A statistical evaluation of the field emission for copper oxide nanostructures

A statistical data analysis methodology was developed to evaluate the field emission properties of many samples of copper oxide nanostructured field emitters. This analysis was largely done in terms of Seppen-Katamuki (SK) charts, field strength and emission current. Some physical and mathematical models were derived to describe the effect of small electric field perturbations in the Fowler-Nordheim (F-N) equation, and then to explain the trend of the data represented in the SK charts. The field enhancement factor and the emission area parameters showed to be very sensitive to variations in the electric field for most of the samples. We have found that the anode-cathode distance is critical in the field emission characterization of samples having a non-rigid nanostructure. (C) 2007 Elsevier B.V. All rights reserved.

EVALUATION OF EUCALYPTUS KRAFT PULP LIGNIN THROUGH THE NITROBENZENE OXIDATION, COPPER OXIDE REDUCTION AND ACIDOLYSIS TECHNIQUES

This study aimed to evaluate the sensitiveness of the information obtained for the residual lignin from Eucalyptus grandis kraft pulps analyzed through the nitrobenzene oxidation, copper oxide (CuO) reduction and acidolysis techniques. The chips were cooked, resulting pulps of kappa number 14,5 and 16,9, respectively. Both lignins' pulps were evaluated through three methods (nitrobenzene oxidation, copper oxide oxidation and acidolysis). Then, they were subjected to an oxygen delignification stage. The 16,9 kappa number pulp resulted in higher levels of non-condensed lignin structures by the acidolysis method, higher syringyl/vanillin ratios (S/V) by the nitrobenzene and copper oxide methods and better performance in the oxygen delignification stage. The different methods allowed to differ the residual lignin pulps with kappa number 14,5 and 16,9, and the nitrobenzene oxidation method showed the highest sensitiveness in this study results.

Structural study of copper oxide supported on a ceria-modified titania catalyst system

A structural study of CuO supported on a CeO2-TiO2 system was undertaken using X-ray diffraction (XRD) and X-ray absorption spectroscopy (XAS) techniques. The results of XRD revealed the presence of only two phases, TiO2 anatase and CeO2 cerianite. A trend towards smaller TiO2 crystallites was observed when cerium content increased. When the amount of cerium increased, Ti K-edge XANES analysis showed an increasing distortion of Ti sites. The results of Ce LIII-edge EXAFS showed that Ce atoms are coordinated by eight oxygen atoms at 2.32 Å. For the sample containing a small amount of cerium, the EXAFS analysis indicated that the local structure around Ce atoms was highly distorted. The catalysts presented quite different Cu K-edge XANES spectra compared to the spectra of the CuO and Cu2O reference compounds. The Cu-O mean bond length was close to that of the CuO and the Cu atoms in the catalysts are surrounded by approximately four oxygen atoms in their first shell. Copper supported on the ceria-modified titania support catalysts displayed a better performance in the methanol dehydrogenation when compared to copper supported only on titania or on ceria. © 2002 Plenum Publishing Corporation.

Cross-dehydrogenative coupling reaction using copper oxide impregnated on magnetite in deep eutectic solvents

The synthesis of different tetrahydroisoquinolines using choline chloride : ethylene glycol as a deep eutectic solvent (DES) and copper(II) oxide impregnated on magnetite as a catalyst has been accomplished successfully. The copper catalyst amount is the lowest loading ever reported. The presence of DES showed to be essential since the reaction in the absence of this medium did not proceed. A direct proportional relationship was found between the conductivity of DES medium and the yield obtained. The DES and the catalyst could be reused up to ten times without any detrimental effect on the yield of the reaction, with the aerobic conditions making the protocol highly sustainable, where the only waste is water.

Hydroxyl radical generation by cactus-like copper oxide nanoporous carbon catalysts for microcystin-LR environmental remediation

Copper oxide supported on nanoporous activated carbon (CuO-NPAC) is reported for the aqueous phase catalytic degradation of cyanotoxin microcystin-LR (MC-LR). The loading and spatial distribution of CuO throughout the NPAC matrix strongly influence the catalytic efficiency. CuO-NPAC synthesis was optimized with respect to the copper loading and thermal processing, and the physicochemical properties of the resulting materials were characterized by XRD, BET, TEM, SEM, EPR, TGA, XPS and FT-IR spectroscopy. EPR spin trapping and fluorescence spectroscopy showed in situ ˙OH formation via H2O2 over CuO-NPAC as the catalytically relevant oxidant. The impact of reaction conditions, notably CuO-NPAC loading, H2O2 concentration and solution pH, is discussed in relation to the reaction kinetics for MC-LR remediation.

Superconducting vortex fluctuations in YBa2Cu3O7-δ

Measurements of magnetization in YBa2Cu3O7-δ single crystals were performed for applied fields H parallel and perpendicular to the ab planes. The data show a temperature T = T* at which the magnetization M(T*) is independent of the applied field. This result is interpreted as due to vortex fluctuations of an anisotropic 3-D superconductor.

Properties of individual YBCO layers in a two-layered design for energy-efficient digital data cables

We are developing two-layered Yttrium Barium Copper Oxide (YBCO) thin film structures for energy efficient data links for superconducting electronics and present the results of their property measurements. High temperature superconductors (HTS) are advantageous for the implementation of energy-efficient cables interconnecting low temperature superconductor-based circuits and other cryogenic electronics circuits at higher temperature stages. The advantages of the HTS cables come from their low loss and low dispersion properties, allowing ballistic transfer of low power signals with very high bandwidth, low heat conduction and negligible inter-line crosstalk. The microstrip line cable geometry for typical materials is a two-layered film, in which the two superconducting layers are separated by an insulation layer with a minimized permittivity. We have made a proof of concept design of two YBCO films grown by pulsed laser deposition and then assembled into a sandwich with uniform insulating interlayer of tens of micrometers thick. We report on results obtained from such systems assembled in different ways. Structural and electromagnetic properties have been examined on individual films and on the corresponding sandwich composite. © 2013 IEEE.

Electrolytic Recovery of Copper and Zinc from Brasses

Reclaimed metals, or secondary metals, are becoming of great im­portance in the metal industries of the world. Secondary metals are an important factor in production. The increase in the secondary production of copper is due to many factors. One of these may be its permenance, that is, the metal does not corrode very readily. Another reason for increase in production is the high price paid for it.

Effects of Natural Organic Matter on the Dissolution Kinetics and Bioavailability of Metal Oxide Nanoparticles

The rapid development of nanotechnology and wider applications of engineered nanomaterials (ENMs) in the last few decades have generated concerns regarding their environmental and health risks. After release into the environment, ENMs undergo aggregation, transformation, and, for metal-based nanomaterials, dissolution processes, which together determine their fate, bioavailability and toxicity to living organisms in the ecosystems. The rates of these processes are dependent on nanomaterial characteristics as well as complex environmental factors, including natural organic matter (NOM). As a ubiquitous component of aquatic systems, NOM plays a key role in the aggregation, dissolution and transformation of metal-based nanomaterials and colloids in aquatic environments.

The goal of this dissertation work is to investigate how NOM fractions with different chemical and molecular properties affect the dissolution kinetics of metal oxide ENMs, such as zinc oxide (ZnO) and copper oxide (CuO) nanoparticles (NPs), and consequently their bioavailability to aquatic vertebrate, with Gulf killifish (Fundulus grandis) embryos as model organisms.

ZnO NPs are known to dissolve at relatively fast rates, and the rate of dissolution is influenced by water chemistry, including the presence of Zn-chelating ligands. A challenge, however, remains in quantifying the dissolution of ZnO NPs, particularly for time scales that are short enough to determine rates. This dissertation assessed the application of anodic stripping voltammetry (ASV) with a hanging mercury drop electrode to directly measure the concentration of dissolved Zn in ZnO NP suspensions, without separation of the ZnO NPs from the aqueous phase. Dissolved zinc concentration measured by ASV ([Zn]ASV) was compared with that measured by inductively coupled plasma mass spectrometry (ICP-MS) after ultracentrifugation ([Zn]ICP-MS), for four types of ZnO NPs with different coatings and primary particle diameters. For small ZnO NPs (4-5 nm), [Zn]ASV was 20% higher than [Zn]ICP-MS, suggesting that these small NPs contributed to the voltammetric measurement. For larger ZnO NPs (approximately 20 nm), [Zn]ASV was (79±19)% of [Zn]ICP-MS, despite the high concentrations of ZnO NPs in suspension, suggesting that ASV can be used to accurately measure the dissolution kinetics of ZnO NPs of this primary particle size.

Using the ASV technique to directly measure dissolved zinc concentration, we examined the effects of 16 different NOM isolates on the dissolution kinetics of ZnO NPs in buffered potassium chloride solution. The observed dissolution rate constants (kobs) and dissolved zinc concentrations at equilibrium increased linearly with NOM concentration (from 0 to 40 mg-C L-1) for Suwannee River humic acid (SRHA), Suwannee River fulvic acid and Pony Lake fulvic acid. When dissolution rates were compared for the 16 NOM isolates, kobs was positively correlated with certain properties of NOM, including specific ultraviolet absorbance (SUVA), aromatic and carbonyl carbon contents, and molecular weight. Dissolution rate constants were negatively correlated to hydrogen/carbon ratio and aliphatic carbon content. The observed correlations indicate that aromatic carbon content is a key factor in determining the rate of NOM-promoted dissolution of ZnO NPs. NOM isolates with higher SUVA were also more effective at enhancing the colloidal stability of the NPs; however, the NOM-promoted dissolution was likely due to enhanced interactions between surface metal ions and NOM rather than smaller aggregate size.

Based on the above results, we designed experiments to quantitatively link the dissolution kinetics and bioavailability of CuO NPs to Gulf killifish embryos under the influence of NOM. The CuO NPs dissolved to varying degrees and at different rates in diluted 5‰ artificial seawater buffered to different pH (6.3-7.5), with or without selected NOM isolates at various concentrations (0.1-10 mg-C L-1). NOM isolates with higher SUVA and aromatic carbon content (such as SRHA) were more effective at promoting the dissolution of CuO NPs, as with ZnO NPs, especially at higher NOM concentrations. On the other hand, the presence of NOM decreased the bioavailability of dissolved Cu ions, with the uptake rate constant negatively correlated to dissolved organic carbon concentration ([DOC]) multiplied by SUVA, a combined parameter indicative of aromatic carbon concentration in the media. When the embryos were exposed to CuO NP suspension, changes in their Cu content were due to the uptake of both dissolved Cu ions and nanoparticulate CuO. The uptake rate constant of nanoparticulate CuO was also negatively correlated to [DOC]×SUVA, in a fashion roughly proportional to changes in dissolved Cu uptake rate constant. Thus, the ratio of uptake rate constants from dissolved Cu and nanoparticulate CuO (ranging from 12 to 22, on average 17±4) were insensitive to NOM type or concentration. Instead, the relative contributions of these two Cu forms were largely determined by the percentage of CuO NP that was dissolved.

Overall, this dissertation elucidated the important role that dissolved NOM plays in affecting the environmental fate and bioavailability of soluble metal-based nanomaterials. This dissertation work identified aromatic carbon content and its indicator SUVA as key NOM properties that influence the dissolution, aggregation and biouptake kinetics of metal oxide NPs and highlighted dissolution rate as a useful functional assay for assessing the relative contributions of dissolved and nanoparticulate forms to metal bioavailability. Findings of this dissertation work will be helpful for predicting the environmental risks of engineered nanomaterials.

Characterization of Copper Covetic Bulk and Films: Copper with High Carbon Content

Incorporation of carbon nanostructures in metals is desirable to combine the strongly bonded electrons in the metal and the free electrons in carbon nanostructures that give rise to high ampacity and high conductivity, respectively. Carbon in copper has the potential to impact industries such as: building construction, power generation and transmission, and microelectronics. This thesis focuses on the structure and properties of bulk and thin films of a new material, Cu covetic, that contains carbon in concentrations up to 16 at.%. X-ray photoelectron spectroscopy (XPS) shows C 1s peak with both sp2 and sp3 bonded C measuring up to 3.5 wt.% (16 at.%). High resolution transmission electron microscopy and electron diffraction of bulk covetic samples show a modulated structure of ≈ 1.6 nm along several crystallographic directions in regions that have high C content suggesting that the carbon incorporates into the copper lattice forming a network. Electron energy loss spectra (EELS) from covetics reveal that the level of graphitization from the source material, activated carbon, is maintained in the covetic structure. Bulk Cu covetics have a slight increase in the lattice constant, as well as <111> texturing, or possibly a different structure, compared to pure Cu. Density functional theory calculations predict bonding between C and Cu at the edges and defects of graphene sheets. The electrical resistivity of bulk covetics first increases and then decreases with increasing C content. Cu covetic films were deposited using e-beam and pulsed laser deposition (PLD) at different temperatures. No copper oxide or any allotropes of carbon are present in the films. The e-beam films show enhanced electrical and optical properties when compared to pure Cu films of the same thickness even though no carbon was detected by XPS or EELS. They also have slightly higher ampacity than Cu metal films. EELS analysis of the C-K-edge in the PLD films indicate that graphitic carbon is transferred from the bulk into the films with uniform carbon distribution. PLD films exhibit flatter and higher transmittance curves and sheet resistance two orders of magnitude lower than e-beam films leading to a high figure of merit as transparent conductors.

A nanometre-scale non-periodic structural variation in high temperature superconducting ceramics and the implications for properties

Non-periodic structural variation has been found in the high T-c cuprates, YBa2Cu3O7-x and Hg0.67Pb0.33Ba2Ca2Cu3O8+delta, by image analysis of high resolution transmission electron microscope (HRTEM) images. We use two methods for analysis of the HRTEM images. The first method is a means for measuring the bending of lattice fringes at twin planes. The second method is a low-pass filter technique which enhances information contained by diffuse-scattered electrons and reveals what appears to be an interference effect between domains of differing lattice parameter in the top and bottom of the thin foil. We believe that these methods of image analysis could be usefully applied to the many thousands of HRTEM images that have been collected by other workers in the high temperature superconductor field. This work provides direct structural evidence for phase separation in high T-c cuprates, and gives support to recent stripes models that have been proposed to explain various angle resolved photoelectron spectroscopy and nuclear magnetic resonance data. We believe that the structural variation is a response to an opening of an electronic solubility gap where holes are not uniformly distributed in the material but are confined to metallic stripes. Optimum doping may occur as a consequence of the diffuse boundaries between stripes which arise from spinodal decomposition. Theoretical ideas about the high T-c cuprates which treat the cuprates as homogeneous may need to be modified in order to take account of this type of structural variation.

Determinació experimental de la temperatura de descomposició d'òxids metàl•lics

L’objecte d’aquest projecte és determinar la temperatura de descomposició de l’YBCO perun rang de diferents pressions parcials d’oxigen en l’atmosfera que es troba. Per obteniraquests resultats, en primer lloc, hem d’aconseguir generar de forma sistemàtica diversespressions parcials dins del forn i, en segon lloc, buscar quin és el mètode experimental mésadequat que ens doni els resultats més fiables utilitzant com a referència la descomposiciódel CuO. A més de realitzar els calibratges necessàries dels aparells utilitzats per poderobtenir uns bons resultats

Síntesi de pólvores de superconductors d’alta temperatura : YBa2Cu3O7 i GdBa2Cu3O7 per via de dissolució-polimerització

L’objectiu del projecte és obtenir pólvores dels superconductors d’alta temperatura YBa2Cu3O7 i GdBa2Cu3O7 per la via de dissolució-polimerització. Aquestes pólvores seran obtingudes a partir d’òxids (Itri o Gadolini i Coure) i carbonat de bari amb àcid nítric en una dissolució aquosa de Polietinenglicol (PEG), per tal de convertir aquests òxids en nitrats coordinats amb les cadenes de PEG. Aquest producte intermedi es sotmetrà a una piròlisis per tal d’obtenir òxids i carbonats, però amb una mida més reduïda respecte als productes inicials i un grau de barreja més íntim, permetent que reaccionin entre ells amb més facilitat. Finalment, per tal d’obtenir els superconductors YBa2Cu3O7 i GdBa2Cu3O7 es farà un últim tractament tèrmic a alta temperatura en el qual es produirà la reacció desitjada. Durant tot el procés es duran a terme anàlisis d’aquest per mitjà de tècniques de Termogravimetria (TGA), d’Anàlisi Tèrmica Diferencial (DTA), espectroscòpia Infraroja (IR) i la difracció de raig X (DRX) . També s’analitzaran els diferents productes que es van obtenint (intermedis i finals) amb l’ajuda de l’espectrometria IR i la difracció de pólvores. En base a aquests resultats, es variaran els paràmetres de la reacció (concentracions, temperatures, etc.) i dels tractaments tèrmics (atmosfera, temperatura, temps, etc.) per tal d’optimitzar el producte

Síntesi de pólvores del superconductor GdBa2Cu3O7 a partir de dissolucions precursores de nitrats

Estudi de l’obtenció de les les pólvores del compost superconductor GdBa2Cu3O7 mitjançant la utilització de diferents mètodes partint de solucions aquoses de nitrat estabilitzades amb PEG, com son apartir del reactor Kjeldhal o a partir d’un assecatge ràpid damunt una placa calefactora.En el procés d’obtenció d’aquestes pólvores es vol fer una caracterització dels productesinicials, intermedis i finals que s’aniran obtenint durant les diferents etapes. Aquest estudi esfarà mitjançant varis tipus d’anàlisi, com la difracció de raig X (XRD), l’espectroscòpiainfraroja (IR) o la termogravimetria (TG).Finalment, també es comprovarà si els nitrats i el PEG que formen la solució aquosa espoden assecar en forma de capa, i si posteriorment, és possible la seva descomposició percombustió

Óxido misto de ítrio-alumínio dopado com Eu(III)

In this work, we report the synthesis and the photoluminescence features of Eu(III)-doped yttrium-aluminium oxide obtained by non-hydrolytic sol-gel routes. After heating the powders above 600 ºC the XRD patterns show the presence of the Y4Al2O9 (YAM) and Y3Al5O12 (YAG) phases. At 800 and at 1500 ºC the PL spectra display the Eu(III) lines characteristic of the YAM monoclinic phase. The 5D0->7F2 transition is favored relatively to the 5D0->7F1 lines. However, at 1100 ºC the cubic YAG is the preferential phase and the 5D0->7F1 transition dominates the spectrum. The Eu(III) ions lie in a centrosymmetrical site. The different solvents used in the sol-gel synthesis also change the relative proportion between these two phases. This is monitored analyzing the modifications in the relative intensity between the 5D0->7F2 and the 5D0->7F1 transitions.