Solution-Processed Cu2ZnSn(S,Se) 4 Thin-Film Solar Cells Using Elemental Cu, Zn, Sn, S, and Se Powders as Source.

PubMed

Guo, Jing; Pei, Yingli; Zhou, Zhengji; Zhou, Wenhui; Kou, Dongxing; Wu, Sixin

2015-12-01

Solution-processed approach for the deposition of Cu2ZnSn (S,Se)4 (CZTSSe) absorbing layer offers a route for fabricating thin film solar cell that is appealing because of simplified and low-cost manufacturing, large-area coverage, and better compatibility with flexible substrates. In this work, we present a simple solution-based approach for simultaneously dissolving the low-cost elemental Cu, Zn, Sn, S, and Se powder, forming a homogeneous CZTSSe precursor solution in a short time. Dense and compact kesterite CZTSSe thin film with high crystallinity and uniform composition was obtained by selenizing the low-temperature annealed spin-coated precursor film. Standard CZTSSe thin film solar cell based on the selenized CZTSSe thin film was fabricated and an efficiency of 6.4 % was achieved.

Preparation & characterization of high purity Cu2 ZnSn(SxSe1-x)4 nanoparticles

NASA Astrophysics Data System (ADS)

Negash, Bethlehem G.

Research in thin film solar cells applies novel techniques to synthesize cost effective and highly efficient absorber materials in order to generate electricity directly from solar energy. Of these materials, copper zinc tin sulfoselenide (Cu2ZnSn(SxSe1-x) 4) nanoparticles have shown great promise in solar cell applications due to optimal material properties as well as low cost & relative abundance of materials.1,2 Sulfoselenide nanoparticles have also a broader impact in other industries including electronics3, LED 4, and biomedical research5. Of the many routes of manufacturing these class of semiconductors, colloidal synthesis of Cu 2ZnSn(SxSe1-x)4 offers a scalable, low cost and high-throughput route for manufacturing high efficiency thin-film solar cells. Hydrazine processed Cu2ZnSn(SxSe1-x )4 devices have reached a record power conversion efficiency (PCE) of 12.6%, much higher than the 9.6% reported for physical vapor deposition (PVD) systems.6,7. Despite high efficiencies, wet synthesis of nanoparticles, however, is made more complicated in multi-element, quaternary and quinary systems such as copper zinc tin sulfoselenide (CZTSSe) and copper indium gallium diselenide (CIGSe). One major disadvantage in these systems is growth of the desired quaternary or quinary phase in competition with unwanted binary and ternary phases with low energy of formation.8,9 Moreover, various reaction parameters such as reaction time, temperature, and choice of ligand also affect, chemical as well as physical properties of resulting nanoparticles. Understanding of the formation mechanisms of the particles is necessary in order to address some of these challenges in wet synthesis of CZTSSe nanoparticles. In this study, we investigate synthesis conditions & reaction parameters which yield high purity Cu2ZnSn(SxSe1-x) 4 nanoparticles as well as attempt to understand the growth mechanism of these nanoparticles. This was achieved by manipulating anion precursor preparation routes as well order in which precursors are introduced into a reaction system. We report a new solution based sulfoselenide preparation route which has been used to synthesize high purity Cu2ZnSn(S xSe1-x)4 nanoparticles. Uniform phase Cu 2ZnSn(SxSe1-x)4 nanoparticles were successfully synthesized over a wide range of varying chalcogen ratios. It was found that anion precursor solution plays a key role in determining the morphology & phase purity of the final nanoparticles, as observed from X-ray Diffraction (XRD) and Raman spectroscopy. A uniform sulfoselenide solution is needed to produce high purity Cu2ZnSn(SxSe1-x )4 nanoparticles with narrow phase distribution. Moreover, the relative reactivity of each anion must be balanced in order to yield uniform phase nanoparticles. The findings of this study as well as the reported mixed chalcogen precursor preparation route can be applied in various industries, including photovoltaics to produce uniform phase, solution processed sulfoselenide nanoparticles.

A comparative study of the properties of five-layered Aurivillius oxides A2Bi4Ti5O18 (A = Ba, Pb, and Sr) synthesized by different wet chemical routes

NASA Astrophysics Data System (ADS)

Dubey, Shivangi; Subohi, Oroosa; Kurchania, Rajnish

2018-07-01

This paper reports the detailed study of the effect of different wet chemical synthesis routes (solution combustion, co-precipitation, and sol-gel route) on the microstructure, phase formation, dielectric, electrical, and ferroelectric properties of five-layered Aurivillius oxides: A2Bi4Ti5O18 (A = Ba, Pb, and Sr). Different synthesis parameters like the precursors used, synthesis temperature, and reaction time affects the morphology of the ceramics. Microstructure in turn influences the dielectric and ferroelectric properties. It was observed that the sol-gel-synthesized ceramics possess higher dielectric constant and remanent polarization, low dielectric loss due to lower conductivity in these samples as a result of higher density in these compounds as compared to those synthesized by other wet chemical synthesis routes such as solution combustion route and co-precipitation technique. The XRD data are used for phase analysis and surface morphology is studied using SEM images. Dielectric and electrical properties are investigated as a function of frequency and temperature.

Solution synthesis of germanium nanocrystals

DOEpatents

Gerung, Henry [Albuquerque, NM; Boyle, Timothy J [Kensington, MD; Bunge, Scott D [Cuyahoga Falls, OH

2009-09-22

A method for providing a route for the synthesis of a Ge(0) nanometer-sized material from. A Ge(II) precursor is dissolved in a ligand heated to a temperature, generally between approximately 100.degree. C. and 400.degree. C., sufficient to thermally reduce the Ge(II) to Ge(0), where the ligand is a compound that can bond to the surface of the germanium nanomaterials to subsequently prevent agglomeration of the nanomaterials. The ligand encapsulates the surface of the Ge(0) material to prevent agglomeration. The resulting solution is cooled for handling, with the cooling characteristics useful in controlling the size and size distribution of the Ge(0) materials. The characteristics of the Ge(II) precursor determine whether the Ge(0) materials that result will be nanocrystals or nanowires.

A general procedure to synthesize highly crystalline metal oxide and mixed oxidenanocrystals in aqueous medium and photocatalytic activity of metal/oxide nanohybrids

NASA Astrophysics Data System (ADS)

Nguyen, Thanh-Dinh; Dinh, Cao-Thang; Do, Trong-On

2011-04-01

A conventional and general route has been exploited to the high yield synthesis of many kinds of highly crystalline metal oxide and mixed oxidenanocrystals with different morphologies including belt, rod, truncated-octahedron, cubic, sphere, sheet via the hydrothermal reaction of inorganic precursors in aqueous solution in the presence of bifunctional 6-aminohexanoic acid (AHA) molecules as a capping agent. This method is a simple, reproducible and general route for the preparation of a variety of high-crystalline inorganic nanocrystals in scale-up. The shape of inorganic nanocrystals such as CoWO4, La2(MoO4)3 can be controlled by simply adjusting the synthesis conditions including pH solution and reaction temperature. Further, by tuning precursor monomer concentration, the mesocrystal hierarchical aggregated microspheres (e.g., MnWO4, La2(MoO4)3) can be achieved, due to the spontaneous assembly of individual AHA-capped nanoparticles. These obtained AHA-capped nanocrystals are excellent supports for the synthesis of a variety of hybrid metal/oxidenanocrystals in which noble metal particles are uniformly deposited on the surface of each individual nanosupport. The photocatalytic activity of Ag/TiO2 nanobelts as a typical hybrid photocatalyst sample for Methylene Blue degradation was also studied.A conventional and general route has been exploited to the high yield synthesis of many kinds of highly crystalline metal oxide and mixed oxidenanocrystals with different morphologies including belt, rod, truncated-octahedron, cubic, sphere, sheet via the hydrothermal reaction of inorganic precursors in aqueous solution in the presence of bifunctional 6-aminohexanoic acid (AHA) molecules as a capping agent. This method is a simple, reproducible and general route for the preparation of a variety of high-crystalline inorganic nanocrystals in scale-up. The shape of inorganic nanocrystals such as CoWO4, La2(MoO4)3 can be controlled by simply adjusting the synthesis conditions including pH solution and reaction temperature. Further, by tuning precursor monomer concentration, the mesocrystal hierarchical aggregated microspheres (e.g., MnWO4, La2(MoO4)3) can be achieved, due to the spontaneous assembly of individual AHA-capped nanoparticles. These obtained AHA-capped nanocrystals are excellent supports for the synthesis of a variety of hybrid metal/oxidenanocrystals in which noble metal particles are uniformly deposited on the surface of each individual nanosupport. The photocatalytic activity of Ag/TiO2 nanobelts as a typical hybrid photocatalyst sample for Methylene Blue degradation was also studied. Electronic supplementary information (ESI) available: Additional TEM, XRD, XPS, FTIR, UV-vis and photoluminescence results of the nanocrystals. See DOI: 10.1039/c1nr10109a

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.

Remarkable lowering in the synthesis temperature of LiMn2O4via citrate solution-gel synthesis facilitated by ethanol.

PubMed

Maino, G; Carleer, R; Marchal, W; Bonneux, G; Hardy, A; Van Bael, M K

2017-11-07

LiMn 2 O 4 (LMO) is interesting from the viewpoint of its energy storage applications as it is a cathode in lithium ion batteries (LIB), which contains no rare, toxic or expansive elements, while it provides a high theoretical capacity (148 mA h g -1 ) at a reasonable voltage (4 V region) and a higher thermal stability compared to cobalt based cathodes and has a good rechargeability and cycling stability due to its spinel structure. Low temperature synthesis routes for cathode materials are currently gaining attention, in order to decrease the ecological footprint of the final LIB. Here, the crystallization temperature of LMO by a citrate based solution-gel synthesis was significantly lowered, to as low as 250 °C by the addition of ethanol to the precursor. The role of ethanol in this synthesis process was explored. It was found to lead to a considerable increase in the oxidation rate of the redox couple Mn 2+ /Mn 3+ , a lowering of the precursor decomposition temperature by 200 °C, besides a drastic decrease in the crystallization temperature (reaching 250 °C). Moreover, the main cause was identified to be an esterification reaction of ethanol with the carboxylic acid in the precursor complexes, taking place before the oxide formation. The insights obtained strengthen the knowledge regarding citrato-Mn 2+ /Mn 3+ complexes present in aqueous solution-gel synthesis routes and are relevant for the preparation of various manganese containing oxides. Moreover, the precursor developed opens up a new possibility for the low temperature synthesis of LMO powders and thin films for application in LIB. In the case of thin film batteries, the low temperature processing provides compatibility with other materials in the thin film battery stack, avoiding undesired oxidations or interfacial reactions.

Effect of Pre-Annealing on Thermal and Optical Properties of ZnO and Al-ZnO Thin Films

NASA Astrophysics Data System (ADS)

Saravanan, P.; Gnanavelbabu, A.; Pandiaraj, P.

Zinc oxide (ZnO) nanoparticles were synthesized by a simple solution route method using zinc acetate as the precursor and ethanol as the solvent. At a temperature of 60∘C, a clear homogenous solution is heated to 100∘C for ethanol evaporation. Then the obtained precursor powder is annealed at 600∘C for the formation of ZnO nanocrystalline structure. Doped ZnO particle is also prepared by using aluminum nitrate nonahydrate to produce aluminum (Al)-doped nanoparticles using the same solution route method followed by annealing. Thin film fabrication is done by air evaporation method using the polymer polyvinyl alcohol (PVA). To analyze the optical and thermal properties for undoped and doped ZnO nanocrystalline thin film by precursor annealing, characterizations such as UV, FTIR, AFM, TGA/DTA, XRD, EDAX and Photoluminescence (PL) were also taken. It was evident that precursor annealing had great influence on thermal and optical properties of thin films while ZnO and AZO film showed low crystallinity and intensity than in the powder form. TGA/DTA suggests pre-annealing effect improves the thermal stability, which ensures that Al ZnO nanoparticle can withstand at high temperature too which is the crucial advantage in the semiconductor devices. UV spectroscopy confirmed the presence of ZnO nanoparticles in the thin film by an absorbance peak observed at 359nm with an energy bandgap of 3.4eV. A peak obtained at 301nm with an energy bandgap of 4.12eV shows a blue shift due to the presence of Al-doped ZnO nanoparticles. Both ZnO and AZO bandgap increased due to precursor annealing. In this research, PL spectrum is also studied in order to determine the optical property of the nanoparticle embedded thin film. From PL spectrum, it is observed that the intensity of the doped ZnO is much more enhanced as the dopant concentration is increased to 1wt.% and 2wt.% of Al in ZnO.

Laser-processing of VO2 thin films synthesized by polymer-assisted-deposition

NASA Astrophysics Data System (ADS)

Breckenfeld, Eric; Kim, Heungsoo; Gorzkowski, Edward P.; Sutto, Thomas E.; Piqué, Alberto

2017-03-01

We investigate a novel route for synthesis and laser-sintering of VO2 thin films via solution-based polymer-assisted-deposition (PAD). By replacing the traditional solvent for PAD (water) with propylene glycol, we are able to control the viscosity and improve the environmental stability of the precursor. The solution stability and ability to control the viscosity makes for an ideal solution to pattern simple or complex shapes via direct-write methods. We demonstrate the potential of our precursor for printing applications by combining PAD with laser induced forward transfer (LIFT). We also demonstrate large-area film synthesis on 4 in. diameter glass wafers. By varying the annealing temperature, we identify the optimal synthesis conditions, obtaining optical transmittance changes of 60% at a 2500 nm wavelength and a two-order-of-magnitude semiconductor-to-metal transition. We go on to demonstrate two routes for improved semiconductor-to-metal characteristics. The first method uses a multi-coating process to produce denser films with large particles. The second method uses a pulsed-UV-laser sintering step in films annealed at low temperatures (<450° C) to promote particle growth and improve the semiconductor-to-metal transition. By comparing the hysteresis width and semiconductor-to-metal transition magnitude in these samples, we demonstrate that both methods yield high quality VO2 with a three-order-of-magnitude transition.

Highly stable precursor solution containing ZnO nanoparticles for the preparation of ZnO thin film transistors.

PubMed

Huang, Heh-Chang; Hsieh, Tsung-Eong

2010-07-23

ZnO particles with an average size of about 5 nm were prepared via a sol-gel chemical route and the silane coupling agent, (3-glycidyloxypropyl)-trimethoxysilane (GPTS), was adopted to enhance the dispersion of the ZnO nanoparticles in ethyl glycol (EG) solution. A ZnO surface potential as high as 66 mV was observed and a sedimentation test showed that the ZnO precursor solution remains transparent for six months of storage, elucidating the success of surface modification on ZnO nanoparticles. The ZnO thin films were then prepared by spin coating the precursor solution on a Si wafer and annealing treatments at temperatures up to 500 degrees C were performed for subsequent preparation of ZnO thin film transistors (TFTs). Microstructure characterization revealed that the coalescence of ZnO nanoparticles occurs at temperatures as low as 200 degrees C to result in a highly uniform, nearly pore-free layer. However, annealing at higher temperatures was required to remove organic residues in the ZnO layer for satisfactory device performance. The 500 degrees C-annealed ZnO TFT sample exhibited the best electrical properties with on/off ratio = 10(5), threshold voltage = 17.1 V and mobility (micro) = 0.104 cm(2) V(-1) s(-1).

Solution based zinc tin oxide TFTs: the dual role of the organic solvent

NASA Astrophysics Data System (ADS)

Salgueiro, Daniela; Kiazadeh, Asal; Branquinho, Rita; Santos, Lídia; Barquinha, Pedro; Martins, Rodrigo; Fortunato, Elvira

2017-02-01

Chemical solution deposition is a low cost, scalable and high performance technique to obtain metal oxide thin films. Recently, solution combustion synthesis has been introduced as a chemical route to reduce the processing temperature. This synthesis method takes advantage of the chemistry of the precursors as a source of energy for localized heating. According to the combustion chemistry some organic solvents can have a dual role in the reaction, acting both as solvent and fuel. In this work, we studied the role of 2-methoxyethanol in solution based synthesis of ZTO thin films and its influence on the performance of ZTO TFTs. The thermal behaviour of ZTO precursor solutions confirmed that 2-methoxyethanol acts simultaneously as a solvent and fuel, replacing the fuel function of urea. The electrical characterization of the solution based ZTO TFTs showed a slightly better performance and lower variability under positive gate bias stress when urea was not used as fuel, confirming that the excess fuel contributes negatively to the device operation and stability. Solution based ZTO TFTs demonstrated a low hysteresis (ΔV  =  -0.3 V) and a saturation mobility of 4-5 cm2 V-1 s-1.

Synthesis of nanocrystalline TiO 2 in toluene by a solvothermal route

NASA Astrophysics Data System (ADS)

Kim, Chung-Sik; Moon, Byung Kee; Park, Jong-Ho; Tae Chung, Su; Son, Se-Mo

2003-07-01

A solvothermal synthetic method to TiO 2 nanoparticles has been investigated in toluene solutions with titanium isopropoxide (TIP) as precursor. Weight ratios of precursor to solvent prepared in the mixture are 5/100, 10/100, 20/100, 30/100 and 40/100. At the weight ratio of 10/100, 20/100 and 30/100, TiO 2 nanocrystalline particles were obtained after synthesis at 250°C for 3 h in an autoclave. X-ray diffraction and tranmission electron microscopy shows that the product has uniform anatase structure with average particle size below 20 nm. As the composition of TIP in the solution increases, the particle size of TiO 2 powder tends to increase. At 5/100 and 40/100, however, pale yellow colloidal solution is obtained after synthesis and crystalline phase of TiO 2 is not produced. The specific surface area of the TiO 2 nanocrystalline powder was also investigated using BET surface area analyzer.

Synthesis of Sol-Gel Precursors for Ceramics from Lunar and Martian Soil Simulars

NASA Technical Reports Server (NTRS)

Sibille, L.; Gavira-Gallardo, J. A.; Hourlier-Bahloul, D.

2004-01-01

Recent NASA mission plans for the human exploration of our Solar System has set new priorities for research and development of technologies necessary to enable a long-term human presence on the Moon and Mars. The recovery and processing of metals and oxides from mineral sources on other planets is under study to enable use of ceramics, glasses and metals by explorer outposts. We report initial results on the production of sol-gel precursors for ceramic products using mineral resources available in martian or lunar soil. The presence of SO2, TiO2, and Al2O3 in both martian (44 wt.% SiO2, 1 wt.% TiO2, 7 wt.% Al2O3) and lunar (48 wt.% SiO2, 1.5 wt.% TiO2, 16 wt.% Al2O3) soils and the recent developments in chemical processes to solubilize silicates using organic reagents and relatively little energy indicate that such an endeavor is possible. In order to eliminate the risks involved in the use of hydrofluoric acid to dissolve silicates, two distinct chemical routes are investigated to obtain soluble silicon oxide precursors from lunar and martian soil simulars. Clear solutions of sol-gel precursors have been obtained by dissolution of silica from lunar soil similar JSC-1 in basic ethylene glycol (C2H4(OH)2) solutions to form silicon glycolates. Similarly, sol-gel solutions produced from martian soil simulars reveal higher contents of iron oxides. Characterization of the precursor molecules and efforts to further concentrate and hydrolyze the products to obtain gel materials will be presented for evaluation as ceramic precursors.

Synthesis of Sol-Gel Precursors for Ceramics from Lunar and Martian Soil Simulars

NASA Technical Reports Server (NTRS)

Sibille, L.; Gavira-Gallardo, J. A.; Hourlier-Bahloul, D.

2003-01-01

Recent NASA mission plans for the human exploration of our Solar System has set new priorities for research and development of technologies necessary to enable a long-term human presence on the Moon and Mars. The recovery and processing of metals and oxides from mineral sources on other planets is under study to enable use of ceramics, glasses and metals by explorer outposts. We report initial results on the production of sol-gel precursors for ceramic products using mineral resources available in martian or lunar soil. The presence of SiO2, TiO2, and Al2O3 in both martian (44 wt.% SiO2, 1 wt.% TiO2,7 wt.% Al2O3) and lunar (48 wt.% SiO2, 1.5 wt.% TiO2, 16 wt.% Al2O3) soils and the recent developments in chemical processes to solubilize silicates using organic reagents and relatively little energy indicate that such an endeavor is possible. In order to eliminate the risks involved in the use of hydrofluoric acid to dissolve silicates, two distinct chemical routes are investigated to obtain soluble silicon oxide precursors from lunar and martian soil simulars. Clear solutions of sol-gel precursors have been obtained by dissolution of silica from lunar soil simular in basic ethylene glycol (C2H4(OH)2) solutions to form silicon glycolates. Similarly, sol-gel solutions produced from martian soil simulars reveal higher contents of iron oxides. The elemental composition and structure of the precursor molecules were characterized. Further concentration and hydrolysis of the products was performed to obtain gel materials for evaluation as ceramic precursors.

Effect of Zn(NO3)2 concentration in hydrothermal-electrochemical deposition on morphology and photoelectrochemical properties of ZnO nanorods

NASA Astrophysics Data System (ADS)

Yilmaz, Ceren; Unal, Ugur

2016-04-01

Zn(NO3)2 concentration had been reported to be significantly influential on electrodeposition of ZnO structures. In this work, this issue is revisited using hydrothermal-electrochemical deposition (HED). Seedless, cathodic electrochemical deposition of ZnO films is carried out on ITO electrode at 130 °C in a closed glass reactor with varying Zn(NO3)2 concentration. Regardless of the concentration of Zn2+ precursor (0.001-0.1 M) in the deposition solution, vertically aligned 1-D ZnO nanorods are obtained as opposed to electrodepositions at lower temperatures (70-80 °C). We also report the effects of high bath temperature and pressure on the photoelectrochemical properties of the ZnO films. Manipulation of precursor concentration in the deposition solution allows adjustment of the aspect ratio of the nanorods and the degree of texturation along the c-axis; hence photoinduced current density. HED is shown to provide a single step synthesis route to prepare ZnO rods with desired aspect ratio specific for the desired application just by controlling the precursor concentration.

Effect of precursor solutions stirring on deep level defects concentration and spatial distribution in low temperature aqueous chemical synthesis of zinc oxide nanorods

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

Alnoor, Hatim, E-mail: hatim.alnoor@liu.se; Chey, Chan Oeurn; Pozina, Galia

Hexagonal c-axis oriented zinc oxide (ZnO) nanorods (NRs) with 120-300 nm diameters are synthesized via the low temperature aqueous chemical route at 80 °C on silver-coated glass substrates. The influence of varying the precursor solutions stirring durations on the concentration and spatial distributions of deep level defects in ZnO NRs is investigated. Room temperature micro-photoluminesnce (μ-PL) spectra were collected for all samples. Cathodoluminescence (CL) spectra of the as-synthesized NRs reveal a significant change in the intensity ratio of the near band edge emission (NBE) to the deep-level emission (DLE) peaks with increasing stirring durations. This is attributed to the variation inmore » the concentration of the oxygen-deficiency with increasing stirring durations as suggested from the X-ray photoelectron spectroscopy analysis. Spatially resolved CL spectra taken along individual NRs revealed that stirring the precursor solutions for relatively short duration (1-3 h), which likely induced high super saturation under thermodynamic equilibrium during the synthesis process, is observed to favor the formation of point defects moving towards the tip of the NRs. In contrary, stirring for longer duration (5-15 h) will induce low super saturation favoring the formation of point defects located at the bottom of the NRs. These findings demonstrate that it is possible to control the concentration and spatial distribution of deep level defects in ZnO NRs by varying the stirring durations of the precursor solutions.« less

Facile Routes To Improve Performance of Solution-Processed Amorphous Metal Oxide Thin Film Transistors by Water Vapor Annealing.

PubMed

Park, Won-Tae; Son, Inyoung; Park, Hyun-Woo; Chung, Kwun-Bum; Xu, Yong; Lee, Taegweon; Noh, Yong-Young

2015-06-24

Here, we report on a simple and high-rate oxidization method for producing solution-based compound mixtures of indium zinc oxide (IZO) and indium gallium zinc oxide (IGZO) metal-oxide semiconductors (MOS) for thin-film transistor (TFT) applications. One of the issues for solution-based MOS fabrication is how to sufficiently oxidize the precursor in order to achieve high performance. As the oxidation rate of solution processing is lower than vacuum-based deposition such as sputtering, devices using solution-processed MOS exhibit relatively poorer performance. Therefore, we propose a method to prepare the metal-oxide precursor upon exposure to saturated water vapor in a closed volume for increasing the oxidization efficiency without requiring additional oxidizing agent. We found that the hydroxide rate of the MOS film exposed to water vapor is lower than when unexposed (≤18%). Hence, we successfully fabricated oxide TFTs with high electron mobility (27.9 cm(2)/V·s) and established a rapid process (annealing at 400 °C for 5 min) that is much shorter than the conventional as-deposited long-duration annealing (at 400 °C for 1 h) whose corresponding mobility is even lower (19.2 cm(2)/V·s).

Chemical routes to nanocrystalline and thin-film III-VI and I-III-VI semiconductors

NASA Astrophysics Data System (ADS)

Hollingsworth, Jennifer Ann

1999-11-01

The work encompasses: (1) catalyzed low-temperature, solution-based routes to nano- and microcrystalline III-VI semiconductor powders and (2) spray chemical vapor deposition (spray CVD) of I-III-VI semiconductor thin films. Prior to this work, few, if any, examples existed of chemical catalysis applied to the synthesis of nonmolecular, covalent solids. New crystallization strategies employing catalysts were developed for the regioselective syntheses of orthorhombic InS (beta-InS), the thermodynamic phase, and rhombohedral InS (R-InS), a new, metastable structural isomer. Growth of beta-InS was facilitated by a solvent-suspended, molten-metal flux in a process similar to the SolutionLiquid-Solid (SLS) growth of InP and GaAs fibers and single-crystal whiskers. In contrast, metastable R-InS, having a pseudo-graphitic layered structure, was prepared selectively when the molecular catalyst, benzenethiol, was present in solution and the inorganic "catalyst" (metal flux) was not present. In the absence of any crystal-growth facilitator, metal flux or benzenethiol, amorphous product was obtained under the mild reaction conditions employed (T ≤ 203°C). The inorganic and organic catalysts permitted the regio-selective syntheses of InS and were also successfully applied to the growth of network and layered InxSey compounds, respectively, as well as nanocrystalline In2S3. Extensive microstructural characterization demonstrated that the layered compounds grew as fullerene-like nanostructures and large, colloidal single crystals. Films of the I-III-VI compounds, CuInS2, CuGaS2, and Cu(In,Ga)S 2, were deposited by spray CVD using the known single-source metalorganic precursor, (Ph3P)2CuIn(SEt)4, a new precursor, (Ph3P)2CuGa(SEt)3, and a mixture of the two precursors, respectively. The CulnS2 films exhibited a variety of microstructures from dense and faceted or platelet-like to porous and dendritic. Crystallographic orientations ranged from strongly [112] to strongly [220] oriented. Microstructure, orientation, and growth kinetics were controlled by changing processing parameters: carrier-gas flow rate, substrate temperature, and precursor-solution concentration. Low resistivities (<50 O cm) were associated with [220]-oriented films. All CuInS2 films were approximately stoichiometric and had the desired bandgap (Eg ≅ 1.4 eV) for application as the absorber layer in thin-film photovoltaic devices.

Effect of precursor on epitaxially grown of ZnO thin film on p-GaN/sapphire (0 0 0 1) substrate by hydrothermal technique

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

Sahoo, Trilochan; Ju, Jin-Woo; Kannan, V.

2008-03-04

Single crystalline ZnO thin film on p-GaN/sapphire (0 0 0 1) substrate, using two different precursors by hydrothermal route at a temperature of 90 deg. C were successfully grown. The effect of starting precursor on crystalline nature, surface morphology and optical emission of the films were studied. ZnO thin films were grown in aqueous solution of zinc acetate and zinc nitrate. X-ray diffraction analysis revealed that all the thin films were single crystalline in nature and exhibited wurtzite symmetry and c-axis orientation. The thin films obtained with zinc nitrate had a more pitted rough surface morphology compared to the filmmore » grown in zinc acetate. However the thickness of the films remained unaffected by the nature of the starting precursor. Sharp luminescence peaks were observed from the thin films almost at identical energies but deep level emission was slightly prominent for the thin film grown in zinc nitrate.« less

Strategies to indium nitride and gallium nitride nanoparticles: Low-temperature, solution-phase and precursor routes

NASA Astrophysics Data System (ADS)

Dingman, Sean Douglas

I present new strategies to low-temperature solution-phase synthesis of indium and gallium nitride (InN and GaN) ceramic materials. The strategies include: direct conversion of precursor molecules to InN by pyrolysis, solution-phase synthesis of nanostructured InN fibers via molecular precursors and co-reactants, and synthesis of powders through reactions derived from molten-salt chemistry. Indium nitride powders are prepared by pyrolysis of the precursors R 2InN3 (R = t-Bu (1), i-Amyl(2), Et(3), i-Pr( 4)). The precursors are synthesized via azide-alkoxide exchange of R2InOMe with Me3SiN3. The precursors are coordination polymers containing five-coordinate indium centers. Pyrolysis of 1 and 2 under N2 at 400°C yields powders consisting primarily of InN with average crystal sizes of 15--35 nm. 1 yields nanocrystalline InN with average particle sizes of 7 nm at 250°C. 3 and 4 yield primarily In metal from pyrolysis. Refluxing 1 in diisopropylbenzene (203°C) in the presence of primary amines yields InN nanofibers 10--100 nm in length. InN nanofibers of up to 1 mum can be synthesized by treating 1 with 1,1-dimethylhydrazine (DMHy) The DMHy appears to control the fiber length by acting as a secondary source of active nitrogen in order to sustain fiber growth. The resulting fibers are attached to droplets of indium metal implying a solution-liquid-solid growth mechanism. Precursor 4 yields crystalline InN whiskers when reacted with DMHy. Reactions of 4 with reducing agents such as HSnBu3, yield InN nanoparticles with an average crystallite size of 16 nm. Gallium precursors R2GaN3 (R = t-Bu( 5), Me3SiCH2(6) and i-Pr( 7)), synthesized by azide-alkoxide exchange, are found to be inert toward solution decomposition and do not yield GaN. These compounds are molecular dimers and trimers unlike the indium analogs. Compound 6 displays a monomer-dimer equilibrium in benzene solution, but exists as a solid-state trimer. InN powders are also synthesized by reactions of InCl3 and LiNH2 in a molten alkali-halide eutectic, KBr: Liar (60:40), at 400°C. The molten salt acts as an appropriate recrystallization medium for InN. Large InN platelets up to 500 nm could be synthesized. This is a significant step in finding mild reaction conditions that yield large InN crystals.

Organometallic Precursor Routes to Si-C-Al-O-N Ceramics

DTIC Science & Technology

1991-05-15

Pyrolysis Chemistry of Polymeric Precursors to SiC and Si3 N 4", Kluwer Academic Publishers, Dordrecht, NATO Workshop or Organometallic Polymers with Special...the polymer to a preceramic SiC . Thus the IR and H CRAMPS spectra confirm the decreasing concentration of hydrogen with increasing pyrolysis ...generality of this polymer pyrolysis route to nanocrystalline composites of refractory nitride and carbide ceramics. Investigation of AlN Precursors Our

Composite Properties of Polyimide Resins Made From "Salt-Like" Solution Precursors

NASA Technical Reports Server (NTRS)

Cano, Roberto J.; Weiser, Erik S.; SaintClair, Terry L.; Echigo, Yoshiaki; Kaneshiro, Hisayasu

1997-01-01

Recent work in high temperature materials at NASA Langley Research Center (LaRC (trademark)) have led to the development of new polyimide resin systems with very attractive properties. The majority of the work done with these resin systems has concentrated on determining engineering mechanical properties of composites prepared from a poly(amide acid) precursor. Three NASA Langley-developed polyimide matrix resins, LaRC (trademark) -IA, LaRC (trademark) -IAX, and LaRC (trademark) -8515, were produced via a salt-like process developed by Unitika Ltd. The 'salt-like' solutions (sixty-five percent solids in NMP) were prepregged onto Hexcel IM7 carbon fiber using the NASA LaRC Multipurpose Tape Machine. Process parameters were determined and composite panels fabricated. Mechanical properties are presented for these three intermediate modulus carbon fiber/polyimide matrix composites and compared to existing data on the same polyimide resin systems and IM7 carbon fiber manufactured via poly(amide acid) solutions (thirty-five percent solids in NMP). This work studies the effects of varying the synthetic route on the processing and mechanical properties of polyimide composites.

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 new gel route to synthesize LiCoO{sub 2} for lithium-ion batteries

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

Ding, N.; Ge, X.W.; Chen, C.H.

2005-09-01

A new synthetic route, i.e. the radiated polymer gel (RPG) method, has been developed and demonstrated for the production of LiCoO{sub 2} powders. The process involved two processes: (1) obtaining a gel by polymerizing a mixed solution of an acrylic monomer and an aqueous solution of lithium and cobalt salts under {gamma}-ray irradiation conditions and (2) obtaining LiCoO{sub 2} powders by drying and calcining the gel. Thermogravimetric analysis (TGA), X-ray diffraction (XRD) and electron scanning microscopy (SEM) were employed to study the reaction process and the structures of the powders. Galvanostatic cell cycling, cyclic voltammetry and ac impedance spectroscopy weremore » used to evaluate the electrochemical properties of the LiCoO{sub 2} powders. It was found that a pure phase of LiCoO{sub 2} can be obtained at the calcination temperature of 800 deg. C. Both the particle size (micrometer range) and specific charge/discharge capacity of an RPG-LiCoO{sub 2} powder increase with increasing the concentration of its precursor solution.« less

Investigation of optimal route to fabricate submicron-sized Sm{sub 2}Fe{sub 17} particles with reduction-diffusion method

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

Okada, Shusuke, E-mail: shusuke-okada@aist.go.jp; Takagi, Kenta; Ozaki, Kimihiro

Submicron-sized Sm{sub 2}Fe{sub 17} powder samples were fabricated by a non-pulverizing process through reduction-diffusion of precursors prepared by a wet-chemical technique. Three precursors having different morphologies, which were micron-sized porous Sm-Fe oxide-impregnated iron nitrate, acicular goethite impregnated-samarium nitrate, and a conventional Sm-Fe coprecipitate, were prepared and subjected to hydrogen reduction and reduction-diffusion treatment to clarify whether these precursors could be convert to Sm{sub 2}Fe{sub 17} without impurity phases and which precursor is the most attractive for producing submicron-sized Sm{sub 2}Fe{sub 17} powder. As a result, all three precursors were successfully converted to Sm{sub 2}Fe{sub 17} powders without impurity phases, andmore » the synthesis route using iron-oxide particle-impregnated samarium oxide was revealed to have the greatest potential among the three routes.« less

Low temperature solution synthesis of silicon, germanium and Si-Ge axial heterostructures in nanorod and nanowire form.

PubMed

Flynn, G; Stokes, K; Ryan, K M

2018-05-31

Herein, we report the formation of silicon, germanium and more complex Si-SixGe1-x and Si-Ge axial 1D heterostructures, at low temperatures in solution. These nanorods/nanowires are grown using phenylated compounds of silicon and germanium as reagents, with precursor decomposition achieved at substantially reduced temperatures (200 °C for single crystal nanostructures and 300 °C for heterostructures), through the addition of a reducing agent. This low energy route for the production of these functional nanostructures as a wet chemical in high yield is attractive to meet the processing needs for next generation photovoltaics, batteries and electronics.

New polymeric precursors to SiNCB, BN, and La(3)Ni(2)B(2)N(3) materials

NASA Astrophysics Data System (ADS)

Wideman, Thomas W.

Boron-containing non-oxide ceramics demonstrate a number of important structural, electronic and physical properties. However, the lack of general synthetic routes to generate these materials with controlled composition, under moderate conditions, and in processed forms, has hampered both scientific studies and practical applications. The goal of the work described in this dissertation was to develop efficient new polymeric precursor routes to boron-containing materials including SiNCB ceramics composites, boron nitride fibers, and quaternary metal boro-nitride superconductors. Two types of polyborosilazane precursors to SiNCB ceramics were developed. Borazine-co-silazane copolymers were prepared through the thermal copolymerization of borazine with two silazanes, tris(trimethylsilylamino)silane, and 1,1,3,3,5,5 -hexamethylcyclotrisilazane. Polyborosilazanes with pendent boron-containing species were obtained by the modification of preformed hydridopolysilazane polymers with three monofunctional boranes: pinacolborane, 2,4-diethylborazine and 1,3-dimethyl-1,3-diaza-2-boracyclopentane. Pyrolyses of both types of polyborosilazanes produced SiNCB ceramics with controllable boron contents, enhanced thermal stabilities, and reduced crystallinity. Processible polymeric precursors to BN were also achieved by the chemical modification of polyborazylene, (Bsb3Nsb3Hsb{˜ 4}rbrack sb{x}, with diethylamine, dipentylamine, and hexamethyldisilazane. The modified polymers, unlike the parent polyborazylene, do not crosslink at low temperatures, and therefore proved to be ideal melt-spinnable precursors to BN ceramic fibers. A new polymeric precursor route to the recently discovered Lasb3Nisb2Bsb2Nsb3 superconductor (Tc = 12K) was developed by reacting lanthanum and nickel powders dispersed in the polyborazylene, to produce the intermetallic in excellent yields. The use of the polymer as a "reagent" provided a controllable, solid state source of nitrogen, and allows for the large scale syntheses of Lasb3Nisb2Bsb2Nsb3 and other quaternary metal boro-nitrides. Two new preparations of borazine, Bsb3Nsb3Hsb6, a key molecular unit in many of the polymers described above, have also been developed. Chemical investigations and practical applications of borazine-based preceramic polymers have been limited by the inefficient syntheses and high cost of borazine, which may now be prepared in 55-65% yields by the convenient, inexpensive the reaction of ammonium and borohydride salts, and the decomposition of ammonia borane, in high-boiling ether solutions.

Microstructure investigation on micropore formation in microporous silica materials prepared via a catalytic sol-gel process by small angle X-ray scattering.

PubMed

Shimizu, Wataru; Hokka, Junsuke; Sato, Takaaki; Usami, Hisanao; Murakami, Yasushi

2011-08-04

The so-called sol-gel technique has been shown to be a template-free, efficient way to create functional porous silica materials having uniform micropores. This appears to be closely linked with a postulation that the formation of weakly branched polymer-like aggregates in a precursor solution is a key to the uniform micropore generation. However, how such a polymer-like structure can precisely be controlled, and further, how the generated low-fractal dimension solution structure is imprinted on the solid silica materials still remain elusive. Here we present fabrication of microporous silica from tetramethyl orthosilicate (TMOS) using a recently developed catalytic sol-gel process based on a nonionic hydroxyacetone (HA) catalyst. Small angle X-ray scattering (SAXS), nitrogen adsorption porosimetry, and transmission electron microscope (TEM) allowed us to observe the whole structural evolution, ranging from polymer-like aggregates in the precursor solution to agglomeration with heat treatment and microporous morphology of silica powders after drying and hydrolysis. Using the HA catalyst with short chain monohydric alcohols (methanol or ethanol) in the precursor solution, polymer-like aggregates having microscopic correlation length (or mesh-size) < 2 nm and low fractal dimensions ∼2, which is identical to that of an ideal coil polymer, can selectively be synthesized, yielding the uniform micropores with diameters <2 nm in the solid materials. In contrast, the absence of HA or substitution of 1-propanol led to considerably different scattering behavior reflecting the particle-like aggregate formation in the precursor solution, which resulted in the formation of mesopores (diameter >2 nm) in the solid product due to apertures between the particle-like aggregates. The data demonstrate that the extremely fine porous silica architecture comes essentially from a gaussian polymer-like nature of the silica aggregates in the precursor having the microscopic mesh-size and their successful imprint on the solid product. The result offers a general but significantly efficient route to creating precisely designed fine porous silica materials under mild condition that serve as low refractive index and efficient thermal insulation materials in their practical applications.

Towards deriving Ni-rich cathode and oxide-based anode materials from hydroxides by sharing a facile co-precipitation method.

PubMed

Qiu, Haifa; Du, Tengfei; Wu, Junfeng; Wang, Yonglong; Liu, Jian; Ye, Shihai; Liu, Sheng

2018-05-22

Although intensive studies have been conducted on layered transition metal oxide(TMO)-based cathode materials and metal oxide-based anode materials for Li-ion batteries, their precursors generally follow different or even complex synthesis routes. To share one route for preparing precursors of the cathode and anode materials, herein, we demonstrate a facile co-precipitation method to fabricate Ni-rich hydroxide precursors of Ni0.8Co0.1Mn0.1(OH)2. Ni-rich layered oxide of LiNi0.8Co0.1Mn0.1O2 is obtained by lithiation of the precursor in air. An NiO-based anode material is prepared by calcining the precursor or multi-walled carbon nanotubes (MWCNTs) incorporated precursors. The pre-addition of ammonia solution can simplify the co-precipitation procedures and the use of an air atmosphere can also make the heat treatment facile. LiNi0.8Co0.1Mn0.1O2 as the cathode material delivers a reversible capacity of 194 mA h g-1 at 40 mA g-1 and a notable cycling retention of 88.8% after 100 cycles at 200 mA g-1. This noticeable performance of the cathode arises from a decent particle morphology and high crystallinity of the layered oxides. As the anode material, the MWCNTs-incorporated oxides deliver a much higher reversible capacity of 811.1 mA h g-1 after 200 cycles compared to the pristine oxides without MWCNTs. The improvement on electrochemical performance can be attributed to synergistic effects from MWCNTs incorporation, including reinforced electronic conductivity, rich meso-pores and an alleviated volume effect. This facile and sharing method may offer an integrated and economical approach for commercial production of Ni-rich electrode materials for Li-ion batteries.

A novel synthesis of SrCO3-SrTiO3 nanocomposites with high photocatalytic activity

NASA Astrophysics Data System (ADS)

Márquez-Herrera, A.; Ovando-Medina, Víctor M.; Castillo-Reyes, Blanca E.; Meléndez-Lira, M.; Zapata-Torres, M.; Saldaña, N.

2014-12-01

The results of the production and characterization of SrCO3-SrTiO3 nanocomposites as a promising candidate for efficient photocatalysts are reported. The production is based on a novelty route employing the solvothermal method with strontium chloride and titanium (IV) butoxide as the precursor solutions. The effect on the properties of the nanocomposites due to changes in the content of SrCO3 and SrTiO3 is reported. The as-prepared materials were tested in the photodegradation of methylene blue dye in aqueous solutions under the solar light. The reported route allows the production of SrCO3-SrTiO3 nanocomposites with particle sizes ranging between 18 and 29 nm. The SrCO3-SrTiO3 nanocomposites obtained with 19 % of SrCO3 phase and 81 % of SrTiO3 (M10) can achieve 94 and 97 % of dye photodegradation after 30 and 120 min, respectively.

A novel low cost non-aqueous chemical route for giant dielectric constant CaCu3Ti4O12 ceramic

NASA Astrophysics Data System (ADS)

Singh, Laxman; Kim, Ill Won; Woo, Won Seok; Sin, Byung Cheol; Lee, Hyung-il; Lee, Youngil

2015-05-01

This paper reports a simple, fast, low cost and environment-friendly route for preparing a highly crystalline giant dielectric material, CaCu3Ti4O12 (CCTO), through combustion of metal nitrates in non-aqueous precursor solution using inexpensive solid TiO2 powder. The route to producing pure phase CCTO ceramic using stable solid TiO2 is better than other several sol-gel routes reported earlier in which expensive alkoxides, oxynitrates, or chlorides of titanium are used as the titanium sources. X-ray diffraction revealed the formation of cubic perovskite CCTO. Scanning electron microscopy image showed the average grain sizes in the range of 1.5-5 μm. At 10 kHz and room temperature, the best CCTO ceramic exhibited a high dielectric constant, ε‧ ∼43325.24, with low dielectric loss, tan δ ∼0.088. The dielectric relaxation behavior was rationalized from impedance and modulus studies and the presence of a non-Debye type of relaxation was confirmed.

Solution processing of chalcogenide materials using thiol-amine "alkahest" solvent systems.

PubMed

McCarthy, Carrie L; Brutchey, Richard L

2017-05-02

Macroelectronics is a major focus in electronics research and is driven by large area applications such as flat panel displays and thin film solar cells. Innovations for these technologies, such as flexible substrates and mass production, will require efficient and affordable semiconductor processing. Low-temperature solution processing offers mild deposition methods, inexpensive processing equipment, and the possibility of high-throughput processing. In recent years, the discovery that binary "alkahest" mixtures of ethylenediamine and short chain thiols possess the ability to dissolve bulk inorganic materials to yield molecular inks has lead to the wide study of such systems and the straightforward recovery of phase pure crystalline chalcogenide thin films upon solution processing and mild annealing of the inks. In this review, we recount the work that has been done toward elucidating the scope of this method for the solution processing of inorganic materials for use in applications such as photovoltaic devices, electrocatalysts, photodetectors, thermoelectrics, and nanocrystal ligand exchange. We also take stock of the wide range of bulk materials that can be used as soluble precursors, and discuss the work that has been done to reveal the nature of the dissolved species. This method has provided a vast toolbox of over 65 bulk precursors, which can be utilized to develop new routes to functional chalcogenide materials. Future studies in this area should work toward a better understanding of the mechanisms involved in the dissolution and recovery of bulk materials, as well as broadening the scope of soluble precursors and recoverable functional materials for innovative applications.

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.

Ceramic porous material and method of making same

DOEpatents

Liu, Jun; Kim, Anthony Y.; Virden, Jud W.

1997-01-01

The invention is a mesoporous ceramic membrane having substantially uniform pore size. Additionally, the invention includes aqueous and non-aqueous processing routes to making the mesoporous ceramic membranes. According to one aspect of the present invention, inserting a substrate into a reaction chamber at pressure results in reaction products collecting on the substrate and forming a membrane thereon. According to another aspect of the present invention, a second aqueous solution that is sufficiently immiscible in the aqueous solution provides an interface between the two solutions whereon the mesoporous membrane is formed. According to a further aspect of the present invention, a porous substrate is placed at the interface between the two solutions permitting formation of a membrane on the surface or within the pores of the porous substrate. According to yet another aspect of the present invention, mesoporous ceramic materials are formed using a non-aqueous solvent and water-sensitive precursors.

Ceramic porous material and method of making same

DOEpatents

Liu, J.; Kim, A.Y.; Virden, J.W.

1997-07-08

The invention is a mesoporous ceramic membrane having substantially uniform pore size. Additionally, the invention includes aqueous and non-aqueous processing routes to making the mesoporous ceramic membranes. According to one aspect of the present invention, inserting a substrate into a reaction chamber at pressure results in reaction products collecting on the substrate and forming a membrane thereon. According to another aspect of the present invention, a second aqueous solution that is sufficiently immiscible in the aqueous solution provides an interface between the two solutions whereon the mesoporous membrane is formed. According to a further aspect of the present invention, a porous substrate is placed at the interface between the two solutions permitting formation of a membrane on the surface or within the pores of the porous substrate. According to yet another aspect of the present invention, mesoporous ceramic materials are formed using a non-aqueous solvent and water-sensitive precursors. 21 figs.

The Porphobilinogen Conundrum in Prebiotic Routes to Tetrapyrrole Macrocycles

NASA Astrophysics Data System (ADS)

Taniguchi, Masahiko; Ptaszek, Marcin; Chandrashaker, Vanampally; Lindsey, Jonathan S.

2017-03-01

Attempts to develop a credible prebiotic route to tetrapyrroles have relied on enzyme-free recapitulation of the extant biosynthesis, but this process has foundered from the inability to form the pyrrole porphobilinogen ( PBG) in good yield by self-condensation of the precursor δ-aminolevulinic acid ( ALA). PBG undergoes robust oligomerization in aqueous solution to give uroporphyrinogen (4 isomers) in good yield. ALA, PBG, and uroporphyrinogen III are universal precursors to all known tetrapyrrole macrocycles. The enzymic formation of PBG entails carbon-carbon bond formation between the less stable enolate/enamine of one ALA molecule (3-position) and the carbonyl/imine (4-position) of the second ALA molecule; without enzymes, the first ALA reacts at the more stable enolate/enamine (5-position) and gives the pyrrole pseudo-PBG. pseudo-PBG cannot self-condense, yet has one open α-pyrrole position and is proposed to be a terminator of oligopyrromethane chain-growth from PBG. Here, 23 analogues of ALA have been subjected to density functional theoretical (DFT) calculations, but no motif has been identified that directs reaction at the 3-position. Deuteriation experiments suggested 5-(phosphonooxy)levulinic acid would react preferentially at the 3- versus 5-position, but a hybrid condensation with ALA gave no observable uroporphyrin. The results suggest efforts toward a biomimetic, enzyme-free route to tetrapyrroles from ALA should turn away from structure-directed reactions and focus on catalysts that orient the two aminoketones to form PBG in a kinetically controlled process, thereby avoiding formation of pseudo-PBG.

Chemical precursors to non-oxide ceramics: Macro to nanoscale materials

NASA Astrophysics Data System (ADS)

Forsthoefel, Kersten M.

Non-oxide ceramics exhibit a number of important properties that make them ideal for technologically important applications (thermal and chemical stability, high strength and hardness, wear-resistance, light weight, and a range of electronic and optical properties). Unfortunately, traditional methodologies to these types of materials are limited to fairly simple shapes and complex processed forms cannot be attained through these methods. The establishment of the polymeric precursor approach has allowed for the generation of advanced materials, such as refractory non-oxide ceramics, with controlled compositions, under moderate conditions, and in processed forms. The goal of the work described in this dissertation was both to develop new processible precursors to technologically important ceramics and to achieve the formation of advanced materials in processed forms. One aspect of this research exploited previously developed preceramic precursors to boron carbide, boron nitride and silicon carbide for the generation of a wide variety of advanced materials: (1) ultra-high temperature ceramic (UHTC) structural materials composed of hafnium boride and related composite materials, (2) the quaternary borocarbide superconductors, and (3) on the nanoscale, non-oxide ceramic nanotubules. The generation of the UHTC and the quaternary borocarbide materials was achieved through a method that employs a processible polymer/metal(s) dispersion followed by subsequent pyrolyses. In the case of the UHTC, hafnium oxide, hafnium, or hafnium boride powders were dispersed in a suitable precursor to afford hafnium borides or related composite materials (HfB2/HfC, HfB2/HfN, HfB2/SiC) in high yields and purities. The quaternary borocarbide superconducting materials were produced from pyrolyses of dispersions containing appropriate stoichiometric amounts of transition metal, lanthanide metal, and the polyhexenyldecaborane polymer. Both chemical vapor deposition (CVD) based routes employing a molecular precursor and porous alumina templating routes paired with solution-based methodologies are shown to generate non-oxide ceramic nanotubules of boron carbide, boron nitride and silicon carbide compositions. In the final phase of this work, a new metal-catalyzed route to poly(1-alkenyl- o-carborane) homopolymers and related copolymers was developed. Both homopolymers of 1-alkenyl-o-carboranes (1-vinyl-, 1-butenyl-, 1-hexenyl-) and copolymers of 1-hexenyl-o-carborane and allyltrimethylsilane or 1-hexenyl-o-carborane and 6-hexenyldecaborane were synthesized via the Cp2ZrMe2/B(C6F5) 3 catalyst system. A copolymer containing 1-hexenyl-o-carborane and the cross-linking agent, 6-hexenyldecaborane, was synthetically designed which exhibits initial cross-linking at ˜250°C and then converts in 75% yields to boron carbide at 1250°C.

Synthesis of Mesoporous α-Fe2O3 Nanoparticles by Non-ionic Soft Template and Their Applications to Heavy Oil Upgrading

NASA Astrophysics Data System (ADS)

Park, Chulwoo; Jung, Jinhwan; Lee, Chul Wee; Cho, Joungmo

2016-12-01

This paper reports the synthetic route of 3-D network shape α-Fe2O3 from aqueous solutions of iron precursor using a non-ionic polymeric soft-template, Pluronic P123. During the synthesis of α-Fe2O3, particle sizes, crystal phases and morphologies were significantly influenced by pH, concentrations of precursor and template. The unique shape of worm-like hematite was obtained only when a starting solution was prepared by a weakly basic pH condition and a very specific composition of constituents. The synthesized nanocrystal at this condition had a narrow pore size distribution and high surface area compared to the bulk α-Fe2O3 or the one synthesized from lower pH conditions. The hydrocracking performance was tested over the synthesized iron oxide catalysts with different morphologies. The worm-like shape of iron oxide showed a superior performance, including overall yield of liquid fuel product and coke formation, over the hydrocracking of heavy petroleum oil.

Synthesis of Mesoporous α-Fe2O3 Nanoparticles by Non-ionic Soft Template and Their Applications to Heavy Oil Upgrading

PubMed Central

Park, Chulwoo; Jung, Jinhwan; Lee, Chul Wee; Cho, Joungmo

2016-01-01

This paper reports the synthetic route of 3-D network shape α-Fe2O3 from aqueous solutions of iron precursor using a non-ionic polymeric soft-template, Pluronic P123. During the synthesis of α-Fe2O3, particle sizes, crystal phases and morphologies were significantly influenced by pH, concentrations of precursor and template. The unique shape of worm-like hematite was obtained only when a starting solution was prepared by a weakly basic pH condition and a very specific composition of constituents. The synthesized nanocrystal at this condition had a narrow pore size distribution and high surface area compared to the bulk α-Fe2O3 or the one synthesized from lower pH conditions. The hydrocracking performance was tested over the synthesized iron oxide catalysts with different morphologies. The worm-like shape of iron oxide showed a superior performance, including overall yield of liquid fuel product and coke formation, over the hydrocracking of heavy petroleum oil. PMID:27966663

Synthesis of Mesoporous α-Fe2O3 Nanoparticles by Non-ionic Soft Template and Their Applications to Heavy Oil Upgrading.

PubMed

Park, Chulwoo; Jung, Jinhwan; Lee, Chul Wee; Cho, Joungmo

2016-12-14

This paper reports the synthetic route of 3-D network shape α-Fe 2 O 3 from aqueous solutions of iron precursor using a non-ionic polymeric soft-template, Pluronic P123. During the synthesis of α-Fe 2 O 3 , particle sizes, crystal phases and morphologies were significantly influenced by pH, concentrations of precursor and template. The unique shape of worm-like hematite was obtained only when a starting solution was prepared by a weakly basic pH condition and a very specific composition of constituents. The synthesized nanocrystal at this condition had a narrow pore size distribution and high surface area compared to the bulk α-Fe 2 O 3 or the one synthesized from lower pH conditions. The hydrocracking performance was tested over the synthesized iron oxide catalysts with different morphologies. The worm-like shape of iron oxide showed a superior performance, including overall yield of liquid fuel product and coke formation, over the hydrocracking of heavy petroleum oil.

Novel borothermal route for the synthesis of lanthanum cerium hexaborides and their field emission properties

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

Menaka; Patra, Rajkumar; Ghosh, Santanu

2012-10-15

The present study describes the development of a simple approach to stabilize polycrystalline lanthanum cerium hexaborides without using any flux and at ambient pressure. The nanostructured lanthanum-cerium borides were synthesized using hydroxide precursors. These precursors (La{sub 1-x}Ce{sub x}(OH){sub 3}, x=0.1, 0.2, 0.3 and 0.5) were synthesized via hydrothermal route in the presence of Tergitol (surfactant, nonylphenol ethoxylate) as a capping agent. The precursors on heating with boron at 1300 Degree-Sign C lead to the formation of nanostructures (cubes, rods and pyramids) of lanthanum cerium hexaboride. We have investigated the field emission behaviour of the hexaboride films fabricated by spin coating.more » It was observed that the pyramidal shaped nanostructures of La{sub 0.5}Ce{sub 0.5}B{sub 6} shows excellent field emission characteristics with high field enhancement factor of 4502. - Graphical abstract: Nanostructured lanthanum cerium hexaboride with efficient field emission have fabricated by low temperature hydroxide precursor mediated route. Highlights: Black-Right-Pointing-Pointer New methodology to prepare lanthanum cerium hexaboride at 1300 Degree-Sign C via borothermal route. Black-Right-Pointing-Pointer Nanostructured lanthanum cerium hexaboride film by spin coating process. Black-Right-Pointing-Pointer Nanopyramids based lanthanum cerium hexaboride shows excellent field emission.« less

Sol-gel preparation of lead magnesium niobate (PMN) powders and thin films

DOEpatents

Boyle, T.J.

1999-01-12

A method of preparing a lead magnesium niobium oxide (PMN), Pb(Mg{sub 1/3}Nb{sub 2/3})O{sub 3}, precursor solution by a solvent method wherein a liquid solution of a lead-complex PMN precursor is combined with a liquid solution of a niobium-complex PMN precursor, the combined lead- and niobium-complex liquid solutions are reacted with a magnesium-alkyl solution, forming a PMN precursor solution and a lead-based precipitate, and the precipitate is separated from the reacted liquid PMN precursor solution to form a precipitate-free PMN precursor solution. This precursor solution can be processed to form both ferroelectric powders and thin films. 3 figs.

Sol-Gel Preparation Of Lead Magnesium Ni Obate (Pmn) Powdersand Thin Films

DOEpatents

Boyle, Timothy J.

1999-01-12

A method of preparing a lead magnesium niobium oxide (PMN), Pb(Mg.sub.1/3 Nb.sub.2/3)O.sub.3, precursor solution by a solvent method wherein a liquid solution of a lead-complex PMN precursor is combined with a liquid solution of a niobium-complex PMN precursor, the combined lead- and niobium-complex liquid solutions are reacted with a magnesium-alkyl solution, forming a PMN precursor solution and a lead-based precipitate, and the precipitate is separated from the reacted liquid PMN precursor solution to form a precipitate-free PMN precursor solution. This precursor solution can be processed to form both ferroelectric powders and thin films.

Metal sulfide and rare-earth phosphate nanostructures and methods of making same

DOEpatents

Wong, Stanislaus; Zhang, Fen

2016-06-28

The present invention provides a method of producing a crystalline rare earth phosphate nanostructure. The method comprising: providing a rare earth metal precursor solution and providing a phosphate precursor solution; placing a porous membrane between the metal precursor solution and the phosphate precursor solution, wherein metal cations of the metal precursor solution and phosphate ions of the phosphate precursor solution react, thereby producing a crystalline rare earth metal phosphate nanostructure.

[Progress in bio-based polyamides].

PubMed

Huang, Zhengqiang; Cui, Zhe; Zhang, Heming; Fu, Peng; Zhao, Qingxiang; Liu, Minying

2016-06-25

Bio-based polyamides are environment-friendly polymers. The precursors of bio-based polyamides come from bio-based materials such as castor oil, glucose and animal oil. Bio-based polyamides precursors include bio-based amino acids, bio-based lactams, bio-based diprotic acid and bio-based diamines. In this paper, we discussed the route of the precursors of bio-based polyamides that come from bio-based materials. We discussed the properties of bio-based polyamides. Bio-based PA11and bio-based PA1010 are well-known bio-based polyamides; we discussed the origin materials of the precursors, the route of manufacturing bio-based PA11 and PA1010, and their modifications status. The variety, classification and commercial production of bio-based polyamides were described in details, as well as bio-based polyamides development in China.

Synthesis of High Molecular Weight Poly(glycerol monomethacrylate) via RAFT Emulsion Polymerization of Isopropylideneglycerol Methacrylate

PubMed Central

2018-01-01

High molecular weight water-soluble polymers are widely used as flocculants or thickeners. However, synthesis of such polymers via solution polymerization invariably results in highly viscous fluids, which makes subsequent processing somewhat problematic. Alternatively, such polymers can be prepared as colloidal dispersions; in principle, this is advantageous because the particulate nature of the polymer chains ensures a much lower fluid viscosity. Herein we exemplify the latter approach by reporting the convenient one-pot synthesis of high molecular weight poly(glycerol monomethacrylate) (PGMA) via the reversible addition–fragmentation chain transfer (RAFT) aqueous emulsion polymerization of a water-immiscible protected monomer precursor, isopropylideneglycerol methacrylate (IPGMA) at 70 °C, using a water-soluble poly(glycerol monomethacrylate) (PGMA) chain transfer agent as a steric stabilizer. This formulation produces a low-viscosity aqueous dispersion of PGMA–PIPGMA diblock copolymer nanoparticles at 20% solids. Subsequent acid deprotection of the hydrophobic core-forming PIPGMA block leads to particle dissolution and affords a viscous aqueous solution comprising high molecular weight PGMA homopolymer chains with a relatively narrow molecular weight distribution. Moreover, it is shown that this latex precursor route offers an important advantage compared to the RAFT aqueous solution polymerization of glycerol monomethacrylate since it provides a significantly faster rate of polymerization (and hence higher monomer conversion) under comparable conditions. PMID:29805184

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.

An acetate precursor process for BSCCO (2223) thin films and coprecipitated powders

NASA Technical Reports Server (NTRS)

Haertling, Gene H.

1992-01-01

Since the discovery of high temperature superconducting oxides much attention has been paid to finding better and useful ways to take advantage of the special properties exhibited by these materials. One such process is the development of thin films for engineering applications. Another such process is the coprecipitation route to producing superconducting powders. An acetate precursor process for use in thin film fabrication and a chemical coprecipitation route to Bismuth based superconducting materials has been developed. Data obtained from the thin film process were inconclusive to date and require more study. The chemical coprecipitation method of producing bulk material is a viable method, and is preferred over the previously used solid state route. This method of powder production appears to be an excellent route to producing thin section tape cast material and screen printed devices, as it requires less calcines than the oxide route to produce quality powders.

Carbon Microfibers with Hierarchical Porous Structure from Electrospun Fiber-Like Natural Biopolymer

NASA Astrophysics Data System (ADS)

Liang, Yeru; Wu, Dingcai; Fu, Ruowen

2013-01-01

Electrospinning offers a powerful route for building one-dimensional (1D) micro/nanostructures, but a common requirement for toxic or corrosive organic solvents during the preparation of precursor solution has limited their large scale synthesis and broad applications. Here we report a facile and low-cost way to prepare 1D porous carbon microfibers by using an electrospun fiber-like natural product, i.e., silk cocoon, as precursor. We surprisingly found that by utilizing a simple carbonization treatment, the cocoon microfiber can be directly transformed into 1D carbon microfiber of ca. 6 μm diameter with a unique three-dimensional porous network structure composed of interconnected carbon nanoparticles of 10~40 nm diameter. We further showed that the as-prepared carbon product presents superior electrochemical performance as binder-free electrodes of supercapacitors and good adsorption property toward organic vapor.

Methylamphetamine synthesized from cold medication as precursor source via two different routes show significantly different stable isotope signatures

NASA Astrophysics Data System (ADS)

Jayaram, S.; Daeid, N. Nic; Kerr, W. J.; Kemp, H. F.; Meier-Augenstein, W.

2012-04-01

This work exposes the variation in light element stable isotopic abundance values of 13C, 2H and 15N) derived from the analysis of methylamphetamine synthesized via 2 different synthetic routes popular with clandestine laboraties, the Hypophosphorous and the Moscow route. We repeatedly prepared the final product using known clandestine synthetic methods where the precursors, catalysts and reducing agents have themselves been derived from house hold products and commonly available cold medications. Methylamphetamine was prepared from both lab grade pseudoephedrine and pseudoephedrine extracted (using three different solvent systems) from Sudafed®, an over-the-counter cold medication widely available in the United Kingdom. Six repetitive batches of the final product were produced in each case to provide within and between batch variations thus yielding a total of 48 samples (24 for each route). We have demonstrated that stable isotope analysis by Isotope Ratio Mass Spectrometry (IRMS) is potentially useful in the comparison and discrimination of batches of methylamphetamine produced for each route and for each precursor depending on the solvent used for extracting the pseudoephedrine starting material. To our knowledge this is the first time multivariate stable isotope analysis has been applied to methylamphetamine samples synthesized from pseudoephedrine extracted from over-the-counter cold medications.

Characteristics of nano-sized yttria powder synthesized by a polyvinyl alcohol solution route at low temperature.

PubMed

Lee, Sang-Jin; Jung, Choong-Hwan

2012-01-01

Nano-sized yttria (Y2O3) powders were successfully synthesized at a low temperature of 400 degrees C by a simple polymer solution route. PVA polymer, as an organic carrier, contributed to an atom-scale homogeneous precursor gel and it resulted in fully crystallized, nano-sized yttria powder with high specific surface area through the low temperature calcination. In this process, the content of PVA, calcination temperature and heating time affected the microstructure and crystallization behavior of the powders. The development of crystalline phase and the final particle size were strongly dependant on the oxidation reaction from the polymer burn-out step and the PVA content. In this paper, the PVA solution technique for the fabrication of nano-sized yttria powders is introduced. The effects of PVA content and holding time on the powder morphology and powder specific surface area are also studied. The characterization of the synthesized powders is examined by using XRD, DTA/TG, SEM, TEM and nitrogen gas adsorption. The yttria powder synthesized from the PVA content of 3:1 ratio and calcined at 400 degrees C had a crystallite size of about 20 nm or less with a high surface areas of 93.95-120.76 m2 g(-1).

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

Carreras, Alejo C., E-mail: acarreras@famaf.unc.edu.ar; Cangiano, María de los A.; Ojeda, Manuel W.

The influence of the amount of complexing agent added to the starting solution on the physicochemical properties of Cu–Ni nanostructured alloys obtained through a chemical route, was studied. For this purpose, three Cu–Ni nanoalloy samples were synthesized by a previously developed procedure, starting from solutions with citric acid to metal molar ratios (C/Me) of 0.73, 1.00 and 1.50. The synthesis technique consisted in preparing a precursor via the citrate-gel method, and carrying out subsequent thermal treatments in controlled atmospheres. Sample characterization was performed by scanning electron microscopy, X-ray microanalysis, X-ray diffraction, transmission electron microscopy, X-ray nanoanalysis and electron diffraction. Inmore » the three cases, copper and nickel formed a solid solution with a Cu/Ni atomic ratio close to 50/50, and free of impurities inside the crystal structure. The citric acid content of the starting solution proved to have an important influence on the morphology, size distribution, porosity, and crystallinity of the Cu–Ni alloy microparticles obtained, but a lesser influence on their chemical composition. The molar ratio C/Me = 1.00 resulted in the alloy with the Cu/Ni atomic ratio closest to 50/50. - Highlights: • We synthesize Cu–Ni nanoalloys by a chemical route based on the citrate-gel method. • We study the influence of the complexing agent content of the starting solution. • We characterize the samples by electron microscopy and X-ray techniques. • Citric acid influences the shape, size, porosity and crystallinity of the alloys.« less

Coprecipitation of nickel zinc malonate: A facile and reproducible synthesis route for Ni{sub 1−x}Zn{sub x}O nanoparticles and Ni{sub 1−x}Zn{sub x}O/ZnO nanocomposites via pyrolysis

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

Lontio Fomekong, Roussin, E-mail: lonforou@yahoo.fr; Institut de la Matière Condensée et des Nanosciences, Université Catholique de Louvain, Croix du Sud 1, 1348 Louvain-La-Neuve; Kenfack Tsobnang, Patrice

2015-10-15

Nanoparticles of Ni{sub 1−x}Zn{sub x}O and Ni{sub 1−x}Zn{sub x}O/ZnO, which can be good candidates for selective gas sensors, were successfully obtained via a two-step synthetic route, in which the nickel zinc malonate precursor was first synthesized by co-precipitation from an aqueous solution, followed by pyrolysis in air at a relatively low temperature (~500 °C). The precursor was characterized by ICP-AES, FTIR and TG and the results indicate the molecular structure of the precursor to be compatible with Ni{sub 1−x}Zn{sub x}(OOCCH{sub 2}COO)·2H{sub 2}O. The decomposition product, characterized using various techniques (FTIR, XRD, ToF-SIMS, SEM, TEM and XPS), was established to bemore » a doped nickel oxide (Ni{sub 1−x}Zn{sub x}O for 0.01≤x≤0.1) and a composite material (Ni{sub 1−x}Zn{sub x}O/ZnO for 0.2≤x≤0.5). To elucidate the form in which the Zn is present in the NiO structure, three analytical techniques were employed: ToF-SIMS, XRD and XPS. While ToF SIMS provided a direct evidence of the presence of Zn in the NiO crystal structure, XRD showed that Zn actually substitutes Ni in the structure and XPS is a bit more specific by indicating that the Zn is present in the form of Zn{sup 2+} ions. - Highlights: • Coprecipitation synthesis of nickel zinc malonate single bath precursor was achieved. • The as synthesized precursors are an homogeneous mixture of nickel and zinc malonate. • XRD, ToF-SIMS, XPS, SEM and TEM was used to characterized decomposition products. • Ni{sub 1−x}Zn{sub x}O nanoparticles (0.01≤x≤0.1) formed after pyrolysis (~500 °C) of precursor. • Ni{sub 1−x}Zn{sub x}O/ZnO nanocomposite (0.2≤x≤0.5) formed after pyrolysis at 500 °C of precursor.« less

L-Cysteine Capped CdSe Quantum Dots Synthesized by Photochemical Route.

PubMed

Singh, Avinash; Kunwar, Amit; Rath, M C

2018-05-01

L-cysteine capped CdSe quantum dots were synthesized via photochemical route in aqueous solution under UV photo-irradiation. The as grown CdSe quantum dots exhibit broad fluorescence at room temperature. The CdSe quantum dots were found to be formed only through the reactions of the precursors, i.e., Cd(NH3)2+4 and SeSO2-3 with the photochemically generated 1-hydroxy-2-propyl radicals, (CH3)2COH radicals, which are formed through the process of H atom abstraction by the photoexcited acetone from 2-propanol. L-Cysteine was found to act as a suitable capping agent for the CdSe quantum dots and increases their biocompatability. Cytotoxicty effects of these quantum dots were evaluated in Chinese Hamster Ovary (CHO) epithelial cells, indicated a significant lower level for the L-cysteine capped CdSe quantum dots as compare to the bare ones.

Optimisation of a sol-gel synthesis route for the preparation of MgF2 particles for a large scale coating process.

PubMed

Scheurell, K; Noack, J; König, R; Hegmann, J; Jahn, R; Hofmann, Th; Löbmann, P; Lintner, B; Garcia-Juan, P; Eicher, J; Kemnitz, E

2015-12-07

A synthesis route for the preparation of optically transparent magnesium fluoride sols using magnesium acetate tetrahydrate as precursor is described. The obtained magnesium fluoride sols are stable for several months and can be applied for antireflective coatings on glass substrates. Reaction parameters in the course of sol synthesis are described in detail. Thus, properties of the precursor materials play a crucial role in the formation of the desired magnesium fluoride nanoparticles, this is drying the precursor has to be performed under defined mild conditions, re-solvation of the dried precursor has to be avoided and addition of water to the final sol-system has to be controlled strictly. Important properties of the magnesium fluoride sols like viscosity, particle size distribution, and structural information are presented as well.

Carbothermal shock synthesis of high-entropy-alloy nanoparticles

NASA Astrophysics Data System (ADS)

Yao, Yonggang; Huang, Zhennan; Xie, Pengfei; Lacey, Steven D.; Jacob, Rohit Jiji; Xie, Hua; Chen, Fengjuan; Nie, Anmin; Pu, Tiancheng; Rehwoldt, Miles; Yu, Daiwei; Zachariah, Michael R.; Wang, Chao; Shahbazian-Yassar, Reza; Li, Ju; Hu, Liangbing

2018-03-01

The controllable incorporation of multiple immiscible elements into a single nanoparticle merits untold scientific and technological potential, yet remains a challenge using conventional synthetic techniques. We present a general route for alloying up to eight dissimilar elements into single-phase solid-solution nanoparticles, referred to as high-entropy-alloy nanoparticles (HEA-NPs), by thermally shocking precursor metal salt mixtures loaded onto carbon supports [temperature ~2000 kelvin (K), 55-millisecond duration, rate of ~105 K per second]. We synthesized a wide range of multicomponent nanoparticles with a desired chemistry (composition), size, and phase (solid solution, phase-separated) by controlling the carbothermal shock (CTS) parameters (substrate, temperature, shock duration, and heating/cooling rate). To prove utility, we synthesized quinary HEA-NPs as ammonia oxidation catalysts with ~100% conversion and >99% nitrogen oxide selectivity over prolonged operations.

Preparation of glass-forming materials from granulated blast furnace slag

NASA Astrophysics Data System (ADS)

Alonso, M.; Sáinz, E.; Lopez, F. A.

1996-10-01

Glass precursor materials, to be used for the vitrification of hazardous wastes, have been prepared from blast furnace slag powder through a sol-gel route. The slag is initially reacted with a mixture of alcohol (ethanol or methanol) and mineral acid (HNO3 or H2SO4) to give a sol principally consisting of Si, Ca, Al, and Mg alkoxides. Gelation is carried out with variable amounts of either ammonia or water. The gelation rate can be made as fast as desired by adding excess hydrolizing agent or else by distilling the excess alcohol out of the alkoxide solution. The resulting gel is first dried at low temperature and ground. The powder thus obtained is then heat treated at several temperatures. The intermediate and final materials are characterized by thermal analysis, infrared (IR) spectroscopy, X-ray diffraction, scanning electron microscopy (SEM), and chemical analysis. From the results, the operating conditions yielding a variety of glass precursors differing in their composition are established. The method, in comparison with direct vitrification of slag, presents a number of advantages: (1) the glass precursor obtained devitrifies at higher temperatures; (2) it enables the adjustment, to a certain extent, of the chemical composition of the glass precursor; and (3) it permits recovering marketable materials at different stages of the process.

Precursor-route ZnO films from a mixed casting solvent for high performance aqueous electrolyte-gated transistors.

PubMed

Althagafi, Talal M; Algarni, Saud A; Al Naim, Abdullah; Mazher, Javed; Grell, Martin

2015-12-14

We significantly improved the performance of precursor-route semiconducting zinc oxide (ZnO) films in electrolyte-gated thin film transistors (TFTs). We find that the organic precursor to ZnO, zinc acetate (ZnAc), dissolves more readily in a 1 : 1 mixture of ethanol (EtOH) and acetone than in pure EtOH, pure acetone, or pure isopropanol. XPS and SEM characterisation show improved morphology of ZnO films converted from a mixed solvent cast ZnAc precursor compared to the EtOH cast precursor. When gated with a biocompatible electrolyte, phosphate buffered saline (PBS), ZnO thin film transistors (TFTs) derived from mixed solvent cast ZnAc give 4 times larger field effect current than similar films derived from ZnAc cast from pure EtOH. The sheet resistance at VG = VD = 1 V is 30 kΩ □(-1), lower than for any organic TFT, and lower than for any electrolyte-gated ZnO TFT reported to date.

Controllable synthesis of (NH4)Fe2(PO4)2(OH)·2H2O using two-step route: Ultrasonic-intensified impinging stream pre-treatment followed by hydrothermal treatment.

PubMed

Dong, Bin; Li, Guang; Yang, Xiaogang; Chen, Luming; Chen, George Z

2018-04-01

(NH 4 )Fe 2 (PO 4 ) 2 (OH)·2H 2 O samples with different morphology are successfully synthesized via two-step synthesis route - ultrasonic-intensified impinging stream pre-treatment followed by hydrothermal treatment (UIHT) method. The effects of the adoption of ultrasonic-intensified impinging stream pre-treatment, reagent concentration (C), pH value of solution and hydrothermal reaction time (T) on the physical and chemical properties of the synthesised (NH 4 )Fe 2 (PO 4 ) 2 (OH)·2H 2 O composites and FePO 4 particles were systematically investigated. Nano-seeds were firstly synthesized using the ultrasonic-intensified T-mixer and these nano-seeds were then transferred into a hydrothermal reactor, heated at 170 °C for 4 h. The obtained samples were characterized by utilising XRD, BET, TG-DTA, SEM, TEM, Mastersizer 3000 and FTIR, respectively. The experimental results have indicated that the particle size and morphology of the obtained samples are remarkably affected by the use of ultrasonic-intensified impinging stream pre-treatment, hydrothermal reaction time, reagent concentration, and pH value of solution. When such (NH 4 )Fe 2 (PO 4 ) 2 (OH)·2H 2 O precursor samples were transformed to FePO 4 products after sintering at 650 °C for 10 h, the SEM images have clearly shown that both the precursor and the final product still retain their monodispersed spherical microstructures with similar particle size of about 3 μm when the samples are synthesised at the optimised condition. Copyright © 2017 Elsevier B.V. All rights reserved.

Low temperature fabrication of metal oxide thin film transistors formed by a heated aqueous precursor solution

NASA Astrophysics Data System (ADS)

Lee, Keun Ho; Han, Sun Woong; Park, Jee Ho; Yoo, Young Bum; Jong Lee, Se; Baik, Hong Koo; Song, Kie Moon

2016-01-01

We introduce an easy process for the fabrication of solution-processed indium oxide (InO) thin film transistors (TFTs) by heating a precursor solution. InO TFTs fabricated from solutions of an InO precursor heated at 90 °C had the highest mobility of 4.61 cm2 V-1 s-1 after being annealed at 200 °C. When the InO precursor solution is heated, HNO3 may be thermally evaporated in the InO precursor solution. Nitrogen atoms can disrupt hydrolysis and condensation reactions. An InO thin film deposited from a solution of the heated InO precursor is advantageous for hydrolysis and condensation reactions due to the absence of nitrogen atoms.

Enhanced Performance of Perovskite CH3NH3PbI3 Solar Cell by Using CH3NH3I as Additive in Sequential Deposition.

PubMed

Xie, Yian; Shao, Feng; Wang, Yaoming; Xu, Tao; Wang, Deliang; Huang, Fuqiang

2015-06-17

Sequential deposition is a widely adopted method to prepare CH3NH3PbI3 on mesostructured TiO2 electrode for organic lead halide perovskite solar cells. However, this method often suffers from the uncontrollable crystal size, surface morphology, and residual PbI2 in the resulting CH3NH3PbI3, which are all detrimental to the device performance. We herein present an optimized sequential solution deposition method by introducing different amount of CH3NH3I in PbI2 precursor solution in the first step to prepare CH3NH3PbI3 absorber on mesoporous TiO2 substrates. The addition of CH3NH3I in PbI2 precursor solution can affect the crystallization and composition of PbI2 raw films, resulting in the variation of UV-vis absorption and surface morphology. Proper addition of CH3NH3I not only enhances the absorption but also improves the efficiency of CH3NH3PbI3 solar cells from 11.13% to 13.37%. Photoluminescence spectra suggest that the improvement of device performance is attributed to the decrease of recombination rate of carriers in CH3NH3PbI3 absorber. This current method provides a highly repeatable route for enhancing the efficiency of CH3NH3PbI3 solar cell in the sequential solution deposition method.

In situ characterization of uranium and americium oxide solid solution formation for CRMP process: first combination of in situ XRD and XANES measurements.

PubMed

Caisso, Marie; Picart, Sébastien; Belin, Renaud C; Lebreton, Florent; Martin, Philippe M; Dardenne, Kathy; Rothe, Jörg; Neuville, Daniel R; Delahaye, Thibaud; Ayral, André

2015-04-14

Transmutation of americium in heterogeneous mode through the use of U1-xAmxO2±δ ceramic pellets, also known as Americium Bearing Blankets (AmBB), has become a major research axis. Nevertheless, in order to consider future large-scale deployment, the processes involved in AmBB fabrication have to minimize fine particle dissemination, due to the presence of americium, which considerably increases the risk of contamination. New synthesis routes avoiding the use of pulverulent precursors are thus currently under development, such as the Calcined Resin Microsphere Pelletization (CRMP) process. It is based on the use of weak-acid resin (WAR) microspheres as precursors, loaded with actinide cations. After two specific calcinations under controlled atmospheres, resin microspheres are converted into oxide microspheres composed of a monophasic U1-xAmxO2±δ phase. Understanding the different mechanisms during thermal conversion, that lead to the release of organic matter and the formation of a solid solution, appear essential. By combining in situ techniques such as XRD and XAS, it has become possible to identify the key temperatures for oxide formation, and the corresponding oxidation states taken by uranium and americium during mineralization. This paper thus presents the first results on the mineralization of (U,Am) loaded resin microspheres into a solid solution, through in situ XAS analysis correlated with HT-XRD.

The low temperature synthesis, characterization and properties of ferroelectrics

NASA Astrophysics Data System (ADS)

Xu, Jie

2000-10-01

PZT 50:50 xerogels prepared by two different sol-gel routes crystallized in a similar fashion to give a mixture of tetragonal and rhombohedral at high temperature (1000°C). Both the diffraction and EXAFS data suggest that the compositional inhomogeneity of the samples prepared by the two routes is similar. The crystallization of CZT gels is complicated. Crystalline CaCO 3 was always detected in the dry gels regardless of the sample composition and preparation methods. At intermediate temperatures a fluorite related phase was always formed and it transformed to perovskite at higher temperatures. The EXAFS data suggest that perovskite CZT samples prepared using alkoxide sol-gel chemistry may not be random solid solutions. All the solution processed ZrTiO4 materials crystallized in the range 600--700°C. The KTN samples prepared using a conventional alkoxide sol-gel route crystallized completely to perovskite at lower temperatures than those prepared using prehydrolyzed precursors. The EXAFS data for the KTN samples prepared using a conventional alkoxide sol-gel route are consistent with a random distribution of tantalum and niobium in the solid solution. However, materials prepared using the inhomogeneous sol-gel route and by the direct reaction of mixed oxides were shown to be compositionally inhomogeneous. The heterogeneity could not be removed by regrinding and heating the mixed oxide samples several times. K2Ta4-xNbxO11 (x = 0, 2, 4) samples were prepared using alkoxide sol-gel chemistry and their crystallization was examined by powder X-ray diffraction. A Rietveld structure analysis of the pyrochlore formed from a gel with bulk composition K2Ta 2Nb2O11 indicated that it was rich in potassium relative to the bulk sample. On heating to high temperatures tetragonal tungsten bronzes were formed. A Rietveld analysis was also performed for K2Ta 2Nb2O11 with tetragonal tungsten bronze structure. The defect pyrochlores "AgTaO3" and GaTaO 3 were synthesized by ion-exchange using pyrochlore KTaO3 as a starting material. The structures of the pyrochlores were examined using the Rietveld method. The pyrochlore-to-perovskite transformations were also explored.

Zinc oxide films chemically grown onto rigid and flexible substrates for TFT applications

NASA Astrophysics Data System (ADS)

Suchea, M.; Kornilios, N.; Koudoumas, E.

2010-10-01

This contribution presents some preliminary results regarding the use of a chemical route for the growth of good quality ZnO thin films that can be used for the fabrication of thin film transistors (TFTs). The films were grown at rather low temperature (60 °C) on glass and PET substrates using non-aqueous (zinc acetate dihydrate in methanol) precursor solution and their surface morphology, crystalline structure, optical transmittance and electrical characteristics were studied. The study indicated that good quality films with desirable ZnO structure onto rigid and flexible substrates can be obtained, using a simple, cheap, low temperature chemical growth method.

The effect of precursor on the optical properties of carbon quantum dots synthesized by hydrothermal/solvothermal method

NASA Astrophysics Data System (ADS)

Mozdbar, Afsaneh; Nouralishahi, Amideddin; Fatemi, Shohreh; Mirakhori, Ghazaleh

2018-01-01

In the recent decade, Carbon Quantum Dots (CQDs) have attracted lots of attention due to their excellent properties such as tunable photoluminescence, high chemical stability, low toxicity, and biocompatibility. Among all synthesis methods, the hydrothermal/solvothermal rout has been considered as one of the most common and simplest method. The type of precursors can affect the size of CQDs and determine their surface functional groups, the essential properties that deeply influence the optical specifications. In this work, the effect of different precursors on the final properties of carbon quantum dots is investigated. The carbon quantum dots were synthesized by hydrothermal/solvothermal rout using citric acid, thiourea, ethylamine and monoethanolamine as precursors in almost the same conditions of time and temperature. Resultant CQDs were characterized by using FTIR, UV-Visible Spectroscopy and Photoluminescence (PL) analysis. The results of UV-Vis spectroscopy showed that quantum dots synthesized from monoethanolamine have wider absorption band rather than the CQDs from other precursors and the absorption edge shifted from about 270 nm for ethylamine to about 470 nm in monoethanolamine. Furthermore, the results demonstrate that using citric acid and monoethanolamine as precursor improved production efficiency and emission quantum yield of the carbon dots.

Solution-Processed Solar Cells via Nanocrystal Inks and Molecular Solutions

NASA Astrophysics Data System (ADS)

Miskin, Caleb K.

On February 15, 2008 the National Academy of Engineering unveiled their fourteen grand challenges of engineering for the 21st century. At the top of the list and voted by the public as the most important challenge was the thrust to make solar energy economical. My research has been dedicated to solving this millennial challenge by developing routes to high-efficiency, solution-processed photovoltaics (PV) for low-cost and low-energy manufacturing. My research has primarily advanced two methods for solution processed PV. In one method, semiconducting nanocrystals are synthesized and then suspended in an appropriate solvent to form an ink. The ink is then applied to a substrate by a variety of high-throughput methods such as spray coating or doctor blading and then annealed to form a polycrystalline absorber layer for solar energy. I have applied this method with great success to Cu2ZnSnS 4, a promising earth-abundant, non-toxic semiconductor. A challenge with this material is its propensity to form binary and ternary undesired phases. Using advanced nano-characterization techniques, my colleagues and I have been able to determine the spatially resolved composition of these nanoparticles and have found them to be highly non-uniform. In addition, I developed synthesis techniques aimed at controlling the nucleation and growth of this material to improve nanocrystal compositional homogeneity. Though particles produced in this work still exhibit some non-uniformities, they are greatly improved. When combined with optimized fabrication techniques, I have been able to advance the efficiency of nanocrystal ink based solar cells of CZTS from 7.2 to 9.0 percent in our lab. Another promising route to solution-processed PV is by directly coating molecular precursor solutions (rather than first forming nanocrystals) and annealing the coating to form the polycrystalline solar absorber layer. Unfortunately, a major challenge is that many metals, metal salts, and chalcogens that would be useful precursors to such films have poor solubility in organic solvents compatible with roll-to-roll manufacturing techniques. Interestingly, we have found that mixtures of commonly available thiols and amines are able to dissolve at room temperature and pressure a host of metals and salts that are otherwise insoluble in either solvent by itself. In this work, I have primarily focused on CdTe--which has been by far the most successful technology in terms of production cost ($/peak watt) and energy payback time for thin-film solar cells. In this research thrust I demonstrate for the first time the fabrication of CdTe thin-films via a solution-processed molecular precursor approach by dissolving CdCl2 and Te in ethylenediamine and 1-propanethiol. The films are formed by spin-coating thin layers of the solution and then annealing each layer until a 1.5 mum thick film is achieved. I have achieved 0.5% efficient devices by this method. As thiol-amine mixtures have the potential to leave residual sulfur in these films, other novel solvent systems are presented as future work. While amine-thiol mixtures are excellent solvents for many materials, they do not dissolve lead chalcogenides with ease. I leverage this to develop room-temperature synthesis routes to PbS, PbSe, PbTe, and PbSxSe 1-x nanoparticles. This is achieved by mixing a lead salt dissolved in thiol-amine with a chalcogen dissolved in thiol-amine at room temperature. We find that when particles produced in this manner are pressed into pellets, they show comparable thermoelectric performance to more complicated and energy intensive synthesis techniques. Ultimately, we wish to enable the use of these particles in room-temperature fabricated quantum dot solar cells. This requires the synthesis of highly monodisperse, stable colloids and is the subject of future work using thiol-amine mixtures and related aqueous analogues.

Controlled fabrication of semiconductor-metal hybrid nano-heterostructures via site-selective metal photodeposition

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

Vela Becerra, Javier; Ruberu, T. Purnima A.

A method of synthesizing colloidal semiconductor-metal hybrid heterostructures is disclosed. The method includes dissolving semiconductor nanorods in a solvent to form a nanorod solution, and adding a precursor solution to the nanorod solution. The precursor solution contains a metal. The method further includes illuminating the combined precursor and nanorod solutions with light of a specific wavelength. The illumination causes the deposition of the metal in the precursor solution onto the surface of the semiconductor nanorods.

High-efficiency Thin-film Fe 2SiS 4 and Fe 2GeS 4-based Solar Cells Prepared from Low-Cost Solution Precursors. Final Report

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

Radu, Daniela Rodica; Liu, Mimi; Hwang, Po-yu

The project aimed to provide solar energy education to students from underrepresented groups and to develop a novel, nano-scale approach, in utilizing Fe 2SiS 4 and Fe 2GeS 4 materials as precursors to the absorber layer in photovoltaic thin-film devices. The objectives of the project were as follows: 1. Develop and implement one solar-related course at Delaware State University and train two graduate students in solar research. 2. Fabricate and characterize high-efficiency (larger than 7%) Fe 2SiS 4 and Fe 2GeS 4-based solar devices. The project has been successful in both the educational components, implementing the solar course at DSUmore » as well as in developing multiple routes to prepare the Fe 2GeS 4 with high purity and in large quantities. The project did not meet the efficiency objective, however, a functional solar device was demonstrated.« less

Preparation of Mesoporous Ceramics from Polymer Nanotubes

NASA Astrophysics Data System (ADS)

Chen, Dian; Park, Soojin; Chen, Jiun-Tai; Redston, Emily; Russell, Thomas

2009-03-01

Poly(styrene-b-4-vinylpyridine) (PS-b-P4VP) nanotubes were prepared by placing polymer solution into the cylindrical nanopores of an anodic aluminum oxide (AAO) membrane. The PS-b-P4VP nanotubes within the AAO membranes were exposed to tetrahydrofuran vapor to produce uniform spherical micelles along the tube. The tubes were removed from the membranes, then suspended in ethylene glycol, a preferential solvent for P4VP. At 95^ oC, near the glass transition temperature (Tg) of PS, nanotubes with uniform nanopores were obtained by a reconstruction of the nanotubes. As the temperature was increased, mesoporous polymer structures were obtained. Tetraethyl orthosilicate or titanium tetraethoxide, ceramic precursors, were introduced into the 4VP microdomains. After exposure to an oxygen plasma or high temperature, the copolymer was removed and the precursor converted to a mesoporous ceramic. This process offers a simple route for the fabrication of tunable mesoporous ceramic or metallic structures by changing molecular weight of copolymers.

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).

Screen-Printing of ZnO Nanostructures from Sol-Gel Solutions for Their Application in Dye-Sensitized Solar Cells.

PubMed

Sarkar, Kuhu; Braden, Erik V; Bonke, Shannon A; Bach, Udo; Müller-Buschbaum, Peter

2015-08-24

Diblock copolymers have been used in sol-gel synthesis to successfully tailor the nanoscale morphology of thin ZnO films. As the fabrication of several-micron-thick mesoporous films such as those required in dye-sensitized solar cells (DSSCs) was difficult with this approach, we exploited the benefits of diblock-copolymer-directed synthesis that made it compatible with screen printing. The simple conversion of the diblock copolymer ZnO precursor sol to a screen-printing paste was not possible as it resulted in poor film properties. To overcome this problem, an alternative route is proposed in which the diblock copolymer ZnO precursor sol is first blade coated and calcined, then converted to a screen-printing paste. This allows the benefits of diblock-copolymer-directed particle formation to be compatible with printing methods. The morphologies of the ZnO nanostructures were studied by SEM and correlated with the current density-voltage characteristics. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Metal sulfide and rare-earth phosphate nanostructures and methods of making same

DOEpatents

Wong, Stanislaus; Zhang, Fen

2014-05-13

The present invention provides a method of producing a crystalline metal sulfide nanostructure. The metal is a transitional metal or a Group IV metal. In the method, a porous membrane is placed between a metal precursor solution and a sulfur precursor solution. The metal cations of the metal precursor solution and sulfur ions of the sulfur precursor solution react, thereby producing a crystalline metal sulfide nanostructure.

Incorporating technetium in minerals and other solids: A review

NASA Astrophysics Data System (ADS)

Luksic, Steven A.; Riley, Brian J.; Schweiger, Michael; Hrma, Pavel

2015-11-01

Technetium (Tc) can be incorporated into a number of different solids including spinel, sodalite, rutile, tin dioxide, pyrochlore, perovskite, goethite, layered double hydroxides, cements, and alloys. Synthetic routes are possible for each of these phases, ranging from high-temperature ceramic sintering to ball-milling of constituent oxides. However, in practice, Tc has only been incorporated into solid materials by a limited number of the possible syntheses. A review of the diverse ways in which Tc-immobilizing materials can be made shows the wide range of options available. Special consideration is given to hypothetical application to the Hanford Tank Waste and Vitrification Plant, such as adding a Tc-bearing mineral to waste glass melter feed. A full survey of solid Tc waste forms, the common synthesis routes to those waste forms, and their potential for application to vitrification processes are presented. The use of tin dioxide or ferrite spinel precursors to reduce Tc(VII) out of solution and into a durable form are shown to be of especially high potential.

Synthesis of quaternary chalcogenide CZTS nanoparticles by a hydrothermal route

NASA Astrophysics Data System (ADS)

Das, S.; Sa, K.; Mahakul, P. C.; Raiguru, J.; Alam, I.; Subramanyam, BVRS; Mahanandia, P.

2018-03-01

Cu2ZnSnS4 (CZTS) has emerged as a potential absorber towards inorganic photovoltaic device application for its outstanding properties like non toxicity, earth abundancy nature, optimal band gap matched with solar spectrum (1.45- 1.65eV), high absorption coefficient (104cm‑1). Here, a low cost, environment friendly facile hydrothermal route to synthesize phase pure CZTS nanoparticles using Cu (II), Zn (II), Sn (II) inorganic metal salts and thiourea as Sulphur source in distilled water solution as precursor is reported. The as synthesized samples characterized by X-Ray diffraction (XRD) and RAMAN confirmed structure and phase of CZTS nanocrystals. The morphology of the prepared CZTS have been characterized by scanning electron microscopy (SEM). The particle size is found in the range 4-5 nm with crystalline nature have been characterized by transmission electron microscope (TEM). The optical band gap of the as prepared samples is calculated to be 1.65eV from UV-Visible analysis which proves it can be used towards photovoltaic applications.

Precursor-controlled synthesis of hierarchical ZnO nanostructures, using oligoaniline-coated Au nanoparticle seeds

NASA Astrophysics Data System (ADS)

Krishnan, Deepti; Pradeep, T.

2009-07-01

Shape-selected synthesis of a large number of zinc oxide (ZnO) nano- and microstructures was achieved by the seed-mediated growth of oligoaniline-coated gold nanoparticle precursors. Distinctive ZnO structures such as nanoplates, nanospheres, microstars, microflowers, microthorns and micromultipods were synthesized by this method. Slightly different shapes were obtained in the absence of the seed solution. This is a fast, low temperature (60 °C) and biomimetic route to make a wide variety of structures. The structure and morphology of the nanostructures were studied by transmission electron microscopy (TEM) and scanning electron microscopy (SEM), respectively. Raman spectroscopy, Fourier-transform infrared (FTIR) spectroscopy and X-ray diffraction (XRD) were utilized for the characterization of the nanostructures. A growth mechanism for these nanostructures was proposed based on these results. The concentrations of the reacting species were the main parameter causing the changes in the morphologies. The variation in morphologies of these structures is believed to be due to the ability of the seed solution as well as polyvinylpyrrolidone (PVP) to selectively suppress/depress the growth of certain planes, allowing growth to occur only in certain specific directions. Changes in the amount of growth nuclei with varying sodium hydroxide (NaOH) concentration is also seen to affect the morphology of these structures.

Synthesis of Magnetic Rattle-Type Silica with Controllable Magnetite and Tunable Size by Pre-Shell-Post-Core Method.

PubMed

Chen, Xue; Tan, Longfei; Meng, Xianwei

2016-03-01

In this study, we have developed the pre-shell-post-core route to synthesize the magnetic rattle-type silica. This method has not only simplified the precursor's process and reduced the reacting time, but also ameliorated the loss of magnetite and made the magnetite content and the inner core size controllable and tunable. The magnetite contents and inner core size can be easily controlled by changing the type and concentration of alkali, reaction system and addition of water. The results show that alkali aqueous solution promotes the escape of the precursor iron ions from the inner space of rattle-type silica and results in the loss of magnetite. In this case, NaOH ethanol solution is better for the formation of magnetite than ammonia because it not only offers an appropriate alkalinity to facilitate the synthesis of. magnetic particles, but also avoids the escape of the iron ions from the mesopores of rattle-type silica. The synthesis process is very simple and efficient, and it takes no more than 2 hours to complete the total preparation and handling of the magnetic rattle-type silica. The end-product Fe3O4@SiO2 nanocomposites also have good magnetic properties which will perform potential application in biomedical science.

Crystallization of perovskite film using ambient moisture and water as co-solvent for efficient planar perovskite solar cell (Conference Presentation)

NASA Astrophysics Data System (ADS)

Dubey, Ashish; Reza, Khan M.; Gaml, Eman; Adhikari, Nirmal; Qiao, Qiquan

2016-09-01

Smooth, compact and defect free morphology of perovskite is highly desired for enhanced device performance. Several routes such as thermal annealing, use of solvent mixtures, growth under controlled humidity has been adopted to obtain crystalline, smooth and defect free perovskite film. Herein we showed direct use of water (H2O) as co-solvent in precursor solution and have optimized the water content required to obtain smooth and dense film. Varying concentration of water was used in precursor solution of CH3NH3I and PbI2 mixed in γ-butyrolactone (GBL) and dimethylsulfoxide (DMSO). Perovskite films were crystallized using toluene assisted solvent engineering method using GBL:DMSO:H2O as solvent mixture. The amount of water was varied from 1% to 25%, which resulted in change in film morphology and perovskite crystallinity. It was concluded that an appropriate amount of water is required to assist the crystallization process to obtain smooth pin-hole free morphology. The change in morphology led to improved fill factor in the device, with highest efficiency 14%, which was significantly higher than devices made from perovskite film without adding water. We also showed that addition of up to 25% by volume of water does not significantly change the device performance.

Ultrasound-assisted fabrication of nanoporous CdS films.

PubMed

Singh, R S; Sanagapalli, S; Jayaraman, V; Singh, V P

2004-01-01

A new method for fabricating nanoporous CdS films is reported. It involves exposing the CdS solution with ultrasound waves during the process of dip coating. Indium tin oxide (ITO)-coated glass and plastic (commercial transparency) were used as substrates. In each case three different precursors were used for dip coating. The precursors used were CdCl2 and thiourea in one case and CdS nanoparticles prepared by sonochemical and microwave-assisted methods in the other two cases. X-ray diffraction studies performed on these powders show a phase corresponding to cubic CdS. The Field Emission Scanning Electron Microscopy (FE-SEM) images of the films on plastic showed uniform pores with a diameter of 80 nm for all three methods. Optical absorption measurements indicated a blue shift and multiple peaks in the absorption curve. The FE-SEM observations of the films on an ITO/glass substrate indicated a crystalline film with voids. The UV-vis absorption results indicated a blue shift in the absorption with an absorption edge at 435, 380, and 365 nm for CdS films made by solution growth, sonochemical, and microwave routes, respectively. The magnitude of the absorption is dependent on film thickness, and the observed blue shift in the absorption can be explained on the basis of quantum confinement effects.

Microscopic mechanism of nanocrystal formation from solution by cluster aggregation and coalescence

PubMed Central

Hassan, Sergio A.

2011-01-01

Solute-cluster aggregation and particle fusion have recently been suggested as alternative routes to the classical mechanism of nucleation from solution. The role of both processes in the crystallization of an aqueous electrolyte under controlled salt addition is here elucidated by molecular dynamics simulation. The time scale of the simulation allows direct observation of the entire crystallization pathway, from early events in the prenucleation stage to the formation of a nanocrystal in equilibrium with concentrated solution. The precursor originates in a small amorphous aggregate stabilized by hydration forces. The core of the nucleus becomes crystalline over time and grows by coalescence of the amorphous phase deposited at the surface. Imperfections of ion packing during coalescence promote growth of two conjoint crystallites. A parameter of order and calculated cohesive energies reflect the increasing crystalline order and stress relief at the grain boundary. Cluster aggregation plays a major role both in the formation of the nucleus and in the early stages of postnucleation growth. The mechanism identified shares common features with nucleation of solids from the melt and of liquid droplets from the vapor. PMID:21428633

Preparation, Structural Characterization and Magnetic Properties of La-SUBSTITUTED co Ferrites via a Modified Citrate Precursor Route

NASA Astrophysics Data System (ADS)

Ai, Lunhong; Jiang, Jing

CoLaxFe2-xO4 (x = 0.00, 0.05 and 0.1) nanoparticles were prepared simply by a modified citrate precursor route. Effects of La-substituting level on the their magnetic properties were investigated on the basis of the structural analysis. The thermal evolution of the precursor, as well as the microstructure of as-prepared products were studied by means of a thermogravimetric analyzer (TGA), X-ray diffractometer (XRD) and Fourier transform infrared (FTIR) spectrometer. The magnetic properties of the as-prepared samples were measured using a vibrating sample magnetometer (VSM). It was found that the magnetic properties were dependent on many factors such as La-substituting level, particle size and microstructure. The observed saturation magnetization decreased with increasing La content, whereas coercivity exhibited reverse behavior.

Precursor of transition to turbulence: spatiotemporal wave front.

PubMed

Bhaumik, S; Sengupta, T K

2014-04-01

To understand transition to turbulence via 3D disturbance growth, we report here results obtained from the solution of Navier-Stokes equation (NSE) to reproduce experimental results obtained by minimizing background disturbances and imposing deterministic excitation inside the shear layer. A similar approach was adopted in Sengupta and Bhaumik [Phys. Rev. Lett. 107, 154501 (2011)], where a route of transition from receptivity to fully developed turbulent stage was explained for 2D flow in terms of the spatio-temporal wave-front (STWF). The STWF was identified as the unit process of 2D turbulence creation for low amplitude wall excitation. Theoretical prediction of STWF for boundary layer was established earlier in Sengupta, Rao, and Venkatasubbaiah [Phys. Rev. Lett. 96, 224504 (2006)] from the Orr-Sommerfeld equation as due to spatiotemporal instability. Here, the same unit process of the STWF during transition is shown to be present for 3D disturbance field from the solution of governing NSE.

Emulsion Synthesis of Size-Tunable CH3NH3PbBr3 Quantum Dots: An Alternative Route toward Efficient Light-Emitting Diodes.

PubMed

Huang, Hailong; Zhao, Fangchao; Liu, Lige; Zhang, Feng; Wu, Xian-gang; Shi, Lijie; Zou, Bingsuo; Pei, Qibing; Zhong, Haizheng

2015-12-30

We report a facile nonaqueous emulsion synthesis of colloidal halide perovskite quantum dots by controlled addition of a demulsifier into an emulsion of precursors. The size of resulting CH3NH3PbBr3 quantum dots can be tuned from 2 to 8 nm by varying the amount of demulsifier. Moreover, this emulsion synthesis also allows the purification of these quantum dots by precipitation from the colloidal solution and obtains solid-state powder which can be redissolved for thin film coating and device fabrication. The photoluminescence quantum yields of the quantum dots is generally in the range of 80-92%, and can be well-preserved after purification (∼80%). Green light-emitting diodes fabricated comprising a spin-cast layer of the colloidal CH3NH3PbBr3 quantum dots exhibited maximum current efficiency of 4.5 cd/A, power efficiency of 3.5 lm/W, and external quantum efficiency of 1.1%. This provides an alternative route toward high efficient solution-processed perovskite-based light-emitting diodes. In addition, the emulsion synthesis is versatile and can be extended for the fabrication of inorganic halide perovskite colloidal CsPbBr3 nanocrystals.

Final Report for Grant "Direct Writing via Novel Aromatic Ladder Polymer Precursors"

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

C. B. Gorman

2010-10-29

This report describes activities and findings under the above entitled grant. These pertain to the development of new synthetic routes to novel precursor polymers and oligomers that are applicable for conversion from electrical insulators to electrical conductors under the application of light (e.g. direct photolithographic writing)

A facile route to synthesize nanogels doped with silver nanoparticles

NASA Astrophysics Data System (ADS)

Coll Ferrer, M. Carme; Ferrier, Robert C.; Eckmann, David M.; Composto, Russell J.

2013-01-01

In this study, we describe a simple method to prepare hybrid nanogels consisting of a biocompatible core-shell polymer host containing silver nanoparticles. First, the nanogels (NG, 160 nm) containing a lysozyme rich core and a dextran rich shell, are prepared via Maillard and heat-gelation reactions. Second, silver nanoparticles (Ag NPs, 5 nm) are synthesized "in situ" in the NG solution without requiring additional reducing agents. This approach leads to stable Ag NPs located in the NG. Furthermore, we demonstrate that the amount of Ag NPs in the NG can be tuned by varying silver precursor concentration. Hybrid nanogels with silver nanoparticles have potential in antimicrobial, optical, and therapeutic applications.

Diazonium cation-exchanged clay: an efficient, unfrequented route for making clay/polymer nanocomposites.

PubMed

Salmi, Zakaria; Benzarti, Karim; Chehimi, Mohamed M

2013-11-05

We describe a simple, off-the-beaten-path strategy for making clay/polymer nanocomposites through tandem diazonium salt interface chemistry and radical photopolymerization. Prior to photopolymerization, sodium montmorillonite (MMT) was ion exchanged with N,N'-dimethylbenzenediazonium cation (DMA) from the tetrafluoroborate salt precursor. DMA acts as a hydrogen donor for benzophenone in solution; this pair of co-initiators permits us to photopolymerize glycidyl methacrylate (GMA) between the lamellae of the diazonium-modified clay, therefore providing intercalated MMT-PGMA nanocomposites with an onset of exfoliation. This work conclusively provides a new approach for bridging reactive and functional polymers to layered nanomaterials via aryl diazonium salts in a simple, fast, efficient cation-exchange approach.

Evolution of Iodoplumbate Complexes in Methylammonium Lead Iodide Perovskite Precursor Solutions

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

Sharenko, Alexander; Mackeen, Cameron; Jewell, Leila

Here in this study we investigate the local structure present in single-step precursor solutions of methylammonium lead iodide (MAPbI 3) perovskite as a function of organic and inorganic precursor ratio, as well as with hydriodic acid (HI), using X-ray absorption spectroscopy. An excess of organic precursor as well as the use of HI as a processing additive has been shown to lead to the formation of smooth, continuous, pinhole free MAPbI 3 films, whereas films produced from precursor solutions containing molar equivalents of methylammonium iodide (MAI) and PbI 2 lead to the formation of a discontinuous, needlelike morphology. We nowmore » show that as the amount of excess MAI in the precursor solution is increased, the iodide coordination of iodoplumbate complexes present in solution increases. The use of HI results in a similar increase in iodide coordination. We therefore offer insight into how solution chemistry can be used to control MAPbI 3 thin film morphology by revealing a strong correlation between the lead coordination chemistry in precursor solutions and the surface coverage and morphology of the resulting MAPbI 3 film.« less

Evolution of Iodoplumbate Complexes in Methylammonium Lead Iodide Perovskite Precursor Solutions

DOE PAGES

Sharenko, Alexander; Mackeen, Cameron; Jewell, Leila; ...

2017-02-02

Here in this study we investigate the local structure present in single-step precursor solutions of methylammonium lead iodide (MAPbI 3) perovskite as a function of organic and inorganic precursor ratio, as well as with hydriodic acid (HI), using X-ray absorption spectroscopy. An excess of organic precursor as well as the use of HI as a processing additive has been shown to lead to the formation of smooth, continuous, pinhole free MAPbI 3 films, whereas films produced from precursor solutions containing molar equivalents of methylammonium iodide (MAI) and PbI 2 lead to the formation of a discontinuous, needlelike morphology. We nowmore » show that as the amount of excess MAI in the precursor solution is increased, the iodide coordination of iodoplumbate complexes present in solution increases. The use of HI results in a similar increase in iodide coordination. We therefore offer insight into how solution chemistry can be used to control MAPbI 3 thin film morphology by revealing a strong correlation between the lead coordination chemistry in precursor solutions and the surface coverage and morphology of the resulting MAPbI 3 film.« less

Soft chemistry routes to GeS2 nanoparticles

NASA Astrophysics Data System (ADS)

Courthéoux, Laurence; Mathiaud, Romain; Ribes, Michel; Pradel, Annie

2018-04-01

Spherical GeS2 particles are prepared by a low temperature liquid route with TEOG as germanium precursor and either H2S or thioacetamide (TAA) as sulfur precursors. The size and agglomeration of the particles change depending upon the temperature and nature of the solvent. Most synthesis lead to preparing amorphous GeS2. When the reaction kinetic is slowed down by using TAA at 25 °C, the obtained GeS2 product presents a larger order in the range of few Å as proven by Raman spectroscopy, even though it is still an amorphous compound as suggested by X-Ray diffraction and TEM experiments.

A New Commercializable Route for the Preparation of Single-Source Precursors for Bulk, Thin-Film, and Nanocrystallite I-III-IV Semiconductors

NASA Technical Reports Server (NTRS)

Banger, Kulbinder K.; Jin, Michael H. C.; Harris, Jerry D.; Fanwick, Philip E.; Hepp, Aloysius F.

2004-01-01

We report a new simplified synthetic procedure for commercial manufacture of ternary single source precursors (SSP). This new synthetic process has been successfully implemented to fabricate known SSPs on bulk scale and the first liquid SSPs to the semiconductors CuInSe2 and AgIn(x)S(y). Single crystal X-ray determination reveals the first unsolvated ternary AgInS SSP. SSPs prepared via this new route have successfully been used in a spray assisted chemical vapor deposition (CVD) process to deposit polycrystalline thin films, and for preparing ternary nanocrystallites.

Role of precursor chemistry in the direct fluorination to form titanium based conversion anodes for lithium ion batteries

DOE PAGES

Adcock, Jamie; Dai, Sheng; Veith, Gabriel M.; ...

2015-10-13

In this study, a new synthetic route for the formation of titanium oxydifluoride (TiOF 2) through the process of direct fluorination via a fluidized bed reactor system and the associated electrochemical properties of the powders formed from this approach are reported. The flexibility of this synthetic route was demonstrated using precursor powders of titanium dioxide (TiO 2) nanoparticles, as well as a reduced TiO xN y. An advantage of this synthetic method is the ability to directly control the extent of fluorination as a function of reaction temperature and time. The reversible capacity of TiOF 2 anodes was found tomore » depend greatly upon the precursor employed. The TiOF 2 synthesized from TiO 2 and TiO xN y showed reversible capacities of 300 mAh g -1 and 440 mAh g -1, respectively, over 100 cycles. The higher reversible capacity of the TiOF 2 powders derived from TiO xN y likely relate to the partial reduction of the Ti in the fluorinated electrode material, highlighting a route to optimize the properties of conversion electrode materials.« less

Obtaining aluminas from the thermal decomposition of their different precursors: An {sup 27}Al MAS NMR and X-ray powder diffraction studies

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

Chagas, L.H.; De Carvalho, G.S.G.; San Gil, R.A.S.

2014-01-01

Graphical abstract: - Highlights: • We synthesized three precursors of alumina from different methods. • The calcination of the precursors generated several alumina polymorphs. • XRD and NMR were used for structural investigation of the polymorphs. • The synthesis route determines the structural and textural properties of the solids. - Abstract: A commercial sample of Boehmite was used as precursor of alumina polymorphs. For comparison, three other precursors were synthesized from different methods. Particularly, the use of excess of urea promoted a very crystalline form of basic aluminum carbonate. The characteristics of the four precursors were investigated by thermal, vibrationalmore » and X-ray powder diffraction (XRD) analysis. Additionally, the nuclear magnetic resonance, with magic angle spinning ({sup 27}Al MAS NMR), was used to verify the coordination of aluminum cations. Each precursor was calcined at various temperatures generating alumina polymorphs, which were structurally analyzed by XRD and {sup 27}Al MAS NMR. Due to interest in catalysis supports, special attention was given to the γ-Al{sub 2}O{sub 3} phase, which in addition to structural investigation was subjected to textural analysis. The results showed that, from different synthesis procedures and common route of calcination, one can obtain materials with the same composition but with different structural and textural properties, which in turn can significantly influence the performance of a supported catalyst.« less

Pathways and Subcellular Compartmentation of NAD Biosynthesis in Human Cells

PubMed Central

Nikiforov, Andrey; Dölle, Christian; Niere, Marc; Ziegler, Mathias

2011-01-01

NAD is a vital redox carrier, and its degradation is a key element of important regulatory pathways. NAD-mediated functions are compartmentalized and have to be fueled by specific biosynthetic routes. However, little is known about the different pathways, their subcellular distribution, and regulation in human cells. In particular, the route(s) to generate mitochondrial NAD, the largest subcellular pool, is still unknown. To visualize organellar NAD changes in cells, we targeted poly(ADP-ribose) polymerase activity into the mitochondrial matrix. This activity synthesized immunodetectable poly(ADP-ribose) depending on mitochondrial NAD availability. Based on this novel detector system, detailed subcellular enzyme localizations, and pharmacological inhibitors, we identified extracellular NAD precursors, their cytosolic conversions, and the pathway of mitochondrial NAD generation. Our results demonstrate that, besides nicotinamide and nicotinic acid, only the corresponding nucleosides readily enter the cells. Nucleotides (e.g. NAD and NMN) undergo extracellular degradation resulting in the formation of permeable precursors. These precursors can all be converted to cytosolic and mitochondrial NAD. For mitochondrial NAD synthesis, precursors are converted to NMN in the cytosol. When taken up into the organelles, NMN (together with ATP) serves as substrate of NMNAT3 to form NAD. NMNAT3 was conclusively localized to the mitochondrial matrix and is the only known enzyme of NAD synthesis residing within these organelles. We thus present a comprehensive dissection of mammalian NAD biosynthesis, the groundwork to understand regulation of NAD-mediated processes, and the organismal homeostasis of this fundamental molecule. PMID:21504897

Performance improvement for solution-processed high-mobility ZnO thin-film transistors

NASA Astrophysics Data System (ADS)

Sha Li, Chen; Li, Yu Ning; Wu, Yi Liang; Ong, Beng S.; Loutfy, Rafik O.

2008-06-01

The fabrication technology of stable, non-toxic, transparent, high performance zinc oxide (ZnO) thin-film semiconductors via the solution process was investigated. Two methods, which were, respectively, annealing a spin-coated precursor solution and annealing a drop-coated precursor solution, were compared. The prepared ZnO thin-film semiconductor transistors have well-controlled, preferential crystal orientation and exhibit superior field-effect performance characteristics. But the ZnO thin-film transistor (TFT) fabricated by annealing a drop-coated precursor solution has a distinctly elevated linear mobility, which further approaches the saturated mobility, compared with that fabricated by annealing a spin-coated precursor solution. The performance of the solution-processed ZnO TFT was further improved when substituting the spin-coating process by the drop-coating process.

A general approach to one-pot fabrication of crumpled graphene-based nanohybrids for energy applications.

PubMed

Mao, Shun; Wen, Zhenhai; Kim, Haejune; Lu, Ganhua; Hurley, Patrick; Chen, Junhong

2012-08-28

Crumpled graphene oxide (GO)/graphene is a new type of carbon nanostructure that has drawn growing attention due to its three-dimensional open structure and excellent stability in an aqueous solution. Here we report a general and one-step approach to produce crumpled graphene (CG)-nanocrystal hybrids, which are produced by direct aerosolization of a GO suspension mixed with precursor ions. Nanocrystals spontaneously grow from precursor ions and assemble on both external and internal surfaces of CG balls during the solvent evaporation and GO crumpling process. More importantly, CG-nanocrystal hybrids can be directly deposited onto various current-collecting substrates, enabling their tremendous potential for energy applications. As a proof of concept, we demonstrate the use of hybrid electrodes of CG-Mn(3)O(4) and CG-SnO(2) in an electrochemical supercapacitor and a lithium-ion battery, respectively. The performance of the resulting capacitor/battery is attractive and outperforms conventional flat graphene-based hybrid devices. This study provides a new and facile route to fabricating high-performance hybrid CG-nanocrystal electrodes for various energy systems.

Effect of pH on film structure and electrical property of PMMA-Au composite particles prepared by redox transmetalation

NASA Astrophysics Data System (ADS)

Wu, Hong-Mao; Lin, Kuan-Ju; Yu, Yi-Hsiuan; Ho, Chan-Yuan; Wei, Ming-Hsiung; Lu, Fu-Hsing; Tseng, Wenjea J.

2014-01-01

Surface-selective deposition of gold (Au) on electroless plated poly(methyl methacrylate)-nickel (PMMA-Ni) beads was prepared chemically by a facile redox-transmetalation route in which the Ni atoms on the PMMA surface were reacted with Au precursors, i.e., chloroauric acid (HAuCl4), in water to form predominately core-shell PMMA-Au composite particles without the need of reducing agent. The Ni layer acted as a sacrificial template to facilitate the selective transmetalation deposition of a metallic Au film. When pH of the precursor solution was adjusted from 6 to 9, morphology of the Au film changed from a uniform particulate film consisting of assemblies of Au nanoparticles, to densely packed, continuous film with platelet Au crystals, and finally to isolated Au islands on the PMMA surface with a raspberry-like core-shell morphology. Uniformly dense Au coating with a thickness of about 200 nm was formed on the PMMA beads at pH of 7 to 8, which gave rise to an electrical resistivity as low as 3 × 10-2 Ω cm.

Uptake of Amino Acids and Their Metabolic Conversion into the Compatible Solute Proline Confers Osmoprotection to Bacillus subtilis

PubMed Central

Zaprasis, Adrienne; Bleisteiner, Monika; Kerres, Anne; Hoffmann, Tamara

2014-01-01

The data presented here reveal a new facet of the physiological adjustment processes through which Bacillus subtilis can derive osmostress protection. We found that the import of proteogenic (Glu, Gln, Asp, Asn, and Arg) and of nonproteogenic (Orn and Cit) amino acids and their metabolic conversion into proline enhances growth under otherwise osmotically unfavorable conditions. Osmoprotection by amino acids depends on the functioning of the ProJ-ProA-ProH enzymes, but different entry points into this biosynthetic route are used by different amino acids to finally yield the compatible solute proline. Glu, Gln, Asp, and Asn are used to replenish the cellular pool of glutamate, the precursor for proline production, whereas Arg, Orn, and Cit are converted into γ-glutamic semialdehyde/Δ1-pyrroline-5-carboxylate, an intermediate in proline biosynthesis. The import of Glu, Gln, Asp, Asn, Arg, Orn, and Cit did not lead to a further increase in the size of the proline pool that is already present in osmotically stressed cells. Hence, our data suggest that osmoprotection of B. subtilis by this group of amino acids rests on the savings in biosynthetic building blocks and energy that would otherwise have to be devoted either to the synthesis of the proline precursor glutamate or of proline itself. Since glutamate is the direct biosynthetic precursor for proline, we studied its uptake and found that GltT, an Na+-coupled symporter, is the main uptake system for both glutamate and aspartate in B. subtilis. Collectively, our data show how effectively B. subtilis can exploit environmental resources to derive osmotic-stress protection through physiological means. PMID:25344233

Chemical oxidative and solid state synthesis of low molecular weight polymers for organic field effect transistors

NASA Astrophysics Data System (ADS)

Mahale, Rajashree Y.; Dharmapurikar, Satej S.; Chini, Mrinmoy Kumar

2018-03-01

Solution processability of the precursor molecules is a major issue owing to their limited solubility for the synthesis of conjugated polymers. Therefore, we favour the solvent free solid state chemical oxidative polymerization route for the synthesis of diketopyrrolopyrrole (DPP) based donor-acceptor (D-A) type conjugated polymers. D-A type polymer Poly(S-OD-EDOT) which contains DPP coupled with EDOT donor units is synthesized via solid state polymerization method. The polymer is employed as an active layer for organic field-effect transistors to measure charge transport properties. The Polymer shows good hole mobility 3.1 × 10-2 cm2 V-1 s-1, with a on/off ratio of 1.1 × 103.

Supercritical fluid route for synthesizing crystalline Barium Strontium Titanate nanoparticles.

PubMed

Reverón, H; Elissalde, C; Aymonier, C; Bidault, O; Maglione, M; Cansell, F

2005-10-01

Pure and well-crystallized Barium Strontium Titanate (BST) nanoparticles with controlled Ba/Sr ratio have been successfully synthesized under supercritical conditions using a continuous-flow reactor in the temperature range of 150-380 degrees C at 26 MPa. To synthesize the Ba0.6Sr0.4TiO3 composition, alkoxides, ethanol and water were used. The resulting nanopowder consists of fine particles with an average particle size of 23 nm. The results show that the Ba/Sr ratio of this powder can be accurately controlled from the composition of precursor. The characterization of the as-synthesized Ba0.6Sr0.4TiO3 solid-solution and the dielectric properties of the sintered ceramics are here reported.

Temperature-assisted photochemical construction of CdS-based ordered porous films with photocatalytic activities on solution surfaces.

PubMed

Huang, Zhenxun; Sun, Fengqiang; Zhang, Yu; Gu, Kaiyuan; Zou, Xueqiong; Huang, Yuying; Wu, Qingsong; Zhang, Zihe

2011-04-15

Taking a colloidal monolayer floating on the surface of a precursor solution as template, free-standing CdS/Cd composites and pure CdS (CdS-based) ordered porous films had been prepared by a temperature-assisted photochemical strategy. After irradiation with UV-light and heat treatment, the films formed hemi-spherical pores due to the preferable deposition of CdS and Cd onto the PS spheres during the photochemical and interfacial reactions. When the temperature increased from 15 to 60°C, the air/water interface gradually changed into a vapor/water interface on the surface of the solution, resulting in variations of the final compositions. The optical properties of the films were hence changed. Because of the free-standing characteristic, the ordered porous films were first transferred on surface of polluted solutions as photocatalysts, which was a new mode in application of photocatalysts. The photocatalytic activities of films showed regular variations with the compositions in photodegradation of Rhodamine B. This method provides a simple route for tuning the properties of porous films through control of its composition and a flexible application of films on any surface. Copyright © 2011 Elsevier Inc. All rights reserved.

Fabrication of solution processed 3D nanostructured CuInGaS₂ thin film solar cells.

PubMed

Chu, Van Ben; Cho, Jin Woo; Park, Se Jin; Hwang, Yun Jeong; Park, Hoo Keun; Do, Young Rag; Min, Byoung Koun

2014-03-28

In this study we demonstrate the fabrication of CuInGaS₂ (CIGS) thin film solar cells with a three-dimensional (3D) nanostructure based on indium tin oxide (ITO) nanorod films and precursor solutions (Cu, In and Ga nitrates in alcohol). To obtain solution processed 3D nanostructured CIGS thin film solar cells, two different precursor solutions were applied to complete gap filling in ITO nanorods and achieve the desirable absorber film thickness. Specifically, a coating of precursor solution without polymer binder material was first applied to fill the gap between ITO nanorods followed by deposition of the second precursor solution in the presence of a binder to generate an absorber film thickness of ∼1.3 μm. A solar cell device with a (Al, Ni)/AZO/i-ZnO/CdS/CIGS/ITO nanorod/glass structure was constructed using the CIGS film, and the highest power conversion efficiency was measured to be ∼6.3% at standard irradiation conditions, which was 22.5% higher than the planar type of CIGS solar cell on ITO substrate fabricated using the same precursor solutions.

Ferroic Materials: Design, Preparation and Characteristics. Ceramic Transactions. Volume 43. Proceedings of International Symposium Held in Honolulu, Hawaii on November 7-10, 1993.

DTIC Science & Technology

1993-11-10

realized. Metal carboxylates are often used as precursors for ceramic oxides since they tend to be air-stable, soluble in organic solvents, and decompose...metalorganic precursors [9] . These include routes based solely on metal alkoxides [9, 101 or metal carboxylates (e.g. the Pechini (or citrate) process

Mesoporous-silica films, fibers, and powders by evaporation

DOEpatents

Bruinsma, Paul J.; Baskaran, Suresh; Bontha, Jagannadha R.; Liu, Jun

2008-05-06

This invention pertains to surfactant-templated nanometer-scale porosity of a silica precursor solution and forming a mesoporous material by first forming the silica precursor solution into a preform having a high surface area to volume ratio, then rapid drying or evaporating a solvent from the silica precursor solution. The mesoporous material may be in any geometric form, but is preferably in the form of a film, fiber, powder or combinations thereof. The rapid drying or evaporation of solvent from the solution is accomplished by layer thinning, for example spin casting, liquid drawing, and liquid spraying respectively. Production of a film is by layer thinning, wherein a layer of the silica precursor solution is formed on a surface followed by removal of an amount of the silica precursor solution and leaving a geometrically thinner layer of the silica precursor solution from which the solvent quickly escapes via evaporation. Layer thinning may be by any method including but not limited to squeegeeing and/or spin casting. In powder formation by spray drying, the same conditions of fast drying exists as in spin-casting (as well as in fiber spinning) because of the high surface-area to volume ratio of the product. When a powder is produced by liquid spraying, the particles or micro-bubbles within the powder are hollow spheres with walls composed of mesoporous silica. Mesoporous fiber formation starts with a similar silica precursor solution but with an added pre-polymer making a pituitous mixture that is drawn into a thin strand from which solvent is evaporated leaving the mesoporous fiber(s).

Mesoporous-silica films, fibers, and powders by evaporation

DOEpatents

Bruinsma, Paul J.; Baskaran, Suresh; Bontha, Jagannadha R.; Liu, Jun

1999-01-01

This invention pertains to surfactant-templated nanometer-scale porosity of a silica precursor solution and forming a mesoporous material by first forming the silica precursor solution into a preform having a high surface area to volume ratio, then rapid drying or evaporating a solvent from the silica precursor solution. The mesoporous material may be in any geometric form, but is preferably in the form of a film, fiber, powder or combinations thereof. The rapid drying or evaporation of solvent from the solution is accomplished by layer thinning, for example spin casting, liquid drawing, and liquid spraying respectively. Production of a film is by layer thinning, wherein a layer of the silica precursor solution is formed on a surface followed by removal of an amount of the silica precursor solution and leaving a geometrically thinner layer of the silica precursor solution from which the solvent quickly escapes via evaporation. Layer thinning may be by any method including but not limited to squeegeeing and/or spin casting. In powder formation by spray drying, the same conditions of fast drying exists as in spin-casting (as well as in fiber spinning) because of the high surface-area to volume ratio of the product. When a powder is produced by liquid spraying, the particles or micro-bubbles within the powder are hollow spheres with walls composed of mesoporous silica. Mesoporous fiber formation starts with a similar silica precursor solution but with an added pre-polymer making a pituitous mixture that is drawn into a thin strand from which solvent is evaporated leaving the mesoporous fiber(s).

Mesoporous-silica films, fibers, and powders by evaporation

DOEpatents

Bruinsma, P.J.; Baskaran, S.; Bontha, J.R.; Liu, J.

1999-07-13

This invention pertains to surfactant-templated nanometer-scale porosity of a silica precursor solution and forming a mesoporous material by first forming the silica precursor solution into a preform having a high surface area to volume ratio, then rapid drying or evaporating a solvent from the silica precursor solution. The mesoporous material may be in any geometric form, but is preferably in the form of a film, fiber, powder or combinations thereof. The rapid drying or evaporation of solvent from the solution is accomplished by layer thinning, for example spin casting, liquid drawing, and liquid spraying respectively. Production of a film is by layer thinning, wherein a layer of the silica precursor solution is formed on a surface followed by removal of an amount of the silica precursor solution and leaving a geometrically thinner layer of the silica precursor solution from which the solvent quickly escapes via evaporation. Layer thinning may be by any method including but not limited to squeegeeing and/or spin casting. In powder formation by spray drying, the same conditions of fast drying exists as in spin-casting (as well as in fiber spinning) because of the high surface-area to volume ratio of the product. When a powder is produced by liquid spraying, the particles or micro-bubbles within the powder are hollow spheres with walls composed of mesoporous silica. Mesoporous fiber formation starts with a similar silica precursor solution but with an added pre-polymer making a pituitous mixture that is drawn into a thin strand from which solvent is evaporated leaving the mesoporous fiber(s). 24 figs.

Preparation of plutonium-bearing ceramics via mechanically activated precursor

NASA Astrophysics Data System (ADS)

Chizhevskaya, S. V.; Stefanovsky, S. V.

2000-07-01

The problem of excess weapons plutonium disposition is suggested to be solved by means of its incorporation in stable ceramics with high chemical durability and radiation resistivity. The most promising host phases for plutonium as well as uranium and neutron poisons (gadolinium, hafnium) are zirconolite, pyrochlore, zircon, zirconia [1,2], and murataite [3]. Their production requires high temperatures and a fine-grained homogeneous precursor to reach final waste form with high quality and low leachability. Currently various routes to homogeneous products preparation such as sol-gel technology, wet-milling, and grinding in a ball or planetary mill are used. The best result demonstrates sol-gel technology but this route is very complicated. An alternative technology for preparation of ceramic precursors is the treatment of the oxide batch with high mechanical energy [4]. Such a treatment produces combination of mechanical (fine milling with formation of various defects, homogenization) and chemical (split bonds with formation of active centers—free radicals, ion-radicals, etc.) effects resulting in higher reactivity of the activated batch.

Highly luminescent core-shell InP/ZnX (X = S, Se) quantum dots prepared via a phosphine synthetic route.

PubMed

Mordvinova, Natalia; Vinokurov, Alexander; Kuznetsova, Tatiana; Lebedev, Oleg I; Dorofeev, Sergey

2017-01-24

Here we report a simple method for the creation of highly luminescent core-shell InP/ZnX (X = S, Se) quantum dots (QDs) on the basis of a phosphine synthetic route. In this method a Zn precursor was added to the reaction mixture at the beginning of the synthesis to form an In(Zn)P alloy structure, which promoted the formation of a ZnX shell. Core-shell InP/ZnX QDs exhibit highly intensive emission with a quantum yield over 50%. The proposed method is primarily important for practical applications. Advantages of this method compared to the widely used SILAR technique are discussed. We further demonstrate that the SILAR approach consisting of consequent addition of Zn and chalcogen precursors to pre-prepared non-doped InP colloidal nanoparticles is not quite suitable for shell growth without the addition of special activator agents or the use of very reactive precursors.

Synthesis and structures of metal chalcogenide precursors

NASA Technical Reports Server (NTRS)

Hepp, Aloysius F.; Duraj, Stan A.; Eckles, William E.; Andras, Maria T.

1990-01-01

The reactivity of early transition metal sandwich complexes with sulfur-rich molecules such as dithiocarboxylic acids was studied. Researchers recently initiated work on precursors to CuInSe2 and related chalcopyrite semiconductors. Th every high radiation tolerance and the high absorption coefficient of CuInSe2 makes this material extremely attractive for lightweight space solar cells. Their general approach in early transition metal chemistry, the reaction of low-valent metal complexes or metal powders with sulfur and selenium rich compounds, was extended to the synthesis of chalcopyrite precursors. Here, the researchers describe synthesis, structures, and and routes to single molecule precursors to metal chalcogenides.

Zinc-aluminum oxide solid solution nanosheets obtained by pyrolysis of layered double hydroxide as the photoanodes for dye-sensitized solar cells.

PubMed

Xu, Zhiyuan; Shi, Jingjing; Haroone, Muhammad Sohail; Chen, Wenpeng; Zheng, Shufang; Lu, Jun

2018-04-01

Due to the superiority of metal-doped ZnO compared to TiO 2 , the Zn-M (M = Al 3+ , Ga 3+ , Cr 3+ , Ti 4+ , Ce 4+ ) mixed metal oxide solid solutions have been extensively studied for photocatalytic and photovoltaic applications. In this work, a systematic research has proceeded for the preparation of a zinc-aluminum oxide semiconductor as a photoanode for the dye-sensitized solar cells (DSSCs) by a simple pyrolysis route with the Zn-Al layered double hydroxide (LDH) as a precursor. The Zn-Al oxide solid solution has been applied for DSSCs as an electron acceptor, which is used to study the influence of different Al content and sintering temperature on the device efficiency. Finally, the Zn-Al oxide solid solution with calcination temperature 600 °C and Al 27 at.% content exhibits the best performance. The photoelectric efficiency improved 100 times when the Al 3+ content decreased from 44 to 27 at.%. The Zn x Al y O solid solution show a reasonable efficiency as photoanode materials in DSSCs, with the best preliminary performance reported so far, and shows its potential application for the photovoltaic devices. Copyright © 2018 Elsevier Inc. All rights reserved.

Superhydrophobicity of electrospray-synthesized fluorinated silica layers.

PubMed

Kim, Eun-Kyeong; Lee, Chul-Sung; Kim, Sang Sub

2012-02-15

The preparation of superhydrophobic SiO(2) layers through a combination of a nanoscale surface roughness and a fluorination treatment is reported. Electrospraying SiO(2) precursor solutions that had been prepared by a sol-gel chemical route produced very rough SiO(2) layers. Subsequent fluorination treatment with a solution containing trichloro(1H,1H,2H,2H-perfluorooctyl)silane resulted in highly rough, fluorinated SiO(2) layers. The fluorinated rough SiO(2) layers exhibited excellent repellency toward various liquid droplets. In particular, water repellency of 168° was observed. On the bases of Cassie-Baxter and Young-Dupre equations, the surface fraction and the work of adhesion of the rough, fluorinated SiO(2) layers were respectively estimated. In light of the durability in water, ultraviolet resistance, and thermal stability, the superhydrophobic SiO(2) layers prepared in this work hold promise in a range of practical applications. Copyright © 2011 Elsevier Inc. All rights reserved.

Sol-Gel Precursors for Ceramics from Minerals Simulating Soils from the Moon and Mars

NASA Technical Reports Server (NTRS)

Sibille, Laurent; Gavira-Gallardo, Jose-Antonio; Hourlier-Bahloul, Djamila

2003-01-01

Recent NASA mission plans for the human exploration of our Solar System has set new priorities for research and development of technologies necessary to enable a long-term human presence on the Moon and Mars. The recovery and processing of metals and oxides from mineral sources on other planets is under study to enable use of ceramics, glasses and metals by explorer outposts. We report some preliminary results on the production of sol-gel precursors for ceramic products using mineral resources available in Martian or Lunar soil. The presence of SiO2, TiO2, and A12O3 in both Martian (44 wt.% SiO2, 1 wt.% TiO2, 7 wt.% Al2O3) and Lunar (48 wt.% SiO2, 1.5 wt.% TiO2, 16 wt.% Al2O3) soils and the recent developments in chemical processes to solubilize silicates using organic reagents and relatively little energy indicate that such an endeavor is possible. In order to eliminate the risks involved in the use of hydrofluoric acid to dissolve silicates, two distinct chemical routes are investigated to obtain soluble silicon oxide precursors from Lunar and Martian simulant soils. Clear sol-gel precursors have been obtained by dissolution of silica from Lunar simulant soil in basic ethylene glycol (C2H4(OH)2) solutions to form silicon glycolates. Thermogravimetric Analysis and X-ray Photoelectron Spectroscopy were used to characterize the elemental composition and structure of the precursor molecules. Further concentration and hydrolysis of the products was performed to obtain gel materials for evaluation as ceramic precursors. In the second set of experiments, we used the same starting materials to synthesize silicate esters in acidified alcohol mixtures. Preliminary results indicate the presence of silicon alkoxides in the product of distillation.

Aqueous silicates in biological sol-gel applications: new perspectives for old precursors.

PubMed

Coradin, Thibaud; Livage, Jacques

2007-09-01

Identification of silica sol-gel chemistry with silicon alkoxide hydrolysis and condensation processes is common in modern materials science. However, aqueous silicates exhibit several features indicating that they may be more suitable precursors for specific fields of research and applications related to biology and medicine. In this Account, we illustrate the potentialities of such aqueous precursors for biomimetic studies, bio-hybrid material design, and bioencapsulation routes. We emphasize that the natural relevance, the biocompatibility, and the low ecological impact of silicate chemistry may balance its lack of diversity, flexibility, and processability.

Degradation of Highly Alloyed Metal Halide Perovskite Precursor Inks: Mechanism and Storage Solutions

DOE PAGES

Dou, Benjia; Wheeler, Lance M.; Christians, Jeffrey A.; ...

2018-03-14

Whereas the promise of metal halide perovskite (MHP) photovoltaics (PV) is that they can combine high efficiency with solution-processability, the chemistry occurring in precursor inks is largely unexplored. Herein, we investigate the degradation of MHP solutions based on the most widely used solvents, dimethylformamide (DMF) and dimethyl sulfoxide (DMSO). For the MHP inks studied, which contain formamidinium (FA+), methylammonium (MA+), cesium (Cs+), lead (Pb2+), bromide (Br-), and iodide (I-), dramatic compositional changes are observed following storage of the inks in nitrogen in the dark. We show that hydrolysis of DMF in the precursor solution forms dimethylammonium formate, which subsequently incorporatesmore » into the MHP film to compromise the ability of Cs+ and MA+ to stabilize FA+-based MHP. The changes in solution chemistry lead to a modification of the perovskite film stoichiometry, band gap, and structure. The solid precursor salts are stable when ball-milled into a powder, allowing for the storage of large quantities of stoichiometric precursor materials.« less

Degradation of Highly Alloyed Metal Halide Perovskite Precursor Inks: Mechanism and Storage Solutions

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

Dou, Benjia; Wheeler, Lance M.; Christians, Jeffrey A.

Whereas the promise of metal halide perovskite (MHP) photovoltaics (PV) is that they can combine high efficiency with solution-processability, the chemistry occurring in precursor inks is largely unexplored. Herein, we investigate the degradation of MHP solutions based on the most widely used solvents, dimethylformamide (DMF) and dimethyl sulfoxide (DMSO). For the MHP inks studied, which contain formamidinium (FA+), methylammonium (MA+), cesium (Cs+), lead (Pb2+), bromide (Br-), and iodide (I-), dramatic compositional changes are observed following storage of the inks in nitrogen in the dark. We show that hydrolysis of DMF in the precursor solution forms dimethylammonium formate, which subsequently incorporatesmore » into the MHP film to compromise the ability of Cs+ and MA+ to stabilize FA+-based MHP. The changes in solution chemistry lead to a modification of the perovskite film stoichiometry, band gap, and structure. The solid precursor salts are stable when ball-milled into a powder, allowing for the storage of large quantities of stoichiometric precursor materials.« less

Non-aqueous solution preparation of doped and undoped lixmnyoz

DOEpatents

Boyle, Timothy J.; Voigt, James A.

1997-01-01

A method for generation of phase-pure doped and undoped Li.sub.x Mn.sub.y O.sub.z precursors. The method of this invention uses organic solutions instead of aqueous solutions or nonsolution ball milling of dry powders to produce phase-pure precursors. These precursors can be used as cathodes for lithium-polymer electrolyte batteries. Dopants may be homogeneously incorporated to alter the characteristics of the powder.

Composite catalysts supported on modified carbon substrates and methods of making the same

DOEpatents

Popov, Branko N [Columbia, SC; Subramanian, Nalini [Kennesaw, GA; Colon-Mercado, Hector R [Columbia, SC

2009-11-17

A method of producing a composite carbon catalyst is generally disclosed. The method includes oxidizing a carbon precursor (e.g., carbon black). Optionally, nitrogen functional groups can be added to the oxidized carbon precursor. Then, the oxidized carbon precursor is refluxed with a non-platinum transitional metal precursor in a solution. Finally, the solution is pyrolyzed at a temperature of at least about 500.degree. C.

The Unique Biosynthetic Route from Lupinus β-Conglutin Gene to Blad

PubMed Central

Monteiro, Sara; Freitas, Regina; Rajasekhar, Baru T.; Teixeira, Artur R.; Ferreira, Ricardo B.

2010-01-01

Background During seed germination, β-conglutin undergoes a major cycle of limited proteolysis in which many of its constituent subunits are processed into a 20 kDa polypeptide termed blad. Blad is the main component of a glycooligomer, accumulating exclusively in the cotyledons of Lupinus species, between days 4 and 12 after the onset of germination. Principal Findings The sequence of the gene encoding β-conglutin precursor (1791 nucleotides) is reported. This gene, which shares 44 to 57% similarity and 20 to 37% identity with other vicilin-like protein genes, includes several features in common with these globulins, but also specific hallmarks. Most notable is the presence of an ubiquitin interacting motif (UIM), which possibly links the unique catabolic route of β-conglutin to the ubiquitin/proteasome proteolytic pathway. Significance Blad forms through a unique route from and is a stable intermediary product of its precursor, β-conglutin, the major Lupinus seed storage protein. It is composed of 173 amino acid residues, is encoded by an intron-containing, internal fragment of the gene that codes for β-conglutin precursor (nucleotides 394 to 913) and exhibits an isoelectric point of 9.6 and a molecular mass of 20,404.85 Da. Consistent with its role as a storage protein, blad contains an extremely high proportion of the nitrogen-rich amino acids. PMID:20066045

High-Solids Polyimide Precursor Solutions

NASA Technical Reports Server (NTRS)

Chuang, Chun-Hua (Inventor)

2004-01-01

The invention is a highly concentrated stable solution of polymide precursors (monometers) having a solids content ranging from about 80 to 98 percent by weight in lower aliphatic alcohols i.e. methyl and/or ethylalcohol. the concentrated polyimide precursos solution comparisons effective amounts of at least one aromatic diamine, at least one aromatic dianhydride, and a monofunctional endcap including monoamines, monoanhydrides and lower alkyl esters of said monoanhydrides. These concentrated polyimide precursor solutions are particularly useful for the preparation of fibrous prepregs and composites for use in structural materials for military and civil applications.

Facile synthesis and enhanced visible light photocatalytic activity of N and Zr co-doped TiO2 nanostructures from nanotubular titanic acid precursors

NASA Astrophysics Data System (ADS)

Zhang, Min; Yu, Xinluan; Lu, Dandan; Yang, Jianjun

2013-12-01

Zr/N co-doped TiO2 nanostructures were successfully synthesized using nanotubular titanic acid (NTA) as precursors by a facile wet chemical route and subsequent calcination. These Zr/N-doped TiO2 nanostructures made by NTA precursors show significantly enhanced visible light absorption and much higher photocatalytic performance than the Zr/N-doped P25 TiO2 nanoparticles. Impacts of Zr/N co-doping on the morphologies, optical properties, and photocatalytic activities of the NTA precursor-based TiO2 were thoroughly investigated. The origin of the enhanced visible light photocatalytic activity is discussed in detail.

Facile synthesis and enhanced visible light photocatalytic activity of N and Zr co-doped TiO2 nanostructures from nanotubular titanic acid precursors

PubMed Central

2013-01-01

Zr/N co-doped TiO2 nanostructures were successfully synthesized using nanotubular titanic acid (NTA) as precursors by a facile wet chemical route and subsequent calcination. These Zr/N-doped TiO2 nanostructures made by NTA precursors show significantly enhanced visible light absorption and much higher photocatalytic performance than the Zr/N-doped P25 TiO2 nanoparticles. Impacts of Zr/N co-doping on the morphologies, optical properties, and photocatalytic activities of the NTA precursor-based TiO2 were thoroughly investigated. The origin of the enhanced visible light photocatalytic activity is discussed in detail. PMID:24369051

Facile synthesis and enhanced visible light photocatalytic activity of N and Zr co-doped TiO2 nanostructures from nanotubular titanic acid precursors.

PubMed

Zhang, Min; Yu, Xinluan; Lu, Dandan; Yang, Jianjun

2013-12-26

Zr/N co-doped TiO2 nanostructures were successfully synthesized using nanotubular titanic acid (NTA) as precursors by a facile wet chemical route and subsequent calcination. These Zr/N-doped TiO2 nanostructures made by NTA precursors show significantly enhanced visible light absorption and much higher photocatalytic performance than the Zr/N-doped P25 TiO2 nanoparticles. Impacts of Zr/N co-doping on the morphologies, optical properties, and photocatalytic activities of the NTA precursor-based TiO2 were thoroughly investigated. The origin of the enhanced visible light photocatalytic activity is discussed in detail.

Characterization of TiO2 films obtained by a wet chemical process

NASA Astrophysics Data System (ADS)

Sedik, Asma; Ferraria, Ana M.; Carapeto, Ana P.; Bellal, Bouzid; Trari, Mohamed; Outemzabet, Ratiba

2017-12-01

TiO2 has an easily tunable bandgap and a great absorption dye ability being widely used in many fields and in a number of fascinating applications. In this study, a wet chemical route, particularly a sol gel method using spin-coating is adopted to deposit TiO2 thin films onto soda lime glass and silicon substrates. TiO2 films were prepared by using an alcoholic solution of analytical reagent grade TiCl4 as titanium precursor at various experimental conditions. The accent was put on the conditions of preparation (spin time, spin speed, precursor concentration, number of coating layers etc), doping and on the post-deposit treatment namely the drying and the crystallization. The results showed a strong dependence on the drying temperature and on the temperature and duration of the crystallization. We found that the solution preparation and its color are important for getting a reproducible final product. The Raman spectra recorded at room temperature, showed the characteristic peaks of anatase which appear at 143 and around 396 cm-1. These peaks confirm the presence of TiO2. The X-ray diffraction (XRD) was used to identify the crystalline characteristic of TiO2 while the chemical states and relative amounts of the main elements existing in the samples were investigated by X-ray Photoelectron Spectroscopy (XPS). The morphology of the samples was visualized by AFM. We show by this work the feasibility to obtain different nanostructured TiO2 by changing the concentration of the solution. Photocatalytic activity of TiO2 films was evaluated. Rhodamine B is a recalcitrant dye and TiO2 was successfully tested for its oxidation. An abatement of 60% was obtained under sunlight for an initial concentration of 10 mg/l.

Sol-gel type synthesis of Bi.sub.2 (Sr,Ta.sub.2)O.sub.9 using an acetate based system

DOEpatents

Boyle, Timothy J.

1997-01-01

A method of forming a layered-perovskite bismuth-strontium-tantalum oxide (SBT) ferroelectric material is performed by dissolving a bismuth compound in a first solvent to form a first solution, mixing a strontium compound and a tantalum compound to form a binary mixture, dissolving the binary mixture in a second solvent to form a second solution, mixing the first solution with the second solution to form a SBT precursor solution, evaporating the first and second solvents to form a SBT precursor material and subsequently sintering said SBT precursor material in the presence of oxygen.

Sol-gel type synthesis of Bi{sub 2}(Sr,Ta{sub 2})O{sub 9} using an acetate based system

DOEpatents

Boyle, T.J.

1997-11-04

A method of forming a layered-perovskite bismuth-strontium-tantalum oxide (SBT) ferroelectric material is performed by dissolving a bismuth compound in a first solvent to form a first solution, mixing a strontium compound and a tantalum compound to form a binary mixture, dissolving the binary mixture in a second solvent to form a second solution, mixing the first solution with the second solution to form a SBT precursor solution, evaporating the first and second solvents to form a SBT precursor material and subsequently sintering said SBT precursor material in the presence of oxygen. 6 figs.

The effect of Ge precursor on the heteroepitaxy of Ge1-x Sn x epilayers on a Si (001) substrate

NASA Astrophysics Data System (ADS)

Jahandar, Pedram; Weisshaupt, David; Colston, Gerard; Allred, Phil; Schulze, Jorg; Myronov, Maksym

2018-03-01

The heteroepitaxial growth of Ge1-x Sn x on a Si (001) substrate, via a relaxed Ge buffer, has been studied using two commonly available commercial Ge precursors, Germane (GeH4) and Digermane (Ge2H6), by means of chemical vapour deposition at reduced pressures (RP-CVD). Both precursors demonstrate growth of strained and relaxed Ge1-x Sn x epilayers, however Sn incorporation is significantly higher when using the more reactive Ge2H6 precursor. As Ge2H6 is significantly more expensive, difficult to handle or store than GeH4, developing high Sn content epilayers using the latter precursor is of great interest. This study demonstrates the key differences between the two precursors and offers routes to process optimisation which will enable high Sn content alloys at relatively low cost.

A facile synthesis of α-MnO2 used as a supercapacitor electrode material: The influence of the Mn-based precursor solutions on the electrochemical performance

NASA Astrophysics Data System (ADS)

Li, Wenyao; Xu, Jiani; Pan, Yishuang; An, Lei; Xu, Kaibing; Wang, Guangjin; Yu, Zhishui; Yu, Li; Hu, Junqing

2015-12-01

Three types of α-MnO2 nanomaterials are synthesized in different Mn-based precursor solutions by using a facile electrochemical deposition at the same depositional condition. The relationships between the precursor solutions and corresponding MnO2 nanomaterials' morphology as well as the electrochemical performance have been studied. As an electrode, electrochemical measurements show that the MnO2 deposited in MnCl2 precursor solution (MnO2-P3) exhibits an enhanced specific capacitance (318.9 F g-1 at 2 mV s-1). Moreover, this electrode demonstrates a good rate capability with 44% retention, which is higher than the MnO2-P1 deposited with Mn(CH3COOH)2 solution and the MnO2-P2 deposited with Mn(NO3)2 precursor solution. Besides, the specific capacitance of the MnO2-P3 electrode nearly has 98.2% retention after 2000 cycles, showing good long-term cycle stability. These findings show that the MnO2-P3 is a promising electrode material for supercapacitors.

Aerosol Synthesis of N and N-S Doped and Crumpled Graphene Nanostructures.

PubMed

Carraro, Francesco; Cattelan, Mattia; Favaro, Marco; Calvillo, Laura

2018-06-06

Chemically modified graphene⁻based materials (CMG) are currently attracting a vast interest in their application in different fields. In particular, heteroatom-doped graphenes have revealed great potentialities in the field of electrocatalysis as substitutes of fuel cell noble metal⁻based catalysts. In this work, we investigate an innovative process for doping graphene nanostructures. We optimize a novel synthetic route based on aerosol preparation, which allows the simultaneous doping, crumpling, and reduction of graphene oxide (GO). Starting from aqueous solutions containing GO and the dopant precursors, we synthesize N- and N,S-dual-doped 3D graphene nanostructures (N-cGO and N,S-cGO). In the aerosol process, every aerosol droplet can be considered as a microreactor where dopant precursors undergo thermal decomposition and react with the GO flakes. Simultaneously, thanks to the relatively high temperature, GO undergoes crumpling and partial reduction. Using a combination of spectroscopic and microscopic characterization techniques, we investigate the morphology of the obtained materials and the chemical nature of the dopants within the crumpled graphene sheets. This study highlights the versatility of the aerosol process for the design of new CMG materials with tailored electrocatalytic properties.

Investigation on structural properties of M-type strontium hexaferrite synthesized in presence of neem and aloe-vera plant leaves extract

NASA Astrophysics Data System (ADS)

Solanki, Neha; Jotania, Rajshree B.

2017-05-01

M-type strontium hexaferrite powder samples were synthesized using a green synthesis route with and without presence of Aloe vera and Neem leaves extract. The dry brownish precursors of strontium hexaferrite were recovered from a mixed solution of metal salts and leaves extract, heated at 100 °C. The obtained precursors were pre-heated at 500 °C for 4 hrs. followed by final heating at 950 °C for 4 hrs. in a muffle furnace to obtain SrFe12O19 hexaferrite powder. The obtained SrFe12O19 hexaferrite powder samples characterized at room temperature in order to check phase purity and structural properties. XRD analysis confirms that samples prepared without and with Aloe vera leaves extract (heated at 950 °C for 4 hrs.) show formation of α-Fe2O3 and M-phase; while the sample prepared in presence of Neem leaves extract (heated at 950 °C for 4 hrs.) show formation of mono phase of strontium hexaferrite. Lattice parameter (a) and cell volume (V) are found to increase in the samples prepared in presence of Aloe vera and Neem leaves extract.

Delta(13)C, delta(15)N and delta(2)H isotope ratio mass spectrometry of ephedrine and pseudoephedrine: application to methylamphetamine profiling.

PubMed

Collins, Michael; Cawley, Adam T; Heagney, Aaron C; Kissane, Luke; Robertson, James; Salouros, Helen

2009-07-01

Conventional chemical profiling of methylamphetamine has been used for many years to determine the synthetic route employed and where possible to identify the precursor chemicals used. In this study stable isotope ratio analysis was investigated as a means of determining the origin of the methylamphetamine precursors, ephedrine and pseudoephedrine. Ephedrine and pseudoephedrine may be prepared industrially by several routes. Results are presented for the stable isotope ratios of carbon (delta(13)C), nitrogen (delta(15)N) and hydrogen (delta(2)H) measured in methylamphetamine samples synthesized from ephedrine and pseudoephedrine of known provenance. It is clear from the results that measurement of the delta(13)C, delta(15)N and delta(2)H stable isotope ratios by elemental analyzer/thermal conversion isotope ratio mass spectrometry (EA/TC-IRMS) in high-purity methylamphetamine samples will allow determination of the synthetic source of the ephedrine or pseudoephedrine precursor as being either of a natural, semi-synthetic, or fully synthetic origin. Copyright (c) 2009 Commonwealth of Australia.

Polyimide Composites from 'Salt-Like' Solution Precursors

NASA Technical Reports Server (NTRS)

Cano, Roberto J.; Hou, Tan H.; Weiser, Erik S.; SaintClair, Terry L.

2001-01-01

Four NASA Langley-developed polyimide matrix resins, LaRC(TM)-IA, LaRC(TM)-IAX, LaRC(TM)-8515 and LaRC(TM)-PETI-5, were produced via a 'saltlike' process developed by Unitika Ltd. The salt-like solutions (65% solids in NMP) were prepregged onto Hexcel IM7 carbon fiber using the NASA LaRC multipurpose tape machine. Process parameters were determined and composite panels fabricated. The temperature dependent volatile depletion rates, the thermal crystallization behavior and the resin rheology were characterized. Composite molding cycles were developed which consistently yielded well consolidated, void-free laminated parts. Composite mechanical properties such as the short beam shear strength; the longitudinal and transverse flexural strength and flexural modulus; the longitudinal compression strength and modulus; and the open hole compression strength and compression after impact strength were measured at room temperature and elevated temperatures. The processing characteristics and the composite mechanical properties of the four intermediate modulus carbon fiber/polyimide matrix composites were compared to existing data on the same polyimide resin systems and IM7 carbon fiber manufactured via poly(amide acid) solutions (30-35% solids in NMP). This work studies the effects of varying the synthetic route on the processing and mechanical properties of the polyimide composites.

Ultrasonic-assisted solution combustion synthesis of porous Na3V2(PO4)3/C: formation mechanism and sodium storage performance

NASA Astrophysics Data System (ADS)

Chen, Qiuyun; Liu, Qing; Chu, Xiangcheng; Zhang, Yiling; Yan, Youwei; Xue, Lihong; Zhang, Wuxing

2017-04-01

Solution combustion synthesis (SCS) is an effective and rapid method for synthesizing nanocrystalline materials. However, the control over size, morphology, and microstructure are rather limited in SCS. Here, we develop a novel ultrasonic-assisted solution combustion route to synthesize the porous and nano-sized Na3V2(PO4)3/C composites, and reveal the effects of ultrasound on the structural evolution of NVP/C. Due to the cavitation effects generated from ultrasonic irradiation, the ultrasonic-assisted SCS can produce honeycomb precursor, which can be further transformed into porous Na3V2(PO4)3/C with reticular and hollow structures after thermal treatment. When used as cathode material for Na-ion batteries, the porous Na3V2(PO4)3/C delivers an initial discharge capacity of 118 mAh g-1 at 0.1 C and an initial coulombic efficiency of 85%. It can retain 93.8% of the initial capacity after 120 cycles at 0.2 C. The results demonstrate that ultrasonic-assisted SCS can be a new strategy to design crystalline nanomaterials with tunable microstructures.

Influence of Water on Chemical Vapor Deposition of Ni and Co thin films from ethanol solutions of acetylacetonate precursors

PubMed Central

Weiss, Theodor; Zielasek, Volkmar; Bäumer, Marcus

2015-01-01

In chemical vapor deposition experiments with pulsed spray evaporation (PSE-CVD) of liquid solutions of Ni and Co acetylacetonate in ethanol as precursors, the influence of water in the feedstock on the composition and growth kinetics of deposited Ni and Co metal films was systematically studied. Varying the water concentration in the precursor solutions, beneficial as well as detrimental effects of water on the metal film growth, strongly depending on the concentration of water and the β-diketonate in the precursor, were identified. For 2.5 mM Ni(acac)2 precursor solutions, addition of 0.5 vol% water improves growth of a metallic Ni film and reduces carbon contamination, while addition of 1.0 vol% water and more leads to significant oxidation of deposited Ni. By tuning the concentration of both, Ni(acac)2 and water in the precursor solution, the fraction of Ni metal and Ni oxide in the film or the film morphology can be adjusted. In the case of Co(acac)2, even smallest amounts of water promote complete oxidation of the deposited film. All deposited films were analyzed with respect to chemical composition quasi in situ by XPS, their morphology was evaluated after deposition by SEM. PMID:26658547

Synthetic Routes to Methylerythritol Phosphate Pathway Intermediates and Downstream Isoprenoids

PubMed Central

Jarchow-Choy, Sarah K; Koppisch, Andrew T; Fox, David T

2014-01-01

Isoprenoids constitute the largest class of natural products with greater than 55,000 identified members. They play essential roles in maintaining proper cellular function leading to maintenance of human health, plant defense mechanisms against predators, and are often exploited for their beneficial properties in the pharmaceutical and nutraceutical industries. Most impressively, all known isoprenoids are derived from one of two C5-precursors, isopentenyl diphosphate (IPP) or dimethylallyl diphosphate (DMAPP). In order to study the enzyme transformations leading to the extensive structural diversity found within this class of compounds there must be access to the substrates. Sometimes, intermediates within a biological pathway can be isolated and used directly to study enzyme/pathway function. However, the primary route to most of the isoprenoid intermediates is through chemical catalysis. As such, this review provides the first exhaustive examination of synthetic routes to isoprenoid and isoprenoid precursors with particular emphasis on the syntheses of intermediates found as part of the 2C-methylerythritol 4-phosphate (MEP) pathway. In addition, representative syntheses are presented for the monoterpenes (C10), sesquiterpenes (C15), diterpenes (C20), triterpenes (C30) and tetraterpenes (C40). Finally, in some instances, the synthetic routes to substrate analogs found both within the MEP pathway and downstream isoprenoids are examined. PMID:25009443

Non-aqueous solution preparation of doped and undoped Li{sub x}Mn{sub y}O{sub z}

DOEpatents

Boyle, T.J.; Voigt, J.A.

1997-05-20

A method is described for generation of phase-pure doped and undoped Li{sub x}Mn{sub y}O{sub z} precursors. The method of this invention uses organic solutions instead of aqueous solutions or nonsolution ball milling of dry powders to produce phase-pure precursors. These precursors can be used as cathodes for lithium-polymer electrolyte batteries. Dopants may be homogeneously incorporated to alter the characteristics of the powder. 1 fig.

Acquisition of business intelligence from human experience in route planning

NASA Astrophysics Data System (ADS)

Bello Orgaz, Gema; Barrero, David F.; R-Moreno, María D.; Camacho, David

2015-04-01

The logistic sector raises a number of highly challenging problems. Probably one of the most important ones is the shipping planning, i.e. plan the routes that the shippers have to follow to deliver the goods. In this article, we present an artificial intelligence-based solution that has been designed to help a logistic company to improve its routes planning process. In order to achieve this goal, the solution uses the knowledge acquired by the company drivers to propose optimised routes. Hence, the proposed solution gathers the experience of the drivers, processes it and optimises the delivery process. The solution uses data mining to extract knowledge from the company information systems and prepares it for analysis with a case-based reasoning (CBR) algorithm. The CBR obtains critical business intelligence knowledge from the drivers experience that is needed by the planner. The design of the routes is done by a genetic algorithm that, given the processed information, optimises the routes following several objectives, such as minimise the distance or time. Experimentation shows that the proposed approach is able to find routes that improve, on average, the routes made by the human experts.

Y2O3:Eu phosphor particles prepared by spray pyrolysis from a solution containing citric acid and polyethylene glycol

NASA Astrophysics Data System (ADS)

Roh, H. S.; Kang, Y. C.; Park, H. D.; Park, S. B.

Y2O3:Eu phosphor particles were prepared by large-scale spray pyrolysis. The morphological control of Y2O3:Eu particles in spray pyrolysis was attempted by adding polymeric precursors to the spray solution. The effect of composition and amount of polymeric precursors on the morphology, crystallinity and photoluminescence characteristics of Y2O3:Eu particles was investigated. Particles prepared from a solution containing polyethylene glycol (PEG) with an average molecular weight of 200 had a hollow structure, while those prepared from solutions containing adequate amounts of citric acid (CA) and PEG had a spherical shape, filled morphology and clean surfaces after post-treatment at high temperature. Y2O3:Eu particles prepared from an aqueous solution with no polymeric precursors had a hollow structure and rough surfaces after post-treatment. The phosphor particles prepared from solutions with inadequate amounts of CA and/or PEG also had hollow and/or fragmented structures. The particles prepared from the solution containing 0.3 M CA and 0.3 M PEG had the highest photoluminescence emission intensity, which was 56% higher than that of the particles prepared from aqueous solution without polymeric precursors.

Ultrathin ZnSe nanowires: one-pot synthesis via a heat-triggered precursor slow releasing route, controllable Mn doping and application in UV and near-visible light detection.

PubMed

Li, Dong; Xing, Guanjie; Tang, Shilin; Li, Xiaohong; Fan, Louzhen; Li, Yunchao

2017-10-12

We report herein a heat-triggered precursor slow releasing route for the one-pot synthesis of ultrathin ZnSe nanowires (NWs), which relies on the gradual dissolving of Se powder into oleylamine containing a soluble Zn precursor under heating. This route allows the reaction system to maintain a high monomer concentration throughout the entire reaction process, thus enabling the generation of ZnSe NWs with diameter down to 2.1 nm and length approaching 400 nm. The size-dependent optical properties and band-edge energy levels of the ZnSe NWs were then explored in depth by UV-visible spectroscopy and cyclic voltammetry, respectively. Considering their unique absorption properties, these NWs were specially utilized for fabricating photoelectrochemical-type photodetectors (PDs). Impressively, the PDs based on the ZnSe NWs with diameters of 2.1 and 4.5 nm exhibited excellent responses to UVA and near-visible light, respectively: both possessed ultrahigh on/off ratios (5150 for UVA and 4213 for near-visible light) and ultrawide linear response ranges (from 2.0 to 9000 μW cm -2 for UVA and 5.0 to 8000 μW cm -2 for near-visible light). Furthermore, these ZnSe NWs were selectively doped with various amounts of Mn 2+ to tune their emission properties. As a result, ZnSe NW film-based photochromic cards were creatively developed for visually detecting UVA and near-visible radiation.

Preparation of titanium dioxide films by sol-gel route for gas sensors

NASA Astrophysics Data System (ADS)

Schiopu, Vasilica; Matei, Alina; Cernica, Ileana; Podaru, Cecilia

2009-01-01

Semiconductor oxides such as SnO2, TiO2, WO3, ZnO2 etc. have been shown to be useful as gas sensor materials for monitoring various pollutant gases like H2S, NOx, NH3 etc. In this work, we would like to present the preparation of titanium dioxide films for gas sensor application, via the sol-gel technique. The coating solution was prepared by using titanium isopropoxide precursor, which was hydrolyzed with distilled water under the catalytic effect of different acids (HNO3, HCl or CH3COOH). Titanium dioxide films have been deposited using spin coating method and then synthesized at different temperatures. Fourier transform infrared spectroscopy observation has been used to analyze the sol-gel process. The morphology and the structure of the thin films were analyzed.

Cytochrome P450-mediated metabolic engineering: current progress and future challenges.

PubMed

Renault, Hugues; Bassard, Jean-Etienne; Hamberger, Björn; Werck-Reichhart, Danièle

2014-06-01

Cytochromes P450 catalyze a broad range of regiospecific, stereospecific and irreversible steps in the biosynthetic routes of plant natural metabolites with important applications in pharmaceutical, cosmetic, fragrance and flavour, or polymer industries. They are consequently essential drivers for the engineered bioproduction of such compounds. Two ground-breaking developments of commercial products driven by the engineering of P450s are the antimalarial drug precursor artemisinic acid and blue roses or carnations. Tedious optimizations were required to generate marketable products. Hurdles encountered in P450 engineering and their potential solutions are summarized here. Together with recent technical developments and novel approaches to metabolic engineering, the lessons from this pioneering work should considerably boost exploitation of the amazing P450 toolkit emerging from accelerated sequencing of plant genomes. Copyright © 2014 The Authors. Published by Elsevier Ltd.. All rights reserved.

Aqueous route to facile, efficient and functional silica coating of metal nanoparticles at room temperature

NASA Astrophysics Data System (ADS)

Shah, Kwok Wei; Sreethawong, Thammanoon; Liu, Shu-Hua; Zhang, Shuang-Yuan; Tan, Li Sirh; Han, Ming-Yong

2014-09-01

Various metal (Ag, Au, and Pt)@thiol-functionalized silica (SiO2-SH) nanoparticles (NPs) are successfully prepared at room temperature by a facile, efficient, functional, universal and scalable coating process in alcohol-free aqueous solution using pre-hydrolyzed 3-(mercaptopropyl)trimethoxysilane (MPTMS). The controlled pre-hydrolysis of the silane precursor in water and the consecutive condensation processes are the key to achieve the effective and uniform silica coating on metal NPs in aqueous solution. The thickness of the silica shell is tuned by simply varying the coating time. The silica shell can act as an effective protecting layer for Ag NPs in Ag@SiO2-SH NPs under conditions for silica coating in aqueous solution; however, it leads to a directional dissolution of Ag NPs in a more strongly basic ammonia solution. The environmentally friendly silica coating process in water is also applied to prepare highly surface-enhanced Raman scattering (SERS)-active Ag@SiO2-SH NPs with different types of Raman molecules for highly sensitive SERS-based applications in various fields.Various metal (Ag, Au, and Pt)@thiol-functionalized silica (SiO2-SH) nanoparticles (NPs) are successfully prepared at room temperature by a facile, efficient, functional, universal and scalable coating process in alcohol-free aqueous solution using pre-hydrolyzed 3-(mercaptopropyl)trimethoxysilane (MPTMS). The controlled pre-hydrolysis of the silane precursor in water and the consecutive condensation processes are the key to achieve the effective and uniform silica coating on metal NPs in aqueous solution. The thickness of the silica shell is tuned by simply varying the coating time. The silica shell can act as an effective protecting layer for Ag NPs in Ag@SiO2-SH NPs under conditions for silica coating in aqueous solution; however, it leads to a directional dissolution of Ag NPs in a more strongly basic ammonia solution. The environmentally friendly silica coating process in water is also applied to prepare highly surface-enhanced Raman scattering (SERS)-active Ag@SiO2-SH NPs with different types of Raman molecules for highly sensitive SERS-based applications in various fields. Electronic supplementary information (ESI) available. See DOI: 10.1039/c4nr03306j

Thermally Activated Delayed Fluorescence in Polymers: A New Route toward Highly Efficient Solution Processable OLEDs.

PubMed

Nikolaenko, Andrey E; Cass, Michael; Bourcet, Florence; Mohamad, David; Roberts, Matthew

2015-11-25

Efficient intermonomer thermally activated delayed fluorescence is demonstrated for the first time, opening a new route to achieving high-efficiency solution processable polymer light-emitting device materials. External quantum efficiency (EQE) of up to 10% is achieved in a simple fully solution-processed device structure, and routes for further EQE improvement identified. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Fluorinated precursors of superconducting ceramics, and methods of making the same

DOEpatents

Wiesmann, Harold; Solovyov, Vyacheslav

2014-02-18

This invention provides a method of making a fluorinated precursor of a superconducting ceramic. The method comprises providing a solution comprising a rare earth salt, an alkaline earth metal salt and a copper salt; spraying the solution onto a substrate to provide a film-covered substrate; and heating the film-covered substrate in an atmosphere containing fluorinated gas to provide the fluorinated precursor.

Fluorinated precursors of superconducting ceramics, and methods of making the same

DOEpatents

Wiesmann, Harold [Stony Brook, NY; Solovyov, Vyacheslav [Rocky Point, NY

2008-04-22

This invention provides a method of making a fluorinated precursor of a superconducting ceramic. The method comprises providing a solution comprising a rare earth salt, an alkaline earth metal salt and a copper salt; spraying the solution onto a substrate to provide a film-covered substrate; and heating the film-covered substrate in an atmosphere containing fluorinated gas to provide the fluorinated precursor.

Fluorinated precursors of superconducting ceramics, and methods of making the same

DOEpatents

Wiesmann, Harold [Stony Brook, NY; Solovyov, Vyacheslav [Rocky Point, NY

2012-07-10

This invention provides a method of making a fluorinated precursor of a superconducting ceramic. The method comprises providing a solution comprising a rare earth salt, an alkaline earth metal salt and a copper salt; spraying the solution onto a substrate to provide a film-covered substrate; and heating the film-covered substrate in an atmosphere containing fluorinated gas to provide the fluorinated precursor.

The effects of preparation conditions for a BaNbO2 N photocatalyst on its physical properties.

PubMed

Hisatomi, Takashi; Katayama, Chisato; Teramura, Kentaro; Takata, Tsuyoshi; Moriya, Yosuke; Minegishi, Tsutomu; Katayama, Masao; Nishiyama, Hiroshi; Yamada, Taro; Domen, Kazunari

2014-07-01

BaNbO2 N is a semiconductor photocatalyst active for water oxidation under visible-light irradiation up to λ=740 nm. It is important to understand the nitridation processes of precursor materials to form BaNbO2 N to tune the physical properties and improve the photocatalytic activity. Comprehensive experiments and analyses of temperatures, durations, ammonia flow rates, and barium/niobium ratios in the precursor during the nitridation process reveals that faster ammonia flow rates and higher barium/niobium ratios in the precursors help to suppress reduction of pentavalent niobium ions in the nitridation products and that the use of a precursor prepared by a soft-chemistry route allows the production of BaNbO2 N at lower temperatures in shorter times than the use of physical mixtures of BaCO3 and Nb2 O5 because the niobium species is dispersed among the barium species. BaNbO2 N prepared by the soft-chemistry route exhibits comparatively higher activity than that prepared from physical mixtures of BaCO3 and Nb2 O5 , probably because of lower nitridation temperatures, which suppress excessive dissociation of ammonia, and thereby reduce pentavalent niobium ions, and intimate interaction of niobium and barium sources, which lowers the densities of mid-gap states associated with defects. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Complex impedance analyses and magnetoelectric effect in ferrite ferroelectric composite ceramics

NASA Astrophysics Data System (ADS)

Patankar, K. K.; Kanade, S. A.; Padalkar, D. S.; Chougule, B. K.

2007-02-01

Magnetoelectric (ME) composites yBa0.8Pb0.2TiO3 (1-y)CuFe2O4 are prepared by ceramic method. The component phases are prepared from two different routes, viz. CuFe2O4 (ferrite phase) is prepared by oxalate precursor route and Ba0.8Pb0.2TiO3 (ferroelectric phase) by solid-state reaction route. No intermediate phases are observed in the composites containing these ferrite and ferroelectric phases. ME conversion factor (measure of ME effect) is found to be enhanced compared to those reported in the composites, in which the component phases were prepared by only one route, i.e. solid-state reaction route. The results on ME conversion are well accounted by measuring the complex impedance and analyzing their Nyquist plots.

Sol-gel precursors and products thereof

DOEpatents

Warren, Scott C.; DiSalvo, Jr., Francis J.; Weisner, Ulrich B.

2017-02-14

The present invention provides a generalizable single-source sol-gel precursor capable of introducing a wide range of functionalities to metal oxides such as silica. The sol-gel precursor facilitates a one-molecule, one-step approach to the synthesis of metal-silica hybrids with combinations of biological, catalytic, magnetic, and optical functionalities. The single-source precursor also provides a flexible route for simultaneously incorporating functional species of many different types. The ligands employed for functionalizing the metal oxides are derived from a library of amino acids, hydroxy acids, or peptides and a silicon alkoxide, allowing many biological functionalities to be built into silica hybrids. The ligands can coordinate with a wide range of metals via a carboxylic acid, thereby allowing direct incorporation of inorganic functionalities from across the periodic table. Using the single-source precursor a wide range of functionalized nanostructures such as monolith structures, mesostructures, multiple metal gradient mesostructures and Stober-type nanoparticles can be synthesized. ##STR00001##

Benzimidazole Based Aerogel Materials

NASA Technical Reports Server (NTRS)

Rhine, Wendell E. (Inventor); Mihalcik, David (Inventor)

2016-01-01

The present invention provides aerogel materials based on imidazoles and polyimidazoles. The polyimidazole based aerogel materials can be thermally stable up to 500 C or more, and can be carbonized to produce a carbon aerogel having a char yield of 60% or more, specifically 70% or more. The present invention also provides methods of producing polyimidazole based aerogel materials by reacting at least one monomer in a suitable solvent to form a polybenzimidazole gel precursor solution, casting the polybenzimidazole gel precursor solution into a fiber reinforcement phase, allowing the at least one gel precursor in the precursor solution to transition into a gel material, and drying the gel materials to remove at least a portion of the solvent, to obtain an polybenzimidazole-based aerogel material.

Mitigating Distributed Denial of Service Attacks with Multi-Protocol Label Switching-Traffic Engineering (MPLS-TE)

DTIC Science & Technology

2009-03-01

time and the router CPU loads are comparable to those reported by two former NPS theses that examined alternative solutions based on BGP blackhole ...routing. 15. NUMBER OF PAGES 135 14. SUBJECT TERMS Traffic Engineering, Distributed Denial of Service Attacks, Sinkhole Routing, Blackhole Routing...alternative solutions based on BGP blackhole routing. vi THIS PAGE INTENTIONALLY LEFT BLANK vii TABLE OF CONTENTS I. INTRODUCTION

A Formal Algorithm for Routing Traces on a Printed Circuit Board

NASA Technical Reports Server (NTRS)

Hedgley, David R., Jr.

1996-01-01

This paper addresses the classical problem of printed circuit board routing: that is, the problem of automatic routing by a computer other than by brute force that causes the execution time to grow exponentially as a function of the complexity. Most of the present solutions are either inexpensive but not efficient and fast, or efficient and fast but very costly. Many solutions are proprietary, so not much is written or known about the actual algorithms upon which these solutions are based. This paper presents a formal algorithm for routing traces on a print- ed circuit board. The solution presented is very fast and efficient and for the first time speaks to the question eloquently by way of symbolic statements.

Synthetic wastewaters treatment by electrocoagulation to remove silver nanoparticles produced by different routes.

PubMed

Matias, M S; Melegari, S P; Vicentini, D S; Matias, W G; Ricordel, C; Hauchard, D

2015-08-15

Nanoscience is a field that has stood out in recent years. The accurate long-term health and environmental risks associated with these emerging materials are unknown. Therefore, this work investigated how to eliminate silver nanoparticles (AgNPs) from synthetic effluents by electrocoagulation (EC) due to the widespread use of this type of nanoparticle (NP) in industry and its potential inhibition power over microorganisms responsible for biological treatment in effluent treatment plants. Synthesized AgNPs were studied via four different routes by chemical reduction in aqueous solutions to simulate the chemical variations of a hypothetical industrial effluent, and efficiency conditions of the EC treatment were determined. All routes used silver nitrate as the source of silver ions, and two synthesis routes were studied with sodium citrate as a stabilizer. In route I, sodium citrate functioned simultaneously as the reducing agent and stabilizing agent, whereas route II used sodium borohydride as a reducing agent. Route III used D-glucose as the reducing agent and sodium pyrophosphate as the stabilizer; route IV used sodium pyrophosphate as the stabilizing agent and sodium borohydride as the reducing agent. The efficiency of the EC process of the different synthesized solutions was studied. For route I, after 85 min of treatment, a significant decrease in the plasmon resonance peak of the sample was observed, which reflects the efficiency in the mass reduction of AgNPs in the solution by 98.6%. In route II, after 12 min of EC, the absorbance results reached the detection limit of the measurement instrument, which indicates a minimum reduction of 99.9% of AgNPs in the solution. During the 4 min of treatment in route III, the absorbance intensities again reached the detection limit, which indicates a minimum reduction of 99.8%. In route IV, after 10 min of treatment, a minimum AgNP reduction of 99.9% was observed. Based on these results, it was possible to verify that the solutions containing citrate considerably increased the necessary times required to eliminate AgNPs from the synthesized effluent, whereas solutions free of this reagent showed better results on floc formation and, therefore, are best for the treatment. The elimination of AgNPs from effluents by EC proved effective for the studied routes. Copyright © 2015 Elsevier Ltd. All rights reserved.

Methods for producing thin film charge selective transport layers

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

Hammond, Scott Ryan; Olson, Dana C.; van Hest, Marinus Franciscus Antonius Maria

Methods for producing thin film charge selective transport layers are provided. In one embodiment, a method for forming a thin film charge selective transport layer comprises: providing a precursor solution comprising a metal containing reactive precursor material dissolved into a complexing solvent; depositing the precursor solution onto a surface of a substrate to form a film; and forming a charge selective transport layer on the substrate by annealing the film.

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.

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.

Investigation on V2O5 Thin Films Prepared by Spray Pyrolysis Technique

NASA Astrophysics Data System (ADS)

Anasthasiya, A. Nancy Anna; Gowtham, K.; Shruthi, R.; Pandeeswari, R.; Jeyaprakash, B. G.

The spray pyrolysis technique was employed to deposit V2O5 thin films on a glass substrate. By varying the precursor solution volume from 10mL to 50mL in steps of 10mL, films of various thicknesses were prepared. Orthorhombic polycrystalline V2O5 films were inferred from the XRD pattern irrespective of precursor solution volume. The micro-Raman studies suggested that annealed V2O5 thin film has good crystallinity. The effect of precursor solution volume on morphological and optical properties were analysed and reported.

CCS-DTN: clustering and network coding-based efficient routing in social DTNs.

PubMed

Zhang, Zhenjing; Ma, Maode; Jin, Zhigang

2014-12-25

With the development of mobile Internet, wireless communication via mobile devices has become a hot research topic, which is typically in the form of Delay Tolerant Networks (DTNs). One critical issue in the development of DTNs is routing. Although there is a lot research work addressing routing issues in DTNs, they cannot produce an advanced solution to the comprehensive challenges since only one or two aspects (nodes' movements, clustering, centricity and so on) are considered when the routing problem is handled. In view of these defects in the existing works, we propose a novel solution to address the routing issue in social DTNs. By this solution, mobile nodes are divided into different clusters. The scheme, Spray and Wait, is used for the intra-cluster communication while a new forwarding mechanism is designed for the inter-cluster version. In our solution, the characteristics of nodes and the relation between nodes are fully considered. The simulation results show that our proposed scheme can significantly improve the performance of the routing scheme in social DTNs.

CCS-DTN: Clustering and Network Coding-Based Efficient Routing in Social DTNs

PubMed Central

Zhang, Zhenjing; Ma, Maode; Jin, Zhigang

2015-01-01

With the development of mobile Internet, wireless communication via mobile devices has become a hot research topic, which is typically in the form of Delay Tolerant Networks (DTNs). One critical issue in the development of DTNs is routing. Although there is a lot research work addressing routing issues in DTNs, they cannot produce an advanced solution to the comprehensive challenges since only one or two aspects (nodes' movements, clustering, centricity and so on) are considered when the routing problem is handled. In view of these defects in the existing works, we propose a novel solution to address the routing issue in social DTNs. By this solution, mobile nodes are divided into different clusters. The scheme, Spray and Wait, is used for the intra-cluster communication while a new forwarding mechanism is designed for the inter-cluster version. In our solution, the characteristics of nodes and the relation between nodes are fully considered. The simulation results show that our proposed scheme can significantly improve the performance of the routing scheme in social DTNs. PMID:25609047

Effect of annealing temperature on optical properties of binary zinc tin oxide nano-composite prepared by sol-gel route using simple precursors: structural and optical studies by DRS, FT-IR, XRD, FESEM investigations.

PubMed

Habibi, Mohammad Hossein; Mardani, Maryam

2015-02-25

Binary zinc tin oxide nano-composite was synthesized by a facile sol-gel method using simple precursors from the solutions consisting of zinc acetate, tin(IV) chloride and ethanol. Effect of annealing temperature on optical and structural properties was investigated using X-ray diffraction (XRD), diffuse reflectance spectra (DRS), field emission scanning electron microscopy (FESEM) and Fourier transform infrared spectroscopy (FTIR). XRD results revealed the existence of the ZnO and SnO2 phases. FESEM results showed that binary zinc tin oxide nano-composites ranges from 56 to 60 nm in diameter at 400°C and 500°C annealing temperatures respectively. The optical band gap was increased from 2.72 eV to 3.11 eV with the increasing of the annealing temperature. FTIR results confirmed the presence of zinc oxide and tin oxide and the broad absorption peaks at 3426 and 1602 cm(-1) can be ascribed to the vibration of absorptive water, and the absorption peaks at 546, 1038 and 1410 cm(-1) are due to the vibration of Zn-O or Sn-O groups in binary zinc tin oxide. Copyright © 2014 Elsevier B.V. All rights reserved.

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.

EFFECTS OF PRECURSOR SOLUTION MODIFICATION ON THE CRYSTALLINITY AND ELECTRICAL PROPERTIES OF Na0.5Bi0.5TiO3-BiFeO3 BASED THIN FILM

NASA Astrophysics Data System (ADS)

Sui, Huiting; Yang, Changhong; Wang, Gaoyun; Feng, Chao

2014-07-01

For chemical solution decomposition process, the precursor solution is a basic factor affecting the quality of the deposited-film. In this paper, we choose (l00)-oriented 0.7[(Bi0.95Ce0.05)0.5Na0.5(Ti0.99Fe0.01)O3]-0.3BiFe0.97Mn0.03O3(0.7NBTCeFe-0.3BFOMn) thin films prepared by various precursor solutions for investigation. The roles of precursor solution modification on crystallinity, ferroelectric and dielectric properties are characterized. With the addition of polyethylene glycol into the solution, phase-pure perovskite structure can be obtained. Furthermore, when the volume ratio for the solvents (ethylene glycol to acetic acid) is modified as 2:1, enhanced ferroelectricity can be achieved with a remanent polarization (Pr) of 27.5 μC/cm2, which coincides well with the capacitance-voltage curve with relatively sharp feature. Also, the 0.7NBTCeFe-0.3BFOMn film exhibits a dielectric constant (ɛr) of 576 and dielectric loss (tan δ) of 0.123 at 100 kHz.

Formulating Precursors for Coating Metals and Ceramics

NASA Technical Reports Server (NTRS)

Morales, Wilfredo; Gatica, Jorge E.; Reye, John T.

2005-01-01

A protocol has been devised for formulating low-vapor-pressure precursors for protective and conversion coatings on metallic and ceramic substrates. The ingredients of a precursor to which the protocol applies include additives with phosphate esters, or aryl phosphate esters in solution. Additives can include iron, chromium, and/or other transition metals. Alternative or additional additives can include magnesium compounds to facilitate growth of films on substrates that do not contain magnesium. Formulation of a precursor begins with mixing of the ingredients into a high-vapor-pressure solvent to form a homogeneous solution. Then the solvent is extracted from the solution by evaporation - aided, if necessary, by vacuum and/or slight heating. The solvent is deemed to be completely extracted when the viscosity of the remaining solution closely resembles the viscosity of the phosphate ester or aryl phosphate ester. In addition, satisfactory removal of the solvent can be verified by means of a differential scanning calorimetry essay: the absence of endothermic processes for temperatures below 150 C would indicate that the residual solvent has been eliminated from the solution beyond a detectable dilution level.

Low-temperature solution route to macroscopic amounts of hydrogen terminated silicon nanoparticles.

PubMed

Neiner, Doinita; Chiu, Hsiang Wei; Kauzlarich, Susan M

2006-08-30

A new solution route for preparing gram-scale, hydrogen terminated silicon nanoparticles is presented. Dimethoxyethane and diocytl ether have been used to prepare silicon nanoparticles via a solution reaction between sodium silicide and ammonium bromide. The reaction products are isolated as a clear yellow-orange solution and a dark black powder. Both the solution and the powder have been characterized.

Precursor routes to quaternary intermetallics: Synthesis, crystal structure, and physical properties of clathrate-II Cs8Na16Al24Si112

NASA Astrophysics Data System (ADS)

Wei, Kaya; Dong, Yongkwan; Nolas, George S.

2016-05-01

A new quaternary clathrate-II composition, Cs8Na16Al24Si112, was synthesized by kinetically controlled thermal decomposition (KCTD) employing both NaSi and NaAlSi as the precursors and CsCl as a reactive flux. The crystal structure and composition of Cs8Na16Al24Si112 were investigated using both Rietveld refinement and elemental analysis, and the temperature dependent transport properties were investigated. Our results indicate that KCTD with multiple precursors is an effective method for the synthesis of multinary inorganic phases that are not easily accessible by traditional solid-state synthesis or crystal growth techniques.

XPS and SEM analysis of the surface of gas atomized powder precursor of ODS ferritic steels obtained through the STARS route

NASA Astrophysics Data System (ADS)

Gil, E.; Cortés, J.; Iturriza, I.; Ordás, N.

2018-01-01

An innovative powder metallurgy route to produce ODS FS, named STARS, has succeeded in atomizing steel powders containing the oxide formers (Y and Ti) and, hence, avoids the mechanical alloying (MA) step to dissolve Y in the matrix. A metastable oxide layer forms at the surface of atomized powders and dissociates during HIP consolidation at high temperatures, leading to precipitation of more stable Y-Ti-O nanoparticles.

Single Particle Dynamic Imaging and Fe3+ Sensing with Bright Carbon Dots Derived from Bovine Serum Albumin Proteins

NASA Astrophysics Data System (ADS)

Yang, Qingxiu; Wei, Lin; Zheng, Xuanfang; Xiao, Lehui

2015-12-01

In this work, we demonstrated a convenient and green strategy for the synthesis of highly luminescent and water-soluble carbon dots (Cdots) by carbonizing carbon precursors, i.e., Bovine serum albumin (BSA) nanoparticles, in water solution. Without post surface modification, the as-synthesized Cdots exhibit fluorescence quantum yield (Q.Y.) as high as 34.8% and display superior colloidal stability not only in concentrated salt solutions (e.g. 2 M KCl) but also in a wide range of pH solutions. According to the FT-IR measurements, the Cdots contain many carboxyl groups, providing a versatile route for further chemical and biological functionalization. Through conjugation of Cdots with the transacting activator of transcription (TAT) peptide (a kind of cell penetration peptide (CPP)) derived from human immunodeficiency virus (HIV), it is possible to directly monitor the dynamic interactions of CPP with living cell membrane at single particle level. Furthermore, these Cdots also exhibit a dosage-dependent selectivity toward Fe3+ among other metal ions, including K+, Na+, Mg2+, Hg2+, Co2+, Cu2+, Pb2+ and Al3+. We believed that the Cdots prepared by this strategy would display promising applications in various areas, including analytical chemistry, nanomedicine, biochemistry and so on.

Short-length and high-density TiO2 nanorod arrays for the efficient charge separation interface in perovskite solar cells

NASA Astrophysics Data System (ADS)

Xiao, Guannan; Shi, Chengwu; Zhang, Zhengguo; Li, Nannan; Li, Long

2017-05-01

The TiO2 nanorod arrays with the length of 70 nm, the diameter of 20 nm, and the areal density of 1000 μm-2 were firstly prepared by the hydrothermal method using the aqueous grown solution of 38 mM titanium isopropoxide and 6 M hydrochloric acid at 170 °C for 60 min. Over-500 nm-thickness CH3NH3PbI3-xBrx absorber layers were successfully obtained by sequential deposition routes using 1.7 M PbI2·DMSO complex precursor solution and 0.465 M isopropanol solution of the methylammonium halide mixture with the molar ratio of CH3NH3I/CH3NH3Br=85/15. The perovskite solar cells based on the TiO2 nanorod array and 560 nm-thickness CH3NH3PbI3-xBrx absorber layer exhibited the best photoelectric conversion efficiency (PCE) of 15.93%, while the corresponding planar perovskite solar cells without the TiO2 nanorod array and with 530 nm-thickness CH3NH3PbI3-xBrx absorber layer gave the best PCE of 12.82% at the relative humidity of 50-54%.

From iron coordination compounds to metal oxide nanoparticles.

PubMed

Iacob, Mihail; Racles, Carmen; Tugui, Codrin; Stiubianu, George; Bele, Adrian; Sacarescu, Liviu; Timpu, Daniel; Cazacu, Maria

2016-01-01

Various types, shapes and sizes of iron oxide nanoparticles were obtained depending on the nature of the precursor, preparation method and reaction conditions. The mixed valence trinuclear iron acetate, [Fe 2 III Fe II O(CH 3 COO) 6 (H 2 O) 3 ]·2H 2 O (FeAc1), μ 3 -oxo trinuclear iron(III) acetate, [Fe 3 O(CH 3 COO) 6 (H 2 O) 3 ]NO 3 ∙4H 2 O (FeAc2), iron furoate, [Fe 3 O(C 4 H 3 OCOO) 6 (CH 3 OH) 3 ]NO 3 ∙2CH 3 OH (FeF), iron chromium furoate, FeCr 2 O(C 4 H 3 OCOO) 6 (CH 3 OH) 3 ]NO 3 ∙2CH 3 OH (FeCrF), and an iron complex with an original macromolecular ligand (FePAZ) were used as precursors for the corresponding oxide nanoparticles. Five series of nanoparticle samples were prepared employing either a classical thermal pathway (i.e., thermal decomposition in solution, solvothermal method, dry thermal decomposition/calcination) or using a nonconventional energy source (i.e., microwave or ultrasonic treatment) to convert precursors into iron oxides. The resulting materials were structurally characterized by wide-angle X-ray diffraction and Fourier transform infrared, Raman, energy-dispersive X-ray, and X-ray fluorescence spectroscopies, as well as thermogravimetric analysis. The morphology was characterized by transmission electron microscopy, atomic force microscopy and dynamic light scattering. The parameters were varied within each route to fine tune the size and shape of the formed nanoparticles.

From iron coordination compounds to metal oxide nanoparticles

PubMed Central

Iacob, Mihail; Racles, Carmen; Tugui, Codrin; Stiubianu, George; Bele, Adrian; Sacarescu, Liviu; Timpu, Daniel

2016-01-01

Various types, shapes and sizes of iron oxide nanoparticles were obtained depending on the nature of the precursor, preparation method and reaction conditions. The mixed valence trinuclear iron acetate, [Fe2 IIIFeIIO(CH3COO)6(H2O)3]·2H2O (FeAc1), μ3-oxo trinuclear iron(III) acetate, [Fe3O(CH3COO)6(H2O)3]NO3∙4H2O (FeAc2), iron furoate, [Fe3O(C4H3OCOO)6(CH3OH)3]NO3∙2CH3OH (FeF), iron chromium furoate, FeCr2O(C4H3OCOO)6(CH3OH)3]NO3∙2CH3OH (FeCrF), and an iron complex with an original macromolecular ligand (FePAZ) were used as precursors for the corresponding oxide nanoparticles. Five series of nanoparticle samples were prepared employing either a classical thermal pathway (i.e., thermal decomposition in solution, solvothermal method, dry thermal decomposition/calcination) or using a nonconventional energy source (i.e., microwave or ultrasonic treatment) to convert precursors into iron oxides. The resulting materials were structurally characterized by wide-angle X-ray diffraction and Fourier transform infrared, Raman, energy-dispersive X-ray, and X-ray fluorescence spectroscopies, as well as thermogravimetric analysis. The morphology was characterized by transmission electron microscopy, atomic force microscopy and dynamic light scattering. The parameters were varied within each route to fine tune the size and shape of the formed nanoparticles. PMID:28144555

Benzoyl Halides as Alternative Precursors for the Colloidal Synthesis of Lead-Based Halide Perovskite Nanocrystals

PubMed Central

2018-01-01

We propose here a new colloidal approach for the synthesis of both all-inorganic and hybrid organic–inorganic lead halide perovskite nanocrystals (NCs). The main limitation of the protocols that are currently in use, such as the hot injection and the ligand-assisted reprecipitation routes, is that they employ PbX2 (X = Cl, Br, or I) salts as both lead and halide precursors. This imposes restrictions on being able to precisely tune the amount of reaction species and, consequently, on being able to regulate the composition of the final NCs. In order to overcome this issue, we show here that benzoyl halides can be efficiently used as halide sources to be injected in a solution of metal cations (mainly in the form of metal carboxylates) for the synthesis of APbX3 NCs (in which A = Cs+, CH3NH3+, or CH(NH2)2+). In this way, it is possible to independently tune the amount of both cations and halide precursors in the synthesis. The APbX3 NCs that were prepared with our protocol show excellent optical properties, such as high photoluminescence quantum yields, low amplified spontaneous emission thresholds, and enhanced stability in air. It is noteworthy that CsPbI3 NCs, which crystallize in the cubic α phase, are stable in air for weeks without any postsynthesis treatment. The improved properties of our CsPbX3 perovskite NCs can be ascribed to the formation of lead halide terminated surfaces, in which Cs cations are replaced by alkylammonium ions. PMID:29378131

Benzoyl Halides as Alternative Precursors for the Colloidal Synthesis of Lead-Based Halide Perovskite Nanocrystals.

PubMed

Imran, Muhammad; Caligiuri, Vincenzo; Wang, Mengjiao; Goldoni, Luca; Prato, Mirko; Krahne, Roman; De Trizio, Luca; Manna, Liberato

2018-02-21

We propose here a new colloidal approach for the synthesis of both all-inorganic and hybrid organic-inorganic lead halide perovskite nanocrystals (NCs). The main limitation of the protocols that are currently in use, such as the hot injection and the ligand-assisted reprecipitation routes, is that they employ PbX 2 (X = Cl, Br, or I) salts as both lead and halide precursors. This imposes restrictions on being able to precisely tune the amount of reaction species and, consequently, on being able to regulate the composition of the final NCs. In order to overcome this issue, we show here that benzoyl halides can be efficiently used as halide sources to be injected in a solution of metal cations (mainly in the form of metal carboxylates) for the synthesis of APbX 3 NCs (in which A = Cs + , CH 3 NH 3 + , or CH(NH 2 ) 2 + ). In this way, it is possible to independently tune the amount of both cations and halide precursors in the synthesis. The APbX 3 NCs that were prepared with our protocol show excellent optical properties, such as high photoluminescence quantum yields, low amplified spontaneous emission thresholds, and enhanced stability in air. It is noteworthy that CsPbI 3 NCs, which crystallize in the cubic α phase, are stable in air for weeks without any postsynthesis treatment. The improved properties of our CsPbX 3 perovskite NCs can be ascribed to the formation of lead halide terminated surfaces, in which Cs cations are replaced by alkylammonium ions.

An antibacterial coating based on a polymer/sol-gel hybrid matrix loaded with silver nanoparticles

NASA Astrophysics Data System (ADS)

Rivero, Pedro José; Urrutia, Aitor; Goicoechea, Javier; Zamarreño, Carlos Ruiz; Arregui, Francisco Javier; Matías, Ignacio Raúl

2011-12-01

In this work a novel antibacterial surface composed of an organic-inorganic hybrid matrix of tetraorthosilicate and a polyelectrolyte is presented. A precursor solution of tetraethoxysilane (TEOS) and poly(acrylic acid sodium salt) (PAA) was prepared and subsequently thin films were fabricated by the dip-coating technique using glass slides as substrates. This hybrid matrix coating is further loaded with silver nanoparticles using an in situ synthesis route. The morphology and composition of the coatings have been studied using UV-VIS spectroscopy and atomic force microscopy (AFM). Energy dispersive X-ray (EDX) was also used to confirm the presence of the resulting silver nanoparticles within the thin films. Finally the coatings have been tested in bacterial cultures of genus Lactobacillus plantarum to observe their antibacterial properties. It has been experimentally demonstrated that these silver loaded organic-inorganic hybrid films have a very good antimicrobial behavior against this type of bacteria.

Generalised syntheses of ordered mesoporous oxides: the atrane route

NASA Astrophysics Data System (ADS)

Cabrera, Saúl; El Haskouri, Jamal; Guillem, Carmen; Latorre, Julio; Beltrán-Porter, Aurelio; Beltrán-Porter, Daniel; Marcos, M. Dolores; Amorós *, Pedro

2000-06-01

A new simple and versatile technique to obtain mesoporous oxides is presented. While implying surfactant-assisted formation of mesostructured intermediates, the original chemical contribution of this approach lies in the use of atrane complexes as precursors. Without prejudice to their inherent unstability in aqueous solution, the atranes show a marked inertness towards hydrolysis. Bringing kinetic factors into play, it becomes possible to control the processes involved in the formation of the surfactant-inorganic phase composite micelles, which constitute the elemental building blocks of the mesostructures. Independent of the starting compositional complexity, both the mesostructured intermediates and the final mesoporous materials are chemically homogeneous. The final ordered mesoporous materials are thermally stable and show unimodal porosity, as well as homogeneous microstructure and texture. Examples of materials synthesised on account of the versatility of this new method, including siliceous, non siliceous and mixed oxides, are presented and discussed.

In Situ X-ray Absorption Near-Edge Structure Spectroscopy of ZnO Nanowire Growth During Chemical Bath Deposition

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

McPeak, Kevin M.; Becker, Matthew A.; Britton, Nathan G.

2010-12-03

Chemical bath deposition (CBD) offers a simple and inexpensive route to deposit semiconductor nanostructures, but lack of fundamental understanding and control of the underlying chemistry has limited its versatility. Here we report the first use of in situ X-ray absorption spectroscopy during CBD, enabling detailed investigation of both reaction mechanisms and kinetics of ZnO nanowire growth from zinc nitrate and hexamethylenetetramine (HMTA) precursors. Time-resolved X-ray absorption near-edge structure (XANES) spectra were used to quantify Zn(II) speciation in both solution and solid phases. ZnO crystallizes directly from [Zn(H{sub 2}O){sub 6}]{sup 2+} without long-lived intermediates. Using ZnO nanowire deposition as an example,more » this study establishes in situ XANES spectroscopy as an excellent quantitative tool to understand CBD of nanomaterials.« less

Platinum CCC-NHC benzimidazolyl pincer complexes: synthesis, characterization, photostability, and theoretical investigation of a blue-green emitter.

PubMed

Huckaba, Aron J; Cao, Bei; Hollis, T Keith; Valle, Henry U; Kelly, John T; Hammer, Nathan I; Oliver, Allen G; Webster, Charles Edwin

2013-06-28

The recently reported metallation/transmetallation route for the synthesis of CCC-bis(NHC) pincer ligand architectures was extended to 1,3-bis(3'-(trimethylsilylmethyl)-benzimidizol-1'-yl)benzene. The precursor was metallated with Zr(NMe2)4 and transmetallated to Pt using [Pt(COD)Cl2]. This Pt complex was found to resist photobleaching under UV irradiation in ambient conditions. Density functional theory (DFT) computations were used to generate the emission spectrum of the complex and reveal that this spectrum is the result of a transition from the triplet excited state (T1) to the ground state (S0). The Pt complex's molecular structure was determined by X-ray crystallography. The UV-vis absorption and emission spectra in solution and the solid-state emission spectra are reported. The solid-state photostability data and the radiative lifetime is also reported.

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

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.

Nanofibrous electrocatalysts

DOEpatents

Liu, Di Jia; Shui, Jianglan; Chen, Chen

2016-05-24

A nanofibrous catalyst and method of manufacture. A precursor solution of a transition metal based material is formed into a plurality of interconnected nanofibers by electro-spinning the precursor solution with the nanofibers converted to a catalytically active material by a heat treatment. Selected subsequent treatments can enhance catalytic activity.

Enabling Surgical Placement of Hydrogels through Achieving Paste-Like Rheological Behavior in Hydrogel Precursor Solutions

PubMed Central

Beck, Emily C.; Lohman, Brooke L.; Tabakh, Daniel B.; Kieweg, Sarah L.; Gehrke, Stevin H.; Berkland, Cory J.; Detamore, Michael S.

2015-01-01

Hydrogels are a promising class of materials for tissue regeneration, but they lack the ability to be molded into a defect site by a surgeon because hydrogel precursors are liquid solutions that are prone to leaking during placement. Therefore, although the main focus of hydrogel technology and developments are on hydrogels in their crosslinked form, our primary focus is on improving the fluid behavior of hydrogel precursor solutions. In this work, we introduce a method to achieve paste-like hydrogel precursor solutions by combining hyaluronic acid nanoparticles with traditional crosslinked hyaluronic acid hydrogels. Prior to crosslinking, the samples underwent rheological testing to assess yield stress and recovery using linear hyaluronic acid as a control. The experimental groups containing nanoparticles were the only solutions that exhibited a yield stress, demonstrating that the nanoparticulate rather than the linear form of hyaluronic acid was necessary to achieve paste-like behavior. The gels were also photocrosslinked and further characterized as solids, where it was demonstrated that the inclusion of nanoparticles did not adversely affect the compressive modulus and that encapsulated bone marrow-derived mesenchymal stem cells remained viable. Overall, this nanoparticle-based approach provides a platform hydrogel system that exhibits a yield stress prior to crosslinking, and can then be crosslinked into a hydrogel that is capable of encapsulating cells that remain viable. This behavior may hold significant impact for hydrogel applications where a paste-like behavior is desired in the hydrogel precursor solution. PMID:25691398

Optical and Morphological Characterization of Sonochemically Assisted Europium Doped Copper (I) Oxide Nanostructures

NASA Astrophysics Data System (ADS)

Cosico, J. A. M.; Ruales, P. K.; Marquez, M. C.

2017-06-01

In the age where application of nanotechnology in our society has proven to be eminent, different routes of synthesizing nanoparticles have emerged. In this study nanoparticles of cuprous oxide (Cu2O) doped with different amounts of europium was prepared by using solution precursor route approach with the aid of ultrasonic sound. Copper sulphate and europium (III) nitrate pentahydrate was used as source for copper ions and europium ions respectively. X-ray diffraction (XRD) and Fourier Transform Infrared spectroscopy (FTIR) were used to elucidate the cubic crystal structure and organic impurities present on Cu2Onanoparticles. UV-Vis spectroscopy was used to determine the absorption spectrum of the nanoparticles in the wavelength range of 400nm to 700nm. The bandgap of the undoped and doped Cu2O were found to fall between 2.1eV - 2.3eV. Scanning Electron Microscopy (SEM) coupled with energy dispersive x-ray was used to observe the dendritic and rodlike morphology and the presence of europium in the synthesized Cu2O nanoparticles. The observed effect on the absorbance of Cu2O upon adding Eu and a facile way of synthesizing Cu2O nanoparticles could bring a positive impact on the production of functional devices for optoelectronic and energy applications.

Precursor preparation for Ca-Al layered double hydroxide to remove hexavalent chromium coexisting with calcium and magnesium chlorides

NASA Astrophysics Data System (ADS)

Zhong, Lihua; He, Xiaoman; Qu, Jun; Li, Xuewei; Lei, Zhiwu; Zhang, Qiwu; Liu, Xinzhong

2017-01-01

Al(OH)3 and Ca(OH)2 powders are co-ground to prepare a precursor which hydrates into a layered double hydroxide (LDH) phase by agitation in aqueous solution with target hexavalent chromium (Cr(VI)) at room temperature, to achieve an obvious improvement in removal efficiency of Cr(VI) through an easy incorporation into the structure. Although the prepared precursor transforms into LDH phases also when agitated in the solutions of calcium and magnesium chlorides, it incorporates Cr(VI) preferentially to the chloride salts when they coexist. The adsorption isotherm and kinetic studies show that the phenomena occurring on the Al-Ca precursor fit a pseudo-second-order kinetics with a Langmuir adsorption capacity of 59.45 mg/g. Besides, characterizations of the prepared precursor and the samples after adsorption are also performed by X-ray diffraction (XRD), Fourier transform infrared (FT-IR), Transmission electron microscope (TEM) to understand the reason of the preferential incorporation of Cr(VI) to the coexisting chloride salts during the LDH phase formation. Ca-Al precursor (C3A) was agitated in a hexavalent chromium (Cr(VI)) solution to form Al-Ca-CrO4 LDH product. Ca-Al-CrO4 LDH phase occurred preferentially to Ca-Al-MCl2 LDH phases in the solutions of calcium and magnesium chlorides, it incorporates Cr(VI) preferentially to the chloride salts when they coexist.

Direct nanoimprint lithography of Al2O3 using a chelated monomer-based precursor

NASA Astrophysics Data System (ADS)

Ganesan, Ramakrishnan; Safari Dinachali, Saman; Lim, Su Hui; Saifullah, M. S. M.; Tit Chong, Wee; Lim, Andrew H. H.; Jie Yong, Jin; San Thian, Eng; He, Chaobin; Low, Hong Yee

2012-08-01

Nanostructuring of Al2O3 is predominantly achieved by the anodization of aluminum film and is limited to obtaining porous anodized aluminum oxide (AAO). One of the main restrictions in developing approaches for direct fabrication of various types of Al2O3 patterns, such as lines, pillars, holes, etc, is the lack of a processable aluminum-containing resist. In this paper, we demonstrate a stable precursor prepared by reacting aluminum tri-sec-butoxide with 2-(methacryloyloxy)ethyl acetoacetate, a chelating monomer, which can be used for large area direct nanoimprint lithography of Al2O3. Chelation in the precursor makes it stable against hydrolysis whilst the presence of a reactive methacrylate group renders it polymerizable. The precursor was mixed with a cross-linker and their in situ thermal free-radical co-polymerization during nanoimprinting rigidly shaped the patterns, trapped the metal atoms, reduced the surface energy and strengthened the structures, thereby giving a ˜100% yield after demolding. The imprinted structures were heat-treated, leading to the loss of organics and their subsequent shrinkage. Amorphous Al2O3 patterns with line-widths as small as 17 nm were obtained. Our process utilizes the advantages of sol-gel and methacrylate routes for imprinting and at the same time alleviates the disadvantages associated with both these methods. With these benefits, the chelating monomer route may be the harbinger of the universal scheme for direct nanoimprinting of metal oxides.

Catalyst Of A Metal Heteropoly Acid Salt That Is Insoluble In A Polar Solvent On A Non-Metallic Porous Support And Method Of Making

DOEpatents

Wang. Yong; Peden. Charles H. F.; Choi. Saemin

2004-11-09

The present invention includes a catalyst having (a) a non-metallic support having a plurality of pores; (b) a metal heteropoly acid salt that is insoluble in a polar solvent on the non-metallic support; wherein at least a portion of the metal heteropoly acid salt is dispersed within said plurality of pores. The present invention also includes a method of depositing a metal heteropoly acid salt that is insoluble in a polar solvent onto a non-metallic support having a plurality of pores. The method has the steps of: (a) obtaining a first solution containing a first precursor of a metal salt cation; (b) obtaining a second solution containing a second precursor of a heteropoly acid anion in a solvent having a limited dissolution potential for said first precursor; (c) impregnating the non-metallic support with the first precursor forming a first precursor deposit within the plurality of pores, forming a first precursor impregnated support; (d) heating said first precursor impregnated support forming a bonded first precursor impregnated support; (e) impregnating the second precursor that reacts with the precursor deposit and forms the metal heteropoly acid salt.

Catalyst of a metal heteropoly acid salt that is insoluble in a polar solvent on a non-metallic porous support and method of making

DOEpatents

Wang, Yong [Richland, WA; Peden, Charles H. F. [West Richland, WA; Choi, Saemin [Richland, WA

2002-10-29

The present invention includes a catalyst having (a) a non-metallic support having a plurality of pores; (b) a metal heteropoly acid salt that is insoluble in a polar solvent on the non-metallic support; wherein at least a portion of the metal heteropoly acid salt is dispersed within said plurality of pores. The present invention also includes a method of depositing a metal heteropoly acid salt that is insoluble in a polar solvent onto a non-metallic support having a plurality of pores. The method has the steps of: (a) obtaining a first solution containing a first precursor of a metal salt cation; (b) obtaining a second solution containing a second precursor of a heteropoly acid anion in a solvent having a limited dissolution potential for said first precursor; (c) impregnating the non-metallic support with the first precursor forming a first precursor deposit within the plurality of pores, forming a first precursor impregnated support; (d) heating said first precursor impregnated support forming a bonded first precursor impregnated support; (e) impregnating the second precursor that reacts with the precursor deposit and forms the metal heteropoly acid salt.

Effect of Silica Nanoparticles on the Photoluminescence Properties of BCNO Phosphor

NASA Astrophysics Data System (ADS)

Nuryadin, Bebeh W.; Faryuni, Irfana Diah; Iskandar, Ferry; Abdullah, Mikrajuddin; Khairurrijal, Khairurrijal

2011-12-01

Effect of additional silica nanoparticles on the photoluminescence (PL) performance of boron carbon oxy-nitride (BCNO) phosphor was investigated. As a precursor, boric acid and urea were used as boron and nitrogen sources, respectively. The carbon sources was polyethylene glycol (PEG) with average molecule weight 20000 g/mol.. Precursor solutions were prepared by mixing these raw materials in pure water, followed by stirring to achieve homogeneous solutions. In this precursor, silica nanoparticles were added at various mass ratio from 0 to 7 %wt in the solution. The precursors were then heated at 750 °C for 60 min in a ceramic crucible under atmospheric pressure. The photoluminescence (PL) spectrum that characterized by spectrophotometer showed a single, distinct, and broad emission band varied from blue to near red color, depend on the PEG, boric acid and urea ratio in the precursor. The addition of silica nanoparticles caused the increasing of PL intensity as well as the shifting of peak wavelength of PL spectrum. The peak shifting of PL was affected by the concentration of silica nanoparticles that added into the precursor. We believe that the BCNO-silica composite phosphor becomes a promising material for the phosphor conversion-based white light-emitting diodes.

Formation of CuAlO2 Film by Ultrasonic Spray Pyrolysis

NASA Astrophysics Data System (ADS)

Iping, S.; Lockman, Zainovia; Hutagalung, S. D.; Kamsul, A.; Matsuda, Atsunori

2011-10-01

Smooth, crack free and homogenous CuAlO2 film was produced by chemical solution deposition process via spray pyrolysis technique on a cleaned Si substrate. The precursor solution used was comprised of a mixture of 45.87 mmol Cu(NO3)2.3H2O and 90 mmol Al(NO3)3.9H2O at ratio of Cu:Al = 1.2:1. The precursor solution was placed in a mist chamber and was atomized by a nebulizer to produce precursor mist. The precursor mist was then carried out by Ar gas and was sprayed onto a heated Si. Two main parameters were studied: the distance between the nozzle of the precursor mist chamber and the Si and the temperature of the Si substrate. It appears that from the XRD data, CuAlO2 can be detected for samples prepared by spraying the precursor mist at temperature of > 550 °C with distance between the nozzle and the substrate of 3cm. Reaction of the Cu and Al ions in the mist near the substrate may have promoted the crystallisation of CuAlO2.

The route of liquid precursor to ZnO nanoparticles in premixed combustion spray pyrolysis

NASA Astrophysics Data System (ADS)

Widiyastuti, W.; Machmudah, Siti; Nurtono, Tantular; Winardi, Sugeng

2018-04-01

Zinc oxide nanoparticles had been successfully synthesized by premixed combustion spray pyrolysis. Zinc acetate was dissolved in distilled water was selected as a liquid precursor. Zinc nitrate was also used for comparison the effect of precursor type on the generated particles morphology and the crystallinity. The premixed combustion reaction used liquefied petroleum gas (LPG) mainly consisting of butane and propane as a fuel and compressed air used as an oxidizer. The liquid precursor was atomized using a custom two fluid nozzle to generate droplets. Then, the droplets were sprayed by the flow of air as a carrier gas into the premixed combustion reactor. The zinc precursor was decomposed to zinc oxide due to the high temperature as a result of combustion reaction inside the reactor resulting in nanoparticles formation. The particle size decreased with the increase of the fuel flow rate. In addition, it can be found that at the same flow rate of fuel, the particle size of zinc oxide synthesized using zinc nitrate is larger than that of the use of zinc acetate as a precursor.

Risk-Hedged Approach for Re-Routing Air Traffic Under Weather Uncertainty

NASA Technical Reports Server (NTRS)

Sadovsky, Alexander V.; Bilimoria, Karl D.

2016-01-01

This presentation corresponds to: our paper explores a new risk-hedged approach for re-routing air traffic around forecast convective weather. In this work, flying through a more likely weather instantiation is considered to pose a higher level of risk. Current operational practice strategically plans re-routes to avoid only the most likely (highest risk) weather instantiation, and then tactically makes any necessary adjustments as the weather evolves. The risk-hedged approach strategically plans re-routes by minimizing the risk-adjusted path length, incorporating multiple possible weather instantiations with associated likelihoods (risks). The resulting model is transparent and is readily analyzed for realism and treated with well-understood shortest-path algorithms. Risk-hedged re-routes are computed for some example weather instantiations. The main result is that in some scenarios, relative to an operational-practice proxy solution, the risk-hedged solution provides the benefits of lower risk as well as shorter path length. In other scenarios, the benefits of the risk-hedged solution are ambiguous, because the solution is characterized by a tradeoff between risk and path length. The risk-hedged solution can be executed in those scenarios where it provides a clear benefit over current operational practice.

Method for the preparation of thallium-containing superconducting materials by precipitation

DOEpatents

Bunker, Bruce C.; Lamppa, Diana L.; Voigt, James A.

1991-01-01

This invention provides improved methods for the preparation of precursor powders that are used in the preparation of superconducting ceramic materials that contain thallium. A first solution that contains the hydrogen peroxide and metal cations, other than thallium, that will be part of the ceramic is quickly mixed with a second solution that contains precipitating anions and thallium (I) to form a precipitate which is dried to yield precursor powders. The precursor powders are calcined an sintered to produce superconducting materials that contain thallium.

Low-field magnetoresistance up to 400 K in double perovskite Sr{sub 2}FeMoO{sub 6} synthesized by a citrate route

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

Harnagea, L., E-mail: harnagealuminita@gmail.com; Jurca, B.; Physical Chemistry Department, University of Bucharest, 4-12 Bd. Elisabeta, 030018 Bucharest

2014-03-15

A wet-chemistry technique, namely the citrate route, has been used to prepare high-quality polycrystalline samples of double perovskite Sr{sub 2}FeMoO{sub 6}. We report on the evolution of magnetic and magnetoresistive properties of the synthesized samples as a function of three parameters (i) the pH of the starting solution, (ii) the decomposition temperature of the citrate precursors and (iii) the sintering conditions. The low-field magnetoresistance (LFMR) value of our best samples is as high as 5% at room temperature for an applied magnetic field of 1 kOe. Additionally, the distinguishing feature of these samples is the persistence of LFMR, with amore » reasonably large value, up to 400 K which is a crucial parameter for any practical application. Our study indicates that the enhancement of LFMR observed is due to a good compromise between the grain size distribution and their magnetic polarization. -- Graphical abstract: The microstructure (left panel) and corresponding low-field magnetoresistance of one of the Sr{sub 2}FeMoO{sub 6} samples synthesized in the course of this work. Highlights: • Samples of Sr{sub 2}FeMoO{sub 6} are prepared using a citrate route under varying conditions. • Magnetoresistive properties are improved and optimized. • Low-field magnetoresitence values as large as 5% at 300 K/1 kOe are reported. • Persistence of low-field magnetoresistance up to 400 K.« less

Micrometric BN powders used as catalyst support: influence of the precursor on the properties of the BN ceramic

NASA Astrophysics Data System (ADS)

Perdigon-Melon, José Antonio; Auroux, Aline; Guimon, Claude; Bonnetot, Bernard

2004-02-01

Thin powders and foams of boron nitride have been prepared from molecular precursors for use as noble metal supports in the catalytic conversion of methane. Different precursors originating from borazines have been tested. The best results were obtained using a precursor derived from trichloroborazine (TCB) which, after reacting with ammonia at room temperature and then thermolyzing up to 1800°C, led to BN powders with a specific area of more than 300 m 2 g -1 and a micrometric spherical texture. Comparable results were obtained using polyborazylene under similar conditions. Aminoborazine-derived precursors did not yield such high specific area ceramics but the BN microstructure resembled a foam with a crystallized skin and amorphous internal part. These differences were related to the chemical mechanism of the conversion of the precursor into BN. Polyhaloborazines and polyborazines yielded BN through gas-solid reactions whereas aminoborazine polymers could be kept waxy up to high temperatures, which favored the glassy foam. Catalysts composed of BN support and platinum have been prepared using two routes: from a mixture of precursor or by impregnation of a BN powder leading to very different catalysts.

Supramolecular self-assembly of graphene oxide and metal nanoparticles into stacked multilayers by means of a multitasking protein ring

NASA Astrophysics Data System (ADS)

Ardini, Matteo; Golia, Giordana; Passaretti, Paolo; Cimini, Annamaria; Pitari, Giuseppina; Giansanti, Francesco; Leandro, Luana Di; Ottaviano, Luca; Perrozzi, Francesco; Santucci, Sandro; Morandi, Vittorio; Ortolani, Luca; Christian, Meganne; Treossi, Emanuele; Palermo, Vincenzo; Angelucci, Francesco; Ippoliti, Rodolfo

2016-03-01

Graphene oxide (GO) is rapidly emerging worldwide as a breakthrough precursor material for next-generation devices. However, this requires the transition of its two-dimensional layered structure into more accessible three-dimensional (3D) arrays. Peroxiredoxins (Prx) are a family of multitasking redox enzymes, self-assembling into ring-like architectures. Taking advantage of both their symmetric structure and function, 3D reduced GO-based composites are hereby built up. Results reveal that the ``double-faced'' Prx rings can adhere flat on single GO layers and partially reduce them by their sulfur-containing amino acids, driving their stacking into 3D multi-layer reduced GO-Prx composites. This process occurs in aqueous solution at a very low GO concentration, i.e. 0.2 mg ml-1. Further, protein engineering allows the Prx ring to be enriched with metal binding sites inside its lumen. This feature is exploited to both capture presynthesized gold nanoparticles and grow in situ palladium nanoparticles paving the way to straightforward and ``green'' routes to 3D reduced GO-metal composite materials.Graphene oxide (GO) is rapidly emerging worldwide as a breakthrough precursor material for next-generation devices. However, this requires the transition of its two-dimensional layered structure into more accessible three-dimensional (3D) arrays. Peroxiredoxins (Prx) are a family of multitasking redox enzymes, self-assembling into ring-like architectures. Taking advantage of both their symmetric structure and function, 3D reduced GO-based composites are hereby built up. Results reveal that the ``double-faced'' Prx rings can adhere flat on single GO layers and partially reduce them by their sulfur-containing amino acids, driving their stacking into 3D multi-layer reduced GO-Prx composites. This process occurs in aqueous solution at a very low GO concentration, i.e. 0.2 mg ml-1. Further, protein engineering allows the Prx ring to be enriched with metal binding sites inside its lumen. This feature is exploited to both capture presynthesized gold nanoparticles and grow in situ palladium nanoparticles paving the way to straightforward and ``green'' routes to 3D reduced GO-metal composite materials. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr08632a

Multi-layer articles and methods of making same

DOEpatents

Fritzemeier, Leslie G.; Zhang, Wei; Palm, Walter C.; Rupich, Martin W.

2005-05-17

The invention relates to superconductor articles, and compositions and methods for making superconductor articles. The methods can include using a precursor solution having a relatively small concentration of total free acid. The articles can include more than one layer of superconductor material in which at least one layer of superconductor material can be formed by a solution process, such as a solution process involving the use of metalorganic precursors.

Preparation of Sic/AIN Solid Solutions Using Organometallic Precursors

DTIC Science & Technology

1989-02-15

pyrolysis of organoaluminum and organosilicon compounds was investigated as a potential source of SiC /AUI solid solutions. Using two different co... pyrolysis methods, homogeneous mixtures of organoaluminum amides and both a vinylic polysilane and a poly- carbosilane were convertec to a preceramic ...solid that transformed to crystalline SiC /AiN solid solutions at 򒸀 C. Moreover, the liquid, polymeric , form of these precursor mixtures provides a

Magnéli phases Ti{sub 4}O{sub 7} and Ti{sub 8}O{sub 15} and their carbon nanocomposites via the thermal decomposition-precursor route

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

Conze, S., E-mail: susan.conze@ikts.fraunhofer.de; Veremchuk, I.; Reibold, M.

2015-09-15

A new synthetic approach for producing nano-powders of the Magnéli phases Ti{sub 4}O{sub 7}, Ti{sub 8}O{sub 15} and their carbon nanocomposites by thermal decomposition-precursor route is proposed. The formation mechanism of the single-phase carbon nanocomposites (Ti{sub 4}O{sub 7}/C and Ti{sub 8}O{sub 15}/C) from metal–organic precursors is studied using FT-IR, elemental analysis, TG, STA-MS and others. The synthesis parameters and conditions were optimized to prepare the target oxides with the desired microstructure and physical properties. The electrical and transport properties of Ti{sub 4}O{sub 7}/C and Ti{sub 8}O{sub 15}/C are investigated. These nano-materials are n-type semiconductors with relatively low thermal conductivity inmore » contrast to the bulk species. The nanostructured carbon nanocomposites of Magnéli phases achieve a low thermal conductivity close to 1 W/m K at RT. The maximum ZT{sub 570} {sub °C} values are 0.04 for Ti{sub 4}O{sub 7}/C powder nanocomposite and 0.01 for Ti{sub 8}O{sub 15}/C bulk nanocomposite. - Graphical abstract: From the precursor to the produced titanium oxide pellet and its microstructure (SEM, TEM micrographs) as well as results of phase and thermoelectric analyses. - Highlights: • Magnéli phases Ti{sub 4}O{sub 7}/Ti{sub 8}O{sub 15} via thermal decomposition-precursor route is proposed. • The formation mechanism of the nanocomposites Ti{sub 4}O{sub 7}/C and Ti{sub 8}O{sub 15}/C are investigated. • Microstructure of Ti{sub 4}O{sub 7}/C and Ti{sub 8}O{sub 15}/C are examined. • The electrical and transport properties of Ti{sub 4}O{sub 7}/C and Ti{sub 8}O{sub 15}/C are investigated. • The maximum figure of mertit ZT{sub 570} {sub °C} of Ti{sub 4}O{sub 7}/C and Ti{sub 8}O{sub 15}/C are 0.01 and 0.04.« less

Cloning, preparation and preliminary crystallographic studies of penicillin V acylase autoproteolytic processing mutants

PubMed Central

Chandra, P. Manish; Brannigan, James A.; Prabhune, Asmita; Pundle, Archana; Turkenburg, Johan P.; Dodson, G. Guy; Suresh, C. G.

2005-01-01

The crystallization of three catalytically inactive mutants of penicillin V acylase (PVA) from Bacillus sphaericus in precursor and processed forms is reported. The mutant proteins crystallize in different primitive monoclinic space groups that are distinct from the crystal forms for the native enzyme. Directed mutants and clone constructs were designed to study the post-translational autoproteolytic processing of PVA. The catalytically inactive mutants will provide three-dimensional structures of precursor PVA forms, plus open a route to the study of enzyme–substrate complexes for this industrially important enzyme. PMID:16508111

Synthesis of an A'B' Precursor to Angelmicin B: Product Diversification in the Suárez Lactol Fragmentation.

PubMed

Li, Jialiang; Todaro, Louis; Mootoo, David R

2011-11-01

We describe a synthetic strategy for the angelimicin family of anthraquinoid natural products that involves converting a central highly oxygenated decalin intermediate to the AB and A'B' subunits. Herein, we report the synthesis of the bicyclic A'B' subunit that complements our earlier route to the tricyclic AB framework. The differentiating tact in the two syntheses focused on controlling the Suárez radical fragmentation of lactol precursors by modulating the substrate's structural rigidity. A more flexible lactol gave the tricyclic AB framework, whereas a more rigid substrate led to the bicyclic A'B' precursor, presumably through divergent pathways from the radical produced in the initial fragmentation step. These results establish a versatile advanced synthetic precursor for the angelimicins, and on a more general note, illustrate strategies for applying the Suárez fragmentation to diverse and complex molecular frameworks.

Distinctive and selective route of PI3K/PKCα-PKCδ/RhoA-Rac1 signaling in osteoclastic cell migration.

PubMed

Kim, Jin-Man; Kim, Mi Yeong; Lee, Kyunghee; Jeong, Daewon

2016-12-05

Cell migration during specialized stages of osteoclast precursors, mononuclear preosteoclasts, and multinucleated mature osteoclasts remain uncertain. M-CSF- and osteopontin-induced osteoclastic cell migration was inhibited by function-blocking monoclonal antibodies specific to the integrin αv and β3 subunits, suggesting that integrin αvβ3 mediates migratory signaling induced by M-CSF and osteopontin. M-CSF and osteopontin stimulation was shown to regulate two branched signaling processes, PI3K/PKCα/RhoA axis and PI3K/PKCδ/Rac1 axis. Interestingly, inactivation of RhoA or Rac1 blocked preosteoclast and mature osteoclast migration but not osteoclast precursor migration in a transwell-based cell migration assay. Moreover, the inhibitory effect on preosteoclast and mature osteoclast migration induced by Rac1 inactivation was more effective than that by RhoA inactivation. Collectively, our findings suggest that osteoclast precursor migration depends on PI3K/PKCα-PKCδ signaling mediated via integrin αvβ3 bypassing RhoA and Rac1, whereas preosteoclast and mature osteoclast migration relies on PI3K/PKCα-PKCδ/RhoA-Rac1 axis signaling mediated via integrin αvβ3 with increased dependency on PKCδ/Rac1 signaling route as differentiation progresses. Copyright © 2016 Elsevier Ireland Ltd. All rights reserved.

Polymeric routes to silicon carbide and silicon oxycarbide CMC

NASA Technical Reports Server (NTRS)

Hurwitz, Frances I.; Heimann, Paul J.; Gyekenyesi, John Z.; Masnovi, John; Bu, Xin YA

1991-01-01

An overview of two approaches to the formation of ceramic composite matrices from polymeric precursors is presented. Copolymerization of alkyl- and alkenylsilanes (RSiH3) represents a new precursor system for the production of Beta-SiC on pyrolysis, with copolymer composition controlling polymer structure, char yield, and ceramic stoichiometry and morphology. Polysilsesquioxanes which are synthesized readily and can be handled in air serve as precursors to Si-C-O ceramics. Copolymers of phenyl and methyl silsesquioxanes display rheological properties favorable for composite fabrication; these can be tailored by control of pH, water/methoxy ratio and copolymer composition. Composites obtained from these utilize a carbon coated, eight harness satin weave Nicalon cloth reinforcement. The material exhibits nonlinear stress-strain behavior in tension.

Controlled synthesis and luminescence properties of β-NaGdF4: Yb3+, Er3+ upconversion nanoparticles

NASA Astrophysics Data System (ADS)

Zhang, Yueli; Yao, Lu; Xu, Dekang; Lin, Hao; Yang, Shenghong

2018-06-01

β-NaGdF4:Yb3+,Er3+ upconversion (UC) nanoparticles (UCNPs) were prepared by a facile hydrothermal process with the assistance of sodium ethylene diaminetetraacetate salt (EDTA-2Na). The morphologies of the β-NaGdF4 UCNPs were controlled by changing the doses of EDTA-2Na and NaOH in precursor. With increasing concentration of EDTA-2Na in precursor, the size of crystals decreased, resulting in the decreasing of luminescence intensity. With increasing concentration of NaOH in precursor, the morphology became more homogeneous. However, due to the reduction of grain size and crystal quality, the luminescence intensity decreased. Nevertheless, the above results demonstrated a simple route to fabricate homogeneous UCNPs.

Controlled Synthesis and Utilization of Metal and Oxide Hybrid Nanoparticles

NASA Astrophysics Data System (ADS)

Crane, Cameron

This dissertation reports the development of synthetic methods concerning rationally-designed, hybrid, and multifunctional nanomaterials. These methods are based on a wet chemical, solution phase approach that utilizes the knowledge of synthetic organic and inorganic chemistry to generate building blocks in solution for the growth of nanocrystals and hybrid nanostructures. This work builds on the prior knowledge of shape-controlled synthesis of noble metal nanocrystals and expands into the challenging realm of the more reactive first row transition metals. Specifically, a microemulsion sol-gel method was developed to synthesize Au-SiO2 dimers as precursors for the synthesis of segmented heterostructures of noble metals that can be used for catalysis. This microemulsion sol-gel method was modified to synthesize an aqueous suspension of oxidation-resistant Cu-SiO2 core-shell nanoparticles that can be used for sensing and catalysis. A thermal decomposition approach was developed, wherein zero-valence metal precursor complexes in the presence of seed nanoparticles produced metal-metal oxide core-shell structures with well-controlled shell thickness. This method was demonstrated on AuCu 3-Fe3O4, AuCu3-NiO, and AuCu3 -MnO core-shell systems. Switching the core from AuCu3 alloy to pure Cu, this method could extend to Cu-Fe3O4 and Cu-MnO systems. Further etching the Cu core in these core-shell structures led to the formation of the hollow metal oxides which provides a versatile route to hollow nanostructures of metal oxides. This work develops the synthetic library of tools for the production of hybrid nanostructures with multiple functionalities.

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.

Micro-structural evolution and biomineralization behavior of carbon nanofiber/bioactive glass composites induced by precursor aging time.

PubMed

Jia, Xiaolong; Tang, Tianhong; Cheng, Dan; Zhang, Cuihua; Zhang, Ran; Cai, Qing; Yang, Xiaoping

2015-12-01

Bioactive glass (BG)-containing carbon nanofibers (CNFs) are promising orthopaedic biomaterials. Herein, CNF composites were produced from electrospinning of polyacrylonitrile (PAN)/BG sol-gel precursor solution, followed by carbonization. Choosing 58S-type BG (mol%: 58.0% SiO2-26.3% CaO-15.7% P2O5) as the model, micro-structural evolution of CNF/BG composites was systematically evaluated in relating to aging times of BG precursor solution. With aging time prolonging, BG precursors underwent morphological changes from small sol clusters with loosely and randomly branched structure to highly crosslinked Si-network structure, showing continuous increase in solution viscosity. BG precursor solution with low viscosity could mix well with PAN solution, resulting in CNF composite with homogeneously distributed BG component. Whereas, BG precursor gel with densely crosslinked Si-network structure led to uneven distribution of BG component along final CNFs due to its significant phase separation from PAN component. Meanwhile, BG nanoparticles in CNFs demonstrated micro-structural evolution that they transited from weak to strong crystal state along with longer aging time. Biomineralization in simulated body fluid and in vitro osteoblasts proliferation were then applied to determine the bioactivity of CNF/BG composites. CNF/BG composites prepared from shorter aging time could induce both faster apatite deposition and cell proliferation rate. It was suggested weakly crystallized BG nanoparticles along CNFs dissolved fast and was able to provide numerous nucleation sites for apatite deposition, which also favored the proliferation of osteoblasts cells. Aging time could thus be a useful tool to regulate the biological features of CNF/BG composites. Copyright © 2015 Elsevier B.V. All rights reserved.

Method for synthesizing carbon nanotubes

DOEpatents

Fan, Hongyou

2012-09-04

A method for preparing a precursor solution for synthesis of carbon nanomaterials, where a polar solvent is added to at least one block copolymer and at least one carbohydrate compound, and the precursor solution is processed using a self-assembly process and subsequent heating to form nanoporous carbon films, porous carbon nanotubes, and porous carbon nanoparticles.

Elegant Face-Down Liquid-Space-Restricted Deposition of CsPbBr3 Films for Efficient Carbon-Based All-Inorganic Planar Perovskite Solar Cells.

PubMed

Teng, Pengpeng; Han, Xiaopeng; Li, Jiawei; Xu, Ya; Kang, Lei; Wang, Yangrunqian; Yang, Ying; Yu, Tao

2018-03-21

It is a great challenge to obtain the uniform films of bromide-rich perovskites such as CsPbBr 3 in the two-step sequential solution process (two-step method), which was mainly due to the decomposition of the precursor films in solution. Herein, we demonstrated a novel and elegant face-down liquid-space-restricted deposition to inhibit the decomposition and fabricate high-quality CsPbBr 3 perovskite films. This method is highly reproducible, and the surface of the films was smooth and uniform with an average grain size of 860 nm. As a consequence, the planar perovskite solar cells (PSCs) without the hole-transport layer based on CsPbBr 3 and carbon electrodes exhibit enhanced power conversion efficiency (PCE) along with high open circuit voltage ( V OC ). The champion device has achieved a PCE of 5.86% with a V OC of 1.34 V, which to our knowledge is the highest performing CsPbBr 3 PSC in planar structure. Our results suggest an efficient and low-cost route to fabricate the high-quality planar all-inorganic PSCs.

Study on the solid solution of YMn{sub 1-x}Fe{sub x}O{sub 3}: Structural, magnetic and dielectric properties

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

Samal, S.L.; Green, W.; Lofland, S.E.

The solid solution of YMn{sub 1-x}Fe{sub x}O{sub 3} (x=0.0, 0.1, 0.2, 0.3, 0.5, 1.0) was synthesized from the citrate precursor route. The hexagonal crystal structure related to YMnO{sub 3} was stable for x{<=}0.3. Rietveld refinement was carried out on the composition for x=0.3 and was refined to a major hexagonal phase ({approx}97%) with 3% of orthorhombic Y(Fe/Mn)O{sub 3} phase. The a-axis lattice constant increases and the c-axis lattice constant decreases with x for x{<=}0.2. The increase in the c-axis lattice constant at x=0.3 could be due to the doping of significant amount of d{sup 5} ion (high spin Fe{sup 3+}more » ion) in a trigonal bipyramidal crystal field. The detailed structural, magnetic and dielectric properties are discussed. - Graphical abstract: Temperature dependence of {epsilon} of YMn{sub 1-x}Fe{sub x}O{sub 3} (0.0{<=}x{<=}0.3) at 100 kHz. Inset shows the temperature variation of inverse magnetic susceptibility.« less

Photoinduced catalytic synthesis of biologically important metabolites from formaldehyde and ammonia under plausible "prebiotic" conditions

NASA Astrophysics Data System (ADS)

Delidovich, I. V.; Taran, O. P.; Simonov, A. N.; Matvienko, L. G.; Parmon, V. N.

2011-08-01

The article analyzes new and previously reported data on several catalytic and photochemical processes yielding biologically important molecules. UV-irradiation of formaldehyde aqueous solution yields acetaldehyde, glyoxal, glycolaldehyde and glyceraldehyde, which can serve as precursors of more complex biochemically relevant compounds. Photolysis of aqueous solution of acetaldehyde and ammonium nitrate results in formation of alanine and pyruvic acid. Dehydration of glyceraldehyde catalyzed by zeolite HZSM-5-17 yields pyruvaldehyde. Monosaccharides are formed in the course of the phosphate-catalyzed aldol condensation reactions of glycolaldehyde, glyceraldehyde and formaldehyde. The possibility of the direct synthesis of tetroses, keto- and aldo-pentoses from pure formaldehyde due to the combination of the photochemical production of glycolahyde and phosphate-catalyzed carbohydrate chain growth is demonstrated. Erythrulose and 3-pentulose are the main products of such combined synthesis with selectivity up to 10%. Biologically relevant aldotetroses, aldo- and ketopentoses are more resistant to the photochemical destruction owing to the stabilization in hemiacetal cyclic forms. They are formed as products of isomerization of erythrulose and 3-pentulose. The conjugation of the concerned reactions results in a plausible route to the formation of sugars, amino and organic acids from formaldehyde and ammonia under presumed 'prebiotic' conditions.

Comparative study of the synthesis of layered transition metal molybdates

NASA Astrophysics Data System (ADS)

Mitchell, S.; Gómez-Avilés, A.; Gardner, C.; Jones, W.

2010-01-01

Mixed metal oxides (MMOs) prepared by the mild thermal decomposition of layered double hydroxides (LDHs) differ in their reactivity on exposure to aqueous molybdate containing solutions. In this study, we investigate the reactivity of some T-Al containing MMOs ( T=Co, Ni, Cu or Zn) towards the formation of layered transition metal molybdates (LTMs) possessing the general formula AT2(OH)(MoO 4) 2·H 2O, where A=NH 4+, Na + or K +. The phase selectivity of the reaction was studied with respect to the source of molybdate, the ratio of T to Mo and the reaction pH. LTMs were obtained on reaction of Cu-Al and Zn-Al containing MMOs with aqueous solutions of ammonium heptamolybdate. Rehydration of these oxides in the presence of sodium or potassium molybdate yielded a rehydrated LDH phase as the only crystalline product. The LTM products obtained by the rehydration of MMO precursors were compared with LTMs prepared by direct precipitation from the metal salts in order to study the influence of preparative route on their chemical and physical properties. Differences were noted in the composition, morphology and thermal properties of the resulting products.

Colloidal synthesis of inorganic fullerene nanoparticles and hollow spheres of titanium disulfide.

PubMed

Prabakar, Sujay; Collins, Sean; Northover, Bryan; Tilley, Richard D

2011-01-07

The synthesis of inorganic fullerene (IF) nanoparticles and IF hollow spheres of titanium disulfide by a simple colloidal route is reported. The injection temperature of the titanium precursor into the solvent mixture was found to be important in controlling the morphology.

Glass-ceramic route of BSCCO superconductors - Fabrication of amorphous precursor

NASA Astrophysics Data System (ADS)

Nilsson, Andreas; Gruner, Wolfgang; Acker, Jörg; Wetzig, Klaus

2007-09-01

It is well known that many Bi-Sr-Ca-Cu-O compositions are glass-forming and some Bi-based glasses such as Bi 2Sr 2CaCu 2O x and Bi 2Sr 2Ca 2Cu 3O x are converted into high critical temperature superconductors after proper annealing. In order to fabricate superconductors having high- Tc and high critical current density using the glass-ceramic route, it is necessary to clarify the total chemical composition of the quenched glasses prepared in most cases by rapid quenching of melts from around 1200 °C in air. The total oxygen content measured directly reflects a significant oxygen deficit due to the melting process. We have also investigated the cation content in quenched Bi 2Sr 2Ca 2Cu 3O x precursors and found that there are substantial differences from the nominal composition to the quenched materials especially for calcium. Such glasses also show some CaO crystalline reflexes in the XRD patterns.

Sol-Gel Processing of MgF₂ Antireflective Coatings.

PubMed

Löbmann, Peer

2018-05-02

There are different approaches for the preparation of porous antireflective λ/4 MgF₂ films from liquid precursors. Among these, the non-aqueous fluorolytic synthesis of precursor solutions offers many advantages in terms of processing simplicity and scalability. In this paper, the structural features and optical performance of the resulting films are highlighted, and their specific interactions with different inorganic substrates are discussed. Due to their excellent abrasion resistance, coatings have a high potential for applications on glass. Using solvothermal treatment of precursor solutions, also the processing of thermally sensitive polymer substrates becomes feasible.

Synthesis of Ge-nanoparticles in organic solution

NASA Astrophysics Data System (ADS)

Pugsley, Andrew James

Much interest is focused on the synthesis of semiconductor particles from organic solution, in order to provide luminescent tracers for biological assays. However, group IV semiconductors have been largely neglected be cause of the lack of suitable nanoparticle formation reactions by solution-phase chemistries. A potentially useful new route to solution-based synthesis of nanocrystalline-Si,Ge involves the reaction between Zintl phases (NaSi, Mg 2Ge) that formally contain anionic semiconducting group species (Si-, Ge4-) and liquid phase SiCU, GeCU, etc. Luminescent nanoparticles formed by these reactions in organic solvents (e.g. diglyme) have been decribed in work from the Kauzlarich group at UC Davis (California, USA). The aim of this project has been to characterise the structural chemistry and luminescent properties of the products of the reaction, as well as following the course of the reaction in situ via synchrotron measurements. The product of the reaction has been characterised by TEM and x-ray absorption spectroscopy as well as other techniques. In order to analyse the x-ray absorption spectroscopy data, a number of model compounds have been studied, including the precursor material which was previously uncharacterised by this technique. An in situ reaction cell has been designed and built and used at a number of synchrotron beamlines to follow the course of the reaction. It has been found that the presence of even low concentrations of water can greatly affect the formation reaction, this is described herein.

Formation Mechanism and Control of Perovskite Films from Solution to Crystalline Phase Studied by in Situ Synchrotron Scattering.

PubMed

Chang, Chun-Yu; Huang, Yu-Ching; Tsao, Cheng-Si; Su, Wei-Fang

2016-10-12

Controlling the crystallization and morphology of perovskite films is crucial for the fabrication of high-efficiency perovskite solar cells. For the first time, we investigate the formation mechanism of the drop-cast perovskite film from its precursor solution, PbCl 2 and CH 3 NH 3 I in N,N-dimethylformamide, to a crystalline CH 3 NH 3 PbI 3-x Cl x film at different substrate temperatures from 70 to 180 °C in ambient air and humidity. We employed an in situ grazing-incidence wide-angle X-ray scattering (GIWAXS) technique for this study. When the substrate temperature is at or below 100 °C, the perovskite film is formed in three stages: the initial solution stage, transition-to-solid film stage, and transformation stage from intermediates into a crystalline perovskite film. In each stage, the multiple routes for phase transformations are preceded concurrently. However, when the substrate temperature is increased from 100 to 180 °C, the formation mechanism of the perovskite film is changed from the "multistage formation mechanism" to the "direct formation mechanism". The proposed mechanism has been applied to understand the formation of a perovskite film containing an additive. The result of this study provides a fundamental understanding of the functions of the solvent and additive in the solution and transition states to the crystalline film. It provides useful knowledge to design and fabricate crystalline perovskite films for high-efficiency solar cells.

Chemical repair of base lesions, AP-sites, and strand breaks on plasmid DNA in dilute aqueous solution by ascorbic acid

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

Hata, Kuniki; Advanced Science Research Center, Japan Atomic Energy Agency, 2-4 Shirakatashirane, Tokai-mura, Naka-gun, Ibaraki 319-1195; Urushibara, Ayumi

Highlights: •We report a novel mechanism of radiation protection of DNA by chemical activity of ascorbic acid. •The “chemical repair” of DNA damage was revealed using biochemical assay and chemical kinetics analysis. •We found that ascorbic acid significantly repairs precursors of nucleobase lesions and abasic sites. •However, ascorbic acid seldom repairs precursors of DNA-strand breaks. -- Abstract: We quantified the damage yields produced in plasmid DNA by γ-irradiation in the presence of low concentrations (10–100 μM) of ascorbic acid, which is a major antioxidant in living systems, to clarify whether it chemically repairs radiation damage in DNA. The yield ofmore » DNA single strand breaks induced by irradiation was analyzed with agarose gel electrophoresis as conformational changes in closed circular plasmids. Base lesions and abasic sites were also observed as additional conformational changes by treating irradiated samples with glycosylase proteins. By comparing the suppression efficiencies to the induction of each DNA lesion, in addition to scavenging of the OH radicals derived from water radiolysis, it was found that ascorbic acid promotes the chemical repair of precursors of AP-sites and base lesions more effectively than those of single strand breaks. We estimated the efficiency of the chemical repair of each lesion using a kinetic model. Approximately 50–60% of base lesions and AP-sites were repaired by 10 μM ascorbic acid, although strand breaks were largely unrepaired by ascorbic acid at low concentrations. The methods in this study will provide a route to understanding the mechanistic aspects of antioxidant activity in living systems.« less

DERMAL, ORAL, AND INHALATION PHARMACOKINETICS OF METHYL TERTIARY BUTYL ETHER (MTBE) IN HUMAN VOLUNTEERS

EPA Science Inventory

Methyl tertiary butyl ether (MTBE), a gasoline additive, used to increase octane and reduce carbon monoxide emissions and ozone precursors has contaminated drinking water leading to exposure by oral, inhalation, and dermal routes. To determine its dermal, oral, and inhalation ki...

Bees do not use nearest-neighbour rules for optimization of multi-location routes.

PubMed

Lihoreau, Mathieu; Chittka, Lars; Le Comber, Steven C; Raine, Nigel E

2012-02-23

Animals collecting patchily distributed resources are faced with complex multi-location routing problems. Rather than comparing all possible routes, they often find reasonably short solutions by simply moving to the nearest unvisited resources when foraging. Here, we report the travel optimization performance of bumble-bees (Bombus terrestris) foraging in a flight cage containing six artificial flowers arranged such that movements between nearest-neighbour locations would lead to a long suboptimal route. After extensive training (80 foraging bouts and at least 640 flower visits), bees reduced their flight distances and prioritized shortest possible routes, while almost never following nearest-neighbour solutions. We discuss possible strategies used during the establishment of stable multi-location routes (or traplines), and how these could allow bees and other animals to solve complex routing problems through experience, without necessarily requiring a sophisticated cognitive representation of space.

Superconductor precursor mixtures made by precipitation method

DOEpatents

Bunker, Bruce C.; Lamppa, Diana L.; Voigt, James A.

1989-01-01

Method and apparatus for preparing highly pure homogeneous precursor powder mixtures for metal oxide superconductive ceramics. The mixes are prepared by instantaneous precipitation from stoichiometric solutions of metal salts such as nitrates at controlled pH's within the 9 to 12 range, by addition of solutions of non-complexing pyrolyzable cations, such as alkyammonium and carbonate ions.

Stress-tuned conductor-polymer composite for use in sensors

DOEpatents

Martin, James E; Read, Douglas H

2013-10-22

A method for making a composite polymeric material with electrical conductivity determined by stress-tuning of the conductor-polymer composite, and sensors made with the stress-tuned conductor-polymer composite made by this method. Stress tuning is achieved by mixing a miscible liquid into the polymer precursor solution or by absorbing into the precursor solution a soluble compound from vapor in contact with the polymer precursor solution. The conductor may or may not be ordered by application of a magnetic field. The composite is formed by polymerization with the stress-tuning agent in the polymer matrix. The stress-tuning agent is removed following polymerization to produce a conductor-polymer composite with a stress field that depends on the amount of stress-tuning agent employed.

Activating Molecules, Ions, and Solid Particles with Acoustic Cavitation

PubMed Central

Pflieger, Rachel; Chave, Tony; Virot, Matthieu; Nikitenko, Sergey I.

2014-01-01

The chemical and physical effects of ultrasound arise not from a direct interaction of molecules with sound waves, but rather from the acoustic cavitation: the nucleation, growth, and implosive collapse of microbubbles in liquids submitted to power ultrasound. The violent implosion of bubbles leads to the formation of chemically reactive species and to the emission of light, named sonoluminescence. In this manuscript, we describe the techniques allowing study of extreme intrabubble conditions and chemical reactivity of acoustic cavitation in solutions. The analysis of sonoluminescence spectra of water sparged with noble gases provides evidence for nonequilibrium plasma formation. The photons and the "hot" particles generated by cavitation bubbles enable to excite the non-volatile species in solutions increasing their chemical reactivity. For example the mechanism of ultrabright sonoluminescence of uranyl ions in acidic solutions varies with uranium concentration: sonophotoluminescence dominates in diluted solutions, and collisional excitation contributes at higher uranium concentration. Secondary sonochemical products may arise from chemically active species that are formed inside the bubble, but then diffuse into the liquid phase and react with solution precursors to form a variety of products. For instance, the sonochemical reduction of Pt(IV) in pure water provides an innovative synthetic route for monodispersed nanoparticles of metallic platinum without any templates or capping agents. Many studies reveal the advantages of ultrasound to activate the divided solids. In general, the mechanical effects of ultrasound strongly contribute in heterogeneous systems in addition to chemical effects. In particular, the sonolysis of PuO2 powder in pure water yields stable colloids of plutonium due to both effects. PMID:24747272

Enhanced Performance of PbS-quantum-dot-sensitized Solar Cells via Optimizing Precursor Solution and Electrolytes

NASA Astrophysics Data System (ADS)

Tian, Jianjun; Shen, Ting; Liu, Xiaoguang; Fei, Chengbin; Lv, Lili; Cao, Guozhong

2016-03-01

This work reports a PbS-quantum-dot-sensitized solar cell (QDSC) with power conversion efficiency (PCE) of 4%. PbS quantum dots (QDs) were grown on mesoporous TiO2 film using a successive ion layer absorption and reaction (SILAR) method. The growth of QDs was found to be profoundly affected by the concentration of the precursor solution. At low concentrations, the rate-limiting factor of the crystal growth was the adsorption of the precursor ions, and the surface growth of the crystal became the limiting factor in the high concentration solution. The optimal concentration of precursor solution with respect to the quantity and size of synthesized QDs was 0.06 M. To further increase the performance of QDSCs, the 30% deionized water of polysulfide electrolyte was replaced with methanol to improve the wettability and permeability of electrolytes in the TiO2 film, which accelerated the redox couple diffusion in the electrolyte solution and improved charge transfer at the interfaces between photoanodes and electrolytes. The stability of PbS QDs in the electrolyte was also improved by methanol to reduce the charge recombination and prolong the electron lifetime. As a result, the PCE of QDSC was increased to 4.01%.

An efficient copper phthalocyanine additive of perovskite precursor for improving the photovoltaic performance of planar perovskite solar cells

NASA Astrophysics Data System (ADS)

Wu, Shufang; Liu, Qingwei; Zheng, Ya; Li, Renjie; Peng, Tianyou

2017-08-01

Solution processable planar heterojunction perovskite solar cell has drawn much attention as a promising low-cost photovoltaic device, and much effort has been made to improve its power conversion efficiency by choosing appropriate additives for the perovskite precursor solution. Different to those additives reported, a soluble and thermal stable tert-butyl substituted copper phthalocyanine (CuPc(tBu)4) as additive is first introduced into the perovskite precursor solution of a planar perovskite solar cell that is fabricated via the one-step solution process. It is found that the pristine device without CuPc(tBu)4 additive exhibits a power conversion efficiency of 15.3%, while an extremely low concentration (4.4 × 10-3 mM) of CuPc(tBu)4 in the precursor solution leads to the corresponding device achieving an enhanced power conversion efficiency of 17.3%. CuPc(tBu)4 as an additive can improve the quality of perovskite layer with higher crystallinity and surface coverage, then resulting in enhanced light absorption and reduced charge recombination, and thus the better power conversion efficiency. The finding presented here provides a new choice for improving the quality of perovskite layer and the photovoltaic performance of the planar heterojunction perovskite solar cells.

Enhanced Performance of PbS-quantum-dot-sensitized Solar Cells via Optimizing Precursor Solution and Electrolytes.

PubMed

Tian, Jianjun; Shen, Ting; Liu, Xiaoguang; Fei, Chengbin; Lv, Lili; Cao, Guozhong

2016-03-15

This work reports a PbS-quantum-dot-sensitized solar cell (QDSC) with power conversion efficiency (PCE) of 4%. PbS quantum dots (QDs) were grown on mesoporous TiO2 film using a successive ion layer absorption and reaction (SILAR) method. The growth of QDs was found to be profoundly affected by the concentration of the precursor solution. At low concentrations, the rate-limiting factor of the crystal growth was the adsorption of the precursor ions, and the surface growth of the crystal became the limiting factor in the high concentration solution. The optimal concentration of precursor solution with respect to the quantity and size of synthesized QDs was 0.06 M. To further increase the performance of QDSCs, the 30% deionized water of polysulfide electrolyte was replaced with methanol to improve the wettability and permeability of electrolytes in the TiO2 film, which accelerated the redox couple diffusion in the electrolyte solution and improved charge transfer at the interfaces between photoanodes and electrolytes. The stability of PbS QDs in the electrolyte was also improved by methanol to reduce the charge recombination and prolong the electron lifetime. As a result, the PCE of QDSC was increased to 4.01%.

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.

Influence of carboxylic acid type on microstructure and magnetic properties of polymeric complex sol-gel driven NiFe2O4

NASA Astrophysics Data System (ADS)

Hessien, M. M.; Mostafa, Nasser Y.; Abd-Elkader, Omar H.

2016-01-01

Citric, oxalic and tartaric acids were used for synthesis of NiFe2O4 using polymeric complex precursor route. The dry precursor gels were calcined at various temperatures (400-1100 °C) for 2 h. All carboxylic acids produce iron-deficient NiFe2O4 with considerable amount of α-Fe2O3 at 400 °C. Increase in the annealing temperature caused reaction of α-Fe2O3 with iron-deficient ferrite phase. The amount of initially formed α-Fe2O3 is directly correlated with stability constant and inversely correlated with the decomposition temperature of Fe(III) carboxylate precursors. In case of tartaric acid precursor, single phase of the ferrite was obtained at 450 °C. However, in case of oxalic acid and citric acid precursors, single phase ferrite was obtained at 550 °C and 700 °C, respectively. The lattice parameters were increased with increasing annealing temperature and with decreasing the amount of α-Fe2O3. Maximum saturation magnetization (55 emu/g) was achieved using tartaric acid precursor annealed at 1100 °C.

Uniform nanoparticles by flame-assisted spray pyrolysis (FASP) of low cost precursors

PubMed Central

Rudin, Thomas; Wegner, Karsten

2013-01-01

A new flame-assisted spray pyrolysis (FASP) reactor design is presented, which allows the use of inexpensive precursors and solvents (e.g., ethanol) for synthesis of nanoparticles (10–20 nm) with uniform characteristics. In this reactor design, a gas-assisted atomizer generates the precursor solution spray that is mixed and combusted with externally fed inexpensive fuel gases (acetylene or methane) at a defined height above the atomizing nozzle. The gaseous fuel feed can be varied to control the combustion enthalpy content of the flame and onset of particle formation. This way, the enthalpy density of the flame is decoupled from the precursor solution composition. Low enthalpy content precursor solutions are prone to synthesis of non-uniform particles (e.g., bimodal particle size distribution) by standard flame spray pyrolysis (FSP) processes. For example, metal nitrates in ethanol typically produce nanosized particles by gas-to-particle conversion along with larger particles by droplet-to-particle conversion. The present FASP design facilitates the use of such low enthalpy precursor solutions for synthesis of homogeneous nanopowders by increasing the combustion enthalpy density of the flame with low-cost, gaseous fuels. The effect of flame enthalpy density on product properties in the FASP configuration is explored by the example of Bi2O3 nanoparticles produced from bismuth nitrate in ethanol. Product powders were characterized by nitrogen adsorption, X-ray diffraction, X-ray disk centrifuge, and transmission electron microscopy. Homogeneous Bi2O3 nanopowders were produced both by increasing the gaseous fuel content and, most notably, by cutting the air entrainment prior to ignition of the spray. PMID:23408113

Ceramic fibers from Si-B-C polymer precursors

NASA Technical Reports Server (NTRS)

Riccitiello, S. R.; Hsu, M. S.; Chen, T. S.

1993-01-01

Non-oxide ceramics such as silicon carbide (SiC), silicon nitride (Si3N4), and silicon borides (SiB4, SiB6) have thermal stability, oxidation resistance, hardness, and varied electrical properties. All these materials can be prepared in a fiber form from a suitable polymer precursor. The above mentioned fibers, when tested over a temperature range from 25 to 1400 C, experience degradation at elevated temperatures. Past work in ceramic materials has shown that the strength of ceramics containing both carbides and borides is sustained at elevated temperatures, with minimum oxidation. The work presented here describes the formation of ceramic fibers containing both elements, boron and silicon, prepared via the polymer precursor route previously reported by the authors, and discusses the fiber mechanical properties that are retained over the temperature range studied.

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

Eilert, André; Roberts, F. Sloan; Friebel, Daniel

Nanostructured copper cathodes are among the most efficient and selective catalysts to date for making multicarbon products from the electrochemical carbon dioxide reduction reaction (CO 2RR). We report an in situ X-ray absorption spectroscopy investigation of the formation of a copper nanocube CO 2RR catalyst with high activity that highly favors ethylene over methane production. The results show that the precursor for the copper nanocube formation is copper(I)-oxide, not copper(I)-chloride as previously assumed. A second route to an electrochemically similar material via a copper(II)–carbonate/hydroxide is also reported. In conclusion, this study highlights the importance of using oxidized copper precursors formore » constructing selective CO 2 reduction catalysts and shows the precursor oxidation state does not affect the electrocatalyst selectivity toward ethylene formation.« less

Cloning, preparation and preliminary crystallographic studies of penicillin V acylase autoproteolytic processing mutants

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

Chandra, P. Manish; Brannigan, James A., E-mail: jab@ysbl.york.ac.uk; Prabhune, Asmita

The production, crystallization and characterization of three inactive mutants of penicillin V acylase from B. sphaericus in their respective precursor and processed forms are reported. The space groups are different for the native enzyme and the mutants. The crystallization of three catalytically inactive mutants of penicillin V acylase (PVA) from Bacillus sphaericus in precursor and processed forms is reported. The mutant proteins crystallize in different primitive monoclinic space groups that are distinct from the crystal forms for the native enzyme. Directed mutants and clone constructs were designed to study the post-translational autoproteolytic processing of PVA. The catalytically inactive mutants willmore » provide three-dimensional structures of precursor PVA forms, plus open a route to the study of enzyme–substrate complexes for this industrially important enzyme.« less

Synthesis metal nanoparticle

DOEpatents

Bunge, Scott D.; Boyle, Timothy J.

2005-08-16

A method for providing an anhydrous route for the synthesis of amine capped coinage-metal (copper, silver, and gold) nanoparticles (NPs) using the coinage-metal mesityl (mesityl=C.sub.6 H.sub.2 (CH.sub.3).sub.3 -2,4,6) derivatives. In this method, a solution of (Cu(C.sub.6 H.sub.2 (CH.sub.3).sub.3).sub.5, (Ag(C.sub.6 H.sub.2 (CH.sub.3).sub.3).sub.4, or (Au(C.sub.6 H.sub.2 (CH.sub.3).sub.3).sub.5 is dissolved in a coordinating solvent, such as a primary, secondary, or tertiary amine; primary, secondary, or tertiary phosphine, or alkyl thiol, to produce a mesityl precursor solution. This solution is subsequently injected into an organic solvent that is heated to a temperature greater than approximately 100.degree. C. After washing with an organic solvent, such as an alcohol (including methanol, ethanol, propanol, and higher molecular-weight alcohols), oxide free coinage NP are prepared that could be extracted with a solvent, such as an aromatic solvent (including, for example, toluene, benzene, and pyridine) or an alkane (including, for example, pentane, hexane, and heptane). Characterization by UV-Vis spectroscopy and transmission electron microscopy showed that the NPs were approximately 9.2.+-.2.3 nm in size for Cu.degree., (no surface oxide present), approximately 8.5.+-.1.1 nm Ag.degree. spheres, and approximately 8-80 nm for Au.degree..

The Critical Role of Thioacetamide Concentration in the Formation of ZnO/ZnS Heterostructures by Sol-Gel Process

PubMed Central

Kiatkoski Kaminski, Renata Cristina; Caetano, Bruno Leonardo; Magnani, Marina; Meneau, Florian; Rochet, Amélie; Santilli, Celso Valentim; Briois, Valérie; Bourgaux, Claudie

2018-01-01

ZnO/ZnS heterostructures have emerged as an attractive approach for tailoring the properties of particles comprising these semiconductors. They can be synthesized using low temperature sol-gel routes. The present work yields insight into the mechanisms involved in the formation of ZnO/ZnS nanostructures. ZnO colloidal suspensions, prepared by hydrolysis and condensation of a Zn acetate precursor solution, were allowed to react with an ethanolic thioacetamide solution (TAA) as sulfur source. The reactions were monitored in situ by Small Angle X-ray Scattering (SAXS) and UV-vis spectroscopy, and the final colloidal suspensions were characterized by High Resolution Transmission Electron Microscopy (HRTEM). The powders extracted at the end of the reactions were analyzed by X-ray Absorption spectroscopy (XAS) and X-ray diffraction (XRD). Depending on TAA concentration, different nanostructures were revealed. ZnO and ZnS phases were mainly obtained at low and high TAA concentrations, respectively. At intermediate TAA concentrations, we evidenced the formation of ZnO/ZnS heterostructures. ZnS formation could take place via direct crystal growth involving Zn ions remaining in solution and S ions provided by TAA and/or chemical conversion of ZnO to ZnS. The combination of all the characterization techniques was crucial to elucidate the reaction steps and the nature of the final products. PMID:29360735

Coordinated Platoon Routing in a Metropolitan Network

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

Larson, Jeffrey; Munson, Todd; Sokolov, Vadim

2016-10-10

Platooning vehicles—connected and automated vehicles traveling with small intervehicle distances—use less fuel because of reduced aerodynamic drag. Given a network de- fined by vertex and edge sets and a set of vehicles with origin/destination nodes/times, we model and solve the combinatorial optimization problem of coordinated routing of vehicles in a manner that routes them to their destination on time while using the least amount of fuel. Common approaches decompose the platoon coordination and vehicle routing into separate problems. Our model addresses both problems simultaneously to obtain the best solution. We use modern modeling techniques and constraints implied from analyzing themore » platoon routing problem to address larger numbers of vehicles and larger networks than previously considered. While the numerical method used is unable to certify optimality for candidate solutions to all networks and parameters considered, we obtain excellent solutions in approximately one minute for much larger networks and vehicle sets than previously considered in the literature.« less

Controlled chemical stabilization of polyvinyl precursor fiber, and high strength carbon fiber produced therefrom

DOEpatents

Naskar, Amit K.

2016-12-27

Method for the preparation of carbon fiber, which comprises: (i) immersing functionalized polyvinyl precursor fiber into a liquid solution having a boiling point of at least 60.degree. C.; (ii) heating the liquid solution to a first temperature of at least 25.degree. C. at which the functionalized precursor fiber engages in an elimination-addition equilibrium while a tension of at least 0.1 MPa is applied to the fiber; (iii) gradually raising the first temperature to a final temperature that is at least 20.degree. C. above the first temperature and up to the boiling point of the liquid solution for sufficient time to convert the functionalized precursor fiber to a pre-carbonized fiber; and (iv) subjecting the pre-carbonized fiber produced according to step (iii) to high temperature carbonization conditions to produce the final carbon fiber. Articles and devices containing the fibers, including woven and non-woven mats or paper forms of the fibers, are also described.

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

DERMAL, ORAL AND INHALATION PHARMACOKINETICS OF METHYL TERTIARY-BUTYL ETHER (MTBE) IN HUMAN VOLUNTEERS

EPA Science Inventory

Methyl tertiary butyl ether (MTBE), a gasoline additive used to increase octane and reduce carbon monoxide emissions and ozone precursors, has contaminated drinking water and can lead to exposure by oral, inhalation, and dermal routes. To determine its dermal, oral, and inhal...

40 CFR 80.1352 - What are the pre-compliance reporting requirements for the gasoline benzene program?

Code of Federal Regulations, 2010 CFR

2010-07-01

...) Benzene concentration. An estimate of the average gasoline benzene concentration corresponding to the time... engineering and permitting, Procurement and Construction, and Commissioning and startup. (7) Basic information regarding the selected technology pathway for compliance (e.g., precursor re-routing or other technologies...

One-step synthesis of mesoporous pentasil zeolite with single-unit-cell lamellar structural features

DOEpatents

Tsapstsis, Michael; Zhang, Xueyi

2015-11-17

A method for making a pentasil zeolite material includes forming an aqueous solution that includes a structure directing agent and a silica precursor; and heating the solution at a sufficient temperature and for sufficient time to form a pentasil zeolite material from the silica precursor, wherein the structure directing agent includes a quaternary phosphonium ion.

Intelligent Processing of Ferroelectric Thin Films

DTIC Science & Technology

1993-09-03

the acetate precursors. The results from these experiments involving coprecipitation, hydrothermal , spray pyrolysis and freeze drying have shown that...Spray Pyrolysis (SP) D. Hydrothermal Processing (HP) The powder produced by each process was characterized by X-ray diffraction (XRD) and scanning...precursors were used as described above. Instead of ammonia solution, an oxalic acid solution was used as the3 precipitating agent. The precipitants

Role of Precursor-Conversion Chemistry in the Crystal-Phase Control of Catalytically Grown Colloidal Semiconductor Quantum Wires.

PubMed

Wang, Fudong; Buhro, William E

2017-12-26

Crystal-phase control is one of the most challenging problems in nanowire growth. We demonstrate that, in the solution-phase catalyzed growth of colloidal cadmium telluride (CdTe) quantum wires (QWs), the crystal phase can be controlled by manipulating the reaction chemistry of the Cd precursors and tri-n-octylphosphine telluride (TOPTe) to favor the production of either a CdTe solute or Te, which consequently determines the composition and (liquid or solid) state of the Bi x Cd y Te z catalyst nanoparticles. Growth of single-phase (e.g., wurtzite) QWs is achieved only from solid catalysts (y ≪ z) that enable the solution-solid-solid growth of the QWs, whereas the liquid catalysts (y ≈ z) fulfill the solution-liquid-solid growth of the polytypic QWs. Factors that affect the precursor-conversion chemistry are systematically accounted for, which are correlated with a kinetic study of the composition and state of the catalyst nanoparticles to understand the mechanism. This work reveals the role of the precursor-reaction chemistry in the crystal-phase control of catalytically grown colloidal QWs, opening the possibility of growing phase-pure QWs of other compositions.

Soft chemistry routes for synthesis of rare earth oxide nanoparticles with well defined morphological and structural characteristics

NASA Astrophysics Data System (ADS)

Mancic, L.; Marinkovic, B. A.; Marinkovic, K.; Dramicanin, M.; Milosevic, O.

2011-11-01

Phosphors of (Y0.75Gd0.25)2O3:Eu3+ (5 at.%) have been prepared through soft chemistry routes. Conversion of the starting nitrates mixture into oxide is performed through two approaches: (a) hydrothermal treatment (HT) at 200 °C/3 h of an ammonium hydrogen carbonate precipitated mixture and (b) by thermally decomposition of pure nitrate precursor solution at 900 °C in dispersed phase (aerosol) within a tubular flow reactor by spray pyrolysis process (SP). The powders are additionally thermally treated at different temperatures: 600, 1000, and 1100 °C for either 3 or 12 h. HT—derived particles present exclusively one-dimensional morphology (nanorods) up to the temperatures of 600 °C, while the leaf-like particles start to grow afterward. SP—derived particles maintain their spherical shape up to the temperatures of 1100 °C. These submicron sized spheres were actually composed of randomly aggregated nanoparticles. All powders exhibits cubic Ia- 3 structure (Y0.75Gd0.25)2O3:Eu and have improved optical characteristics due to their nanocrystalline nature. The detailed study of the influence of structural and morphological powder characteristics on their emission properties is performed based on the results of X-ray powder diffractometry, scanning electron microscopy, X-ray energy dispersive spectroscopy, transmission electron microscopy, and photoluminescence measurements.

Structural, chemical and optical properties of SnO2 NPs obtained by three different synthesis routes

NASA Astrophysics Data System (ADS)

Drzymała, Elżbieta; Gruzeł, Grzegorz; Depciuch, Joanna; Budziak, Andrzej; Kowal, Andrzej; Parlinska-Wojtan, Magdalena

2017-08-01

Polyol (P), chemical precipitation (C) and microwave-assisted (M) syntheses were chosen to produce SnO2 nanoparticles with uniform size and minimum agglomeration. Their structural, chemical and optical properties were investigated using dynamic light scattering (DLS), scanning transmission electron microscopy (STEM), Raman, Fourier Transform Infrared (FTIR) using the Attenuated Total Reflectance (ATR) technique and Ultraviolet-Visible (UV-Vis) spectroscopies. STEM observations showed that the SnO2(P) and SnO2(C) nanoparticles (NPs) are combined into larger agglomerates with heterogeneous thickness, while the microwave-assisted NPs form a uniform thin layer across the TEM grid. The strongest agglomeration of the SnO2(C) NPs, observed by DLS, STEM and UV-Vis is explained by the very moderate amount of water present on the surface of the NPs identified by FTIR spectroscopy. High resolution STEM combined with SAED and X-ray diffraction (XRD) patterns confirmed the crystalline character of the NPs. In the nanoparticles from polyol synthesis, chlorine from the remains of metal precursors during reduction was detected by energy dispersive spectroscopy (EDS), contrary to the NPs obtained by the chemical precipitation and microwave-assisted methods. All three syntheses routes lead to small, 2-10 nm SnO2 NPs, which were the result of the low concentration of Cl ions in the solutions.

Size- and Shape-Dependent Antibacterial Studies of Silver Nanoparticles Synthesized by Wet Chemical Routes

PubMed Central

Raza, Muhammad Akram; Kanwal, Zakia; Rauf, Anum; Sabri, Anjum Nasim; Riaz, Saira; Naseem, Shahzad

2016-01-01

Silver nanoparticles (AgNPs) of different shapes and sizes were prepared by solution-based chemical reduction routes. Silver nitrate was used as a precursor, tri-sodium citrate (TSC) and sodium borohydride as reducing agents, while polyvinylpyrrolidone (PVP) was used as a stabilizing agent. The morphology, size, and structural properties of obtained nanoparticles were characterized by scanning electron microscopy (SEM), UV-visible spectroscopy (UV-VIS), and X-ray diffraction (XRD) techniques. Spherical AgNPs, as depicted by SEM, were found to have diameters in the range of 15 to 90 nm while lengths of the edges of the triangular particles were about 150 nm. The characteristic surface plasmon resonance (SPR) peaks of different spherical silver colloids occurring in the wavelength range of 397 to 504 nm, whereas triangular particles showed two peaks, first at 392 nm and second at 789 nm as measured by UV-VIS. The XRD spectra of the prepared samples indicated the face-centered cubic crystalline structure of metallic AgNPs. The in vitro antibacterial properties of all synthesized AgNPs against two types of Gram-negative bacteria, Pseudomonas aeruginosa and Escherichia coli were examined by Kirby–Bauer disk diffusion susceptibility method. It was noticed that the smallest-sized spherical AgNPs demonstrated a better antibacterial activity against both bacterial strains as compared to the triangular and larger spherical shaped AgNPs. PMID:28335201

Surfactant-directed synthesis of mesoporous films made single-step by a tandem photosol-gel/photocalcination route

NASA Astrophysics Data System (ADS)

De Paz-Simon, Héloïse; Chemtob, Abraham; Croutxé-Barghorn, Céline; Rigolet, Séverinne; Michelin, Laure; Vidal, Loïc; Lebeau, Bénédicte

2014-11-01

In view of their technological impact in materials chemistry, a simplified and more efficient synthetic route to mesoporous films is highly sought. We report, herein, a smart UV-mediated approach coupling in a one-stage process sol-gel photopolymerization and photoinduced template decomposition/ablation to making mesoporous silica films. Performed at room temperature with a solvent-free solution of silicate precursor and amphiphilic poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) block copolymer, the synthesis relies on photoacid generation to induce the fast formation (≈10 min) of mesostructured silica/surfactant domains. Continuation of UV exposure for three additional hours enables subsequent and complete photodegradation of the polyether copolymer, resulting in ordered or disordered mesoporous silica film. One of the most attractive features is that the one-step procedure relies on a continuous illumination provided by the same conventional medium-pressure Hg-Xe arc lamp equipped with a 254 nm reflector to enhance the emission of energetic photons <300 nm. In addition to X-ray diffraction and transmission electron microscopy, time-resolved Fourier transform infrared spectroscopy has proved to be a powerful in situ technique to probe the different chemical transformations accompanying irradiation. Photocalcination strengthens the inorganic network, while allowing to preserve a higher fraction of residual silanol groups compared with thermal calcination. A polyether chain degradation mechanism based on oxygen reactive species-mediated photo-oxidation is proposed.

Double emulsions for the compatibilization of hydrophilic nanocellulose with non-polar polymers and validation in the synthesis of composite fibers.

PubMed

Carrillo, Carlos A; Nypelö, Tiina; Rojas, Orlando J

2016-03-14

A route for the compatibilization of aqueous dispersions of cellulose nanofibrils (CNFs) with a non-polar polymer matrix is proposed to overcome a major challenge in CNF-based material synthesis. Non-ionic surfactants were used in CNF aqueous dispersions equilibrated with an organic phase (for demonstration, a polystyrene solution, PS, was used). Stable water-in-oil-in-water (W/O/W) double emulsions were produced as a result of the compromise between composition and formulation variables. Most remarkably, the proposed route for CNF integration with hydrophobic polymers removed the need for drying or solvent-exchange of the CNF aqueous dispersion prior to processing. The rheological behavior of the double emulsions showed strong shear thinning behavior and facilitated CNF-PS co-mixing in solid nanofibers upon electrospinning. The morphology and thermal properties of the resultant nanofibers revealed that CNFs were efficiently integrated in the hydrophobic matrix which was consistent with the high interfacial area of the precursor double emulsion. In addition, the morphology and quality of the composite nanofibers can be controlled by the conductivity (ionic strength) of the CNF dispersion. Overall, double emulsion systems are proposed as a novel, efficient and scalable platform for CNF co-processing with non-polar systems and they open up the possibility for the redispersion of CNFs after removal of the organic phase.

Sol-Gel Processing of MgF2 Antireflective Coatings

PubMed Central

Löbmann, Peer

2018-01-01

There are different approaches for the preparation of porous antireflective λ/4 MgF2 films from liquid precursors. Among these, the non-aqueous fluorolytic synthesis of precursor solutions offers many advantages in terms of processing simplicity and scalability. In this paper, the structural features and optical performance of the resulting films are highlighted, and their specific interactions with different inorganic substrates are discussed. Due to their excellent abrasion resistance, coatings have a high potential for applications on glass. Using solvothermal treatment of precursor solutions, also the processing of thermally sensitive polymer substrates becomes feasible. PMID:29724064

Mechanistic studies on the Pd-catalyzed vinylation of aryl halides with vinylalkoxysilanes in water: the effect of the solvent and NaOH promoter.

PubMed

Gordillo, Alvaro; Ortuño, Manuel A; López-Mardomingo, Carmen; Lledós, Agustí; Ujaque, Gregori; de Jesús, Ernesto

2013-09-18

The mechanism of the Pd-catalyzed vinylation of aryl halides with vinylalkoxysilanes in water has been studied using different catalytic precursors. The NaOH promoter converts the initial vinylalkoxysilane into a highly reactive water-soluble vinylsilanolate species. Similarly, deuterium-labeling experiments have shown that, irrespective of the catalytic precursor used, vinylation occurs exclusively at the CH vinylic functionality via a Heck reaction and not at the C-Si bond via a Hiyama cross-coupling. The involvement of a Heck mechanism is interpreted in terms of the reduced nucleophilicity of the base in water, which disfavors the transmetalation step. The Heck product (β-silylvinylarene) undergoes partial desilylation, with formation of a vinylarene, by three different routes: (a) hydrolytic desilylation by the aqueous solvent (only at high temperature); (b) transmetalation of the silyl olefin on the PdH Heck intermediate followed by reductive elimination of vinylarene; (c) reinsertion of the silyl olefin into the PdH bond of the Heck intermediate followed by β-Si syn-elimination. Both the Hiyama and Heck catalytic cycles and desilylation mechanisms b and c have been computationally evaluated for the [Pd(en)Cl2] precursor in water as solvent. The calculated Gibbs energy barriers support the reinsertion route proposed on the basis of the experimental results.

Method for synthesizing thin film electrodes

DOEpatents

Boyle, Timothy J [Albuquerque, NM

2007-03-13

A method for making a thin-film electrode, either an anode or a cathode, by preparing a precursor solution using an alkoxide reactant, depositing multiple thin film layers with each layer approximately 500 1000 .ANG. in thickness, and heating the layers to above 600.degree. C. to achieve a material with electrochemical properties suitable for use in a thin film battery. The preparation of the anode precursor solution uses Sn(OCH.sub.2C(CH.sub.3).sub.3).sub.2 dissolved in a solvent in the presence of HO.sub.2CCH.sub.3 and the cathode precursor solution is formed by dissolving a mixture of (Li(OCH.sub.2C(CH.sub.3).sub.3)).sub.8 and Co(O.sub.2CCH.sub.3).H.sub.2O in at least one polar solvent.

Synthesis of silicon containing materials using liquid hydrosilane compositions through direct injection

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

Srinivasan, Guruvenket; Sailer, Robert A.; Hoey, Justin

An apparatus and a non-vapor-pressure dependent method of chemical vapor deposition of Si based materials using direct injection of liquid hydrosilane(s) are presented. Liquid silane precursor solutions may also include metal, non-metal or metalloid dopants, nanomaterials and solvents. An illustrative apparatus has a precursor solution and carrier gas system, atomizer and deposit head with interior chamber and a hot plate supporting the substrate. Atomized liquid silane precursor solutions and carrier gas moves through a confined reaction zone that may be heated and the aerosol and vapor are deposited on a substrate to form a thin film. The substrate may bemore » heated prior to deposition. The deposited film may be processed further with thermal or laser processing.« less

Towards the Rational Design of Nanoparticle Catalysts

NASA Astrophysics Data System (ADS)

Dash, Priyabrat

This research is focused on development of routes towards the rational design of nanoparticle catalysts. Primarily, it is focused on two main projects; (1) the use of imidazolium-based ionic liquids (ILs) as greener media for the design of quasi-homogeneous nanoparticle catalysts and (2) the rational design of heterogeneous-supported nanoparticle catalysts from structured nanoparticle precursors. Each project has different studies associated with the main objective of the design of nanoparticle catalysts. In the first project, imidazolium-based ionic liquids have been used for the synthesis of nanoparticle catalysts. In particular, studies on recyclability, reuse, mode-of-stability, and long-term stability of these ionic-liquid supported nanoparticle catalysts have been done; all of which are important factors in determining the overall "greenness" of such synthetic routes. Three papers have been published/submitted for this project. In the first publication, highly stable polymer-stabilized Au, Pd and bimetallic Au-Pd nanoparticle catalysts have been synthesized in imidazolium-based 1-butyl-3-methylimidazolium hexafluorophosphate ([BMIM]PF6) ionic liquid (Journal of Molecular Catalysis A: Chemical, 2008, 286, 114). The resulting nanoparticles were found to be effective and selective quasi-homogeneous catalysts towards a wide-range of hydrogenation reactions and the catalyst solution was reused for further catalytic reactions with minimal loss in activity. The synthesis of very pure and clean ILs has allowed a platform to study the effects of impurities in the imidazolium ILs on nanoparticle stability. In a later study, a new mode of stabilization was postulated where the presence of low amounts of 1-methylimidazole has substantial effects on the resulting stability of Au and Pd-Au nanoparticles in these ILs (Chemical Communications, 2009, 812). In further continuation of this study, a comparative study involving four stabilization protocols for nanoparticle stabilization in BMIMPF6 IL is described, and have shown that nanoparticle stability and catalytic activity of nanoparticles is dependent on the overall stability of the nanoparticles towards aggregation (manuscript submitted). The second major project is focused on synthesizing structurally well-defined supported catalysts by incorporating the nanoparticle precursors (both alloy and core shell) into oxide frameworks (TiO2 and Al2O 3), and examining their structure-property relationships and catalytic activity. a full article has been published on this project (Journal of Physical Chemistry C, 2009, 113, 12719) in which a route to rationally design supported catalysts from structured nanoparticle precursors with precise control over size, composition, and internal structure of the nanoparticles has been shown. In a continuation of this methodology for the synthesis of heterogeneous catalysts, efforts were carried out to apply the same methodology in imidazolium-based ILs as a one-pot media for the synthesis of supported-nanoparticle heterogeneous catalysts via the trapping of pre-synthesized nanoparticles into porous inorganic oxide materials. Nanoparticle catalysts in highly porous titania supports were synthesized using this methodology (manuscript to be submitted).

Precursor preparation for Ca-Al layered double hydroxide to remove hexavalent chromium coexisting with calcium and magnesium chlorides

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

Zhong, Lihua; He, Xiaoman; Qu, Jun

Al(OH){sub 3} and Ca(OH){sub 2} powders are co-ground to prepare a precursor which hydrates into a layered double hydroxide (LDH) phase by agitation in aqueous solution with target hexavalent chromium (Cr(VI)) at room temperature, to achieve an obvious improvement in removal efficiency of Cr(VI) through an easy incorporation into the structure. Although the prepared precursor transforms into LDH phases also when agitated in the solutions of calcium and magnesium chlorides, it incorporates Cr(VI) preferentially to the chloride salts when they coexist. The adsorption isotherm and kinetic studies show that the phenomena occurring on the Al-Ca precursor fit a pseudo-second-order kineticsmore » with a Langmuir adsorption capacity of 59.45 mg/g. Besides, characterizations of the prepared precursor and the samples after adsorption are also performed by X-ray diffraction (XRD), Fourier transform infrared (FT-IR), Transmission electron microscope (TEM) to understand the reason of the preferential incorporation of Cr(VI) to the coexisting chloride salts during the LDH phase formation. - Graphical abstract: Activated Ca-Al hydroxides (C{sub 3}A) transformed into Ca-Al-OH compound when agitated in water. Ca-Al precursor (C{sub 3}A) was agitated in a hexavalent chromium (Cr(VI)) solution to form Al-Ca-CrO{sub 4} LDH product. Ca-Al-CrO{sub 4} LDH phase occurred preferentially to Ca-Al-MCl{sub 2} LDH phases in the solutions of calcium and magnesium chlorides, it incorporates Cr(VI) preferentially to the chloride salts when they coexist. - Highlights: • Activated Ca-Al hydroxides transformed into LDH when agitated in water with some inorganic substances. • Hexavalent Cr was incorporated in the LDH structure at high adsorption capacity. • Ca-Al-Cr LDH phase occurred preferentially to Ca-Al-MCl{sub 2} LDH phases with coexistence. • The prepared Ca-Al hydroxides had high performance as adsorbent even with high salinity of the solution.« less

Effects of Residual Lithium in the precursors of Li[Ni1/3Co1/3Mn1/3]O2 on their lithium-ion battery performance

NASA Astrophysics Data System (ADS)

Jo, Minsang; Ku, Heesuk; Park, Sanghyuk; Song, Junho; Kwon, Kyungjung

2018-07-01

Li[Ni1/3Co1/3Mn1/3]O2 cathode active materials are synthesized from co-precipitated hydroxide precursors Lix[Ni1/3Co1/3Mn1/3]1-x(OH)2, and the effect of residual Li in the precursors on the lithium-ion battery (LIB) performance of their corresponding cathode active materials is investigated. Three kinds of precursors that contain different amounts of Li are selected depending on different conditions of the solution composition for the co-precipitation and washing process. It is confirmed that the introduction of Li to the precursors reduces the degree of structural perfection by X-ray diffraction analysis. Undesirable cation mixing occurs with the increasing Li content of the precursors, which is inferred from a decline in lattice parameters and the calculated intensity ratio of (003) and (104) peaks. In the voltage range of 3.0-4.3 V, the initial charge/discharge capacities and the rate capability of the cathode active materials are aggravated when Li exists in the precursors. Therefore, it could be concluded that the strict control of Li in a solution for co-precipitation of precursors is necessary in the resynthesis of cathode active materials from spent LIBs.

Aqueous citrato-oxovanadate(IV) precursor solutions for VO2: synthesis, spectroscopic investigation and thermal analysis.

PubMed

Peys, Nick; Adriaensens, Peter; Van Doorslaer, Sabine; Gielis, Sven; Peeters, Ellen; De Dobbelaere, Christopher; De Gendt, Stefan; Hardy, An; Van Bael, Marlies K

2014-09-07

An aqueous precursor solution, containing citrato-VO(2+) complexes, is synthesized for the formation of monoclinic VO2. With regard to the decomposition of the VO(2+) complexes towards vanadium oxide formation, it is important to gain insights into the chemical structure and transformations of the precursor during synthesis and thermal treatment. Hence, the conversion of the cyclic [V4O12](4-) ion to the VO(2+) ion in aqueous solution, using oxalic acid as an acidifier and a reducing agent, is studied by (51)Vanadium nuclear magnetic resonance spectroscopy. The citrate complexation of this VO(2+) ion and the differentiation between a solution containing citrato-oxalato-VO(2+) and citrato-VO(2+) complexes are studied by electron paramagnetic resonance and Fourier transform infra-red spectroscopy. In both solutions, the VO(2+) containing complex is mononuclear and has a distorted octahedral geometry with a fourfold R-CO2(-) ligation at the equatorial positions and likely a fifth R-CO2(-) ligation at the axial position. Small differences in the thermal decomposition pathway between the gel containing citrato-oxalato-VO(2+) complexes and the oxalate-free gel containing citrato-VO(2+) complexes are observed between 150 and 200 °C in air and are assigned to the presence of (NH4)2C2O4 in the citrato-oxalato-VO(2+) solution. Both precursor solutions are successfully used for the formation of crystalline vanadium oxide nanostructures on SiO2, after thermal annealing at 500 °C in a 0.1% O2 atmosphere. However, the citrato-oxalato-VO(2+) and the oxalate-free citrato-VO(2+) solution result in the formation of monoclinic V6O13 and monoclinic VO2, respectively.

Self-Assembled Fe-N-Doped Carbon Nanotube Aerogels with Single-Atom Catalyst Feature as High-Efficiency Oxygen Reduction Electrocatalysts

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

Zhu, Chengzhou; Fu, Shaofang; Song, Junhua

Finely controlled synthesis of high active and robust non-precious metal catalysts with excellent electrocatalytic efficiency towards oxygen reduction reaction is extremely vital for successful implementation of fuel cells and metal batteries. Unprecedented oxygen reduction reaction electrocatalytic performances and the diversified synthetic procedure in term of favorable structure/morphology characteristics make transition metals-derived M–N–C (M=Fe, Co) structures the most promising nanocatalysts. Herein, using the nitrogen-containing small molecular and inorganic salt as precursors and ultrathin tellurium nanowires as templates, we successfully synthesized a series of well-defined M-N-doped hollow carbon nanowire aerogels through one step hydrothermal route and subsequent facile annealing treatment. Taking advantagemore » of the porous nanostructures, one-dimensional building block as well as homogeneity of active sites, the resultant Fe-N-doped carbon hollow nanowire aerogels exhibited excellent ORR electrocatalytic performance even better than commercial Pt/C in alkaline solution, holding great potential in fuel cell applications.« less

Mechanochemical synthesis of dodecyl sulfate anion (DS-) intercalated Cu-Al layered double hydroxide

NASA Astrophysics Data System (ADS)

Qu, Jun; He, Xiaoman; Lei, Zhiwu; Zhang, Qiwu; Liu, Xinzhong

2017-12-01

Dodecyl sulfate anion (DS-) was successfully intercalated into the gallery space of Cu-Al layered double hydroxides (LDH) by a non-heating mechanochemical route, in which basic cupric carbonate (Cu2(OH)2CO3) and aluminum hydroxide (Al(OH)3) were first dry ground and then agitated in SDS solution under ambient environment. The organics modified Cu-Al LDH showed good adsorption ability toward 2,4-dichlorophenoxyacetic acid (2, 4-D). The prepared samples were characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), CHS elemental analysis and Scanning electron microscopy (SEM). The LDH precursor prepared by ball-milling could directly react with SDS molecules forming a pure phase of DS- pillared Cu-Al LDH, which was not observed with the LDH product through the ion-exchange of DS- at room temperature. The process introduced here may be applied to manufacture other types of organic modified composites for pollutants removal and other applications.

Ce, Ti modified MCM-48 mesoporous photocatalysts: Effect of the synthesis route on support and metal ion properties

NASA Astrophysics Data System (ADS)

Mureseanu, Mihaela; Filip, Mihaela; Somacescu, Simona; Baran, Adriana; Carja, Gabriela; Parvulescu, Viorica

2018-06-01

New Ti-MCM-48 and CeTi-MCM-48 photocatalysts were obtained by impregnation of the MCM-48 silica support synthesized by a hydrothermal process with aqueous solution of Ti and Ce precursors. The immobilization of metal cations presented a low effect on the porosity, morphology and structure of MCM-48 mesoporous silica support as was evidenced by N2 adsorption-desorption, X-ray diffraction, SEM and TEM electron microscopy. EDAX analysis and X-ray photoelectron microscopy (XPS) indicated that titanium cations were present on the mesoporous silica surface only as Ti4+ species and the effect of ceria on titanium speciation was different, compared to the CeTi-MCM-48 sample, previously obtained by direct synthesis. The photocatalytic properties of mono- and bimetallic catalysts were evaluated in degradation of phenol from water and correlated with the active metallic species concentration, distribution, speciation and their interaction with the support or each other. An advanced oxidation mechanism for phenol degradation by radical species was proposed.

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

Gao, Shan, E-mail: coralgao@hotmail.com; Engineering Ceramics Key Laboratory of Shandong Province, Shandong University, Jinan 250061; Sun, Kangning, E-mail: sunkangning@sdu.edu.cn

Highlights: ► We succeeded in synthesizing hydroxyapatite nano fibers by a chemical method. ► The reaction temperature is only 90 °C. ► The synthetic hydroxyapatite nano fiber is single crystal. - Abstract: We report a novel chemical precipitation route for the synthesis of hydroxyapatite (Ca{sub 10}(PO{sub 4}){sub 6}(OH){sub 2}, HA) fibers using surfactants as templates. Fourier transform infrared spectroscopy (FTIR) and powder X-ray diffraction (PXRD) reveal the characteristic peaks of HA. Transmission electron microscope (TEM) and high-resolution TEM revealed the nano structure, crystallinity and morphology of the HA fibers. The morphology of the HA fibers after calcinations were characterized bymore » scanning electron microscope (SEM). Br{sup −} ions were quickly replaced by the excess PO{sub 4}{sup 3−} ions in the solution after the addition of cetyltrime-thylammonium bromide (CTAB). Meanwhile, CTAB formed a rod-like micelles. Precursors reacted with PO{sub 4}{sup 3−} at the surface of CTAB micelles and finally formed the nanofiber structure.« less

Synthesis of α-MoC1-x Nanoparticles with a Surface-Modified SBA-15 Hard Template: Determination of Structure-Function Relationships in Acetic Acid Deoxygenation.

PubMed

Baddour, Frederick G; Nash, Connor P; Schaidle, Joshua A; Ruddy, Daniel A

2016-07-25

Surface modification of mesoporous SBA-15 silica generated a hydrophobic environment for a molybdenum diamine (Mo-diamine) precursor solution, enabling direct growth of isolated 1.9±0.4 nm α-MoC1-x nanoparticles (NPs) inside the pores of the support. The resulting NP catalysts are bifunctional, and compared to bulk α-MoC1-x and β-Mo2 C, the NPs exhibit a greater acid-site:H-site ratio and a fraction of stronger acid sites. The greater acid-site:H-site ratio results in higher decarbonylation (DCO) selectivity during acetic acid hydrodeoxygenation (HDO) reactions, and the stronger acid sites lead to higher activity and ketonization (KET) selectivity at high temperatures. The hard-templating synthetic method could be a versatile route toward carbide NPs of varying size, composition, and phase, on a range of mesoporous oxide supports. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

A new route for synthesis of spherical NiO nanoparticles via emulsion nano-reactors with enhanced photocatalytic activity

NASA Astrophysics Data System (ADS)

Fazlali, Farnaz; Mahjoub, Ali reza; Abazari, Reza

2015-10-01

This study has sought to draw a comparison among the nickel oxide nanostructures (NSs) with multiple shapes in terms of their photocatalytic properties. These NSs have been synthesized using a set of wet chemical methods (thermal-decomposition, sol-gel, hydrothermal, and emulsion nano-reactors), for which a similar precursor has been considered. For evaluation of the photocatalytic properties of the suggested NSs, methyl orange (MeO) solution photocatalytic degradation has been estimated based on UV-Vis spectroscopy. As shown by our results, the photocatalytic efficiency of the prepared NSs is highly dependent upon the shape of the corresponding structures. In this context, the emulsion nano-reactors (ENRs) method has been developed for the synthesis of pure nickel oxide nanoparticles (NPs) with unaggregated, quite spherical, and homogeneous NPs at environmental conditions. Compared with the other methods in this work, ENRs method shows high photocatalytic efficiency in the MeO dye decomposition.

Synthesis of α-MoC 1-x Nanoparticles with a Surface-Modified SBA-15 Hard Template: Determination of Structure-Function Relationships in Acetic Acid Deoxygenation

DOE PAGES

Baddour, Frederick G.; Nash, Connor P.; Schaidle, Joshua A.; ...

2016-06-07

Surface modification of mesoporous SBA-15 silica generated a hydrophobic environment for a molybdenum diamine (Mo-diamine) precursor solution, enabling direct growth of isolated 1.9 ± 0.4 nm α-MoC 1-x nanoparticles (NPs) inside the pores of the support. The resulting NP catalysts are bifunctional, and compared to bulk α-MoC 1-x and β-Mo 2C, the NPs exhibit a greater acid-site:H-site ratio and a fraction of stronger acid sites. The greater acid-site:H-site ratio results in higher decarbonylation (DCO) selectivity during acetic acid hydrodeoxygenation (HDO) reactions, and the stronger acid sites lead to higher activity and ketonization (KET) selectivity at high temperatures. Lastly, the hard-templatingmore » synthetic method could be a versatile route toward carbide NPs of varying size, composition, and phase, on a range of mesoporous oxide supports.« less

Sustainable production of valuable compound 3-succinoyl-pyridine by genetically engineering Pseudomonas putida using the tobacco waste.

PubMed

Wang, Weiwei; Xu, Ping; Tang, Hongzhi

2015-11-17

Treatment of solid and liquid tobacco wastes with high nicotine content remains a longstanding challenge. Here, we explored an environmentally friendly approach to replace tobacco waste disposal with resource recovery by genetically engineering Pseudomonas putida. The biosynthesis of 3-succinoyl-pyridine (SP), a precursor in the production of hypotensive agents, from the tobacco waste was developed using whole cells of the engineered Pseudomonas strain, S16dspm. Under optimal conditions in fed-batch biotransformation, the final concentrations of product SP reached 9.8 g/L and 8.9 g/L from aqueous nicotine solution and crude suspension of the tobacco waste, respectively. In addition, the crystal compound SP produced from aqueous nicotine of the tobacco waste in batch biotransformation was of high purity and its isolation yield on nicotine was 54.2%. This study shows a promising route for processing environmental wastes as raw materials in order to produce valuable compounds.

Morphology dependent catalytic activity of TiO{sub 2} nanostructures towards photodegradation of Rose Bengal

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

Malik, Ritu; Kumar, Ashok; Rana, Pawan S., E-mail: drpawansrana.phy@dcrustm.org

2015-08-28

This work deals with the synthesis of TiO{sub 2} nanostructures using sol-gel and hydrothermal method for evaluating their photodegradation performance towards decolorization of Rose Bengal (RB). A combination of characterization techniques including X-ray diffraction (XRD), Field emission scanning electron microscopy (FESEM) and UV–Vis spectroscopy were utilized to evaluate the structural, morphological and optical properties of the obtained nanostructures. It was observed that the TiO{sub 2} nanoparticles prepared using hydrothermal method were highly crystalline and possess higher band gap value, even when same conditions of temperature, pressure, precursor ratios and solvent amount was kept constant while synthesizing TiO{sub 2} nanostructures viamore » sol-gel method. The obvious effect of porous morphology exhibited by TiO{sub 2} nanoparticles prepared using hydrothermal route is reflected in its decolorization performance whereby 92.5% of the RB dye solution was degraded in 70 min of irradiation time.« less

Belite cement clinker from coal fly ash of high Ca content. Optimization of synthesis parameters.

PubMed

Guerrero, A; Goñi, S; Campillo, I; Moragues, A

2004-06-01

The optimization of parameters of synthesis of belite cement clinker from coal fly ash of high Ca content is presented in this paper. The synthesis process is based on the hydrothermal-calcination-route of the fly ash without extra additions. The hydrothermal treatment was carried out in demineralized water and a 1 M NaOH solution for 4 h at the temperatures of 100 degrees C, 150 degrees C, and 200 degrees C. The precursors obtained during the hydrothermal treatmentwere heated at temperatures of 700 degrees C, 800 degrees C, 900 degrees C, and 1000 degrees C. The changes of fly ash composition after the different treatments were characterized by X-ray diffraction (XRD), FT infrared (FTIR) spectroscopy, surface area (BET-N2), and thermal analyses. From the results obtained we concluded that the optimum temperature of the hydrothermal treatment was 200 degrees C, and the optimum temperature for obtaining the belite cement clinker was 800 degrees C.

[Ambient pressure synthesis and characterization of silica aerogel as adsorbent for dieldrin].

PubMed

Sha, Wei; Liu, Rui-ping; Liu, Hui-juan; Qu, Jiu-hui

2008-12-01

Hydrophobic silica aerogels were prepared from cheap waterglass precursors via surface modification of wet gels and ambient pressure drying route. Its adsorption capacity of Dieldrin, a typical of persistent organic pollutants (POPs), was examined. It is characterized via BET, FTIR, and DSC-TGA. The silica aerogels were highly hydrophobic with contact angles of 135 degrees-142 degrees, and the hydrophobicity of the aerogels could be maintained up to the temperature of 380 degrees C. The silica aerogels were porous with, pore size distribution of 17.5-23.4 nm, porosity of 94.8%-95.6%, and surface area of 444-560 m2 x g(-1). The results of adsorption experiments indicated that the hydrophobic aerogels could remove 84% of dieldrin from aqueous solution within 4 h; the adsorption process followed the pseudo-second-order kinetics process. Based on the adsorption equilibrium results, the adsorption capacity of silica aerogel was 11 times bigger than by active carbon.

Real time monitoring system used in route planning for the electric vehicle

NASA Astrophysics Data System (ADS)

Ionescu, LM; Mazare, A.; Serban, G.; Ionita, S.

2017-10-01

The electric vehicle is a new consumer of electricity that is becoming more and more widespread. Under these circumstances, new strategies for optimizing power consumption and increasing vehicle autonomy must be designed. These must include route planning along with consumption, fuelling points and points of interest. The hardware and software solution proposed by us allows: non-invasive monitoring of power consumption, energy autonomy - it does not add any extra consumption, data transmission to a server and data fusion with the route, the points of interest of the route and the power supply points. As a result: an optimal route planning service will be provided to the driver, considering the route, the requirements of the electric vehicle and the consumer profile. The solution can be easily installed on any type of electric car - it does not involve any intervention on the equipment.

An integer programming approach to a real-world recyclable waste collection problem in Argentina.

PubMed

Braier, Gustavo; Durán, Guillermo; Marenco, Javier; Wesner, Francisco

2017-05-01

This article reports on the use of mathematical programming techniques to optimise the routes of a recyclable waste collection system servicing Morón, a large municipality outside Buenos Aires, Argentina. The truck routing problem posed by the system is a particular case of the generalised directed open rural postman problem. An integer programming model is developed with a solving procedure built around a subtour-merging algorithm and the addition of subtour elimination constraints. The route solutions generated by the proposed methodology perform significantly better than the previously used, manually designed routes, the main improvement being that coverage of blocks within the municipality with the model solutions is 100% by construction, whereas with the manual routes as much as 16% of the blocks went unserviced. The model-generated routes were adopted by the municipality in 2014 and the national government is planning to introduce the methodology elsewhere in the country.

Assessment of silicone as support to investigate the transformation routes of organic chemicals under environmental conditions and UV exposure. Application to selected fungicides.

PubMed

Rodríguez-Cabo, T; Rodríguez, I; Ramil, M; Cela, R

2013-05-01

The suitability of bulk silicone as support to follow the degradation of chemical compounds under environmental conditions and UV radiation is illustrated selecting three fungicides (fenhexamid, FEN; triadimenol, TRI and difenoconazole, DIF) as model compounds. These precursor species were first absorbed in silicone supports (10 mm length × 2 mm i.d. and 0.5 mm thickness) and then kept outdoors for several days (up to 2 months) or exposed to UV radiation (254 nm), from a low pressure mercury lamp, in the laboratory. Degradation of precursor fungicides and by-products formation was followed by liquid chromatography (LC) quadrupole time-of-flight (QTOF) mass spectrometry (MS), after desorption of silicone supports using 0.5 mL of acetonitrile. Half-lives (t(1/2)) measured under UV exposure varied from 5 to 100 min. As regards environmental conditions, the most stable fungicide was DIF, degraded by just 15 % after 2 months; whereas, t(1/2) values of 30 and 83 h were calculated for FEN during summer and autumn, respectively. Supports contained by-products arising from precursor species through de-chlorination, cleavage, hydroxylation, intra-molecular cyclation and oligomerization reactions. Most of them have been previously identified in soil surface, vegetable leaves and water after application of fungicides in agriculture fields. The low cost of silicone tubes (ca. 0.4 Euros), added to their excellent chemical stability and capability to retain precursor species and their by-products, make them ideal supports to follow the transformation routes of organic compounds under environmental and simulated conditions, even for relatively stable species with t(1/2) in the range of weeks or months.

Nonreciprocal signal routing in an active quantum network

NASA Astrophysics Data System (ADS)

Metelmann, A.; Türeci, H. E.

2018-04-01

As superconductor quantum technologies are moving towards large-scale integrated circuits, a robust and flexible approach to routing photons at the quantum level becomes a critical problem. Active circuits, which contain parametrically driven elements selectively embedded in the circuit, offer a viable solution. Here, we present a general strategy for routing nonreciprocally quantum signals between two sites of a given lattice of oscillators, implementable with existing superconducting circuit components. Our approach makes use of a dual lattice of overdamped oscillators linking the nodes of the main lattice. Solutions for spatially selective driving of the lattice elements can be found, which optimally balance coherent and dissipative hopping of microwave photons to nonreciprocally route signals between two given nodes. In certain lattices these optimal solutions are obtained at the exceptional point of the dynamical matrix of the network. We also demonstrate that signal and noise transmission characteristics can be separately optimized.

Modification of Different Zirconium Propoxide Precursors by Diethanolamine. Is There a Shelf Stability Issue for Sol-Gel Applications?

PubMed Central

Spijksma, Gerald I.; Blank, Dave H. A.; Bouwmeester, Henny J. M.; Kessler, Vadim G.

2009-01-01

Modification of different zirconium propoxide precursors with H2dea was investigated by characterization of the isolated modified species. Upon modification of zirconium n-propoxide and [Zr(OnPr)(OiPr)3(iPrOH)]2 with ½ a mol equivalent of H2dea the complexes [Zr2(OnPr)6(OCH2CH2)2NH]2 (1) and [Zr2(OnPr)2(OiPr)4(OCH2CH2)2NH]2 (2) were obtained. However, 1H-NMR studies of these tetranuclear compounds showed that these are not time-stable either in solution or solid form. The effect of this time instability on material properties is demonstrated by light scattering and TEM experiments. Modification of zirconium isopropoxide with either ½ or 1 equivalent mol of H2dea results in formation of the trinuclear complex, Zr{η3μ2-NH(C2H4O)2}3[Zr(OiPr)3]2(iPrOH)2 (3) countering a unique nona-coordinated central zirconium atom. This complex 3 is one of the first modified zirconium propoxide precursors shown to be stable in solution for long periods of time. The particle size and morphology of the products of sol-gel synthesis are strongly dependent on the time factor and eventual heat treatment of the precursor solution. Reproducible sol-gel synthesis requires the use of solution stable precursors. PMID:20087472

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.

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.

Organic impurity profiling of 3,4-methylenedioxymethamphetamine (MDMA) synthesised from catechol.

PubMed

Heather, Erin; Shimmon, Ronald; McDonagh, Andrew M

2015-03-01

This work examines the organic impurity profile of 3,4-methylenedioxymethamphetamine (MDMA) that has been synthesised from catechol (1,2-dihydroxybenzene), a common chemical reagent available in industrial quantities. The synthesis of MDMA from catechol proceeded via the common MDMA precursor safrole. Methylenation of catechol yielded 1,3-benzodioxole, which was brominated and then reacted with magnesium allyl bromide to form safrole. Eight organic impurities were identified in the synthetic safrole. Safrole was then converted to 3,4-methylenedioxyphenyl-2-propanone (MDP2P) using two synthetic methods: Wacker oxidation (Route 1) and an isomerisation/peracid oxidation/acid dehydration method (Route 2). MDMA was then synthesised by reductive amination of MDP2P. Thirteen organic impurities were identified in MDMA synthesised via Route 1 and eleven organic impurities were identified in MDMA synthesised via Route 2. Overall, organic impurities in MDMA prepared from catechol indicated that synthetic safrole was used in the synthesis. The impurities also indicated which of the two synthetic routes was utilised. Copyright © 2015 Elsevier Ireland Ltd. All rights reserved.

Adaptive routing in wireless communication networks using swarm intelligence

NASA Technical Reports Server (NTRS)

Arabshahi, P.; Gray, A.; Kassabalidis, I.; Das, A.; Narayanan, S.; Sharkawi, M. El; Marks, R. J.

2001-01-01

In this paper we focus on the network routing problem, and survey swarm intelligent approaches for its efficient solution, after a brief overview of power-aware routing schemes, which are important in the network examples outlined above.

Chemiluminescence of Secondary Peroxyesters.

DTIC Science & Technology

1980-11-14

phenylethylperoxybenzoates was investiqlated. Thermolysis in benzene gives acetophenone and the corresponding carboxYlic acid . The study of the reactiol...these compounds undergo unimolecular thermolysis to qenerate the appropriate carboxylic acid add carbonyl compound; eq. 2. We estimated, using...prepared by reaction of 1 -phenylethyl hydroperoxide with the appropriate activated acid precursor. We prepared the hydroperoxide by two different routes

Microemulsion flame pyrolysis for hopcalite nanoparticle synthesis: a new concept for catalyst preparation.

PubMed

Biemelt, T; Wegner, K; Teichert, J; Kaskel, S

2015-04-07

A new route to highly active hopcalite catalysts via flame spray pyrolysis of an inverse microemulsion precursor is reported. The nitrate derived nanoparticles are around 15 nm in diameter and show excellent conversion of CO under ambient conditions, outperforming commercial reference hopcalite materials produced by co-precipitation.

Microwave assisted synthesis of bridgehead alkenes.

PubMed

Cleary, Leah; Yoo, Hoseong; Shea, Kenneth J

2011-04-01

A new, concise method to synthesize triene precursors for the type 2 intramolecular Diels-Alder reaction has been developed. Microwave irradiation of the trienes provides a convenient method for the synthesis of bridgehead alkenes. Higher yields, shorter reaction times, and lower reaction temperatures provide a general and efficient route to this interesting class of molecules.

Microwave Assisted Synthesis of Bridgehead Alkenes

PubMed Central

Cleary, Leah; Yoo, Hoseong; Shea, Kenneth J.

2011-01-01

A new, concise method to synthesize triene precursors for the type 2 intramolecular Diels–Alder reaction has been developed. Microwave irradiation of the trienes provides a convenient method for the synthesis of bridgehead alkenes. Higher yields, shorter reaction times and lower reaction temperatures provide a general and efficient route to this interesting class of molecules. PMID:21384818

High-fraction brookite films from amorphous precursors.

PubMed

Haggerty, James E S; Schelhas, Laura T; Kitchaev, Daniil A; Mangum, John S; Garten, Lauren M; Sun, Wenhao; Stone, Kevin H; Perkins, John D; Toney, Michael F; Ceder, Gerbrand; Ginley, David S; Gorman, Brian P; Tate, Janet

2017-11-09

Structure-specific synthesis processes are of key importance to the growth of polymorphic functional compounds such as TiO 2 , where material properties strongly depend on structure as well as chemistry. The robust growth of the brookite polymorph of TiO 2 , a promising photocatalyst, has been difficult in both powder and thin-film forms due to the disparity of reported synthesis techniques, their highly specific nature, and lack of mechanistic understanding. In this work, we report the growth of high-fraction (~95%) brookite thin films prepared by annealing amorphous titania precursor films deposited by pulsed laser deposition. We characterize the crystallization process, eliminating the previously suggested roles of substrate templating and Na helper ions in driving brookite formation. Instead, we link phase selection directly to film thickness, offering a novel, generalizable route to brookite growth that does not rely on the presence of extraneous elements or particular lattice-matched substrates. In addition to providing a new synthesis route to brookite thin films, our results take a step towards resolving the problem of phase selection in TiO 2 growth, contributing to the further development of this promising functional material.

CVD growth of graphene at low temperature

NASA Astrophysics Data System (ADS)

Zeng, Changgan

2012-02-01

Graphene has attracted a lot of research interest owing to its exotic properties and a wide spectrum of potential applications. Chemical vapor deposition (CVD) from gaseous hydrocarbon sources has shown great promises for large-scale graphene growth. However, high growth temperature, typically 1000^oC, is required for such growth. In this talk, I will show a revised CVD route to grow graphene on Cu foils at low temperature, adopting solid and liquid hydrocarbon feedstocks. For solid PMMA and polystyrene precursors, centimeter-scale monolayer graphene films are synthesized at a growth temperature down to 400^oC. When benzene is used as the hydrocarbon source, monolayer graphene flakes with excellent quality are achieved at a growth temperature as low as 300^oC. I will also talk about our recent progress on low-temperature graphene growth using paraterphenyl as precursor. The successful low-temperature growth can be qualitatively understood from the first principles calculations. Our work might pave a way to economical and convenient growth route of graphene, as well as better control of the growth pattern of graphene at low temperature.

Microstructure and Mechanics of Superconductor Epitaxy via the Chemical Solution Deposition Method

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

Frederick F. Lange

2006-11-30

Executive Summary: Initially the funds were sufficient funds were awarded to support one graduate student and one post-doc. Lange, though other funds, also supported a graduate intern from ETH Zurich, Switzerland for a period of 6 months. The initial direction was to study the chemical solution deposition method to understand the microstructural and mechanical phenomena that currently limit the production of thick film, reliable superconductor wires. The study was focused on producing thicker buffer layer(s) on Ni-alloy substrates produced by the RABiTS method. It focused on the development of the microstructure during epitaxy, and the mechanical phenomena that produce cracksmore » during dip-coating, pyrolysis (decomposition of precursors during heating), crystallization and epitaxy. The initial direction of producing thicker layers of a know buffer layer material was redirected by co-workers at ORNL, in an attempt to epitaxially synthesize a potential buffer layer material, LaMnO3, via the solution route. After a more than a period of 6 months that showed that the LaMnO3 reacted with the Ni-W substrate at temperatures that could produce epitaxy, reviewers at the annual program review strongly recommended that the research was not yielding positive results. The only positive result presented at the meeting was that much thicker films could be produce by incorporating a polymer into the precursor that appeared to increase the precursor’s resistance to crack growth. Thus, to continue the program, the objectives were changed to find compositions with the perovskite structure that would be a) chemically compatible with either the Ni-W RABiTS or the MgO IBAD Ni-alloy substrates, and produce a better lattice parameter fit between either of the two substrates. At the start of the second year, the funding was reduced to 2/3’s of the first year level, which required the termination of the post-doc after approximately 5 months into the second year. From then on, further funding was intermittent to say the least, and funding to support the student and the research expenses has to be supplemented by Lange’s gift funds. During the first part of the second year, strontium zirconate was identified as an alternative to lanthanum manganite as a buffer layer for use on the IBAD MgO superconducting wire. A lattice parameter of 4.101 Angstroms offers a reduced lattice mismatch between the MgO and SrZrO3. Studies were focused on investigating hybrid precursor routes, combining Sr acetate with a number of different Zr alkoxides. Initial results from heat treating precursors to form powders are positive with the formation of orthorhombic SrZrO3 at temperatures between 800°C and 1100°C under a reducing atmosphere of Ar – 5% H2. Buffer layer research on RABiTS substrates were centered on GdAlO3 (3.71 Å) and YAlO3 (3.68 Å) buffer layer materials. Powder experiments in YAlO3 have shown the perovskite phase to be metastable at processing temperatures below 1500 °C. Experiments involving spin coating of YAlO3 precursors have found significant problems involved with wettability of the YAlO3 precursor (Yttrium acetate, Aluminum tri-sec butoxide, DI water and Formic Acid) on RABiTS substrates; this, and the demise of the funds precluded further research using YAlO3. The diminished funds for the second year, and the small, tricked funds during the third year lead to a redirection of the student to another research area., and a stop to any experimental achievements that were much too ambition relative to the available funds. The only positive results obtained during this latter period was the understanding why two dissimilar structures could result in an epitaxial relation. It was shown that two rules of crystal chemistry, cation/anion coordination and charge balance, could be applied to understand the epitaxy of SrTiO3 on Ni c(2 X 2)S, TiO2 (anatase) on LaAlO3, TiO2 (rutile) on r-plane Al2O3, and Zr1-x(Yx)O2 on (0001) Al2O3. This new understanding of the interface between two dissimilar structures has important implications that include the buffer layers used for the superconductor program, namely, the epitaxy of perovskites such as the epitaxy of SrTiO3 on the Ni c(2 X 2)S wire. This discovery is the major part of the finial report that follows.« less

Method for forming polymerized microfluidic devices

DOEpatents

Sommer, Gregory J [Livermore, CA; Hatch, Anson V [Tracy, CA; Wang, Ying-Chih [Pleasanton, CA; Singh, Anup K [Danville, CA; Renzi, Ronald F [Tracy, CA; Claudnic, Mark R [Livermore, CA

2011-11-01

Methods for making a micofluidic device according to embodiments of the present invention include defining a cavity. Polymer precursor solution is positioned in the cavity, and exposed to light to begin the polymerization process and define a microchannel. In some embodiments, after the polymerization process is partially complete, a solvent rinse is performed, or fresh polymer precursor introduced into the microchannel. This may promote removal of unpolymerized material from the microchannel and enable smaller feature sizes. The polymer precursor solution may contain an iniferter. Polymerized features therefore may be capped with the iniferter, which is photoactive. The iniferter may aid later binding of a polyacrylamide gel to the microchannel surface.

Method for forming polymerized microfluidic devices

DOEpatents

Sommer, Gregory J.; Hatch, Anson V.; Wang, Ying-Chih; Singh, Anup K.; Renzi, Ronald F.; Claudnic, Mark R.

2013-03-12

Methods for making a microfluidic device according to embodiments of the present invention include defining.about.cavity. Polymer precursor solution is positioned in the cavity, and exposed to light to begin the polymerization process and define a microchannel. In some embodiments, after the polymerization process is partially complete, a solvent rinse is performed, or fresh polymer precursor introduced into the microchannel. This may promote removal of unpolymerized material from the microchannel and enable smaller feature sizes. The polymer precursor solution may contain an iniferter. Polymerized features therefore may be capped with the iniferter, which is photoactive. The iniferter may aid later binding of a polyacrylamide gel to the microchannel surface.

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.

Nonclassical crystallization in vivo et in vitro (II): Nanogranular features in biomimetic minerals disclose a general colloid-mediated crystal growth mechanism.

PubMed

Rodríguez-Navarro, Carlos; Ruiz-Agudo, Encarnación; Harris, Joe; Wolf, Stephan E

2016-11-01

Recent research has shown that biominerals and their biomimetics (i) typically form via an amorphous precursor phase, and (ii) commonly display a nanogranular texture. Apparently, these two key features are closely related, underlining the fact that the formation of biominerals and their biomimetics does not necessarily follow classical crystallization routes, and leaves a characteristic nanotextural imprint which may help to disclose their origins and formation mechanisms. Here we present a general overview of the current theories and models of nonclassical crystallization and their applicability for the advance of our current understanding of biomineralization and biomimetic mineralization. We pay particular attention to the link between nonclassical crystallization routes and the resulting nanogranular textures of biomimetic CaCO 3 mineral structures. After a general introductory section, we present an overview of classical nucleation and crystal growth theories and their limitations. Then, we introduce the Ostwald's step rule as a general framework to explain nonclassical crystallization. Subsequently, we describe nonclassical crystallization routes involving stable prenucleation clusters, dense liquid and solid amorphous precursor phases, as well as current nonclassical crystal growth models. The latter include oriented attachment, mesocrystallization and the new model based on the colloidal growth of crystals via attachment of amorphous nanoparticles. Biomimetic examples of nanostructured CaCO 3 minerals formed via these nonclassical routes are presented which help us to show that colloid-mediated crystal growth can be regarded as a wide-spread growth mechanism. Implications of these observations for the advance in the current understanding on the formation of biomimetic materials and biominerals are finally outlined. Copyright © 2016 Elsevier Inc. All rights reserved.

Migration of mononuclear cells expressing β-actin through the adventitia into media and intima in coronary arteriogenesis and venogenesis in ischemic myocardium.

PubMed

Uchida, Yasuto; Uchida, Yasumi; Maezawa, Yoshiro; Maezawa, Yuko; Tabata, Tsuyoshi

2012-01-01

It was previously thought that arteriogenesis and venogenesis are induced not only by proliferation of vessel-resident smooth muscle cells (SMCs) and endothelial cells (ECs) but also by migration of their precursors. However, it is not well understood through what route(s) the precursors migrate into the existing vessels.We examined through what route or routes circulating mononuclear cells expressing β-actin (β-MNCs), which we identified in canine coronary vessels, migrate into coronary vessel walls and cause arteriogenesis and venogenesis at 1, 2, 4 and 8 weeks after induction of myocardial infarction.The following changes were observed: (1) The β-MNCs migrated via coronary microvessels to the interstitial space at one week; (2) β-MNCs traversed the adventitia into the media and settled in parallel with pre-existing smooth muscle cells (SMCs) in arterioles and arteries and lost β-actin and acquired α-smooth muscle actin (α-SMA) to become mature SMCs at 2-4 weeks; (3) at the same time, other β-MNCs migrated across the adventitia and media into the intima and settled in parallel with pre-existing endothelial cells (ECs) and lost β-actin, while acquiring CD(31), to become mature ECs, resulting in arteriogenesis; (4) Similarly, β-MNCs migrated into venular and venous walls and became SMCs or ECs, resulting in venogenesis.β-MNCs in the interstitial space expressed CD(34) but not other major vascular cell markers.β-MNCs, possibly a vascular progenitor, migrate not from the lumen but across the adventitia into the media or intima of coronary vessels and transit to SMCs or ECs, and participate in arteriogenesis and venogenesis in ischemic myocardium.

Path Diversity Improved Opportunistic Routing for Underwater Sensor Networks

PubMed Central

Wang, Haiyan; He, Ke

2018-01-01

The packets carried along a pre-defined route in underwater sensor networks are very vulnerble. Node mobility or intermittent channel availability easily leads to unreachable routing. Opportunistic routing has been proven to be a promising paradigm to design routing protocols for underwater sensor networks. It takes advantage of the broadcast nature of the wireless medium to combat packet losses and selects potential paths on the fly. Finding an appropriate forwarding candidate set is a key issue in opportunistic routing. Many existing solutions ignore the impact of candidates location distribution on packet forwarding. In this paper, a path diversity improved candidate selection strategy is applied in opportunistic routing to improve packet forwarding efficiency. It not only maximizes the packet forwarding advancements but also takes the candidate’s location distribution into account. Based on this strategy, we propose two effective routing protocols: position improved candidates selection (PICS) and position random candidates selection (PRCS). PICS employs two-hop neighbor information to make routing decisions. PRCS only uses one-hop neighbor information. Simulation results show that both PICS and PRCS can significantly improve network performance when compared with the previous solutions, in terms of packet delivery ratio, average energy consumption and end-to-end delay. PMID:29690621

Path Diversity Improved Opportunistic Routing for Underwater Sensor Networks.

PubMed

Bai, Weigang; Wang, Haiyan; He, Ke; Zhao, Ruiqin

2018-04-23

The packets carried along a pre-defined route in underwater sensor networks are very vulnerble. Node mobility or intermittent channel availability easily leads to unreachable routing. Opportunistic routing has been proven to be a promising paradigm to design routing protocols for underwater sensor networks. It takes advantage of the broadcast nature of the wireless medium to combat packet losses and selects potential paths on the fly. Finding an appropriate forwarding candidate set is a key issue in opportunistic routing. Many existing solutions ignore the impact of candidates location distribution on packet forwarding. In this paper, a path diversity improved candidate selection strategy is applied in opportunistic routing to improve packet forwarding efficiency. It not only maximizes the packet forwarding advancements but also takes the candidate’s location distribution into account. Based on this strategy, we propose two effective routing protocols: position improved candidates selection (PICS) and position random candidates selection (PRCS). PICS employs two-hop neighbor information to make routing decisions. PRCS only uses one-hop neighbor information. Simulation results show that both PICS and PRCS can significantly improve network performance when compared with the previous solutions, in terms of packet delivery ratio, average energy consumption and end-to-end delay.

N-nitrosodimethylamine (NDMA) formation from the ozonation of model compounds.

PubMed

Marti, Erica J; Pisarenko, Aleksey N; Peller, Julie R; Dickenson, Eric R V

2015-04-01

Nitrosamines are a class of toxic disinfection byproducts commonly associated with chloramination, of which several were included on the most recent U.S. EPA Contaminant Candidate List. Nitrosamine formation may be a significant barrier to ozonation in water reuse applications, particularly for direct or indirect potable reuse, since recent studies show direct formation during ozonation of natural water and treated wastewaters. Only a few studies have identified precursors which react with ozone to form N-nitrosodimethylamine (NDMA). In this study, several precursor compound solutions, prepared in ultrapure water and treated wastewater, were subjected to a 10 M excess of ozone. In parallel experiments, the precursor solutions in ultrapure water were exposed to gamma radiation to determine NDMA formation as a byproduct of reactions of precursor compounds with hydroxyl radicals. The results show six new NDMA precursor compounds that have not been previously reported in the literature, including compounds with hydrazone and carbamate moieties. Molar yields in deionized water were 61-78% for 3 precursors, 12-23% for 5 precursors and <4% for 2 precursors. Bromide concentration was important for three compounds (1,1-dimethylhydrazine, acetone dimethylhydrazone and dimethylsulfamide), but did not enhance NDMA formation for the other precursors. NDMA formation due to chloramination was minimal compared to formation due to ozonation, suggesting distinct groups of precursor compounds for these two oxidants. Hydroxyl radical reactions with the precursors will produce NDMA, but formation is much greater in the presence of molecular ozone. Also, hydroxyl radical scavenging during ozonation leads to increased NDMA formation. Molar conversion yields were higher for several precursors in wastewater as compared to deionized water, which could be due to catalyzed reactions with constituents found in wastewater or hydroxyl radical scavenging. Copyright © 2014 Elsevier Ltd. All rights reserved.

Spacewire router IP-core with priority adaptive routing

NASA Astrophysics Data System (ADS)

Shakhmatov, A. V.; Chekmarev, S. A.; Vergasov, M. Y.; Khanov, V. Kh

2015-10-01

Design of modern spacecraft focuses on using network principles of interaction on-board equipment, in particular in network SpaceWire. Routers are an integral part of most SpaceWire networks. The paper presents an adaptive routing algorithm with a prioritization, allowing more flexibility to manage the routing process. This algorithm is designed to transmit SpaceWire packets over a redundant network. Also a method is proposed for rapid restoration of working capacity after power by saving the routing table and the router configuration in an external non-volatile memory. The proposed solutions used to create IP-core router, and then tested in the FPGA device. The results illustrate the realizability and rationality of the proposed solutions.

Synthesis and Characterization of Solution and Melt Processible Poly(Acrylonitrile-Co-Methyl Acrylate) Statistical Copolymers

NASA Astrophysics Data System (ADS)

Pisipati, Padmapriya

Polyacrylonitrile (PAN) and its copolymers are used in a wide variety of applications ranging from textiles to purification membranes, packaging material and carbon fiber precursors. High performance polyacrylonitrile copolymer fiber is the most dominant precursor for carbon fibers. Synthesis of very high molecular weight poly(acrylonitrile-co-methyl acrylate) copolymers with weight average molecular weights of at least 1.7 million g/mole were synthesized on a laboratory scale using low temperature, emulsion copolymerization in a closed pressure reactor. Single filaments were spun via hybrid dry-jet gel solution spinning. These very high molecular weight copolymers produced precursor fibers with tensile strengths averaging 954 MPa with an elastic modulus of 15.9 GPa (N = 296). The small filament diameters were approximately 5 im. Results indicated that the low filament diameter that was achieved with a high draw ratio, combined with the hybrid dry-jet gel spinning process lead to an exponential enhancement of the tensile properties of these fibers. Carbon fibers for polymer matrix composites are currently derived from polyacrylonitrile copolymer fiber precursors where solution spinning accounts for ˜40 % of the total fiber production cost. To expand carbon fiber applications into the automotive industry, the cost of the carbon fiber needs to be reduced from 8 to ˜3-5. In order to develop an alternative melt processing route several benign plasticizers have been investigated. A low temperature, persulfate-metabisulfite initiated emulsion copolymerization was developed to synthesize poly(acrylonitrile-co-methyl acrylate) copolymers with acrylonitrile contents between 91-96 wt% with a molecular weight range of 100-200 kg/mol. This method was designed for a potential industrial scale up. Furthermore, water was investigated as a potential melting point depressant for these copolymers. Twenty-five wt% water lead to a decrease in the Tm of a 93/7 wt/wt % poly(acrylonitrile-co-methyl acrylate) of Mw = 200 kg/mol to 160 0C as measured via DSC. Glycerin, ethylene glycol and glycerin/water combinations were investigated as potential plasticizers for high molecular weight (˜200,000 g/mol), high acrylonitrile (93-96 mole:mole %) content poly(acrylonitrile-co-methyl acrylate) statistical copolymers. Pure glycerin (25 wt %) induced crystallization followed by a reduced "Tm" of about 213 0C via DSC. However this composition did not melt process well. A lower M W (˜35 kg/mol) copolymer did extrude with no apparent degradation. Our hypothesis is that the hydroxyl groups in glycerin (or water) disrupt the strong dipole-dipole interactions between the chains enabling the copolymer endothermic transition (Tm) to be reduced and enable melting before the onset of degradation. Additionally high molecular weight (Mw = 200-230 kg/mol) poly(acrylonitrile-co-methyl acrylate) copolymers with lower acrylonitrile content (82-85 wt %) were synthesized via emulsion copolymerization and successfully melt pressed. These materials will be further investigated for their utility in packaging applications.

Oxygen-free atomic layer deposition of indium sulfide

DOEpatents

Martinson, Alex B.; Hock, Adam S.; McCarthy, Robert; Weimer, Matthew S.

2016-07-05

A method for synthesizing an In(III) N,N'-diisopropylacetamidinate precursor including cooling a mixture comprised of diisopropylcarbodiimide and diethyl ether to approximately -30.degree. C., adding methyllithium drop-wise into the mixture, allowing the mixture to warm to room temperature, adding indium(III) chloride as a solid to the mixture to produce a white solid, dissolving the white solid in pentane to form a clear and colorless solution, filtering the mixture over a celite plug, and evaporating the solution under reduced pressure to obtain a solid In(III) N,N'-diisopropylacetamidinate precursor. This precursor has been further used to develop a novel atomic layer deposition technique for indium sulfide by dosing a reactor with the precursor, purging with nitrogen, dosing with dilute hydrogen sulfide, purging again with nitrogen, and repeating these steps to increase growth.

Rapid Solid-State Metathesis Routes to Nanostructured Silicon-Germainum

NASA Technical Reports Server (NTRS)

Rodriguez, Marc (Inventor); Kaner, Richard B. (Inventor); Bux, Sabah K. (Inventor); Fleurial, Jean-Pierre (Inventor)

2014-01-01

Methods for producing nanostructured silicon and silicon-germanium via solid state metathesis (SSM). The method of forming nanostructured silicon comprises the steps of combining a stoichiometric mixture of silicon tetraiodide (SiI4) and an alkaline earth metal silicide into a homogeneous powder, and initating the reaction between the silicon tetraiodide (SiI4) with the alkaline earth metal silicide. The method of forming nanostructured silicon-germanium comprises the steps of combining a stoichiometric mixture of silicon tetraiodide (SiI4) and a germanium based precursor into a homogeneous powder, and initiating the reaction between the silicon tetraiodide (SiI4) with the germanium based precursors.

The role of amorphous precursors in the crystallization of La and Nd carbonates

NASA Astrophysics Data System (ADS)

Vallina, Beatriz; Rodriguez-Blanco, Juan Diego; Brown, Andrew P.; Blanco, Jesus A.; Benning, Liane G.

2015-07-01

Crystalline La and Nd carbonates can be formed from poorly-ordered nanoparticulate precursors, termed amorphous lanthanum carbonate (ALC) and amorphous neodymium carbonate (ANC). When reacted in air or in aqueous solutions these precursors show highly variable lifetimes and crystallization pathways. We have characterized these precursors and the crystallization pathways and products with solid-state, spectroscopic and microscopic techniques to explain the differences in crystallization mechanisms between the La and Nd systems. ALC and ANC consist of highly hydrated, 10-20 nm spherical nanoparticles with a general formula of REE2(CO3)3.5H2O (REE = La, Nd). The stabilities differ by ~2 orders of magnitude, with ANC being far more stable than ALC. This difference is due to the Nd3+ ion having a far higher hydration energy compared to the La3+ ion. This, together with temperature and reaction times, leads to clear differences not only in the kinetics and mechanisms of crystallization of the amorphous precursor La- and Nd-carbonate phases but also in the resulting crystallite sizes and morphologies of the end products. All crystalline La and Nd carbonates developed spherulitic morphologies when crystallization occurred from hydrous phases in solution at temperatures above 60 °C (La system) and 95 °C (Nd system). We suggest that spherulitic growth occurs due to a rapid breakdown of the amorphous precursors and a concurrent rapid increase in supersaturation levels in the aqueous solution. The kinetic data show that the crystallization pathway for both La and Nd carbonate systems is dependent on the reaction temperature and the ionic potential of the REE3+ ion.Crystalline La and Nd carbonates can be formed from poorly-ordered nanoparticulate precursors, termed amorphous lanthanum carbonate (ALC) and amorphous neodymium carbonate (ANC). When reacted in air or in aqueous solutions these precursors show highly variable lifetimes and crystallization pathways. We have characterized these precursors and the crystallization pathways and products with solid-state, spectroscopic and microscopic techniques to explain the differences in crystallization mechanisms between the La and Nd systems. ALC and ANC consist of highly hydrated, 10-20 nm spherical nanoparticles with a general formula of REE2(CO3)3.5H2O (REE = La, Nd). The stabilities differ by ~2 orders of magnitude, with ANC being far more stable than ALC. This difference is due to the Nd3+ ion having a far higher hydration energy compared to the La3+ ion. This, together with temperature and reaction times, leads to clear differences not only in the kinetics and mechanisms of crystallization of the amorphous precursor La- and Nd-carbonate phases but also in the resulting crystallite sizes and morphologies of the end products. All crystalline La and Nd carbonates developed spherulitic morphologies when crystallization occurred from hydrous phases in solution at temperatures above 60 °C (La system) and 95 °C (Nd system). We suggest that spherulitic growth occurs due to a rapid breakdown of the amorphous precursors and a concurrent rapid increase in supersaturation levels in the aqueous solution. The kinetic data show that the crystallization pathway for both La and Nd carbonate systems is dependent on the reaction temperature and the ionic potential of the REE3+ ion. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr01497b

Modified artificial bee colony for the vehicle routing problems with time windows.

PubMed

Alzaqebah, Malek; Abdullah, Salwani; Jawarneh, Sana

2016-01-01

The natural behaviour of the honeybee has attracted the attention of researchers in recent years and several algorithms have been developed that mimic swarm behaviour to solve optimisation problems. This paper introduces an artificial bee colony (ABC) algorithm for the vehicle routing problem with time windows (VRPTW). A Modified ABC algorithm is proposed to improve the solution quality of the original ABC. The high exploration ability of the ABC slows-down its convergence speed, which may due to the mechanism used by scout bees in replacing abandoned (unimproved) solutions with new ones. In the Modified ABC a list of abandoned solutions is used by the scout bees to memorise the abandoned solutions, then the scout bees select a solution from the list based on roulette wheel selection and replace by a new solution with random routs selected from the best solution. The performance of the Modified ABC is evaluated on Solomon benchmark datasets and compared with the original ABC. The computational results demonstrate that the Modified ABC outperforms the original ABC also produce good solutions when compared with the best-known results in the literature. Computational investigations show that the proposed algorithm is a good and promising approach for the VRPTW.

Sex Differences in Using Spatial and Verbal Abilities Influence Route Learning Performance in a Virtual Environment: A Comparison of 6- to 12-Year Old Boys and Girls.

PubMed

Merrill, Edward C; Yang, Yingying; Roskos, Beverly; Steele, Sara

2016-01-01

Previous studies have reported sex differences in wayfinding performance among adults. Men are typically better at using Euclidean information and survey strategies while women are better at using landmark information and route strategies. However, relatively few studies have examined sex differences in wayfinding in children. This research investigated relationships between route learning performance and two general abilities: spatial ability and verbal memory in 153 boys and girls between 6- to 12-years-old. Children completed a battery of spatial ability tasks (a two-dimension mental rotation task, a paper folding task, a visuo-spatial working memory task, and a Piagetian water level task) and a verbal memory task. In the route learning task, they had to learn a route through a series of hallways presented via computer. Boys had better overall route learning performance than did girls. In fact, the difference between boys and girls was constant across the age range tested. Structural equation modeling of the children's performance revealed that spatial abilities and verbal memory were significant contributors to route learning performance. However, there were different patterns of correlates for boys and girls. For boys, spatial abilities contributed to route learning while verbal memory did not. In contrast, for girls both spatial abilities and verbal memory contributed to their route learning performance. This difference may reflect the precursor of a strategic difference between boys and girls in wayfinding that is commonly observed in adults.

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.

Dry Process for Manufacturing Hybridized Boron Fiber/Carbon Fiber Thermoplastic Composite Materials from a Solution Coated Precursor

NASA Technical Reports Server (NTRS)

Belvin, Harry L. (Inventor); Cano, Roberto J. (Inventor)

2003-01-01

An apparatus for producing a hybrid boron reinforced polymer matrix composite from precursor tape and a linear array of boron fibers. The boron fibers are applied onto the precursor tapes and the precursor tape processed within a processing component having an impregnation bar assembly. After passing through variable-dimension forming nip-rollers, the precursor tape with the boron fibers becomes a hybrid boron reinforced polymer matrix composite. A driving mechanism is used to pulled the precursor tape through the method and a take-up spool is used to collect the formed hybrid boron reinforced polymer matrix composite.

Deposition and Characterization of Thin Films on Metallic Substrates

NASA Technical Reports Server (NTRS)

Gatica, Jorge E.

2005-01-01

A CVD method was successfully developed to produce conversion coatings on aluminum alloys surfaces with reproducible results with a variety of precursors. A well defined protocol to prepare the precursor solutions formulated in a previous research was extended to other additives. It was demonstrated that solutions prepared following such a protocol could be used to systematically generate protective coatings onto aluminum surfaces. Experiments with a variety of formulations revealed that a refined deposition protocol yields reproducible conversion coatings of controlled composition. A preliminary correlation between solution formulations and successful precursors was derived. Coatings were tested for adhesion properties enhancement for commercial paints. A standard testing method was followed and clear trends were identified. Only one precursors was tested systematically. Anticipated work on other precursors should allow a better characterization of the effect of intermetallics on the production of conversion/protective coatings on metals and ceramics. The significance of this work was the practical demonstration that chemical vapor deposition (CVD) techniques can be used to systematically generate protective/conversion coating on non-ferrous surfaces. In order to become an effective approach to replace chromate-based pre- treatment processes, namely in the aerospace or automobile industry, the process parameters must be defined more precisely. Moreover, the feasibility of scale-up designs necessitates a more comprehensive characterization of the fluid flow, transport phenomena, and chemical kinetics interacting in the process. Kinetic characterization showed a significantly different effect of magnesium-based precursors when compared to iron-based precursors. Future work will concentrate on refining the process through computer simulations and further experimental studies on the effect of other transition metals to induce deposition of conversion/protective films on aluminum and other metallic substrates.

A self-adaptive memeplexes robust search scheme for solving stochastic demands vehicle routing problem

NASA Astrophysics Data System (ADS)

Chen, Xianshun; Feng, Liang; Ong, Yew Soon

2012-07-01

In this article, we proposed a self-adaptive memeplex robust search (SAMRS) for finding robust and reliable solutions that are less sensitive to stochastic behaviours of customer demands and have low probability of route failures, respectively, in vehicle routing problem with stochastic demands (VRPSD). In particular, the contribution of this article is three-fold. First, the proposed SAMRS employs the robust solution search scheme (RS 3) as an approximation of the computationally intensive Monte Carlo simulation, thus reducing the computation cost of fitness evaluation in VRPSD, while directing the search towards robust and reliable solutions. Furthermore, a self-adaptive individual learning based on the conceptual modelling of memeplex is introduced in the SAMRS. Finally, SAMRS incorporates a gene-meme co-evolution model with genetic and memetic representation to effectively manage the search for solutions in VRPSD. Extensive experimental results are then presented for benchmark problems to demonstrate that the proposed SAMRS serves as an efficable means of generating high-quality robust and reliable solutions in VRPSD.

Protocol Independent Adaptive Route Update for VANET

PubMed Central

Rasheed, Asim; Qayyum, Amir

2014-01-01

High relative node velocity and high active node density have presented challenges to existing routing approaches within highly scaled ad hoc wireless networks, such as Vehicular Ad hoc Networks (VANET). Efficient routing requires finding optimum route with minimum delay, updating it on availability of a better one, and repairing it on link breakages. Current routing protocols are generally focused on finding and maintaining an efficient route, with very less emphasis on route update. Adaptive route update usually becomes impractical for dense networks due to large routing overheads. This paper presents an adaptive route update approach which can provide solution for any baseline routing protocol. The proposed adaptation eliminates the classification of reactive and proactive by categorizing them as logical conditions to find and update the route. PMID:24723807

Effect of CTAB on structural and optical properties of CuO nanoparticles prepared by coprecipitation route

NASA Astrophysics Data System (ADS)

Varghese, Donna; Tom, Catherine; Krishna Chandar, N.

2017-11-01

CuO (Copper Oxide) nanoparticles were synthesized by a simple coprecipitation route by using copper acetate, sodium hydroxide as precursors and cetyltrimethyl ammonium bromide (CTAB) as surfactant. For the purpose of the study, the surfactant-CTAB treated and non-treated samples were synthesized separately. Both the synthesized samples were studied to understand their structural and optical properties. The formation of CuO and its crystallinity was confirmed by XRD. Further, the optical studies showed a defined blue shift in CTAB treated sample which is clear evidence that the particles undergo confinement when they are nano-regime.

A facile precursor route to highly loaded metal/ceramic nanofibers as a robust surface-enhanced Raman template

NASA Astrophysics Data System (ADS)

Park, Jay Hoon; Joo, Yong Lak

2017-09-01

We report silver (Ag)/ceramic nanofibers with highly robust and sensitive optical sensory capabilities that can withstand harsh conditions. These nanofibers are fabricated by first electrospinning solutions of poly vinyl alcohol (PVA) and metal precursor polymers, followed by subsequent series of heat treatment. The reported fabrication method demonstrate the effects of (i) the location of Ag crystals, (ii) crystal size and shape, and (iii) constituents of the ceramic matrix as surface-enhanced Raman spectroscopy (SERS) templates with 10-6 M 4-mercaptobenzoic acid (4-MBA). Notably, these silver/ceramic nanofibers preserved most of their highly sensitive localized surface plasmon resonance (LSPR) even under high temperature of 400 °C, in contrast to preformed Ag nanoparticles (NPs) in PVA nanofibers which lost most of its optical property presumably due to (i) Ag oxidation and (ii) loss of the matrix material. Among the ceramic substrates of ZrO2, Al2O3, and ZnO with silver crystals, we discovered that the ZnO substrate showed the most consistent and the strongest signal strength owing to the synergistic chemical and optical properties of the ZnO substrate. Moreover, the pure Ag nanofiber proved to be the best heat-resistant SERS template, owing to its (i) anisotropic morphology and (ii) thicker diameter when compared with other conventional Ag nanomaterials. These results demonstrated simple yet highly controllable fabrication of robust SERS templates, with potential applications in a catalytic sensory which is often exposed to harsh conditions.

Colloidal Synthesis and Thermoelectric Properties of CuFeSe2 Nanocrystals

PubMed Central

Zhang, Bing-Qian; Zuo, Yong; Chen, Jing-Shuai; Niu, He-Lin; Mao, Chang-Jie

2017-01-01

Copper-based chalcogenides that contain abundant, low-cost and environmentally-friendly elements, are excellent materials for numerous energy conversion applications, such as photocatalysis, photovoltaics, photoelectricity and thermoelectrics (TE). Here, we present a high-yield and upscalable colloidal synthesis route for the production of monodisperse ternary I-III-VI2 chalcogenides nanocrystals (NCs), particularly stannite CuFeSe2, with uniform shape and narrow size distributions by using selenium powder as the anion precursor and CuCl2·2H2O and FeCl3 as the cationic precursors. The composition, the state of valence, size and morphology of the CuFeSe2 materials were examined by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), scanning electron microscope (SEM), transmission electron microscope (TEM) and high resolution transmission electron microscope (HRTEM), respectively. Furthermore, the TE properties characterization of these dense nanomaterials compacted from monodisperse CuFeSe2 NCs by hot press at 623 K were preliminarily studied after ligand removal by means of hydrazine and hexane solution. The TE performances of the sintered CuFeSe2 pellets were characterized in the temperature range from room temperature to 653 K. Finally, the dimensionless TE figure of merit (ZT) of this Earth-abundant and intrinsic p-type CuFeSe2 NCs is significantly increased to 0.22 at 653 K in this work, which is demonstrated to show a promising TE materialand makes it a possible p-type candidate for medium-temperature TE applications. PMID:29278381

Metal-doped single-walled carbon nanotubes and production thereof

DOEpatents

Dillon, Anne C.; Heben, Michael J.; Gennett, Thomas; Parilla, Philip A.

2007-01-09

Metal-doped single-walled carbon nanotubes and production thereof. The metal-doped single-walled carbon nanotubes may be produced according to one embodiment of the invention by combining single-walled carbon nanotube precursor material and metal in a solution, and mixing the solution to incorporate at least a portion of the metal with the single-walled carbon nanotube precursor material. Other embodiments may comprise sputter deposition, evaporation, and other mixing techniques.

Rapid preparation of solution-processed InGaZnO thin films by microwave annealing and photoirradiation

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

Cheong, Heajeong; Ogura, Shintaro; Ushijima, Hirobumi

We fabricated solution-processed indium–gallium–zinc oxide (IGZO) thin-film transistors (TFTs) by microwave (MW) annealing an IGZO precursor film followed by irradiating with vacuum ultraviolet (VUV) light. MW annealing allows more rapid heating of the precursor film than conventional annealing processes using a hot plate or electric oven and promotes the crystallization of IGZO. VUV irradiation was used to reduce the duration and temperature of the post-annealing step. Consequently, the IGZO TFTs fabricated through MW annealing for 5 min and VUV irradiation for 1 min exhibited an on/off current ratio of 10{sup 8} and a field-effect mobility of 0.3 cm{sup 2} V{sup −1} s{supmore » −1}. These results indicate that MW annealing and photoirradiation is an effective combination for annealing solution processed IGZO precursor films to prepare the semiconductor layers of TFTs.« less

One-step synthesis of titania nanoparticles from PS-P4VP diblock copolymer solution

NASA Astrophysics Data System (ADS)

Song, Lixin; Lam, Yeng Ming; Boothroyd, Chris; Teo, Puat Wen

2007-04-01

Polymeric films containing titania nanoparticles have potential as dielectric films for flexible electronic applications. For this purpose, the nanoparticles must be homogeneously distributed. Self-assembly is emerging as a neat, elegant method for fabricating such nanostructured hybrid materials with well-distributed nanoparticles. In this work, we report a micellar solution approach for the assembly of copolymer-titanium precursor nanostructures in which titania nanoparticles were synthesized. The ratio of the amount of titanium precursor, titanium isopropoxide, to the blocks forming the micellar core, poly(4-vinylpyridine), was found to play a key role in controlling film morphology. A sphere-to-ribbon transition was observed when the amount of titanium isopropoxide was increased. The thin film morphology can be tuned using the precursor-copolymer interaction rather than just the polymer-polymer interaction or the polymer-solution interaction. This method provides yet another way to control the morphology of nanostructures.

Synthesis and characterization of superparamagnetic iron-oxide nanoparticles (SPIONs) and utilization of SPIONs in X-ray imaging

NASA Astrophysics Data System (ADS)

Justin, C.; Philip, Sheryl Ann; Samrot, Antony V.

2017-10-01

The versatility of superparamagnetic iron-oxide nanoparticles (SPIONs) have been extensively investigated, especially for their applications in therapeutics and diagnostics. Considering their intriguing feature of contrasting agent, in terms of medical applications, it is still in its infancy. Various physicochemical parameters like magnetism, crystallinity, and optical parameters contribute to their better contrasting agent. In this study, SPIONs were synthesized with different concentrations of precursor iron molecular solution in the presence of magnetic field and the optimum concentration of precursor iron molecular solution was determined as 0.133%. SPIONs obtained at optimum concentration were further analyzed by both microscopic and spectroscopic analysis. The difference occurred in the elemental nature of SPIONs as they were synthesized in the magnetic field out of precursor iron molecular solution was analyzed with a specific reference to NMR spectroscopy. SPIONs as contrasting agent against X-ray imaging was also investigated in quail's egg.

Economic and quality of life impacts of route 21 freeway construction : final report, October 2009.

DOT National Transportation Integrated Search

2009-10-01

Opened to traffic in December 2000, the missing section of the Route 21 Freeway in Clifton : and Passaic (Hope Ave. to the Route 46 Interchange) was designed utilizing the equivalent to : the Context Sensitive Solutions (CSS) approach at ...

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.

An Adaptive QoS Routing Solution for MANET Based Multimedia Communications in Emergency Cases

NASA Astrophysics Data System (ADS)

Ramrekha, Tipu Arvind; Politis, Christos

The Mobile Ad hoc Networks (MANET) is a wireless network deprived of any fixed central authoritative routing entity. It relies entirely on collaborating nodes forwarding packets from source to destination. This paper describes the design, implementation and performance evaluation of CHAMELEON, an adaptive Quality of Service (QoS) routing solution, with improved delay and jitter performances, enabling multimedia communication for MANETs in extreme emergency situations such as forest fire and terrorist attacks as defined in the PEACE project. CHAMELEON is designed to adapt its routing behaviour according to the size of a MANET. The reactive Ad Hoc on-Demand Distance Vector Routing (AODV) and proactive Optimized Link State Routing (OLSR) protocols are deemed appropriate for CHAMELEON through their performance evaluation in terms of delay and jitter for different MANET sizes in a building fire emergency scenario. CHAMELEON is then implemented in NS-2 and evaluated similarly. The paper concludes with a summary of findings so far and intended future work.

Formation of Copper Catalysts for CO 2 Reduction with High Ethylene/Methane Product Ratio Investigated with In Situ X-ray Absorption Spectroscopy

DOE PAGES

Eilert, André; Roberts, F. Sloan; Friebel, Daniel; ...

2016-04-04

Nanostructured copper cathodes are among the most efficient and selective catalysts to date for making multicarbon products from the electrochemical carbon dioxide reduction reaction (CO 2RR). We report an in situ X-ray absorption spectroscopy investigation of the formation of a copper nanocube CO 2RR catalyst with high activity that highly favors ethylene over methane production. The results show that the precursor for the copper nanocube formation is copper(I)-oxide, not copper(I)-chloride as previously assumed. A second route to an electrochemically similar material via a copper(II)–carbonate/hydroxide is also reported. In conclusion, this study highlights the importance of using oxidized copper precursors formore » constructing selective CO 2 reduction catalysts and shows the precursor oxidation state does not affect the electrocatalyst selectivity toward ethylene formation.« less

Facile electrosynthesis of silicon carbide nanowires from silica/carbon precursors in molten salt.

PubMed

Zou, Xingli; Ji, Li; Lu, Xionggang; Zhou, Zhongfu

2017-08-30

Silicon carbide nanowires (SiC NWs) have attracted intensive attention in recent years due to their outstanding performances in many applications. A large-scale and facile production of SiC NWs is critical to its successful application. Here, we report a simple method for the production of SiC NWs from inexpensive and abundantly available silica/carbon (SiO 2 /C) precursors in molten calcium chloride. The solid-to-solid electroreduction and dissolution-electrodeposition mechanisms can easily lead to the formation of homogenous SiC NWs. This template/catalyst-free approach greatly simplifies the synthesis procedure compared to conventional methods. This general strategy opens a direct electrochemical route for the conversion of SiO 2 /C into SiC NWs, and may also have implications for the electrosynthesis of other micro/nanostructured metal carbides/composites from metal oxides/carbon precursors.

Solution properties and spectroscopic characterization of polymeric precursors to SiNCB and BN ceramic materials

NASA Astrophysics Data System (ADS)

Cortez, E.; Remsen, E.; Chlanda, V.; Wideman, T.; Zank, G.; Carrol, P.; Sneddon, L.

1998-06-01

Boron Nitride, BN, and composite SiNCB ceramic fibers are important structural materials because of their excellent thermal and oxidative stabilities. Consequently, polymeric materials as precursors to ceramic composites are receiving increasing attention. Characterization of these materials requires the ability to evaluate simultaneous molecular weight and compositional heterogeneity within the polymer. Size exclusion chromatography equipped with viscometric and refractive index detection as well as coupled to a LC-transform device for infrared absorption analysis has been employed to examine these heterogeneities. Using these combined approaches, the solution properties and the relative amounts of individual functional groups distributed through the molecular weight distribution of SiNCB and BN polymeric precursors were characterized.

Experiences with serial and parallel algorithms for channel routing using simulated annealing

NASA Technical Reports Server (NTRS)

Brouwer, Randall Jay

1988-01-01

Two algorithms for channel routing using simulated annealing are presented. Simulated annealing is an optimization methodology which allows the solution process to back up out of local minima that may be encountered by inappropriate selections. By properly controlling the annealing process, it is very likely that the optimal solution to an NP-complete problem such as channel routing may be found. The algorithm presented proposes very relaxed restrictions on the types of allowable transformations, including overlapping nets. By freeing that restriction and controlling overlap situations with an appropriate cost function, the algorithm becomes very flexible and can be applied to many extensions of channel routing. The selection of the transformation utilizes a number of heuristics, still retaining the pseudorandom nature of simulated annealing. The algorithm was implemented as a serial program for a workstation, and a parallel program designed for a hypercube computer. The details of the serial implementation are presented, including many of the heuristics used and some of the resulting solutions.

Energy consumption and control response evaluations of AODV routing in WSANs for building-temperature control.

PubMed

Booranawong, Apidet; Teerapabkajorndet, Wiklom; Limsakul, Chusak

2013-06-27

The main objective of this paper is to investigate the effects of routing protocols on wireless sensor and actuator networks (WSANs), focusing on the control system response and the energy consumption of nodes in a network. We demonstrate that routing algorithms designed without considering the relationship between communication and control cannot be appropriately used in wireless networked control applications. For this purpose, an ad-hoc on-demand distance vector (AODV) routing, an IEEE 802.15.4, and a building-temperature control system are employed for this exploration. The findings from our scenarios show that the AODV routing can select a path with a high traffic load for data transmission. It takes a long time before deciding to change a new route although it experiences the unsuccessful transmission of packets. As a result, the desirable control target cannot be achieved in time, and nodes consume more energy due to frequent packet collisions and retransmissions. Consequently, we propose a simple routing solution to alleviate these research problems by modifying the original AODV routing protocol. The delay-threshold is considered to avoid any congested connection during routing procedures. The simulation results demonstrate that our solution can be appropriately applied in WSANs. Both the energy consumption and the control system response are improved.

Self-assembly of water-soluble nanocrystals

DOEpatents

Fan, Hongyou [Albuquerque, NM; Brinker, C Jeffrey [Albuquerque, NM; Lopez, Gabriel P [Albuquerque, NM

2012-01-10

A method for forming an ordered array of nanocrystals where a hydrophobic precursor solution with a hydrophobic core material in an organic solvent is added to a solution of a surfactant in water, followed by removal of a least a portion of the organic solvent to form a micellar solution of nanocrystals. A precursor co-assembling material, generally water-soluble, that can co-assemble with individual micelles formed in the micellar solution of nanocrystals can be added to this micellar solution under specified reaction conditions (for example, pH conditions) to form an ordered-array mesophase material. For example, basic conditions are used to precipitate an ordered nanocrystal/silica array material in bulk form and acidic conditions are used to form an ordered nanocrystal/silica array material as a thin film.

Colloidal nanocrystals and method of making

DOEpatents

Kahen, Keith

2015-10-06

A tight confinement nanocrystal comprises a homogeneous center region having a first composition and a smoothly varying region having a second composition wherein a confining potential barrier monotonically increases and then monotonically decreases as the smoothly varying region extends from the surface of the homogeneous center region to an outer surface of the nanocrystal. A method of producing the nanocrystal comprises forming a first solution by combining a solvent and at most two nanocrystal precursors; heating the first solution to a nucleation temperature; adding to the first solution, a second solution having a solvent, at least one additional and different precursor to form the homogeneous center region and at most an initial portion of the smoothly varying region; and lowering the solution temperature to a growth temperature to complete growth of the smoothly varying region.

Surfactant-directed synthesis of mesoporous films made single-step by a tandem photosol-gel/photocalcination route

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

De Paz-Simon, Héloïse; Chemtob, Abraham, E-mail: abraham.chemtob@uha.fr; Croutxé-Barghorn, Céline

2014-11-01

In view of their technological impact in materials chemistry, a simplified and more efficient synthetic route to mesoporous films is highly sought. We report, herein, a smart UV-mediated approach coupling in a one-stage process sol-gel photopolymerization and photoinduced template decomposition/ablation to making mesoporous silica films. Performed at room temperature with a solvent-free solution of silicate precursor and amphiphilic poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) block copolymer, the synthesis relies on photoacid generation to induce the fast formation (≈10 min) of mesostructured silica/surfactant domains. Continuation of UV exposure for three additional hours enables subsequent and complete photodegradation of the polyether copolymer, resulting inmore » ordered or disordered mesoporous silica film. One of the most attractive features is that the one-step procedure relies on a continuous illumination provided by the same conventional medium-pressure Hg-Xe arc lamp equipped with a 254 nm reflector to enhance the emission of energetic photons <300 nm. In addition to X-ray diffraction and transmission electron microscopy, time-resolved Fourier transform infrared spectroscopy has proved to be a powerful in situ technique to probe the different chemical transformations accompanying irradiation. Photocalcination strengthens the inorganic network, while allowing to preserve a higher fraction of residual silanol groups compared with thermal calcination. A polyether chain degradation mechanism based on oxygen reactive species-mediated photo-oxidation is proposed.« less

Mechanical Properties and Microstructure of Biomorphic Silicon Carbide Ceramics Fabricated from Wood Precursors

NASA Technical Reports Server (NTRS)

Singh, Mrityunjay; Salem, J. A.; Gray, Hugh R. (Technical Monitor)

2002-01-01

Silicon carbide based, environment friendly, biomorphic ceramics have been fabricated by the pyrolysis and infiltration of natural wood (maple and mahogany) precursors. This technology provides an eco-friendly route to advanced ceramic materials. These biomorphic silicon carbide ceramics have tailorable properties and behave like silicon carbide based materials manufactured by conventional approaches. The elastic moduli and fracture toughness of biomorphic ceramics strongly depend on the properties of starting wood preforms and the degree of molten silicon infiltration. Mechanical properties of silicon carbide ceramics fabricated from maple wood precursors indicate the flexural strengths of 3441+/-58 MPa at room temperature and 230136 MPa at 1350C. Room temperature fracture toughness of the maple based material is 2.6 +/- 0.2 MPa(square root of)m while the mahogany precursor derived ceramics show a fracture toughness of 2.0 +/- 0.2 Mpa(square root of)m. The fracture toughness and the strength increase as the density of final material increases. Fractographic characterization indicates the failure origins to be pores and chipped pockets of silicon.

Precursor Routes to Complex Ternary Intermetallics: Single-Crystal and Microcrystalline Preparation of Clathrate-I Na8Al8Si38 from NaSi + NaAlSi.

PubMed

Dong, Yongkwan; Chai, Ping; Beekman, Matt; Zeng, Xiaoyu; Tritt, Terry M; Nolas, George S

2015-06-01

Single crystals of the ternary clathrate-I Na8Al8Si38 were synthesized by kinetically controlled thermal decomposition (KCTD), and microcrystalline Na8Al8Si38 was synthesized by spark plasma sintering (SPS) using a NaSi + NaAlSi mixture as the precursor. Na8AlxSi46-x compositions with x ≤ 8 were also synthesized by SPS from precursor mixtures of different ratios. The crystal structure of Na8Al8Si38 was investigated using both Rietveld and single-crystal refinements. Temperature-dependent transport and UV/vis measurements were employed in the characterization of Na8Al8Si38, with diffuse-reflectance measurement indicating an indirect optical gap of 0.64 eV. Our results indicate that, when more than one precursor is used, both SPS and KCTD are effective methods for the synthesis of multinary inorganic phases that are not easily accessible by traditional solid-state synthesis or crystal growth techniques.

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.

Bellman Ford algorithm - in Routing Information Protocol (RIP)

NASA Astrophysics Data System (ADS)

Krianto Sulaiman, Oris; Mahmud Siregar, Amir; Nasution, Khairuddin; Haramaini, Tasliyah

2018-04-01

In a large scale network need a routing that can handle a lot number of users, one of the solutions to cope with large scale network is by using a routing protocol, There are 2 types of routing protocol that is static and dynamic, Static routing is manually route input based on network admin, while dynamic routing is automatically route input formed based on existing network. Dynamic routing is efficient used to network extensively because of the input of route automatic formed, Routing Information Protocol (RIP) is one of dynamic routing that uses the bellman-ford algorithm where this algorithm will search for the best path that traversed the network by leveraging the value of each link, so with the bellman-ford algorithm owned by RIP can optimize existing networks.

Synthesis of Biocompatible Surfaces by Different Techniques

DTIC Science & Technology

2002-04-01

production . In the other hand, polymers are widely used in bone/cartilage implants, both, as polymeric materials themselves and as a polymeric surface on a...focus on the production of HA scaffolds by a sol-gel method using different drying processes, and on the study of the plasma polymerization technique to...precursor at 3. SA-stoichiometric amount (to maintain Ca/P= 1,67) of the calcium precursor solution (3 M solution in anhidrous etanol ) was added dropwise

Preparation of UO2, ThO2 and (Th,U)O2 pellets from photochemically-prepared nano-powders

NASA Astrophysics Data System (ADS)

Pavelková, Tereza; Čuba, Václav; de Visser-Týnová, Eva; Ekberg, Christian; Persson, Ingmar

2016-02-01

Photochemically-induced preparation of nano-powders of crystalline uranium and/or thorium oxides and their subsequent pelletizing has been investigated. The preparative method was based on the photochemically induced formation of amorphous solid precursors in aqueous solution containing uranyl and/or thorium nitrate and ammonium formate. The EXAFS analyses of the precursors shown that photon irradiation of thorium containing solutions yields a compound with little long-range order but likely "ThO2 like" and the irradiation of uranium containing solutions yields the mixture of U(IV) and U(VI) compounds. The U-containing precursors were carbon free, thus allowing direct heat treatment in reducing atmosphere without pre-treatment in the air. Subsequent heat treatment of amorphous solid precursors at 300-550 °C yielded nano-crystalline UO2, ThO2 or solid (Th,U)O2 solutions with high purity, well-developed crystals with linear crystallite size <15 nm. The prepared nano-powders of crystalline oxides were pelletized without any binder (pressure 500 MPa), the green pellets were subsequently sintered at 1300 °C under an Ar:H2 (20:1) mixture (UO2 and (Th,U)O2 pellets) or at 1600 °C in ambient air (ThO2 pellets). The theoretical density of the sintered pellets varied from 91 to 97%.

Neighboring Optimal Aircraft Guidance in a General Wind Environment

NASA Technical Reports Server (NTRS)

Jardin, Matthew R. (Inventor)

2003-01-01

Method and system for determining an optimal route for an aircraft moving between first and second waypoints in a general wind environment. A selected first wind environment is analyzed for which a nominal solution can be determined. A second wind environment is then incorporated; and a neighboring optimal control (NOC) analysis is performed to estimate an optimal route for the second wind environment. In particular examples with flight distances of 2500 and 6000 nautical miles in the presence of constant or piecewise linearly varying winds, the difference in flight time between a nominal solution and an optimal solution is 3.4 to 5 percent. Constant or variable winds and aircraft speeds can be used. Updated second wind environment information can be provided and used to obtain an updated optimal route.

Effect of precursor solutions on ZnO film via solution precursor plasma spray and corresponding gas sensing performances

NASA Astrophysics Data System (ADS)

Yu, Z. X.; Ma, Y. Z.; Zhao, Y. L.; Huang, J. B.; Wang, W. Z.; Moliere, M.; Liao, H. L.

2017-08-01

Solution precursor plasma spraying (SPPS) as a novel thermal spray method was employed to deposit nano-structured ZnO thin film using different formulations of the precursor solution. This article focuses on the influence of the solution composition on the preferential orientation of crystal growth, on crystal size and surface morphology of the resulting ZnO films. The trend of preferential growth along (002) lattice plane of ZnO film was studied by slow scanning X-ray diffraction using a specific coefficient P(002). It appears that the thermal spray process promotes the buildup of ZnO films preferentially oriented along the c-axis. The shape of single particle tends to change from round shaped beads to hexagonal plates by increasing the volume ratio of ethanol in the solvent. Both cauliflower and honeycomb-like surface morphologies featuring high specific surface area and roughness were obtained through the SPPS process by varying solution composition. These ZnO films are hydrophobic with contact angle as high as 136°, which is seemingly associated with micro reliefs developing high surface specific area. Then the gas sensing performances of ZnO films preferentially oriented along (002) face were tentatively predicted using the "first principle calculation method" and were compared with those of conventional films that are mainly oriented along the (101) face. The (002) face displays better hydrogen adsorption capability than the (101) face with much larger resulting changes in electrical resistance. In conclusion, the c-axis oriented ZnO films obtained through SSPS have favorable performances to be used as sensitive layer in gas sensing applications.

Fabrication of Carbonate Apatite Block through a Dissolution-Precipitation Reaction Using Calcium Hydrogen Phosphate Dihydrate Block as a Precursor.

PubMed

Tsuru, Kanji; Yoshimoto, Ayami; Kanazawa, Masayuki; Sugiura, Yuki; Nakashima, Yasuharu; Ishikawa, Kunio

2017-03-31

Carbonate apatite (CO₃Ap) block, which is a bone replacement used to repair defects, was fabricated through a dissolution-precipitation reaction using a calcium hydrogen phosphate dihydrate (DCPD) block as a precursor. When the DCPD block was immersed in NaHCO₃ or Na₂CO₃ solution at 80 °C, DCPD converted to CO₃Ap within 3 days. β-Tricalcium phosphate was formed as an intermediate phase, and it was completely converted to CO₃Ap within 2 weeks when the DCPD block was immersed in Na₂CO₃ solution. Although the crystal structures of the DCPD and CO₃Ap blocks were different, the macroscopic structure was maintained during the compositional transformation through the dissolution-precipitation reaction. CO₃Ap block fabricated in NaHCO₃ or Na₂CO₃ solution contained 12.9 and 15.8 wt % carbonate, respectively. The diametral tensile strength of the CO₃Ap block was 2 MPa, and the porosity was approximately 57% regardless of the carbonate solution. DCPD is a useful precursor for the fabrication of CO₃Ap block.

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.

Fabrication of compact and stable perovskite films with optimized precursor composition in the fast-growing procedure

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

Liu, Tanghao; Zhou, Yuanyuan; Hu, Qin

The fast-growing procedure (FGP) provides a simple, high-yield and lead (Pb)-release free method to prepare perovskite films. In the FGP, the ultra-dilute perovskite precursor solution is drop-cast onto a hot (~240 degrees C) substrate, where a perovskite film grows immediately accompanied by the rapid evaporation of the host solvent. In this process, all the raw materials in the precursor solution are deposited into the final perovskite film. The potential pollution caused by Pb can be significantly reduced. Properties of the FGP-processed perovskite films can be modulated by the precursor composition. While CH3NH3Cl (MACl) affects the crystallization process and leads tomore » full surface coverage, CH(NH2)2I (FAI) enhances the thermal stability of the film. Based on the optimized precursor composition of PbI2(1-x)FAI xMACl, x=0.75, FGP-processed planar heterojunction perovskite solar cells exhibit power conversion efficiencies (PCEs) exceeding 15% with suppressed hysteresis and excellent reproducibility.« less

Requirement of zebrafish pcdh10a and pcdh10b in melanocyte precursor migration.

PubMed

Williams, Jason S; Hsu, Jessica Y; Rossi, Christy Cortez; Artinger, Kristin Bruk

2018-03-29

Melanocytes derive from neural crest cells, which are a highly migratory population of cells that play an important role in pigmentation of the skin and epidermal appendages. In most vertebrates, melanocyte precursor cells migrate solely along the dorsolateral pathway to populate the skin. However, zebrafish melanocyte precursors also migrate along the ventromedial pathway, in route to the yolk, where they interact with other neural crest derivative populations. Here, we demonstrate the requirement for zebrafish paralogs pcdh10a and pcdh10b in zebrafish melanocyte precursor migration. pcdh10a and pcdh10b are expressed in a subset of melanocyte precursor and somatic cells respectively, and knockdown and TALEN mediated gene disruption of pcdh10a results in aberrant migration of melanocyte precursors resulting in fully melanized melanocytes that differentiate precociously in the ventromedial pathway. Live cell imaging analysis demonstrates that loss of pchd10a results in a reduction of directed cell migration of melanocyte precursors, caused by both increased adhesion and a loss of cell-cell contact with other migratory neural crest cells. Also, we determined that the paralog pcdh10b is upregulated and can compensate for the genetic loss of pcdh10a. Disruption of pcdh10b alone by CRISPR mutagenesis results in somite defects, while the loss of both paralogs results in enhanced migratory melanocyte precursor phenotype and embryonic lethality. These results reveal a novel role for pcdh10a and pcdh10b in zebrafish melanocyte precursor migration and suggest that pcdh10 paralogs potentially interact for proper transient migration along the ventromedial pathway. Copyright © 2018 Elsevier Inc. All rights reserved.

Graphitic carbon stabilized silver nanoparticles synthesized by a simple chemical precursor method

NASA Astrophysics Data System (ADS)

Soni, Bhasker; Biswas, Somnath

2018-04-01

Monodispersed graphitic carbon stabilized silver nanoparticles (AgNPs) were synthesized following a simple chemical precursor method. The precursor was obtained by a controlled reduction of Ag+ in aqueous solution of poly-vinyl alcohol (PVA) and sucrose. The process allows precise control over the morphology of the AgNPs along with in situ formation of a surface stabilization layer of graphitic carbon.

A Python Analytical Pipeline to Identify Prohormone Precursors and Predict Prohormone Cleavage Sites

PubMed Central

Southey, Bruce R.; Sweedler, Jonathan V.; Rodriguez-Zas, Sandra L.

2008-01-01

Neuropeptides and hormones are signaling molecules that support cell–cell communication in the central nervous system. Experimentally characterizing neuropeptides requires significant efforts because of the complex and variable processing of prohormone precursor proteins into neuropeptides and hormones. We demonstrate the power and flexibility of the Python language to develop components of an bioinformatic analytical pipeline to identify precursors from genomic data and to predict cleavage as these precursors are en route to the final bioactive peptides. We identified 75 precursors in the rhesus genome, predicted cleavage sites using support vector machines and compared the rhesus predictions to putative assignments based on homology to human sequences. The correct classification rate of cleavage using the support vector machines was over 97% for both human and rhesus data sets. The functionality of Python has been important to develop and maintain NeuroPred (http://neuroproteomics.scs.uiuc.edu/neuropred.html), a user-centered web application for the neuroscience community that provides cleavage site prediction from a wide range of models, precision and accuracy statistics, post-translational modifications, and the molecular mass of potential peptides. The combined results illustrate the suitability of the Python language to implement an all-inclusive bioinformatics approach to predict neuropeptides that encompasses a large number of interdependent steps, from scanning genomes for precursor genes to identification of potential bioactive neuropeptides. PMID:19169350

Import routes and nuclear functions of Argonaute and other small RNA-silencing proteins.

PubMed

Schraivogel, Daniel; Meister, Gunter

2014-09-01

Small RNAs are important regulators of gene expression in many different organisms. Nuclear and cytoplasmic biogenesis enzymes generate functional small RNAs from double-stranded (ds) or single-stranded (ss) RNA precursors, and mature small RNAs are loaded into Argonaute proteins. In the cytoplasm, small RNAs guide Argonaute proteins to complementary RNAs leading to cleavage of these targets, translational silencing, or mRNA decay. In the nucleus Argonaute proteins engage in transcriptional silencing processes such as epigenetic silencing of repetitive elements at the chromatin level. During the past few years many novel functions of small RNA-guided gene silencing proteins in the nucleus have been reported. However, their specific import routes are largely unknown. In this review we summarize the current knowledge on nuclear transport routes that Argonaute and other RNA-silencing proteins take to carry out their various functions in the nucleus. Copyright © 2014 Elsevier Ltd. All rights reserved.

A facile molten-salt route to graphene synthesis.

PubMed

Liu, Xiaofeng; Giordano, Cristina; Antonietti, Markus

2014-01-15

Efficient synthetic routes are continuously pursued for graphene in order to implement its applications in different areas. However, direct conversion of simple monomers to graphene through polymerization in a scalable manner remains a major challenge for chemists. Herein, a molten-salt (MS) route for the synthesis of carbon nanostructures and graphene by controlled carbonization of glucose in molten metal chloride is reported. In this process, carbohydrate undergoes polymerization in the presence of strongly interacting ionic species, which leads to nanoporous carbon with amorphous nature and adjustable pore size. At a low precursor concentration, the process converts the sugar molecules (glucose) to rather pure few-layer graphenes. The MS-derived graphenes are strongly hydrophobic and exhibit remarkable selectivity and capacity for absorption of organics. The methodology described may open up a new avenue towards the synthesis and manipulation of carbon materials in liquid media. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Planning chemical syntheses with deep neural networks and symbolic AI

NASA Astrophysics Data System (ADS)

Segler, Marwin H. S.; Preuss, Mike; Waller, Mark P.

2018-03-01

To plan the syntheses of small organic molecules, chemists use retrosynthesis, a problem-solving technique in which target molecules are recursively transformed into increasingly simpler precursors. Computer-aided retrosynthesis would be a valuable tool but at present it is slow and provides results of unsatisfactory quality. Here we use Monte Carlo tree search and symbolic artificial intelligence (AI) to discover retrosynthetic routes. We combined Monte Carlo tree search with an expansion policy network that guides the search, and a filter network to pre-select the most promising retrosynthetic steps. These deep neural networks were trained on essentially all reactions ever published in organic chemistry. Our system solves for almost twice as many molecules, thirty times faster than the traditional computer-aided search method, which is based on extracted rules and hand-designed heuristics. In a double-blind AB test, chemists on average considered our computer-generated routes to be equivalent to reported literature routes.

Engineering a new class of thermal spray nano-based microstructures from agglomerated nanostructured particles, suspensions and solutions: an invited review

NASA Astrophysics Data System (ADS)

Fauchais, P.; Montavon, G.; Lima, R. S.; Marple, B. R.

2011-03-01

From the pioneering works of McPherson in 1973 who identified nanometre-sized features in thermal spray conventional alumina coatings (using sprayed particles in the tens of micrometres size range) to the most recent and most advanced work aimed at manufacturing nanostructured coatings from nanometre-sized feedstock particles, the thermal spray community has been involved with nanometre-sized features and feedstock for more than 30 years. Both the development of feedstock (especially through cryo-milling, and processes able to manufacture coatings structured at the sub-micrometre or nanometre sizes, such as micrometre-sized agglomerates made of nanometre-sized particles for feedstock) and the emergence of thermal spray processes such as suspension and liquid precursor thermal spray techniques have been driven by the need to manufacture coatings with enhanced properties. These techniques result in two different types of coatings: on the one hand, those with a so-called bimodal structure having nanometre-sized zones embedded within micrometre ones, for which the spray process is similar to that of conventional coatings and on the other hand, sub-micrometre or nanostructured coatings achieved by suspension or solution spraying. Compared with suspension spraying, solution precursor spraying uses molecularly mixed precursors as liquids, avoiding a separate processing route for the preparation of powders and enabling the synthesis of a wide range of oxide powders and coatings. Such coatings are intended for use in various applications ranging from improved thermal barrier layers and wear-resistant surfaces to thin solid electrolytes for solid oxide fuel cell systems, among other numerous applications. Meanwhile these processes are more complex to operate since they are more sensitive to parameter variations compared with conventional thermal spray processes. Progress in this area has resulted from the unique combination of modelling activities, the evolution of diagnostic tools and strategies, and experimental advances that have enabled the development of a wide range of coating structures exhibiting in numerous cases unique properties. Several examples are detailed. In this paper the following aspects are presented successively (i) the two spray techniques used for manufacturing such coatings: thermal plasma and HVOF, (ii) sensors developed for in-flight diagnostics of micrometre-sized particles and the interaction of a liquid and hot gas flow, (iii) three spray processes: conventional spraying using micrometre-sized agglomerates of nanometre-sized particles, suspension spraying and solution spraying and (iv) the emerging issues resulting from the specific structures of these materials, particularly the characterization of these coatings and (v) the potential industrial applications. Further advances require the scientific and industrial communities to undertake new research and development activities to address, understand and control the complex mechanisms occurring, in particular, thermal flow—liquid drops or stream interactions when considering suspension and liquid precursor thermal spray techniques. Work is still needed to develop new measurement devices to diagnose in-flight droplets or particles below 2 µm average diameter and to validate that the assumptions made for liquid-hot gas interactions. Efforts are also required to further develop some of the characterization protocols suitable to address the specificities of such nanostructured coatings, as some existing 'conventional' protocols usually implemented on thermal spray coatings are not suitable anymore, in particular to address the void network architectures from which numerous coatings properties are derived.

Sex Differences in Using Spatial and Verbal Abilities Influence Route Learning Performance in a Virtual Environment: A Comparison of 6- to 12-Year Old Boys and Girls

PubMed Central

Merrill, Edward C.; Yang, Yingying; Roskos, Beverly; Steele, Sara

2016-01-01

Previous studies have reported sex differences in wayfinding performance among adults. Men are typically better at using Euclidean information and survey strategies while women are better at using landmark information and route strategies. However, relatively few studies have examined sex differences in wayfinding in children. This research investigated relationships between route learning performance and two general abilities: spatial ability and verbal memory in 153 boys and girls between 6- to 12-years-old. Children completed a battery of spatial ability tasks (a two-dimension mental rotation task, a paper folding task, a visuo-spatial working memory task, and a Piagetian water level task) and a verbal memory task. In the route learning task, they had to learn a route through a series of hallways presented via computer. Boys had better overall route learning performance than did girls. In fact, the difference between boys and girls was constant across the age range tested. Structural equation modeling of the children’s performance revealed that spatial abilities and verbal memory were significant contributors to route learning performance. However, there were different patterns of correlates for boys and girls. For boys, spatial abilities contributed to route learning while verbal memory did not. In contrast, for girls both spatial abilities and verbal memory contributed to their route learning performance. This difference may reflect the precursor of a strategic difference between boys and girls in wayfinding that is commonly observed in adults. PMID:26941701

Films, Preimpregnated Tapes and Composites Made from Polyimide "Salt-Like" Solutions

NASA Technical Reports Server (NTRS)

Cano, Roberto J. (Inventor); Weiser, Erik S. (Inventor); St.Clair, Terry L. (Inventor); Echigo, Yoshiaki (Inventor); Kaneshiro, Hisayasu (Inventor)

2001-01-01

High quality films, preimpregnated tape (prepegs), and composites have been fabricated from polyimide precursor 'saltlike' solutions. These salt-like solutions have a low viscosity (5,000 to 10,000 cp) and a high solids content (50-65% by weight) and can be coated onto reinforcing fiber to produce prepegs with excellent tack and drape at 12-15% residual solvent (approximately 4-6% water from thermal imidization reaction). The processing of these types of prepegs significantly overcomes solvent removal problems and allows excellent fiber wet out. In addition, the physical characteristics of the polyimide precursor salt-like solutions permits processing into high-performance materials through the use of standard prepregging and composite fabrication equipment. The resultant composites are of high quality.

Genetic algorithms for the vehicle routing problem

NASA Astrophysics Data System (ADS)

Volna, Eva

2016-06-01

The Vehicle Routing Problem (VRP) is one of the most challenging combinatorial optimization tasks. This problem consists in designing the optimal set of routes for fleet of vehicles in order to serve a given set of customers. Evolutionary algorithms are general iterative algorithms for combinatorial optimization. These algorithms have been found to be very effective and robust in solving numerous problems from a wide range of application domains. This problem is known to be NP-hard; hence many heuristic procedures for its solution have been suggested. For such problems it is often desirable to obtain approximate solutions, so they can be found fast enough and are sufficiently accurate for the purpose. In this paper we have performed an experimental study that indicates the suitable use of genetic algorithms for the vehicle routing problem.

Titanium Dioxide Coating Prepared by Use of a Suspension-Solution Plasma-Spray Process

NASA Astrophysics Data System (ADS)

Du, Lingzhong; Coyle, Thomas W.; Chien, Ken; Pershin, Larry; Li, Tiegang; Golozar, Mehdi

2015-08-01

Titanium dioxide coatings were prepared from titanium isopropoxide solution containing nano TiO2 particles by use of a plasma-spray process. The effects of stand-off distance on coating composition and microstructure were investigated and compared with those for pure solution precursor and a water-based suspension of TiO2. The results showed that the anatase content of the coating increased with increasing stand-off distance and the rate of deposition decreased with increasing spray distance. Anatase nanoparticles in solution were incorporated into the coatings without phase transformation whereas most of the TiO2 in the precursor solution was transformed into rutile. The microstructure of preserved anatase particles bound by rutile improved the efficiency of deposition of the coating. The amount of anatase phase can be adjusted by variation of the ratio of solution to added anatase TiO2 nanoparticles.

A Simple and Green Route for Room-Temperature Synthesis of Gold Nanoparticles and Selective Colorimetric Detection of Cysteine.

PubMed

Bagci, Pelin Onsekizoglu; Wang, Yi-Cheng; Gunasekaran, Sundaram

2015-09-01

Gold nanoparticles (AuNPs) were synthesized at room temperature following a simple, rapid, and green route using fresh-squeezed apple juice as a reducing reagent. The optimal AuNPs, based on the particle color, stability, and color change suitable for colorimetric detection of cysteine (Cys), are synthesized using 5 mL of 10% apple juice, 1 mL of 10 mM gold precursor solution, and 1 mL of 0.1 M NaOH. Under this set of parameters, the AuNPs are synthesized within 30 min at room temperature. The average size (11.1 ± 3.2 nm) and ζ potential (-36.5 mV) of the AuNPs synthesized were similar to those of AuNPs prepared via the conventional citrate-reduction method. In the presence of Cys, unlike with any other amino acid, the AuNPs aggregated, possibly due to the gold-sulfur covalent interaction, yielding red-to-purple color change of the sample solution. The red-shift of the localized surface plasmon resonance peak of the AuNPs responsible for the color change was recorded by UV-vis spectrometer. The effect of other potential interferents such as glucose, ascorbic acid, K(+) , Na(+) , Ca(2+) , Zn(2+) , Ag(+) , Ni(2+) , Cu(2+) , Co(2+) , and Hg(2+) were also examined. The results show that AuNPs can be used to selectively detect and measure Cys with a linear dependency in the range of 2 to 100 μM and a limit of detection (signal-to-noise ratio > 3) of 50 nM. The results suggest that the green-synthesized AuNPs are useful for simple, rapid, and sensitive colorimetric detection of Cys, which is an essential amino acid in food and biological systems. © 2015 Institute of Food Technologists®

Green synthesis of gold-chitosan nanocomposites for caffeic acid sensing.

PubMed

Di Carlo, Gabriella; Curulli, Antonella; Toro, Roberta G; Bianchini, Chiara; De Caro, Tilde; Padeletti, Giuseppina; Zane, Daniela; Ingo, Gabriel M

2012-03-27

In this work, colloidal gold nanoparticles (AuNPs) stabilized into a chitosan matrix were prepared using a green route. The synthesis was carried out by reducing Au(III) to Au(0) in an aqueous solution of chitosan and different organic acids (i.e., acetic, malonic, or oxalic acid). We have demonstrated that by varying the nature of the acid it is possible to tune the reduction rate of the gold precursor (HAuCl(4)) and to modify the morphology of the resulting metal nanoparticles. The use of chitosan, a biocompatible and biodegradable polymer with a large number of amino and hydroxyl functional groups, enables the simultaneous synthesis and surface modification of AuNPs in one pot. Because of the excellent film-forming capability of this polymer, AuNPs-chitosan solutions were used to obtain hybrid nanocomposite films that combine highly conductive AuNPs with a large number of organic functional groups. Herein, Au-chitosan nanocomposites are successfully proposed as sensitive and selective electrochemical sensors for the determination of caffeic acid, an antioxidant that has recently attracted much attention because of its benefits to human health. A linear response was obtained over a wide range of concentration from 5.00 × 10(-8) M to 2.00 × 10(-3) M, and the limit of detection (LOD) was estimated to be 2.50 × 10(-8) M. Moreover, further analyses have demonstrated that a high selectivity toward caffeic acid can be achieved without interference from catechin or ascorbic acid (flavonoid and nonphenolic antioxidants, respectively). This novel synthesis approach and the high performances of Au-chitosan hybrid materials in the determination of caffeic acid open up new routes in the design of highly efficient sensors, which are of great interest for the analysis of complex matrices such as wine, soft drinks, and fruit beverages. © 2012 American Chemical Society

Facile synthesis of hydrophilic multi-colour and upconversion photoluminescent mesoporous carbon nanoparticles for bioapplications.

PubMed

Kong, Qinglu; Zhang, Lingxia; Liu, Jianan; Wu, Meiying; Chen, Yu; Feng, Jingwei; Shi, Jianlin

2014-12-25

Hydrophilic mesoporous carbon nanoparticles (MCNs) have been synthesized via an extremely facile precursor carbonization-in-hot solvent route. The synthesized MCNs show well-defined particle and pore size distribution at around 100 nm and 2.7 nm, respectively, and multicolor and upconversion photoluminescence, which endow the MCNs with multicolor/upconversion bioimaging and drug delivery properties.

Tandem isomerization-decarboxylation of unsaturated fatty acids to olefins via ruthenium metal-as-ligand catalysts

USDA-ARS?s Scientific Manuscript database

A new facile Ru-catalyzed route to bio-olefins3 from unsaturated fatty acids via readily accessible metal-as-ligand type catalyst precursors, [Ru(CO)2RCO2]n and Ru3(CO)12, will be described. The catalyst apparently functions in a tandem mode by dynamically isomerizing the positions of double bonds i...

Design of a universal logic block for fault-tolerant realization of any logic operation in trapped-ion quantum circuits

NASA Astrophysics Data System (ADS)

Goudarzi, H.; Dousti, M. J.; Shafaei, A.; Pedram, M.

2014-05-01

This paper presents a physical mapping tool for quantum circuits, which generates the optimal universal logic block (ULB) that can, on average, perform any logical fault-tolerant (FT) quantum operations with the minimum latency. The operation scheduling, placement, and qubit routing problems tackled by the quantum physical mapper are highly dependent on one another. More precisely, the scheduling solution affects the quality of the achievable placement solution due to resource pressures that may be created as a result of operation scheduling, whereas the operation placement and qubit routing solutions influence the scheduling solution due to resulting distances between predecessor and current operations, which in turn determines routing latencies. The proposed flow for the quantum physical mapper captures these dependencies by applying (1) a loose scheduling step, which transforms an initial quantum data flow graph into one that explicitly captures the no-cloning theorem of the quantum computing and then performs instruction scheduling based on a modified force-directed scheduling approach to minimize the resource contention and quantum circuit latency, (2) a placement step, which uses timing-driven instruction placement to minimize the approximate routing latencies while making iterative calls to the aforesaid force-directed scheduler to correct scheduling levels of quantum operations as needed, and (3) a routing step that finds dynamic values of routing latencies for the qubits. In addition to the quantum physical mapper, an approach is presented to determine the single best ULB size for a target quantum circuit by examining the latency of different FT quantum operations mapped onto different ULB sizes and using information about the occurrence frequency of operations on critical paths of the target quantum algorithm to weigh these latencies. Experimental results show an average latency reduction of about 40 % compared to previous work.

Solution-processed high-mobility neodymium-substituted indium oxide thin-film transistors formed by facile patterning based on aqueous precursors

NASA Astrophysics Data System (ADS)

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

2017-03-01

Solution-processed neodymium-substituted indium oxide (InNdO) thin-film transistors (TFTs) based on gel-like aqueous precursors were fabricated with a surface-selective deposition technique associated with ultraviolet irradiation. The Nd concentration can be easily tuned by changing the ratio of Nd2O3 to In2O3 precursors. It was found that Nd played roles of suppressing grain growth, suppressing oxygen vacancy formation, and increasing the electrical stability of TFTs. The InNdO TFT with a Nd:In ratio of 0.02:1 exhibited a mobility of as high as 15.6 cm2 V-1 s-1 with improved stability under gate-bias stress.

High-fraction brookite films from amorphous precursors

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

Haggerty, James E. S.; Schelhas, Laura T.; Kitchaev, Daniil A.

2017-11-09

Structure-specific synthesis processes are of key importance to the growth of polymorphic functional compounds such as TiO 2, where material properties strongly depend on structure as well as chemistry. The robust growth of the brookite polymorph of TiO 2, a promising photocatalyst, has been difficult in both powder and thin-film forms due to the disparity of reported synthesis techniques, their highly specific nature, and lack of mechanistic understanding. In this work, we report the growth of high-fraction (~95%) brookite thin films prepared by annealing amorphous titania precursor films deposited by pulsed laser deposition. We characterize the crystallization process, eliminating themore » previously suggested roles of substrate templating and Na helper ions in driving brookite formation. Instead, we link phase selection directly to film thickness, offering a novel, generalizable route to brookite growth that does not rely on the presence of extraneous elements or particular lattice-matched substrates. In addition to providing a new synthesis route to brookite thin films, our results take a step towards resolving the problem of phase selection in TiO 2 growth, contributing to the further development of this promising functional material.« less

Oxalate co-precipitation synthesis of calcium zirconate and calcium titanate powders.

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

Hernandez-Sanchez, Bernadette A.; Tuttle, Bruce Andrew

2009-06-01

Fine powders of calcium zirconate (CaZrO{sub 3}, CZ) and calcium titanate (CaTiO{sub 3}, CT) were synthesized using a nonaqueous oxalate co-precipitation route from Ca(NO{sub 3}){sub 2}{center_dot}4 H{sub 2}O and group(IV) n-butoxides (Ti(OBu{sup n}){sub 4} or Zr(OBu{sup n}){sub 4}). Several reaction conditions and batch sizes (2-35 g) were explored to determine their influence on final particle size, morphology, and phase. Characterization of the as-prepared oxalate precursors, oven dried oxalate precursors (60-90 C), and calcined powders (635-900 C) were analyzed with TGA/DTA, XRD, TEM, and SEM. Densification and sintering studies on pressed CZ pellets at 1375 and 1400 C were also performed.more » Through the developed oxalate co-precipitation route, densification temperatures for CZ were lowered by 125 C from the 1500 C firing temperature required for conventional mixed oxide powders. Low field electrical tests of the CZ pellets indicated excellent dielectric properties with dielectric constants of {approx}30 and a dissipation factor of 0.0004 were measured at 1 kHz.« less

Monodisperse Iron Oxide Nanoparticles by Thermal Decomposition: Elucidating Particle Formation by Second-Resolved in Situ Small-Angle X-ray Scattering

PubMed Central

2017-01-01

The synthesis of iron oxide nanoparticles (NPs) by thermal decomposition of iron precursors using oleic acid as surfactant has evolved to a state-of-the-art method to produce monodisperse, spherical NPs. The principles behind such monodisperse syntheses are well-known: the key is a separation between burst nucleation and growth phase, whereas the size of the population is set by the precursor-to-surfactant ratio. Here we follow the thermal decomposition of iron pentacarbonyl in the presence of oleic acid via in situ X-ray scattering. This method allows reaction kinetics and precursor states to be followed with high time resolution and statistical significance. Our investigation demonstrates that the final particle size is directly related to a phase of inorganic cluster formation that takes place between precursor decomposition and particle nucleation. The size and concentration of clusters were shown to be dependent on precursor-to-surfactant ratio and heating rate, which in turn led to differences in the onset of nucleation and concentration of nuclei after the burst nucleation phase. This first direct observation of prenucleation formation of inorganic and micellar structures in iron oxide nanoparticle synthesis by thermal decomposition likely has implications for synthesis of other NPs by similar routes. PMID:28572705

Preparation of transition metal nanoparticles and surfaces modified with (CO)polymers synthesized by RAFT

DOEpatents

McCormick, III., Charles L.; Lowe, Andrew B.; Sumerlin, Brent S.

2006-11-21

A new, facile, general one-phase method of generating thio-functionalized transition metal nanoparticles and surfaces modified by (co)polymers synthesized by the RAFT method is described. The method includes the stops of forming a (co)polymer in aqueous solution using the RAFT methodology, forming a colloidal transition metal precursor solution from an appropriate transition metal; adding the metal precursor solution or surface to the (co)polymer solution, adding a reducing agent into the solution to reduce the metal colloid in situ to produce the stabilized nanoparticles or surface, and isolating the stabilized nanoparticles or surface in a manner such that aggregation is minimized. The functionalized surfaces generated using these methods can further undergo planar surface modifications, such as functionalization with a variety of different chemical groups, expanding their utility and application.

Preparation of transition metal nanoparticles and surfaces modified with (co)polymers synthesized by RAFT

DOEpatents

McCormick, III, Charles L.; Lowe, Andrew B [Hattiesburg, MS; Sumerlin, Brent S [Pittsburgh, PA

2011-12-27

A new, facile, general one-phase method of generating thiol-functionalized transition metal nanoparticles and surfaces modified by (co)polymers synthesized by the RAFT method is described. The method includes the steps of forming a (co)polymer in aqueous solution using the RAFT methodology, forming a colloidal transition metal precursor solution from an appropriate transition metal; adding the metal precursor solution or surface to the (co)polymer solution, adding a reducing agent into the solution to reduce the metal colloid in situ to produce the stabilized nanoparticles or surface, and isolating the stabilized nanoparticles or surface in a manner such that aggregation is minimized. The functionalized surfaces generated using these methods can further undergo planar surface modifications, such as functionalization with a variety of different chemical groups, expanding their utility and application.

Enhanced method of fast re-routing with load balancing in software-defined networks

NASA Astrophysics Data System (ADS)

Lemeshko, Oleksandr; Yeremenko, Oleksandra

2017-11-01

A two-level method of fast re-routing with load balancing in a software-defined network (SDN) is proposed. The novelty of the method consists, firstly, in the introduction of a two-level hierarchy of calculating the routing variables responsible for the formation of the primary and backup paths, and secondly, in ensuring a balanced load of the communication links of the network, which meets the requirements of the traffic engineering concept. The method provides implementation of link, node, path, and bandwidth protection schemes for fast re-routing in SDN. The separation in accordance with the interaction prediction principle along two hierarchical levels of the calculation functions of the primary (lower level) and backup (upper level) routes allowed to abandon the initial sufficiently large and nonlinear optimization problem by transiting to the iterative solution of linear optimization problems of half the dimension. The analysis of the proposed method confirmed its efficiency and effectiveness in terms of obtaining optimal solutions for ensuring balanced load of communication links and implementing the required network element protection schemes for fast re-routing in SDN.

Strategic parameter-driven routing models for multidestination traffic in telecommunication networks.

PubMed

Lee, Y; Tien, J M

2001-01-01

We present mathematical models that determine the optimal parameters for strategically routing multidestination traffic in an end-to-end network setting. Multidestination traffic refers to a traffic type that can be routed to any one of a multiple number of destinations. A growing number of communication services is based on multidestination routing. In this parameter-driven approach, a multidestination call is routed to one of the candidate destination nodes in accordance with predetermined decision parameters associated with each candidate node. We present three different approaches: (1) a link utilization (LU) approach, (2) a network cost (NC) approach, and (3) a combined parametric (CP) approach. The LU approach provides the solution that would result in an optimally balanced link utilization, whereas the NC approach provides the least expensive way to route traffic to destinations. The CP approach, on the other hand, provides multiple solutions that help leverage link utilization and cost. The LU approach has in fact been implemented by a long distance carrier resulting in a considerable efficiency improvement in its international direct services, as summarized.

Nearest greedy for solving the waste collection vehicle routing problem: A case study

NASA Astrophysics Data System (ADS)

Mat, Nur Azriati; Benjamin, Aida Mauziah; Abdul-Rahman, Syariza; Wibowo, Antoni

2017-11-01

This paper presents a real case study pertaining to an issue related to waste collection in the northern part of Malaysia by using a constructive heuristic algorithm known as the Nearest Greedy (NG) technique. This technique has been widely used to devise initial solutions for issues concerning vehicle routing. Basically, the waste collection cycle involves the following steps: i) each vehicle starts from a depot, ii) visits a number of customers to collect waste, iii) unloads waste at the disposal site, and lastly, iv) returns to the depot. Moreover, the sample data set used in this paper consisted of six areas, where each area involved up to 103 customers. In this paper, the NG technique was employed to construct an initial route for each area. The solution proposed from the technique was compared with the present vehicle routes implemented by a waste collection company within the city. The comparison results portrayed that NG offered better vehicle routes with a 11.07% reduction of the total distance traveled, in comparison to the present vehicle routes.

A next generation advanced traveler information precursor system (ATIS 2.0 precursor system) concept of operations.

DOT National Transportation Integrated Search

2016-10-27

Advanced Traveler Information Systems (ATIS) have experienced significant growth since its initial inception in the 1990s. Technologies have continued to evolve at a rapid pace, enabling the integration of advanced solutions for traveler information ...

A next generation advanced traveler information precursor system (ATIS 2.0 precursor system) system requirements.

DOT National Transportation Integrated Search

2016-12-01

Advanced Traveler Information Systems (ATIS) have experienced significant growth since their initial inception in the 1990s. Technologies have continued to evolve at a rapid pace, enabling the integration of advanced solutions for traveler informatio...

A next generation advanced traveler information precursor system (ATIS 2.0 precursor system) use cases report.

DOT National Transportation Integrated Search

2017-05-01

Advanced Traveler Information Systems (ATIS) have experienced significant growth since their initial inception in the 1990s. Technologies have continued to evolve at a rapid pace, enabling the integration of advanced solutions for traveler informatio...

Fat body, hemolymph and ovary routes for delivery of substances to ovary in Melipona quadrifasciata anthidioides: differences among castes through the use of electron-opaque tracers.

PubMed

da Cruz-Landim, Carminda; Roat, Thaisa Cristina; Berger, Bruno

2013-08-01

The yolk protein precursor, vitellogenin (Vg), in bees is synthesized in the fat body trophocytes, delivered to the hemolymph and ultimately absorbed from there during the vitellogenic phase of oocytes in the active ovary. The routes tracing the material exchange that occurs between the trophocytes and the hemolymph, in addition to the transportation from the hemolymph to the ovarian follicles, were marked by alkaline phosphatase and lanthanum nitrate (LN). Active ovaries from nurse workers and physogastric queens, as well as inactive ovaries of virgin queens, were examined by transmission electron microscopy. The LN permitted better visualization of the routes of exchanges between the organs and the hemolymph. Both methods demonstrate the apparent differences between the phases of the ovary and the bee caste. In inactive ovaries of the virgin queens, the routes from the follicular epithelium to the oocyte remain closed; conversely, they are open in active ovaries of the nurse workers and physogastric queens. The differences between the methods and classes of bees are discussed.

Split delivery vehicle routing problem with time windows: a case study

NASA Astrophysics Data System (ADS)

Latiffianti, E.; Siswanto, N.; Firmandani, R. A.

2018-04-01

This paper aims to implement an extension of VRP so called split delivery vehicle routing problem (SDVRP) with time windows in a case study involving pickups and deliveries of workers from several points of origin and several destinations. Each origin represents a bus stop and the destination represents either site or office location. An integer linear programming of the SDVRP problem is presented. The solution was generated using three stages of defining the starting points, assigning busses, and solving the SDVRP with time windows using an exact method. Although the overall computational time was relatively lengthy, the results indicated that the produced solution was better than the existing routing and scheduling that the firm used. The produced solution was also capable of reducing fuel cost by 9% that was obtained from shorter total distance travelled by the shuttle buses.

Potassium Ions Promote Solution-Route Li2O2 Formation in the Positive Electrode Reaction of Li-O2 Batteries.

PubMed

Matsuda, Shoichi; Kubo, Yoshimi; Uosaki, Kohei; Nakanishi, Shuji

2017-03-16

Lithium-oxygen system has attracted much attention as a battery with high energy density that could satisfy the demands for electric vehicles. However, because lithium peroxide (Li 2 O 2 ) is formed as an insoluble and insulative discharge product at the positive electrode, Li-O 2 batteries have poor energy capacities. Although Li 2 O 2 deposition on the positive electrode can be avoided by inducing solution-route pathway using electrolytes composed of high donor number (DN) solvents, such systems generally have poor stability. Herein we report that potassium ions promote the solution-route formation of Li 2 O 2 . The present findings suggest that potassium or other monovalent ions have the potential to increase the volumetric energy density and life cycles of Li-O 2 batteries.

Role of reduced precursor and solvolytic reagent molar ratio on preparation and properties of ionogel

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

Gupta, Abhishek Kumar; Verma, Yogendra Lal; Singh, Manish Pratap

In the present study, ionogels have been synthesized by immobilizing IL (1-ethyl-3-methylimidazolium tetrafluoroborate) in silica gel matrices using non-aqueous route. In this process, tetraethyl orho-silane (TEOS) as a precursor to silicon dioxide and formic acid as a solvolytic gelating reagent in reduced molar ratio 1:4 were used. We find that reduced molar concentration of formic acid results the formation of ionogels having less number of closed pores (totally isolated from their neighbours), larger density and stable monolithic form. TEM and SEM measurements are used to visualize the morphology of sample and closed pores present in the sample. N{sub 2}-sorption measurementmore » is used to measure the pore parameters of the silica matrices which shows the mesoporous structure. DSC and TGA results show the change in phase transition temperature and thermal stability of IL upon confinement in silica matrices. Moreover, ionic conductivity of bulk and confined IL is measured using impedance spectroscopy and it has been found that it increases with increasing the temperature as well as concentration of IL in ionogels. Apart from these characterization techniques, ionogels have been characterized using FTIR and fluorescence spectroscopy which exhibit the change in vibrational frequencies and fluorescence behaviour of confined IL. - Highlights: • Synthesis of stable ionogel using non-hydrolytic route with reduced precursor and solvolytic reagent molar ratio. • Ionogels are free from entrapped residual reaction product. • The ionogels synthesized with higher amount of ionic liquids show bulk liquid like electrical behaviour.« less

Assessing Routing Strategies for Cognitive Radio Sensor Networks

PubMed Central

Zubair, Suleiman; Fisal, Norsheila; Baguda, Yakubu S.; Saleem, Kashif

2013-01-01

Interest in the cognitive radio sensor network (CRSN) paradigm has gradually grown among researchers. This concept seeks to fuse the benefits of dynamic spectrum access into the sensor network, making it a potential player in the next generation (NextGen) network, which is characterized by ubiquity. Notwithstanding its massive potential, little research activity has been dedicated to the network layer. By contrast, we find recent research trends focusing on the physical layer, the link layer and the transport layers. The fact that the cross-layer approach is imperative, due to the resource-constrained nature of CRSNs, can make the design of unique solutions non-trivial in this respect. This paper seeks to explore possible design opportunities with wireless sensor networks (WSNs), cognitive radio ad-hoc networks (CRAHNs) and cross-layer considerations for implementing viable CRSN routing solutions. Additionally, a detailed performance evaluation of WSN routing strategies in a cognitive radio environment is performed to expose research gaps. With this work, we intend to lay a foundation for developing CRSN routing solutions and to establish a basis for future work in this area. PMID:24077319

STEADY-STATE SOLUTIONS TO PBPK MODELS AND THEIR APPLICATIONS TO RISK ASSESSMENT I: ROUTE-TO-ROUTE EXTRAPOLATION OF VOLATILE CHEMICALS - AUTHORS' RESPONSE TO LETTER BY DR. KENNETH BOGEN

EPA Science Inventory

Dear Editor: We are disappointed that Dr. Bogen felt our paper(1) “adds little new” to previously published work utilizing steady state solutions to PBPK models. Moreover, it was not our intention to be either “dismissive” or “misleading” in our admittedly brief citation of the...

3D Modeling of Transport Phenomena and the Injection of the Solution Droplets in the Solution Precursor Plasma Spraying

NASA Astrophysics Data System (ADS)

Shan, Yanguang; Coyle, Thomas W.; Mostaghimi, Javad

2007-12-01

Solution precursor plasma spraying has been used to produce finely structured ceramic coatings with nano- and sub-micrometric features. This process involves the injection of a solution spray of ceramic salts into a DC plasma jet under atmospheric condition. During the process, the solvent vaporizes as the droplet travel downstream. Solid particles are finally formed due to the precipitation of the solute, and the particle are heated up and accelerated to the substrate to generate the coating. This article describes a 3D model to simulate the transport phenomena and the trajectory and heating of the solution spray in the process. The jet-spray two-way interactions are considered. A simplified model is employed to simulate the evolution process and the formation of the solid particle from the solution droplet in the plasma jet. The temperature and velocity fields of the jet are obtained and validated. The particle size, velocity, temperature, and position distribution on the substrate are predicted.

Assembly and Characterization ofWell-DefinedHigh-Molecular-Weight Poly(p-phenylene) Polymer Brushes

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

Chen, Jihua; Dadmun, Mark D; Mays, Jimmy

2011-01-01

The assembly and characterization of well-de ned, end-tethered poly- (p-phenylene) (PPP) brushes having high molecular weight, low polydispersity and high 1,4-stereoregularity are presented. The PPP brushes are formed using a precursor route that relies on either self-assembly or spin coating of high molecular weight (degrees of poly- merizations 54, 146, and 238) end-functionalized poly(1,3-cyclohexadiene) (PCHD) chains from benzene solutions onto silicon or quartz substrates, followed by aromatization of the end-attached PCHD chains on the surface. The approach allows the thickness (grafting density) of the brushes to be easily varied. The dry brushes before and after aromatization are characterized by ellipsometry,more » atomic force microscopy, grazing angle attenuated total re ectance Fourier transform infrared spectroscopy, and UV-Vis spectros- copy. The properties of the PPP brushes are compared with those of lms made using oligo- paraphenylenes and with ab initio density functional theory simulations of optical proper- ties. Our results suggest conversion to fully aromatized, end-tetheredPPPpolymerbrusheshaving eective conjugation lengths of 5 phenyl units.« less

Assembly and Characterization of Well Defined High Molecular Weight Poly(p-phenylene) Polymer Brushes

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

Alonzo Calderon, Jose E; Kilbey, II, S Michael; Ankner, John Francis

2011-01-01

The assembly and characterization of well-defined, end-tethered poly(p-phenylene) (PPP) brushes having high molecular weight, low polydispersity and high 1,4-stereoregularity are presented. The PPP brushes are formed using a precursor route that relies on either self-assembly or spin coating of high molecular weight (degrees of polymerizations 54, 146, and 238) end-functionalized poly(1,3-cyclohexadiene) (PCHD) chains from benzene solutions onto silicon or quartz substrates, followed by aromatization of the end-attached PCHD chains on the surface. The approach allows the thickness (grafting density) of the brushes to be easily varied. The dry brushes before and after aromatization are characterized by ellipsometry, atomic force microscopy,more » grazing angle attenuated total reflectance Fourier transform infrared spectroscopy, and UV-Vis spectroscopy. The properties of the PPP brushes are compared with those of films made using oligo-paraphenylenes and with ab initio density functional theory simulations of optical properties. Our results suggest conversion to fully aromatized, end-tethered PPP polymer brushes having effective conjugation lengths of 5 phenyl units.« less

Supramolecular self-assembly of graphene oxide and metal nanoparticles into stacked multilayers by means of a multitasking protein ring.

PubMed

Ardini, Matteo; Golia, Giordana; Passaretti, Paolo; Cimini, Annamaria; Pitari, Giuseppina; Giansanti, Francesco; Di Leandro, Luana; Ottaviano, Luca; Perrozzi, Francesco; Santucci, Sandro; Morandi, Vittorio; Ortolani, Luca; Christian, Meganne; Treossi, Emanuele; Palermo, Vincenzo; Angelucci, Francesco; Ippoliti, Rodolfo

2016-03-28

Graphene oxide (GO) is rapidly emerging worldwide as a breakthrough precursor material for next-generation devices. However, this requires the transition of its two-dimensional layered structure into more accessible three-dimensional (3D) arrays. Peroxiredoxins (Prx) are a family of multitasking redox enzymes, self-assembling into ring-like architectures. Taking advantage of both their symmetric structure and function, 3D reduced GO-based composites are hereby built up. Results reveal that the "double-faced" Prx rings can adhere flat on single GO layers and partially reduce them by their sulfur-containing amino acids, driving their stacking into 3D multi-layer reduced GO-Prx composites. This process occurs in aqueous solution at a very low GO concentration, i.e. 0.2 mg ml(-1). Further, protein engineering allows the Prx ring to be enriched with metal binding sites inside its lumen. This feature is exploited to both capture presynthesized gold nanoparticles and grow in situ palladium nanoparticles paving the way to straightforward and "green" routes to 3D reduced GO-metal composite materials.

Porphyrins as Templates for Site-Selective Atomic Layer Deposition: Vapor Metalation and in Situ Monitoring of Island Growth

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

Avila, Jason R.; Emery, Jonathan D.; Pellin, Michael J.

Examinations of enzymatic catalysts suggest one key to efficient catalytic activity is discrete size metallo clusters. Mimicking enzymatic cluster systems is synthetically challenging because conventional solution methods are prone to aggregation or require capping of the cluster, thereby limiting its catalytic activity. We introduce site-selective atomic layer deposition (ALD) on porphyrins as an alternative approach to grow isolated metal oxide islands that are spatially separated. Surface-bound tetra-acid free base porphyrins (H2TCPP) may be metalated with Mn using conventional ALD precursor exposure to induce homogeneous hydroxide synthetic handles which acts as a nucleation point for subsequent ALD MnO island growth. Analyticalmore » fitting of in situ QCM mass uptake reveals island growth to be hemispherical with a convergence radius of 1.74 nm. This growth mode is confirmed with synchrotron grazing-incidence small-angle X-ray scattering (GISAXS) measurements. Finally, we extend this approach to other ALD chemistries to demonstrate the generality of this route to discrete metallo island materials.« less

Aerogel and xerogel composites for use as carbon anodes

DOEpatents

Cooper, John F.; Tillotson, Thomas M.; Hrubesh, Lawrence W.

2010-10-12

A method for forming a reinforced rigid anode monolith and fuel and product of such method. The method includes providing a solution of organic aerogel or xerogel precursors including at least one of a phenolic resin, phenol (hydroxybenzene), resorcinol(1,3-dihydroxybenzene), or catechol(1,2-dihydroxybenzene); at least one aldehyde compound selected from the group consisting of formaldehyde, acetaldehyde, and furfuraldehyde; and an alkali carbonate or phosphoric acid catalyst; adding internal reinforcement materials comprising carbon to said precursor solution to form a precursor mixture; gelling said precursor mixture to form a composite gel; drying said composite gel; and pyrolyzing said composite gel to form a wettable aerogel/carbon composite or a wettable xerogel/carbon composite, wherein said composites comprise chars and said internal reinforcement materials, and wherein said composite is suitable for use as an anode with the chars being fuel capable of being combusted in a molten salt electrochemical fuel cell in the range from 500 C to 800 C to produce electrical energy. Additional methods and systems/compositions are also provided.

The influences of microwave irradiation and polyol precursor pH on Cu/AC catalyst and its CO oxidation performance

NASA Astrophysics Data System (ADS)

Chuang, Kui-Hao; Shih, Kaimin; Wey, Ming-Yen

2012-10-01

This study evaluated the effects of microwave irradiation parameters and the pH of the polyol precursor on the morphological features and catalytic performances of Cu/activated carbon (AC) catalysts. Experimental results of carbon monoxide (CO) oxidation indicated that the highest catalytic activity is achieved when the Cu/AC catalyst is prepared with microwave irradiation at 700 W for 60 s. Scanning electron microscopy revealed the presence of beneficial small copper aciculae on the Cu/AC catalyst under such a microwave irradiation scheme. Further investigation of operational parameters found that the performance of Cu/AC catalysts is enhanced by adopting a pH = 12 polyol precursor solution. With the observation that small cube copper ( 16 nm) aggregates form when a pH = 12 polyol precursor solution is used, this study also demonstrated the importance of controlling the morphology of metal nanoparticles on Cu/AC catalysts when using the microwave-assisted polyol method.

Regulation of endogenous neural stem/progenitor cells for neural repair—factors that promote neurogenesis and gliogenesis in the normal and damaged brain

PubMed Central

Christie, Kimberly J.; Turnley, Ann M.

2012-01-01

Neural stem/precursor cells in the adult brain reside in the subventricular zone (SVZ) of the lateral ventricles and the subgranular zone (SGZ) of the dentate gyrus in the hippocampus. These cells primarily generate neuroblasts that normally migrate to the olfactory bulb (OB) and the dentate granule cell layer respectively. Following brain damage, such as traumatic brain injury, ischemic stroke or in degenerative disease models, neural precursor cells from the SVZ in particular, can migrate from their normal route along the rostral migratory stream (RMS) to the site of neural damage. This neural precursor cell response to neural damage is mediated by release of endogenous factors, including cytokines and chemokines produced by the inflammatory response at the injury site, and by the production of growth and neurotrophic factors. Endogenous hippocampal neurogenesis is frequently also directly or indirectly affected by neural damage. Administration of a variety of factors that regulate different aspects of neural stem/precursor biology often leads to improved functional motor and/or behavioral outcomes. Such factors can target neural stem/precursor proliferation, survival, migration and differentiation into appropriate neuronal or glial lineages. Newborn cells also need to subsequently survive and functionally integrate into extant neural circuitry, which may be the major bottleneck to the current therapeutic potential of neural stem/precursor cells. This review will cover the effects of a range of intrinsic and extrinsic factors that regulate neural stem/precursor cell functions. In particular it focuses on factors that may be harnessed to enhance the endogenous neural stem/precursor cell response to neural damage, highlighting those that have already shown evidence of preclinical effectiveness and discussing others that warrant further preclinical investigation. PMID:23346046

Structural Evolution of Iron Antimonides from Amorphous Precursors to Crystalline Products Studied by Total Scattering Techniques.

PubMed

Bauers, Sage R; Wood, Suzannah R; Jensen, Kirsten M Ø; Blichfeld, Anders B; Iversen, Bo B; Billinge, Simon J L; Johnson, David C

2015-08-05

Homogeneous reaction precursors may be used to form several solid-state compounds inaccessible by traditional synthetic routes, but there has been little development of techniques that allow for a priori prediction of what may crystallize in a given material system. Here, the local structures of FeSbx designed precursors are determined and compared with the structural motifs of their crystalline products. X-ray total scattering and atomic pair distribution function (PDF) analysis are used to show that precursors that first nucleate a metastable FeSb3 compound share similar local structure to the product. Interestingly, precursors that directly crystallize to thermodynamically stable FeSb2 products also contain local structural motifs of the metastable phase, despite their compositional disagreement. While both crystalline phases consist of distorted FeSb6 octahedra with Sb shared between either two or three octahedra as required for stoichiometry, a corner-sharing arrangement indicative of AX3-type structures is the only motif apparent in the PDF of either precursor. Prior speculation was that local composition controlled which compounds nucleate from amorphous intermediates, with different compositions favoring different local arrangements and hence different products. This data suggests that local environments in these amorphous intermediates may not be very sensitive to overall composition. This can provide insight into potential metastable phases which may form in a material system, even with a precursor that does not crystallize to the kinetically stabilized product. Determination of local structure in homogeneous amorphous reaction intermediates from techniques such as PDF can be a valuable asset in the development of systematic methods to prepare targeted solid-state compounds from designed precursors.

A simple route to alloyed quaternary nanocrystals Ag-In-Zn-S with shape and size control.

PubMed

Gabka, Grzegorz; Bujak, Piotr; Giedyk, Kamila; Ostrowski, Andrzej; Malinowska, Karolina; Herbich, Jerzy; Golec, Barbara; Wielgus, Ireneusz; Pron, Adam

2014-05-19

A convenient method of the preparation of alloyed quaternary Ag-In-Zn-S nanocrystals is elaborated, in which a multicomponent mixture of simple and commercially available precursors, namely, silver nitrate, indium(III) chloride, zinc stearate, 1-dodecanethiol, and sulfur, is used with 1-octadecene as a solvent. The formation of quaternary nanocrystals necessitates the use of an auxiliary sulfur precursor, namely, elemental sulfur dissolved in oleylamine, in addition to 1-dodecanethiol. Without this additional precursor binary ZnS nanocrystals are formed. The optimum reaction temperature of 180 °C was also established. In these conditions shape, size, and composition of the resulting nanocrystals can be adjusted in a controlled manner by changing the molar ratio of the precursors in the reaction mixture. For low zinc stearate contents anisotropic rodlike (ca.3 nm x 10 nm) and In-rich nanocrystals are obtained. This is caused by a significantly higher reactivity of the indium precursor as compared to the zinc one. With increasing zinc precursor content the reactivities of both precursors become more balanced, and the resulting nanocrystals are smaller (1.5-4.0 nm) and become Zn-rich as evidenced by transmission electron microscopy, X-ray diffraction, and energy-dispersive spectrometry investigations. Simultaneous increases in the zinc and sulfur precursor content result in an enlargement of nanocrystals (2.5 to 5.0 nm) and further increase in the molar ZnS content (up to 0.76). The prepared nanoparticles show stable photoluminescence with the quantum yield up to 37% for In and Zn-rich nanocrystals. Their hydrodynamic diameter in toluene dispersion, determined by dynamic light scattering, is roughly twice larger than the diameter of their inorganic core.

Epitaxial YBa2Cu3O7-x nanocomposite films and coated conductors from BaMO3 (M = Zr, Hf) colloidal solutions

NASA Astrophysics Data System (ADS)

Obradors, X.; Puig, T.; Li, Z.; Pop, C.; Mundet, B.; Chamorro, N.; Vallés, F.; Coll, M.; Ricart, S.; Vallejo, B.; Pino, F.; Palau, A.; Gázquez, J.; Ros, J.; Usoskin, A.

2018-04-01

Superconducting nanocomposites are the best material choice to address the performance required in power applications and magnets working under high magnetic fields. However, it is still challenging to sort out how to achieve the highest superconducting performance using attractive and competitive manufacturing processes. Colloidal solutions have been recently developed as a novel and very promising low cost route to manufacture nanocomposite coated conductors. Well dispersed and stabilized preformance nanoparticle solutions are first prepared with high concentrations and then mixed with the YBa2Cu3O7 metalorganic precursor solutions to generate colloidal solutions to grow the nanocomposite films. Here we demonstrate, for the first time, that non-reactive BaZrO3 and BaHfO3 perovskite preformed nanoparticles are suitable for growing high quality thin and thick films, and coated conductors with a homogeneous distribution and controlled particle size using this fabrication method. Additionally, we extend the nanoparticle content of the nanocomposites up to 20%-25% mol without any degradation of the superconducting properties. Thick nanocomposite films, up to 0.8 μm, have been prepared with a single deposition of low-fluorine solutions using an ink jet printing dispenser and we demonstrate that the preformed nanoparticles display only a very limited coarsening during the growth process and so high critical current densities J c (B) under high magnetic fields. These films show the highest critical currents achieved so far based on the colloidal solution approach, I c = 220 A/cm-w at 77 K and self-field, and they still have a high potential for further increase in the film thickness. Finally, we also show that nanocomposite YBa2Cu3O7-BaZrO3 coated conductors based on an alternating beam assisted deposited YSZ buffer layer on stainless steel metallic substrates can be developed based on these novel colloidal solutions. Non-reactive preformed oxide perovskite nanoparticles are therefore very promising elements to further advance the colloidal solution approach in the implementation of low cost and high performance coated conductors for high magnetic field applications.

Binary ferrihydrite catalysts

DOEpatents

Huffman, Gerald P.; Zhao, Jianmin; Feng, Zhen

1996-01-01

A method of preparing a catalyst precursor comprises dissolving an iron salt and a salt of an oxoanion forming agent, in water so that a solution of the iron salt and oxoanion forming agent salt has a ratio of oxoanion/Fe of between 0.0001:1 to 0.5:1. Next is increasing the pH of the solution to 10 by adding a strong base followed by collecting of precipitate having a binary ferrihydrite structure. A binary ferrihydrite catalyst precursor is also prepared by dissolving an iron salt in water. The solution is brought to a pH of substantially 10 to obtain ferrihydrite precipitate. The precipitate is then filtered and washed with distilled water and subsequently admixed with a hydroxy carboxylic acid solution. The admixture is mixed/agitated and the binary ferrihydrite precipitate is then filtered and recovered.

Precursors for the polymer-assisted deposition of films

DOEpatents

McCleskey, Thomas M.; Burrell, Anthony K.; Jia, Quanxi; Lin, Yuan

2013-09-10

A polymer assisted deposition process for deposition of metal oxide films 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 to yield metal oxide films. Such films can be epitaxial in structure and can be of optical quality. The process can be organic solvent-free.

H2 Production Under Visible Light Irradiation from Aqueous Methanol Solution on CaTiO3:Cu Prepared by Spray Pyrolysis

NASA Astrophysics Data System (ADS)

Lim, Sung Nam; Song, Shin Ae; Jeong, Yong-Cheol; Kang, Hyun Woo; Park, Seung Bin; Kim, Ki Young

2017-10-01

Perovskite-type photocatalysts of CaCu x Ti1- x O3 (0 ≤ x ≤ 0.02) powder were prepared by spray pyrolysis of aqueous solution or aqueous solution with polymeric additive. The effects of the amount of copper ions doped in the photocatalyst and the precursor type on the photocatalytic activity under visible-light irradiation were investigated. The crystal structure, oxidation state, and light adsorption properties of the prepared photocatalysts were analyzed using x-ray diffraction, x-ray photoelectron spectroscopy, and diffuse reflectance spectroscopy, respectively. The doping of copper ions in CaTiO3 allowed visible-light absorption owing to a narrowing of the band gap energy of the host material through the formation of a new donor level for copper ions. Among the doped samples prepared from the aqueous precursor, CaTiO3 doped with 1 mol.% copper ions had the highest hydrogen evolution rate (140.7 μmol g-1 h-1). Notably, the hydrogen evolution rate of the photocatalyst doped with 1 mol.% copper ions prepared from the aqueous precursor with polymeric additive (295.0 μmol g-1 h-1) was two times greater than that prepared from the aqueous precursor, due to the morphology effect.

ZnO-based regenerable sulfur sorbents for fluid-bed/transport reactor applications

DOEpatents

Slimane, Rachid B.; Abbasian, Javad; Williams, Brett E.

2004-09-21

A method for producing regenerable sulfur sorbents in which a support material precursor is mixed with isopropanol and a first portion of deionized water at an elevated temperature to form a sol mixture. A metal oxide precursor comprising a metal suitable for use as a sulfur sorbent is dissolved in a second portion of deionized water, forming a metal salt solution. The metal salt solution and the sol mixture are mixed with a sol peptizing agent while heating and stirring, resulting in formation of a peptized sol mixture. The metal oxide precursor is dispersed substantially throughout the peptized sol mixture, which is then dried, forming a dry peptized sol mixture. The dry peptized sol mixture is then calcined and the resulting calcined material is then converted to particles.

Investigations of temporal and spatial distribution of precursors SO2 and NO2 vertical columns in the North China Plain using mobile DOAS

NASA Astrophysics Data System (ADS)

Wu, Fengcheng; Xie, Pinhua; Li, Ang; Mou, Fusheng; Chen, Hao; Zhu, Yi; Zhu, Tong; Liu, Jianguo; Liu, Wenqing

2018-02-01

Recently, Chinese cities have suffered severe events of haze air pollution, particularly in the North China Plain (NCP). Investigating the temporal and spatial distribution of pollutants, emissions, and pollution transport is necessary to better understand the effect of various sources on air quality. We report on mobile differential optical absorption spectroscopy (mobile DOAS) observations of precursors SO2 and NO2 vertical columns in the NCP in the summer of 2013 (from 11 June to 7 July) in this study. The different temporal and spatial distributions of SO2 and NO2 vertical column density (VCD) over this area are characterized under various wind fields. The results show that transport from the southern NCP strongly affects air quality in Beijing, and the transport route, particularly SO2 transport on the route of Shijiazhuang-Baoding-Beijing, is identified. In addition, the major contributors to SO2 along the route of Shijiazhuang-Baoding-Beijing are elevated sources compared to low area sources for the route of Dezhou-Cangzhou-Tianjin-Beijing; this is found using the interrelated analysis between in situ and mobile DOAS observations during the measurement periods. Furthermore, the discussions on hot spots near the city of JiNan show that average observed width of polluted air mass is 11.83 and 17.23 km associated with air mass diffusion, which is approximately 60 km away from emission sources based on geometrical estimation. Finally, a reasonable agreement exists between the Ozone Monitoring Instrument (OMI) and mobile DOAS observations, with a correlation coefficient (R2) of 0.65 for NO2 VCDs. Both datasets also have a similar spatial pattern. The fitted slope of 0.55 is significantly less than unity, which can reflect the contamination of local sources, and OMI observations are needed to improve the sensitivities to the near-surface emission sources through improvements of the retrieval algorithm or the resolution of satellites.

An effective approach to synthesize monolayer tungsten disulphide crystals using tungsten halide precursor

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

Thangaraja, Amutha; Shinde, Sachin M.; Kalita, Golap, E-mail: kalita.golap@nitech.ac.jp

2016-02-01

The synthesis of large-area monolayer tungsten disulphide (WS{sub 2}) single crystal is critical for realistic application in electronic and optical devices. Here, we demonstrate an effective approach to synthesize monolayer WS{sub 2} crystals using tungsten hexachloride (WCl{sub 6}) as a solid precursor in atmospheric chemical vapor deposition process. In this technique, 0.05M solution of WCl{sub 6} in ethanol was drop-casted on SiO{sub 2}/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 WS{sub 2} crystals on the substrate. The crystalmore » 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 WS{sub 2} single crystalline monolayer can be grown using the WCl{sub 6} precursor. Our finding shows an easier and effective approach to grow WS{sub 2} monolayer using tungsten halide solution-casting, rather than evaporating the precursor for gas phase reaction.« less

Chemical Routes to Ceramics With Tunable Properties and Structures

DTIC Science & Technology

2006-07-26

thermolytic or chemical reactions, and then dissolution of the alumina membrane to leave the free standing fibers. In our work, we used alumina membranes ...converted the precursor to a boron carbide coating. Dissolution of the coated alumina membranes with HF then yielded free-standing nanocylindrical...construct, via sol-gel condensations, ordered macroporous arrays of titania , zirconia, and alumina . Other work employing the silica templates have

Efficient synthesis of cysteine-rich cyclic peptides through intramolecular native chemical ligation of N-Hnb-Cys peptide crypto-thioesters.

PubMed

Terrier, Victor P; Delmas, Agnès F; Aucagne, Vincent

2017-01-04

We herein introduce a straightforward synthetic route to cysteine-containing cyclic peptides based on the intramolecular native chemical ligation of in situ generated thioesters. Key precursors are N-Hnb-Cys crypto-thioesters, easily synthesized by Fmoc-based SPPS. The strategy is applied to a representative range of naturally occurring cyclic disulfide-rich peptide sequences.

Rapid, General Access to Chiral β-Fluoroamines and β, β-Difluoroamines via Organocatalysis

PubMed Central

Fadeyi, Olugbeminiyi O.; Lindsley, Craig W.

2011-01-01

A rapid, general route to enantiopure β-fluoroamines and β,β-difluoroamines has been developed employing organocatalysis in both a two-pot and a one-pot procedure. Both chemical yields (64–82%) and enantioselectivity (94–98% ee) were excellent and represent a significant improvement in the art of preparing chemically diverse β-fluoroamines from readily available precursors. PMID:19159275

New high boron content polyborane precursors to advanced ceramic materials: New syntheses, new applications

NASA Astrophysics Data System (ADS)

Guron, Marta

There is a need for new synthetic routes to high boron content materials for applications as polymeric precursors to ceramics, as well as in neutron shielding and potential medical applications. To this end, new ruthenium-catalyzed olefin metathesis routes have been devised to form new complex polyboranes and polymeric species. Metathesis of di-alkenyl substituted o-carboranes allowed the synthesis of ring-closed products fused to the carborane cage, many of which are new compounds and one that offers a superior synthetic method to one previously published. Acyclic diene metathesis of di-alkenyl substituted m-carboranes resulted in the formation of new main-chain carborane-containing polymers of modest molecular weights. Due to their extremely low char yields, and in order to explore other metathesis routes, ring opening metathesis polymerization (ROMP) was used to generate the first examples of poly(norbornenyl- o-carboranes). Monomer synthesis was achieved via a two-step process, incorporating Ti-catalyzed hydroboration to make 6-(5-norbornenyl)-decaborane, followed by alkyne insertion in ionic liquid media to achieve 1,2-R2 -3-norbornenyl o-carborane species. The monomers were then polymerized using ROMP to afford several examples of poly(norbornenyl- o-carboranes) with relatively high molecular weights. One such polymer, [1-Ph, 3-(=CH2-C5H7-CH2=)-1,2-C 2B10H10]n, had a char yield very close to the theoretical char yield of 44%. Upon random copolymerization with poly(6-(5-norbornenyl) decaborane), char yields significantly increased to 80%, but this number was well above the theoretical value implicating the formation of a boron-carbide/carbon ceramic. Finally, applications of polyboranes were explored via polymer blends toward the synthesis of ceramic composites and the use of polymer precursors as reagents for potential ultra high temperature ceramic applications. Upon pyrolysis, polymer blends of poly(6-(5-norbornenyl)-decaborane) and poly(methylcarbosilane) converted into boron-carbide/silicon-carbide ceramics with high char yields. These polymer blends were also shown to be useful as reagents for synthesis of hafnium-boride/hafnium-carbide/silicon carbide and zirconium-boride/zirconium-carbide/silicon carbide composites.

Photocatalysis of zinc oxide nanotip array/titanium oxide film heterojunction prepared by aqueous solution deposition

NASA Astrophysics Data System (ADS)

Lee, Ming-Kwei; Lee, Bo-Wei; Kao, Chen-Yu

2017-05-01

A TiO2 film was prepared on indium tin oxide (ITO)/glass by aqueous solution deposition (ASD) with precursors of ammonium hexafluoro-titanate and boric acid at 40 °C. The photocatalysis of annealed TiO2 film increases with increasing growth time and decreases with increasing growth times longer than 60 min. A ZnO nanotip array was prepared on ZnO seed layer/TiO2 film/glass by aqueous solution deposition with precursors of zinc nitrate and ammonium hydroxide at 70 °C. The photocatalysis of ASD-ZnO/ASD-TiO2 film/ITO glass can be better than that of P25.

Convergent synthesis of 13N-labelled Peptidic structures using aqueous [13N]NH3.

PubMed

Blower, Julia E; Cousin, Samuel F; Gee, Antony D

2017-01-01

Nitrogen-13 has a 10-min half-life which places time constraints on the complexity of viable synthetic methods for its incorporation into PET imaging agents. In exploring ways to overcome this limitation, we have used the Ugi reaction to develop a rapid one-pot method for radiolabelling peptidic molecules using [ 13 N]NH 3 as a synthetic precursor. Carrier-added [ 13 N]NH 3 (50 μL) was added to a solution of carboxylic acid, aldehyde, and isocyanide in 2,2,2-TFE (200 μL). The mixture was heated in a microwave synthesiser at 120 °C for 10 min. Reactions were analysed by radio-HPLC and radio-LCMS. Isolation of the target 13 N-labelled peptidic Ugi compound was achieved via semi-preparative radio-HPLC as demonstrated for Ugi 1. Radio-HPLC analysis of each reaction confirmed the formation of radioactive products co-eluting with their respective reference standards with radiochemical yields of the crude products ranging from 11% to 23%. Two cyclic γ-lactam structures were also achieved via intra-molecular reactions. Additional radioactive by-products observed in the radio-chromatogram were identified as 13 N-labelled di-imines formed from the reaction of [ 13 N]NH 3 with two isocyanide molecules. The desired 13 N-labelled Ugi product was isolated using semi-preparative HPLC. We have developed a one-pot method that opens up new routes to radiolabel complex, peptidic molecules with 13 N using aqueous [ 13 N]NH 3 as a synthetic precursor.

A new approach to the side chain formation of 24-alkyl-22-hydroxy steroids: application to the preparation of early brassinolide biosynthetic precursors.

PubMed

Hurski, Alaksiej L; Zhabinskii, Vladimir N; Khripach, Vladimir A

2012-06-01

A new synthetic route to 22S-hydroxy-24R-methyl steroids has been developed and applied for the preparation of cathasterone, (22S)-hydroxycampesterol, and 6-deoxocathasterone, which are precursors in the early stages of the biosynthesis of brassinolide. The construction of the steroid side chain with the correct stereochemistry at C-24 is based on the use of Claisen rearrangement. The introduction of the 22-hydroxyl group has been achieved by epoxidation of the Δ(22)-double bond, nucleophilic opening of the intermediate mesyl epoxide with sodium sulfide, and desulfurization of the formed tetrahydrothiophenes with Raney nickel. Copyright © 2012 Elsevier Inc. All rights reserved.

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.

The influence of precursor addition order on the porosity of sol-gel bioactive glasses.

PubMed

Fernando, Delihta; Colon, Pierre; Cresswell, Mark; Journet, Catherine; Pradelle-Plasse, Nelly; Jackson, Phil; Grosgogeat, Brigitte; Attik, Nina

2018-06-16

The superior textural properties of sol-gel derived bioactive glasses compared to conventional melt quench glasses accounts for their accelerated bioactivity in vitro. Several studies have explored ways to improve the surface properties of sol-gel glasses in order to maximise their efficiency for bone and tooth regeneration. In this study, we investigated the effect of order of network modifying precursor addition on the textural properties of sol-gel derived bioactive glasses. The effect of precursor addition order on the glass characteristics was assessed by switching the order of network modifying precursor (calcium acetate monohydrate and sodium acetate anhydrous) addition for a fixed composition of bioactive glass (75SiO 2 :5CaO:10Na 2 O:10P 2 O 5 ). The results of this study showed that the order of precursor addition does influence the porosity of these glasses. For the glasses of a fixed composition and preparation conditions we achieved a doubling of surface area, a 1.5 times increase in pore volume and a 1.2 times decrease in pore size just by the mixing the network modifying precursors and adding them together in the sol-gel preparation. This simple and straightforward route adaptation to the preparation of bioactive glasses would allow us to enhance the textural properties of existing and novel composition of bioactive glasses and thus accelerate their bioactivity. Copyright © 2018 The Academy of Dental Materials. Published by Elsevier Inc. All rights reserved.

Early Failures Benefit Subsequent Task Performance.

PubMed

Igata, Hideyoshi; Sasaki, Takuya; Ikegaya, Yuji

2016-02-17

Animals navigate using cognitive maps. However, how they adaptively exploit these maps in changing environments is not fully understood. In this study, we investigated the problem-solving behaviors of mice in a complicated maze in which multiple routes with different intersections were available (Test 1). Although all mice eventually settled on the shortest route, mice that initially exhibited more trial-and-error exploration solved the maze more rapidly. We then introduced one or two barriers that obstructed learned routes such that mice had to establish novel roundabout detours (Tests 2/3). Solutions varied among mice but were predictable based on individual early trial-and-error patterns observed in Test 1: mice that had initially explored more extensively found better solutions. Finally, when the barriers were removed (Test 4), all mice reverted to the best solution after active exploration. Thus, early active exploration helps mice to develop optimal strategies.

Processing effects on the microstructure and dielectric properties of hydrothermal barium titanate and (barium,strontium)titanate thin films

NASA Astrophysics Data System (ADS)

McCormick, Mark Alan

The goal of this work was to produce BaTiO3 and BaxSr (1-x)TiO3 (BST) thin films with high dielectric constants, using a low-temperature (<100°C) hydrothermal synthesis route. To accomplish this, titanium metal-organic precursor films were spin-cast onto metal-coated glass substrates and converted to polycrystalline BaTiO3 or BST upon reacting in aqueous solutions of Ba(OH)2 or Ba(OH)2 and Sr(OH)2. The influences of solution molarity, processing temperature, and reaction time on thin film reaction kinetics, microstructure, and dielectric properties were examined for BaTiO3 films. Post-deposition annealing at temperatures as low as 200°C substantially affected the lattice parameter, dielectric constant, and dielectric loss. This behavior is explained in terms of hydroxyl defect incorporation during film formation. Current-voltage (I-V) measurements were performed to determine the dominant conduction mechanism(s) during application of a do field, and to extract the metal/ceramic barrier height. In particular, Schottky barrier-limited conduction and Poole-Frenkel conduction were investigated as potential leakage mechanisms. For BST thin films, film stoichiometry deviated from the initial solution composition, with a preferred incorporation of Sr2+ into the perovskite lattice. The dielectric constant of the BST films was measured as a function of composition (Ba:Sr ratio) and temperature over the range 25--150°C. Finally, capacitance-voltage (C-V) measurements were made for BST films to determine the influence of film composition on dielectric tunability.

Synthesis and Study of Gel Calcined Cd-Sn Oxide Nanocomposites

NASA Astrophysics Data System (ADS)

De, Arijit; Kundu, Susmita

2016-07-01

Cd-Sn oxide nanocomposites were synthesized by sol-gel method from precursor sol containing Cd:Sn = 2:1 and 1:1 mol ratio. Instead of coprecipitation, a simple novel gel calcination route was followed. Cd (NO3)2. 4H2O and SnCl4. 5H2O were used as starting materials. Gel was calcined at 1050 °C for 2 h to obtain nanocomposites. XRD analysis reveals the presence of orthorhombic, cubic Cd2SnO4 along with orthorhombic, hexagonal CdSnO3 phases in both the composites. SEM and TEM studies indicate the development of nanocomposites of different shapes suggesting different degrees of polymerization in precursor sol of different composition. UV-Vis absorption spectra show a blue shift for both the composites compared to bulk values. Decrease of polarization with frequency, dipole contribution to the polarization, and more sensitivity to ethanol vapor were observed for the nanocomposite derived from precursor sol containing Cd:Sn = 2:1 mol ratio.

High Tc superconducting films from metallo-organic precursors

NASA Astrophysics Data System (ADS)

Davison, W. W.; Shyu, S. G.; Buchanan, R. C.

High Tc superconducting films of heavy metal soaps (derived from carboxylic acid precursors) have been prepared on Si and other substrates. The precursors were synthesized and mixed in appropriate molar ratios to form the high Tc compound YBa2Cu3O(7-x), using a high boiling point common solvent base. The precursor solution was deposited by a spin casting technique on the substrates. Film thicknesses of 0.1-1.0 micron were achieved after heat treatment at 550-850 C at not longer than 4 hours. Films were analyzed as to orientation, appropriate phase, interfacial reaction, and superconducting properties.

Conformal dynamics of precursors to fracture

NASA Astrophysics Data System (ADS)

Barra, F.; Herrera, M.; Procaccia, I.

2003-09-01

An exact integro-differential equation for the conformal map from the unit circle to the boundary of an evolving cavity in a stressed 2-dimensional solid is derived. This equation provides an accurate description of the dynamics of precursors to fracture when surface diffusion is important. The solution predicts the creation of sharp grooves that eventually lead to material failure via rapid fracture. Solutions of the new equation are demonstrated for the dynamics of an elliptical cavity and the stability of a circular cavity under biaxial stress, including the effects of surface stress.

Preparation of tungsten oxide

DOEpatents

Bulian, Christopher J [Yankton, SD; Dye, Robert C [Los Alamos, NM; Son, Steven F [Los Alamos, NM; Jorgensen, Betty S [Jemez Springs, NM; Perry, W Lee [Jemez Springs, NM

2009-09-22

Tungsten trioxide hydrate (WO.sub.3.H.sub.2O) was prepared from a precursor solution of ammonium paratungstate in concentrated aqueous hydrochloric acid. The precursor solution was rapidly added to water, resulting in the crash precipitation of a yellow white powder identified as WO.sub.3.H.sub.2O nanosized platelets by x-ray diffraction and scanning electron microscopy. Annealing of the powder at 200.degree. C. provided cubic phase WO.sub.3 nanopowder, and at 400.degree. C. provided WO.sub.3 nanopowder as a mixture of monoclinic and orthorhombic phases.

Biocompatible silicon quantum dots by ultrasound-induced solution route

NASA Astrophysics Data System (ADS)

Lee, Soojin; Cho, Woon-Jo

2004-10-01

The water-soluble silicon quantum dots (QDs) of average diameter ~3 nm were prepared in organic solvent by ultrasound-induced solution route. This speedy rout produces the silicon QDs in the size range from 2 nm to 4 nm at room temperature and ambient pressure. The product yield of QDs was estimated to be higher than 60 % based on the initial NaSi weight. The surfaces of QDs were terminated with organic molecules including biocompatible ending groups (hydroxyl, amine and carboxyl) during simple preparation. Covalent attached molecules were characterized by FT-IR spectroscopy. These water-soluble passivation of QDs has just a little effect on the optical properties of original QDs.

Synthesis and phase behavior of end-functionalized associating polymers

NASA Astrophysics Data System (ADS)

Wrue, Michelle H.

We have explored polymer blend phase behavior in the presence of multiple hydrogen bonding end-groups. This work details the synthesis of functionalized polymers and their subsequent use in miscibility studies. The synthesis of end-functionalized hydrogen bonding polymers and the investigation of their physical properties and miscibility is presented. Mono-functional and telechelic ureidopyrimidinone (UPy) functionalized polymers were prepared by two main routes: post-polymerization functionalization (of commercially available or synthesized polymers); and polymerization of monomers using a functionalized initiator. UPy-functionalized polymers were prepared with a variety of polymer backbones including poly(ethylene oxide)s; poly(butadiene)s, poly(dimethyl siloxanxe)s; poly(styrene)s and poly(methyl methacrylate)s. The most successful route to polymers with UPy end-groups was atom transfer radical polymerization (ATRP) using a UPy-functionalized initiator, followed by atom transfer radical coupling (ATRC). The incorporation of ureidopyrimidinone end-groups was shown to affect the physical properties of the polymer backbone. Parent polymers that were liquids became viscous liquids or waxy solids upon UPy-functionalization of chain end. UPy-functionalization of a hydroxyl-terminated polybutadiene (HO-PB-OH) resulted in a waxy solid while the HO-PB-OH precursor was a viscous liquid. The thermal properties of functionalized polymers also differed from those of the unfunctionalized parent polymers. Hot-stage optical microscopy revealed that UPy-functionalized PEO displayed a depressed melting point relative to the analogous unfunctionalized precursor. Differential scanning calorimetry was also used to investigate the synthesized UPy-polymers. UPy-functionalized polystyrenes and poly(methyl methacrylate)s showed an increased T g compared to the equivalent homopolymer standards. This increased Tg was determined to be dependent upon the fraction of UPy groups present and chemical cleavage of the end-groups resulted in Tgs near those observed for polymer standards of comparable molecular weight. Aggregation of UPy end-groups in solution was observed using gel permeation chromatography. Aggregation was only observed for telechelic samples of low molecular weight, indicating that the aggregation of end-groups is dependent upon the concentration of the end-groups. The effect of UPy end-groups on blend miscibility was studied in solution using laser light scattering and in the melt state was using laser light scattering, optical microscopy and differential scanning calorimetry. The incorporation of associating groups onto one end of either blend component decreases miscibility relative to unfunctionalized parent blends. Lower miscibility was also observed for blends in which both components were mono-functionalized with associating end-groups. The largest decrease in miscibility was observed for blends containing telechelic UPy-functionalized polymers, which were immiscible across the entire composition range.

Scalable Routes to Efficient Thermoelectric Materials

NASA Astrophysics Data System (ADS)

Feser, Joseph Patrick

Thermoelectrics are solid-state materials with the ability to directly convert heat to electricity and visa versa. Despite their advantages in power density and reliability, state-of-the-art bulk alloy materials have not been efficient enough or inexpensive enough to be deployed widely. Newer nanostructured materials show significantly improved efficiencies and could overcome these long-standing problems. This dissertation studies the conditions that govern efficiency improvements in nanostructured materials with particular attention paid to lattice thermal conductivity reductions as well as methods to make such materials inexpensively using solution processing. Measurements of a new p-type material system, In1-xGa xSb doped with epitaxially embedded metallic ErSb nanocrystals show that lattice thermal conductivity is reduced significantly below the alloy limit with as little as 1% nanocrystal loading by volume. Theoretical modeling based on the Boltzmann transport equation (BTE) is able to explain the reductions on the basis of an increased scattering cross section for long wavelength phonons which are scattered much less effectively by phonon-phonon and alloy impurity interactions. The optimal conditions for nanoparticle size, concentration, alloy composition are explored and the existence of an optimal nanocrystal size which depends on the alloy composition and temperature is predicted. A variety of colloidal nanocrystals are explored as inexpensive building blocks for nanostructured thermoelectric materials with tunable electronic and thermal properties. First, the electronic properties of superlattices of PbSe nanocrystals are studied in the limit of strong quantum confinement (d<10nm). PbSe quantum dot superlattices show size-dependent Seebeck coefficient which exceed that of the bulk material at equivalent carrier concentrations. Reversible control of the carrier concentration is shown by surface exposure of the superlattices to oxidizing and reducing agents and in-situ monitoring of the thermopower. Next, phonon transport in ultra-fine grained nanocomposites with tunable grain size are studied using colloidal nanocrystals. Particles of CdSe are coated with a hydrazine-based metal chalcogenide ligand which serves as a functional "glue." Composites with grain size between 3nm-6nm display ultra-low thermal conductivity approaching the theoretical limit for a crystalline solid, nearly 30 times lower than the bulk compound. Modeling shows that boundary scattering in the framework of BTE cannot adequately explain the measured properties and alternative mechanisms are discussed. Finally, a solution processable route to Bi2Te3-xSex thermoelectrics is developed by reacting Bi2S3 in hydrazine to form a universal precursor. The precursor is spin-coated in the presence of excess Se and Te and annealed to form a thermoelectrics material with a maximum ZT˜0.4 at room temperature, which is the highest for any spin-coated material currently reported.

Morphology control of anisotropic BaTiO 3 and BaTiOF 4 using organic-inorganic interaction

NASA Astrophysics Data System (ADS)

Masuda, Yoshitake; Tanaka, Yuki; Gao, Yanfeng; Koumoto, Kunihito

2009-01-01

We proposed a novel concept for morphology control of barium titanate precursor to fabricate platy particles. Organic molecules play an essential role in the crystallization of BaTiOF 4 to synthesize multi-needle particles, polyhedron particles or platy particles in an aqueous solution. Precursors were successfully transformed to barium titanate single phase by annealing. Platy barium titanate precursor particles are expected for future multilayer ceramic capacitors.

Spray drying of silica microparticles for sustained release application with a new sol-gel precursor.

PubMed

Wang, Bifeng; Friess, Wolfgang

2017-10-30

A new precursor, tetrakis(2-methoxyethyl) orthosilicate (TMEOS) was used to fabricate microparticles for sustained release application, specifically for biopharmaceuticals, by spray drying. The advantages of TMEOS over the currently applied precursors are its water solubility and hydrolysis at moderate pH without the need of organic solvents or catalyzers. Thus a detrimental effect on biomolecular drug is avoided. By generating spray-dried silica particles encapsulating the high molecular weight model compound FITC-dextran 150 via the nano spray dryer Büchi-90, we demonstrated how formulation parameters affect and enable control of drug release properties. The implemented strategies to regulate release included incorporating different quantities of dextrans with varying molecular weight as well as adjusting the pH of the precursor solution to modify the internal microstructures. The addition of dextran significantly altered the released amount, while the release became faster with increasing dextran molecular weight. A sustained release over 35days could be achieved with addition of 60 kD dextran. The rate of FITC-Dextran 150 release from the dextran 60 containing particles decreased with higher precursor solution pH. In conclusion, the new precursor TMEOS presents a promising alternative sol-gel technology based carrier material for sustained release application of high molecular weight biopharmaceutical drugs. Copyright © 2017 Elsevier B.V. All rights reserved.

LBMR: Load-Balanced Multipath Routing for Wireless Data-Intensive Transmission in Real-Time Medical Monitoring.

PubMed

Tseng, Chinyang Henry

2016-05-31

In wireless networks, low-power Zigbee is an excellent network solution for wireless medical monitoring systems. Medical monitoring generally involves transmission of a large amount of data and easily causes bottleneck problems. Although Zigbee's AODV mesh routing provides extensible multi-hop data transmission to extend network coverage, it originally does not, and needs to support some form of load balancing mechanism to avoid bottlenecks. To guarantee a more reliable multi-hop data transmission for life-critical medical applications, we have developed a multipath solution, called Load-Balanced Multipath Routing (LBMR) to replace Zigbee's routing mechanism. LBMR consists of three main parts: Layer Routing Construction (LRC), a Load Estimation Algorithm (LEA), and a Route Maintenance (RM) mechanism. LRC assigns nodes into different layers based on the node's distance to the medical data gateway. Nodes can have multiple next-hops delivering medical data toward the gateway. All neighboring layer-nodes exchange flow information containing current load, which is the used by the LEA to estimate future load of next-hops to the gateway. With LBMR, nodes can choose the neighbors with the least load as the next-hops and thus can achieve load balancing and avoid bottlenecks. Furthermore, RM can detect route failures in real-time and perform route redirection to ensure routing robustness. Since LRC and LEA prevent bottlenecks while RM ensures routing fault tolerance, LBMR provides a highly reliable routing service for medical monitoring. To evaluate these accomplishments, we compare LBMR with Zigbee's AODV and another multipath protocol, AOMDV. The simulation results demonstrate LBMR achieves better load balancing, less unreachable nodes, and better packet delivery ratio than either AODV or AOMDV.

LBMR: Load-Balanced Multipath Routing for Wireless Data-Intensive Transmission in Real-Time Medical Monitoring

PubMed Central

Tseng, Chinyang Henry

2016-01-01

In wireless networks, low-power Zigbee is an excellent network solution for wireless medical monitoring systems. Medical monitoring generally involves transmission of a large amount of data and easily causes bottleneck problems. Although Zigbee’s AODV mesh routing provides extensible multi-hop data transmission to extend network coverage, it originally does not, and needs to support some form of load balancing mechanism to avoid bottlenecks. To guarantee a more reliable multi-hop data transmission for life-critical medical applications, we have developed a multipath solution, called Load-Balanced Multipath Routing (LBMR) to replace Zigbee’s routing mechanism. LBMR consists of three main parts: Layer Routing Construction (LRC), a Load Estimation Algorithm (LEA), and a Route Maintenance (RM) mechanism. LRC assigns nodes into different layers based on the node’s distance to the medical data gateway. Nodes can have multiple next-hops delivering medical data toward the gateway. All neighboring layer-nodes exchange flow information containing current load, which is the used by the LEA to estimate future load of next-hops to the gateway. With LBMR, nodes can choose the neighbors with the least load as the next-hops and thus can achieve load balancing and avoid bottlenecks. Furthermore, RM can detect route failures in real-time and perform route redirection to ensure routing robustness. Since LRC and LEA prevent bottlenecks while RM ensures routing fault tolerance, LBMR provides a highly reliable routing service for medical monitoring. To evaluate these accomplishments, we compare LBMR with Zigbee’s AODV and another multipath protocol, AOMDV. The simulation results demonstrate LBMR achieves better load balancing, less unreachable nodes, and better packet delivery ratio than either AODV or AOMDV. PMID:27258297

Solution-phase synthesis of nanomaterials at low temperature

NASA Astrophysics Data System (ADS)

Zhu, Yongchun; Qian, Yitai

2009-01-01

This paper reviews the solution-phase synthesis of nanoparticles via some routes at low temperatures, such as room temperature route, wave-assisted synthesis (γ-irradiation route and sonochemical route), directly heating at low temperatures, and hydrothermal/solvothermal methods. A number of strategies were developed to control the shape, the size, as well as the dispersion of nanostructures. Using diethylamine or n-butylamine as solvent, semiconductor nanorods were yielded. By the hydrothermal treatment of amorphous colloids, Bi2S3 nanorods and Se nanowires were obtained. CdS nanowires were prepared in the presence of polyacrylamide. ZnS nanowires were obtained using liquid crystal. The polymer poly (vinyl acetate) tubule acted as both nanoreactor and template for the CdSe nanowire growth. Assisted by the surfactant of sodium dodecyl benzenesulfonate (SDBS), nickel nanobelts were synthesized. In addition, Ag nanowires, Te nanotubes and ZnO nanorod arrays could be prepared without adding any additives or templates.

Approximate solution of the multiple watchman routes problem with restricted visibility range.

PubMed

Faigl, Jan

2010-10-01

In this paper, a new self-organizing map (SOM) based adaptation procedure is proposed to address the multiple watchman route problem with the restricted visibility range in the polygonal domain W. A watchman route is represented by a ring of connected neuron weights that evolves in W, while obstacles are considered by approximation of the shortest path. The adaptation procedure considers a coverage of W by the ring in order to attract nodes toward uncovered parts of W. The proposed procedure is experimentally verified in a set of environments and several visibility ranges. Performance of the procedure is compared with the decoupled approach based on solutions of the art gallery problem and the consecutive traveling salesman problem. The experimental results show the suitability of the proposed procedure based on relatively simple supporting geometrical structures, enabling application of the SOM principles to watchman route problems in W.

Surfactant-assisted Nanocasting Route for Synthesis of Highly Ordered Mesoporous Graphitic Carbon and Its Application in CO2 Adsorption

NASA Astrophysics Data System (ADS)

Wang, Yangang; Bai, Xia; Wang, Fei; Qin, Hengfei; Yin, Chaochuang; Kang, Shifei; Li, Xi; Zuo, Yuanhui; Cui, Lifeng

2016-05-01

Highly ordered mesoporous graphitic carbon was synthesized from a simple surfactant-assisted nanocasting route, in which ordered mesoporous silica SBA-15 maintaining its triblock copolymer surfactant was used as a hard template and natural soybean oil (SBO) as a carbon precursor. The hydrophobic domain of the surfactant assisted SBO in infiltration into the template’s mesoporous channels. After the silica template was carbonized and removed, a higher yield of highly-ordered graphitic mesoporous carbon with rod-like morphology was obtained. Because of the improved structural ordering, the mesoporous carbon after amine modification could adsorb more CO2 compared with the amine-functionalized carbon prepared without the assistance of surfactant.

Binary ferrihydrite catalysts

DOEpatents

Huffman, G.P.; Zhao, J.; Feng, Z.

1996-12-03

A method of preparing a catalyst precursor comprises dissolving an iron salt and a salt of an oxoanion forming agent, in water so that a solution of the iron salt and oxoanion forming agent salt has a ratio of oxoanion/Fe of between 0.0001:1 to 0.5:1. Next is increasing the pH of the solution to 10 by adding a strong base followed by collecting of precipitate having a binary ferrihydrite structure. A binary ferrihydrite catalyst precursor is also prepared by dissolving an iron salt in water. The solution is brought to a pH of substantially 10 to obtain ferrihydrite precipitate. The precipitate is then filtered and washed with distilled water and subsequently admixed with a hydroxy carboxylic acid solution. The admixture is mixed/agitated and the binary ferrihydrite precipitate is then filtered and recovered. 3 figs.

Routing a High Value Unit for Optimized Missile Defense in Coastal Waters

DTIC Science & Technology

2008-03-01

model ( XRP ), whose solution yields an optimal transit path for the CSG through a notional sea space called the “area of transit” (AT). XRP discretizes... XRP calculates and then writes to a text file the maximum-reliability route through the AT by vertex location, configuration, and direction of travel...in order to keep this research unclassified, no real threat data, such as probabilities of kill, are used. The XRP solution algorithm is written in

Combined Simulated Annealing and Genetic Algorithm Approach to Bus Network Design

NASA Astrophysics Data System (ADS)

Liu, Li; Olszewski, Piotr; Goh, Pong-Chai

A new method - combined simulated annealing (SA) and genetic algorithm (GA) approach is proposed to solve the problem of bus route design and frequency setting for a given road network with fixed bus stop locations and fixed travel demand. The method involves two steps: a set of candidate routes is generated first and then the best subset of these routes is selected by the combined SA and GA procedure. SA is the main process to search for a better solution to minimize the total system cost, comprising user and operator costs. GA is used as a sub-process to generate new solutions. Bus demand assignment on two alternative paths is performed at the solution evaluation stage. The method was implemented on four theoretical grid networks of different size and a benchmark network. Several GA operators (crossover and mutation) were utilized and tested for their effectiveness. The results show that the proposed method can efficiently converge to the optimal solution on a small network but computation time increases significantly with network size. The method can also be used for other transport operation management problems.

Synergistic Malaria Parasite Killing by Two Types of Plasmodial Surface Anion Channel Inhibitors

PubMed Central

Pain, Margaret; Fuller, Alexandra W.; Basore, Katherine; Pillai, Ajay D.; Solomon, Tsione; Bokhari, Abdullah A. B.; Desai, Sanjay A.

2016-01-01

Malaria parasites increase their host erythrocyte’s permeability to a broad range of ions and organic solutes. The plasmodial surface anion channel (PSAC) mediates this uptake and is an established drug target. Development of therapies targeting this channel is limited by several problems including interactions between known inhibitors and permeating solutes that lead to incomplete channel block. Here, we designed and executed a high-throughput screen to identify a novel class of PSAC inhibitors that overcome this solute-inhibitor interaction. These new inhibitors differ from existing blockers and have distinct effects on channel-mediated transport, supporting a model of two separate routes for solute permeation though PSAC. Combinations of inhibitors specific for the two routes had strong synergistic action against in vitro parasite propagation, whereas combinations acting on a single route produced only additive effects. The magnitude of synergism depended on external nutrient concentrations, consistent with an essential role of the channel in parasite nutrient acquisition. The identified inhibitors will enable a better understanding of the channel’s structure-function and may be starting points for novel combination therapies that produce synergistic parasite killing. PMID:26866812

Scheduling of an aircraft fleet

NASA Technical Reports Server (NTRS)

Paltrinieri, Massimo; Momigliano, Alberto; Torquati, Franco

1992-01-01

Scheduling is the task of assigning resources to operations. When the resources are mobile vehicles, they describe routes through the served stations. To emphasize such aspect, this problem is usually referred to as the routing problem. In particular, if vehicles are aircraft and stations are airports, the problem is known as aircraft routing. This paper describes the solution to such a problem developed in OMAR (Operative Management of Aircraft Routing), a system implemented by Bull HN for Alitalia. In our approach, aircraft routing is viewed as a Constraint Satisfaction Problem. The solving strategy combines network consistency and tree search techniques.

Extreme and superextreme events in a loss-modulated CO2 laser: Nonlinear resonance route and precursors

NASA Astrophysics Data System (ADS)

Bonatto, Cristian; Endler, Antonio

2017-07-01

We investigate the occurrence of extreme and rare events, i.e., giant and rare light pulses, in a periodically modulated CO2 laser model. Due to nonlinear resonant processes, we show a scenario of interaction between chaotic bands of different orders, which may lead to the formation of extreme and rare events. We identify a crisis line in the modulation parameter space, and we show that, when the modulation amplitude increases, remaining in the vicinity of the crisis, some statistical properties of the laser pulses, such as the average and dispersion of amplitudes, do not change much, whereas the amplitude of extreme events grows enormously, giving rise to extreme events with much larger deviations than usually reported, with a significant probability of occurrence, i.e., with a long-tailed non-Gaussian distribution. We identify recurrent regular patterns, i.e., precursors, that anticipate the emergence of extreme and rare events, and we associate these regular patterns with unstable periodic orbits embedded in a chaotic attractor. We show that the precursors may or may not lead to the emergence of extreme events. Thus, we compute the probability of success or failure (false alarm) in the prediction of the extreme events, once a precursor is identified in the deterministic time series. We show that this probability depends on the accuracy with which the precursor is identified in the laser intensity time series.

Polymer/Nanocrystal Hybrid Solar Cells: Influence of Molecular Precursor Design on Film Nanomorphology, Charge Generation and Device Performance

PubMed Central

MacLachlan, Andrew J; Rath, Thomas; Cappel, Ute B; Dowland, Simon A; Amenitsch, Heinz; Knall, Astrid-Caroline; Buchmaier, Christine; Trimmel, Gregor; Nelson, Jenny; Haque, Saif A

2015-01-01

In this work, molecular tuning of metal xanthate precursors is shown to have a marked effect on the heterojunction morphology of hybrid poly(3-hexylthiophene-2,5-diyl) (P3HT)/CdS blends and, as a result, the photochemical processes and overall performance of in situ fabricated hybrid solar cells. A series of cadmium xanthate complexes is synthesized for use as in situ precursors to cadmium sulfide nanoparticles in hybrid P3HT/CdS solar cells. The formation of CdS domains is studied by simultaneous GIWAXS (grazing incidence wide-angle X-ray scattering) and GISAXS (grazing incidence small-angle X-ray scattering), revealing knowledge about crystal growth and the formation of different morphologies observed using TEM (transmission electron microscopy). These measurements show that there is a strong relationship between precursor structure and heterojunction nanomorphology. A combination of TAS (transient absorption spectroscopy) and photovoltaic device performance measurements is used to show the intricate balance required between charge photogeneration and percolated domains in order to effectively extract charges to maximize device power conversion efficiencies. This study presents a strong case for xanthate complexes as a useful route to designing optimal heterojunction morphologies for use in the emerging field of hybrid organic/inorganic solar cells, due to the fact that the nanomorphology can be tuned via careful design of these precursor materials. PMID:25866496

E-beam and UV induced fabrication of CeO2, Eu2O3 and their mixed oxides with UO2

NASA Astrophysics Data System (ADS)

Pavelková, Tereza; Vaněček, Vojtěch; Jakubec, Ivo; Čuba, Václav

2016-07-01

CeO2, Eu2O3 and mixed oxides of CeO2-UO2, Eu2O3-UO2 were fabricated. The preparative method was based on the irradiation of aqueous solutions containing cerium/europium (and uranyl) nitrates and ammonium formate. In the course of irradiation, the solid phase (precursor) was precipitated. The composition of irradiated solutions significantly affected the properties of precursor formed in the course of the irradiation. However, subsequent heat treatment of (amorphous) precursors at temperatures ≤650 °C invariably resulted in the formation of powder oxides with well-developed nanocrystals with linear crystallite size 13-27 nm and specific surface area 10-46 m2 g-1. The applicability of both ionizing (e-beam) and non-ionizing (UV) radiation was studied.

Nonequilibrium radiation and chemistry models for aerocapture vehicle flowfields, volume 3

NASA Technical Reports Server (NTRS)

Carlson, Leland A.

1991-01-01

The computer programs developed to calculate the shock wave precursor and the method of using them are described. This method calculated the precursor flow field in a nitrogen gas including the effects of emission and absorption of radiation on the energy and composition of gas. The radiative transfer is calculated including the effects of absorption and emission through the line as well as the continuum process in the shock layer and through the continuum processes only in the precursor. The effects of local thermodynamic nonequilibrium in the shock layer and precursor regions are also included in the radiative transfer calculations. Three computer programs utilized by this computational scheme to calculate the precursor flow field solution for a given shock layer flow field are discussed.

Nonreciprocal Signal Routing in an Active Quantum Network

NASA Astrophysics Data System (ADS)

Tureci, Hakan E.; Metelmann, Anja

As superconductor quantum technologies are moving towards large-scale integrated circuits, a robust and flexible approach to routing photons at the quantum level becomes a critical problem. Active circuits, which contain driven linear or non-linear elements judiciously embedded in the circuit offer a viable solution. We present a general strategy for routing non-reciprocally quantum signals between two sites of a given lattice of resonators, implementable with existing superconducting circuit components. Our approach makes use of a dual lattice of superconducting non-linear elements on the links connecting the nodes of the main lattice. Solutions for spatially selective driving of the link-elements can be found, which optimally balance coherent and dissipative hopping of microwave photons to non-reciprocally route signals between two given nodes. In certain lattices these optimal solutions are obtained at the exceptional point of the scattering matrix of the network. The presented strategy provides a design space that is governed by a dynamically tunable non-Hermitian generator that can be used to minimize the added quantum noise as well. This work was supported by the U.S. Army Research Office (ARO) under Grant No. W911NF-15-1-0299.

Computational investigation of intense short-wavelength laser interaction with rare gas clusters

NASA Astrophysics Data System (ADS)

Bigaouette, Nicolas

Current Very High Temperature Reactor designs incorporate TRi-structural ISOtropic (TRISO) particle fuel, which consists of a spherical fissile fuel kernel surrounded by layers of pyrolytic carbon and silicon carbide. An internal sol-gel process forms the fuel kernel by dropping a cold precursor solution into a column of hot trichloroethylene (TCE). The temperature difference drives the liquid precursor solution to precipitate the metal solution into gel spheres before reaching the bottom of a production column. Over time, gelation byproducts inhibit complete gelation and the TCE must be purified or discarded. The resulting mixed-waste stream is expensive to dispose of or recycle, and changing the forming fluid to a non-hazardous alternative could greatly improve the economics of kernel production. Selection criteria for a replacement forming fluid narrowed a list of ~10,800 chemicals to yield ten potential replacements. The physical properties of the alternatives were measured as a function of temperature between 25 °C and 80 °C. Calculated terminal velocities and heat transfer rates provided an overall column height approximation. 1-bromotetradecane, 1-chlorooctadecane, and 1-iodododecane were selected for further testing, and surrogate yttria-stabilized zirconia (YSZ) kernels were produced using these selected fluids. The kernels were characterized for density, geometry, composition, and crystallinity and compared to a control group of kernels produced in silicone oil. Production in 1-bromotetradecane showed positive results, producing dense (93.8 %TD) and spherical (1.03 aspect ratio) kernels, but proper gelation did not occur in the other alternative forming fluids. With many of the YSZ kernels not properly gelling within the length of the column, this project further investigated the heat transfer properties of the forming fluids and precursor solution. A sensitivity study revealed that the heat transfer properties of the precursor solution have the strongest impact on gelation time. A COMSOL heat transfer model estimated an effective thermal diffusivity range for the YSZ precursor solution as 1.13x10 -8 m2/s to 3.35x10-8 m 2/s, which is an order of magnitude smaller than the value used in previous studies. 1-bromotetradecane is recommended for further investigation with the production of uranium-based kernels.

On the formulation and solution of an emergency routing problem.

DOT National Transportation Integrated Search

2007-10-01

In this work, we will identify important variables that contribute to : vehicular movement in an emergency environment. In particular, we for- : mulate and pose the Convoy Routing Problem (using far fewer variables : than other important models witho...

A Sharp methodology for VLSI layout

NASA Astrophysics Data System (ADS)

Bapat, Shekhar

1993-01-01

The layout problem for VLSI circuits is recognized as a very difficult problem and has been traditionally decomposed into the several seemingly independent sub-problems of placement, global routing, and detailed routing. Although this structure achieves a reduction in programming complexity, it is also typically accompanied by a reduction in solution quality. Most current placement research recognizes that the separation is artificial, and that the placement and routing problems should be solved ideally in tandem. We propose a new interconnection model, Sharp and an associated partitioning algorithm. The Sharp interconnection model uses a partitioning shape that roughly resembles the musical sharp 'number sign' and makes extensive use of pre-computed rectilinear Steiner trees. The model is designed to generate strategic routing information along with the partitioning results. Additionally, the Sharp model also generates estimates of the routing congestion. We also propose the Sharp layout heuristic that solves the layout problem in its entirety. The Sharp layout heuristic makes extensive use of the Sharp partitioning model. The use of precomputed Steiner tree forms enables the method to model accurately net characteristics. For example, the Steiner tree forms can model both the length of the net and more importantly its route. In fact, the tree forms are also appropriate for modeling the timing delays of nets. The Sharp heuristic works to minimize both the total layout area by minimizing total net length (thus reducing the total wiring area), and the congestion imbalances in the various channels (thus reducing the unused or wasted channel area). Our heuristic uses circuit element movements amongst the different partitioning blocks and selection of alternate minimal Steiner tree forms to achieve this goal. The objective function for the algorithm can be modified readily to include other important circuit constraints like propagation delays. The layout technique first computes a very high-level approximation of the layout solution (i.e., the positions of the circuit elements and the associated net routes). The approximate solution is alternately refined, objective function. The technique creates well defined sub-problems and offers intermediary steps that can be solved in parallel, as well as a parallel mechanism to merge the sub-problem solutions.

Ceramics Derived from Organo-Metallic Precursors

DTIC Science & Technology

1991-10-01

spraying, and roller-coating may also be used to good effect . The films deposited by any of these techniques are ready to be fired immediately...films. The wet chemical route offers great potential for highly cost- effective processing; and the critical issue for its wide-scale implementation is...glasses and subsequently to crystallize single phase HTSC materials. The fourth composition, 4223, was made in order to test the effect of Bi on glass

Design of Polymers with Semiconductor, NLO and Structural Properties.

DTIC Science & Technology

1991-04-22

polymer thin films. + 14 KV Needle electrod Polymer layer ITO electrode Substrate Heater and temperature control unit The second harmonic coefficients of...the solubily and processability through utilization of derivitization and precursor routes we have been able to form the first optical quality films...ethylene spacer, and therefore 14 possesses a great degree of solubility in organic solvents, necessary for the fabrication of optical quality thin films

Stereocontrolled synthesis of polyhydroxylated bicyclic azetidines as a new class of iminosugars.

PubMed

Malinowski, Maciej; Hensienne, Raphaël; Kern, Nicolas; Tardieu, Damien; Bodlenner, Anne; Hazelard, Damien; Compain, Philippe

2018-06-12

We report herein the development of a stereodivergent route towards polyhydroxylated bicyclic azetidine scaffolds, namely 6-azabicyclo[3.2.0]heptane derivatives. The strategy hinges on a common bicyclic β-lactam precursor, which is forged by way of a rare example of a cationic Dieckmann-type reaction, followed by IBX-mediated desaturation. Substrate-controlled diastereoselective oxidations then allow the divergent preparation of novel iminosugar mimics.

High-performance and scalable metal-chalcogenide semiconductors and devices via chalco-gel routes

PubMed Central

Jo, Jeong-Wan; Kim, Hee-Joong; Kwon, Hyuck-In; Kim, Jaekyun; Ahn, Sangdoo; Kim, Yong-Hoon; Lee, Hyung-ik

2018-01-01

We report a general strategy for obtaining high-quality, large-area metal-chalcogenide semiconductor films from precursors combining chelated metal salts with chalcoureas or chalcoamides. Using conventional organic solvents, such precursors enable the expeditious formation of chalco-gels, which are easily transformed into the corresponding high-performance metal-chalcogenide thin films with large, uniform areas. Diverse metal chalcogenides and their alloys (MQx: M = Zn, Cd, In, Sb, Pb; Q = S, Se, Te) are successfully synthesized at relatively low processing temperatures (<400°C). The versatility of this scalable route is demonstrated by the fabrication of large-area thin-film transistors (TFTs), optoelectronic devices, and integrated circuits on a 4-inch Si wafer and 2.5-inch borosilicate glass substrates in ambient air using CdS, CdSe, and In2Se3 active layers. The CdSe TFTs exhibit a maximum field-effect mobility greater than 300 cm2 V−1 s−1 with an on/off current ratio of >107 and good operational stability (threshold voltage shift < 0.5 V at a positive gate bias stress of 10 ks). In addition, metal chalcogenide–based phototransistors with a photodetectivity of >1013 Jones and seven-stage ring oscillators operating at a speed of ~2.6 MHz (propagation delay of < 27 ns per stage) are demonstrated. PMID:29662951

Growth mechanisms of MgO nanocrystals via a sol-gel synthesis using different complexing agents

PubMed Central

2014-01-01

In the preparation of nanostructured materials, it is important to optimize synthesis parameters in order to obtain the desired material. This work investigates the role of complexing agents, oxalic acid and tartaric acid, in the production of MgO nanocrystals. Results from simultaneous thermogravimetric analysis (STA) show that the two different synthesis routes yield precursors with different thermal profiles. It is found that the thermal profiles of the precursors can reveal the effects of crystal growth during thermal annealing. X-ray diffraction confirms that the final products are pure, single phase and of cubic shape. It is also found that complexing agents can affect the rate of crystal growth. The structures of the oxalic acid and tartaric acid as well as the complexation sites play very important roles in the formation of the nanocrystals. The complexing agents influence the rate of growth which affects the final crystallite size of the materials. Surprisingly, it is also found that oxalic acid and tartaric acid act as surfactants inhibiting crystal growth even at a high temperature of 950°C and a long annealing time of 36 h. The crystallite formation routes are proposed to be via linear and branched polymer networks due to the different structures of the complexing agents. PMID:24650322

A Phosphine-Free Route to Size-Adjustable CdSe and CdSe/CdS Core-Shell Quantum Dots for White-Light-Emitting Diodes.

PubMed

Zhang, Yugang; Li, Guopeng; Zhang, Ting; Song, Zihang; Wang, Hui; Zhang, Zhongping; Jiang, Yang

2018-03-01

The selenium dioxide was used as the precursor to synthesize wide-size-ranged CdSe quantum dots (2.4-5.7 nm) via hot-injection route. The CdSe quantum dots are featured with high crystalline, monodisperse, zinc blende structure and wide emission region (530-635 nm). In order to improve the stability and quantum yield, a phosphine-free single-molecular precursor approach is used to obtain CdSe/CdS core/shell quantum dots. The CdSe/CdS quantum dots are highly fluorescent with quantum yield up to 65%, and persist the good monodispersity and high crystallinity. Moreover, the quantum dots white light-emitting-diodes are fabricated by using the resultant red emission core/shell quantum dots and Y3Al5O12:Ce3+ yellow phosphors as color-conversion layers on a blue InGaN chip. The prepared light-emitting-diodes show good performance with CIE-1931 coordinated of (0.3583, 0.3349), an Ra of 92.9, and a Tc of 4410 K at 20 mA, which indicate that the combination of red-emission QDs and yellow phophors as a promising approach to obtain warm WLEDs with good color rendering.

Recent advances in the metabolic engineering of microorganisms for the production of 3-hydroxypropionic acid as C3 platform chemical.

PubMed

Valdehuesa, Kris Niño G; Liu, Huaiwei; Nisola, Grace M; Chung, Wook-Jin; Lee, Seung Hwan; Park, Si Jae

2013-04-01

Development of sustainable technologies for the production of 3-hydroxypropionic acid (3HP) as a platform chemical has recently been gaining much attention owing to its versatility in applications for the synthesis of other specialty chemicals. Several proposed biological synthesis routes and strategies for producing 3HP from glucose and glycerol are reviewed presently. Ten proposed routes for 3HP production from glucose are described and one of which was recently constructed successfully in Escherichia coli with malonyl-Coenzyme A as a precursor. This resulted in a yield still far from the required level for industrial application. On the other hand, strategies employing engineered E. coli and Klebsiella pneumoniae capable of producing 3HP from glycerol are also evaluated. The titers produced by these recombinant strains reached around 3 %. At its current state, it is evident that a bulk of engineering works is yet to be done to acquire a biosynthesis route for 3HP that is acceptable for industrial-scale production.

Condensation polyimides

NASA Technical Reports Server (NTRS)

Hergenrother, P. M.

1989-01-01

Polyimides belong to a class of polymers known as polyheterocyclics. Unlike most other high temperature polymers, polyimides can be prepared from a variety of inexpensive monomers by several synthetic routes. The glass transition and crystalline melt temperature, thermooxidative stability, toughness, dielectric constant, coefficient of thermal expansion, chemical stability, mechanical performance, etc. of polyimides can be controlled within certain boundaries. This versatility has permitted the development of various forms of polyimides. These include adhesives, composite matrices, coatings, films, moldings, fibers, foams and membranes. Polyimides are synthesized through both condensation (step-polymerization) and addition (chain growth polymerization) routes. The precursor materials used in addition polyimides or imide oligomers are prepared by condensation method. High molecular weight polyimide made via polycondensation or step-growth polymerization is studied. The various synthetic routes to condensation polyimides, structure/property relationships of condensation polyimides and composite properties of condensation polyimides are all studied. The focus is on the synthesis and chemical structure/property relationships of polyimides with particular emphasis on materials for composite application.

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.

Organic-Inorganic Hybrids Using Novel Phenylethynyl Imide Silanes

NASA Technical Reports Server (NTRS)

Park, C.; Lowther, S. E.; Smith, J. G., Jr.

2001-01-01

In this presentation, polyimide-silica hybrids using novel phenylethynyl imide silanes are reported. The phenylethynyl group is present in the organic precursor as either a pendent or an end group to bond chemically with the polyimide adhesive containing phenylethynyl groups during processing, while the silane group of the organic precursor would chemically react with the inorganic precursor through oxane bond formation. The chemical compositions of these novel hybrids were examined using X-ray mapping modes of scanning electron microscopy (SEM), which revealed a silicon gradient interphase between the high surface energy substrate and the polyimide adhesive. Novel aromatic phenylethynyl imide silanes (APEISs) and pendent phenylethynyl imide oligomeric disilanes (PPEIDSs) have been synthesized, and sol-gel solutions containing the new silanes, a phenylethynyl terminated imide oligomer (PETI-5), and an inorganic precursor were formulated to develop a gradient hybrid interphase between a titanium alloy and the adhesive. Two different sol-gel systems were investigated to develop organic-inorganic hybrids. Hybrid I was composed of an organic precursor containing both phenylethynyl and silane groups (PPEIDS) and an inorganic precursor. Functional group concentrations were controlled by the variation of the molecular weight of the imide backbone of PPEIDS. Hybrid II was composed of organic and inorganic precursors and a coupling agent containing both phenylethynyl and silane groups. Morphology and chemical composition of the hybrid interphase between the inorganic substrate and the adhesive were investigated, and the bond strength and durability were evaluated using lap shear tests at various conditions. The assessment of how the bonding at an interface is affected by various sol-gel solution compositions and environments is reported.

Pseudo-Capacitors: SPPS Deposition and Electrochemical Analysis of α-MoO3 and Mo2N Coatings

NASA Astrophysics Data System (ADS)

Golozar, Mehdi; Chien, Ken; Lian, Keryn; Coyle, Thomas W.

2013-06-01

Solution precursor plasma spraying (SPPS) is a novel thermal spray process in which a solution precursor is injected into the high-temperature zone of a DC-arc plasma jet to allow solvent evaporation from the precursor droplets, solute precipitation, and precipitate pyrolysis prior to substrate impact. This investigation explored the potential of SPPS to fabricate α-MoO3 coatings with fine grain sizes, high porosity levels, and high surface area: characteristics needed for application as pseudo-capacitor electrodes. Since molybdenum nitride has shown a larger electrochemical stability window and higher specific area capacitance, the α-MoO3 deposits were subsequently converted into molybdenum nitride. A multistep heat-treatment procedure resulted in a topotactic phase-transformation mechanism, which retained the high surface area lath-shaped features of the original α-MoO3. The electrochemical behaviors of molybdenum oxide and molybdenum nitride deposits formed under different deposition conditions were studied using cyclic voltammetry to assess the influence of the resulting microstructure on the charge storage behavior and potential for use in pseudo-capacitors.

Fabrication of Semiconducting Methylammonium Lead Halide Perovskite Particles by Spray Technology

NASA Astrophysics Data System (ADS)

Ahmadian-Yazdi, Mohammad-Reza; Eslamian, Morteza

2018-01-01

In this "nano idea" paper, three concepts for the preparation of methylammonium lead halide perovskite particles are proposed, discussed, and tested. The first idea is based on the wet chemistry preparation of the perovskite particles, through the addition of the perovskite precursor solution to an anti-solvent to facilitate the precipitation of the perovskite particles in the solution. The second idea is based on the milling of a blend of the perovskite precursors in the dry form, in order to allow for the conversion of the precursors to the perovskite particles. The third idea is based on the atomization of the perovskite solution by a spray nozzle, introducing the spray droplets into a hot wall reactor, so as to prepare perovskite particles, using the droplet-to-particle spray approach (spray pyrolysis). Preliminary results show that the spray technology is the most successful method for the preparation of impurity-free perovskite particles and perovskite paste to deposit perovskite thin films. As a proof of concept, a perovskite solar cell with the paste prepared by the sprayed perovskite powder was successfully fabricated.

Fabrication of Semiconducting Methylammonium Lead Halide Perovskite Particles by Spray Technology.

PubMed

Ahmadian-Yazdi, Mohammad-Reza; Eslamian, Morteza

2018-01-10

In this "nano idea" paper, three concepts for the preparation of methylammonium lead halide perovskite particles are proposed, discussed, and tested. The first idea is based on the wet chemistry preparation of the perovskite particles, through the addition of the perovskite precursor solution to an anti-solvent to facilitate the precipitation of the perovskite particles in the solution. The second idea is based on the milling of a blend of the perovskite precursors in the dry form, in order to allow for the conversion of the precursors to the perovskite particles. The third idea is based on the atomization of the perovskite solution by a spray nozzle, introducing the spray droplets into a hot wall reactor, so as to prepare perovskite particles, using the droplet-to-particle spray approach (spray pyrolysis). Preliminary results show that the spray technology is the most successful method for the preparation of impurity-free perovskite particles and perovskite paste to deposit perovskite thin films. As a proof of concept, a perovskite solar cell with the paste prepared by the sprayed perovskite powder was successfully fabricated.

Simultaneous detection and quantitation of organic impurities in methamphetamine by ultra-high-performance liquid chromatography-tandem mass spectrometry, a complementary technique for methamphetamine profiling.

PubMed

Li, Li; Brown, Jaclyn L; Toske, Steven G

2018-04-06

The analysis of organic impurities plays an important role in the impurity profiling of methamphetamine, which in turn provides valuable information about methamphetamine manufacturing, in particular its synthetic route, chemicals, and precursors used. Ultra-high-performance liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS) is ideally suited for this purpose due to its excellent sensitivity, selectivity, and wide linear range in multiple reaction monitoring (MRM) mode. In this study, a dilute-and-shoot UHPLC-MS/MS method was developed for the simultaneous identification and quantitation of 23 organic manufacturing impurities in illicit methamphetamine. The developed method was validated in terms of stability, limit of detection (LOD), lower limit of quantification (LLOQ), accuracy, and precision. More than 100 illicitly prepared methamphetamine samples were analyzed. Due to its ability to detect ephedrine/pseudoephedrine and its high sensitivity for critical target markers (eg, chloro-pseudoephedrine, N-cyclohexylamphetamine, and compounds B and P), more impurities and precursor/pre-precursors were identified and quantified versus the current procedure by gas chromatography-mass spectrometry (GC-MS). Consequently, more samples could be classified by their synthetic routes. However, the UHPLC-MS/MS method has difficulty in detecting neutral and untargeted emerging manufacturing impurities and can therefore only serve as a complement to the current method. Despite this deficiency, the quantitative information acquired by the presented UHPLC-MS/MS methodology increased the sample discrimination power, thereby enhancing the capacity of methamphetamine profiling program (MPP) to conduct sample-sample comparisons. Published 2018. This article is a U.S. Government work and is in the public domain in the USA.

Identification of specific markers for amphetamine synthesised from the pre-precursor APAAN following the Leuckart route and retrospective search for APAAN markers in profiling databases from Germany and the Netherlands.

PubMed

Hauser, Frank M; Rößler, Thorsten; Hulshof, Janneke W; Weigel, Diana; Zimmermann, Ralf; Pütz, Michael

2018-04-01

α-Phenylacetoacetonitrile (APAAN) is one of the most important pre-precursors for amphetamine production in recent years. This assumption is based on seizure data but there is little analytical data available showing how much amphetamine really originated from APAAN. In this study, several syntheses of amphetamine following the Leuckart route were performed starting from different organic compounds including APAAN. The organic phases were analysed using gas chromatography-mass spectrometry (GC-MS) to search for signals caused by possible APAAN markers. Three compounds were discovered, isolated, and based on the performed syntheses it was found that they are highly specific for the use of APAAN. Using mass spectra, high resolution MS and nuclear magnetic resonance (NMR) data the compounds were characterised and identified as 2-phenyl-2-butenenitrile, 3-amino-2-phenyl-2-butenenitrile, and 4-amino-6-methyl-5-phenylpyrimidine. To investigate their significance, they were searched in data from seized amphetamine samples to determine to what extent they were present in illicitly produced amphetamine. Data of more than 580 cases from amphetamine profiling databases in Germany and the Netherlands were used for this purpose. These databases allowed analysis of the yearly occurrence of the markers going back to 2009. The markers revealed a trend that was in agreement with seizure reports and reflected an increasing use of APAAN from 2010 on. This paper presents experimental proof that APAAN is indeed the most important pre-precursor of amphetamine in recent years. It also illustrates how important it is to look for new ways to identify current trends in drug production since such trends can change within a few years. Copyright © 2017 John Wiley & Sons, Ltd.

Red Bell Pepper Chromoplasts Exhibit in Vitro Import Competency and Membrane Targeting of Passenger Proteins from the Thylakoidal Sec and ΔpH Pathways but Not the Chloroplast Signal Recognition Particle Pathway1

PubMed Central

Summer, Elizabeth J.; Cline, Kenneth

1999-01-01

Chloroplast to chromoplast development involves new synthesis and plastid localization of nuclear-encoded proteins, as well as changes in the organization of internal plastid membrane compartments. We have demonstrated that isolated red bell pepper (Capsicum annuum) chromoplasts contain the 75-kD component of the chloroplast outer envelope translocon (Toc75) and are capable of importing chloroplast precursors in an ATP-dependent fashion, indicating a functional general import apparatus. The isolated chromoplasts were able to further localize the 33- and 17-kD subunits of the photosystem II O2-evolution complex (OE33 and OE17, respectively), lumen-targeted precursors that utilize the thylakoidal Sec and ΔpH pathways, respectively, to the lumen of an internal membrane compartment. Chromoplasts contained the thylakoid Sec component protein, cpSecA, at levels comparable to chloroplasts. Routing of OE17 to the lumen was abolished by ionophores, suggesting that routing is dependent on a transmembrane ΔpH. The chloroplast signal recognition particle pathway precursor major photosystem II light-harvesting chlorophyll a/b protein failed to associate with chromoplast membranes and instead accumulated in the stroma following import. The Pftf (plastid fusion/translocation factor), a chromoplast protein, integrated into the internal membranes of chromoplasts during in vitro assays, and immunoblot analysis indicated that endogenous plastid fusion/translocation factor was also an integral membrane protein of chromoplasts. These data demonstrate that the internal membranes of chromoplasts are functional with respect to protein translocation on the thylakoid Sec and ΔpH pathways. PMID:9952453

Method for dispersing catalyst onto particulate material and product thereof

DOEpatents

Utz, Bruce R.; Cugini, Anthony V.

1992-01-01

A method for dispersing finely divided catalyst precursors onto the surface of coal or other particulate material includes the steps of forming a wet paste mixture of the particulate material and a liquid solution containing a dissolved transition metal salt, for instance a solution of ferric nitrate. The wet paste mixture is in a state of incipient wetness with all of this solution adsorbed onto the surfaces of the particulate material without the presence of free moisture. On adding a precipitating agent such as ammonia, a catalyst precursor such as hydrated iron oxide is deposited on the surfaces of the coal. The catalyst is activated by converting it to the sulfide form for the hydrogenation or direct liquefaction of the coal.

Method for dispersing catalyst onto particulate material

DOEpatents

Utz, Bruce R.; Cugini, Anthony V.

1992-01-01

A method for dispersing finely divided catalyst precursors onto the surface of coal or other particulate material includes the steps of forming a wet paste mixture of the particulate material and a liquid solution containing a dissolved transition metal salt, for instance a solution of ferric nitrate. The wet paste mixture is in a state of incipient wetness with all of this solution adsorbed onto the surfaces of the particulate material without the presence of free moisture. On adding a precipitating agent such as ammonia, a catalyst precursor such as hydrated iron oxide is deposited on the surfaces of the coal. The catalyst is activated by converting it to the sulfide form for the hydrogenation or direct liquefaction of the coal.

Wakes and precursor soliton excitations by a moving charged object in a plasma

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

Kumar Tiwari, Sanat, E-mail: sanat-tiwari@uiowa.edu; Department of Physics and Astronomy, University of Iowa, Iowa City, Iowa 52242; Sen, Abhijit, E-mail: senabhijit@gmail.com

2016-02-15

We study the evolution of nonlinear ion acoustic wave excitations due to a moving charged source in a plasma. Our numerical investigations of the full set of cold fluid equations go beyond the usual weak nonlinearity approximation and show the existence of a rich variety of solutions including wakes, precursor solitons, and “pinned” solitons that travel with the source velocity. These solutions represent a large amplitude generalization of solutions obtained in the past for the forced Korteweg deVries equation and can find useful applications in a variety of situations in the laboratory and in space, wherever there is a largemore » relative velocity between the plasma and a charged object.« less

A new approach on auxiliary vehicle assignment in capacitated location routing problem

NASA Astrophysics Data System (ADS)

Bashiri, Mahdi; Rasoulinejad, Zeinab; Fallahzade, Ehsan

2016-03-01

The location routing problem (LRP) considers locating depots and vehicle routing decisions simultaneously. In classic LRP the number of customers in each route depends on the capacity of the vehicle. In this paper a capacitated LRP model with auxiliary vehicle assignment is presented in which the length of each route is not restricted by main vehicle capacity. Two kinds of vehicles are considered: main vehicles with higher capacity and fixed cost and auxiliary vehicles with lower capacity and fixed cost. The auxiliary vehicles can be added to the transportation system as an alternative strategy to cover the capacity limitations and they are just used to transfer goods from depots to vehicles and cannot serve the customers by themselves. To show the applicability of the proposed model, some numerical examples derived from the well-known instances are used. Moreover the model has been solved by some meta-heuristics for large sized instances. The results show the efficiency of the proposed model and the solution approach, considering the classic model and the exact solution approach, respectively.

Entanglement-Gradient Routing for Quantum Networks.

PubMed

Gyongyosi, Laszlo; Imre, Sandor

2017-10-27

We define the entanglement-gradient routing scheme for quantum repeater networks. The routing framework fuses the fundamentals of swarm intelligence and quantum Shannon theory. Swarm intelligence provides nature-inspired solutions for problem solving. Motivated by models of social insect behavior, the routing is performed using parallel threads to determine the shortest path via the entanglement gradient coefficient, which describes the feasibility of the entangled links and paths of the network. The routing metrics are derived from the characteristics of entanglement transmission and relevant measures of entanglement distribution in quantum networks. The method allows a moderate complexity decentralized routing in quantum repeater networks. The results can be applied in experimental quantum networking, future quantum Internet, and long-distance quantum communications.

Removal efficiency of methylene blue using activated carbon from waste banana stem: Study on pH influence

NASA Astrophysics Data System (ADS)

Misran, E.; Bani, O.; Situmeang, E. M.; Purba, A. S.

2018-02-01

The effort to remove methylene blue in artificial solution had been conducted using adsorption process. The abundant banana stem waste was utilized as activated carbon precursor. This study aimed to analyse the influence of solution pH to removal efficiency of methylene blue using activated carbon from banana stem as adsorbent. Activated carbon from banana stem was obtained by chemical activation using H3PO4 solution. Proximate analysis result showed that the activated carbon has 47.22% of fixed carbon. This value exhibited that banana stem was a potential adsorbent precursor. Methylene blue solutions were prepared at initial concentration of 50 ppm. The influence of solution pH was investigated with the use of 0.2 g adsorbent for 100 mL dye solution. The adsorption was conducted using shaker with at a constant rate of 100 rpm at room temperature for 90 minutes. The results showed that solution pH influenced the adsorption. The activated carbon from banana stem demonstrated satisfying performance since removal efficiencies of methylene blue were higher than 99%.

Aqueous solution-chemical derived Nisbnd Al2O3 solar selective absorbing coatings. 2. Wetting agents and spreading of aqueous solutions on aluminum substrate

NASA Astrophysics Data System (ADS)

Li, Zhenxiang; Zhao, Jianxi

2013-03-01

Wettability of aluminum substrate by the aqueous solutions containing ethoxylated alcohol nonionic surfactants C12En- or Triton X-series was studied using dynamic contact angle measurements. The efficiency of wetting was found to strongly depend on the length of polyoxyethylene (POE) chain of C12En- or Triton X surfactants. For C12E4 that has a very short POE chain, it hardly made the aqueous solution spreading over aluminum. The others with a long POE chain were indeed very efficient in promoting the solution spreading. Moreover, all the spreading process could be completed within 10 s. The single-layer Nisbnd Al2O3 coatings were fabricated from the precursor solutions containing C12En- or Triton X surfactants and the reflectance spectra were measured by a UV/vis spectrophotometer equipped with an integrating sphere. The results indicated that the precursor solution with a long POE chain surfactant as wetting agent favored to fabricate a uniform film on the aluminum substrate and therefore to get a high solar absorptance.

Developing teaching process for enhancing students' mathematical problem solving in the 21st century through STEM education

NASA Astrophysics Data System (ADS)

Prawvichien, Sutthaporn; Siripun, Kulpatsorn; Yuenyong, Chokchai

2018-01-01

The STEM education could provide the context for students' learning in the 21st century. The Mathematical problem solving requires a context which simulates real life in order to give students experience of the power of mathematics in the world around them. This study aimed to develop the teaching process for enhancing students' mathematical problem solving in the 21st century through STEM education. The paper will clarify the STEM learning activities about graph theories regarding on the 6 steps of engineering design process. These include identify a challenge, exploring ideas, designing and planning, doing and developing, test and evaluate, and present the solution. The learning activities will start from the Identify a challenge stage which provides the northern part of Thailand flooding situation in order to set the students' tasks of develop the solutions of providing the routes of fastest moving people away from the flooding areas. The explore ideas stage will provide activities for enhance students to learn some knowledge based for designing the possible solutions. This knowledge based could focus on measuring, geometry, graph theory, and mathematical process. The design and plan stage will ask students to model the city based on the map and then provide the possible routes. The doing and development stage will ask students to develop the routes based on their possible model. The test and evaluating will ask students to clarify how to test and evaluate the possible routes, and then test it. The present solution stage will ask students to present the whole process of designing routes. Then, the paper will discuss how these learning activities could enhance students' mathematical problem solving. The paper may have implication for STEM education in school setting.

A set-covering based heuristic algorithm for the periodic vehicle routing problem.

PubMed

Cacchiani, V; Hemmelmayr, V C; Tricoire, F

2014-01-30

We present a hybrid optimization algorithm for mixed-integer linear programming, embedding both heuristic and exact components. In order to validate it we use the periodic vehicle routing problem (PVRP) as a case study. This problem consists of determining a set of minimum cost routes for each day of a given planning horizon, with the constraints that each customer must be visited a required number of times (chosen among a set of valid day combinations), must receive every time the required quantity of product, and that the number of routes per day (each respecting the capacity of the vehicle) does not exceed the total number of available vehicles. This is a generalization of the well-known vehicle routing problem (VRP). Our algorithm is based on the linear programming (LP) relaxation of a set-covering-like integer linear programming formulation of the problem, with additional constraints. The LP-relaxation is solved by column generation, where columns are generated heuristically by an iterated local search algorithm. The whole solution method takes advantage of the LP-solution and applies techniques of fixing and releasing of the columns as a local search, making use of a tabu list to avoid cycling. We show the results of the proposed algorithm on benchmark instances from the literature and compare them to the state-of-the-art algorithms, showing the effectiveness of our approach in producing good quality solutions. In addition, we report the results on realistic instances of the PVRP introduced in Pacheco et al. (2011)  [24] and on benchmark instances of the periodic traveling salesman problem (PTSP), showing the efficacy of the proposed algorithm on these as well. Finally, we report the new best known solutions found for all the tested problems.

A set-covering based heuristic algorithm for the periodic vehicle routing problem

PubMed Central

Cacchiani, V.; Hemmelmayr, V.C.; Tricoire, F.

2014-01-01

We present a hybrid optimization algorithm for mixed-integer linear programming, embedding both heuristic and exact components. In order to validate it we use the periodic vehicle routing problem (PVRP) as a case study. This problem consists of determining a set of minimum cost routes for each day of a given planning horizon, with the constraints that each customer must be visited a required number of times (chosen among a set of valid day combinations), must receive every time the required quantity of product, and that the number of routes per day (each respecting the capacity of the vehicle) does not exceed the total number of available vehicles. This is a generalization of the well-known vehicle routing problem (VRP). Our algorithm is based on the linear programming (LP) relaxation of a set-covering-like integer linear programming formulation of the problem, with additional constraints. The LP-relaxation is solved by column generation, where columns are generated heuristically by an iterated local search algorithm. The whole solution method takes advantage of the LP-solution and applies techniques of fixing and releasing of the columns as a local search, making use of a tabu list to avoid cycling. We show the results of the proposed algorithm on benchmark instances from the literature and compare them to the state-of-the-art algorithms, showing the effectiveness of our approach in producing good quality solutions. In addition, we report the results on realistic instances of the PVRP introduced in Pacheco et al. (2011)  [24] and on benchmark instances of the periodic traveling salesman problem (PTSP), showing the efficacy of the proposed algorithm on these as well. Finally, we report the new best known solutions found for all the tested problems. PMID:24748696

Synthesis of Er-doped Lu2O3 nanoparticles and transparent ceramics

NASA Astrophysics Data System (ADS)

Serivalsatit, K.; Wasanapiarnpong, T.; Kucera, C.; Ballato, J.

2013-05-01

Transparent rare earth-doped Lu2O3 ceramics have received much attention for use in solid-state scintillator and laser applications. The fabrication of these ceramics, however, requires ultrafine and uniform powders as precursors. Presented here is the synthesis of Er-doped Lu2O3 nanopowders by a solution precipitation method using Er-doped lutetium sulfate solution and hexamethylenetetramine as a precipitant and the fabrication of Er-doped Lu2O3 transparent ceramics from these nanopowders. The precipitated precursors were calcined at 1100 °C for 4 h in order to convert the precursors into Lu2O3 nanoparticles with an average particle size of 60 nm. Thermal decomposition and phase evolution of the precursors were studied by simultaneous thermal analysis (STA), Fourier transform infrared spectroscopy (FTIR) and X-ray diffraction (XRD). Er-doped Lu2O3 transparent ceramics were fabricated from these nanopowders using vacuum sintering followed by hot isostatic pressing at 1700 °C for 8 h. The transparent ceramics exhibit an optical transmittance of 78% at a wavelength of 1.55 μm.

VizieR Online Data Catalog: Effects of preionization in radiative shocks (Sutherland+, 2017)

NASA Astrophysics Data System (ADS)

Sutherland, R. S.; Dopita, M. A.

2017-06-01

In this paper we treat the preionization problem in shocks over the velocity range 10

Routing and Scheduling Algorithms for WirelessHART Networks: A Survey

PubMed Central

Nobre, Marcelo; Silva, Ivanovitch; Guedes, Luiz Affonso

2015-01-01

Wireless communication is a trend nowadays for the industrial environment. A number of different technologies have emerged as solutions satisfying strict industrial requirements (e.g., WirelessHART, ISA100.11a, WIA-PA). As the industrial environment presents a vast range of applications, adopting an adequate solution for each case is vital to obtain good performance of the system. In this context, the routing and scheduling schemes associated with these technologies have a direct impact on important features, like latency and energy consumption. This situation has led to the development of a vast number of routing and scheduling schemes. In the present paper, we focus on the WirelessHART technology, emphasizing its most important routing and scheduling aspects in order to guide both end users and the developers of new algorithms. Furthermore, we provide a detailed literature review of the newest routing and scheduling techniques for WirelessHART, discussing each of their features. These routing algorithms have been evaluated in terms of their objectives, metrics, the usage of the WirelessHART structures and validation method. In addition, the scheduling algorithms were also evaluated by metrics, validation, objectives and, in addition, by multiple superframe support, as well as by the redundancy method used. Moreover, this paper briefly presents some insights into the main WirelessHART simulation modules available, in order to provide viable test platforms for the routing and scheduling algorithms. Finally, some open issues in WirelessHART routing and scheduling algorithms are discussed. PMID:25919371

Rapid Formation of Metal-Organic Frameworks (MOFs) Based Nanocomposites in Microdroplets and Their Applications for CO2 Photoreduction.

PubMed

He, Xiang; Gan, Zhuoran; Fisenko, Sergey; Wang, Dawei; El-Kaderi, Hani M; Wang, Wei-Ning

2017-03-22

A copper-based metal-organic framework (MOF), [Cu 3 (TMA) 2 (H 2 O) 3 ] n (also known as HKUST-1, where TMA stands for trimesic acid), and its TiO 2 nanocomposites were directly synthesized in micrometer-sized droplets via a rapid aerosol route for the first time. The effects of synthesis temperature and precursor component ratio on the physicochemical properties of the materials were systematically investigated. Theoretical calculations on the mass and heat transfer within the microdroplets revealed that the fast solvent evaporation and high heat transfer rates are the major driving forces. The fast droplet shrinkage because of evaporation induces the drastic increase in the supersaturation ratio of the precursor, and subsequently promotes the rapid nucleation and crystal growth of the materials. The HKUST-1-based nanomaterials synthesized via the aerosol route demonstrated good crystallinity, large surface area, and great photostability, comparable with those fabricated by wet-chemistry methods. With TiO 2 embedded in the HKUST-1 matrix, the surface area of the composite is largely maintained, which enables significant improvement in the CO 2 photoreduction efficiency, as compared with pristine TiO 2 . In situ diffuse reflectance infrared Fourier transform spectroscopy analysis suggests that the performance enhancement was due to the stable and high-capacity reactant adsorption by HKUST-1. The current work shows great promise in the aerosol route's capability to address the mass and heat transfer issues of MOFs formation at the microscale level, and ability to synthesize a series of MOFs-based nanomaterials in a rapid and scalable manner for energy and environmental applications.

Metal–metal chalcogenide molecular precursors to binary, ternary, and quaternary metal chalcogenide thin films for electronic devices

DOE PAGES

Zhang, Ruihong; Cho, Seonghyuk; Lim, Daw Gen; ...

2016-03-15

We found that bulk metals and metal chalcogenides dissolve in primary amine–dithiol solvent mixtures at ambient conditions. Thin-films of CuS, SnS, ZnS, Cu 2Sn(Sx,Se 1-x) 3, and Cu 2ZnSn(SxSe 1-x) 4 (0 ≤ x ≤ 1) were deposited using the as-dissolved solutions. Furthermore, Cu 2ZnSn(SxSe 1-x) 4 solar cells with efficiencies of 6.84% and 7.02% under AM1.5 illumination were fabricated from two example solution precursors, respectively.

A new powder production route for transparent spinel windows: powder synthesis and window properties

NASA Astrophysics Data System (ADS)

Cook, Ronald; Kochis, Michael; Reimanis, Ivar; Kleebe, Hans-Joachim

2005-05-01

Spinel powders for the production of transparent polycrystalline ceramic windows have been produced using a number of traditional ceramic and sol-gel methods. We have demonstrated that magnesium aluminate spinel powders produced from the reaction of organo-magnesium compounds with surface modified boehmite precursors can be used to produce high quality transparent spinel parts. The new powder production method allows fine control over the starting particle size, size distribution, purity and stoichiometry. The new process involves formation of a boehmite sol-gel from the hydrolysis of aluminum alkoxides followed by surface modification of the boehmite nanoparticles using carboxylic acids. The resulting surface modified boehmite nanoparticles can then be metal exchanged at room temperature with magnesium acetylacetonate to make a precursor powder that is readily transformed into pure phase spinel.

Numerical Simulation of Droplet Breakup and Collision in the Solution Precursor Plasma Spraying

NASA Astrophysics Data System (ADS)

Shan, Y.; Coyle, T. W.; Mostaghimi, J.

2007-12-01

Finely structured ceramic coatings can be obtained by solution precursor plasma spraying. The final structure of the coating highly depends on the droplet size and velocity distribution at the injection, the evolution of the spray in the jet, and droplet breakup and collision within the spray. This article describes a 3D model to simulate the transport phenomena and the trajectory and heating of the solution spray in the process. O’Rourke’s droplet collision model is used to take into account the influence of droplet collision. The influence of droplet breakup is also considered by implementing TAB droplet breakup models into the plasma jet model. The effects of droplet collisions and breakup on the droplet size, velocity, and temperature distribution of the solution spray are investigated. The results indicate that droplet breakup and collision play an important role in determining the final particle size and velocity distributions on the substrate.

Single-phase and well-dispersed Cu1.75S nanocrystals by ambient pressure diethylene glycol solution synthesis

NASA Astrophysics Data System (ADS)

Zheng, Xuerong; Jin, Zhengguo; Liu, Hui; Wang, Yueqiu; Wang, Xin; Du, Haiyan

2013-02-01

Single-phase, well-dispersed Cu1.75S nanocrystals were synthesized by an ambient pressure, hydrazine hydrate and ethylenediamine co-assisted diethylene glycol based solution chemical process using copper chloride and thioacetamide as precursors at the temperature range from 180 to 210 °C. Influence of hydrazine hydrate and ethylenediamine adding amounts, synthetic temperature on crystal growth, size distribution and optical properties of the synthesized Cu1.75S nanocrystals were investigated by XRD, TEM, HRTEM, EDX and UV-vis measurements. The synthetic reaction at above 200 °C grew flaky-shaped nanocrystals with relatively narrow size distribution. The formation of single-phase Cu1.75S nanocrystals in the diethylene glycol based solution process might be involved in the presence of intermediate [Cu(en)n]1+ and [Cu(NH3)4]2+ complexes in reaction solution, providing a stable Cu(I) and Cu(II) valent-mixed precursor.

Hydrothermal synthesis and characterization of Si and Sr co-substituted hydroxyapatite nanowires using strontium containing calcium silicate as precursors.

PubMed

Zhang, Na; Zhai, Dong; Chen, Lei; Zou, Zhaoyong; Lin, Kaili; Chang, Jiang

2014-04-01

In the absence of any organic surfactants and solvents, the silicon (Si) and strontium (Sr) co-substituted hydroxyapatite [Ca10(PO4)6(OH)2, Si/Sr-HAp] nanowires were synthesized via hydrothermal treatment of the Sr-containing calcium silicate (Sr-CS) powders as the precursors in trisodium phosphate (Na3PO4) aqueous solution. The morphology, phase, chemical compositions, lattice constants and the degradability of the products were characterized. The Si/Sr-HAp nanowires with diameter of about 60nm and up to 2μm in length were obtained after hydrothermal treatment of the Sr-CS precursors. The Sr and Si substitution amount of the HAp nanowires could be well regulated by facile tailoring the Sr substitution level of the precursors and the reaction ratio of the precursor/solution, respectively. The SiO4 tetrahedra and Sr(2+) ions occupied the crystal sites of the HAp, and the lattice constants increased apparently with the increase of the substitution amount. EDS mapping also suggested the uniform distribution of Si and Sr in the synthetic nanowires. Moreover, the Si/Sr-substitution apparently improved the degradability of the HAp materials. Our study suggested that the precursor transformation method provided a facile approach to synthesize the Si/Sr co-substituted HAp nanowires with controllable substitution amount, and the synthetic Si/Sr-HAp nanowires might be used as bioactive materials for hard tissue regeneration applications. Copyright © 2014 Elsevier B.V. All rights reserved.

S-Doped Sb2O3 Nanocrystal: an Efficient Visible-Light Catalyst for Organic Degradation

NASA Astrophysics Data System (ADS)

Xue, Hun; Lin, Xinyi; Chen, Qinghua; Qian, Qingrong; Lin, Suying; Zhang, Xiaoyan; Yang, Da-Peng; Xiao, Liren

2018-04-01

The S-doped Sb2O3 nanocrystals were successfully synthesized using SbCl3 and thioacetamide (TAA) as precursors via a facile one-step hydrothermal method. The effects of pH of the precursor reaction solution on the product composition and property were determined. The results indicated that the doping amount of S could be tuned by adjusting the pH of the precursor solution. Furthermore, the S entered into the interstitial site of Sb2O3 crystals as S2-, which broadened the absorption wavelength range of the Sb2O3 nanocrystal. The S-doped Sb2O3 exhibited an excellent visible-light-driven photocatalytic activity in the decomposition of methyl orange and 4-phenylazophenol. Last, a possible photocatalytic mechanism of the S-doped Sb2O3 under visible light irradiation was proposed.

Method for producing microcomposite powders using a soap solution

DOEpatents

Maginnis, Michael A.; Robinson, David A.

1996-01-01

A method for producing microcomposite powders for use in superconducting and non-superconducting applications. A particular method to produce microcomposite powders for use in superconducting applications includes the steps of: (a) preparing a solution including ammonium soap; (b) dissolving a preselected amount of a soluble metallic such as silver nitrate in the solution including ammonium soap to form a first solution; (c) adding a primary phase material such as a single phase YBC superconducting material in particle form to the first solution; (d) preparing a second solution formed from a mixture of a weak acid and an alkyl-mono-ether; (e) adding the second solution to the first solution to form a resultant mixture; (f) allowing the resultant mixture to set until the resultant mixture begins to cloud and thicken into a gel precipitating around individual particles of the primary phase material; (g) thereafter drying the resultant mixture to form a YBC superconducting material/silver nitrate precursor powder; and (h) calcining the YBC superconducting material/silver nitrate precursor powder to convert the silver nitrate to silver and thereby form a YBC/silver microcomposite powder wherein the silver is substantially uniformly dispersed in the matrix of the YBC material.

Synthesis of substituted isoquinolines utilizing palladium-catalyzed α-arylation of ketones

PubMed Central

Donohoe, Timothy J.; Pilgrim, Ben S.; Jones, Geraint R.; Bassuto, José A.

2012-01-01

The utilization of sequential palladium-catalyzed α-arylation and cyclization reactions provides a general approach to an array of isoquinolines and their corresponding N-oxides. This methodology allows the convergent combination of readily available precursors in a regioselective manner and in excellent overall yields. This powerful route to polysubstituted isoquinolines, which is not limited to electron rich moieties, also allows rapid access to analogues of biologically active compounds. PMID:22753504

Method to produce nanocrystalline powders of oxide-based phosphors for lighting applications

DOEpatents

Loureiro, Sergio Paulo Martins; Setlur, Anant Achyut; Williams, Darryl Stephen; Manoharan, Mohan; Srivastava, Alok Mani

2007-12-25

Some embodiments of the present invention are directed toward nanocrystalline oxide-based phosphor materials, and methods for making same. Typically, such methods comprise a steric entrapment route for converting precursors into such phosphor material. In some embodiments, the nanocrystalline oxide-based phosphor materials are quantum splitting phosphors. In some or other embodiments, such nanocrystalline oxide based phosphor materials provide reduced scattering, leading to greater efficiency, when used in lighting applications.

Convenient approaches to synthesis of furanoid sugar-aza-crown ethers from C-ribosyl azido aldehyde via a reductive amination/amidation.

PubMed

Hsieh, Yu-Chi; Chir, Jiun-Ly; Zou, Wei; Wu, Hsiu-Han; Wu, An-Tai

2009-05-26

A short and highly efficient route to the alpha-anomer of a furanoid sugar-aza-crown ether was developed by a one-pot reductive amination of an alpha-anomer C-ribosyl azido aldehyde. In addition, the beta-anomer furanoid sugar-aza-crown ether was synthesized from a linear disaccharide precursor via amidation and then followed by microwave-assisted amide reduction.

Coated electroactive materials

DOEpatents

Amine, Khalil; Abouimrane, Ali

2016-08-30

A process includes suspending an electroactive material in a solvent, suspending or dissolving a carbon precursor in the solvent; and depositing the carbon precursor on the electroactive material to form a carbon-coated electroactive material. Compositions include a graphene-coated electroactive material prepared from a solution phase mixture or suspension of an electroactive material and graphene, graphene oxide, or a mixture thereof.

Synthesis and development of low cost, high temperature N-arylene polybenzimidazole foam material

NASA Technical Reports Server (NTRS)

Harrison, E. S.

1975-01-01

Polymer (and foam) studies followed two basic routes: (1) formation of high molecular weight uncyclized polyamide followed by subsequent fusion and cyclodehydration to yield NABI (foam) and (2) polymer and foam formation by reaction of diphenyl esters (or anhydrides) with the tetramine. The latter route was found much more attractive since considerable versatility in both basic polymer structure and crosslinkability is achievable. Preliminary studies on BAB, phthalic anhydride (PA), and 3, 3 (prime), 4, 4(prime) benzo pheno netetracarboxylic acid dianhydride (BTDA) as crosslinked polymer precursors were conducted. Nonmelting rigid char forming foams with densities as low as 2.7 lb/cubic ft. were achieved. The program was successful in the preparation of a potentially low cost, low density, high char yield, high temperature foam material.

Solid-state NMR study of geopolymer prepared by sol-gel chemistry

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

Tsai, Yi-Ling; Hanna, John V.; Lee, Yuan-Ling, E-mail: yuanlinglee@ntu.edu.t

2010-12-15

Geopolymers are a new class of materials formed by the condensation of aluminosilicates and silicates obtained from natural minerals or industrial wastes. In this work, the sol-gel method is used to synthesize precursor materials for the preparation of geopolymers. The geopolymer samples prepared by our synthetic route have been characterized by a series of physical techniques, including Fourier-transform infrared, X-ray diffraction, and multinuclear solid-state NMR. The results are very similar to those obtained for the geopolymers prepared from natural kaolinite. We believe that our synthetic approach can offer a good opportunity for the medical applications of geopolymer. -- Graphical abstract:more » Geopolymer prepared by the sol-gel route has the same spectroscopic properties as the sample prepared from the natural kaolinite. Display Omitted« less

Lead Acetate Based Hybrid Perovskite Through Hot Casting for Planar Heterojunction Solar Cells

NASA Astrophysics Data System (ADS)

Shin, Gwang Su; Choi, Won-Gyu; Na, Sungjae; Gökdemir, Fatma Pinar; Moon, Taeho

2018-03-01

Flawless coverage of a perovskite layer is essential in order to achieve realistic high-performance planar heterojunction solar cells. We present that high-quality perovskite layers can be efficiently formed by a novel hot casting route combined with MAI (CH3NH3I) and non-halide lead acetate (PbAc2) precursors under ambient atmosphere. Casting temperature is controlled to produce various perovskite microstructures and the resulted crystalline layers are found to be comprised of closely packed islands with a smooth surface structure. Lead acetate employed perovskite solar cells are fabricated using PEDOT:PSS and PCBM charge transporting layers, in p- i- n type planar architecture. Especially, the outstanding open-circuit voltage demonstrates the high crystallinity and dense coverage of the produced perovskite layers by this facile route.

Design of a mesoscale continuous flow route towards lithiated methoxyallene.

PubMed

Seghers, Sofie; Heugebaert, Thomas S A; Moens, Matthias; Sonck, Jolien; Thybaut, Joris; Stevens, Chris Victor

2018-05-11

The unique nucleophilic properties of lithiated methoxyallene allow for C-C bond formation with a wide variety of electrophiles, thus introducing an allenic group for further functionalization. This approach has yielded a tremendously broad range of (hetero)cyclic scaffolds, including API precursors. To date, however, its valorization at scale is hampered by the batch synthesis protocol which suffers from serious safety issues. Hence, the attractive heat and mass transfer properties of flow technology were exploited to establish a mesoscale continuous flow route towards lithiated methoxyallene. An excellent conversion of 94% was obtained, corresponding to a methoxyallene throughput of 8.2 g/h. The process is characterized by short reaction times, mild reaction conditions and a stoichiometric use of reagents. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

(ZrO 2) 0.85( REO 1.5) 0.15 ( RE=Sc, Y) solid solutions prepared via three Pechini-type gel routes: 1—gel formation and calcination behaviors

NASA Astrophysics Data System (ADS)

Zhang, Yawen; Li, Ang; Yan, Zhengguang; Xu, Gang; Liao, Chunsheng; Yan, Chunhua

2003-02-01

(ZrO2)0.85(REO1.5)0.15 (RE=Sc, Y) nanoparticles with pure cubic fluorite structure have been synthesized by three Pechini-type gel routes, viz. poly(vinyl alcohol) containing-process (route I), poly(ethylene glycol) and formic acid-containing process (route II), and in situ polymerizable complex method (route III). The coordination modes between metal ions and polymers in the gels are shown to be highly correlative with the synthesis route used. The gels prepared by route III have the strongest coordination throughout their network and therefore the best chemical homogeneity. The altered variety of polymer and cross-linking within the gels adopted by these three routes has made the as-synthesized samples show appreciable differences in thermal behavior, powder reactivity and nanoparticle properties.

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

Solid-gel precursor solutions and methods for the fabrication of polymetallicsiloxane coating films

DOEpatents

Sugama, Toshifumi

1992-01-01

Solutions and preparation methods necessary for the fabrication of metal oxide cross-linked polysiloxane coating films are disclosed. The films are useful in provide heat resistance against oxidation, wear resistance, thermal insulation, and corrosion resistance of substrates. The sol-gel precursor solution comprises a mixture of a monomeric organoalkoxysilane, a metal alkoxide M(OR).sub.n (wherein M is Ti, Zr, Ge or Al; R is CH.sub.3, C.sub.2 H.sub.5 or C.sub.3 H.sub.7 ; and n is 3 or 4), methanol, water, HCl and NaOH. The invention provides a sol-gel solution, and a method of use thereof, which can be applied and processed at low temperatures (i.e., <1000.degree. C.). The substrate can be coated by immersing it in the above mentioned solution at ambient temperature. The substrate is then withdrawn from the solution. Next, the coated substrate is heated for a time sufficient and at a temperature sufficient to yield a solid coating. The coated substrate is then heated for a time sufficient, and temperature sufficient to produce a polymetallicsiloxane coating.

Solid-gel precursor solutions and methods for the fabrication of polymetallicsiloxane coating films

DOEpatents

Sugama, Toshifumi

1993-01-01

Solutions and preparation methods necessary for the fabrication of metal oxide cross-linked polysiloxane coating films are disclosed. The films are useful in provide heat resistance against oxidation, wear resistance, thermal insulation, and corrosion resistance of substrates. The sol-gel precursor solution comprises a mixture of a monomeric organoalkoxysilane, a metal alkoxide M(OR).sub.n (wherein M is Ti, Zr, Ge or Al; R is CH.sub.3, C.sub.2 H.sub.5 or C.sub.3 H.sub.7 ; and n is 3 or 4), methanol, water, HCl and NaOH. The invention provides a sol-gel solution, and a method of use thereof, which can be applied and processed at low temperatures (i.e., <1000.degree. C.). The substrate can be coated by immersing it in the above mentioned solution at ambient temperature. The substrate is then withdrawn from the solution. Next, the coated substrate is heated for a time sufficient and at a temperature sufficient to yield a solid coating. The coated substrate is then heated for a time sufficient, and temperature sufficient to produce a polymetallicsiloxane coating.

Solid-gel precursor solutions and methods for the fabrication of polymetallicsiloxane coating films

DOEpatents

Toshifumi Sugama.

1993-04-06

Solutions and preparation methods necessary for the fabrication of metal oxide cross-linked polysiloxane coating films are disclosed. The films are useful in provide heat resistance against oxidation, wear resistance, thermal insulation, and corrosion resistance of substrates. The sol-gel precursor solution comprises a mixture of a monomeric organoalkoxysilane, a metal alkoxide M(OR)[sub n] (wherein M is Ti, Zr, Ge or Al; R is CH[sub 3], C[sub 2]H[sub 5] or C[sub 3]H[sub 7]; and n is 3 or 4), methanol, water, HCl and NaOH. The invention provides a sol-gel solution, and a method of use thereof, which can be applied and processed at low temperatures (i.e., < 1,000 C.). The substrate can be coated by immersing it in the above mentioned solution at ambient temperature. The substrate is then withdrawn from the solution. Next, the coated substrate is heated for a time sufficient and at a temperature sufficient to yield a solid coating. The coated substrate is then heated for a time sufficient, and temperature sufficient to produce a polymetallicsiloxane coating.

MPATHav: A software prototype for multiobjective routing in transportation risk assessment

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

Ganter, J.H.; Smith, J.D.

Most routing problems depend on several important variables: transport distance, population exposure, accident rate, mandated roads (e.g., HM-164 regulations), and proximity to emergency response resources are typical. These variables may need to be minimized or maximized, and often are weighted. `Objectives` to be satisfied by the analysis are thus created. The resulting problems can be approached by combining spatial analysis techniques from geographic information systems (GIS) with multiobjective analysis techniques from the field of operations research (OR); we call this hybrid multiobjective spatial analysis` (MOSA). MOSA can be used to discover, display, and compare a range of solutions that satisfymore » a set of objectives to varying degrees. For instance, a suite of solutions may include: one solution that provides short transport distances, but at a cost of high exposure; another solution that provides low exposure, but long distances; and a range of solutions between these two extremes.« less

A Linear Programming Approach to Routing Control in Networks of Constrained Nonlinear Positive Systems with Concave Flow Rates

NASA Technical Reports Server (NTRS)

Arneson, Heather M.; Dousse, Nicholas; Langbort, Cedric

2014-01-01

We consider control design for positive compartmental systems in which each compartment's outflow rate is described by a concave function of the amount of material in the compartment.We address the problem of determining the routing of material between compartments to satisfy time-varying state constraints while ensuring that material reaches its intended destination over a finite time horizon. We give sufficient conditions for the existence of a time-varying state-dependent routing strategy which ensures that the closed-loop system satisfies basic network properties of positivity, conservation and interconnection while ensuring that capacity constraints are satisfied, when possible, or adjusted if a solution cannot be found. These conditions are formulated as a linear programming problem. Instances of this linear programming problem can be solved iteratively to generate a solution to the finite horizon routing problem. Results are given for the application of this control design method to an example problem. Key words: linear programming; control of networks; positive systems; controller constraints and structure.

Some factors affecting performance of rats in the traveling salesman problem.

PubMed

Bellizzi, C; Goldsteinholm, K; Blaser, R E

2015-11-01

The traveling salesman problem (TSP) is used to measure the efficiency of spatial route selection. Among researchers in cognitive psychology and neuroscience, it has been utilized to examine the mechanisms of decision making, planning, and spatial navigation. While both human and non-human animals produce good solutions to the TSP, the solution strategies engaged by non-human species are not well understood. We conducted two experiments on the TSP using Long-Evans laboratory rats as subjects. The first experiment examined the role of arena walls in route selection. Rats tend to display thigmotaxis in testing conditions comparable to the TSP, which could produce results similar to a convex hull type strategy suggested for humans. The second experiment examined the role of turn angle between targets along the optimal route, to determine whether rats exhibit a preferential turning bias. Our results indicated that both thigmotaxis and preferential turn angles do affect performance in the TSP, but neither is sufficient as a predictor of route choice in this task.

Effect of chain length on thermal conversion of alkoxy-substituted copper phthalocyanine precursors.

PubMed

Fukuda, Takamitsu; Kikukawa, Yuu; Tsuruya, Ryota; Fuyuhiro, Akira; Ishikawa, Naoto; Kobayashi, Nagao

2011-11-21

A series of dialkoxy-substituted copper phthalocyanine (CuPc) precursors (4a-4d) have been prepared by treating phthalonitrile with the corresponding lithium alkoxide under mild conditions. The precursors exhibited high solubilities in common organic solvents, including acetone, toluene, tetrahydrofuran (THF), CH(2)Cl(2), and CHCl(3). Elongation of the alkoxy chains improved the solubilities of the precursors effectively, and accordingly, the butoxy-substituted derivative (4d) showed the highest solubility among 4a-4d. X-ray crystallography clarified that the conjugated skeletons of 4a-4d are all isostructural, and have two alkoxy groups in a syn-conformation fashion, leading to highly bent structures. Thermal conversions of the precursors examined by thermogravimetry (TG) and differential thermal analysis (DTA) demonstrate that 4a was converted into CuPc via two distinct exothermic processes in the 200-250 °C temperature range, while 4d exhibits only one exothermic signal in the DTA. In the field emission scanning electron microscopy (FESEM) images of 4a, the presence of two types of distinct crystal morphology (prismatic and plate-like crystals) can be recognized, implying that the two observed exothermic processes in the DTA can be attributed to the different crystal morphologies of the samples rather than the step-by-step elimination of the alkoxy groups. The thermal formation of CuPc from the precursors has been unambiguously confirmed by X-ray powder diffraction, UV-vis spectroscopy, and elemental analysis. The precursors were converted into CuPc at lower temperature with increasing chain length, presumably because of the increased void volume in the crystals. Thermal conversion performed in the solution phase results in a bright blue-colored solution with prominent absorption bands in the 650-700 nm region, strongly supporting the formation of CuPc.

Supporting BPMN choreography with system integration artefacts for enterprise process collaboration

NASA Astrophysics Data System (ADS)

Nie, Hongchao; Lu, Xudong; Duan, Huilong

2014-07-01

Business Process Model and Notation (BPMN) choreography modelling depicts externally visible message exchanges between collaborating processes of enterprise information systems. Implementation of choreography relies on designing system integration solutions to realise message exchanges between independently developed systems. Enterprise integration patterns (EIPs) are widely accepted artefacts to design integration solutions. If the choreography model represents coordination requirements between processes with behaviour mismatches, the integration designer needs to analyse the routing requirements and address these requirements by manually designing EIP message routers. As collaboration scales and complexity increases, manual design becomes inefficient. Thus, the research problem of this paper is to explore a method to automatically identify routing requirements from BPMN choreography model and to accordingly design routing in the integration solution. To achieve this goal, recurring behaviour mismatch scenarios are analysed as patterns, and corresponding solutions are proposed as EIP routers. Using this method, a choreography model can be analysed by computer to identify occurrences of mismatch patterns, leading to corresponding router selection. A case study demonstrates that the proposed method enables computer-assisted integration design to implement choreography. A further experiment reveals that the method is effective to improve the design quality and reduce time cost.

Promoting Wired Links in Wireless Mesh Networks: An Efficient Engineering Solution

PubMed Central

Barekatain, Behrang; Raahemifar, Kaamran; Ariza Quintana, Alfonso; Triviño Cabrera, Alicia

2015-01-01

Wireless Mesh Networks (WMNs) cannot completely guarantee good performance of traffic sources such as video streaming. To improve the network performance, this study proposes an efficient engineering solution named Wireless-to-Ethernet-Mesh-Portal-Passageway (WEMPP) that allows effective use of wired communication in WMNs. WEMPP permits transmitting data through wired and stable paths even when the destination is in the same network as the source (Intra-traffic). Tested with four popular routing protocols (Optimized Link State Routing or OLSR as a proactive protocol, Dynamic MANET On-demand or DYMO as a reactive protocol, DYMO with spanning tree ability and HWMP), WEMPP considerably decreases the end-to-end delay, jitter, contentions and interferences on nodes, even when the network size or density varies. WEMPP is also cost-effective and increases the network throughput. Moreover, in contrast to solutions proposed by previous studies, WEMPP is easily implemented by modifying the firmware of the actual Ethernet hardware without altering the routing protocols and/or the functionality of the IP/MAC/Upper layers. In fact, there is no need for modifying the functionalities of other mesh components in order to work with WEMPPs. The results of this study show that WEMPP significantly increases the performance of all routing protocols, thus leading to better video quality on nodes. PMID:25793516

Research on vehicle routing optimization for the terminal distribution of B2C E-commerce firms

NASA Astrophysics Data System (ADS)

Zhang, Shiyun; Lu, Yapei; Li, Shasha

2018-05-01

In this paper, we established a half open multi-objective optimization model for the vehicle routing problem of B2C (business-to-customer) E-Commerce firms. To minimize the current transport distance as well as the disparity between the excepted shipments and the transport capacity in the next distribution, we applied the concept of dominated solution and Pareto solutions to the standard particle swarm optimization and proposed a MOPSO (multi-objective particle swarm optimization) algorithm to support the model. Besides, we also obtained the optimization solution of MOPSO algorithm based on data randomly generated through the system, which verified the validity of the model.

Synthesis, characterization, and properties of low-dimensional nanostructured materials

NASA Astrophysics Data System (ADS)

Hu, Xianluo

2007-05-01

Nanometer scale structures represent an exciting and rapidly expanding area of research. Studies on new physical/chemical properties and applications of nanomaterials and nanostructures are possible only when nanostructured materials are made available with desired size, morphology, crystal and microstructure, and composition. Thus, controlled synthesis of nanomaterials is the essential aspect of nanotechnology. This thesis describes the development of simple and versatile solution-based approaches to synthesize low-dimensional nanostructures. The first major goal of this research is to design and fabricate morphology-controlled alpha-Fe 2O3 nanoarchitectures in aqueous solution through a programmed microwave-assisted hydrothermal route, taking advantage of microwave irradiation and hydrothermal effects. Free-standing alpha-Fe2O3 nanorings are prepared by hydrolysis of FeCl3 in the presence of phosphate ions. The as-formed architecture of alpha-Fe2O 3 nanorings is an exciting new member in the family of iron oxide nanostructures. Our preliminary results demonstrate that sensors made of the alpha-Fe 2O3 nanorings exhibit high sensitivity not only for bio-sensing of hydrogen peroxide in a physiological solution but also for gas-sensing of alcohol vapor at room temperature. Moreover, monodisperse alpha-Fe 2O3 nanocrystals with continuous aspect-ratio tuning and fine shape control are achieved by controlling the experimental conditions. The as-formed alpha-Fe2O3 exhibits shape-dependent infrared optical properties. The growth process of colloidal alpha-Fe 2O3 crystals in the presence of phosphate ions is discussed. In addition, through an efficient microwave-assisted hydrothermal process, self-assembled hierarchical alpha-Fe2O3 nanoarchitectures are synthesized on a large scale. The second major goal of this research is to develop convenient microwave-hydrothermal approaches for the fabrication of carbon-based nanocomposites: (1) A one-pot solution-phase route, namely microwave-assisted hydrothermal reduction/carbonization (MAHRC), is developed to prepare coaxial Ag/amorphous-carbon (a-C) nanocables. The as-grown Ag/C nanocables can self-assemble in an end-to-end fashion. (2) A novel Se/C nanocomposite with core-shell structures is prepared. The new material consists of a trigonal-Se (t-Se) core and an amorphous-C (a-C) shell. The Se/C composite can be converted to hollow carbon capsules by thermal treatment. (3) A Fe 3O4/C nanocomposite is synthesized by a green wet-chemical approach. The product possesses porous microstructures and exhibits superparamagnetic behavior. The third major goal of this research is develop facile solution-based methods for preparing carbonaceous nano test tubes, thin films of metal iodides, and spherical selenium spheres: (1) Carbonaceous nano test tubes are fabricated by a facile "decoring" route using a core-sheath Te carbon nanocomposite as the precursor. The as-formed carbonaceous material looks like a "test tube" with an average diameter of about 120 nm and lengths up to 5 mum. (2) Tetrahedral-shaped CuI crystals were formed on a variety of copper substrates (e.g. grids, flat/porous foils, and macro-/nano- wires) via an interfacial reaction between a copper substrate and iodine in water at room temperature. This preparation approach can also be used to grow PbI2 and AgI nano- and micro-crystals with different morphologies on corresponding substrates. (3) Colloidal trigonal selenium (t-Se) microspheres are synthesized through a mild hydrothermal reduction reaction, using glucose as a reducing regent and water as an environmentally friendly solvent. Importantly, the resulting t-Se microspheres inherit functional groups from the starting materials and possess hydrophilic and biocompatible surfaces.

Phosphorescent heterobimetallic complexes involving platinum(iv) and rhenium(vii) centers connected by an unsupported μ-oxido bridge.

PubMed

Molaee, Hajar; Nabavizadeh, S Masoud; Jamshidi, Mahboubeh; Vilsmeier, Max; Pfitzner, Arno; Samandar Sangari, Mozhgan

2017-11-28

Heterobimetallic compounds [(C^N)LMe 2 Pt(μ-O)ReO 3 ] (C^N = ppy, L = PPh 3 , 2a; C^N = ppy, L = PMePh 2 , 2b; C^N = bhq, L = PPh 3 , 2c; C^N = bhq, L = PMePh 2 , 2d) containing a discrete unsupported Pt(iv)-O-Re(vii) bridge have been synthesized through a targeted synthesis route. The compounds have been prepared by a single-pot synthesis in which the Pt(iv) precursor [PtMe 2 I(C^N)L] complexes are allowed to react easily with AgReO 4 in which the iodide ligand of the starting Pt(iv) complex is replaced by an ReO 4 - anion. In these Pt-O-Re complexes, the Pt(iv) centers have an octahedral geometry, completed by a cyclometalated bidentate ligand (C^N), two methyl groups and a phosphine ligand, while the Re(vii) centers have a tetrahedral geometry. Elemental analysis, single crystal X-ray diffraction analysis and multinuclear NMR spectroscopy are used to establish their identities. The new complexes exhibit phosphorescence emission in the solid and solution states at 298 and 77 K, which is an uncommon property of platinum complexes with an oxidation state of +4. According to DFT calculations, we found that this emission behavior in the new complexes originates from ligand centered 3 LC (C^N) character with a slight amount of metal to ligand charge transfer ( 3 MLCT). The solid-state emission data of the corresponding cycloplatinated(iv) precursor complexes [PtMe 2 I(C^N)L], 1a-1d, pointed out that the replacement of I - by an ReO 4 - anion helps enhancing the emission efficiency besides shifting the emission wavelengths.

Synthesis and characterization of a series of nickel( ii ) alkoxide precursors and their utility for Ni(0) nanoparticle production

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

Treadwell, LaRico J.; Boyle, Timothy J.; Phelan, W. Adam

2017-02-22

We synthesized a series of nickel(II) aryloxide ([Ni(OAr) 2(py) x]) precursors from an amide-alcohol exchange using [Ni(NR 2) 2] in the presence of pyridine (py). The H-OAr selected were the mono- and di-ortho-substituted 2-alkyl phenols: alkyl = methyl (H-oMP), iso-propyl (H-oPP), tert-butyl (H-oBP) and 2,6-di-alkyl phenols (alkyl = di-iso-propyl (H-DIP), di-tert-butyl (H-DBP), di-phenyl (H-DPhP)). Furthermore, the crystalline products were solved as solvated monomers and structurally characterized as [Ni(OAr) 2(py) x], where x = 4: OAr = oMP (1), oPP (2); x = 3: OAr = oBP (3), DIP (4); x = 2: OAr = DBP (5), DPhP (6). The excitedmore » states (singlet or triplet) and various geometries of 1–6 were identified by experimental UV-vis and verified by computational modeling. Magnetic susceptibility of the representative compound 4 was fit to a Curie Weiss model that yielded a magnetic moment of 4.38(3)μ B consistent with a Ni 2+ center. Compounds 1 and 6 were selected for decomposition studied under solution precipitation routes since they represent the two extremes of coordination. The particle size and crystalline structure were characterized using transmission electron microscopy (TEM) and powder X-ray diffraction (PXRD). Finally, the materials isolated from 1 and 6 were found by TEM to form irregular shape nanomaterials (8–15 nm), which by PXRD were found to be Ni 0 hcp (PDF: 01-089-7129) and fcc (PDF: 01-070-0989), respectively.« less

Biomimetic routes to nanoscale-toughened oxide ceramics

NASA Astrophysics Data System (ADS)

Deschaume, Olivier

In this work, a novel anion exchange technique has been developed and optimised in order to prepare extra-pure, hydroxide-free solutions of aluminium polyoxocations (A113 and A130) as well as for the preparation of nanosized, highly monodisperse aluminium hydroxide particles in the particle size range 20-200nm. In order for the evolution and composition of the resulting systems to be monitored, an array of characterisation techniques including 27A1 NMR, dynamic light scattering, po-tentiometry, conductometry and UV-Vis spectroscopy, have been implemented and complemented with successful data treatment strategies. The quantitative data obtained indicates that the static anion exchange method is a soft, environmentally friendly, low-cost, energy-saving and convenient procedure for the preparation of Al- containing model systems. The A1 species obtained can be used for high-precision model studies on A1 speciation, and serve as nanosize precursors to a variety of Al-containing materials. The use of these pure A1 precursors has a clear advantage in materials synthesis arising from an improved understanding and better control of A1 speciation. In a second development of the project, the model systems have been used in a nanotectonic approach to biomimetic materials synthesis, with possible applications to the optimisation of Al-containing materials such as ceramics or composite films. Bearing this aim in mind, the interactions of the prepared aluminium species with the model protein BSA and a bioelastomer, elastin, were monitored and the resulting composite materials characterised. The methodology developed for the synthesis and characterisation of pure A1 species and A1 species/biomolecule systems is a robust base for further studies spanning research fields such as Chemistry, Biology or Environmental sciences, and possess a large potential for application to industrial products and processes.

Controlled electrodeposition of Cu-Ga from a deep eutectic solvent for low cost fabrication of CuGaSe2 thin film solar cells.

PubMed

Steichen, Marc; Thomassey, Matthieu; Siebentritt, Susanne; Dale, Phillip J

2011-03-14

The electrochemical deposition of Ga and Cu-Ga alloys from the deep eutectic solvent choline chloride/urea (Reline) is investigated to prepare CuGaSe(2) (CGS) semiconductors for their use in thin film solar cells. Ga electrodeposition is difficult from aqueous solution due to its low standard potential and the interfering hydrogen evolution reaction (HER). Ionic liquid electrolytes offer a better thermal stability and larger potential window and thus eliminate the interference of solvent breakdown reactions during Ga deposition. We demonstrate that metallic Ga can be electrodeposited from Reline without HER interference with high plating efficiency on Mo and Cu electrodes. A new low cost synthetic route for the preparation of CuGaSe(2) absorber thin films is presented and involves the one-step electrodeposition of Cu-Ga precursors from Reline followed by thermal annealing. Rotating disk electrode (RDE) cyclic voltammetry (CV) is used in combination with viscosity measurements to determine the diffusion coefficients of gallium and copper ions in Reline. The composition of the codeposited Cu-Ga precursor layers can be controlled to form Cu/Ga thin films with precise stoichiometry, which is important for achieving good optoelectronic properties of the final CuGaSe(2) absorbers. The morphology, the chemical composition and the crystal structure of the deposited thin films are analysed by scanning electron microscopy/energy dispersive X-ray spectroscopy (SEM/EDX) and X-ray diffraction (XRD). Annealing of the Cu-Ga films in a selenium atmosphere allowed the formation of high quality CuGaSe(2) absorber layers. Completed CGS solar cells achieved a 4.1% total area power conversion efficiency.

A chemical bath deposition route to facet-controlled Ag{sub 3}PO{sub 4} thin films with improved visible light photocatalytic activity

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

Gunjakar, Jayavant L.; Jo, Yun Kyung; Kim, In Young

A facile, economic, and reproducible chemical bath deposition (CBD) method is developed for the fabrication of facet-controlled Ag{sub 3}PO{sub 4} thin films with enhanced visible light photocatalytic activity. The fine-control of bath temperature, precursor, complexing agent, substrate, and solution pH is fairly crucial in preparing the facet-selective thin film of Ag{sub 3}PO{sub 4} nanocrystal. The change of precursor from silver nitrate to silver acetate makes possible the tailoring of the crystal shape of Ag{sub 3}PO{sub 4} from cube to rhombic dodecahedron and also the bandgap tuning of the deposited films. The control of [Ag{sup +}]/[phosphate] ratio enables to maximize themore » loading amount of Ag{sub 3}PO{sub 4} crystals per the unit area of the deposited film. All the fabricated Ag{sub 3}PO{sub 4} thin films show high photocatalytic activity for visible light-induced degradation of organic molecules, which can be optimized by tailoring the crystal shape of the deposited crystals. This CBD method is also useful in preparing the facet-controlled hybrid film of Ag{sub 3}PO{sub 4}–ZnO photocatalyst. The present study clearly demonstrates the usefulness of the present CBD method for fabricating facet-controlled thin films of metal oxosalt and its nanohybrid. - Highlights: • The crystal facet of Ag{sub 3}PO{sub 4} films can be tuned by chemical bath deposition. • The crystal shape of Ag{sub 3}PO{sub 4} is tailorable from cube to rhombic dodecahedron. • Facet-tuned Ag{sub 3}PO{sub 4} film shows enhanced visible light photocatalyst activity.« less

Solution based synthesis of mixed-phase materials in the Li2TiO3-Li4SiO4 system

NASA Astrophysics Data System (ADS)

Hanaor, Dorian A. H.; Kolb, Matthias H. H.; Gan, Yixiang; Kamlah, Marc; Knitter, Regina

2015-01-01

As candidate tritium breeder materials for use in the ITER helium cooled pebble bed, ceramic multiphasic compounds lying in the region of the quasi-binary lithium metatitanate-lithium orthosilicate system may exhibit mechanical and physical advantages relative to single phase materials. Here we present an organometallic solution-based synthesis procedure for the low-temperature fabrication of compounds in the Li2TiO3-Li4SiO4 region and investigate phase stability and transformations through temperature varied X-ray diffraction and scanning calorimetry. Results demonstrate that the metatitanate and metasilicate phases Li2TiO3 and Li2SiO3 readily crystallise in nanocrystalline form at temperatures below 180 °C. Lithium deficiency in the region of 5% results from Li sublimation from Li4SiO4 and/or from excess Li incorporation in the metatitanate phase and brings about a stoichiometry shift, with product compounds exhibiting mixed lithium orthosilicate/metasilicate content towards the Si rich region and predominantly Li2TiO3 content towards the Ti rich region. Above 1150 °C the transformation of monoclinic to cubic γ-Li2TiO3 disordered solid-solution occurs while the melting of silicate phases indicates a likely monotectic type system with a solidus line in the region 1050-1100 °C. Synthesis procedures involving a lithium chloride precursor are not likely to be a viable option for breeder pebble synthesis as this route was found to yield materials with a more significant Li-deficiency exhibiting the crystallisation of the Li2TiSiO5 phase at intermediate compositions.