in D region [Nemec et al., GRL, 2008; Nemec et al., JGR, 2009; Pisa et al, JGR, 2013]. Although these reported anomalies are plausible from a statistical correlation mostly satisfying the above criteria. In this presentation, I review recent studies of preseismic atmospheric-ionospheric coupling and introduce the plausible mechanisms.

New metal catalyzed syntheses of nanostructured boron nitride and alkenyldecaboranes

NASA Astrophysics Data System (ADS)

Chatterjee, Shahana

The goals of the research described in this dissertation were two-fold. The first goal was to develop new methods, employing metal-catalyzed chemical vapor deposition reactions of molecular polyborane precursors, for the production of boron nitride nanostructured materials, including both boron nitride nanotubes (BNNTs) and boron nitride nanosheets (BNNS). The second goal was to develop new systematic metal-catalyzed reactions for polyboranes that would facilitate their functionalization for possible biomedical and/or materials applications. The syntheses of multi- and double-walled BNNTs were achieved with the aid of a floating nickel catalyst via the catalytic chemical vapor deposition (CCVD) of borazine (B3N3H6) or decaborane (B10H14) molecular precursors in ammonia atmospheres, with each precursor having its own advantages. While borazine is a single-source precursor containing both boron and nitrogen, the decaborane-based syntheses required the additional step of reaction with ammonia. However, the higher observed BNNT yields and the ease of handling and commercial availability of decaborane are distinct advantages. The BNNTs derived from both precursors were crystalline with highly ordered structures. The BNNTs grown at 1200 ºC from borazine were mainly double walled, with lengths up to 0.2 µm and ˜2 nm diameters. The BNNTs grown at 1200-1300 ºC from decaborane were double- and multi-walled, with the double-walled nanotubes having ˜2 nm inner diameters and the multi-walled nanotubes (˜10 walls) having ˜4-5 nm inner diameters and ˜12-14 nm outer diameters. BNNTs grown from decaborane at 1300 ºC were longer, averaging ˜0.6 µm, whereas those grown at 1200 ºC had average lengths of ˜0.2 µm. The BNNTs were characterized using scanning and transmission electron microscopies (SEM and TEM), and electron energy loss spectroscopy (EELS). This floating catalyst method now provides a catalytic and potentially scalable route to BNNTs with low defect density from safe and commercially available precursor compounds. A catalytic CVD method, employing the thermally induced reactions of ammonia with decaborane on polycrystalline nickel and copper foils, was also successfully developed for the production of BNNS. The metals were readily etched and the BNNS transferred to other substrates. The EELS and Raman spectra and the electron diffraction patterns of the BNNS confirmed the formation of h-BN and their optical, AFM and TEM characterizations showed BNNS with large micron-scale areas with some crumpling and folding. Most of the BNNS deposited on Ni were two- or three-layered; however, some regions were thicker containing up to six BN sheets. The films on Cu also contained two- and three-layered BNNS, but had large amorphous BN regions. Many of the BNNS grown on Ni exhibited well-defined angular edges, with near regular angles of 30º, 60º or 90º, suggesting that with a fine-tuning of the decaborane/ammonia pressure and growth conditions, controlled growth of regular polygonal BNNS structures can be achieved. To achieve the second goal, transition-metal-catalyzed decaborane-alkyne hydroboration reactions were developed that provide high-yield routes to the previously unknown di- and monoalkenyldecaboranes. An unusual catalyst product selectivity was observed, with the reactions catalyzed by the [RuCl2 (p-cymene)]2 and [Cp*IrCl2]2 complexes giving the β-E alkenyldecaboranes and the corresponding reactions with the [RuI2(p-cymene)]2 complex giving the α-alkenyldecaborane isomers. These product selectivities coupled with the differences observed in NMR studies of catalyzed reactions in progress, suggest quite distinct mechanistic steps for the different catalysts. It was further demonstrated that the new alkenyldecaboranes could be easily modified with the aid of metal-catalyzed hydroborations and homo and cross metathesis reactions to yield both linked cage and chemically active derivatives. These results demonstrate that the alkenyldecaboranes could serve as important materials for many potential polyborane biomedical and/or materials applications.

Electronic energy density in chemical reaction systems

NASA Astrophysics Data System (ADS)

Tachibana, Akitomo

2001-08-01

The energy of chemical reaction is visualized in real space using the electronic energy density nE(r⃗) associated with the electron density n(r⃗). The electronic energy density nE(r⃗) is decomposed into the kinetic energy density nT(r⃗), the external potential energy density nV(r⃗), and the interelectron potential energy density nW(r⃗). Using the electronic energy density nE(r⃗) we can pick up any point in a chemical reaction system and find how the electronic energy E is assigned to the selected point. We can then integrate the electronic energy density nE(r⃗) in any region R surrounding the point and find out the regional electronic energy ER to the global E. The kinetic energy density nT(r⃗) is used to identify the intrinsic shape of the reactants, the electronic transition state, and the reaction products along the course of the chemical reaction coordinate. The intrinsic shape is identified with the electronic interface S that discriminates the region RD of the electronic drop from the region RA of the electronic atmosphere in the density distribution of the electron gas. If the R spans the whole space, then the integral gives the total E. The regional electronic energy ER in thermodynamic ensemble is realized in electrochemistry as the intrinsic Volta electric potential φR and the intrinsic Herring-Nichols work function ΦR. We have picked up first a hydrogen-like atom for which we have analytical exact expressions of the relativistic kinetic energy density nTM(r⃗) and its nonrelativistic version nT(r⃗). These expressions are valid for any excited bound states as well as the ground state. Second, we have selected the following five reaction systems and show the figures of the nT(r⃗) as well as the other energy densities along the intrinsic reaction coordinates: a protonation reaction to He, addition reactions of HF to C2H4 and C2H2, hydrogen abstraction reactions of NH3+ from HF and NH3. Valence electrons possess their unique delocalized drop region remote from those heavily localized drop regions adhered to core electrons. The kinetic energy density nT(r⃗) and the tension density τ⃗S(r⃗) can vividly demonstrate the formation of the chemical bond. Various basic chemical concepts in these chemical reaction systems have been clearly visualized in real three-dimensional space.

High-mobility ultrathin semiconducting films prepared by spin coating.

PubMed

Mitzi, David B; Kosbar, Laura L; Murray, Conal E; Copel, Matthew; Afzali, Ali

2004-03-18

The ability to deposit and tailor reliable semiconducting films (with a particular recent emphasis on ultrathin systems) is indispensable for contemporary solid-state electronics. The search for thin-film semiconductors that provide simultaneously high carrier mobility and convenient solution-based deposition is also an important research direction, with the resulting expectations of new technologies (such as flexible or wearable computers, large-area high-resolution displays and electronic paper) and lower-cost device fabrication. Here we demonstrate a technique for spin coating ultrathin (approximately 50 A), crystalline and continuous metal chalcogenide films, based on the low-temperature decomposition of highly soluble hydrazinium precursors. We fabricate thin-film field-effect transistors (TFTs) based on semiconducting SnS(2-x)Se(x) films, which exhibit n-type transport, large current densities (>10(5) A cm(-2)) and mobilities greater than 10 cm2 V(-1) s(-1)--an order of magnitude higher than previously reported values for spin-coated semiconductors. The spin-coating technique is expected to be applicable to a range of metal chalcogenides, particularly those based on main group metals, as well as for the fabrication of a variety of thin-film-based devices (for example, solar cells, thermoelectrics and memory devices).

High-mobility ultrathin semiconducting films prepared by spin coating

NASA Astrophysics Data System (ADS)

Mitzi, David B.; Kosbar, Laura L.; Murray, Conal E.; Copel, Matthew; Afzali, Ali

2004-03-01

The ability to deposit and tailor reliable semiconducting films (with a particular recent emphasis on ultrathin systems) is indispensable for contemporary solid-state electronics. The search for thin-film semiconductors that provide simultaneously high carrier mobility and convenient solution-based deposition is also an important research direction, with the resulting expectations of new technologies (such as flexible or wearable computers, large-area high-resolution displays and electronic paper) and lower-cost device fabrication. Here we demonstrate a technique for spin coating ultrathin (~50Å), crystalline and continuous metal chalcogenide films, based on the low-temperature decomposition of highly soluble hydrazinium precursors. We fabricate thin-film field-effect transistors (TFTs) based on semiconducting SnS2-xSex films, which exhibit n-type transport, large current densities (>105Acm-2) and mobilities greater than 10cm2V-1s-1-an order of magnitude higher than previously reported values for spin-coated semiconductors. The spin-coating technique is expected to be applicable to a range of metal chalcogenides, particularly those based on main group metals, as well as for the fabrication of a variety of thin-film-based devices (for example, solar cells, thermoelectrics and memory devices).

Self-standing paper based anodes prepared from siliconcarbonitride-MoS2 composite for Li-ion battery applications

NASA Astrophysics Data System (ADS)

David, Lamuel; Singh, Gurpreet

2013-03-01

We study synthesis of free-standing polymer derived SiCN/ MoS2 composite paper anode for Li-ion battery application. This was achieved following a two-step approach: First, polysilazane was interfaced with exfoliated MoS2 nanosheets which upon pyrolysis resulted in SiCN/MoS2 composite. Second, dispersion of SiCN/MoS2 in isopropanol was vacuum filtered resulting in formation of a self-standing composite paper. Physical and chemical characterization of the composite was carried out by use of electron microscopy, Fourier transform infrared spectroscopy (FT-IR) and Thermo-gravimetric analysis (TGA). FT-IR data indicated complete conversion of polysilazane precursor to SiCN ceramic, while electron microscopy confirmed layered structure of the paper. Thermo-gravimetric analysis showed enhanced thermodynamic stability of the composite paper up to 800 °C. Electrochemical analysis of SiCN/MoS2 composite paper anodes showed that Li-ion can reversible intercalate in the voltage range of 0-2.5 V with a first cycle discharge capacity of 770 mAh/g at a current density of 100 mA/g.

A novel route for synthesis of nanocrystalline hydroxyapatite from eggshell waste.

PubMed

Siva Rama Krishna, D; Siddharthan, A; Seshadri, S K; Sampath Kumar, T S

2007-09-01

The eggshell waste has been value engineered to a nanocrystalline hydroxyapatite (HA) by microwave processing. To highlight the advantages of eggshell as calcium precursor in the synthesis of HA (OHA), synthetic calcium hydroxide was also used to form HA (SHA) following similar procedure and were compared with a commercially available pure HA (CHA). All the HAs were characterized by X-ray powder diffraction (XRD) method, Fourier transform infrared (FT-IR) spectroscopy, scanning electron microscopy (SEM), transmission electron microscopy (TEM) and specific surface area measurements. Nanocrystalline nature of OHA is revealed through characteristic broad peaks in XRD patterns, platelets of length 33-50 nm and width 8-14 nm in TEM micrograph and size calculations from specific surface area measurements. FT-IR spectra showed characteristic bands of HA and additionally peaks of carbonate ions. The cell parameter calculations suggest the formation of carbonated HA of B-type. The OHA exhibits superior sinterability in terms of hardness and density than both SHA and CHA may be due to larger surface area of its spherulite structure. The in vitro dissolution study shows longer stability in phosphate buffer and cell culture test using osteoblast cells establishes biocompatibility of OHA.

Investigating the Formation and Sub-Structure of Unmagnetized Collisionless Shocks

NASA Astrophysics Data System (ADS)

Endrizzi, Douglass; Egedal, J.; Forest, C.; Greess, S.; Millet-Ayala, A.; Olson, J.; Ready, A.; Waleffe, R.; Gota, H.

2017-10-01

Collisionless shocks, where the shock thickness is much smaller than the collisional mean free path, are ubiquitous astrophysical phenomena. In all shocks, the Rankine-Hugoniot jump conditions are satisfied through entropy generation at the interface; the shock propagation angle with respect to the magnetic field affects the mechanism by which this entropy is generated. Two experiments on the Big Red Ball (BRB) at UW-Madison explored the formation mechanisms of parallel and perpendicular, unmagnetized and magnetized collisionless shocks with large (1 - 3 m) system sizes. In the first experiment, a 1 m diameter theta-pinch drove a supersonic (3 < M < 4) compressive flow perpendicular to the background magnetic field. In the second, a compact toroid ([cite TriAlpha]) was fired supersonically (4 < M < 5) parallel to the background magnetic field. Triple, Langmuir, emissive, and magnetic probes were used to measure electron density, temperature, plasma potential, and fluctuations in magnetic fields. Results showing the transition from above to below MA = 1 , measurements of electron precursors, exploration of subshock structure, evidence of instabilities in the shock formation process, and future work will be presented. This material is based upon work supported by the National Science Foundation Graduate Research Fellowship under Grant No. DGE 1256259.

Preparation of NiCoP Hollow Quasi-Polyhedra and Their Electrocatalytic Properties for Hydrogen Evolution in Alkaline Solution.

PubMed

Li, Yapeng; Liu, Jindou; Chen, Chen; Zhang, Xiaohua; Chen, Jinhua

2017-02-22

Double metal phosphide (NiCoP) with hollow quasi-polyhedron structure was prepared by acidic etching and precipitation of ZIF-67 polyhedra and further phosphorization treatment with NaH 2 PO 2 . The morphology and microstructure of NiCoP quasi-polyhedron and its precursors were investigated by scanning electron microscopy, transmission electron microscopy, X-ray diffraction, and a micropore and chemisorption analyzer. Electrocatalytic properties were examined by typical electrochemical methods, such as linear sweep voltammetry, cyclic voltammetry, chronoamperometry, and electrochemical impedance spectroscopy in 1.0 M KOH aqueous solution. Results reveal that, compared with CoP hollow polyhedra, NiCoP hollow quasi-polyhedra exhibit better electrochemical properties for hydrogen evolution with a low onset overpotential of 74 mV and a small Tafel slope of 42 mV dec -1 . When the current density is 10 mA cm -2 , the corresponding overpotential is merely 124 mV, and 93% of its electrocatalytic activity can be maintained for 12 h. This indicates that NiCoP with hollow quasi-polyhedron structure, bimetallic merit, and low cost may be a good candidate as electrocatalyst in the practical application of hydrogen evolution.

Ultra-small Ag clusters in zeolite A4: Antibacterial and thermochromic applications

NASA Astrophysics Data System (ADS)

Horta-Fraijo, P.; Cortez-Valadez, M.; Flores-Lopez, N. S.; Britto Hurtado, R.; Vargas-Ortiz, R. A.; Perez-Rodriguez, A.; Flores-Acosta, M.

2018-03-01

The physical and chemical properties of metal clusters depend on their atomic structure, therefore, it is important to determine the lowest-energy structures of the clusters in order to understand and utilize their properties. In this work, we use the Density Functional Theory (DFT) at the generalized gradient approximation level Becke's three-parameter and the gradient corrected functional of Lee, Yang and Puar (B3LYP) in combination with the basis set LANL2DZ (the effective core potentials and associated double-zeta valence) to determine some of the structural, electronic and vibrational properties of the planar silver clusters (Agn clusters n = 2-24). Additionally, the study reports the experimental synthesis of small silver clusters in synthetic zeolite A4. The synthesis was possible using the ion exchange method with some precursors like silver nitrate (AgNO3) and synthetic zeolite A4. The silver clusters in zeolite powder underwent thermal treatment at 450 °C to release the remaining water or humidity on it. The morphology of the particles was determined by Transmission Electron microscopy. The nanomaterials obtained show thermochromic properties. The structural parameters were correlated theoretically and experimentally.

Direct visualization of atomically precise nitrogen-doped graphene nanoribbons

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

Zhang, Yi; Zhang, Yanfang; Li, Geng

2014-07-14

We have fabricated atomically precise nitrogen-doped chevron-type graphene nanoribbons by using the on-surface synthesis technique combined with the nitrogen substitution of the precursors. Scanning tunneling microscopy and spectroscopy indicate that the well-defined nanoribbons tend to align with the neighbors side-by-side with a band gap of 1.02 eV, which is in good agreement with the density functional theory calculation result. The influence of the high precursor coverage on the quality of the nanoribbons is also studied. We find that graphene nanoribbons with sufficient aspect ratios can only be fabricated at sub-monolayer precursor coverage. This work provides a way to construct atomically precisemore » nitrogen-doped graphene nanoribbons.« less

Metallopolymer precursors to L10-CoPt nanoparticles: synthesis, characterization, nanopatterning and potential application

NASA Astrophysics Data System (ADS)

Dong, Qingchen; Qu, Wenshan; Liang, Wenqing; Guo, Kunpeng; Xue, Haibin; Guo, Yuanyuan; Meng, Zhengong; Ho, Cheuk-Lam; Leung, Chi-Wah; Wong, Wai-Yeung

2016-03-01

Ferromagnetic (L10 phase) CoPt alloy nanoparticles (NPs) with extremely high magnetocrystalline anisotropy are promising candidates for the next generation of ultrahigh-density data storage systems. It is a challenge to generate L10 CoPt NPs with high coercivity, controllable size, and a narrow size distribution. We report here the fabrication of L10 CoPt NPs by employing a heterobimetallic CoPt-containing polymer as a single-source precursor. The average size of the resulting L10 CoPt NPs is 3.4 nm with a reasonably narrow size standard deviation of 0.58 nm. The coercivity of L10 CoPt NPs is 0.54 T which is suitable for practical application. We also fabricated the L10 CoPt NP-based nanoline and nanodot arrays through nanoimprinting the polymer blend of CoPt-containing metallopolymer and polystyrene followed by pyrolysis. The successful transfer of the pre-defined patterns of the stamps onto the surface of the polymer blend implies that this material holds great application potential as a data storage medium.Ferromagnetic (L10 phase) CoPt alloy nanoparticles (NPs) with extremely high magnetocrystalline anisotropy are promising candidates for the next generation of ultrahigh-density data storage systems. It is a challenge to generate L10 CoPt NPs with high coercivity, controllable size, and a narrow size distribution. We report here the fabrication of L10 CoPt NPs by employing a heterobimetallic CoPt-containing polymer as a single-source precursor. The average size of the resulting L10 CoPt NPs is 3.4 nm with a reasonably narrow size standard deviation of 0.58 nm. The coercivity of L10 CoPt NPs is 0.54 T which is suitable for practical application. We also fabricated the L10 CoPt NP-based nanoline and nanodot arrays through nanoimprinting the polymer blend of CoPt-containing metallopolymer and polystyrene followed by pyrolysis. The successful transfer of the pre-defined patterns of the stamps onto the surface of the polymer blend implies that this material holds great application potential as a data storage medium. Electronic supplementary information (ESI) available: PXRD, EDX and SEM original data. See DOI: 10.1039/c6nr00034g

Patterning at the 10 nanometer length scale using a strongly segregating block copolymer thin film and vapor phase infiltration of inorganic precursors

NASA Astrophysics Data System (ADS)

Choi, Jonathan W.; Li, Zhaodong; Black, Charles T.; Sweat, Daniel P.; Wang, Xudong; Gopalan, Padma

2016-06-01

In this work, we demonstrate the use of self-assembled thin films of the cylinder-forming block copolymer poly(4-tert-butylstyrene-block-2-vinylpyridine) to pattern high density features at the 10 nm length scale. This material's large interaction parameter facilitates pattern formation in single-digit nanometer dimensions. This block copolymer's accessible order-disorder transition temperature allows thermal annealing to drive the assembly of ordered 2-vinylpyridine cylinders that can be selectively complexed with the organometallic precursor trimethylaluminum. This unique chemistry converts organic 2-vinylpyridine cylinders into alumina nanowires with diameters ranging from 8 to 11 nm, depending on the copolymer molecular weight. Graphoepitaxy of this block copolymer aligns and registers sub-12 nm diameter nanowires to larger-scale rectangular, curved, and circular features patterned by optical lithography. The alumina nanowires function as a robust hard mask to withstand the conditions required for patterning the underlying silicon by plasma etching. We conclude with a discussion of some of the challenges that arise with using block copolymers for patterning at sub-10 nm feature sizes.In this work, we demonstrate the use of self-assembled thin films of the cylinder-forming block copolymer poly(4-tert-butylstyrene-block-2-vinylpyridine) to pattern high density features at the 10 nm length scale. This material's large interaction parameter facilitates pattern formation in single-digit nanometer dimensions. This block copolymer's accessible order-disorder transition temperature allows thermal annealing to drive the assembly of ordered 2-vinylpyridine cylinders that can be selectively complexed with the organometallic precursor trimethylaluminum. This unique chemistry converts organic 2-vinylpyridine cylinders into alumina nanowires with diameters ranging from 8 to 11 nm, depending on the copolymer molecular weight. Graphoepitaxy of this block copolymer aligns and registers sub-12 nm diameter nanowires to larger-scale rectangular, curved, and circular features patterned by optical lithography. The alumina nanowires function as a robust hard mask to withstand the conditions required for patterning the underlying silicon by plasma etching. We conclude with a discussion of some of the challenges that arise with using block copolymers for patterning at sub-10 nm feature sizes. Electronic supplementary information (ESI) available. See DOI: 10.1039/c6nr01409g

Understanding the Mechanism of SiC Plasma-Enhanced Chemical Vapor Deposition (PECVD) and Developing Routes toward SiC Atomic Layer Deposition (ALD) with Density Functional Theory.

PubMed

Filatova, Ekaterina A; Hausmann, Dennis; Elliott, Simon D

2018-05-02

Understanding the mechanism of SiC chemical vapor deposition (CVD) is an important step in investigating the routes toward future atomic layer deposition (ALD) of SiC. The energetics of various silicon and carbon precursors reacting with bare and H-terminated 3C-SiC (011) are analyzed using ab initio density functional theory (DFT). Bare SiC is found to be reactive to silicon and carbon precursors, while H-terminated SiC is found to be not reactive with these precursors at 0 K. Furthermore, the reaction pathways of silane plasma fragments SiH 3 and SiH 2 are calculated along with the energetics for the methane plasma fragments CH 3 and CH 2 . SiH 3 and SiH 2 fragments follow different mechanisms toward Si growth, of which the SiH 3 mechanism is found to be more thermodynamically favorable. Moreover, both of the fragments were found to show selectivity toward the Si-H bond and not C-H bond of the surface. On the basis of this, a selective Si deposition process is suggested for silicon versus carbon-doped silicon oxide surfaces.

Sustaining PICA for Future NASA Robotic Science Missions Including NF-4 and Discovery

NASA Technical Reports Server (NTRS)

Stackpoole, Mairead; Venkatapathy, Ethiraj; Violette, Steve

2018-01-01

Phenolic Impregnated Carbon Ablator (PICA), invented in the mid 1990's, is a low-density ablative thermal protection material proven capable of meeting sample return mission needs from the moon, asteroids, comets and other unrestricted class V destinations as well as for Mars. Its low density and efficient performance characteristics have proven effective for use from Discovery to Flag-ship class missions. It is important that NASA maintain this thermal protection material capability and ensure its availability for future NASA use. The rayon based carbon precursor raw material used in PICA preform manufacturing has experienced multiple supply chain issues and required replacement and requalification at least twice in the past 25 years and a third substitution is now needed. The carbon precursor replacement challenge is twofold - the first involves finding a long-term replacement for the current rayon and the second is to assess its future availability periodically to ensure it is sustainable and be alerted if additional replacement efforts need to be initiated. This paper reviews current PICA sustainability activities to identify a rayon replacement and to establish that the capability of the new PICA derived from an alternative precursor is in family with previous versions.

Shack-Hartmann Electron Densitometer (SHED): An Optical System for Diagnosing Free Electron Density in Laser-Produced Plasmas

DTIC Science & Technology

2016-11-01

a few nanoseconds. The challenge remains to diagnose plasmas via the free electron density in this short window of time and often in a small volume ...Free Electron Density in Laser-Produced Plasmas by Anthony R Valenzuela Approved for public release; distribution is...US Army Research Laboratory Shack-Hartmann Electron Densitometer (SHED): An Optical System for Diagnosing Free Electron Density in Laser

Conjugated Polymers Atypically Prepared in Water

PubMed Central

Invernale, Michael A.; Pendergraph, Samuel A.; Yavuz, Mustafa S.; Ombaba, Matthew; Sotzing, Gregory A.

2010-01-01

Processability remains a fundamental issue for the implementation of conducting polymer technology. A simple synthetic route towards processable precursors to conducting polymers (main chain and side chain) was developed using commercially available materials. These soluble precursor systems were converted to conjugated polymers electrochemically in aqueous media, offering a cheaper and greener method of processing. Oxidative conversion in aqueous and organic media each produced equivalent electrochromics. The precursor method enhances the yield of the electrochromic polymer obtained over that of electrodeposition, and it relies on a less corruptible electrolyte bath. However, electrochemical conversion of the precursor polymers often relies on organic salts and solvents. The ability to achieve oxidative conversion in brine offers a less costly and a more environmentally friendly processing step. It is also beneficial for biological applications. The electrochromics obtained herein were evaluated for electronic, spectral, and morphological properties. PMID:20959869

A structural investigation of a synthesized precursor for optical fiber applications; the heterobimetallic ErNb 2(OPr i) 13

NASA Astrophysics Data System (ADS)

Engholm, M.; Norin, L.; Edvardsson, S.; Lashgari, K.; Westin, G.

2006-12-01

A structural investigation of a synthesized precursor in a silica glass matrix is performed. Silica soot samples are doped with the heterobimetallic precursor ErNb 2(OPr i) 13 by using a conventional solution doping technique and heat treatments to different temperatures. The precursor has also been introduced into a silica fiber preform by using the modified chemical vapor deposition technique. Analyses are made by using ultraviolet-visible-near infrared absorption spectroscopy, scanning electron microscopy, energy dispersive spectroscopy and powder X-ray diffraction. It is concluded that an immiscible system of ErNbO 4 crystallites and Nb 2O 5 is formed in the silica soot samples at high temperatures. Colloidal particles of ErNbO 4 are also formed in the silica glass fiber preform showing interesting features.

Electron dynamics in high energy density plasma bunch generation driven by intense picosecond laser pulse

NASA Astrophysics Data System (ADS)

Li, M.; Yuan, T.; Xu, Y. X.; Luo, S. N.

2018-05-01

When an intense picosecond laser pulse is loaded upon a dense plasma, a high energy density plasma bunch, including electron bunch and ion bunch, can be generated in the target. We simulate this process through one-dimensional particle-in-cell simulation and find that the electron bunch generation is mainly due to a local high energy density electron sphere originated in the plasma skin layer. Once generated the sphere rapidly expands to compress the surrounding electrons and induce high density electron layer, coupled with that, hot electrons are efficiently triggered in the local sphere and traveling in the whole target. Under the compressions of light pressure, forward-running and backward-running hot electrons, a high energy density electron bunch generates. The bunch energy density is as high as TJ/m3 order of magnitude in our conditions, which is significant in laser driven dynamic high pressure generation and may find applications in high energy density physics.

Creation of high-refractive-index amorphous titanium oxide thin films from low-fractal-dimension polymeric precursors synthesized by a sol-gel technique with a hydrazine monohydrochloride catalyst.

PubMed

Shimizu, Wataru; Nakamura, Satoshi; Sato, Takaaki; Murakami, Yasushi

2012-08-21

Amorphous titanium dioxide (TiO(2)) thin films exhibiting high refractive indices (n ≈ 2.1) and high transparency were fabricated by spin-coating titanium oxide liquid precursors having a weakly branched polymeric structure. The precursor solution was prepared from titanium tetra-n-butoxide (TTBO) via the catalytic sol-gel process with hydrazine monohydrochloride used as a salt catalyst, which serves as a conjugate acid-base pair catalyst. Our unique catalytic sol-gel technique accelerated the overall polycondensation reaction of partially hydrolyzed alkoxides, which facilitated the formation of liner polymer-like titanium oxide aggregates having a low fractal dimension of ca. (5)/(3), known as a characteristic of the so-called "expanded polymer chain". Such linear polymeric features are essential to the production of highly dense amorphous TiO(2) thin films; mutual interpenetration of the linear polymeric aggregates avoided the creation of void space that is often generated by the densification of high-fractal-dimension (particle-like) aggregates produced in a conventional sol-gel process. The mesh size of the titanium oxide polymers can be tuned either by water concentration or the reaction time, and the smaller mesh size in the liquid precursor led to a higher n value of the solid thin film, thanks to its higher local electron density. The reaction that required no addition of organic ligand to stabilize titanium alkoxides was advantageous to overcoming issues from organic residues such as coloration. The dense amorphous film structure suppressed light scattering loss owing to its extremely smooth surface and the absence of inhomogeneous grains or particles. Furthermore, the fabrication can be accomplished at a low heating temperature of <80 °C. Indeed, we successfully obtained a transparent film with a high refractive index of n = 2.064 (at λ = 633 nm) on a low-heat-resistance plastic, poly(methyl methacrylate), at 60 °C. The result offers an efficient route to high-refractive-index amorphous TiO(2) films as well as base materials for a wider range of applications.

Highly Efficient and Stable MAPbI₃ Perovskite Solar Cell Induced by Regulated Nucleation and Ostwald Recrystallization.

PubMed

Huang, Zhen; Wang, Duofa; Wang, Song; Zhang, Tianjin

2018-05-11

Perovskite solar cells have attracted great attention in recent years, due to their high conversion efficiency and solution-processable fabrication. However, most of the solar cells with high efficiency in the literature are prepared employing TiO₂ as electron transport material, which needs sintering at a temperature higher than 450 °C, and is not applicable to flexible device and low-cost fabrication. Herein, the MAPbI₃ perovskite solar cells are fabricated at a low temperature of 150 °C with SnO₂ as the electron transport layer. By dropping the antisolvent of ethyl acetate onto the perovskite precursor films during the spin coating process, compact MAPbI₃ films without pinholes are obtained. The addition of ethyl acetate is found to play an important role in regulating the nucleation, which subsequently improves the compactness of the film. The quality of MAPbI₃ films are further improved significantly through Ostwald recrystallization by optimizing the thermal treatment. The crystallinity is enhanced, the grain size is enlarged, and the defect density is reduced. Accordingly, the prepared MAPbI₃ perovskite solar cell exhibits a record-high conversion efficiency, outstanding reproducibility, and stability, owing to the reduced electron recombination. The average and best efficiency reaches 19.2% and 20.3%, respectively. The device without encapsulation maintains 94% of the original efficiency after storage in ambient air for 600 h.

Confirmed assignments of isomeric dimethylbenzyl radicals generated by corona discharge.

PubMed

Yoon, Young Wook; Lee, Sang Kuk

2011-12-07

The controversial vibronic assignments of isomeric dimethylbenzyl radicals were clearly resolved by using different precursors. By employing corresponding dimethylbenzyl chlorides as precursors, we identified the origins of the vibronic bands of the dimethylbenzyl radicals generated by corona discharge of 1,2,4-trimethylbenzene. From the analysis of the spectra observed from the dimethylbenzyl chlorides in a corona excited supersonic expansion, we revised previous assignments of the 3,4-, 2,4-, and 2,5-dimethylbenzyl radicals. Spectroscopic data of electronic transition and vibrational mode frequencies in the ground electronic state of each isomer were accurately determined by comparing them with those obtained by an ab initio calculation and with the known vibrational data of 1,2,4-trimethylbenzene. © 2011 American Institute of Physics

Synthesis of noble metal/carbon nanotube composites in supercritical methanol.

PubMed

Sun, Zhenyu; Fu, Lei; Liu, Zhimin; Han, Buxing; Liu, Yunqi; Du, Jimin

2006-03-01

A simple and efficient route has been employed to deposit noble metal nanoparticles (Pt, Ru, Pt-Ru, Rh, Ru-Sn) onto carbon nanotubes (CNTs) in supercritical methanol solution. In this method, the inorganic metallic salts acted as metal precursors, and methanol as solvent as well as reductant for the precursors. The as-prepared nanocomposites were structurally and morphologically characterized by X-ray diffraction spectroscopy, transmission electron microscopy (TEM), scanning electron microscopy, and X-ray photoelectron spectroscopy analyses. It was demonstrated that the CNTs were decorated by crystalline metal nanoparticles with uniform sizes and a narrow particle size distribution. The size and loading content of the nanoparticles on CNTs could be tuned by manipulating reaction parameters. Furthermore, the formation mechanism of the composites was also discussed.

A hybrid-drive nonisobaric-ignition scheme for inertial confinement fusion

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

He, X. T., E-mail: xthe@iapcm.ac.cn; Center for Applied Physics and Technology, HEDPS, Peking University, Beijing 100871; IFSA Collaborative Innovation Center of MoE, Shanghai Jiao-Tong University, Shanghai 200240

A new hybrid-drive (HD) nonisobaric ignition scheme of inertial confinement fusion (ICF) is proposed, in which a HD pressure to drive implosion dynamics increases via increasing density rather than temperature in the conventional indirect drive (ID) and direct drive (DD) approaches. In this HD (combination of ID and DD) scheme, an assembled target of a spherical hohlraum and a layered deuterium-tritium capsule inside is used. The ID lasers first drive the shock to perform a spherical symmetry implosion and produce a large-scale corona plasma. Then, the DD lasers, whose critical surface in ID corona plasma is far from the radiationmore » ablation front, drive a supersonic electron thermal wave, which slows down to a high-pressure electron compression wave, like a snowplow, piling up the corona plasma into high density and forming a HD pressurized plateau with a large width. The HD pressure is several times the conventional ID and DD ablation pressure and launches an enhanced precursor shock and a continuous compression wave, which give rise to the HD capsule implosion dynamics in a large implosion velocity. The hydrodynamic instabilities at imploding capsule interfaces are suppressed, and the continuous HD compression wave provides main pdV work large enough to hotspot, resulting in the HD nonisobaric ignition. The ignition condition and target design based on this scheme are given theoretically and by numerical simulations. It shows that the novel scheme can significantly suppress implosion asymmetry and hydrodynamic instabilities of current isobaric hotspot ignition design, and a high-gain ICF is promising.« less

The topology of the Coulomb potential density. A comparison with the electron density, the virial energy density, and the Ehrenfest force density.

PubMed

Ferreira, Lizé-Mari; Eaby, Alan; Dillen, Jan

2017-12-15

The topology of the Coulomb potential density has been studied within the context of the theory of Atoms in Molecules and has been compared with the topologies of the electron density, the virial energy density and the Ehrenfest force density. The Coulomb potential density is found to be mainly structurally homeomorphic with the electron density. The Coulomb potential density reproduces the non-nuclear attractor which is observed experimentally in the molecular graph of the electron density of a Mg dimer, thus, for the first time ever providing an alternative and energetic foundation for the existence of this critical point. © 2017 Wiley Periodicals, Inc. © 2017 Wiley Periodicals, Inc.

Effect of Sn Content in a CuSnZn Metal Precursor on Formation of MoSe2 Film during Selenization in Se+SnSe Vapor

PubMed Central

Yao, Liyong; Ao, Jianping; Jeng, Ming-Jer; Bi, Jinlian; Gao, Shoushuai; Sun, Guozhong; He, Qing; Zhou, Zhiqiang; Sun, Yun; Chang, Liann-Be

2016-01-01

The preparation of Cu2ZnSnSe4 (CZTSe) thin films by the selenization of an electrodeposited copper–tin–zinc (CuSnZn) precursor with various Sn contents in low-pressure Se+SnSex vapor was studied. Scanning electron microscope (SEM) and energy dispersive spectroscopy (EDS) measurements revealed that the Sn content of the precursor that is used in selenization in a low-pressure Se+SnSex vapor atmosphere only slightly affects the elemental composition of the formed CZTSe films. However, the Sn content of the precursor significantly affects the grain size and surface morphology of CZTSe films. A metal precursor with a very Sn-poor composition produces CZTSe films with large grains and a rough surface, while a metal precursor with a very Sn-rich composition procures CZTSe films with small grains and a compact surface. X-ray diffraction (XRD) and SEM revealed that the metal precursor with a Sn-rich composition can grow a thicker MoSe2 thin film at CZTSe/Mo interface than one with a Sn-poor composition, possibly because excess Sn in the precursor may catalyze the formation of MoSe2 thin film. A CZTSe solar cell with an efficiency of 7.94%was realized by using an electrodeposited metal precursor with a Sn/Cu ratio of 0.5 in selenization in a low-pressure Se+SnSex vapor. PMID:28773366

Modulation of beta-amyloid precursor protein trafficking and processing by the low density lipoprotein receptor family.

PubMed

Cam, Judy A; Bu, Guojun

2006-08-18

Amyloid-beta peptide (Abeta) accumulation in the brain is an early, toxic event in the pathogenesis of Alzheimer's disease (AD). Abeta is produced by proteolytic processing of a transmembrane protein, beta-amyloid precursor protein (APP), by beta- and gamma-secretases. Mounting evidence has demonstrated that alterations in APP cellular trafficking and localization directly impact its processing to Abeta. Recent studies have shown that members of the low-density lipoprotein receptor family, including LRP, LRP1B, SorLA/LR11, and apolipoprotein E (apoE) receptor 2, interact with APP and regulate its endocytic trafficking. Another common feature of these receptors is their ability to bind apoE, which exists in three isoforms in humans and the presence of the epsilon4 allele represents a genetic risk factor for AD. In this review, we summarize the current understanding of the function of these apoE receptors with a focus on their role in APP trafficking and processing. Knowledge of the interactions between these distinct low-density lipoprotein receptor family members and APP may ultimately influence future therapies for AD.

Amyloid-β production via cleavage of amyloid-β protein precursor is modulated by cell density.

PubMed

Zhang, Can; Browne, Andrew; Divito, Jason R; Stevenson, Jesse A; Romano, Donna; Dong, Yuanlin; Xie, Zhongcong; Tanzi, Rudolph E

2010-01-01

Mounting evidence suggests that Alzheimer's disease (AD) is caused by the accumulation of the small peptide, amyloid-β (Aβ), a proteolytic cleavage product of amyloid-β protein precursor (AβPP). Aβ is generated through a serial cleavage of AβPP by β- and γ-secretase. Aβ40 and Aβ42 are the two main components of amyloid plaques in AD brains, with Aβ42 being more prone to aggregation. AβPP can also be processed by α-secretase, which cleaves AβPP within the Aβ sequence, thereby preventing the generation of Aβ. Little is currently known regarding the effects of cell density on AβPP processing and Aβ generation. Here we assessed the effects of cell density on AβPP processing in neuronal and non-neuronal cell lines, as well as mouse primary cortical neurons. We found that decreased cell density significantly increases levels of Aβ40, Aβ42, total Aβ, and the ratio of Aβ42: Aβ40. These results also indicate that cell density is a significant modulator of AβPP processing. Overall, these findings carry profound implications for both previous and forthcoming studies aiming to assess the effects of various conditions and genetic/chemical factors, e.g., novel drugs on AβPP processing and Aβ generation in cell-based systems. Moreover, it is interesting to speculate whether cell density changes in vivo may also affect AβPP processing and Aβ levels in the AD brain.

Encapsulating Metal Clusters and Acid Sites within Small Voids: Synthetic Strategies and Catalytic Consequences

NASA Astrophysics Data System (ADS)

Goel, Sarika

The selective encapsulation of metal clusters within zeolites can be used to prepare clusters that are uniform in diameter and to protect them against sintering and contact with feed impurities, while concurrently allowing active sites to select reactants based on their molecular size, thus conferring enzyme-like specificity to chemical catalysis. The apertures in small and medium-pore zeolites preclude the use of post-synthetic protocols to encapsulate the relevant metal precursors because cationic or anionic precursors with their charge-balancing double layer and gaseous complexes cannot diffuse through their windows or channels. We have developed general strategies to encapsulate metal clusters within small-pore zeolites by using metal precursors stabilized by ammonia or organic amine ligands, which stabilize metal precursors against their premature precipitation at the high temperature and pH conditions required for the hydrothermal synthesis of the target zeolite structures and favor interactions between metal precursors and incipient aluminosilicate nuclei during the self-assembly of microporous frameworks. When synthesis temperatures were higher than 400 K, available ligands were unable to prevent the premature precipitation of the metal precursors. In such cases, encapsulation was achieved instead via interzeolite transformations after successfully encapsulating metal precursors or clusters via post-synthesis exchange or ligand protection into parent zeolites and subsequently converting them into the target structures while retaining the encapsulated clusters or precursors. Such strategies led to the successful selective encapsulation of a wide range of metal clusters (Pt, Pd, Ru, Rh, Ir, Re, and Ag) within small-pore (SOD (sodalite), LTA (Linde type A (zeolite A)), GIS (gismondine), and ANA (analcime)) and medium-pore (MFI (ZSM-5)) zeolites. These protocols provide novel and diverse mechanism-based strategies for the design of catalysts with protected active sites. We have demonstrated the selectivity of the encapsulation processes by combining transmission electron microscopy and chemisorptive titrations with rigorous catalytic assessments of the ability of these materials to catalyze reactions of small molecules, which can access the intracrystalline voids, but not of larger molecules that cannot access the metal clusters within such voids. The selective confinement of clusters also prevented their contact with sulfur compounds (e.g., thiophene and H2S), thus allowing reactions to occur at conditions that otherwise render unconfined clusters unreactive. We have also developed synthetic protocols and guiding principles, inspired by mechanistic considerations, for the synthesis of zeolites via interzeolite transformations without the use of organic structure-directing agents (OSDA). More specifically, we have synthesized high-silica MFI (ZSM-5), CHA (chabazite), STF (SSZ-35) and MTW (ZSM-12) zeolites from FAU (faujasite) or BEA (beta) parent materials. Structures with lower framework densities (FAU or BEA) were successfully transformed into thermodynamically-favored, more stable structures with higher framework densities (MFI, CHA, STF, and MTW); to date, target materials with higher Si/Al ratios (Si/Al >10) have not been synthesized via interzeolite transformations without the aid of the OSDA species used to discover these zeolite structures and deemed essential up until now for their successful synthesis. Overcoming kinetic hurdles in such transformations required either the presence of common composite building units (CBU) between parent and target structures or, in their absence, the introduction of small amount of seeds of the daughter structures. The NaOH/SiO2 ratio, H2O/SiO2 ratio and Al content in reagents are used to enforce synchronization between the swelling and local restructuring within parent zeolite domains with the spalling of fragments or building units from seeds of the target structure. The pseudomorphic nature of these seed-mediated transformations, which conserve the volume occupied by the parent crystals and lead to similar size and crystal shape in products, reflect incipient nucleation of target structures occurring at the outer regions of the parent domains and lead to the formation of mesoporosity as a natural consequence of the space-conserving nature of these structural changes and of the higher density of the daughter frameworks. The synthesis mechanism and the guidelines developed enable us to enforce conditions required for the formation of zeolites that previously required OSDA species for their synthesis, thus expanding to a significant extent the diversity of zeolite frameworks that are accessible via these synthesis protocols and providing potential savings in the time and cost involved in the synthesis of some of these zeolite structures.

Method for removing atomic-model bias in macromolecular crystallography

DOEpatents

Terwilliger, Thomas C [Santa Fe, NM

2006-08-01

Structure factor bias in an electron density map for an unknown crystallographic structure is minimized by using information in a first electron density map to elicit expected structure factor information. Observed structure factor amplitudes are combined with a starting set of crystallographic phases to form a first set of structure factors. A first electron density map is then derived and features of the first electron density map are identified to obtain expected distributions of electron density. Crystallographic phase probability distributions are established for possible crystallographic phases of reflection k, and the process is repeated as k is indexed through all of the plurality of reflections. An updated electron density map is derived from the crystallographic phase probability distributions for each one of the reflections. The entire process is then iterated to obtain a final set of crystallographic phases with minimum bias from known electron density maps.

MOCVD of aluminium oxide films using aluminium β-diketonates as precursors

NASA Astrophysics Data System (ADS)

Devi, A.; Shivashankar, S. A.; Samuelson, A. G.

2002-06-01

Deposition of Al203 coatings by CVD is of importance because they are often used as abrading material in cemented carbide cutting tools. The conventionally used CVD process for Al203 involves the corrosive reactant AICl3. In this paper, we report on the thermal characterisation of the metalorganic precursors namely aluminium tris-tetramethyl-heptanedionate [ Al(thd)3] and aluminium tris-acetylacetonate [ Al(acac)3] and their application to the CVD of Al203 films. Crystalline A1203 films were deposited by MOCVD at low temperatures by the pyrolysis of Al(thd)3 and AI(acac)3. The films were deposited on a TiN-coated tungsten carbide (TiN/WC) and Si(100) substrates in the temperature range 500-1100 °C. The as-deposited films were characterised by x-ray diffraction, optical microscopy, scanning and transmission electron microscopy, Auger electron spectroscopy. The observed crystallinity of films grown at low temperatures, their microstructure, and composition may be interpreted in terms of a growth process that involves the melting of the metalorganic precursor on the hot growth surface.

Spectroscopic Identification of p-CHLORO-α-METHYLBENZYL Radical in the Gas Phase

NASA Astrophysics Data System (ADS)

Lee, Seung Woon; Lee, Gi Woo; Lee, Sang Kuk

2009-06-01

We report the first spectroscopic identification of the p-fluoro-α-methylbenzyl radical in the gas phase. Precursor p-fluoro-ethylbenzene seeded in a large amount of inert carrier gas helium was electrically discharged to produce the benzyl-type radicals in a corona excited supersonic expansion using a pinhole-type glass nozzle, from which the vibronic emission spectrum was recorded in the visible region using a long path monochromator. From an analysis of the spectrum observed, we found the formation of p-fluoro-α-methylbenzyl radical as well as p-fluorobenzyl radical in the jet from the precursor. After eliminating the bands belonging to p-fluorobenzyl radical using the known data, we identified spectroscopically the formation of the p-fluoro-α-methylbenzyl radical, in which the energy of the D_1 → D_0 electronic transition and a few vibrational mode frequencies in the ground electronic state were determined by comparison with those from an ab initio calculation and with those from the known data of the precursor. S. K. Lee and D. Y. Baek Chem. Phys. Lett. 301(3-4), 407-412 (1999).

Theoretical and experimental studies on silica-coated carbon spheres composites

NASA Astrophysics Data System (ADS)

Guo, Xingmei; Liu, Haixing; Shen, Yinghua; Niu, Mei; Yang, Yongzhen; Liu, Xuguang

2013-10-01

In order to prepare carbon-based photonic crystals, first of all, theoretical modeling calculation was used to predict the bandgap characteristics of silica-coated carbon spheres. Then, silica-coated carbon spheres composites were synthesized using tetraethyl orthosilicate as precursor of silica by a sol-gel method combined with Stöber method. Effect of reaction conditions on surface coating of carbon spheres with silica, including the pH, the amount of precursor and reaction time, was emphasized. The morphology and structure of the composites and the effect coating of carbon spheres with silica were characterized by field-emission scanning electron microscopy, high resolution transmission electron microscopy and Fourier-transform infrared spectrometry. The coating ratio of silica was investigated by thermogravimetry. The results show that pH value played an important role in coating reaction, the dosage of the precursor and reaction time had significant effect on coating layer thickness, that is, coating ratio. Carbon spheres coated with silica had good dispersibility and dispersion stability in water and ethanol, which is preconditions of reactivity of carbon spheres in liquid phase and lays the basis for the application of carbon spheres.

Hydrothermal development and characterization of the wear-resistant boron carbide from Pandanus: a natural carbon precursor

NASA Astrophysics Data System (ADS)

Saritha Devi, H. V.; Swapna, M. S.; Ambadas, G.; Sankararaman, S.

2018-04-01

Boron carbide (B4C) is a prominent semiconducting material that finds applications in the field of science and technology. The excellent physical, thermal and electronic properties make it suitable as ceramic armor, wear-resistant, lens polisher and neutron absorber in the nuclear industry. The existing methods of synthesis of boron carbide involve the use of toxic chemicals that adversely affect the environment. In the present work, we report for the first time the use of the hydrothermal method, for converting the cellulose from Pandanus leaves as the carbon precursor for the synthesis of B4C. The carbon precursor is changed into porous functionalized carbon by treating with sodium borohydride (NaBH4), followed by treating with boric acid to obtain B4C. The samples are characterized by scanning electron microscopy, X-ray diffraction, Fourier transform infrared, Raman, photoluminescent and Ultraviolet-Visible absorption spectroscopy. The formation of B4C from natural carbon source— Pandanus presents an eco-friendly, economic and non-toxic approach for the synthesis of refractory carbides.

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

Prakash, Abhinav, E-mail: praka019@umn.edu; Dewey, John; Yun, Hwanhui

Owing to its high room-temperature electron mobility and wide bandgap, BaSnO{sub 3} has recently become of significant interest for potential room-temperature oxide electronics. A hybrid molecular beam epitaxy (MBE) approach for the growth of high-quality BaSnO{sub 3} films is developed in this work. This approach employs hexamethylditin as a chemical precursor for tin, an effusion cell for barium, and a radio frequency plasma source for oxygen. BaSnO{sub 3} films were thus grown on SrTiO{sub 3} (001) and LaAlO{sub 3} (001) substrates. Growth conditions for stoichiometric BaSnO{sub 3} were identified. Reflection high-energy electron diffraction (RHEED) intensity oscillations, characteristic of a layer-by-layermore » growth mode were observed. A critical thickness of ∼1 nm for strain relaxation was determined for films grown on SrTiO{sub 3} using in situ RHEED. Scanning transmission electron microscopy combined with electron energy-loss spectroscopy and energy dispersive x-ray spectroscopy confirmed the cube-on-cube epitaxy and composition. The importance of precursor chemistry is discussed in the context of the MBE growth of BaSnO{sub 3}.« less

Surface reaction of silicon chlorides during atomic layer deposition of silicon nitride

NASA Astrophysics Data System (ADS)

Yusup, Luchana L.; Park, Jae-Min; Mayangsari, Tirta R.; Kwon, Young-Kyun; Lee, Won-Jun

2018-02-01

The reaction of precursor with surface active site is the critical step in atomic layer deposition (ALD) process. We performed the density functional theory calculation with DFT-D correction to study the surface reaction of different silicon chloride precursors during the first half cycle of ALD process. SiCl4, SiH2Cl2, Si2Cl6 and Si3Cl8 were considered as the silicon precursors, and an NH/SiNH2*-terminated silicon nitride surface was constructed to model the thermal ALD processes using NH3 as well as the PEALD processes using NH3 plasma. The total energies of the system were calculated for the geometry-optimized structures of physisorption, chemisorption, and transition state. The order of silicon precursors in energy barrier, from lowest to highest, is Si3Cl8 (0.92 eV), Si2Cl6 (3.22 eV), SiH2Cl2 (3.93 eV) and SiCl4 (4.49 eV). Silicon precursor with lower energy barrier in DFT calculation showed lower saturation dose in literature for both thermal and plasma-enhanced ALD of silicon nitride. Therefore, DFT calculation is a promising tool in predicting the reactivity of precursor during ALD process.

The hybrid nanostructure of MnCo2O4.5 nanoneedle/carbon aerogel for symmetric supercapacitors with high energy density.

PubMed

Hao, Pin; Zhao, Zhenhuan; Li, Liyi; Tuan, Chia-Chi; Li, Haidong; Sang, Yuanhua; Jiang, Huaidong; Wong, C P; Liu, Hong

2015-09-14

Current applications of carbon-based supercapacitors are limited by their low energy density. One promising strategy to enhance the energy density is to couple metal oxides with carbon materials. In this study, a porous MnCo2O4.5 nanoneedle/carbon aerogel hybrid nanostructure was synthesized by assembling MnCo2O4.5 nanoneedle arrays on the surface of channel walls of hierarchical porous carbon aerogels derived from chitosan for the supercapacitor application. The synthetic process of the hybrid nanostructure involves two steps, i.e. the growth of Mn-Co precursors on carbon aerogel by a hydrothermal process and the conversion of the precursor into MnCo2O4.5 nanoneedles by calcination. The carbon aerogel exhibits a high electrical conductivity, high specific surface area and porous structure, ensuring high electrochemical performance of the hybrid nanostructure when coupled with the porous MnCo2O4.5 nanoneedles. The symmetric supercapacitor using the MnCo2O4.5 nanoneedle/carbon aerogel hybrid nanostructure as the active electrode material exhibits a high energy density of about 84.3 Wh kg(-1) at a power density of 600 W kg(-1). The voltage window is as high as 1.5 V in neutral aqueous electrolytes. Due to the unique nanostructure of the electrodes, the capacitance retention reaches 86% over 5000 cycles.

Device and method for electron beam heating of a high density plasma

DOEpatents

Thode, Lester E.

1981-01-01

A device and method for relativistic electron beam heating of a high density plasma in a small localized region. A relativistic electron beam generator produces a high voltage electron beam which propagates along a vacuum drift tube and is modulated to initiate electron bunching within the beam. The beam is then directed through a low density gas chamber which provides isolation between the vacuum modulator and the relativistic electron beam target. The relativistic beam is then applied to a high density target plasma which typically comprises DT, DD, hydrogen boron or similar thermonuclear gas at a density of 10.sup.17 to 10.sup.20 electrons per cubic centimeter. The target plasma is ionized prior to application of the electron beam by means of a laser or other preionization source. Utilizing a relativistic electron beam with an individual particle energy exceeding 3 MeV, classical scattering by relativistic electrons passing through isolation foils is negligible. As a result, relativistic streaming instabilities are initiated within the high density target plasma causing the relativistic electron beam to efficiently deposit its energy into a small localized region within the high density plasma target.

Handling Density Conversion in TPS.

PubMed

Isobe, Tomonori; Mori, Yutaro; Takei, Hideyuki; Sato, Eisuke; Tadano, Kiichi; Kobayashi, Daisuke; Tomita, Tetsuya; Sakae, Takeji

2016-01-01

Conversion from CT value to density is essential to a radiation treatment planning system. Generally CT value is converted to the electron density in photon therapy. In the energy range of therapeutic photon, interactions between photons and materials are dominated with Compton scattering which the cross-section depends on the electron density. The dose distribution is obtained by calculating TERMA and kernel using electron density where TERMA is the energy transferred from primary photons and kernel is a volume considering spread electrons. Recently, a new method was introduced which uses the physical density. This method is expected to be faster and more accurate than that using the electron density. As for particle therapy, dose can be calculated with CT-to-stopping power conversion since the stopping power depends on the electron density. CT-to-stopping power conversion table is also called as CT-to-water-equivalent range and is an essential concept for the particle therapy.

Production of O2 on icy satellites by electronic excitation of low-temperature water ice.

PubMed

Sieger, M T; Simpson, W C; Orlando, T M

1998-08-06

The signature of condensed molecular oxygen has been reported in recent optical-reflectance measurements of the jovian moon Ganymede, and a tenuous oxygen atmosphere has been observed on Europa. The surfaces of these moons contain large amounts of water ice, and it is thought that O2 is formed by the sputtering of ice by energetic particles from the jovian magnetosphere. Understanding how O2 might be formed from low-temperature ice is crucial for theoretical and experimental simulations of the surfaces and atmospheres of icy bodies in the Solar System. Here we report laboratory measurements of the threshold energy, cross-section and temperature dependence of O2 production by electronic excitation of ice in vacuum, following electron-beam irradiation. Molecular oxygen is formed by direct excitation and dissociation of a stable precursor molecule, rather than (as has been previously thought) by diffusion and chemical recombination of precursor fragments. The large cross-section for O2 production suggests that electronic excitation plays an important part in the formation of O2 on Ganymede and Europa.

Synthesis and Photoluminescence Characteristics of Eu(3+)-Doped Molybdates Nanocrystals.

PubMed

Li, Fuhai; Yu, Lixin; Wei, Shuilin; Sun, Jiaju; Chen, Weiqing; Sun, Wei

2015-12-01

In this paper, the Eu(3+)-doped molybdate (CaMoO4, ZnMoO4 and BaMoO4) phosphors have been prepared by a hydrothermal method through modulating the pH value of the precursor solution (pH = 8, 10, and 12, respectively). The crystalline phase, morphology, photoluminescent properties of the prepared samples were systematically characterized by means of X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM) and photoluminescence (PL) spectra. The results indicate that the photoluminescence and morphology can be affected by the precursor solution. And the growth of the ZnMoO4 crystals also can be affected by the pH value of the precursor solution.

Reactive Processing of Environmentally Conscious, Biomorphic Ceramics from Natural Wood Precursors

NASA Technical Reports Server (NTRS)

Singh, M.; Yee, Bo-Moon

2003-01-01

Environmentally conscious, biomorphic ceramics (Ecoceramics) are a new class of materials that are manufactured from renewable resources and wastes. In this study, silicon carbide and oxide-based biomorphic ceramics have been fabricated from pine and jelutong wood precursors. A carbonaceous preform is produced through wood pyrolysis and subsequent infiltration with oxides (ZrO2 sols) and liquid silicon to form ceramics. These biomorphic ceramics show a wide variety of microstructures, densities, and hardness behavior that are determined by the type of wood and infiltrants selected.

Incorporation of Deoxyribonucleic Acid Precursors by T4 Deoxyribonucleic Acid-Protein Complexes Retained on Glass Fiber Filters

PubMed Central

Miller, Robert C.; Kozinski, Andrzej W.

1970-01-01

Bacteriophage T4 deoxyribonucleic acid (DNA)-protein complexes were retained preferentially on glass fiber filters. DNA polymerase activity in the complex was detected through the incorporation of 3H-labeled DNA precursors. The primer-product DNA hybridized with both phage and Escherichia coli DNA. Density labeling experiments showed that about 30% of incorporated 3H-deoxyadenosine triphosphate was found in DNA which hybridized with phage DNA; this DNA was found to be covalently attached to the primer DNA. PMID:5497903

Method of Cross-Linking Aerogels Using a One-Pot Reaction Scheme

NASA Technical Reports Server (NTRS)

Meador, Ann B.; Capadona, Lynn A.

2008-01-01

A document discusses a new, simplified method for cross-linking silica and other oxide aerogels, with a polymeric material to increase strength of such materials without adversely affecting porosity or low density. This innovation introduces the polymer precursor into the sol before gelation either as an agent, which co-reacts with the oxide gel, or as soluble polymer precursors, which do not interact with the oxide gel in any way. Subsequent exposure to heat, light, catalyst or other method of promoting polymerization causes cross-linking without any additional infiltration steps.

Influence of Boehmite Precursor on Aluminosilicate Aerogel Pore Structure, Phase Stability and Resistance to Densification at High Temperatures

NASA Technical Reports Server (NTRS)

Hurwitz, Frances I.; Guo, Haiquan; Newlin, Katy N.

2011-01-01

Aluminosilicate aerogels are of interest as constituents of thermal insulation systems for use at temperatures higher than those attainable with silica aerogels. It is anticipated that their effectiveness as thermal insulators will be influenced by their morphology, pore size distribution, physical and skeletal densities. The present study focuses on the synthesis of aluminosilicate aerogel from a variety of Boehmite (precursors as the Al source, and tetraethylorthosilicate (TEOS) as the Si source, and the influence of starting powder on pore structure and thermal stability.

How "Hot Precursors" Modify Island Nucleation: A Rate-Equation Model

NASA Astrophysics Data System (ADS)

Morales-Cifuentes, Josue R.; Einstein, T. L.; Pimpinelli, A.

2014-12-01

We propose a novel island nucleation and growth model explicitly including transient (ballistic) mobility of the monomers deposited at rate F , assumed to be in a hot precursor state before thermalizing. In limiting regimes, corresponding to fast (diffusive) and slow (ballistic) thermalization, the island density N obeys scaling N ∝Fα . In between is found a rich, complex behavior, with various distinctive scaling regimes, characterized by effective exponents αeff and activation energies that we compute exactly. Application to N (F ,T ) of recent organic-molecule deposition experiments yields an excellent fit.

From Carbon-Based Nanotubes to Nanocages for Advanced Energy Conversion and Storage.

PubMed

Wu, Qiang; Yang, Lijun; Wang, Xizhang; Hu, Zheng

2017-02-21

Carbon-based nanomaterials have been the focus of research interests in the past 30 years due to their abundant microstructures and morphologies, excellent properties, and wide potential applications, as landmarked by 0D fullerene, 1D nanotubes, and 2D graphene. With the availability of high specific surface area (SSA), well-balanced pore distribution, high conductivity, and tunable wettability, carbon-based nanomaterials are highly expected as advanced materials for energy conversion and storage to meet the increasing demands for clean and renewable energies. In this context, attention is usually attracted by the star material of graphene in recent years. In this Account, we overview our studies on carbon-based nanotubes to nanocages for energy conversion and storage, including their synthesis, performances, and related mechanisms. The two carbon nanostructures have the common features of interior cavity, high conductivity, and easy doping but much different SSAs and pore distributions, leading to different performances. We demonstrated a six-membered-ring-based growth mechanism of carbon nanotubes (CNTs) with benzene precursor based on the structural similarity of the benzene ring to the building unit of CNTs. By this mechanism, nitrogen-doped CNTs (NCNTs) with homogeneous N distribution and predominant pyridinic N were obtained with pyridine precursor, providing a new kind of support for convenient surface functionalization via N-participation. Accordingly, various transition-metal nanoparticles were directly immobilized onto NCNTs without premodification. The so-constructed catalysts featured high dispersion, narrow size distribution and tunable composition, which presented superior catalytic performances for energy conversions, for example, the oxygen reduction reaction (ORR) and methanol oxidation in fuel cells. With the advent of the new field of carbon-based metal-free electrocatalysts, we first extended ORR catalysts from the electron-rich N-doped to the electron-deficient B-doped sp 2 carbon. The combined experimental and theoretical study indicated the ORR activity originated from the activation of carbon π electrons by breaking the integrity of π conjugation, despite the electron-rich or electron-deficient nature of the dopants. With this understanding, metal-free electrocatalysts were further extended to the dopant-free defective carbon nanomaterials. Moreover, we developed novel 3D hierarchical carbon-based nanocages by the in situ MgO template method, which featured coexisting micro-meso-macropores and much larger SSA than the nanotubes. The unique 3D architecture avoids the restacking generally faced by 2D graphene due to the intrinsic π-π interaction. Consequently, the hierarchical nanocages presented superior performances not only as new catalyst supports and metal-free electrocatalysts but also as electrode materials for energy storage. State-of-the-art supercapacitive performances were achieved with high energy density and power density, as well as excellent rate capability and cycling stability. The large interior space of the nanocages enabled the encapsulation of high-loading sulfur to alleviate polysulfide dissolution while greatly enhancing the electron conduction and Li-ion diffusion, leading to top level performance of lithium-sulfur battery. These results not only provide unique carbon-based nanomaterials but also lead to in-depth understanding of growth mechanisms, material design, and structure-performance relationships, which is significant to promote their energy applications and also to enrich the exciting field of carbon-based nanomaterials.

X-Ray Sum Frequency Diffraction for Direct Imaging of Ultrafast Electron Dynamics

NASA Astrophysics Data System (ADS)

Rouxel, Jérémy R.; Kowalewski, Markus; Bennett, Kochise; Mukamel, Shaul

2018-06-01

X-ray diffraction from molecules in the ground state produces an image of their charge density, and time-resolved x-ray diffraction can thus monitor the motion of the nuclei. However, the density change of excited valence electrons upon optical excitation can barely be monitored with regular diffraction techniques due to the overwhelming background contribution of the core electrons. We present a nonlinear x-ray technique made possible by novel free electron laser sources, which provides a spatial electron density image of valence electron excitations. The technique, sum frequency generation carried out with a visible pump and a broadband x-ray diffraction pulse, yields snapshots of the transition charge densities, which represent the electron density variations upon optical excitation. The technique is illustrated by ab initio simulations of transition charge density imaging for the optically induced electronic dynamics in a donor or acceptor substituted stilbene.

Anomalous evolution of Ar metastable density with electron density in high density Ar discharge

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

Park, Min; Chang, Hong-Young; You, Shin-Jae

2011-10-15

Recently, an anomalous evolution of argon metastable density with plasma discharge power (electron density) was reported [A. M. Daltrini, S. A. Moshkalev, T. J. Morgan, R. B. Piejak, and W. G. Graham, Appl. Phys. Lett. 92, 061504 (2008)]. Although the importance of the metastable atom and its density has been reported in a lot of literature, however, a basic physics behind the anomalous evolution of metastable density has not been clearly understood yet. In this study, we investigated a simple global model to elucidate the underlying physics of the anomalous evolution of argon metastable density with the electron density. Onmore » the basis of the proposed simple model, we reproduced the anomalous evolution of the metastable density and disclosed the detailed physics for the anomalous result. Drastic changes of dominant mechanisms for the population and depopulation processes of Ar metastable atoms with electron density, which take place even in relatively low electron density regime, is the clue to understand the result.« less

MAVEN observations of dayside peak electron densities in the ionosphere of Mars

NASA Astrophysics Data System (ADS)

Vogt, Marissa F.; Withers, Paul; Fallows, Kathryn; Andersson, Laila; Girazian, Zachary; Mahaffy, Paul R.; Benna, Mehdi; Elrod, Meredith K.; Connerney, John E. P.; Espley, Jared R.; Eparvier, Frank G.; Jakosky, Bruce M.

2017-01-01

The peak electron density in the dayside Martian ionosphere is a valuable diagnostic of the state of the ionosphere. Its dependence on factors like the solar zenith angle, ionizing solar irradiance, neutral scale height, and electron temperature has been well studied. The Mars Atmosphere and Volatile EvolutioN spacecraft's September 2015 "deep dip" orbits, in which the orbital periapsis was lowered to 125 km, provided the first opportunity since Viking to sample in situ a complete dayside electron density profile including the main peak. Here we present peak electron density measurements from 37 deep dip orbits and describe conditions at the altitude of the main peak, including the electron temperature and composition of the ionosphere and neutral atmosphere. We find that the dependence of the peak electron density and the altitude of the main peak on solar zenith angle are well described by analytical photochemical theory. Additionally, we find that the electron temperatures at the main peak display a dependence on solar zenith angle that is consistent with the observed variability in the peak electron density. Several peak density measurements were made in regions of large crustal magnetic field, but there is no clear evidence that the crustal magnetic field strength influences the peak electron density, peak altitude, or electron temperature. Finally, we find that the fractional abundance of O2+ and CO2+ at the peak altitude is variable but that the two species together consistently represent 95% of the total ion density.

Cubic nitride templates

DOEpatents

Burrell, Anthony K; McCleskey, Thomas Mark; Jia, Quanxi; Mueller, Alexander H; Luo, Hongmei

2013-04-30

A polymer-assisted deposition process for deposition of epitaxial cubic metal nitride films and the like is presented. The process includes solutions of one or more metal precursor and soluble polymers having binding properties for the one or more metal precursor. After a coating operation, the resultant coating is heated at high temperatures under a suitable atmosphere to yield metal nitride films and the like. Such films can be used as templates for the development of high quality cubic GaN based electronic devices.

Synthesis of stable TiO2 nanotubes: effect of hydrothermal treatment, acid washing and annealing temperature.

PubMed

López Zavala, Miguel Ángel; Lozano Morales, Samuel Alejandro; Ávila-Santos, Manuel

2017-11-01

Effect of hydrothermal treatment, acid washing and annealing temperature on the structure and morphology of TiO 2 nanotubes during the formation process was assessed. X-ray diffraction, scanning electron microscopy (SEM), transmission electron microscopy (TEM) and energy dispersive X-ray spectroscopy analysis were conducted to describe the formation and characterization of the structure and morphology of nanotubes. Hydrothermal treatment of TiO 2 precursor nanoparticles and acid washing are fundamental to form and define the nanotubes structure. Hydrothermal treatment causes a change in the crystallinity of the precursor nanoparticles from anatase phase to a monoclinic phase, which characterizes the TiO 2 nanosheets structure. The acid washing promotes the formation of high purity nanotubes due to Na + is exchanged from the titanate structure to the hydrochloric acid (HCl) solution. The annealing temperature affects the dimensions, structure and the morphology of the nanotubes. Annealing temperatures in the range of 400 °C and 600 °C are optimum to maintain a highly stable tubular morphology of nanotubes. Additionally, nanotubes conserve the physicochemical properties of the precursor Degussa P25 nanoparticles. Temperatures greater than 600 °C alter the morphology of nanotubes from tubular to an irregular structure of nanoparticles, which are bigger than those of the precursor material, i.e., the crystallinity turn from anatase phase to rutile phase inducing the collapse of the nanotubes.

Method for fabricating light weight carbon-bonded carbon fiber composites

DOEpatents

Wrenn, Jr., George E.; Abbatiello, Leonard A.; Lewis, Jr., John

1989-01-01

Ultralight carbon-bonded carbon fiber composites of densities in the range of about 0.04 to 0.10 grams per cubic centimeter are fabricated by forming an aqueous slurry of carbonaceous fibers which include carbonized fibers and 0-50 weight percent fugitive fibers and a particulate thermosetting resin precursor. The slurry is brought into contact with a perforated mandrel and the water is drained from the slurry through the perforations at a controlled flow rate of about 0.03 to 0.30 liters per minutes per square inch of mandrel surface. The deposited billet of fibers and resin precursor is heated to cure the resin precursor to bind the fibers together, removed from the mandrel, and then the resin and fugitive fibers, if any, are carbonized.

Tuning the optical properties of ZnO nanorods by variation of precursor concentration through hydrothermal method

NASA Astrophysics Data System (ADS)

Kumari, Lakshmi; Kar, Asit Kumar

2018-05-01

ZnO nanorods with varying precursor concentration have been successfully synthesized by the hydrothermal method. The effect of the precursor concentration on the structural, morphological and optical properties of the resulting nanorods was investigated by means of X-ray diffraction (XRD), Field emission scanning electron microscopy (FESEM), UV-Vis spectroscopy and photoluminescence (PL) spectroscopy. The crystalline structural characterization demonstrated that the synthesized materials crystallize in pure ZnO wurtzite structure without any other secondary phase. SEM micrographs demonstrate nanorod type features in all the samples. In addition, they show that increase of precursor concentration changes the length and diameter of nanorods. The UV-Vis studies show a strong absorption band in UV region at 373 nm attributed to the band-edge absorption of wurtzite hexagonal ZnO, blue shifted relative to its bulk form (380 nm). The PL spectra of obtained nanorods excited at 360 nm present broad visible emission. Moreover, as the visible region (from 510 to 550 nm) is concerned, it is speculated that the increase of the precursor concentration affects strongly the kind of interstitial defects (Oi, Zni and Vo) formed in ZnO nanorods. The luminescence intensity decreases with the increase of precursor concentration.

Assessment of the migration potential of nanosilver from nanoparticle-coated low-density polyethylene food packaging into food simulants.

PubMed

Hannon, Joseph Christopher; Kerry, Joseph P; Cruz-Romero, Malco; Azlin-Hasim, Shafrina; Morris, Michael; Cummins, Enda

2016-01-01

An experimental nanosilver-coated low-density polyethylene (LDPE) food packaging was incubated with food simulants using a conventional oven and tested for migration according to European Commission Regulation No. 10/2011. The commercial LDPE films were coated using a layer-by-layer (LbL) technique and three levels of silver (Ag) precursor concentration (0.5%, 2% and 5% silver nitrate (AgNO3), respectively) were used to attach antimicrobial Ag. The experimental migration study conditions (time, temperature and food simulant) under conventional oven heating (10 days at 60°C, 2 h at 70°C, 2 h at 60°C or 10 days at 70°C) were chosen to simulate the worst-case storage period of over 6 months. In addition, migration was quantified under microwave heating. The total Ag migrant levels in the food simulants were quantified by inductively coupled plasma-atomic emission spectroscopy (ICP-AES). Mean migration levels obtained by ICP-AES for oven heating were in the range 0.01-1.75 mg l(-1). Migration observed for microwave heating was found to be significantly higher when compared with oven heating for similar temperatures (100°C) and identical exposure times (2 min). In each of the packaging materials and food simulants tested, the presence of nanoparticles (NPs) was confirmed by scanning electron microscopy (SEM). On inspection of the migration observed under conventional oven heating, an important finding was the significant reduction in migration resulting from the increased Ag precursor concentration used to attach Ag on the LDPE LbL-coated films. This observation merits further investigation into the LbL coating process used, as it suggests potential for process modifications to reduce migration. In turn, any reduction in NP migration below regulatory limits could greatly support the antimicrobial silver nanoparticle (AgNP)-LDPE LbL-coated films being used as a food packaging material.

Electrical conductivity of activated carbon-metal oxide nanocomposites under compression: a comparison study.

PubMed

Barroso-Bogeat, A; Alexandre-Franco, M; Fernández-González, C; Macías-García, A; Gómez-Serrano, V

2014-12-07

From a granular commercial activated carbon (AC) and six metal oxide (Al2O3, Fe2O3, SnO2, TiO2, WO3 and ZnO) precursors, two series of AC-metal oxide nanocomposites were prepared by wet impregnation, oven-drying at 120 °C, and subsequent heat treatment at 200 or 850 °C in an inert atmosphere. Here, the electrical conductivity of the resulting products was studied under moderate compression. The influence of the applied pressure, sample volume, mechanical work, and density of the hybrid materials was thoroughly investigated. The DC electrical conductivity of the compressed samples was measured at room temperature by the four-probe method. Compaction assays suggest that the mechanical properties of the nanocomposites are largely determined by the carbon matrix. Both the decrease in volume and the increase in density were relatively small and only significant at pressures lower than 100 kPa for AC and most nanocomposites. In contrast, the bulk electrical conductivity of the hybrid materials was strongly influenced by the intrinsic conductivity, mean crystallite size, content and chemical nature of the supported phases, which ultimately depend on the metal oxide precursor and heat treatment temperature. The supported nanoparticles may be considered to act as electrical switches either hindering or favouring the effective electron transport between the AC cores of neighbouring composite particles in contact under compression. Conductivity values as a rule were lower for the nanocomposites than for the raw AC, all of them falling in the range of semiconductor materials. With the increase in heat treatment temperature, the trend is toward the improvement of conductivity due to the increase in the crystallite size and, in some cases, to the formation of metals in the elemental state and even metal carbides. The patterns of variation of the electrical conductivity with pressure and mechanical work were slightly similar, thus suggesting the predominance of the pressure effects rather than the volume ones.

Precursor of superfluidity in a strongly interacting Fermi gas with negative effective range

NASA Astrophysics Data System (ADS)

Tajima, Hiroyuki

2018-04-01

We investigate theoretically the effects of pairing fluctuations in an ultracold Fermi gas near a Feshbach resonance with a negative effective range. By employing a many-body T -matrix theory with a coupled fermion-boson model, we show that the single-particle density of states exhibits the so-called pseudogap phenomenon, which is a precursor of superfluidity induced by strong pairing fluctuations. We clarify the region where strong pairing fluctuations play a crucial role in single-particle properties, from the broad-resonance region to the narrow-resonance limit at the divergent two-body scattering length. We also extrapolate the effects of pairing fluctuations to the positive-effective-range region from our results near the narrow Feshbach resonance. Results shown in this paper are relevant to the connection between ultracold Fermi gases and low-density neutron matter from the viewpoint of finite-effective-range corrections.

Hierarchical porous carbon microspheres derived from porous starch for use in high-rate electrochemical double-layer capacitors.

PubMed

Du, Si-Hong; Wang, Li-Qun; Fu, Xiao-Ting; Chen, Ming-Ming; Wang, Cheng-Yang

2013-07-01

Porous starch was used as a precursor for hierarchical porous carbon microspheres. The preparation consisted of stabilisation, carbonisation and KOH activation, and the resultant hierarchical porous carbon microspheres had a large BET surface area of 3251 m(2)g(-1). Due to the large surface area and the hierarchical pore structure, electrodes made of the hierarchical porous carbon microsphere materials had high specific capacitances of 304 Fg(-1) at a current density of 0.05 Ag(-1) and 197 Fg(-1) at a current density of 180 Ag(-1) when used in a symmetric capacitor with 6M KOH as the electrolyte. After 10,000 cycles, the capacitor still exhibited a stable performance with a capacitance retention of 98%. These results indicate that porous starch is an excellent precursor to prepare high performance electrode materials for EDLCs. Copyright © 2013 Elsevier Ltd. All rights reserved.

High performance porous Si@C anodes synthesized by low temperature aluminothermic reaction

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

Mishra, Kuber; Zheng, Jianming; Patel, Rajankumar

A low temperature (210°C) aluminothermic reduction reaction process has been developed to synthesis porous silicon (Si) as an anode for Li ion battery applications. An eutectic mixture of AlCl3 and ZnCl2 is used as the mediator to reduce the reaction temperature. With carbon pre-coated on the porous SiO2 precursor, porous Si@C core shell structured anodes could be obtained with structure and morphology similar to that of the porous precursor. In addition, carbon coated porous Si also exhibits superior cyclic stability, higher rate performance, and higher coulombic efficiency. The porous Si anode demonstrates a high specific capacity of ~2100 mAh/g atmore » the current density of 1.2 A/g and has a good cycling stability with ~76% capacity retention over 250 cycles. Therefore, it will be a good candidate for anode used in high energy density Li-ion batteries.« less

Fabrication and properties of SiNO continuous fiber reinforced BN wave-transparent composites

NASA Astrophysics Data System (ADS)

Cao, F.; Fang, Z.; Chen, F.; Shen, Q.; Zhang, C.

2012-06-01

SiNO continuous fiber reinforced boron nitride (BN) wave-transparent composites (SiNO f /BN) have been fabricated by a precursor infiltration pyrolysis (PIP) method using borazine as the precursor. The densification behavior, microstructures, mechanical properties, and dielectric properties of the composites have been investigated. After four PIP cycles, the density of the composites had increased from 1.1 g·cm-3 to 1.81 g·cm-3. A flexural strength of 128.9 MPa and an elastic modulus of 23.5 GPa were achieved. The obtained composites have relatively high density and the fracture faces show distinct fiber pull-out and interface de-bonding features. The dielectric properties of the SiNO f /BN composites, including the dielectric constant of 3.61 and the dielectric loss angle tangent of 5.7×10-3, are excellent for application as wave-transparent materials.

A series of uranium (IV, V, VI) tritylimido complexes, their molecular and electronic structures and reactivity with CO2.

PubMed

Schmidt, Anna-Corina; Heinemann, Frank W; Maron, Laurent; Meyer, Karsten

2014-12-15

A series of uranium tritylimido complexes with structural continuity across complexes in different oxidation states, namely U(IV), U(V), and U(VI), is reported. This series was successfully synthesized by employing the trivalent uranium precursor, [(((nP,Me)ArO)3tacn)U(III)] (1) (where ((nP,Me)ArO)3tacn(3-) = trianion of 1,4,7-tris(2-hydroxy-5-methyl-3-neopentylbenzyl)-1,4,7-triazacyclononane), with the organic azides Me3SiN3, Me3SnN3, and Ph3CN3 (tritylazide). While the reaction with Me3SiN3 yields an inseparable mixture of both the azido and imido uranium complexes, applying the heavier Sn homologue yields the bis-μ-azido complex [{(((nP,Me)ArO)3tacn)U(IV)}2(μ-N3)2] (2) exclusively. In contrast to this one-electron redox chemistry, the reaction of precursor 1 with tritylazide solely leads to the two-electron oxidized U(V) imido [(((nP,Me)ArO)3tacn)U(V)(N-CPh3)] (3). Oxidation and reduction of 3 yield the corresponding U(VI) and U(IV) complexes [(((nP,Me)ArO)3tacn)U(VI)(N-CPh3)][B(C6F5)4] (4) and K[(((nP,Me)ArO)3tacn)U(IV)(N-CPh3)] (5), respectively. In addition, the U(V) imido 3 engages in a H atom abstraction reaction with toluene to yield the closely related amido complex [(((nP,Me)ArO)3tacn)U(IV)(N(H)-CPh3)] (6). Complex 6 and the three tritylimido complexes 3, 4, and 5, with oxidation states ranging from +IV to +VI and homologous core structures, were investigated by X-ray diffraction analyses and magnetochemical and spectroscopic studies as well as density functional theory (DFT) computational analysis. The series of structurally very similar imido complexes provides a unique opportunity to study electronic properties and to probe the uranium imido reactivity solely as a function of electron count of the metal-imido entity. Evidence for the U-N bond covalency and f-orbital participation in complexes 3-6 was drawn from the in-depth and comparative DFT study. The reactivity of the imido and amido complexes with CO2 was probed, and conclusions about the influence of the formal oxidation state are reported.

Formation of crystalline InGaO₃(ZnO)n nanowires via the solid-phase diffusion process using a solution-based precursor.

PubMed

Guo, Yujie; Van Bilzen, Bart; Locquet, Jean Pierre; Seo, Jin Won

2015-12-11

One-dimensional single crystalline InGaO3(ZnO)n (IGZO) nanostructures have great potential for various electrical and optical applications. This paper demonstrates for the first time, to our knowledge, a non-vacuum route for the synthesis of IGZO nanowires by annealing ZnO nanowires covered with solution-based IGZO precursor. This method results in nanowires with highly periodic IGZO superlattice structure. The phase transition of IGZO precursor during thermal treatment was systematically studied. Transmission electron microscopy studies reveal that the formation of the IGZO structure is driven by anisotropic inter-diffusion of In, Ga, and Zn atoms, and also by the crystallization of the IGZO precursor. Optical measurements using cathodoluminescence and UV-vis spectroscopy confirm that the nanowires consist of the IGZO compound with wide optical band gap and suppressed luminescence.

Controlled nucleation and growth of CdS nanoparticles in a polymer matrix.

PubMed

Di Luccio, Tiziana; Laera, Anna Maria; Tapfer, Leander; Kempter, Susanne; Kraus, Robert; Nickel, Bert

2006-06-29

In-situ synchrotron X-ray diffraction (XRD) was used to monitor the thermal decomposition (thermolysis) of Cd thiolates precursors embedded in a polymer matrix and the nucleation of CdS nanoparticles. A thiolate precursor/polymer solid foil was heated to 300 degrees C in the X-ray diffraction setup of beamline W1.1 at Hasylab, and the diffraction curves were each recorded at 10 degrees C. At temperatures above 240 degrees C, the precursor decomposition is complete and CdS nanoparticles grow within the polymer matrix forming a nanocomposite with interesting optical properties. The nanoparticle structural properties (size and crystal structure) depend on the annealing temperature. Transmission electron microscopy (TEM) and photoluminescence (PL) analyses were used to characterize the nanoparticles. A possible mechanism driving the structural transformation of the precursor is inferred from the diffraction features arising at the different temperatures.

Correlation between Na/K ratio and electron densities in blood samples of breast cancer patients.

PubMed

Topdağı, Ömer; Toker, Ozan; Bakırdere, Sezgin; Bursalıoğlu, Ertuğrul Osman; Öz, Ersoy; Eyecioğlu, Önder; Demir, Mustafa; İçelli, Orhan

2018-05-31

The main purpose of this study was to investigate the relationship between the electron densities and Na/K ratio which has important role in breast cancer disease. Determinations of sodium and potassium concentrations in blood samples performed with inductive coupled plasma-atomic emission spectrometry. Electron density values of blood samples were determined via ZXCOM. Statistical analyses were performed for electron densities and Na/K ratio including Kolmogorov-Smirnov normality tests, Spearman's rank correlation test and Mann-Whitney U test. It was found that the electron densities significantly differ between control and breast cancer groups. In addition, statistically significant positive correlation was found between the electron density and Na/K ratios in breast cancer group.

TiO2/WO3 photoactive bilayers in the UV-Vis light region

NASA Astrophysics Data System (ADS)

Vasilaki, E.; Vernardou, D.; Kenanakis, G.; Vamvakaki, M.; Katsarakis, N.

2017-04-01

In this work, photoactive bilayered films consisting of anatase TiO2 and monoclinic WO3 were synthesized by a sol-gel route. Titanium isopropoxide and tungsten hexachloride were used as metal precursors and deposition was achieved by spin-coating on Corning glass substrates. The samples were characterized by X-ray diffraction, photoluminescence, UV-Vis, and Raman spectroscopy, as well as field emission scanning electron microscopy. The prepared immobilized catalysts were tested for their photocatalytic performance by the decolorization of methylene blue in aqueous matrices, under UV-Vis light irradiation. The annealing process influenced the crystallinity of the bilayered films, while the concentration of the tungsten precursor solution and the position of the tungsten trioxide layer further affected their photocatalytic performance. In particular, the photocatalytic performance of the bilayered films was optimized at a concentration of 0.1 M of the WO3 precursor solution, when deposited as an overlying layer on TiO2 by two annealing steps ( 76% methylene blue decolorization in 300 min of irradiation versus 59% in the case of a bare TiO2 film). In general, the coupled layer catalysts exhibited superior photoactivity compared to that of bare TiO2 films with WO3 acting as an electron trap, resulting, therefore, in a more efficient electron-hole separation and inhibiting their recombination.

Growth and characterization of Al2O3 films on fluorine functionalized epitaxial graphene

NASA Astrophysics Data System (ADS)

Robinson, Zachary R.; Jernigan, Glenn G.; Wheeler, Virginia D.; Hernández, Sandra C.; Eddy, Charles R.; Mowll, Tyler R.; Ong, Eng Wen; Ventrice, Carl A.; Geisler, Heike; Pletikosic, Ivo; Yang, Hongbo; Valla, Tonica

2016-08-01

Intelligent engineering of graphene-based electronic devices on SiC(0001) requires a better understanding of processes used to deposit gate-dielectric materials on graphene. Recently, Al2O3 dielectrics have been shown to form conformal, pinhole-free thin films by functionalizing the top surface of the graphene with fluorine prior to atomic layer deposition (ALD) of the Al2O3 using a trimethylaluminum (TMA) precursor. In this work, the functionalization and ALD-precursor adsorption processes have been studied with angle-resolved photoelectron spectroscopy, low energy electron diffraction, and X-ray photoelectron spectroscopy. It has been found that the functionalization process has a negligible effect on the electronic structure of the graphene, and that it results in a twofold increase in the adsorption of the ALD-precursor. In situ TMA-dosing and XPS studies were also performed on three different Si(100) substrates that were terminated with H, OH, or dangling Si-bonds. This dosing experiment revealed that OH is required for TMA adsorption. Based on those data along with supportive in situ measurements that showed F-functionalization increases the amount of oxygen (in the form of adsorbed H2O) on the surface of the graphene, a model for TMA-adsorption on graphene is proposed that is based on a reaction of a TMA molecule with OH.

Device and method for electron beam heating of a high density plasma

DOEpatents

Thode, L.E.

A device and method for relativistic electron beam heating of a high density plasma in a small localized region are described. A relativistic electron beam generator produces a high voltage electron beam which propagates along a vacuum drift tube and is modulated to initiate electron bunching within the beam. The beam is then directed through a low density gas chamber which provides isolation between the vacuum modulator and the relativistic electron beam target. The relativistic beam is then applied to a high density target plasma which typically comprises DT, DD, hydrogen boron or similar thermonuclear gas at a density of 10/sup 17/ to 10/sup 20/.

Distribution of E/N and N/e/ in a cross-flow electric discharge laser. [electric field to neutral gas density and electron number density

NASA Technical Reports Server (NTRS)

Dunning, J. W., Jr.; Lancashire, R. B.; Manista, E. J.

1976-01-01

Measurements have been conducted of the effect of the convection of ions and electrons on the discharge characteristics in a large scale laser. The results are presented for one particular distribution of ballast resistance. Values of electric field, current density, input power density, ratio of electric field to neutral gas density (E/N), and electron number density were calculated on the basis of measurements of the discharge properties. In a number of graphs, the E/N ratio, current density, power density, and electron density are plotted as a function of row number (downstream position) with total discharge current and gas velocity as parameters. From the dependence of the current distribution on the total current, it appears that the electron production in the first two rows significantly affects the current flowing in the succeeding rows.

Infrared gas phase study on plasma-polymer interactions in high-current diffuse dielectric barrier discharge

NASA Astrophysics Data System (ADS)

Liu, Y.; Welzel, S.; Starostin, S. A.; van de Sanden, M. C. M.; Engeln, R.; de Vries, H. W.

2017-06-01

A roll-to-roll high-current diffuse dielectric barrier discharge at atmospheric pressure was operated in air and Ar/N2/O2 gas mixtures. The exhaust gas from the discharge was studied using a high-resolution Fourier-transform infrared spectrometer in the range from 3000 to 750 cm-1 to unravel the plasma-polymer interactions. The absorption features of HxNyOz, COx, and HCOOH (formic acid) were identified, and the relative densities were deduced by fitting the absorption bands of the detected molecules. Strong interactions between plasma and polymer (Polyethylene-2,6-naphthalate, or PEN) in precursor-free oxygen-containing gas mixtures were observed as evidenced by a high COx production. The presence of HCOOH in the gas effluent, formed through plasma-chemical synthesis of COx, turns out to be a sensitive indicator for etching. By adding tetraethylorthosilicate precursor in the plasma, dramatic changes in the COx production were measured, and two distinct deposition regimes were identified. At high precursor flows, a good agreement with the precursor combustion and the COx production was observed, whereas at low precursor flows an etching-deposition regime transpires, and the COx production is dominated by polymer etching.

Radiation source

DOEpatents

Thode, Lester E.

1981-01-01

A device and method for relativistic electron beam heating of a high-density plasma in a small localized region. A relativistic electron beam generator or accelerator produces a high-voltage electron beam which propagates along a vacuum drift tube and is modulated to initiate electron bunching within the beam. The beam is then directed through a low-density gas chamber which provides isolation between the vacuum modulator and the relativistic electron beam target. The relativistic beam is then applied to a high-density target plasma which typically comprises DT, DD, or similar thermonuclear gas at a density of 10.sup.17 to 10.sup.20 electrons per cubic centimeter. The target gas is ionized prior to application of the relativistic electron beam by means of a laser or other preionization source to form a plasma. Utilizing a relativistic electron beam with an individual particle energy exceeding 3 MeV, classical scattering by relativistic electrons passing through isolation foils is negligible. As a result, relativistic streaming instabilities are initiated within the high-density target plasma causing the relativistic electron beam to efficiently deposit its energy into a small localized region of the high-density plasma target.

Direct comparison of Viking 2.3-GHz signal phase fluctuation and columnar electron density between 2 and 160 solar radii

NASA Technical Reports Server (NTRS)

Berman, A. L.; Wackley, J. A.; Hietzke, W. H.

1982-01-01

The relationship between solar wind induced signal phase fluctuation and solar wind columnar electron density has been the subject of intensive analysis during the last two decades. In this article, a sizeable volume of 2.3-GHz signal phase fluctuation and columnar electron density measurements separately and concurrently inferred from Viking spacecraft signals are compared as a function of solar geometry. These data demonstrate that signal phase fluctuation and columnar electron density are proportional over a very wide span of solar elongation angle. A radially dependent electron density model which provides a good fit to the columnar electron density measurements and, when appropriately scaled, to the signal phase fluctuation measurements, is given. This model is also in good agreement with K-coronameter observations at 2 solar radii (2r0), with pulsar time delay measurements at 10r0, and with spacecraft in situ electron density measurements at 1 AU.

Spectroscopic identification of jet-cooled p-fluoro-α-methylbenzyl radical in corona discharge

NASA Astrophysics Data System (ADS)

Lee, Gi Woo; Lee, Sang Kuk

2009-02-01

We report the first spectroscopic identification of the p-fluoro-α-methylbenzyl radical in the gas phase. Precursor p-fluoro-ethylbenzene seeded in a large amount of carrier gas was electrically discharged to produce the benzyl-type radicals in a corona excited supersonic expansion using a pinhole-type glass nozzle, from which the vibronic emission spectrum was recorded in the visible region. From an analysis of the spectrum observed, we identified spectroscopically the formation of the p-fluoro-α-methylbenzyl, in which the energy of the D 1 → D 0 electronic transition and a few vibrational mode frequencies in the ground electronic state were determined by comparison with those from an ab initio calculation and with those from the known data of the precursor.

In-Situ-Activated N-Doped Mesoporous Carbon from a Protic Salt and Its Performance in Supercapacitors.

PubMed

Mendes, Tiago C; Xiao, Changlong; Zhou, Fengling; Li, Haitao; Knowles, Gregory P; Hilder, Matthias; Somers, Anthony; Howlett, Patrick C; MacFarlane, Douglas R

2016-12-28

Protic salts have been recently recognized to be an excellent carbon source to obtain highly ordered N-doped carbon without the need of tedious and time-consuming preparation steps that are usually involved in traditional polymer-based precursors. Herein, we report a direct co-pyrolysis of an easily synthesized protic salt (benzimidazolium triflate) with calcium and sodium citrate at 850 °C to obtain N-doped mesoporous carbons from a single calcination procedure. It was found that sodium citrate plays a role in the final carbon porosity and acts as an in situ activator. This results in a large surface area as high as 1738 m 2 /g with a homogeneous pore size distribution and a moderate nitrogen doping level of 3.1%. X-ray photoelectron spectroscopy (XPS) measurements revealed that graphitic and pyridinic groups are the main nitrogen species present in the material, and their content depends on the amount of sodium citrate used during pyrolysis. Transmission electron microscopy (TEM) investigation showed that sodium citrate assists the formation of graphitic domains and many carbon nanosheets were observed. When applied as supercapacitor electrodes, a specific capacitance of 111 F/g in organic electrolyte was obtained and an excellent capacitance retention of 85.9% was observed at a current density of 10 A/g. At an operating voltage of 3.0 V, the device provided a maximum energy density of 35 W h/kg and a maximum power density of 12 kW/kg.

Atomic Layer Deposition of GeSe Films Using HGeCl3 and [(CH3)3Si]2Se with the Discrete Feeding Method for the Ovonic Threshold Switch.

PubMed

Kim, Woohyun; Yoo, Sijung; Yoo, Chanyoung; Park, Eui-Sang; Jeon, Jeongwoo; Kwon, Young Jae; Woo, Kyung Seok; Kim, Han Joon; Lee, Yoon Kyeung; Hwang, Cheol Seong

2018-06-19

The ovonic threshold switch (OTS) based on the voltage snapback of amorphous chalcogenides possesses several desirable characteristics for passive memory array. Among the materials that can be used as OTS, GeSe has a strong glass-forming ability (~350°C crystallization temperature), with a simple binary composition. Described herein is a new method of depositing GeSe films through atomic layer deposition (ALD), in which HGeCl3 and [(CH3)3Si]2Se are used as Ge and Se precursors, respectively. The stoichiometric GeSe thin films were formed through a ligand exchange reaction between the two precursor molecules, without the adoption of an additional reaction gas, at low substrate temperatures ranging from 70 to 150°C. The pseudo-saturation behavior of ALD, however, which requires a long time to achieve the saturation growth rate, was observed. This was due to the adverse influence of the physisorbed precursor and byproduct molecules on the efficient chemical adsorption reaction between the precursors and reaction sites. To overcome the slow saturation and excessive use of the Ge precursor, the discrete feeding method (DFM), where HGeCl3 is supplied multiple times consecutively with subdivided pulse times, was adopted. DFM led to the saturation of the GeSe growth rate at a much shorter total injection time of the Ge precursor, and improved the film density and oxidation resistance properties. The GeSe film grown via DFM exhibited a short OTS time of ~40 ns, a ~107 ON/OFF current ratio, and ~104 selectivity. The OTS behavior was consistent with the modified Poole-Frenkel (PF) mechanism in the OFF state. In contrast, the similar GeSe film grown through the conventional ALD showed a low density and high vulnerability to oxidation, which prevented the OTS performance. The ALD method of GeSe films introduced here will contribute to the fabrication of a three-dimensionally integrated memory as a selector device for preventing sneak current. © 2018 IOP Publishing Ltd.

Electron (charge) density studies of cellulose models

USDA-ARS?s Scientific Manuscript database

Introductory material first describes electron density approaches and demonstrates visualization of electron lone pairs and bonding as concentrations of electron density. Then it focuses on the application of Bader’s Quantum Theory of Atoms-in-Molecules (AIM) to cellulose models. The purpose of the ...

Electron densities in the ionosphere of Mars: A comparison of MARSIS and radio occultation measurements

NASA Astrophysics Data System (ADS)

Vogt, Marissa F.; Withers, Paul; Fallows, Kathryn; Flynn, Casey L.; Andrews, David J.; Duru, Firdevs; Morgan, David D.

2016-10-01

Radio occultation electron densities measurements from the Mariner 9 and Viking spacecraft, which orbited Mars in the 1970s, have recently become available in a digital format. These data are highly complementary to the radio occultation electron density profiles from Mars Global Surveyor, which were restricted in solar zenith angle and altitude. We have compiled data from the Mariner 9, Viking, and Mars Global Surveyor radio occultation experiments for comparison to electron density measurements made by Mars Advanced Radar for Subsurface and Ionosphere Sounding (MARSIS), the topside radar sounder on Mars Express, and MARSIS-based empirical density models. We find that the electron densities measured by radio occultation are in generally good agreement with the MARSIS data and model, especially near the altitude of the peak electron density but that the MARSIS data and model display a larger plasma scale height than the radio occultation profiles at altitudes between the peak density and 200 km. Consequently, the MARSIS-measured and model electron densities are consistently larger than radio occultation densities at altitudes 200-300 km. Finally, we have analyzed transitions in the topside ionosphere, at the boundary between the photochemically controlled and transport-controlled regions, and identified the average transition altitude, or altitude at which a change in scale height occurs. The average transition altitude is 200 km in the Mariner 9 and Viking radio occultation profiles and in profiles of the median MARSIS radar sounding electron densities.

Sustaining Phenolic Impregnated Carbon Ablator (PICA) TPS for Future NASA Robotic Science Missions Including NF-4 and Discovery

NASA Technical Reports Server (NTRS)

Venkatapathy, E.; Stackpoole, M.; Violette, S.

2018-01-01

Phenolic Impregnated Carbon Ablator (PICA), invented in the mid 1990s, is a low-density ablative thermal protection material proven capable of meeting sample return mission needs from the moon, asteroids, comets and other unrestricted class V destinations as well as for Mars. Its low density and efficient performance characteristics have proven effective for use from Discovery to Flagship class missions. It is important that NASA maintain this TPS material capability and ensure its availability for future NASA use. The rayon based carbon precursor raw material used in PICA preform manufacturing required replacement and requalification at least twice in the past 25 years and a third substitution is now needed. The carbon precursor replacement challenge is twofold the first involves finding a long-term replacement for the current rayon and the second is to assess its future availability periodically to ensure it is sustainable and be alerted if additional replacement efforts need to be initiated. Rayon is no longer a viable process in the US and Europe due to environmental concerns. In the early 80s rayon producers began investigating a new method of producing a cellulosic fiber through a more environmentally responsible process. This cellulosic fiber, lyocell, is a viable replacement precursor for PICA fiberform. This presentation reviews current SMD-PSD funded PICA sustainability activities in ensuring a rayon replacement for the long term is identified and in establishing that the capability of the new PICA derived from an alternative precursor is in family with previous versions of the so called heritage PICA.

Sustaining PICA for Future NASA Robotic Science Missions Including NF-4 and Discovery

NASA Technical Reports Server (NTRS)

Stackpoole, Mairead; Venkatapathy, Ethiraj; Violette, Steven

2018-01-01

Phenolic Impregnated Carbon Ablator (PICA), invented in the mid 1990's, is a low-density ablative thermal protection material proven capable of meeting sample return mission needs from the moon, asteroids, comets and other "unrestricted class V destinations" as well as for Mars. Its low density and efficient performance characteristics have proven effective for use from Discovery to Flagship class missions. It is important that NASA maintain this TPS material capability and ensure its availability for future NASA use. The rayon based carbon precursor raw material used in PICA preform manufacturing required replacement and requalification at least twice in the past 25 years and a third substitution is now needed. The carbon precursor replacement challenge is twofold - the first involves finding a long-term replacement for the current rayon and the second is to assess its future availability periodically to ensure it is sustainable and be alerted if additional replacement efforts need to be initiated. Rayon is no longer a viable process in the US and Europe due to environmental concerns. In the early 80's rayon producers began investigating a new method of producing a cellulosic fiber through a more environmentally responsible process. This cellulosic fiber, lyocell, is a viable replacement precursor for PICA fiberform. This presentation reviews current SMD-PSD funded PICA sustainability activities in ensuring a rayon replacement for the long term is identified and in establishing that the capability of the new PICA derived from an alternative precursor is in family with previous versions of the so called "heritage" PICA.

Synthesis of SnO2 and Ag Nanoparticles from Electronic Wastes with the Assistance of Ultrasound and Microwaves

NASA Astrophysics Data System (ADS)

Cerchier, Pietrogiovanni; Dabalà, Manuele; Brunelli, Katya

2017-09-01

In this work, SnO2 and Ag nanoparticles were produced with a raw material nitric acid solution, which came from the leaching of printed circuit boards. First, a precursor of tin oxide was precipitated from the nitric acid solution by three different techniques: (I) conventional heating, (II) microwave irradiation, and (III) ultrasound treatment. Second, this precursor was transformed into tin oxide nanoparticles by heat treatment in a furnace. Third, hydrochloric acid was added to the nitric acid solution to induce the precipitation of silver chloride. Fourth, silver chloride was reduced to metallic silver nanoparticles in an ammonia solution using glucose syrup as both the reducing agent and the capping agent. The reduction reaction was carried out through (I) conventional heating, (II) microwave irradiation, and (III) ultrasound treatment. The nanoparticles were characterized by scanning electron microscope (SEM), x-ray diffractometer (XRD), infrared (IR)-spectroscopy, transmission electron microscope (TEM), ultraviolet (UV)-spectroscopy, and laser diffraction particle size analyzer.

Novel lithium titanate-graphene hybrid containing two graphene conductive frameworks for lithium-ion battery with excellent electrochemical performance

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

Ruiyi, Li; Tengyuan, Chen; Beibei, Sun

Graphical abstract: We developed a new Novel lithium titanate-graphene nanohybrid containing two graphene conductive frameworks. The unique architecture creates fast electron transfer and rapid mass transport of electrolyte. The hybrid electrode provides excellent electrochemical performances for lithium-ion batteries, including high specific capacity, outstanding rate capability and intriguing cycling stability. - Highlights: • We reported a new LTO-graphene nanohybrid containing two graphene conductive frameworks. • One graphene framework greatly improves the electrical conductivity of LTO crystal. • Another graphene framework enhances electrical conductivity of between LTO crystals and electrolyte transport. • The unique architecture creates big tap density, ultrafast electron transfermore » and rapid mass transport. • The hybrid electrode provides excellent electrochemical performance for lithium-ion batteries. - ABSTRACT: The paper reported the synthesis of lithium titanate(LTO)-graphene hybrid containing two graphene conductive frameworks (G@LTO@G). Tetrabutyl titanate and graphene were dispersed in tertbutanol and heated to reflux state by microwave irradiation. Followed by adding lithium acetate to produce LTO precursor/graphene (p-LTO/G). The resulting p-LTO/G offers homogeneous morphology and ultra small size. All graphene sheets were buried in the spherical agglomerates composed of primitive particles through the second agglomeration. The p-LTO/G was calcined to LTO@graphene (LTO@G). To obtain G@LTO@G, the LTO@G was further hybridized with graphene. The as-prepared G@LTO@G shows well-defined three-dimensional structure and hierarchical porous distribution. Its unique architecture creates big tap density, fast electron transfer and rapid electrolyte transport. As a result, the G@LTO@G provides high specific capacity (175.2 mA h g{sup −1} and 293.5 mA cm{sup −3}), outstanding rate capability (155.7 mAh g{sup −1} at 10C) and intriguing cycling stability (97.2% capacity retention at 5C after 1000 cycles)« less

Influence of Nb-doped TiO2 blocking layers as a cascading band structure for enhanced photovoltaic properties

NASA Astrophysics Data System (ADS)

Koo, Bon-Ryul; Oh, Dong-Hyeun; Ahn, Hyo-Jin

2018-03-01

Nb-doped TiO2 (Nb-TiO2) blocking layers (BLs) were developed using horizontal ultrasonic spray pyrolysis deposition (HUSPD). In order to improve the photovoltaic properties of the dye-sensitized solar cells (DSSCs), we optimized the Nb doping level of the Nb-TiO2 BLs by controlling the Nb/Ti molar ratio (0, 5, 6, and 7) of the precursor solution for HUSPD. Compared to bare TiO2 BLs, the Nb-TiO2 BLs formed a cascading band structure using the positive shift of the conduction band minimum of the Nb-TiO2 positioned between fluorine-doped tin oxide (FTO) and TiO2. This results in the increase of the potential current and the suppression of the electron recombination. Hence, it led to the improvement of the electrical conductivity, due to the increased electron concentration by the Nb doping into TiO2. Therefore, the DSSC fabricated with the Nb-TiO2 BLs at a Nb/Ti molar ratio of 6 showed superior photoconversion efficiency (∼7.50 ± 0.20%) as a result of the improved short-circuit current density. This is higher than those with the other Nb-TiO2 BLs and without BL. This improvement of the photovoltaic properties for the DSSCs can be attributed to the synergistic effects of uniform and compact BL relative to the prevention of the backward electron transport at the FTO/electrolyte interface, efficient electron transport at interfaces relative to a cascading band structure of FTO/Nb-TiO2/TiO2 multilayers and the facilitated electron transport at the BLs relative to the increased electrical conductivity of the optimized Nb-TiO2 BLs.

Electron attachment to C{sub 2} fluorocarbon radicals at high temperature

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

Shuman, Nicholas S.; Miller, Thomas M.; Viggiano, Albert A., E-mail: afrl.rvborgmailbox@kirtland.af.mil

Thermal electron attachment to the radical species C{sub 2}F{sub 3} and C{sub 2}F{sub 5} has been studied over the temperature range 300–890 K using the Variable Electron and Neutral Density Attachment Mass Spectrometry technique. Both radicals exclusively undergo dissociative attachment to yield F{sup −}. The rate constant for C{sub 2}F{sub 5} shows little dependence over the temperature range, remaining ∼4 × 10{sup −9} cm{sup 3} s{sup −1}. The rate constant for C{sub 2}F{sub 3} attachment rises steeply with temperature from 3 × 10{sup −11} cm{sup 3} s{sup −1} at 300 K to 1 × 10{sup −9} cm{sup 3} s{sup −1} at 890 K.more » The behaviors of both species at high temperature are in agreement with extrapolations previously made from data below 600 K using a recently developed kinetic modeling approach. Measurements were also made on C{sub 2}F{sub 3}Br and C{sub 2}F{sub 5}Br (used in this work as precursors to the radicals) over the same temperature range, and, for C{sub 2}F{sub 5}Br as a function of electron temperature. The attachment rate constants to both species rise with temperature following Arrhenius behavior. The attachment rate constant to C{sub 2}F{sub 5}Br falls with increasing electron temperature, in agreement with the kinetic modeling. The current data fall in line with past predictions of the kinetic modeling approach, again showing the utility of this simplified approach.« less

What controls deposition rate in electron-beam chemical vapor deposition?

PubMed

White, William B; Rykaczewski, Konrad; Fedorov, Andrei G

2006-08-25

The key physical processes governing electron-beam-assisted chemical vapor deposition are analyzed via a combination of theoretical modeling and supporting experiments. The scaling laws that define growth of the nanoscale deposits are developed and verified using carefully designed experiments of carbon deposition from methane onto a silicon substrate. The results suggest that the chamber-scale continuous transport of the precursor gas is the rate controlling process in electron-beam chemical vapor deposition.

The electrons and ion characteristics of Saturn's plasma disk inside the Enceladus orbit

NASA Astrophysics Data System (ADS)

Morooka, Michiko; Wahlund, Jan-Erik; Ye, Sheng-Yi; Kurth, William; Persoon, Ann; Holmberg, Mika

2017-04-01

Cassini observations revealed that Saturn's icy moon Enceladus and surrounding E ring are the significant plasma source of the magnetosphere. However, the observations sometimes show the electron density enhancement even inside the Enceladus orbiting distance, 4RS. Further plasma contribution from the inner rings, the G and the F rings and main A ring are the natural candidate as an additional plasma source. The Cassini/RPWS Langmuir Probe (LP) measurement provides the characteristics of the electrons and ions independently in a cold dense plasma. The observations near the center of the E ring showed that the ion density being larger than the electron density, indicating that there is additional particle as a negative charge carrier. Those are the small nm and μm sized dust grains that are negatively charged by the electron attachments. The faint F and G rings, located at R=2RS and 3RS, consist of small grains and similar electron/ion density discrepancies can be expected. We will show different types of the LP observations when Cassini traveled the equator region of the plasma disk down to 3RS. One with the electron density increasing inside 4RS, and another with the electron density decreasing inside 4RS. During the orbit 016 (2005 doy-284/285), the electron density continued to increase toward the planet. On the other hand, the ion currents, the LP measured currents from the negative bias voltage, turn to decreasing inside 4RS, implying the density decrease of the ions. By comparing the observed LP ion current characteristics and the modeled values using the obtained electron density, we found that the characteristic ion mass can be several times larger than the water ions (AMU=18) that we expected in this region. During the orbit 015 (2005 doy-266/267), on the other hand, the LP observed sharp electron density drop near 3RS. The dust signals from the RPWS antenna showed the density enhancement of the μm sized grains coincide the electron density drop and we have estimated that the characteristic ion mass can exceed AMU=100. Throughout the whole Cassini observation near the equator inside 4RS, we didn't find the case with the ion densities larger than the electron densities as were found near the E ring and the Enceladus plume. We suggest that Saturn's plasmadisk inside the Enceladus orbit is dynamic in ion characteristics where the water molecules coagulate and grow into a small icy dust grains. In the presentation we discuss the relationship between the electron/ion density and the density of the nm and μm sized grains.

An effective approach to synthesize monolayer tungsten disulphide crystals using tungsten halide precursor

NASA Astrophysics Data System (ADS)

Thangaraja, Amutha; Shinde, Sachin M.; Kalita, Golap; Tanemura, Masaki

2016-02-01

The synthesis of large-area monolayer tungsten disulphide (WS2) single crystal is critical for realistic application in electronic and optical devices. Here, we demonstrate an effective approach to synthesize monolayer WS2 crystals using tungsten hexachloride (WCl6) as a solid precursor in atmospheric chemical vapor deposition process. In this technique, 0.05M solution of WCl6 in ethanol was drop-casted on SiO2/Si substrate to create an even distribution of the precursor, which was reduced and sulfurized at 750 °C in Ar atmosphere. We observed growth of triangular, star-shaped, as well as dendritic WS2 crystals on the substrate. The crystal geometry evolves with the shape and size of the nuclei as observed from the dendritic structures. These results show that controlling the initial nucleation and growth process, large WS2 single crystalline monolayer can be grown using the WCl6 precursor. Our finding shows an easier and effective approach to grow WS2 monolayer using tungsten halide solution-casting, rather than evaporating the precursor for gas phase reaction.

Facile synthesis of a conjugation-grafted-TiO2 nanohybrid with enhanced visible-light photocatalytic properties from nanotube titanic acid precursors

NASA Astrophysics Data System (ADS)

Guo, Yanru; Zhang, Min; Zhang, Zhihua; Li, Qiuye; Yang, Jianjun

2016-08-01

A conjugation-grafted-TiO2 nanohybrid was synthesized by chemically grafting conjugated structures on the surface of nanotube titanic acid (NTA) precursor-based TiO2 through the controlled thermal degradation of a coacervated polymer layer of polyvinyl alcohol (PVA). The interfacial interactions between the NTA precursor-based TiO2 and conjugated structures were characterized using Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy. Moreover, the effects of the NTA's pretreatment temperature and the weight ratio of NTA to PVA on the photocatalytic degradation of methyl orange were also investigated. A higher NTA pretreatment temperature and a lower NTA to PVA weight ratio were found to enhance photogenerated electron-hole separation efficiency and photocatalytic activity. Moreover, the conjugation-grafted-TiO2 nanohybrid synthesized from the NTA precursor displayed a much higher visible-light photocatalytic activity than that of the sample obtained from the P25 precursor. The origin of the enhanced photocatalytic activity under visible-light irradiation is also discussed in detail.

Processing and interpretation of experiments in the microwave interferometry of shock waves in a weakly ionized plasma

NASA Astrophysics Data System (ADS)

Ershov, A. P.; Klishin, S. V.; Kuzovnikov, S. V.; Ponomareva, S. E.; Pyt'ev, Iu. P.

1990-12-01

The reduction method is applied to the microwave interferometry of shock waves in a weakly ionized plasma, making it possible to improve the spatial resolution of the instrument. It is shown experimentally that the structure of the shock wave electron component in a high-frequency discharge plasma in atomic and molecular gases is characterized by the presence of a precursor in the form of a rarefaction wave. The origin of the precursor is examined.

Low-temperature liquid precursors of crystalline metal oxides assisted by heterogeneous photocatalysis.

PubMed

Bretos, Iñigo; Jiménez, Ricardo; Pérez-Mezcua, Dulce; Salazar, Norberto; Ricote, Jesús; Calzada, M Lourdes

2015-04-24

The photocatalytically assisted decomposition of liquid precursors of metal oxides incorporating TiO2 particles enables the preparation of functional layers from the ferroelectric Pb(Zr,Ti)O3 and multiferroic BiFeO3 perovskite systems at temperatures not exceeding 350 ºC. This enables direct deposition on flexible plastic, where the multifunctionality provided by these complex-oxide materials guarantees their potential use in next-generation flexible electronics. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Nanopatterning of Group V Elements for Tailoring the Electronic Properties of Semiconductors by Monolayer Doping.

PubMed

Thissen, Peter; Cho, Kyeongjae; Longo, Roberto C

2017-01-18

Control of the electronic properties of semiconductors is primarily achieved through doping. While scaling down the device dimensions to the molecular regime presents an increasing number of difficulties, doping control at the nanoscale is still regarded as one of the major challenges of the electronic industry. Within this context, new techniques such as monolayer doping (MLD) represent a substantial improvement toward surface doping with atomic and specific doping dose control at the nanoscale. Our previous work has explained in detail the atomistic mechanism behind MLD by means of density-functional theory calculations (Chem. Mater. 2016, 28, 1975). Here, we address the key questions that will ultimately allow one to optimize the scalability of the MLD process. First, we show that dopant coverage control cannot be achieved by simultaneous reaction of several group V elements, but stepwise reactions make it possible. Second, using ab initio molecular dynamics, we investigate the thermal decomposition of the molecular precursors, together with the stability of the corresponding binary and ternary dopant oxides, prior to the dopant diffusion into the semiconductor surface. Finally, the effect of the coverage and type of dopant on the electronic properties of the semiconductor is also analyzed. Furthermore, the atomistic characterization of the MLD process raises unexpected questions regarding possible crystal damage effects by dopant exchange with the semiconductor ions or the final distribution of the doping impurities within the crystal structure. By combining all our results, optimization recipes to create ultrashallow doped junctions at the nanoscale are finally proposed.

Effect of Dopants and Sintering Method on the Properties of Ceria-Based Electrolytes for IT-SOFCs Applications

NASA Astrophysics Data System (ADS)

Sharma, Payal; Sharma, Chetan; Singh, Kanchan L.; Singh, Anirudh P.

2018-05-01

Doped and co-doped ceria ceramics are used as electrolyte materials in solid oxide fuel cells. In this work, ceria-based oxides, Ce0.90Gd0.06Y0.02M0.02O2-δ (M = Ca, Fe, La, and Sr) were prepared by conventional as well as microwave processing from the precursors prepared by the mixed oxide method. The consolidated calcined powders in pellet form were sintered in microwave energy at 1400°C for 20 min and in an electric furnace of IR radiation at 1400°C for 6 h. The x-ray diffraction analysis confirmed that all the compositions were crystallized into a cubic fluorite structure. Surface morphology of the sintered products was studied using scanning electron microscopy and the microhardness was investigated using the Vickers hardness test. The comparative results analysis shows that the microwave-sintered samples have uniform grain growth, higher density and higher microhardness than the corresponding conventionally sintered products. The microwave-sintered sample of composition Ce0.90Gd0.06Y0.02Sr0.02O2-δ was found to have the highest microhardness among the four compositions due to its high density and smallest grain size.

Synthesis of BaTiO3 and Ba(ZrxTi1-X)O3 by using the soft combustion method

NASA Astrophysics Data System (ADS)

Ahmad, Atiqah; Razak, Khairunisak Abdul

2017-07-01

In this work, barium titanate, BaTiO3 (BT) and Zr doped BT, BaZrxTi1-xO3 (BZT) with powders were successfully produced using the soft combustion method. Barium nitrate and titanium (IV) isopropoxide were used as the starting materials while zirconium (IV) oxynitrate hydrate as the doping precursors, and glycine as the combustion agent. The produced powders were pressed into 12 mm diameter pellets by using 150 MPa cold press. The effect of Zr dopant in BT was studied with molar ratio of x = 0.00, 0.03, 0.05, 0.08 and 0.10. The phase presence was identified using X-ray diffractometer. Morphology of powders and sintered pellets was observed using a scanning electron microscope. Density of the sintered pellets was measured by using Archimedes' principle, while dielectric properties were analysed by using an LCR meter. Pure perovskite BT and BZT structure were obtained after sintering at 1400 °C for 5 h. BZT with x = 0.03 has grain size of 3.9 µm and shows the highest dielectric constant of 525, compared to undoped BT that has the average grain size of 4.2 µm with dielectric constant 223. The results is in agreement with microstructure observation and density of the sample.

Electron density profile measurements at a self-focusing ion beam with high current density and low energy extracted through concave electrodes.

PubMed

Fujiwara, Y; Hirano, Y; Kiyama, S; Nakamiya, A; Koguchi, H; Sakakita, H

2014-02-01

The self-focusing phenomenon has been observed in a high current density and low energy ion beam. In order to study the mechanism of this phenomenon, a special designed double probe to measure the electron density and temperature is installed into the chamber where the high current density ion beam is injected. Electron density profile is successfully measured without the influence of the ion beam components. Estimated electron temperature and density are ∼0.9 eV and ∼8 × 10(8) cm(-3) at the center of ion beam cross section, respectively. It was found that a large amount of electrons are spontaneously accumulated in the ion beam line in the case of self-forcing state.

Device and method for relativistic electron beam heating of a high-density plasma to drive fast liners

DOEpatents

Thode, Lester E.

1981-01-01

A device and method for relativistic electron beam heating of a high-density plasma in a small localized region. A relativistic electron beam generator or accelerator produces a high-voltage electron beam which propagates along a vacuum drift tube and is modulated to initiate electron bunching within the beam. The beam is then directed through a low-density gas chamber which provides isolation between the vacuum modulator and the relativistic electron beam target. The relativistic beam is then applied to a high-density target plasma which typically comprises DT, DD, hydrogen boron or similar thermonuclear gas at a density of 10.sup.17 to 10.sup.20 electrons per cubic centimeter. The target gas is ionized prior to application of the electron beam by means of a laser or other preionization source to form a plasma. Utilizing a relativistic electron beam with an individual particle energy exceeding 3 MeV, classical scattering by relativistic electrons passing through isolation foils is negligible. As a result, relativistic streaming instabilities are initiated within the high-density target plasma causing the relativistic electron beam to efficiently deposit its energy and momentum into a small localized region of the high-density plasma target. Fast liners disposed in the high-density target plasma are explosively or ablatively driven to implosion by a heated annular plasma surrounding the fast liner which is generated by an annular relativistic electron beam. An azimuthal magnetic field produced by axial current flow in the annular plasma, causes the energy in the heated annular plasma to converge on the fast liner.

IV INTERNATIONAL CONFERENCE ON ATOM AND MOLECULAR PULSED LASERS (AMPL'99): Critical electron density in a self-contained copper vapour laser in the restricted pulse repetition rate

NASA Astrophysics Data System (ADS)

Yakovlenko, Sergei I.

2000-06-01

One of the mechanisms of the inversion breaking in copper vapour lasers caused by a high prepulse electron density is considered. Inversion breaking occurs at a critical electron density Ne cr. If the prepulse electron density exceeds Ne cr, the electron temperature Te cr cannot reach, during a plasma heating pulse, the temperature of ~2eV required for lasing. A simple estimate of Ne cr is made.

Electromagnetic Whistler Precursors at Supercritical Interplanetary Shocks

NASA Technical Reports Server (NTRS)

Wilson, L. B., III

2012-01-01

We present observations of electromagnetic precursor waves, identified as whistler mode waves, at supercritical interplanetary shocks using the Wind search coil magnetometer. The precursors propagate obliquely with respect to the local magnetic field, shock normal vector, solar wind velocity, and they are not phase standing structures. All are right-hand polarized with respect to the magnetic field (spacecraft frame), and all but one are right-hand polarized with respect to the shock normal vector in the normal incidence frame. Particle distributions show signatures of specularly reflected gyrating ions, which may be a source of free energy for the observed modes. In one event, we simultaneously observe perpendicular ion heating and parallel electron acceleration, consistent with wave heating/acceleration due to these waves.

Vertical and Lateral Electron Content in the Martian Ionosphere

NASA Astrophysics Data System (ADS)

Paetzold, M. P.; Peter, K.; Bird, M. K.; Häusler, B.; Tellmann, S.

2016-12-01

The radio-science experiment MaRS (Mars Express Radio Science) on the Mars Express spacecraft sounds the neutral atmosphere and ionosphere of Mars since 2004. Approximately 800 vertical profiles of the ionospheric electron density have been acquired until today. The vertical electron content (TEC) is easily computed from the vertical electron density profile by integrating along the altitude. The TEC is typically a fraction of a TEC unit (1E16 m^-2) and depends on the solar zenith angle. The magnitude of the TEC is however fully dominated by the electron density contained in the main layer M2. The contributions by the M1 layer below M2 or the topside is marginal. MaRS is using two radio frequencies for the sounding of the ionosphere. The directly observed differential Doppler from the two received frequencies is a measure of the lateral electron content that means along the ray path and perpendicular to the vertical electron density profile. Combining both the vertical electron density profile, the vertical TEC and the directly observed lateral TEC describes the lateral electron density distribution in the ionosphere.

Investigation of mid-latitude electron density enhancement using total electron content measurements and FORMOSAT-3/COSMIC electron density profiles

NASA Astrophysics Data System (ADS)

Rajesh, P. K.; Nanan, Balan; Liu, Jann-Yenq; Lin, Charles C. H.; Chang, S. Y.; Chen, Chia-Hung

This study investigates the mid-latitude electron density enhancement (MEDE) using global ionospheric map (GIM) total electron content (TEC) measurements and FORMOSAT-3/COSMIC (F3/C) electron density profiles. Diurnal, seasonal, latitudinal, and solar activity variations in the occurrence and strength of MEDE are examined using global GIM TEC data in the years 2002 and 2009. The results show that MEDE occurrence is pronounced during 2200-0400 LT, the feature also appears during day. The strength of MEDE maximizes around 0400 LT, and is very weak during daytime. The occurrence and strength show significant longitude dependence, and vary with season and solar activity. Concurrent F3/C electron density profiles also reveal enhancement of the peak electron density and total electron content. Further studies are carried out by examining the role of neutral wind in re-organizing the plasma using SAMI2 and HWM93 models. The results indicate that meridional neutral wind could cause the plasma to converge over mid-latitudes, and thus support in maintaining the enhancement.

Development of fire-resistant, low smoke generating, thermally stable end items for commercial aircraft and spacecraft using a basic polyimide resin

NASA Technical Reports Server (NTRS)

Gagliani, J.; Lee, R.; Sorathia, U. A.; Wilcoxson, A. L.

1980-01-01

A terpolyimide precursor was developed which can be foamed by microwave methods and yields foams possessing the best seating properties. A continuous process, based on spray drying techniques, permits production of polyimide powder precursors in large quantities. The constrained rise foaming process permits fabrication of rigid foam panels with improved mechanical properties and almost unlimited density characteristics. Polyimide foam core rigid panels were produced by this technique with woven fiberglass fabric bonded to each side of the panel in a one step microwave process. The fire resistance of polyimide foams was significantly improved by the addition of ceramic fibers to the powder precursors. Foams produced from these compositions are flexible, possess good acoustical attenuation and meet the minimum burnthrough requirements when impinged by high flux flame sources.

RhoGTPase Regulators Orchestrate Distinct Stages of Synaptic Development

PubMed Central

Martin-Vilchez, Samuel; Whitmore, Leanna; Asmussen, Hannelore; Zareno, Jessica; Horwitz, Rick; Newell-Litwa, Karen

2017-01-01

Small RhoGTPases regulate changes in post-synaptic spine morphology and density that support learning and memory. They are also major targets of synaptic disorders, including Autism. Here we sought to determine whether upstream RhoGTPase regulators, including GEFs, GAPs, and GDIs, sculpt specific stages of synaptic development. The majority of examined molecules uniquely regulate either early spine precursor formation or later maturation. Specifically, an activator of actin polymerization, the Rac1 GEF β-PIX, drives spine precursor formation, whereas both FRABIN, a Cdc42 GEF, and OLIGOPHRENIN-1, a RhoA GAP, regulate spine precursor elongation. However, in later development, a novel Rac1 GAP, ARHGAP23, and RhoGDIs inactivate actomyosin dynamics to stabilize mature synapses. Our observations demonstrate that specific combinations of RhoGTPase regulatory proteins temporally balance RhoGTPase activity during post-synaptic spine development. PMID:28114311

Method for fabricating light weight carbon-bonded carbon fiber composites

DOEpatents

Wrenn, G.E. Jr.; Abbatiello, L.A.; Lewis, J. Jr.

1987-06-17

The invention is directed to the fabrication of ultralight carbon- bonded carbon fiber composites of densities in the range of about 0. 04 to 0.10 grams per cubic centimeter. The composites are fabricated by forming an aqueous slurry of carbonaceous fibers which include carbonized fibers and 0-50 weight percent fugitive fibers and a particulate thermosetting resin precursor. The slurry is brought into contact with a perforated mandrel and the water is drained from the slurry through the perforations at a controlled flow rate of about 0. 03 to 0.30 liters per minutes per square inch of a mandrel surface. The deposited billet of fibers and resin precursor is heated to cure the resin precursor to bind the fibers together, removed from the mandrel, and then the resin and fugitive fibers, if any, are carbonized.

The Infrared Spectrum of Matrix Isolated Aminoacetonitrile: A Precursor to the Amino Acid Glycine

NASA Technical Reports Server (NTRS)

Bernstein, Max P.; Bauschlicher, Charles W., Jr.; Sandford, Scott A.

2003-01-01

We present infrared (IR) spectral data from matrix isolation experiments and density functional theory calculations on the pre-biologically interesting molecule aminoacetonitrile, a precursor to glycine. We find that this nitrile has an unusually weak nitrile (C=N) stretch in the infrared, in contrast to expectations based on measurements and models of other nitriles under astrophysical conditions. The absence of an observable nitrile absorption feature in the infrared will make the IR search for this molecule considerably more difficult, and will raise estimates of upper limits on nitriles in interstellar and outer Solar System ices. This is also of relevance to assessing the formation routes of the amino acid glycine, since aminoacetonitrile is the putative precursor to glycine via the Strecker synthesis, the mechanism postulated to have produced the amino acids in meteorites.

Using ADOPT Algorithm and Operational Data to Discover Precursors to Aviation Adverse Events

NASA Technical Reports Server (NTRS)

Janakiraman, Vijay; Matthews, Bryan; Oza, Nikunj

2018-01-01

The US National Airspace System (NAS) is making its transition to the NextGen system and assuring safety is one of the top priorities in NextGen. At present, safety is managed reactively (correct after occurrence of an unsafe event). While this strategy works for current operations, it may soon become ineffective for future airspace designs and high density operations. There is a need for proactive management of safety risks by identifying hidden and "unknown" risks and evaluating the impacts on future operations. To this end, NASA Ames has developed data mining algorithms that finds anomalies and precursors (high-risk states) to safety issues in the NAS. In this paper, we describe a recently developed algorithm called ADOPT that analyzes large volumes of data and automatically identifies precursors from real world data. Precursors help in detecting safety risks early so that the operator can mitigate the risk in time. In addition, precursors also help identify causal factors and help predict the safety incident. The ADOPT algorithm scales well to large data sets and to multidimensional time series, reduce analyst time significantly, quantify multiple safety risks giving a holistic view of safety among other benefits. This paper details the algorithm and includes several case studies to demonstrate its application to discover the "known" and "unknown" safety precursors in aviation operation.

Analysis of Total Electron Content and Electron Density Profile during Different Geomagnetic Storms

NASA Astrophysics Data System (ADS)

Chapagain, N. P.; Rana, B.; Adhikari, B.

2017-12-01

Total Electron content (TEC) and electron density are the key parameters in the mitigation of ionospheric effects on radio communication system. Detail study of the TEC and electron density variations has been carried out during geomagnetic storms, with longitude and latitude, for four different locations: (13˚N -17˚N, 88˚E -98˚E), (30˚N-50˚N, 120˚W -95˚W), (29˚S-26˚S, 167˚W-163˚W,) and (60˚S-45˚S, 120˚W-105˚W) using the Gravity Recovery and Climate Experiment (GRACE) satellite observations. In order to find the geomagnetic activity, the solar wind parameters such as north-south component of inter planetary magnetic field (Bz), plasma drift velocity (Vsw), flow pressure (nPa), AE, Dst and Kp indices were obtained from Operating Mission as Nodes on the Internet (OMNI) web system. The data for geomagnetic indices have been correlated with the TEC and electron density for four different events of geomagnetic storms on 6 April 2008, 27 March 2008, 4 September 2008, and 11 October 2008. The result illustrates that the observed TEC and electron density profile significantly vary with longitudes and latitudes. This study illustrates that the values of TEC and the vertical electron density profile are influenced by the solar wind parameters associated with solar activities. The peak values of electron density and TEC increase as the geomagnetic storms become stronger. Similarly, the electron density profile varies with altitudes, which peaks around the altitude range of about 250- 350 km, depending on the strength of geomagnetic storms. The results clearly show that the peak electron density shifted to higher altitude (from about 250 km to 350 km) as the geomagnetic disturbances becomes stronger.

Profiles of Ionospheric Storm-enhanced Density during the 17 March 2015 Great Storm

NASA Astrophysics Data System (ADS)

Liu, J.; Wang, W.; Burns, A. G.; Yue, X.; Zhang, S.; Zhang, Y.

2015-12-01

Ionospheric F2 region peak densities (NmF2) are expected to show a positive phase correlation with total electron content (TEC), and electron density is expected to have an anti-correlation with electron temperature near the ionospheric F2 peak. However, we show that, during the 17 March 2015 great storm, TEC and F2 region electron density peak height (hmF2) over Millstone Hill increased, but the F2 region electron density peak (NmF2) decreased significantly during the storm-enhanced density (SED) phase of the storm compared with the quiet-time ionosphere. This SED occurred where there was a negative ionospheric storm near the F2 peak and below it. The weak ionosphere below the F2 peak resulted in much reduced downward heat conduction for the electrons, trapping the heat in the topside. This, in turn, increased the topside scale height, so that, even though electron densities at the F2 peak were depleted, TEC increased in the SED. The depletion in NmF2 was probably caused by an increase in the density of the molecular neutrals, resulting in enhanced recombination. In addition, the storm-time topside ionospheric electron density profile was much closer to diffusive equilibrium than non-storm time profile because of less daytime plasma flow from the ionosphere to the plasmasphere.

SU-G-JeP2-02: A Unifying Multi-Atlas Approach to Electron Density Mapping Using Multi-Parametric MRI for Radiation Treatment Planning

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

Ren, S; Tianjin University, Tianjin; Hara, W

Purpose: MRI has a number of advantages over CT as a primary modality for radiation treatment planning (RTP). However, one key bottleneck problem still remains, which is the lack of electron density information in MRI. In the work, a reliable method to map electron density is developed by leveraging the differential contrast of multi-parametric MRI. Methods: We propose a probabilistic Bayesian approach for electron density mapping based on T1 and T2-weighted MRI, using multiple patients as atlases. For each voxel, we compute two conditional probabilities: (1) electron density given its image intensity on T1 and T2-weighted MR images, and (2)more » electron density given its geometric location in a reference anatomy. The two sources of information (image intensity and spatial location) are combined into a unifying posterior probability density function using the Bayesian formalism. The mean value of the posterior probability density function provides the estimated electron density. Results: We evaluated the method on 10 head and neck patients and performed leave-one-out cross validation (9 patients as atlases and remaining 1 as test). The proposed method significantly reduced the errors in electron density estimation, with a mean absolute HU error of 138, compared with 193 for the T1-weighted intensity approach and 261 without density correction. For bone detection (HU>200), the proposed method had an accuracy of 84% and a sensitivity of 73% at specificity of 90% (AUC = 87%). In comparison, the AUC for bone detection is 73% and 50% using the intensity approach and without density correction, respectively. Conclusion: The proposed unifying method provides accurate electron density estimation and bone detection based on multi-parametric MRI of the head with highly heterogeneous anatomy. This could allow for accurate dose calculation and reference image generation for patient setup in MRI-based radiation treatment planning.« less

Hierarchical nanostructured WO3-SnO2 for selective sensing of volatile organic compounds

NASA Astrophysics Data System (ADS)

Nayak, Arpan Kumar; Ghosh, Ruma; Santra, Sumita; Guha, Prasanta Kumar; Pradhan, Debabrata

2015-07-01

It remains a challenge to find a suitable gas sensing material that shows a high response and shows selectivity towards various gases simultaneously. Here, we report a mixed metal oxide WO3-SnO2 nanostructured material synthesized in situ by a simple, single-step, one-pot hydrothermal method at 200 °C in 12 h, and demonstrate its superior sensing behavior towards volatile organic compounds (VOCs) such as ammonia, ethanol and acetone. SnO2 nanoparticles with controlled size and density were uniformly grown on WO3 nanoplates by varying the tin precursor. The density of the SnO2 nanoparticles on the WO3 nanoplates plays a crucial role in the VOC selectivity. The responses of the present mixed metal oxides are found to be much higher than the previously reported results based on single/mixed oxides and noble metal-doped oxides. In addition, the VOC selectivity is found to be highly temperature-dependent, with optimum performance obtained at 200 °C, 300 °C and 350 °C for ammonia, ethanol and acetone, respectively. The present results on the cost-effective noble metal-free WO3-SnO2 sensor could find potential application in human breath analysis by non-invasive detection.It remains a challenge to find a suitable gas sensing material that shows a high response and shows selectivity towards various gases simultaneously. Here, we report a mixed metal oxide WO3-SnO2 nanostructured material synthesized in situ by a simple, single-step, one-pot hydrothermal method at 200 °C in 12 h, and demonstrate its superior sensing behavior towards volatile organic compounds (VOCs) such as ammonia, ethanol and acetone. SnO2 nanoparticles with controlled size and density were uniformly grown on WO3 nanoplates by varying the tin precursor. The density of the SnO2 nanoparticles on the WO3 nanoplates plays a crucial role in the VOC selectivity. The responses of the present mixed metal oxides are found to be much higher than the previously reported results based on single/mixed oxides and noble metal-doped oxides. In addition, the VOC selectivity is found to be highly temperature-dependent, with optimum performance obtained at 200 °C, 300 °C and 350 °C for ammonia, ethanol and acetone, respectively. The present results on the cost-effective noble metal-free WO3-SnO2 sensor could find potential application in human breath analysis by non-invasive detection. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr02571k

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

Finzel, Kati, E-mail: kati.finzel@liu.se

The local conditions for the Pauli potential that are necessary in order to yield self-consistent electron densities from orbital-free calculations are investigated for approximations that are expressed with the help of a local position variable. It is shown that those local conditions also apply when the Pauli potential is given in terms of the electron density. An explicit formula for the Ne atom is given, preserving the local conditions during the iterative procedure. The resulting orbital-free electron density exhibits proper shell structure behavior and is in close agreement with the Kohn-Sham electron density. This study demonstrates that it is possiblemore » to obtain self-consistent orbital-free electron densities with proper atomic shell structure from simple one-point approximations for the Pauli potential at local density level.« less

Relationship between the Geotail spacecraft potential and the magnetospheric electron number density including the distant tail regions

NASA Astrophysics Data System (ADS)

Ishisaka, K.; Okada, T.; Tsuruda, K.; Hayakawa, H.; Mukai, T.; Matsumoto, H.

2001-04-01

The spacecraft potential has been used to derive the electron number density surrounding the spacecraft in the magnetosphere and solar wind. We have investigated the correlation between the spacecraft potential of the Geotail spacecraft and the electron number density derived from the plasma waves in the solar wind and almost all the regions of the magnetosphere, except for the high-density plasmasphere, and obtained an empirical formula to show their relation. The new formula is effective in the range of spacecraft potential from a few volts up to 90 V, corresponding to the electron number density from 0.001 to 50 cm-3. We compared the electron number density obtained by the empirical formula with the density obtained by the plasma wave and plasma particle measurements. On occasions the density determined by plasma wave measurements in the lobe region is different from that calculated by the empirical formula. Using the difference in the densities measured by two methods, we discuss whether or not the lower cutoff frequency of the plasma waves, such as continuum radiation, indicates the local electron density near the spacecraft. Then we applied the new relation to the spacecraft potential measured by the Geotail spacecraft during the period from October 1993 to December 1995, and obtained the electron spatial distribution in the solar wind and magnetosphere, including the distant tail region. Higher electron number density is clearly observed on the dawnside than on the duskside of the magnetosphere in the distant tail beyond 100RE.

[Study on the distribution of plasma parameters in electrodeless lamp using emission spectrometry].

PubMed

Wang, Chang-Quan; Zhang, Gui-Xin; Wang, Xin-Xin; Shao, Ming-Song; Dong, Jin-Yang; Wang, Zan-Ji

2011-09-01

Electrodeless lamp in pear shape was ignited using inductively coupled discharge setup and Ar-Hg mixtures as working gas. The changes in electronic temperature and density with axial and radial positions at 5 s of igniting were studied by means of emission spectrometry. The changes in electronic temperature were obtained according to the Ar line intensity ratio of 425.9 nm/ 750.4 nm. And the variations in electronic density were analyzed using 750.4 nm line intensity. It was found that plasma electronic temperature and density is various at different axial or radial positions. The electronic temperatures first increase, then decrease, and then increase quickly, and finally decline. While the electronic density firstly increase quickly, the decrease, and then rise slowly and finally decline again with axial distance increasing. With radial distance increasing, electronic temperature increases to a stable area, then continues to rise, while electronic density decreases.

The Holographic Electron Density Theorem, de-quantization, re-quantization, and nuclear charge space extrapolations of the Universal Molecule Model

NASA Astrophysics Data System (ADS)

Mezey, Paul G.

2017-11-01

Two strongly related theorems on non-degenerate ground state electron densities serve as the basis of "Molecular Informatics". The Hohenberg-Kohn theorem is a statement on global molecular information, ensuring that the complete electron density contains the complete molecular information. However, the Holographic Electron Density Theorem states more: the local information present in each and every positive volume density fragment is already complete: the information in the fragment is equivalent to the complete molecular information. In other words, the complete molecular information provided by the Hohenberg-Kohn Theorem is already provided, in full, by any positive volume, otherwise arbitrarily small electron density fragment. In this contribution some of the consequences of the Holographic Electron Density Theorem are discussed within the framework of the "Nuclear Charge Space" and the Universal Molecule Model. In the Nuclear Charge Space" the nuclear charges are regarded as continuous variables, and in the more general Universal Molecule Model some other quantized parameteres are also allowed to become "de-quantized and then re-quantized, leading to interrelations among real molecules through abstract molecules. Here the specific role of the Holographic Electron Density Theorem is discussed within the above context.

Analysis of rapid increase in the plasma density during the ramp-up phase in a radio frequency negative ion source by large-scale particle simulation

NASA Astrophysics Data System (ADS)

Yasumoto, M.; Ohta, M.; Kawamura, Y.; Hatayama, A.

2014-02-01

Numerical simulations become useful for the developing RF-ICP (Radio Frequency Inductively Coupled Plasma) negative ion sources. We are developing and parallelizing a two-dimensional three velocity electromagnetic Particle-In-Cell code. The result shows rapid increase in the electron density during the density ramp-up phase. A radial electric field due to the space charge is produced with increase in the electron density and the electron transport in the radial direction is suppressed. As a result, electrons stay for a long period in the region where the inductive electric field is strong, and this leads efficient electron acceleration and a rapid increasing of the electron density.

Fibrous selective emitter structures from sol-gel process

NASA Astrophysics Data System (ADS)

Chen, K. C.

1999-03-01

Selective emitters have the potential benefit of high efficiency due to the matching of emission spectra to the response of photovoltaic (PV) cells. Continuous uniform rare-earth oxide selective emitter fibers were successfully fabricated using a viscous solution made from metal organic precursors. Cylindrical- and planar configuration emitter structures were made by direct cross-winding or stacking of precursor fiber layers. The combustion and optical performance of the planar emitter structures were tested. The results indicates that both the designing of the fiber packing density and the thickness is critical for high photon and power output.

Improved quality of graphene in the absence of hydrogen in a low-temperature growth process using an alcohol precursor

NASA Astrophysics Data System (ADS)

Choi, Kyeonggon; Lee, Kiyeol; Jeong, Jaehoon; Ye, Jongpil

2017-03-01

We present the results of low-temperature growth of graphene on polycrystalline copper foil surfaces at 800 °C by using low-pressure chemical-vapor deposition of alcohol precursors. The structural quality of the graphene sample was found to depend significantly on the ambient conditions during the annealing and the growth processes. The improved quality of graphene grown in an oxidizing environment was found to be associated with a lower nucleation density, suggesting that chemisorbed oxygen atoms play a critical role in determining the quality of graphene.

Solar Wind Electron Interaction with the Dayside Lunar Surface and Crustal Magnetic Fields: Evidence for Precursor Effects

NASA Technical Reports Server (NTRS)

Halekas, Jasper S.; Poppe, A.; Delory, G. T.; Farrell, W. M.; Horanyi, M.

2012-01-01

Electron distributions measured by Lunar Prospector above the dayside lunar surface in the solar wind often have an energy dependent loss cone, inconsistent with adiabatic magnetic reflection. Energy dependent reflection suggests the presence of downward parallel electric fields below the spacecraft, possibly indicating the presence of a standing electrostatic structure. Many electron distributions contain apparent low energy (<100 eV) upwardgoing conics (58% of the time) and beams (12% of the time), primarily in regions with non-zero crustal magnetic fields, implying the presence of parallel electric fields and/or wave-particle interactions below the spacecraft. Some, but not all, of the observed energy dependence comes from the energy gained during reflection from a moving obstacle; correctly characterizing electron reflection requires the use of the proper reference frame. Nonadiabatic reflection may also play a role, but cannot fully explain observations. In cases with upward-going beams, we observe partial isotropization of incoming solar wind electrons, possibly indicating streaming and/or whistler instabilities. The Moon may therefore influence solar wind plasma well upstream from its surface. Magnetic anomaly interactions and/or non-monotonic near surface potentials provide the most likely candidates to produce the observed precursor effects, which may help ensure quasi-neutrality upstream from the Moon.

Electron-beam Induced Processes and their Applicability to Mask Repair

NASA Astrophysics Data System (ADS)

Boegli, Volker A.; Koops, Hans W. P.; Budach, Michael; Edinger, Klaus; Hoinkis, Ottmar; Weyrauch, Bernd; Becker, Rainer; Schmidt, Rudolf; Kaya, Alexander; Reinhardt, Andreas; Braeuer, Stephan; Honold, Heinz; Bihr, Johannes; Greiser, Jens; Eisenmann, Michael

2002-12-01

The applicability of electron-beam induced chemical reactions to mask repair is investigated. To achieve deposition and chemical etching with a focused electron-beam system, it is required to disperse chemicals in a molecular beam to the area of interest with a well-defined amount of molecules and monolayers per second. For repair of opaque defects the precursor gas reacts with the absorber material of the mask and forms a volatile reaction product, which leaves the surface. In this way the surface atoms are removed layer by layer. For clear defect repair, additional material, which is light absorbing in the UV, is deposited onto the defect area. This material is rendered as a nanocrystalline deposit from metal containing precursors. An experimental electron-beam mask repair system is developed and used to perform exploratory work applicable to photo mask, EUV mask, EPL and LEEPL stencil mask repair. The tool is described and specific repair actions are demonstrated. Platinum deposited features with lateral dimensions down to 20 nm demonstrate the high resolution obtainable with electron beam induced processes, while AFM and AIMS measurements indicate, that specifications for mask repair at the 70 nm device node can be met. In addition, examples of etching quartz and TaN are given.

Transient nutation electron spin resonance spectroscopy on spin-correlated radical pairs: A theoretical analysis on hyperfine-induced nuclear modulations

NASA Astrophysics Data System (ADS)

Weber, Stefan; Kothe, Gerd; Norris, James R.

1997-04-01

The influence of anisotropic hyperfine interaction on transient nutation electron paramagnetic resonance (EPR) of light-induced spin-correlated radical pairs is studied theoretically using the density operator formalism. Analytical expressions for the time evolution of the transient EPR signal during selective microwave excitation of single transitions are derived for a model system comprised of a weakly coupled radical pair and one hyperfine-coupled nucleus with I=1/2. Zero-quantum electron coherence and single-quantum nuclear coherence are created as a result of the sudden light-induced generation of the radical pair state from a singlet-state precursor. Depending on the relative sizes of the nuclear Zeeman frequency and the secular and pseudo-secular parts of the hyperfine coupling, transitions between levels with different nuclear spin orientations are predicted to modulate the time-dependent EPR signal. These modulations are in addition to the well-known transient nutations and electron zero-quantum precessions. Our calculations provide insight into the mechanism of recent experimental observations of coherent nuclear modulations in the time-resolved EPR signals of doublets and radical pairs. Two distinct mechanisms of the modulations are presented for various microwave magnetic field strengths. The first modulation scheme arises from electron and nuclear coherences initiated by the laser excitation pulse and is "read out" by the weak microwave magnetic field. While the relative modulation depth of these oscillations with respect to the signal intensity is independent of the Rabi frequency, ω1, the frequencies of this coherence phenomenon are modulated by the effective microwave amplitude and determined by the nuclear Zeeman interaction and hyperfine coupling constants as well as the electron-electron spin exchange and dipolar interactions between the two radical pair halves. In a second mechanism the modulations are both created and detected by the microwave radiation. Here, the laser pulse merely defines the beginning of the microwave-induced coherent time evolution. This second mechanism appears the most consistent with current experimental observations.

Preparation of LiFePO{sub 4} with inverse opal structure and its satisfactory electrochemical properties

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

Lu Junbiao; Tang Zilong; Zhang Zhongtai

Phase pure, well-crystallized and homogeneous LiFePO{sub 4} powder with inverse opal structure was obtained by calcining the precursors of Li{sup +}, Fe{sup 2+} and PO{sub 4} {sup 3-} in the presence of organic template of poly(styrene-methyl methacrylate-acrylic acid) latex micro-spheres under nitrogen atmosphere. The resultant products were characterized by X-ray powder diffraction (XRD), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), chemical titration, Fourier transform infrared (FTIR) and Land 2001A electrochemical measurement system. Results indicated that after the decomposition of organic template, inverse opal structure and conductive carbon were left in the resultant products. With the large specific surface areamore » resulting from inverse opal structure and with the conductive carbon, the products delivered satisfactory capacity and superior rate capability at room temperature, i.e., over 100 mAh/g at the high current density of 5.9C.« less

Effect of Sintering Temperature on Structural, Dielectric, and Magnetic Properties of Multiferroic YFeO₃ Ceramics Fabricated by Spark Plasma Sintering.

PubMed

Wang, Meng; Wang, Ting; Song, Shenhua; Ma, Qing; Liu, Renchen

2017-03-07

Based on precursor powders with a size of 200-300 nm prepared by the low-temperature solid reaction method, phase-pure YFeO₃ ceramics are fabricated using spark plasma sintering (SPS) at different temperatures. X-ray diffraction (XRD) and scanning electron microscopy (SEM) reveal that the high-purity YFeO₃ ceramics can be prepared using SPS, while the results from X-ray photoelectron spectroscopy (XPS) show that the concentration of oxygen vacancies resulting from transformation from Fe 3+ to Fe 2+ is low. The relative density of the 1000 °C-sintered sample is as high as 97.7%, which is much higher than those of the samples sintered at other temperatures. The present dielectric and magnetic properties are much better than those of the samples fabricated by conventional methods. These findings indicate that the YFeO₃ ceramics prepared by the low temperature solid reaction and SPS methods possess excellent dielectric and magnetic properties, making them suitable for potential applications involving magnetic storage.

Dendritic core-shell nickel-iron-copper metal/metal oxide electrode for efficient electrocatalytic water oxidation.

PubMed

Zhang, Peili; Li, Lin; Nordlund, Dennis; Chen, Hong; Fan, Lizhou; Zhang, Biaobiao; Sheng, Xia; Daniel, Quentin; Sun, Licheng

2018-01-26

Electrochemical water splitting requires efficient water oxidation catalysts to accelerate the sluggish kinetics of water oxidation reaction. Here, we report a promisingly dendritic core-shell nickel-iron-copper metal/metal oxide electrode, prepared via dealloying with an electrodeposited nickel-iron-copper alloy as a precursor, as the catalyst for water oxidation. The as-prepared core-shell nickel-iron-copper electrode is characterized with porous oxide shells and metallic cores. This tri-metal-based core-shell nickel-iron-copper electrode exhibits a remarkable activity toward water oxidation in alkaline medium with an overpotential of only 180 mV at a current density of 10 mA cm -2 . The core-shell NiFeCu electrode exhibits pH-dependent oxygen evolution reaction activity on the reversible hydrogen electrode scale, suggesting that non-concerted proton-electron transfers participate in catalyzing the oxygen evolution reaction. To the best of our knowledge, the as-fabricated core-shell nickel-iron-copper is one of the most promising oxygen evolution catalysts.

Silicon oxycarbide glass-graphene composite paper electrode for long-cycle lithium-ion batteries.

PubMed

David, Lamuel; Bhandavat, Romil; Barrera, Uriel; Singh, Gurpreet

2016-03-30

Silicon and graphene are promising anode materials for lithium-ion batteries because of their high theoretical capacity; however, low volumetric energy density, poor efficiency and instability in high loading electrodes limit their practical application. Here we report a large area (approximately 15 cm × 2.5 cm) self-standing anode material consisting of molecular precursor-derived silicon oxycarbide glass particles embedded in a chemically-modified reduced graphene oxide matrix. The porous reduced graphene oxide matrix serves as an effective electron conductor and current collector with a stable mechanical structure, and the amorphous silicon oxycarbide particles cycle lithium-ions with high Coulombic efficiency. The paper electrode (mass loading of 2 mg cm(-2)) delivers a charge capacity of ∼588 mAh g(-1)electrode (∼393 mAh cm(-3)electrode) at 1,020th cycle and shows no evidence of mechanical failure. Elimination of inactive ingredients such as metal current collector and polymeric binder reduces the total electrode weight and may provide the means to produce efficient lightweight batteries.

Grassy Silica Nanoribbons and Strong Blue Luminescence

NASA Astrophysics Data System (ADS)

Wang, Shengping; Xie, Shuang; Huang, Guowei; Guo, Hongxuan; Cho, Yujin; Chen, Jun; Fujita, Daisuke; Xu, Mingsheng

2016-09-01

Silicon dioxide (SiO2) is one of the key materials in many modern technological applications such as in metal oxide semiconductor transistors, photovoltaic solar cells, pollution removal, and biomedicine. We report the accidental discovery of free-standing grassy silica nanoribbons directly grown on SiO2/Si platform which is commonly used for field-effect transistors fabrication without other precursor. We investigate the formation mechanism of this novel silica nanostructure that has not been previously documented. The silica nanoribbons are flexible and can be manipulated by electron-beam. The silica nanoribbons exhibit strong blue emission at about 467 nm, together with UV and red emissions as investigated by cathodoluminescence technique. The origins of the luminescence are attributed to various defects in the silica nanoribbons; and the intensity change of the blue emission and green emission at about 550 nm is discussed in the frame of the defect density. Our study may lead to rational design of the new silica-based materials for a wide range of applications.

Metalorganic Vapor-Phase Epitaxy Growth Parameters for Two-Dimensional MoS2

NASA Astrophysics Data System (ADS)

Marx, M.; Grundmann, A.; Lin, Y.-R.; Andrzejewski, D.; Kümmell, T.; Bacher, G.; Heuken, M.; Kalisch, H.; Vescan, A.

2018-02-01

The influence of the main growth parameters on the growth mechanism and film formation processes during metalorganic vapor-phase epitaxy (MOVPE) of two-dimensional MoS2 on sapphire (0001) have been investigated. Deposition was performed using molybdenum hexacarbonyl and di- tert-butyl sulfide as metalorganic precursors in a horizontal hot-wall MOVPE reactor from AIXTRON. The structural properties of the MoS2 films were analyzed by atomic force microscopy, scanning electron microscopy, and Raman spectroscopy. It was found that a substrate prebake step prior to growth reduced the nucleation density of the polycrystalline film. Simultaneously, the size of the MoS2 domains increased and the formation of parasitic carbonaceous film was suppressed. Additionally, the influence of growth parameters such as reactor pressure and surface temperature is discussed. An upper limit for these parameters was found, beyond which strong parasitic deposition or incorporation of carbon into MoS2 took place. This carbon contamination became significant at reactor pressure above 100 hPa and temperature above 900°C.

Pressure-Sensitive and Conductive Carbon Aerogels from Poplars Catkins for Selective Oil Absorption and Oil/Water Separation.

PubMed

Li, Lingxiao; Hu, Tao; Sun, Hanxue; Zhang, Junping; Wang, Aiqin

2017-05-31

Multifunctional carbon aerogels that are both highly compressible and conductive have broad potential applications in the range of sound insulator, sensor, oil absorption, and electronics. However, the preparation of such carbon aerogels has been proven to be very challenging. Here, we report fabrication of pressure-sensitive and conductive (PSC) carbon aerogels by pyrolysis of cellulose aerogels composed of poplars catkin (PC) microfibers with a tubular structure. The wet PC gels can be dried directly in an oven without any deformation, in marked contrast to the brittle nature of traditional carbon aerogels. The resultant PSC aerogels exhibit ultralow density (4.3 mg cm -3 ), high compressibility (80%), high electrical conductivity (0.47 S cm -1 ), and high absorbency (80-161 g g -1 ) for oils and organic liquids. The PSC aerogels have potential applications in various fields such as elastomeric conductors, absorption of oils from water and oil/water separation, as the PSC aerogels feature simple preparation process with low-cost biomass as the precursor.

Tuning electronic properties of boron nitride nanoplate via doping carbon for enhanced adsorptive performance.

PubMed

Pang, Jingyu; Chao, Yanhong; Chang, Honghong; Li, Hongping; Xiong, Jun; He, Minqiang; Zhang, Qi; Li, Huaming; Zhu, Wenshuai

2017-12-15

In this paper, the carbon-doped boron nitride nanoplate (C-BNNP) was prepared by pyrolyzing the precursor under N 2 and served as an excellent adsorbent for removal of Rhodamine B (RhB). The structure and composition of C-BNNP were characterized and its adsorption behavior for RhB was investigated. Compared with boron nitride nanoplate (BNNP) which was synthesized under NH 3 , C-BNNP displayed an enhancement of the adsorption capacity for RhB (833mg/g). The adsorption activity was comprehensibly studied by kinetics, isotherm and thermodynamics. The adsorption kinetics followed pseudo-second-order model. The equilibrium adsorption data agreed well with the Langmuir isotherm. And the thermodynamics indicated that the adsorption process was a spontaneous, exothermic and physisorption process. In addition, the density functional theory was proposed that doping carbon in the BNNP decreased the chemical hardness of the adsorbent and enhanced the adsorption capacity of C-BNNP for RhB. Copyright © 2017 Elsevier Inc. All rights reserved.

Phase transitions and proton ordering in hemimorphite: new insights from single-crystal EPR experiments and DFT calculations

NASA Astrophysics Data System (ADS)

Mao, Mao; Li, Zucheng; Pan, Yuanming

2013-02-01

Single-crystal electron paramagnetic resonance spectra of gamma-ray-irradiated hemimorphite (Mapimi, Durango, Mexico) after storage at room temperature for 3 months, measured from 4 to 275 K, reveal a hydroperoxy radical HO2 derived from the water molecule in the channel. The EPR spectra of the HO2 radical confirm that hemimorphite undergoes two reversible phase transitions at ~98 and ~21 K and allow determinations of its spin Hamiltonian parameters, including superhyperfine coupling constants of two more-distant protons from the neighboring hydroxyl groups, at 110, 85, 40 and 7 K. These EPR results show that the HO2 radical changes in site symmetry from monoclinic to triclinic related to the ordering and rotation of its precursor water molecule in the channel at <98 K. The monoclinic structure of hemimorphite with completely ordered O-H systems at low temperature has been evaluated by both the EPR spectra of the HO2 radical at <21 K and periodic density functional theory calculations.

Phase transformation strengthening of high-temperature superalloys

PubMed Central

Smith, T. M.; Esser, B. D.; Antolin, N.; Carlsson, A.; Williams, R. E. A.; Wessman, A.; Hanlon, T.; Fraser, H. L.; Windl, W.; McComb, D. W.; Mills, M. J.

2016-01-01

Decades of research has been focused on improving the high-temperature properties of nickel-based superalloys, an essential class of materials used in the hot section of jet turbine engines, allowing increased engine efficiency and reduced CO2 emissions. Here we introduce a new ‘phase-transformation strengthening' mechanism that resists high-temperature creep deformation in nickel-based superalloys, where specific alloying elements inhibit the deleterious deformation mode of nanotwinning at temperatures above 700 °C. Ultra-high-resolution structure and composition analysis via scanning transmission electron microscopy, combined with density functional theory calculations, reveals that a superalloy with higher concentrations of the elements titanium, tantalum and niobium encourage a shear-induced solid-state transformation from the γ′ to η phase along stacking faults in γ′ precipitates, which would normally be the precursors of deformation twins. This nanoscale η phase creates a low-energy structure that inhibits thickening of stacking faults into twins, leading to significant improvement in creep properties. PMID:27874007

Influence of Sm2O3 microalloying and Yb contamination on Y211 particles coarsening and superconducting properties of IG YBCO bulk superconductors

NASA Astrophysics Data System (ADS)

Vojtkova, L.; Diko, P.; Kovac, J.; Vojtko, M.

2018-06-01

Single grain YBa2Cu3O7‑x (YBCO or Y123) bulk superconductors were produced by an infiltration growth process. The solid phase precursor was prepared by solid state synthesis from Y2O3 + BaCuO2 powders. The influence of the addition of Sm2O3 and YB contamination from the substrate on the microstructure and superconducting properties was analyzed. The dependences of Yb concentration on the distance from the bottom of the samples measured by energy dispersive spectroscopy microanalysis used in conjunction with scanning electron microscopy confirmed the contamination of the samples during the melting stage of the sample preparation. It is shown that the addition of Sm in low concentration and its combination with Yb from the substrate modify the coarsening of the Y211 particles as well as lead to the appearance of a secondary peak effect in the field dependences of the critical current density.

X-ray irradiation-induced structural changes on Single Wall Carbon Nanotubes

NASA Astrophysics Data System (ADS)

Bardi, N.; Jurewicz, I.; King, A. K.; Alkhorayef, M. A.; Bradley, D.; Dalton, A. B.

2017-11-01

Dosimetry devices based on Carbon Nanotubes are a promising new technology. In particular using devices based on single wall Carbon Nanotubes may offer a tissue equivalent response with the possibility for device miniaturisation, high scale manufacturing and low cost. An important precursor to device fabrication requires a quantitative study of the effects of X-ray radiation on the physical and chemical properties of the individual nanotubes. In this study, we concentrate on the effects of relatively low doses, 20 cGy and 45 cGy , respectively. We use a range of characterization techniques including scanning electron microscopy, Raman spectroscopy and X-ray photoelectron spectroscopy to quantify the effects of the radiation dose on inherent properties of the nanotubes. Specifically we find that the radiation exposure results in a reduction in the sp2 nature of the nanotube bond structure. Moreover, our analysis indicates that the exposure results in nanotubes that have an increased defect density which ultimately effects the electrical properties of the nanotubes.

The protocol for the isolation and cryopreservation of osteoclast precursors from mouse bone marrow and spleen.

PubMed

Boraschi-Diaz, Iris; Komarova, Svetlana V

2016-01-01

Osteoclasts are responsible for physiological bone remodeling as well as pathological bone destruction in osteoporosis, periodontitis and rheumatoid arthritis, and thus represent a pharmacological target for drug development. We aimed to characterize and compare the cytokine-induced osteoclastogenesis of bone marrow and spleen precursors. Established protocols used to generate osteoclasts from bone marrow were modified to examine osteoclastogenesis of the spleen cells of healthy mice. Osteoclast formation was successfully induced from spleen precursors using receptor activator of nuclear factor κB ligand (50 ng/ml) and macrophage colony stimulating factor (50 ng/ml). Compared to bone marrow cultures, differentiation from spleen required a longer cultivation time (9 days for spleen, as compared to 5 days for marrow cultures) and a higher plating density of non-adherent cells (75,000/cm(2) for spleen, as compared to 50,000/cm(2) for bone marrow). Osteoclasts generated from spleen precursors expressed osteoclast marker genes calcitonin receptor, cathepsin K and matrix metalloproteinase 9 and were capable of resorbing hydroxyapatite. The differentiation capacity of spleen and bone marrow precursors was comparable for BALB/c, C57BL/6 and FVB mice. We also developed and tested a cryopreservation protocol for the osteoclast precursors. While 70-80 % of cells were lost during the first week of freezing, during the subsequent 5 weeks the losses were within 2-5 % per week. Osteoclastogenesis from the recovered bone marrow precursors was successful up to 5 weeks after freezing. Spleen precursors retained their osteoclastogenic capacity for 1 week after freezing, but not thereafter. The described protocol is useful for the studies of genetically modified animals as well as for screening new osteoclast-targeting therapeutics.

Atomic layer deposition of Al{sub 2}O{sub 3} for single electron transistors utilizing Pt oxidation and reduction

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

McConnell, Michael S., E-mail: mmcconn5@nd.edu; Schneider, Louisa C.; Karbasian, Golnaz

This work describes the fabrication of single electron transistors using electron beam lithography and atomic layer deposition to form nanoscale tunnel transparent junctions of alumina (Al{sub 2}O{sub 3}) on platinum nanowires using either water or ozone as the oxygen precursor and trimethylaluminum as the aluminum precursor. Using room temperature, low frequency conductance measurements between the source and drain, it was found that devices fabricated using water had higher conductance than devices fabricated with ozone. Subsequent annealing caused both water- and ozone-based devices to increase in conductance by more than 2 orders of magnitude. Furthermore, comparison of devices at low temperaturesmore » (∼4 K) showed that annealed devices displayed much closer to the ideal behavior (i.e., constant differential conductance) outside of the Coulomb blockade region and that untreated devices showed nonlinear behavior outside of the Coulomb blockade region (i.e., an increase in differential conductance with source-drain voltage bias). Transmission electron microscopy cross-sectional images showed that annealing did not significantly change device geometry, but energy dispersive x-ray spectroscopy showed an unusually large amount of oxygen in the bottom platinum layer. This suggests that the atomic layer deposition process results in the formation of a thin platinum surface oxide, which either decomposes or is reduced during the anneal step, resulting in a tunnel barrier without the in-series native oxide contribution. Furthermore, the difference between ozone- and water-based devices suggests that ozone promotes atomic layer deposition nucleation by oxidizing the surface but that water relies on physisorption of the precursors. To test this theory, devices were exposed to forming gas at room temperature, which also reduces platinum oxide, and a decrease in resistance was observed, as expected.« less

Qualification of a sublimation tool applied to the case of metalorganic chemical vapor deposition of In{sub 2}O{sub 3} from In(tmhd){sub 3} as a solid precursor

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

Szkutnik, P. D., E-mail: pierre.szkutnik@cea.fr; Jiménez, C.; Angélidès, L.

2016-02-15

A solid delivery system consisting of a source canister, a gas management, and temperature controlled enclosure designed and manufactured by Air Liquide Electronics Systems was tested in the context of gas-phase delivery of the In(tmhd){sub 3} solid precursor. The precursor stream was delivered to a thermal metalorganic chemical vapor deposition reactor to quantify deposition yield under various conditions of carrier gas flow and sublimation temperature. The data collected allowed the determination of characteristic parameters such as the maximum precursor flow rate (18.2 mg min{sup −1} in specified conditions) and the critical mass (defined as the minimum amount of precursor ablemore » to attain the maximum flow rate) found to be about 2.4 g, as well as an understanding of the influence of powder distribution inside the canister. Furthermore, this qualification enabled the determination of optimal delivery conditions which allowed for stable and reproducible precursor flow rates over long deposition times (equivalent to more than 47 h of experiment). The resulting In{sub 2}O{sub 3} layers was compared with those elaborated via pulsed liquid injection obtained in the same chemical vapor deposition chamber and under the same deposition conditions.« less

Novel porous CuO microrods: synthesis, characterization, and their photocatalysis property

NASA Astrophysics Data System (ADS)

Huang, Jiarui; Fu, Guijun; Shi, Chengcheng; Wang, Xinyue; Zhai, Muheng; Gu, Cuiping

2014-09-01

Porous copper oxide microrods have been synthesized via calcining copper glycinate monohydrate microrod precursor which was prepared in mild conditions without any template or additive. Several techniques, such as X-ray diffraction, field emission scanning electron microscopy, thermogravimetric analysis, Fourier transform infrared spectroscopy, and Brunauer-Emmett-Teller (BET) N2 adsorption-desorption analyses, were used to characterize the structure and morphology of the products. Scanning electron microscopy (SEM) analyses show that the precursor consists of a large quantity of uniform rod-like micro/nanostructures with typical lengths in the range of 25-40 μm and diameters in the range of 0.1-0.35 μm. The microrod-like precursors transformed into porous microrod products after calcination at 450 °C in flow air for 2 h. The BET surface area of the porous CuO microrods was calculated to be 8.5 m² g-1. In addition, the obtained porous CuO microrods were used as catalysts to photodegrade rhodamine B (RhB), methyl orange, methylene blue, eosin B, and p-nitrophenol. Compared with commercial CuO powders, the as-prepared porous CuO microrods exhibit superior properties on photocatalytic decomposition of RhB due to their porous hierarchical structures.

Synthesis, Optical and Structural Properties of Copper Sulfide Nanocrystals from Single Molecule Precursors

PubMed Central

Ajibade, Peter A.; Botha, Nandipha L.

2017-01-01

We report the synthesis and structural studies of copper sulfide nanocrystals from copper (II) dithiocarbamate single molecule precursors. The precursors were thermolysed in hexadecylamine (HDA) to prepare HDA-capped CuS nanocrystals. The optical properties of the nanocrystals studied using UV–visible and photoluminescence spectroscopy showed absorption band edges at 287 nm that are blue shifted, and the photoluminescence spectra show emission curves that are red-shifted with respect to the absorption band edges. These shifts are as a result of the small crystallite sizes of the nanoparticles leading to quantum size effects. The structural studies were carried out using powder X-ray diffraction (XRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDS), and atomic force microscopy. The XRD patterns indicates that the CuS nanocrystals are in hexagonal covellite crystalline phases with estimated particles sizes of 17.3–18.6 nm. The TEM images showed particles with almost spherical or rod shapes, with average crystallite sizes of 3–9.8 nm. SEM images showed morphology with ball-like microspheres on the surfaces, and EDS spectra confirmed the presence of CuS nanoparticles. PMID:28336865

A Dual-Phase Ceramic Membrane with Extremely High H2 Permeation Flux Prepared by Autoseparation of a Ceramic Precursor.

PubMed

Cheng, Shunfan; Wang, Yanjie; Zhuang, Libin; Xue, Jian; Wei, Yanying; Feldhoff, Armin; Caro, Jürgen; Wang, Haihui

2016-08-26

A novel concept for the preparation of multiphase composite ceramics based on demixing of a single ceramic precursor has been developed and used for the synthesis of a dual-phase H2 -permeable ceramic membrane. The precursor BaCe0.5 Fe0.5 O3-δ decomposes on calcination at 1370 °C for 10 h into two thermodynamically stable oxides with perovskite structures: the cerium-rich oxide BaCe0.85 Fe0.15 O3-δ (BCF8515) and the iron-rich oxide BaCe0.15 Fe0.85 O3-δ (BCF1585), 50 mol % each. In the resulting dual-phase material, the orthorhombic perovskite BCF8515 acts as the main proton conductor and the cubic perovskite BCF1585 as the main electron conductor. The dual-phase membrane shows an extremely high H2 permeation flux of 0.76 mL min(-1)  cm(-2) at 950 °C with 1.0 mm thickness. This auto-demixing concept should be applicable to the synthesis of other ionic-electronic conducting ceramics. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Gedanken densities and exact constraints in density functional theory.

PubMed

Perdew, John P; Ruzsinszky, Adrienn; Sun, Jianwei; Burke, Kieron

2014-05-14

Approximations to the exact density functional for the exchange-correlation energy of a many-electron ground state can be constructed by satisfying constraints that are universal, i.e., valid for all electron densities. Gedanken densities are designed for the purpose of this construction, but need not be realistic. The uniform electron gas is an old gedanken density. Here, we propose a spherical two-electron gedanken density in which the dimensionless density gradient can be an arbitrary positive constant wherever the density is non-zero. The Lieb-Oxford lower bound on the exchange energy can be satisfied within a generalized gradient approximation (GGA) by bounding its enhancement factor or simplest GGA exchange-energy density. This enhancement-factor bound is well known to be sufficient, but our gedanken density shows that it is also necessary. The conventional exact exchange-energy density satisfies no such local bound, but energy densities are not unique, and the simplest GGA exchange-energy density is not an approximation to it. We further derive a strongly and optimally tightened bound on the exchange enhancement factor of a two-electron density, which is satisfied by the local density approximation but is violated by all published GGA's or meta-GGA's. Finally, some consequences of the non-uniform density-scaling behavior for the asymptotics of the exchange enhancement factor of a GGA or meta-GGA are given.

Unbiased total electron content (UTEC), their fluctuations, and correlation with seismic activity over Japan

NASA Astrophysics Data System (ADS)

Cornely, Pierre-Richard; Hughes, John

2018-02-01

Earthquakes are among the most dangerous events that occur on earth and many scientists have been investigating the underlying processes that take place before earthquakes occur. These investigations are fueling efforts towards developing both single and multiple parameter earthquake forecasting methods based on earthquake precursors. One potential earthquake precursor parameter that has received significant attention within the last few years is the ionospheric total electron content (TEC). Despite its growing popularity as an earthquake precursor, TEC has been under great scrutiny because of the underlying biases associated with the process of acquiring and processing TEC data. Future work in the field will need to demonstrate our ability to acquire TEC data with the least amount of biases possible thereby preserving the integrity of the data. This paper describes a process for removing biases using raw TEC data from the standard Rinex files obtained from any global positioning satellites system. The process is based on developing an unbiased TEC (UTEC) data and model that can be more adaptable to serving as a precursor signal for earthquake forecasting. The model was used during the days and hours leading to the earthquake off the coast of Tohoku, Japan on March 11, 2011 with interesting results. The model takes advantage of the large amount of data available from the GPS Earth Observation Network of Japan to display near real-time UTEC data as the earthquake approaches and for a period of time after the earthquake occurred.

Optical and Photovoltaic Properties of Thieno[3,2-b]thiophene-Based Push-Pull Organic Dyes with Different Anchoring Groups for Dye-Sensitized Solar Cells.

PubMed

Fernandes, Sara S M; Castro, M Cidália R; Pereira, Ana Isabel; Mendes, Adélio; Serpa, Carlos; Pina, João; Justino, Licínia L G; Burrows, Hugh D; Raposo, M Manuela M

2017-12-31

The effect of anchoring groups on the optical and electrochemical properties of triphenylamine-thienothiophenes, and on the photovoltaic performance of DSSCs photosensitized with the prepared dyes, was studied using newly synthesized compounds with cyanoacetic acid or rhodanine-3-acetic acid groups. Precursor aldehydes were synthesized through Suzuki cross-coupling, whereas Knoevenagel condensation of these with 2-cyanoacetic acid or rhodanine-3-acetic acid afforded the final push-pull dyes. A comprehensive photophysical study was performed in solution and in the solid state. The femtosecond time-resolved transient absorption spectra for the synthesized dyes were obtained following photoexcitation in solution and for the dyes adsorbed to TiO 2 mesoporous films. Information on conformation, electronic structure, and electron distribution was obtained by density functional theory (DFT) and time-dependent DFT calculations. Triphenylamine-thienothiophene functionalized with a cyanoacetic acid anchoring group displayed the highest conversion efficiency (3.68%) as the dye sensitizer in nanocrystalline TiO 2 solar cells. Coadsorption studies were performed for this dye with the ruthenium-based N719 dye, and they showed dye power conversion efficiencies enhanced by 20-64%. The best cell performance obtained with the coadsorbed N719 and cyanoacetic dye showed an efficiency of 6.05%.

Optical and Photovoltaic Properties of Thieno[3,2-b]thiophene-Based Push–Pull Organic Dyes with Different Anchoring Groups for Dye-Sensitized Solar Cells

PubMed Central

2017-01-01

The effect of anchoring groups on the optical and electrochemical properties of triphenylamine-thienothiophenes, and on the photovoltaic performance of DSSCs photosensitized with the prepared dyes, was studied using newly synthesized compounds with cyanoacetic acid or rhodanine-3-acetic acid groups. Precursor aldehydes were synthesized through Suzuki cross-coupling, whereas Knoevenagel condensation of these with 2-cyanoacetic acid or rhodanine-3-acetic acid afforded the final push–pull dyes. A comprehensive photophysical study was performed in solution and in the solid state. The femtosecond time-resolved transient absorption spectra for the synthesized dyes were obtained following photoexcitation in solution and for the dyes adsorbed to TiO2 mesoporous films. Information on conformation, electronic structure, and electron distribution was obtained by density functional theory (DFT) and time-dependent DFT calculations. Triphenylamine–thienothiophene functionalized with a cyanoacetic acid anchoring group displayed the highest conversion efficiency (3.68%) as the dye sensitizer in nanocrystalline TiO2 solar cells. Coadsorption studies were performed for this dye with the ruthenium-based N719 dye, and they showed dye power conversion efficiencies enhanced by 20–64%. The best cell performance obtained with the coadsorbed N719 and cyanoacetic dye showed an efficiency of 6.05%. PMID:29302638

Reversibility and intermediate steps as key tools for the growth of extended ordered polymers via on-surface synthesis

NASA Astrophysics Data System (ADS)

Di Giovannantonio, Marco; Contini, Giorgio

2018-03-01

Surface-confined polymerization is a bottom-up strategy to create one- and two-dimensional covalent organic nanostructures with a π-conjugated backbone, which are suitable to be employed in real-life electronic devices, due to their high mechanical resistance and electronic charge transport efficiency. This strategy makes it possible to change the properties of the final nanostructures by a careful choice of the monomer architecture (i.e. of its constituent atoms and their spatial arrangement). Several chemical reactions have been proven to form low-dimensional polymers on surfaces, exploiting a variety of precursors in combination with metal (e.g. Cu, Ag, Au) and insulating (e.g. NaCl, CaCO3) surfaces. One of the main challenges of such an approach is to obtain nanostructures with long-range order, to boost the conductance performances of these materials. Most of the exploited chemical reactions use irreversible coupling between the monomers and, as a consequence, the resulting structures often suffer from poor order and high defect density. This review focuses on the state-of-the-art surface-confined polymerization reactions, with particular attention paid to reversible coupling pathways and irreversible processes including intermediate states, which are key aspects to control to increase the order of the final nanostructure.

Synthesis and characterization of triangulene

NASA Astrophysics Data System (ADS)

Pavliček, Niko; Mistry, Anish; Majzik, Zsolt; Moll, Nikolaj; Meyer, Gerhard; Fox, David J.; Gross, Leo

2017-05-01

Triangulene, the smallest triplet-ground-state polybenzenoid (also known as Clar's hydrocarbon), has been an enigmatic molecule ever since its existence was first hypothesized. Despite containing an even number of carbons (22, in six fused benzene rings), it is not possible to draw Kekulé-style resonant structures for the whole molecule: any attempt results in two unpaired valence electrons. Synthesis and characterization of unsubstituted triangulene has not been achieved because of its extreme reactivity, although the addition of substituents has allowed the stabilization and synthesis of the triangulene core and verification of the triplet ground state via electron paramagnetic resonance measurements. Here we show the on-surface generation of unsubstituted triangulene that consists of six fused benzene rings. The tip of a combined scanning tunnelling and atomic force microscope (STM/AFM) was used to dehydrogenate precursor molecules. STM measurements in combination with density functional theory (DFT) calculations confirmed that triangulene keeps its free-molecule properties on the surface, whereas AFM measurements resolved its planar, threefold symmetric molecular structure. The unique topology of such non-Kekulé hydrocarbons results in open-shell π-conjugated graphene fragments that give rise to high-spin ground states, potentially useful in organic spintronic devices. Our generation method renders manifold experiments possible to investigate triangulene and related open-shell fragments at the single-molecule level.

Structural evolution of atomically precise thiolated bimetallic [Au(12+n)Cu₃₂(SR)(30+n)]⁴⁻ (n = 0, 2, 4, 6) nanoclusters.

PubMed

Yang, Huayan; Wang, Yu; Yan, Juanzhu; Chen, Xi; Zhang, Xin; Häkkinen, Hannu; Zheng, Nanfeng

2014-05-21

A series of all-thiol stabilized bimetallic Au-Cu nanoclusters, [Au(12+n)Cu32(SR)(30+n)](4-) (n = 0, 2, 4, 6 and SR = SPhCF3), are successfully synthesized and characterized by X-ray single-crystal analysis and density functional theory (DFT) calculations. Each cluster consists of a Keplerate two-shell Au12@Cu20 core protected by (6 - n) units of Cu2(SR)5 and n units of Cu2Au(SR)6 (n = 0, 2, 4, 6) motifs on its surface. The size and structural evolution of the clusters is atomically controlled by the Au precursors and countercations used in the syntheses. The clusters exhibit similar optical absorption properties that are not dependent on the number of surface Cu2Au(SR)6 units. Although DFT suggests an electronic structure with an 18-electron superatom shell closure, the clusters display different thermal stabilities. [Au(12+n)Cu32(SR)(30+n)](4-) clusters with n = 0 and 2 are more stable than those with n = 4 and 6. Moreover, an oxidation product of the clusters, [Au13Cu12(SR)20](4-), is structurally identified to gain insight into how the clusters are oxidized.

Facile Synthesis of Core/Shell-like NiCo2O4-Decorated MWCNTs and its Excellent Electrocatalytic Activity for Methanol Oxidation

PubMed Central

Ko, Tae-Hoon; Devarayan, Kesavan; Seo, Min-Kang; Kim, Hak-Yong; Kim, Byoung-Suhk

2016-01-01

The design and development of an economic and highly active non-precious electrocatalyst for methanol electrooxidation is challenging due to expensiveness of the precursors as well as processes and non-ecofriendliness. In this study, a facile preparation of core-shell-like NiCo2O4 decorated MWCNTs based on a dry synthesis technique was proposed. The synthesized NiCo2O4/MWCNTs were characterized by infrared spectroscopy, scanning electron microscopy, transmission electron microscopy, X-ray diffraction, and selected area energy dispersive spectrum. The bimetal oxide nanoparticles with an average size of 6 ± 2 nm were homogeneously distributed onto the surface of the MWCNTs to form a core-shell-like nanostructure. The NiCo2O4/MWCNTs exhibited excellent electrocatalytic activity for the oxidation of methanol in an alkaline solution. The NiCo2O4/MWCNTs exhibited remarkably higher current density of 327 mA/cm2 and a lower onset potential of 0.128 V in 1.0 M KOH with as high as 5.0 M methanol. The impressive electrocatalytic activity of the NiCo2O4/MWCNTs is promising for development of direct methanol fuel cell based on non-Pt catalysts. PMID:26828633

Multifunctional Carbon Foams for Aerospace Applications

NASA Technical Reports Server (NTRS)

Rogers, D. K.; Plucinski, J.

2001-01-01

Carbon foams produced by the controlled thermal decomposition of inexpensive coal extracts exhibit a combination of structural and thermal properties that make them attractive for aerospace applications. Their thermal conductivity can be tailored between 0.5 and 100 W/mK through precursor selection/modification and heat treatment conditions; thus, they can serve in either thermal protection or heat transfer systems such as heat exchangers. Because their structure is essentially a 3D random network of graphite-like members, they also can be considered low-cost, easily fabricated replacements for multi-directional structural carbon fiber preforms. Strengths of over 4000 psi in compression are common. Their density can be designed between 0.1 and 0.8 g/cc, and they can be impregnated with a variety of matrices or used, unfilled, in sandwich structures. These foams also exhibit intriguing electrochemical properties that offer potential in high-efficiency fuel cell and battery applications, mandrels and tooling for composite manufacture, ablative performance, and fire resistance. This paper presents the results of research conducted under NASA SBIR Topic 99.04.01, General Aviation Technology, supported from Langley Research Center. The potential of foam design through precursor selection, cell size and density control, density grading, and heat treatment is demonstrated.

The fast development of solar terrestrial sciences in Taiwan

NASA Astrophysics Data System (ADS)

Liu, Jann-Yenq; Chang, Loren Chee-Wei; Chao, Chi-Kuang; Chen, Ming-Quey; Chu, Yen-Hsyang; Hau, Lin-Ni; Huang, Chien-Ming; Kuo, Cheng-Ling; Lee, Lou-Chuang; Lyu, Ling-Hsiao; Lin, Chia-Hsien; Pan, Chen-Jeih; Shue, Jih-Hong; Su, Ching-Lun; Tsai, Lung-Chih; Yang, Ya-Hui; Lin, Chien-Hung; Hsu, Rue-Ron; Su, Han-Tzong

2016-12-01

In Taiwan, research and education of solar terrestrial sciences began with a ground-based ionosonde operated by Ministry of Communications in 1952 and courses of ionospheric physics and space physics offered by National Central University (NCU) in 1959, respectively. Since 1990, to enhance both research and education, the Institute of Space Science at NCU has been setting up and operating ground-based observations of micropulsations, very high-frequency radar, low-latitude ionospheric tomography network, high-frequency Doppler sounder, digital ionosondes, and total electron content (TEC) derived from ground-based GPS receivers to study the morphology of the ionosphere for diurnal, seasonal, geophysical, and solar activity variations, as well as the ionosphere response to solar flares, solar wind, solar eclipses, magnetic storms, earthquakes, tsunami, and so on. Meanwhile, to have better understanding on physics and mechanisms, model simulations for the heliosphere, solar wind, magnetosphere, and ionosphere are also introduced and developed. After the 21 September 1999 Mw7.6 Chi-Chi earthquake, seismo-ionospheric precursors and seismo-traveling ionospheric disturbances induced by earthquakes become the most interesting and challenging research topics of the world. The development of solar terrestrial sciences grows even much faster after National Space Origination has been launching a series of FORMOSAT satellites since 1999. ROCSAT-1 (now renamed FORMOSAT-1) measures the ion composition, density, temperature, and drift velocity at the 600-km altitude in the low-latitude ionosphere; FORMOSAT-2 is to investigate lightning-induced transient luminous events, polar aurora, and upper atmospheric airglow, and FORMOSAT-3 probes ionospheric electron density profiles of the globe. In the near future, FORMOSAT-5 and FORMOSAT-7/COSMIC-2 will be employed for studying solar terrestrial sciences. These satellite missions play an important role on the recent development of solar terrestrial sciences in Taiwan.

X-ray Raman scattering study of MgSiO3 glass at high pressure: Implication for triclustered MgSiO3 melt in Earth's mantle

PubMed Central

Lee, Sung Keun; Lin, Jung-Fu; Cai, Yong Q.; Hiraoka, Nozomu; Eng, Peter J.; Okuchi, Takuo; Mao, Ho-kwang; Meng, Yue; Hu, Michael Y.; Chow, Paul; Shu, Jinfu; Li, Baosheng; Fukui, Hiroshi; Lee, Bum Han; Kim, Hyun Na; Yoo, Choong-Shik

2008-01-01

Silicate melts at the top of the transition zone and the core-mantle boundary have significant influences on the dynamics and properties of Earth's interior. MgSiO3-rich silicate melts were among the primary components of the magma ocean and thus played essential roles in the chemical differentiation of the early Earth. Diverse macroscopic properties of silicate melts in Earth's interior, such as density, viscosity, and crystal-melt partitioning, depend on their electronic and short-range local structures at high pressures and temperatures. Despite essential roles of silicate melts in many geophysical and geodynamic problems, little is known about their nature under the conditions of Earth's interior, including the densification mechanisms and the atomistic origins of the macroscopic properties at high pressures. Here, we have probed local electronic structures of MgSiO3 glass (as a precursor to Mg-silicate melts), using high-pressure x-ray Raman spectroscopy up to 39 GPa, in which high-pressure oxygen K-edge features suggest the formation of tricluster oxygens (oxygen coordinated with three Si frameworks; [3]O) between 12 and 20 GPa. Our results indicate that the densification in MgSiO3 melt is thus likely to be accompanied with the formation of triculster, in addition to a reduction in nonbridging oxygens. The pressure-induced increase in the fraction of oxygen triclusters >20 GPa would result in enhanced density, viscosity, and crystal-melt partitioning, and reduced element diffusivity in the MgSiO3 melt toward deeper part of the Earth's lower mantle. PMID:18535140

Quantitative electron density characterization of soft tissue substitute plastic materials using grating-based x-ray phase-contrast imaging

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

Sarapata, A.; Chabior, M.; Zanette, I.

2014-10-15

Many scientific research areas rely on accurate electron density characterization of various materials. For instance in X-ray optics and radiation therapy, there is a need for a fast and reliable technique to quantitatively characterize samples for electron density. We present how a precise measurement of electron density can be performed using an X-ray phase-contrast grating interferometer in a radiographic mode of a homogenous sample in a controlled geometry. A batch of various plastic materials was characterized quantitatively and compared with calculated results. We found that the measured electron densities closely match theoretical values. The technique yields comparable results between amore » monochromatic and a polychromatic X-ray source. Measured electron densities can be further used to design dedicated X-ray phase contrast phantoms and the additional information on small angle scattering should be taken into account in order to exclude unsuitable materials.« less

Ion Densities in the Nightside Ionosphere of Mars: Effects of Electron Impact Ionization

NASA Astrophysics Data System (ADS)

Girazian, Z.; Mahaffy, P.; Lillis, R. J.; Benna, M.; Elrod, M.; Fowler, C. M.; Mitchell, D. L.

2017-11-01

We use observations from the Mars Atmosphere and Volatile EvolutioN (MAVEN) mission to show how superthermal electron fluxes and crustal magnetic fields affect ion densities in the nightside ionosphere of Mars. We find that due to electron impact ionization, high electron fluxes significantly increase the CO2+, O+, and O2+ densities below 200 km but only modestly increase the NO+ density. High electron fluxes also produce distinct peaks in the CO2+, O+, and O2+ altitude profiles. We also find that superthermal electron fluxes are smaller near strong crustal magnetic fields. Consequently, nightside ion densities are also smaller near strong crustal fields because they decay without being replenished by electron impact ionization. Furthermore, the NO+/O2+ ratio is enhanced near strong crustal fields because, in the absence of electron impact ionization, O2+ is converted into NO+ and not replenished. Our results show that electron impact ionization is a significant source of CO2+, O+, and O2+ in the nightside ionosphere of Mars.

Dimension-controlled assemblies of anion-responsive π-electronic systems bearing aryl substituents with fan-shaped geometries.

PubMed

Lakshmi, Vellanki; Haketa, Yohei; Yamakado, Ryohei; Yasuda, Nobuhiro; Maeda, Hiromitsu

2017-03-30

Pyrrole-4-aryl-substituted dipyrrolyldiketone BF 2 complexes as anion-responsive π-electronic molecules were synthesized via a 3,5-dimethylpyrrole precursor. Mesophases were observed in derivatives that possessed long alkyl chains on the pyrrole-4-aryl groups along with their anion complexes as ion-pairing assemblies in combination with appropriate cations.

Formation mechanisms of boron oxide films fabricated by large-area electron beam-induced deposition of trimethyl borate [Formation Mechanisms of Boron Oxide Fillms Fabricated by Large Area Electron Beam-Induced Deposition of Trimethyl Borate

DOE PAGES

Martin, Aiden A.; Depond, Philip J.

2018-04-24

Boron-containing materials are increasingly drawing interest for the use in electronics, optics, laser targets, neutron absorbers, and high-temperature and chemically resistant ceramics. In this article, the first investigation into the deposition of boron-based material via electron beam-induced deposition (EBID) is reported. Thin films were deposited using a novel, large-area EBID system that is shown to deposit material at rates comparable to conventional techniques such as laser-induced chemical vapor deposition. The deposition rate and stoichiometry of boron oxide fabricated by EBID using trimethyl borate (TMB) as precursor is found to be critically dependent on the substrate temperature. By comparing the depositionmore » mechanisms of TMB to the conventional, alkoxide-based precursor tetraethyl orthosilicate it is revealed that ligand chemistry does not precisely predict the pathways leading to deposition of material via EBID. Lastly, the results demonstrate the first boron-containing material deposited by the EBID process and the potential for EBID as a scalable fabrication technique that could have a transformative effect on the athermal deposition of materials.« less

Mechanics of hydrogenated amorphous carbon deposits from electron-beam-induced deposition of a paraffin precursor

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

Ding, W.; Dikin, D.A.; Chen, X.

2005-07-01

Many experiments on the mechanics of nanostructures require the creation of rigid clamps at specific locations. In this work, electron-beam-induced deposition (EBID) has been used to deposit carbon films that are similar to those that have recently been used for clamping nanostructures. The film deposition rate was accelerated by placing a paraffin source of hydrocarbon near the area where the EBID deposits were made. High-resolution transmission electron microscopy, electron-energy-loss spectroscopy, Raman spectroscopy, secondary-ion-mass spectrometry, and nanoindentation were used to characterize the chemical composition and the mechanics of the carbonaceous deposits. The typical EBID deposit was found to be hydrogenated amorphousmore » carbon (a-C:H) having more sp{sup 2}- than sp{sup 3}-bonded carbon. Nanoindentation tests revealed a hardness of {approx}4 GPa and an elastic modulus of 30-60 GPa, depending on the accelerating voltage. This reflects a relatively soft film, which is built out of precursor molecular ions impacting the growing surface layer with low energies. The use of such deposits as clamps for tensile tests of poly(acrylonitrile)-based carbon nanofibers loaded between opposing atomic force microscope cantilevers is presented as an example application.« less

Formation mechanisms of boron oxide films fabricated by large-area electron beam-induced deposition of trimethyl borate [Formation Mechanisms of Boron Oxide Fillms Fabricated by Large Area Electron Beam-Induced Deposition of Trimethyl Borate

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

Martin, Aiden A.; Depond, Philip J.

Boron-containing materials are increasingly drawing interest for the use in electronics, optics, laser targets, neutron absorbers, and high-temperature and chemically resistant ceramics. In this article, the first investigation into the deposition of boron-based material via electron beam-induced deposition (EBID) is reported. Thin films were deposited using a novel, large-area EBID system that is shown to deposit material at rates comparable to conventional techniques such as laser-induced chemical vapor deposition. The deposition rate and stoichiometry of boron oxide fabricated by EBID using trimethyl borate (TMB) as precursor is found to be critically dependent on the substrate temperature. By comparing the depositionmore » mechanisms of TMB to the conventional, alkoxide-based precursor tetraethyl orthosilicate it is revealed that ligand chemistry does not precisely predict the pathways leading to deposition of material via EBID. Lastly, the results demonstrate the first boron-containing material deposited by the EBID process and the potential for EBID as a scalable fabrication technique that could have a transformative effect on the athermal deposition of materials.« less

Deterministic Nanopatterning of Diamond Using Electron Beams.

PubMed

Bishop, James; Fronzi, Marco; Elbadawi, Christopher; Nikam, Vikram; Pritchard, Joshua; Fröch, Johannes E; Duong, Ngoc My Hanh; Ford, Michael J; Aharonovich, Igor; Lobo, Charlene J; Toth, Milos

2018-03-27

Diamond is an ideal material for a broad range of current and emerging applications in tribology, quantum photonics, high-power electronics, and sensing. However, top-down processing is very challenging due to its extreme chemical and physical properties. Gas-mediated electron beam-induced etching (EBIE) has recently emerged as a minimally invasive, facile means to dry etch and pattern diamond at the nanoscale using oxidizing precursor gases such as O 2 and H 2 O. Here we explain the roles of oxygen and hydrogen in the etch process and show that oxygen gives rise to rapid, isotropic etching, while the addition of hydrogen gives rise to anisotropic etching and the formation of topographic surface patterns. We identify the etch reaction pathways and show that the anisotropy is caused by preferential passivation of specific crystal planes. The anisotropy can be controlled by the partial pressure of hydrogen and by using a remote RF plasma source to radicalize the precursor gas. It can be used to manipulate the geometries of topographic surface patterns as well as nano- and microstructures fabricated by EBIE. Our findings constitute a comprehensive explanation of the anisotropic etch process and advance present understanding of electron-surface interactions.

Temporal-spatial measurement of electron relaxation time in femtosecond laser induced plasma using two-color pump-probe imaging technique

NASA Astrophysics Data System (ADS)

Pan, Changji; Jiang, Lan; Wang, Qingsong; Sun, Jingya; Wang, Guoyan; Lu, Yongfeng

2018-05-01

The femtosecond (fs) laser is a powerful tool to study ultrafast plasma dynamics, especially electron relaxation in strong ionization of dielectrics. Herein, temporal-spatial evolution of femtosecond laser induced plasma in fused silica was investigated using a two-color pump-probe technique (i.e., 400 nm and 800 nm, respectively). We demonstrated that when ionized electron density is lower than the critical density, free electron relaxation time is inversely proportional to electron density, which can be explained by the electron-ion scattering regime. In addition, electron density evolution within plasma was analyzed in an early stage (first 800 fs) of the laser-material interaction.

Ionospheric E-region electron density and neutral atmosphere variations

NASA Technical Reports Server (NTRS)

Stick, T. L.

1976-01-01

Electron density deviations from a basic variation with the solar zenith angle were investigated. A model study was conducted in which the effects of changes in neutral and relative densities of atomic and molecular oxygen on calculated electron densities were compared with incoherent scatter measurements in the height range 100-117 km at Arecibo, Puerto Rico. The feasibility of determining tides in the neutral atmosphere from electron density profiles was studied. It was determined that variations in phase between the density and temperature variation and the comparable magnitudes of their components make it appear improbable that the useful information on tidal modes can be obtained in this way.

Self-focusing and defocusing of Gaussian laser beams in collisional inhomogeneous plasmas with linear density and temperature ramps

NASA Astrophysics Data System (ADS)

Hashemzadeh, M.

2018-01-01

Self-focusing and defocusing of Gaussian laser beams in collisional inhomogeneous plasmas are investigated in the presence of various laser intensities and linear density and temperature ramps. Considering the ponderomotive force and using the momentum transfer and energy equations, the nonlinear electron density is derived. Taking into account the paraxial approximation and nonlinear electron density, a nonlinear differential equation, governing the focusing and defocusing of the laser beam, is obtained. Results show that in the absence of ramps the laser beam is focused between a minimum and a maximum value of laser intensity. For a certain value of laser intensity and initial electron density, the self-focusing process occurs in a temperature range which reaches its maximum at turning point temperature. However, the laser beam is converged in a narrow range for various amounts of initial electron density. It is indicated that the σ2 parameter and its sign can affect the self-focusing process for different values of laser intensity, initial temperature, and initial density. Finally, it is found that although the electron density ramp-down diverges the laser beam, electron density ramp-up improves the self-focusing process.

Highly Efficient and Stable MAPbI3 Perovskite Solar Cell Induced by Regulated Nucleation and Ostwald Recrystallization

PubMed Central

Huang, Zhen; Wang, Song; Zhang, Tianjin

2018-01-01

Perovskite solar cells have attracted great attention in recent years, due to their high conversion efficiency and solution-processable fabrication. However, most of the solar cells with high efficiency in the literature are prepared employing TiO2 as electron transport material, which needs sintering at a temperature higher than 450 °C, and is not applicable to flexible device and low-cost fabrication. Herein, the MAPbI3 perovskite solar cells are fabricated at a low temperature of 150 °C with SnO2 as the electron transport layer. By dropping the antisolvent of ethyl acetate onto the perovskite precursor films during the spin coating process, compact MAPbI3 films without pinholes are obtained. The addition of ethyl acetate is found to play an important role in regulating the nucleation, which subsequently improves the compactness of the film. The quality of MAPbI3 films are further improved significantly through Ostwald recrystallization by optimizing the thermal treatment. The crystallinity is enhanced, the grain size is enlarged, and the defect density is reduced. Accordingly, the prepared MAPbI3 perovskite solar cell exhibits a record-high conversion efficiency, outstanding reproducibility, and stability, owing to the reduced electron recombination. The average and best efficiency reaches 19.2% and 20.3%, respectively. The device without encapsulation maintains 94% of the original efficiency after storage in ambient air for 600 h. PMID:29751646

Improved oxidation resistance of organic/inorganic composite atomic layer deposition coated cellulose nanocrystal aerogels

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

Smith, Sean W.; Matthews, David J.; Conley, John F., E-mail: jconley@eecs.oregonstate.edu

2014-07-01

Cellulose nanocrystal (CNC) aerogels are coated with thin conformal layers of Al{sub 2}O{sub 3} using atomic layer deposition to form hybrid organic/inorganic nanocomposites. Electron probe microanalysis and scanning electron microscopy analysis indicated the Al{sub 2}O{sub 3} penetrated more than 1500 μm into the aerogel for extended precursor pulse and exposure/purge times. The measured profile of coated fiber radius versus depth from the aerogel surface agrees well with simulations of precursor penetration depth in modeled aerogel structures. Thermogravimetric analysis shows that Al{sub 2}O{sub 3} coated CNC aerogel nanocomposites do not show significant thermal degradation below 295 °C as compared with 175 °C for uncoatedmore » CNC aerogels, an improvement of over 100 °C.« less

Spray pyrolytic deposition of α-MoO3 film and its use in dye-sensitized solar cell

NASA Astrophysics Data System (ADS)

Tamboli, Parvin S.; Jagtap, Chaitali V.; Kadam, Vishal S.; Ingle, Ravi V.; Vhatkar, Rajiv S.; Mahajan, Smita S.; Pathan, Habib M.

2018-04-01

Thermal decomposition of ammonium para molybdate tetrahydrate precursor has been studied to determine degradation temperatures in air atmosphere. Current work explores the synthesis of α-MoO3 films by an economical spray pyrolysis technique using ammonium para molybdate tetrahydrate precursor in the presence of compressed air. A variety of characterization techniques such as X-ray diffraction, scanning electron microscopy, transmission electron microscopy, UV-visible spectroscopy, Fourier transform infrared, and Raman spectroscopy were carried out, and the studies have confirmed that orthorhombic phase formation of MoO3 takes place with spongy mesh-type structure. The study of electro-catalytic activity of α-MoO3 in titania-based dye-sensitized solar cell is also carried out by cyclic voltammetry, electrochemical impedance spectroscopy, and Tafel curves to evaluate its performance as a counter electrode.

Nucleophilic fluorination of aromatic compounds

DOEpatents

Satyamurthy, Nagichettiar; Barrio, Jorge R

2014-03-18

Iodylbenzene derivatives substituted with electron donating as well as electron withdrawing groups on the aromatic ring are used as precursors in aromatic nucleophilic substitution reactions. The iodyl group (IO.sub.2) is regiospecifically substituted by nucleophilic fluoride to provide the corresponding fluoroaryl derivatives. No-carrier-added [F-18]fluoride ion derived from anhydrous [F-18](F/Kryptofix, [F-18]CsF or a quaternary ammonium fluoride (e.g., Me.sub.4NF, Et.sub.4NF, n-Bu.sub.4NF, (PhCH.sub.2).sub.4NF) exclusively substitutes the iodyl moiety in these derivatives and provides high specific activity F-18 labeled fluoroaryl analogs. Iodyl derivatives of a benzothiazole analog and 6-iodyl-L-dopa derivatives have been synthesized as precursors and have been used in the preparation of no-carrier-added [F-18]fluorobenzothiazole as well as 6-[F-18]fluoro-L-dopa.