The structural properties of Zr-based bulk metallic glasses subjected to high pressure torsion at different temperatures

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

Boltynjuk, E. V., E-mail: boltynjuk@gmail.com; Ubyivovk, E. V.; Kshumanev, A. M.

2016-06-17

The structural properties of a Zr{sub 62}Cu{sub 22}Al{sub 10}Fe{sub 5}Dy{sub 1} bulk metallic glasses were investigated. Cylindrical rods of the Zr{sub 62}Cu{sub 22}Al{sub 10}Fe{sub 5}Dy{sub 1} BMG were subjected to high pressure torsion at temperatures of 20°C and 150°C. X-ray diffraction, transmission electron microscopy were used to determine peculiarities of the modified structure. Analysis of fracture surfaces, nanohardness measurements were conducted to investigate the influence of structural changes on mechanical behavior of processed samples.

High Pressure Properties of a Ba-Cu-Zn-P Clathrate-I

DOE PAGES

Dolyniuk, Juli -Anna; Kovnir, Kirill

2016-08-12

Here, the high pressure properties of the novel tetrel-free clathrate, Ba 8Cu 13.1Zn 3.3P 29.6, were investigated using synchrotron powder X-ray diffraction. The pressure was applied using a diamond anvil cell. No structural transitions or decomposition were detected in the studied pressure range of 0.1–7 GPa. The calculated bulk modulus for Ba 8Cu 13.1Zn 3.3P 29.6 using a third-order Birch-Murnaghan equation of state is 65(6) GPa at 300 K. This bulk modulus is comparable to the bulk moduli of Ge- and Sn-based clathrates, like A 8Ga 16Ge 30 (A = Sr, Ba) and Sn 19.3Cu 4.7P 22I 8, but lowermore » than those for the transition metal-containing silicon-based clathrates, Ba 8 T xSi46–x, T = Ni, Cu; 3 ≤ x ≤ 5.« less

An environment-dependent semi-empirical tight binding model suitable for electron transport in bulk metals, metal alloys, metallic interfaces, and metallic nanostructures. II. Application—Effect of quantum confinement and homogeneous strain on Cu conductance

NASA Astrophysics Data System (ADS)

Hegde, Ganesh; Povolotskyi, Michael; Kubis, Tillmann; Charles, James; Klimeck, Gerhard

2014-03-01

The Semi-Empirical tight binding model developed in Part I Hegde et al. [J. Appl. Phys. 115, 123703 (2014)] is applied to metal transport problems of current relevance in Part II. A systematic study of the effect of quantum confinement, transport orientation, and homogeneous strain on electronic transport properties of Cu is carried out. It is found that quantum confinement from bulk to nanowire boundary conditions leads to significant anisotropy in conductance of Cu along different transport orientations. Compressive homogeneous strain is found to reduce resistivity by increasing the density of conducting modes in Cu. The [110] transport orientation in Cu nanowires is found to be the most favorable for mitigating conductivity degradation since it shows least reduction in conductance with confinement and responds most favorably to compressive strain.

Effect of shock pressure on the structure and superconducting properties of Y-Ba-Cu-O in explosively fabricated bulk metal-matrix composites

NASA Technical Reports Server (NTRS)

Murr, L. E.; Niou, C. S.; Pradhan-Advani, M.

1991-01-01

While it is now well established that copper-oxide-based power, or virtually any other ceramic superconductor powder, can be consolidated and encapsulated within a metal matrix by explosive consolidation, the erratic superconductivity following fabrication has posed a major problem for bulk applications. The nature of this behavior was found to arise from microstructural damage created in the shock wave front, and the residual degradation in superconductivity was demonstrated to be directly related to the peak shock pressure. The explosively fabricated or shock loaded YBa2Cu3Ox examples exhibit drastically altered rho (or R) - T curves. The deterioration in superconductivity is even more noticeable in the measurement of ac magnetic susceptibility and flux exclusion or shielding fraction which is also reduced in proportion to increasing peak shock pressure. The high frequency surface resistance (in the GHz range) is also correspondingly compromised in explosively fabricated, bulk metal-matrix composites based on YBa2Cu3O7. Transmission electron microscopy (including lattice imaging techniques) is being applied in an effort to elucidate the fundamental (microstructural) nature of the shock-induced degradation of superconductivity and normal state conductivity. One focus of TEM observations has assumed that oxygen displaced from b-chains rather than oxygen-vacancy disorder in the basal plane of oxygen deficient YBa2Cu3Ox may be a prime mechanism. Shock-wave displaced oxygen may also be locked into new positions or interstitial clusters or chemically bound to displaced metal (possibly copper) atoms to form precipitates, or such displacements may cause the equivalent of local lattice cell changes as a result of stoichiometric changes. While the shock-induced suppression of T(sub c) is not desirable in the explosive fabrication of bulk metal-matrix superconductors, it may be turned into an advantage if the atomic-scale distortion can be understood and controlled as local flux pinning sites.

Effect of shock pressure on the structure and superconducting properties of Y-Ba-Cu-O in explosively fabricated bulk metal-matrix composites

NASA Technical Reports Server (NTRS)

Murr, L. E.; Niou, C. S.; Pradhan, M.; Schoenlein, L. H.

1990-01-01

While it is now well established that copper-oxide-based powder, or virtually any other ceramic superconductor powder, can be consolidated and encapsulated within a metal matrix by explosive consolidation, the erratic superconductivity following fabrication has posed a major problem for bulk applications. The nature of this behavior was found to arise from microstructural damage created in the shock wave front, and the residual degradation in superconductivity was demonstrated to be directly related to the peak shock pressure. The explosively fabricated or shock loaded YBa2Cu3Ox examples exhibit drastically altered rho (or R) - T curves. The deterioration in superconductivity is even more noticeable in the measurement of ac magnetic susceptibility and flux exclusion or shielding fraction which is also reduced in proportion to increasing peak shock pressure. The high-frequency surface resistance (in the GHz range) is also correspondingly compromised in explosively fabricated, bulk metal-matrix composites based on YBa2Cu3O7. Transmission electron microscopy (including lattice imaging techniques) is being applied in an effort to elucidate the fundamental (microstructural) nature of the shock-induced degradation of superconductivity and normal state conductivity. One focus of TEM observations has assumed that oxygen displaced from b-chains rather than oxygen-vacancy disorder in the basal plane of oxygen deficient YBa2Cu3Ox may be a prime mechanism. Shock-wave displaced oxygen may also be locked into new positions or interstitial clusters or chemically bound to displaced metal (possibly copper) atoms to form precipitates, or such displacements may cause the equivalent of local lattice cell changes as a result of stoichiometric changes. While the shock-induced suppression of T(sub c) is not desirable in the explosive fabrication of bulk metal-matrix superconductors, it may be turned into an advantage if the atomic-scale distortion can be understood and controlled as local flux pinning sites.

Electronic, Mechanical, and Dielectric Properties of Two-Dimensional Atomic Layers of Noble Metals

NASA Astrophysics Data System (ADS)

Kapoor, Pooja; Kumar, Jagdish; Kumar, Arun; Kumar, Ashok; Ahluwalia, P. K.

2017-01-01

We present density functional theory-based electronic, mechanical, and dielectric properties of monolayers and bilayers of noble metals (Au, Ag, Cu, and Pt) taken with graphene-like hexagonal structure. The Au, Ag, and Pt bilayers stabilize in AA-stacked configuration, while the Cu bilayer favors the AB stacking pattern. The quantum ballistic conductance of the noble-metal mono- and bilayers is remarkably increased compared with their bulk counterparts. Among the studied systems, the tensile strength is found to be highest for the Pt monolayer and bilayer. The noble metals in mono- and bilayer form show distinctly different electron energy loss spectra and reflectance spectra due to the quantum confinement effect on going from bulk to the monolayer limit. Such tunability of the electronic and dielectric properties of noble metals by reducing the degrees of freedom of electrons offers promise for their use in nanoelectronics and optoelectronics applications.

Zr-based bulk metallic glass as a cylinder material for high pressure apparatuses

DOE PAGES

Komatsu, Kazuki; Munakata, Koji; Matsubayashi, Kazuyuki; ...

2015-05-12

Zirconium-based bulk metallic glass (Zr-based BMG) has outstanding properties as a cylinder mate- rial for piston-cylinder high pressure apparatuses and is especially useful for neutron scattering. The piston-cylinder consisting of a Zr-based BMG cylinder with outer/inner diameters of 8.8/2.5 mm sustains pressures up to 1.81 GPa and ruptured at 2.0 GPa, with pressure values determined by the superconduct- ing temperature of lead. The neutron attenuation of Zr-based BMG is similar to that of TiZr null-scattering alloy and more transparent than that of CuBe alloy. No contamination of sharp Bragg reflections is observed in the neutron diffraction pattern for Zr-based BMG.more » The magnetic susceptibility of Zr-based BMG is similar to that of CuBe alloy; this leads to a potential application for measurements of magnetic properties under pressure.« less

Copper, zinc, and cadmium in various fractions of soil and fungi in a Swedish forest.

PubMed

Vinichuk, Mykhailo M

2013-01-01

Ectomycorrhizal fungi profoundly affect forest ecosystems through mediating nutrient uptake and maintaining forest food webs. The accumulation of metals in each transfer step from bulk soil to fungal sporocarps is not well known. The accumulation of three metals copper (Cu), zinc (Zn) and cadmium (Cd) in bulk soil, rhizosphere, soil-root interface, fungal mycelium and sporocarps of mycorrhizal fungi in a Swedish forest were compared. Concentrations of all three metals increased in the order: bulk soil < soil-root interface (or rhizosphere) < fungal mycelium < fungal sporocarps. The uptake of Cu, Zn and Cd during the entire transfer process in natural conditions between soil and sporocarps occurred against a concentration gradient. In fungal mycelium, the concentration of all three metals was about three times higher than in bulk soil, and the concentration in sporocarps was about two times higher than in mycelium. In terms of accumulation, fungi (mycelium and sporocarps) preferred Cd to Zn and Cu. Zinc concentration in sporocarps and to a lesser extent in mycelium depended on the concentration in soil, whereas, the uptake of Cu and Cd by both sporocarps and mycelium did not correlate with metal concentration in soil. Heavy metal accumulation within the fungal mycelium biomass in the top forest soil layer (0-5 cm) might account for ca. 5-9% of the total amount of Cu, 5-11% of Zn, and 16-32% of Cd. As the uptake of zinc and copper by fungi may be balanced, this implied similarities in the uptake mechanism.

Effect of MoSi2 Content on Dry Sliding Tribological Properties of Zr-Based Bulk Metallic Glass Composites

NASA Astrophysics Data System (ADS)

Liu, Longfei; Yang, Jun

2017-12-01

Zr55Cu30Al10Ni5 bulk metallic glass and its composites were prepared by suction casting into a copper mold. The effect of MoSi2 content on the tribological behavior of Zr55Cu30Al10Ni5 BMG was studied by using a high-speed reciprocating friction and wear tester. The results indicate that the friction coefficient and wear resistance of the BMGs can be improved by a certain amount of crystalline phase induced by MoSi2 content from 1 to 3% and deteriorated with MoSi2 content of 4%. The wear mechanism of both the metallic glass and its composite is abrasive wear. The mechanism of crystalline phase-dependent tribological properties of the composite was discussed based on the wear track and mechanical properties in the present work. The wear behavior of Zr55Cu30Al10Ni5 BMG and its composite indicates that a good combination of the toughness and the hardness can make the composite be well wear resistant.

Shock wave response of a zirconium-based bulk metallic glass and its composite

NASA Astrophysics Data System (ADS)

Zhuang, Shiming; Lu, Jun; Ravichandran, Guruswami

2002-06-01

A zirconium-based bulk metallic glass, Zr41.2Ti13.8Cu12.5Ni10Be22.5 (Vit 1), and its composite, Zr56.3Ti13.8Cu6.9Ni5.6Nb5.0Be12.5 (beta-Vit), were subjected to planar impact loading. A surprisingly low amplitude elastic precursor and bulk wave, corresponding to the elastic response of the "frozen structure" of the intact metallic glasses, were observed to precede the rate-dependent large deformation shock wave. A concave downward curvature after the initial increase of the Us-Up shock Hugoniots suggests that a phase-change-like transition occurred during shock compression. Further, compression damage occurred due to the shear localization. The spalling in Vit 1 was induced by shear localization, while in beta-Vit, it was due to debonding of the beta-phase boundary from the matrix. The spall strengths at strain rate of 2 x106 s-1 were determined to be 2.35 and 2.11 GPa for Vit 1 and beta-Vit, respectively.

CuO and ZnO nanoparticles: phytotoxicity, metal speciation, and induction of oxidative stress in sand-grown wheat

NASA Astrophysics Data System (ADS)

Dimkpa, Christian O.; McLean, Joan E.; Latta, Drew E.; Manangón, Eliana; Britt, David W.; Johnson, William P.; Boyanov, Maxim I.; Anderson, Anne J.

2012-09-01

Metal oxide nanoparticles (NPs) are reported to impact plant growth in hydroponic systems. This study describes the impact of commercial CuO (<50 nm) and ZnO (<100 nm) NPs on wheat ( Triticum aestivum) grown in a solid matrix, sand. The NPs contained both metallic and non-metallic impurities to different extents. Dynamic light scattering and atomic force microscopy (AFM) assessments confirmed aggregation of the NPs to submicron sizes. AFM showed transformation of ZnO NPs from initial rhomboid shapes in water to elongated rods in the aqueous phase of the sand matrix. Solubilization of metals occurred in the sand at similar rates from CuO or ZnO NPs as their bulk equivalents. Amendment of the sand with 500 mg Cu and Zn/kg sand from the NPs significantly ( p = 0.05) reduced root growth, but only CuO NPs impaired shoot growth; growth reductions were less with the bulk amendments. Dissolved Cu from CuO NPs contributed to their phytotoxicity but Zn release did not account for the changes in plant growth. Bioaccumulation of Cu, mainly as CuO and Cu(I)-sulfur complexes, and Zn as Zn-phosphate was detected in the shoots of NP-challenged plants. Total Cu and Zn levels in shoot were similar whether NP or bulk materials were used. Oxidative stress in the NP-treated plants was evidenced by increased lipid peroxidation and oxidized glutathione in roots and decreased chlorophyll content in shoots; higher peroxidase and catalase activities were present in roots. These findings correlate with the NPs causing increased production of reactive oxygen species. The accumulation of Cu and Zn from NPs into edible plants has relevance to the food chain.

Caltech Center for Structural and Amorphous Metals

DTIC Science & Technology

2005-05-10

Flores, D. Suh, R. Howell, P. Asoka -Kumar, P.A. Sterne, and R. H. Dauskardt, "Flow and Fracture of Bulk Metallic Glass Alloys and Their Composites...Behavior of Zr-Ti-Cu-Ni-Be Bulk Metallic Glass Alloys," Materials Transactions, JIM, 42 [4], 638-641, 2001. K. M. Flores, D. Suh, P. Asoka -Kumar, P.A...Materials Research, 17[5], 1153-1161, 2002. D. Suh, P. Asoka -Kumar and R. H. Dauskardt, "The Effects of Hydrogen on Viscoelastic Relaxation in Zr-Ti-Ni-Cu

Mechanical properties of Zr41.2Ti13.8Ni10Cu12.5Be22.5 bulk metallic glass with different geometric confinements

NASA Astrophysics Data System (ADS)

Zhang, Changqin; Zhang, Haifeng; Sun, Qilei; Liu, Kegao

2018-03-01

Zr41.2Ti13.8Ni10Cu12.5Be22.5 (Vit 1) bulk metallic glass with Cu sleeves at different positions was prepared by the Cu mold casting method, and the effects of different geometric confinements offered by Cu sleeves on the mechanical properties of Vit 1 were investigated. It was found that the mechanical properties were prominently influenced by different geometric confinements and the plasticity could be modified by optimizing the positions of Cu sleeves. The results revealed that shear band initiation and propagation could be efficiently intervened by changing the radial boundary restraints, which led to quite different mechanical behaviors.

Modeling deformation behavior of Cu-Zr-Al bulk metallic glass matrix composites

NASA Astrophysics Data System (ADS)

Pauly, S.; Liu, G.; Wang, G.; Das, J.; Kim, K. B.; Kühn, U.; Kim, D. H.; Eckert, J.

2009-09-01

In the present work we prepared an in situ Cu47.5Zr47.5Al5 bulk metallic glass matrix composite derived from the shape memory alloy CuZr. We use a strength model, which considers percolation and a three-microstructural-element body approach, to understand the effect of the crystalline phase on the yield stress and the fracture strain under compressive loading, respectively. The intrinsic work-hardenability due to the martensitic transformation of the crystalline phase causes significant work hardening also of the composite material.

Bulk-surface relationship of an electronic structure for high-throughput screening of metal oxide catalysts

NASA Astrophysics Data System (ADS)

Kweun, Joshua Minwoo; Li, Chenzhe; Zheng, Yongping; Cho, Maenghyo; Kim, Yoon Young; Cho, Kyeongjae

2016-05-01

Designing metal-oxides consisting of earth-abundant elements has been a crucial issue to replace precious metal catalysts. To achieve efficient screening of metal-oxide catalysts via bulk descriptors rather than surface descriptors, we investigated the relationship between the electronic structure of bulk and that of the surface for lanthanum-based perovskite oxides, LaMO3 (M = Ti, V, Cr, Mn, Fe, Co, Ni, Cu). Through density functional theory calculations, we examined the d-band occupancy of the bulk and surface transition-metal atoms (nBulk and nSurf) and the adsorption energy of an oxygen atom (Eads) on (001), (110), and (111) surfaces. For the (001) surface, we observed strong correlation between the nBulk and nSurf with an R-squared value over 94%, and the result was interpreted in terms of ligand field splitting and antibonding/bonding level splitting. Moreover, the Eads on the surfaces was highly correlated with the nBulk with an R-squared value of more than 94%, and different surface relaxations could be explained by the bulk electronic structure (e.g., LaMnO3 vs. LaTiO3). These results suggest that a bulk-derived descriptor such as nBulk can be used to screen metal-oxide catalysts.

Mechanical relaxation in a Zr-based bulk metallic glass: Analysis based on physical models

NASA Astrophysics Data System (ADS)

Qiao, J. C.; Pelletier, J. M.

2012-08-01

The mechanical relaxation behavior in a Zr55Cu30Ni5Al10 bulk metallic glass is investigated by dynamic mechanical analysis in both temperature and frequency domains. Master curves can be obtained for the storage modulus G' and for the loss modulus G'', confirming the validity of the time-temperature superposition principle. Different models are discussed to describe the main (α) relaxation, e.g., Debye model, Havriliak-Negami (HN) model, Kohlrausch-Williams-Watt (KWW) model, and quasi-point defects (QPDs) model. The main relaxation in bulk metallic glass cannot be described using a single relaxation time. The HN model, the KWW model, and the QPD theory can be used to fit the data of mechanical spectroscopy experiments. However, unlike the HN model and the KWW model, some physical parameters are introduced in QPD model, i.e., atomic mobility and correlation factor, giving, therefore, a new physical approach to understand the mechanical relaxation in bulk metallic glasses.

Imprinting bulk amorphous alloy at room temperature

DOE PAGES

Kim, Song-Yi; Park, Eun-Soo; Ott, Ryan T.; ...

2015-11-13

We present investigations on the plastic deformation behavior of a brittle bulk amorphous alloy by simple uniaxial compressive loading at room temperature. A patterning is possible by cold-plastic forming of the typically brittle Hf-based bulk amorphous alloy through controlling homogenous flow without the need for thermal energy or shaping at elevated temperatures. The experimental evidence suggests that there is an inconsistency between macroscopic plasticity and deformability of an amorphous alloy. Moreover, imprinting of specific geometrical features on Cu foil and Zr-based metallic glass is represented by using the patterned bulk amorphous alloy as a die. These results demonstrate the abilitymore » of amorphous alloys or metallic glasses to precisely replicate patterning features onto both conventional metals and the other amorphous alloys. In conclusion, our work presents an avenue for avoiding the embrittlement of amorphous alloys associated with thermoplastic forming and yields new insight the forming application of bulk amorphous alloys at room temperature without using heat treatment.« less

Trace metals in bulk precipitation and throughfall in a suburban area of Japan

NASA Astrophysics Data System (ADS)

Hou, H.; Takamatsu, T.; Koshikawa, M. K.; Hosomi, M.

Throughfall and bulk precipitation samples were collected monthly for 1.5 years over bare land and under canopies of Japanese cedar ( Cryptomeria japonica), Japanese red pine ( Pinus densiflora), Japanese cypress ( Chamaecyparis obtusa), and bamboo-leafed oak ( Quercus myrsinaefolia) in a suburban area of Japan. Samples were analyzed for dissolved Al, Mn, Fe, Cu, Zn, Ag, In, Sn, Sb and Bi by ICP-AES and ICP-MS. The metal concentrations were higher in throughfall, especially that of C. japonica, than bulk precipitation. Enrichment ratios (ERs: ratios of metal concentrations in throughfall to those in bulk precipitation) ranged from 2.5 (Zn) to 5.3 (Ag) (3.9 on average), and ERs for slightly soluble metals were generally higher than those for easily soluble metals. Concentrations of Mn, Fe, Cu, and Zn accounted for 99% of the total concentration of heavy metals in rainwater, whereas those of rare metals such as Ag, In, Sn, and Bi totaled <0.23%. Average concentrations of rare metals were 0.002 and 0.010 μg l -1 for Ag, 0.001 and 0.005 μg l -1 for In, 0.062 and 0.21 μg l -1 for Sn, and 0.006 and 0.023 μg l -1 for Bi in bulk precipitation and throughfall, respectively. The metal concentrations in rainwater were negatively correlated to the volume of rainwater, indicating that washout is the main mechanism that incorporates metals into rainwater. From the enrichment factors, that is, (X/Al) rain/(X/Al) crust, metals other than Fe were shown to be more enriched in rainwater than in the Earth's crust, including those present as a result of leaching from soil dust (Mn) and from anthropogenic sources (Cu, Zn, Ag, In, Sn, Sb, and Bi).

Plastic deformation behaviors of Ni- and Zr-based bulk metallic glasses subjected to nanoindentation

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

Weizhong, Liang, E-mail: wzliang1966@126.com; Zhiliang, Ning; Zhenqian, Dang

2013-12-15

Plastic deformation behaviors of Ni{sub 42}Ti{sub 20}Zr{sub 21.5}Al{sub 8}Cu{sub 5}Si{sub 3.5} and Zr{sub 51}Ti{sub 5}Ni{sub 10}Cu{sub 25}Al{sub 9} bulk metallic glasses at room temperature were studied by nanoindentation testing and atomic force microscopy under equivalent indentation experimental conditions. The different chemical composition of these two bulk metallic glasses produced variant tendencies for displacement serrated flow to occur during the loading process. The nanoindentation strain rate was calculated as a function of indentation displacement in order to verify the occurrence of displacement serrated flow at different loading rates. Atomic force microscopy revealed decreasing numbers of discrete shear bands around the indentationmore » sites as loading rates increased from 0.025 to 2.5 mNs{sup −1}. Variations in plastic deformation behaviors between Ni and Zr-based glasses materials can be explained by the different metastable microstructures and thermal stabilities of the two materials. The mechanism governing plastic deformation of these metallic glasses was analyzed in terms of an established model of the shear transformation zone. - Highlights: • Plastic deformation of Ni- and Zr-based BMG is studied under identical conditions • Zr-based BMG undergoes a greater extent of plastic deformation than Ni-based BMG • Nanoindentation strain rate is studied to clarify variation in plastic deformation • Metastable microstructure, thermal stability affect BMG plastic deformation.« less

Atomic structure and glass forming ability of Cu46Zr46Al8 bulk metallic glass

NASA Astrophysics Data System (ADS)

Wang, X. D.; Jiang, Q. K.; Cao, Q. P.; Bednarcik, J.; Franz, H.; Jiang, J. Z.

2008-11-01

By using a combination of state-of-the-art experimental and computational methods, the high glass forming ability (GFA) of Cu46Zr46Al8 alloy is studied from the view of its atomic packing. Three-dimensional atomic configuration is well established. It is found that Al atoms almost homogeneously distribute around Cu and Zr atoms without segregation, causing the local environment around Cu and Zr atoms in Cu46Zr46Al8 bulk metallic glass different from that of the major competing phase of Cu10Zr7. Furthermore, the addition of Al not only increases the amount of icosahedronlike clusters but also makes them more homogeneous distribution, which can enhance the GFA by increasing the structural incompatibility with the competing crystalline phases.

Friction stir welding of Zr-based bulk metallic glass

NASA Astrophysics Data System (ADS)

Ji, Y. S.; Fujii, H.; Maeda, M.; Nakata, K.; Kimura, H.; Inoue, A.; Nogi, K.

2009-05-01

A Zr55Cu30Al10Ni5 bulk metallic glass plate was successfully welded below its crystallization temperature by friction stir welding. The flash formation and heat concentration at the shoulder edge was minimized using a wider tool and the angle of the recessed shoulder surface was 3°. To analyze the crystallization of the base material and stir zone, the microstructure and mechanical properties were analyzed using DSC, XRD, TEM, and micro-hardness. As a result, it was found that the amorphous structure and original mechanical properties were maintained in the whole joints.

Development of interface-dominant bulk Cu/V nanolamellar composites by cross accumulative roll bonding

PubMed Central

Zeng, L. F.; Gao, R.; Xie, Z. M.; Miao, S.; Fang, Q. F.; Wang, X. P.; Zhang, T.; Liu, C. S.

2017-01-01

Traditional nanostructured metals are inherently comprised of a high density of high-energy interfaces that make this class of materials not stable in extreme conditions. Therefore, high performance bulk nanostructured metals containing stable interfaces are highly desirable for extreme environments applications. Here, we reported an attractive bulk Cu/V nanolamellar composite that was successfully developed by integrating interface engineering and severe plastic deformation techniques. The layered morphology and ordered Cu/V interfaces remained stable with respect to continued rolling (total strain exceeding 12). Most importantly, for layer thickness of 25 nm, this bulk Cu/V nanocomposite simultaneously achieves high strength (hardness of 3.68 GPa) and outstanding thermal stability (up to 700 °C), which are quite difficult to realize simultaneously in traditional nanostructured materials. Such extraordinary property in our Cu/V nanocomposite is achieved via an extreme rolling process that creates extremely high density of stable Cu/V heterophase interfaces and low density of unstable grain boundaries. In addition, high temperature annealing result illustrates that Rayleigh instability is the dominant mechanism driving the onset of thermal instability after exposure to 800 °C. PMID:28094346

Preparation, glass forming ability, crystallization and deformation of (zirconium, hafnium)-copper-nickel-aluminum-titanium-based bulk metallic glasses

NASA Astrophysics Data System (ADS)

Gu, Xiaofeng

Multicomponent Zr-based bulk metallic glasses are the most promising metallic glass forming systems. They exhibit great glass forming ability and fascinating mechanical properties, and thus are considered as potential structural materials. One potential application is that they could be replacements of the depleted uranium for making kinetic energy armor-piercing projectiles, but the density of existing Zr-based alloys is too low for this application. Based on the chemical and crystallographic similarities between Zr and Hf, we have developed two series of bulk metallic glasses with compositions of (HfxZr1-x) 52.5Cu17.9Ni14.6Al10Ti5 and (HfxZr1-x) 57Cu20Ni8Al10Ti5 ( x = 0--1) by gradually replacing Zr by Hf. Remarkably increased density and improved mechanical properties have been achieved in these alloys. In these glasses, Hf and Zr play an interchangeable role in determining the short range order. Although the glass forming ability decreases continuously with Hf addition, most of these alloys remain bulk glass-forming. Recently, nanocomposites produced from bulk metallic glasses have attracted wide attention due to improved mechanical properties. However, their crystalline microstructure (the grain size and the crystalline volume fraction) has to be optimized. We have investigated crystallization of (Zr, Hf)-based bulk metallic glasses, including the composition dependence of crystallization paths and crystallization mechanisms. Our results indicate that the formation of high number density nanocomposites from bulk metallic glasses can be attributed to easy nucleation and slowing-down growth processes, while the multistage crystallization behavior makes it more convenient to control the microstructure evolution. Metallic glasses are known to exhibit unique plastic deformation behavior. At low temperature and high stress, plastic flow is localized in narrow shear bands. Macroscopic investigations of shear bands (e.g., chemical etching) suggest that the internal structure of shear bands is different from that of undeformed surroundings, but the direct structural characterization of shear bands down to the atomic level has been lacking. In this work, we have used transmission electron microscopy to explore the structural and chemical changes inside the shear bands. Nanometer-scale defects (void-like and high density regions) have been identified as a result of plastic deformation. It is these defects that distinguish shear bands from undeformed regions. Processes occurring in an active shear band and after stress removal are analogous to a thermally activated relaxation except that the relaxation time is much shorter in the former case.

Toughness of Wear-Resistant Cu-Zr-Based Bulk Metallic Glasses

NASA Astrophysics Data System (ADS)

Andersen, Laura M.

Bulk metallic glasses (BMGs) have the potential to exhibit exceptional wear-resistance due to their high hardness and strength. Combined with their other unique properties, this makes them ideal candidates for a wide range of technological applications (e.g. gears, bearings, biomaterials). In the course of this dissertation, high-glass-forming bulk metallic glasses are prepared and characterized in order to identify wear-resistant compositions and optimize their toughness. First, a comprehensive study identifies a class of Cu-Zr-based BMGs that exhibit more exceptional wear performance than other BMGs. The results demonstrate that when BMGs are designed properly, they exhibit wear properties that compete with, and can surpass, state-of-the-art engineering materials. It is identified that, in order to optimize the wear performance of Cu-Zr-based BMG gears, toughness should be maximized. Second, the notch toughness of wear-resistant Cu43Zr 43Al7Be7 BMGs with in-situ crystallization is investigated. In order to identify in-situ crystallization using X-ray diffraction (XRD) with Cu K? radiation, extremely long dwell times and high X-ray fluxes are required. This demonstrates the importance of reporting operating parameters when trying to evaluate the amorphous nature of BMGs. XRD, energy-dispersive X-ray spectroscopy (EDS) and electron backscatter diffraction (EBSD) are used to identify the metastable crystalline phase. The notch toughness is found to correlate closely with the amount of crystallization and the composition of the remaining amorphous matrix. Finally, the effect of substituting standard-grade zirconium lump (99.8% excluding up to 4% hafnium) for high-purity zirconium crystal bar (99.5%) in Cu43Zr43Al7Be7 is investigated. Introducing low-purity zirconium significantly decreases the glass-forming-ability and reduces the notch toughness of the BMG. Furthermore, Weibull statistics provide an analysis of the variability in toughness for high-purity ingots synthesized both in a small laboratory arc-melter and synthesized commercially. The dissertation concludes with a summary of key findings that have led to our increase in knowledge and a discussion of particularly pressing directions for future research in this field.

Electrodeposition of Metal on GaAs Nanowires

NASA Astrophysics Data System (ADS)

Liu, Chao; Einabad, Omid; Watkins, Simon; Kavanagh, Karen

2010-10-01

Copper (Cu) electrical contacts to freestanding gallium arsenide (GaAs) nanowires have been fabricated via electrodeposition. The nanowires are zincblende (111) oriented grown epitaxially on n-type Si-doped GaAs (111)B substrates by gold-catalyzed Vapor Liquid Solid (VLS) growth in a metal organic vapour phase epitaxy (MOVPE) reactor. The epitaxial electrodeposition process, based on previous work with bulk GaAs substrates, consists of a substrate oxide pre-etch in dilute ammonium-hydroxide carried out prior to galvanostatic electrodeposition in a pure Cu sulphate aqueous electrolyte at 20-60^oC. For GaAs nanowires, we find that Cu or Fe has a preference for growth on the gold catalyst avoiding the sidewalls. After removing gold, both metals still prefer to grow only on top of the nanowire, which has the largest potential field.

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.

Phonon dispersion relation of Mg-Cu-Gd bulk metallic glasses

NASA Astrophysics Data System (ADS)

Suthar, P. H.

2016-05-01

Collective dynamics and elastic constants of bulk metallic glasses Mg65Cu25Gd10 and Mg60Cu25Gd15 are computed using the Hubbard -Beeby approach and our well recognized model potential. The important ingredients in the present study are the pair potential and local field correction functions (LFCF). The local field correction functions due to Hartree (H), Farid et al (F) and Sarkar Sen et al (S) are employed to investigation the influence of the screening effects on the longitudinal and traversed of phonon modes of glassy system. The results for the elastic constants are found to be in good agreement with experimental data.

Pair distribution function study and mechanical behavior of as-cast and structurally relaxed Zr-based bulk metallic glasses

NASA Astrophysics Data System (ADS)

Fan, Cang; Liaw, P. K.; Wilson, T. W.; Choo, H.; Gao, Y. F.; Liu, C. T.; Proffen, Th.; Richardson, J. W.

2006-12-01

Contrary to reported results on structural relaxation inducing brittleness in amorphous alloys, the authors found that structural relaxation actually caused an increase in the strength of Zr55Cu35Al10 bulk metallic glass (BMG) without changing the plasticity. Three dimensional models were rebuilt for the as-cast and structurally relaxed BMGs by reverse Monte Carlo (RMC) simulations based on the pair distribution function (PDF) measured by neutron scattering. Only a small portion of the atom pairs was found to change to more dense packing. The concept of free volume was defined based on the PDF and RMC studies, and the mechanism of mechanical behavior was discussed.

Investigation on Explosive Welding of Zr53Cu35Al12 Bulk Metallic Glass with Crystalline Copper

NASA Astrophysics Data System (ADS)

Feng, Jianrui; Chen, Pengwan; Zhou, Qiang

2018-05-01

A Zr53Cu35Al12 bulk metallic glass (BMG) was welded to a crystalline Cu using explosive welding technique. The morphology and the composition of the composite were characterized using optical microscopy, scanning electron microscopy, energy-dispersive x-ray spectroscopy and transmission electron microscopy. The investigation indicated that the BMG and Cu were tightly joined together without visible defects, and a thin diffusion layer appeared at the interface. The captured jet at the end of the welding region mostly comes from the Cu side. Amorphous and partially crystallized structures have been observed within the diffusion layer, but the BMG in close proximity to the interface still retains its amorphous state. Nanoindentation tests reveal that the interface exhibits an increment in hardness compared with the matrix on both sides.

Origin of the world-class PGE-Au mineralisation in the Skaergaard intrusion by bulk S-saturation, accumulation, partial dissolution, and secondary reef formation.

NASA Astrophysics Data System (ADS)

Daugaard Nielsen, Troels Frederik

2013-04-01

The Skaergaard intrusion is the type locality for stratiform "Skaergaard-type" PGE-Au mineralisations with layers rich in PGE, followed by Au and Cu. Models for stratiform PGE mineralisations divide into uppers and downers models. Downers models assume bulk liquid S-saturation followed by a variety of accumulation processes and the second model the scavenging of metals by fluids deep in intrusions and deposition in chemical traps above. This investigation is based on continuous profiling in roof, walls and floor. Cu anomalies in roof, walls and floor are contemporaneous and systematics in Pd/Pt and Pd/Au ratios document bulk liquid S-saturation, no loss of precious metal below the mineralisation and no obvious chemical traps. A classic downers process is documented. The timing of the mineralisation is controlled by composition of liquidus plagioclase and fraction of residual magma (F). PGE concentrations are an order of magnitude higher in the floor mineralisation due to accumulation. Systematics across the mineralisation shows in the centre of the intrusion 5 main levels of Pd-concentration followed by an Au and a Cu-level. All levels PGE and Au levels have c. 100 ppm Cu and show no correlation to PGE and Au. 90% of all PGE is contained in one phase, skaergaardite (PdCu).The lower and main PGE concentration has moderate Pd/Pt ratios. Overlying secondary reefs have high, basal Pd/Pt and show local S-saturation reflecting d-values of PGE between sulphide and silicate liquid. No basal high Pd/Pt anomaly occurs at Au and Cu levels and the floor shows four types of mineralisation. The main PGE reef (Pd5) has gradual increase and decrease in PGE and Pd/Pt, dissolution of sulphide, increasing PGE+Au/Cu due to reaction between interstial and documented reactive Fe-rich silicate melt and the bulk magma sulfides. Dissolution of Cu-sulfide increases PGE/Cu, reduces the size of droplets to 30µ (av.) and provides metals for secondary reefs above - formed by migration of interstitial melt - and show expected decrease in Pd/Pt and increase in Au/Pd due to fractionation and substitutions in Skaergaardite (PdCu) and tetra-auricupride (AuCu). The main Au level is elevated relative to the top Pd-level (Pd1). High resolution X-ray tomography and petrography shows the precious metal phases on grain boundaries. The paragenesis is complex with many tellurides, arsenite and sulfides, and primary hydrous phases including amphiboles, ferrosaponite and chlorite. The Au mineralisation level is the residual of the Fe-rich interstitial silicate melt trapped by the layering of the gabbros. The Cu levels above are like the secondary Pd-levels secondary mineralisation levels caused by reaction between primary sulphide and Fe-rich melt. The Skaergaard-type mineralisation owes its characteristics to the concentration of Fe-rich interstitial melt and loss of immiscible granophyric melt from the mush zone at the floor of the residual bulk magma and a continuum of dissolution and S-saturation in an ever changing interstitial melt environment.

A proof for substitution of endogenous iron (II) in lipoxygenase by exogenous Cu2+.

PubMed

Cai, Yan; Xu, Hong; Xia, Yongmei; Su, Yafen; Fang, Yun

2010-10-01

Soybean lipoxygenase (LOX) contains endogenous iron (II) at the active site, which is important for the enzyme activity. The activity of LOX can be accelerated by some exogenous metal ions including Cu2+. However, the mechanism of the activity improvement caused by exogenous metal ions remains unclear, not only for LOX but for most other metalloenzymes. Meanwhile, the possibility that exogenous metal ions can displace endogenous iron (II) is still in discussion for a lack of a direct and quantitative proof. In this paper, a quantitative proof of replacing iron (II) inside LOX by exogenous Cu2+ was provided, simply using UV-Vis spectrometry with two indicators p-carboxylantipyrylazo and 9-(4-carboxyphenyl)-2,3,7-trihydroxyl-6-fluorine. A 0.56 microM free iron (II) was observed in the bulk solution after incubating 9.45 microM Cu2+ with 16.10 microM LOX at 20 degrees C for 5 min, which is in coincidence with the decrement of Cu2+ in the bulk solution (0.53 microM), implying that iron (II) was replaced by Cu2+.

The Relationship between Bulk and Mobile Forms of Heavy Metals in Soils of Kursk

NASA Astrophysics Data System (ADS)

Nevedrov, N. P.; Protsenko, E. P.; Glebova, I. V.

2018-01-01

The contamination of Kursk urboecotopes by heavy metals (Pb, Cd, Zn, Cu, Ni) is considered. The relationships between the contents of bulk and mobile forms of heavy metal ions have been examined. The results of monitoring studies attest to a tendency for the accumulation of both bulk and mobile forms of heavy metals in the humus-accumulative horizon, except for bulk cadmium and mobile nickel. Linear and nonlinear regression models of the bulk contents of Pb, Cd, Zn, and Ni as dependent on the contents of their mobile forms have been developed. These models allow us to calculate the bulk content of heavy metal ions in the soils of urboecotopes using simpler methods of the extraction and laboratory determination of their mobile forms.

The effect of Nb addition on mechanical properties, corrosion behavior, and metal-ion release of ZrAlCuNi bulk metallic glasses in artificial body fluid.

PubMed

Qiu, C L; Liu, L; Sun, M; Zhang, S M

2005-12-15

Bulk metallic glasses (BMGs) of Zr(65 - x)Nb(x)- Cu(17.5)Ni(10)Al(7.5) with Nb = 0, 2, and 5 at % were prepared by copper mold casting. Compression tests reveal that the two BMGs containing Nb exhibited superior strength and plasticity to the base alloy. The corrosion behavior of the alloys obtained was investigated in artificial body fluid by electrochemical measurements. It was found that the addition of Nb significantly enhanced the corrosion resistance of the Zr-based BMG, as indicated by a remarkable increase in corrosion potential and pitting potential. XPS analysis revealed that the passive film formed after anodic polarization was enriched in aluminum oxide and depleted in phosphate ions for the BMGs containing Nb, which accounts for the improvement of corrosion resistance. On the other hand, metal-ion release of different BMGs were determined in PPb (ng/mL) level with inductively coupled plasma mass spectrometry (ICP-MS) after being immersed in artificial body fluid at 37 degrees C for 20 days. It was found that the addition of Nb considerably reduced the ion release of all kinds of metals of the base system. This is probably attributed to the promoting effect of Nb on a rapid formation of highly protective film.

Long-term field metal extraction by Pelargonium: phytoextraction efficiency in relation to plant maturity.

PubMed

Shahid, Muhammad; Arshad, Muhammad; Kaemmerer, Michel; Pinelli, Eric; Probst, Anne; Baque, David; Pradere, Philippe; Dumat, Camille

2012-01-01

The long length of periods required for effective soil remediation via phytoextraction constitutes a weak point that reduces its industrial use. However, these calculated periods are mainly based on short-term and/or hydroponic controlled experiments. Moreover, only a few studies concern more than one metal, although soils are scarcely polluted by only one element. In this scientific context, the phytoextraction of metals and metalloids (Pb, Cd, Zn, Cu, and As) by Pelargonium was measured after a long-term field experiment. Both bulk and rhizosphere soils were analyzed in order to determine the mechanisms involved in soil-root transfer. First, a strong increase in lead phytoextraction was observed with plant maturity, significantly reducing the length of the period required for remediation. Rhizosphere Pb, Zn, Cu, Cd, and As accumulation was observed (compared to bulk soil), indicating metal mobilization by the plant, perhaps in relation to root activity. Moreover, metal phytoextraction and translocation were found to be a function of the metals' nature. These results, taken altogether, suggest that Pelargonium could be used as a multi-metal hyperaccumulator under multi-metal soil contamination conditions, and they also provide an interesting insight for improving field phytoextraction remediation in terms of the length of time required, promoting this biological technique.

Liquid-solid joining of bulk metallic glasses

NASA Astrophysics Data System (ADS)

Huang, Yongjiang; Xue, Peng; Guo, Shu; Wu, Yang; Cheng, Xiang; Fan, Hongbo; Ning, Zhiliang; Cao, Fuyang; Xing, Dawei; Sun, Jianfei; Liaw, Peter K.

2016-07-01

Here, we successfully welded two bulk metallic glass (BMG) materials, Zr51Ti5Ni10Cu25Al9 and Zr50.7Cu28Ni9Al12.3 (at. %), using a liquid-solid joining process. An atomic-scale metallurgical bonding between two BMGs can be achieved. The interface has a transition layer of ~50 μm thick. The liquid-solid joining of BMGs can shed more insights on overcoming their size limitation resulting from their limited glass-forming ability and then promoting their applications in structural components.

Liquid-solid joining of bulk metallic glasses

PubMed Central

Huang, Yongjiang; Xue, Peng; Guo, Shu; Wu, Yang; Cheng, Xiang; Fan, Hongbo; Ning, Zhiliang; Cao, Fuyang; Xing, Dawei; Sun, Jianfei; Liaw, Peter K.

2016-01-01

Here, we successfully welded two bulk metallic glass (BMG) materials, Zr51Ti5Ni10Cu25Al9 and Zr50.7Cu28Ni9Al12.3 (at. %), using a liquid-solid joining process. An atomic-scale metallurgical bonding between two BMGs can be achieved. The interface has a transition layer of ~50 μm thick. The liquid-solid joining of BMGs can shed more insights on overcoming their size limitation resulting from their limited glass-forming ability and then promoting their applications in structural components. PMID:27471073

Liquid-solid joining of bulk metallic glasses.

PubMed

Huang, Yongjiang; Xue, Peng; Guo, Shu; Wu, Yang; Cheng, Xiang; Fan, Hongbo; Ning, Zhiliang; Cao, Fuyang; Xing, Dawei; Sun, Jianfei; Liaw, Peter K

2016-07-29

Here, we successfully welded two bulk metallic glass (BMG) materials, Zr51Ti5Ni10Cu25Al9 and Zr50.7Cu28Ni9Al12.3 (at. %), using a liquid-solid joining process. An atomic-scale metallurgical bonding between two BMGs can be achieved. The interface has a transition layer of ~50 μm thick. The liquid-solid joining of BMGs can shed more insights on overcoming their size limitation resulting from their limited glass-forming ability and then promoting their applications in structural components.

Liquid-solid joining of bulk metallic glasses

DOE PAGES

Huang, Yongjiang; Xue, Peng; Guo, Shu; ...

2016-07-29

Here, we successfully welded two bulk metallic glass (BMG) materials, Zr 51Ti 5Ni 10Cu 25Al 9 and Zr 50.7Cu 28Ni 9Al 12.3 (at. %), using a liquid-solid joining process. An atomic-scale metallurgical bonding between two BMGs can be achieved. The interface has a transition layer of ~50 μm thick. In conclusion, the liquid-solid joining of BMGs can shed more insights on overcoming their size limitation resulting from their limited glass-forming ability and then promoting their applications in structural components.

Local melting to design strong and plastically deformable bulk metallic glass composites

PubMed Central

Qin, Yue-Sheng; Han, Xiao-Liang; Song, Kai-Kai; Tian, Yu-Hao; Peng, Chuan-Xiao; Wang, Li; Sun, Bao-An; Wang, Gang; Kaban, Ivan; Eckert, Jürgen

2017-01-01

Recently, CuZr-based bulk metallic glass (BMG) composites reinforced by the TRIP (transformation-induced plasticity) effect have been explored in attempt to accomplish an optimal of trade-off between strength and ductility. However, the design of such BMG composites with advanced mechanical properties still remains a big challenge for materials engineering. In this work, we proposed a technique of instantaneously and locally arc-melting BMG plate to artificially induce the precipitation of B2 crystals in the glassy matrix and then to tune mechanical properties. Through adjusting local melting process parameters (i.e. input powers, local melting positions, and distances between the electrode and amorphous plate), the size, volume fraction, and distribution of B2 crystals were well tailored and the corresponding formation mechanism was clearly clarified. The resultant BMG composites exhibit large compressive plasticity and high strength together with obvious work-hardening ability. This compelling approach could be of great significance for the steady development of metastable CuZr-based alloys with excellent mechanical properties. PMID:28211890

Source apportionment of atmospheric bulk deposition in the Belgrade urban area using Positive Matrix factorization

NASA Astrophysics Data System (ADS)

Tasić, M.; Mijić, Z.; Rajšić, S.; Stojić, A.; Radenković, M.; Joksić, J.

2009-04-01

The primary objective of the present study was to assess anthropogenic impacts of heavy metals to the environment by determination of total atmospheric deposition of heavy metals. Atmospheric depositions (wet + dry) were collected monthly, from June 2002 to December 2006, at three urban locations in Belgrade, using bulk deposition samplers. Concentrations of Fe, Al, Pb, Zn, Cu, Ni, Mn, Cr, V, As and Cd were analyzed using atomic absorption spectrometry. Based upon these results, the study attempted to examine elemental associations in atmospheric deposition and to elucidate the potential sources of heavy metal contaminants in the region by the use of multivariate receptor model Positive Matrix Factorization (PMF).

Comparative Toxicity of Nanoparticulate CuO and ZnO to Soil Bacterial Communities

PubMed Central

Rousk, Johannes; Ackermann, Kathrin; Curling, Simon F.; Jones, Davey L.

2012-01-01

The increasing industrial application of metal oxide Engineered Nano-Particles (ENPs) is likely to increase their environmental release to soils. While the potential of metal oxide ENPs as environmental toxicants has been shown, lack of suitable control treatments have compromised the power of many previous assessments. We evaluated the ecotoxicity of ENP (nano) forms of Zn and Cu oxides in two different soils by measuring their ability to inhibit bacterial growth. We could show a direct acute toxicity of nano-CuO acting on soil bacteria while the macroparticulate (bulk) form of CuO was not toxic. In comparison, CuSO4 was more toxic than either oxide form. Unlike Cu, all forms of Zn were toxic to soil bacteria, and the bulk-ZnO was more toxic than the nano-ZnO. The ZnSO4 addition was not consistently more toxic than the oxide forms. Consistently, we found a tight link between the dissolved concentration of metal in solution and the inhibition of bacterial growth. The inconsistent toxicological response between soils could be explained by different resulting concentrations of metals in soil solution. Our findings suggested that the principal mechanism of toxicity was dissolution of metal oxides and sulphates into a metal ion form known to be highly toxic to bacteria, and not a direct effect of nano-sized particles acting on bacteria. We propose that integrated efforts toward directly assessing bioavailable metal concentrations are more valuable than spending resources to reassess ecotoxicology of ENPs separately from general metal toxicity. PMID:22479561

Microstructural Characterization of Base Metal Alloys with Conductive Native Oxides for Electrical Contact Applications

NASA Astrophysics Data System (ADS)

Senturk, Bilge Seda

Metallic contacts are a ubiquitous method of connecting electrical and electronic components/systems. These contacts are usually fabricated from base metals because they are inexpensive, have high bulk electrical conductivities and exhibit excellent formability. Unfortunately, such base metals oxidize in air under ambient conditions, and the characteristics of the native oxide scales leads to contact resistances orders of magnitude higher than those for mating bare metal surface. This is a critical technological issue since the development of unacceptably high contact resistances over time is now by far the most common cause of failure in electrical/electronic devices and systems. To overcome these problems, several distinct approaches are developed for alloying base metals to promote the formation of self-healing inherently conductive native oxide scales. The objective of this dissertation study is to demonstrate the viability of these approaches through analyzing the data from Cu-9La (at%) and Fe-V binary alloy systems. The Cu-9 La alloy structure consists of eutectic colonies tens of microns in diameter wherein a rod-like Cu phase lies within a Cu6La matrix phase. The thin oxide scale formed on the Cu phase was found to be Cu2O as expected while the thicker oxide scale formed on the Cu6La phase was found to be a polycrystalline La-rich Cu2O. The enhanced electrical conductivity in the native oxide scale of the Cu-9La alloy arises from heavy n-type doping of the Cu2O lattice by La3+. The Fe-V alloy structures consist of a mixture of large elongated and equiaxed grains. A thin polycrystalline Fe3O4 oxide scale formed on all of the Fe-V alloys. The electrical conductivities of the oxide scales formed on the Fe-V alloys are higher than that formed on pure Fe. It is inferred that this enhanced conductivity arises from doping of the magnetite with V+4 which promotes electron-polaron hopping. Thus, it has been demonstrated that even in simple binary alloy systems one can obtain a dramatic reduction in the contact resistances of alloy oxidized surfaces as compared with those of the pure base metals.

Second amorphous-to-crystalline phase transformation in Cu(60)Ti(20)Zr(20) bulk metallic glass.

PubMed

Cao, Q P; Li, J F; Zhang, P N; Horsewell, A; Jiang, J Z; Zhou, Y H

2007-06-20

The second amorphous-to-crystalline phase transformation in Cu(60)Ti(20)Zr(20) bulk metallic glass was investigated by differential scanning calorimetry and x-ray diffractometry. The difference of the Gibbs free energies between the amorphous phase and the crystalline products during the transformation is estimated to be about 2.46 kJ mol(-1) at 753 K, much smaller than the 61 kJ mol(-1) obtained assuming that it is a polymorphic transformation. It was revealed that the phase transformation occurs through a eutectic crystallization of Cu(51)Zr(14) and Cu(2)TiZr, having an effective activation energy of the order of 400 kJ mol(-1). The average Avrami exponent n is about 2.0, indicating that the crystallization is diffusion controlled.

Metal transport and remobilisation in a basin affected by acid mine drainage: the role of ochreous amorphous precipitates.

PubMed

Consani, Sirio; Carbone, Cristina; Dinelli, Enrico; Balić-Žunić, Tonci; Cutroneo, Laura; Capello, Marco; Salviulo, Gabriella; Lucchetti, Gabriella

2017-06-01

Metal-polluted mine waters represent a major threat to the quality of waters and sediments in a downstream basin. At the confluence between acidic mine waters and the unpolluted waters of the Gromolo Torrent (Liguria, North-West Italy), the massive formation of an ochreous amorphous precipitate takes place. This precipitate forms a soft blanket that covers the torrent bed and can be observed down to its mouth in the sea. The aim of this work is to evaluate the dispersion of metals in the Gromolo Torrent basin from the abandoned Cu-Fe sulphide mine of Libiola to the Ligurian Sea and to assess the metal remobilisation from the amorphous precipitates. The mineralogy of the superficial sediments collected in the torrent bed and the concentrations of different elements of environmental concern (Cu, Zn, Cd, Co, Cr, Mn, Ni, Pb, As, and Sb) were therefore analysed. The results showed that the precipitates contain high concentration of Fe, Al, Cu, and Zn, significantly modifying the bulk chemistry of the Gromolo Torrent sediments. In order to evaluate the possible remobilisation of ecotoxic elements from the amorphous precipitates, bulk leaching tests were performed with both deionised and seawater. Bulk leaching tests with deionised water mobilised primarily high Pb amounts, but also relatively high concentrations of Fe, Al, Cu, and Zn are released in the leachate. In seawater tests, Fe, Al, Cu, and Zn were released in smaller amounts, while other elements like Mn, Cd, Co, and Ni increased in the released fraction. Pb was still strongly released as in deionised water experiments. The results show that the interaction of precipitates and seawater can remobilise high concentrations of metals, thus affecting the surrounding environment.

In-situ study of crystallization kinetics in ternary bulk metallic glass alloys with different glass forming abilities

DOE PAGES

Lan, Si; Wei, Xiaoya; Zhou, Jie; ...

2014-11-18

In-situ transmission electron microcopy and time-resolved neutron diffraction were used to study crystallization kinetics of two ternary bulk metallic glasses during isothermal annealing in the supercooled liquid region. It is found that the crystallization of Zr 56Cu 36Al 8, an average glass former, follows continuous nucleation and growth, while that of Zr 46Cu 46Al 8, a better glass former, is characterized by site-saturated nucleation, followed by slow growth. Possible mechanisms for the observed differences and the relationship to the glass forming ability are discussed.

Tribological studies of a Zr-based bulk metallic glass with different states

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

Jiang, Feng; Qu, Jun; Fan, Guojiang

The tribological characteristics of a bulk-metallic glass (BMG) Zr52.5Cu17.9Ni14.6Al10.0Ti5.0 (Vit 105) with different states have been studied. Friction and wear tests were conducted using a ball-on-flat reciprocating sliding apparatus against AISI E52100 bearing steel under dry condition. The observed wear resistance in an ascending order is deformed, crept, relaxed, and as-cast. Results suggested that the wear process of BMG alloys involved abrasion, adhesion, and oxidation. The differences in hardness, free volume, and embrittlement at different states significantly affected the friction and wear behaviors of the BMG alloys.

Toxicity of nanoparticles of CuO, ZnO and TiO2 to microalgae Pseudokirchneriella subcapitata.

PubMed

Aruoja, Villem; Dubourguier, Henri-Charles; Kasemets, Kaja; Kahru, Anne

2009-02-01

Toxicities of ZnO, TiO2 and CuO nanoparticles to Pseudokirchneriella subcapitata were determined using OECD 201 algal growth inhibition test taking in account potential shading of light. The results showed that the shading effect by nanoparticles was negligible. ZnO nanoparticles were most toxic followed by nano CuO and nano TiO2. The toxicities of bulk and nano ZnO particles were both similar to that of ZnSO4 (72 h EC50 approximately 0.04 mg Zn/l). Thus, in this low concentration range the toxicity was attributed solely to solubilized Zn2+ ions. Bulk TiO2 (EC50=35.9 mg Ti/l) and bulk CuO (EC50=11.55 mg Cu/l) were less toxic than their nano formulations (EC50=5.83 mg Ti/l and 0.71 mg Cu/l). NOEC (no-observed-effect-concentrations) that may be used for risk assessment purposes for bulk and nano ZnO did not differ (approximately 0.02 mg Zn/l). NOEC for nano CuO was 0.42 mg Cu/l and for bulk CuO 8.03 mg Cu/l. For nano TiO2 the NOEC was 0.98 mg Ti/l and for bulk TiO2 10.1 mg Ti/l. Nano TiO2 formed characteristic aggregates entrapping algal cells that may contribute to the toxic effect of nano TiO2 to algae. At 72 h EC50 values of nano CuO and CuO, 25% of copper from nano CuO was bioavailable and only 0.18% of copper from bulk CuO. Thus, according to recombinant bacterial and yeast Cu-sensors, copper from nano CuO was 141-fold more bioavailable than from bulk CuO. Also, toxic effects of Cu oxides to algae were due to bioavailable copper ions. To our knowledge, this is one of the first systematic studies on effects of metal oxide nanoparticles on algal growth and the first describing toxic effects of nano CuO towards algae.

Tribological characterisation of Zr-based bulk metallic glass in simulated physiological media

NASA Astrophysics Data System (ADS)

Chen, Q.; Chan, K. C.; Liu, L.

2011-10-01

Due to their excellent wear resistant properties and high strength, as well as a low Young's modulus, Zr-based bulk metallic glasses (BMGs) are potentially suitable biomaterials for low-friction arthroplasty. The wear characteristics of the Zr60.14Cu22.31Fe4.85Al9.7Ag3 bulk amorphous alloy against ultra-high-molecular-weight polyethylene (UHMWPE) compared to a CoCrMo/UHMWPE combination were investigated in two different wear screening test devices, reciprocating and unidirectional. Hank's solution and sterile calf bovine serum were selected as the lubricant fluid media. It was found that different fluid media had insignificant effect on polyethylene wear against BMG counterfaces. The wear behaviour obtained on both test devices demonstrated that Zr-based BMG achieved UHMWPE counterface wear rates superior to conventional cast CoCrMo alloy, where the wear rate of UHMWPE is decreased by over 20 times. The tribological performance of these joints is superior to that of conventional metal-on-polymer designs. Contact angle measurements suggested that the advantage of BMG over a CoCrMo alloy counterface is attributed to its highly hydrophilic surfaces.

Structure, bonding, and catalytic activity of monodisperse, transition-metal-substituted CeO2 nanoparticles.

PubMed

Elias, Joseph S; Risch, Marcel; Giordano, Livia; Mansour, Azzam N; Shao-Horn, Yang

2014-12-10

We present a simple and generalizable synthetic route toward phase-pure, monodisperse transition-metal-substituted ceria nanoparticles (M0.1Ce0.9O2-x, M = Mn, Fe, Co, Ni, Cu). The solution-based pyrolysis of a series of heterobimetallic Schiff base complexes ensures a rigorous control of the size, morphology and composition of 3 nm M0.1Ce0.9O2-x crystallites for CO oxidation catalysis and other applications. X-ray absorption spectroscopy confirms the dispersion of aliovalent (M(3+) and M(2+)) transition metal ions into the ceria matrix without the formation of any bulk transition metal oxide phases, while steady-state CO oxidation catalysis reveals an order of magnitude increase in catalytic activity with copper substitution. Density functional calculations of model slabs of these compounds confirm the stabilization of M(3+) and M(2+) in the lattice of CeO2. These results highlight the role of the host CeO2 lattice in stabilizing high oxidation states of aliovalent transition metal dopants that ordinarily would be intractable, such as Cu(3+), as well as demonstrating a rational approach to catalyst design. The current work demonstrates, for the first time, a generalizable approach for the preparation of transition-metal-substituted CeO2 for a broad range of transition metals with unparalleled synthetic control and illustrates that Cu(3+) is implicated in the mechanism for CO oxidation on CuO-CeO2 catalysts.

Crystallization kinetics of Mg–Cu–Yb–Ca–Ag metallic glasses

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

Tsarkov, Andrey A., E-mail: tsarkov@misis.ru; WPI Advanced Institute for Materials Research, Tohoku University, Katahira 2-1-1, Aoba-Ku, Sendai 980-8577; Zanaeva, Erzhena N.

The paper presents research into a Mg–Cu–Yb system based metallic glassy alloys. Metallic glasses were prepared using induction melting and further injection on a spinning copper wheel. The effect of alloying by Ag and Ca on the glass forming ability and the kinetics of crystallization of Mg–Cu–Yb system based alloys were studied. The differential scanning calorimeter and X-ray diffractometer were used to investigate the kinetics of crystallization and the phase composition of the samples. An indicator of glass forming ability, effective activation energy of crystallization, and enthalpy of mixing were calculated. An increase of the Ca and Ag content hasmore » a positive effect on the glass forming ability, the effective activation energy of crystallization, and the enthalpy of mixing. The highest indicators of the glass forming ability and the thermal stability were found for alloys that contain both alloying elements. The Ag addition suppresses precipitation of the Mg{sub 2}Cu phase during crystallization. A dual-phase glassy-nanocrystalline Mg structure was obtained in Mg{sub 65}Cu{sub 25}Yb{sub 10} and Mg{sub 59.5}Cu{sub 22.9}Yb{sub 11}Ag{sub 6.6} alloys after annealing. Bulk samples with a composite glassy-crystalline structure were obtained in Mg{sub 59.5}Cu{sub 22.9}Yb{sub 11}Ag{sub 6.6} and Mg{sub 64}Cu{sub 21}Yb{sub 9.5}Ag{sub 5.5} alloys. A thermodynamic database for the Mg–Cu–Yb–Ca–Ag system was created to compare the process of crystallization of alloys with polythermal sections of the Mg–Cu–Yb–Ca–Ag phase diagram. - Highlights: • New alloy compositions based on Mg–Cu–Yb system were developed and investigated. • Increasing content of Ag and Ca leads to improving GFA. • Bulk samples with a composite glassy-crystalline structure were obtained. • Thermodynamic database for Mg–Cu–Yb–Ca–Ag system was created.« less

Acidity of a Cu-bound histidine in the binuclear center of cytochrome C oxidase.

PubMed

Fadda, Elisa; Chakrabarti, Nilmadhab; Pomès, Régis

2005-12-01

Cytochrome c oxidase (CcO) is a crucial enzyme in the respiratory chain. Its function is to couple the reduction of molecular oxygen, which takes place in the Fea3-CuB binuclear center, to proton translocation across the mitochondrial membrane. Although several high-resolution structures of the enzyme are known, the molecular basis of proton pumping activation and its mechanism remain to be elucidated. We examine a recently proposed scheme (J. Am. Chem. Soc. 2004, 126, 1858; FEBS Lett. 2004, 566, 126) that involves the deprotonation of the CuB-bound imidazole ring of a histidine (H291 in mammalian CcO) as a key element in the proton pumping mechanism. The central feature of that proposed mechanism is that the pKa values of the imidazole vary significantly depending on the redox state of the metals in the binuclear center. We use density functional theory in combination with continuum electrostatics to calculate the pKa values, successively in bulk water and within the protein, of the Cu-bound imidazole in various Cu- and Cu-Fe complexes. From pKas in bulk water, we derived a value of -266.34 kcal.mol(-1) for the proton solvation free energy (Delta). This estimate is in close agreement with the experimental value of -264.61 kcal.mol(-1) (J. Am. Chem. Soc. 2001, 123, 7314), which reinforces the conclusion that Delta is more negative than previous values used for pKa calculations. Our approach, on the basis of the study of increasingly more detailed models of the CcO binuclear center at different stages of the catalysis, allows us to examine successively the effect of each of the two metals' redox states and of solvation on the acidity of imidazole, whose pKa is approximately 14 in bulk water. This analysis leads to the following conclusions: first, the effect of Cu ligation on the imidazole acidity is negligible regardless of the redox state of the metal. Second, results obtained for Cu-Fe complexes in bulk water indicate that Cu-bound imidazole pKa values lie within the range of 14.8-16.6 throughout binuclear redox states corresponding to the catalytic cycle, demonstrating that the effect of the Fe oxidation states is also negligible. Finally, the low-dielectric CcO proteic environment shifts the acid-base equilibrium toward a neutral imidazole, further increasing the corresponding pKa values. These results are inconsistent with the proposed role of the Cu-bound histidine as a key element in the pumping mechanism. Limitations of continuum solvation models in pKa calculations are discussed.

Medium-range structure and glass forming ability in Zr–Cu–Al bulk metallic glasses

DOE PAGES

Zhang, Pei; Maldonis, Jason J.; Besser, M. F.; ...

2016-03-05

Fluctuation electron microscopy experiments combined with hybrid reverse Monte Carlo modeling show a correlation between medium-range structure at the nanometer scale and glass forming ability in two Zr–Cu–Al bulk metallic glass (BMG) alloys. Both Zr 50Cu 35Al 15 and Zr 50Cu 45Al 5 exhibit two nanoscale structure types, one icosahedral and the other more crystal-like. In Zr 50Cu 35Al 15, the poorer glass former, the crystal-like structure is more stable under annealing below the glass transition temperature, T g, than in Zr 50Cu 45Al 5. Variable resolution fluctuation microscopy of the MRO clusters show that in Zr 50Cu 35Al 15more » on sub-Tg annealing, the crystal-like clusters shrink even as they grow more ordered, while icosahedral-like clusters grow. Furthermore, the results suggest that achieving better glass forming ability in this alloy system may depend more on destabilizing crystal-like structures than enhancing non-crystalline structures.« less

Self-optimized superconductivity attainable by interlayer phase separation at cuprate interfaces.

PubMed

Misawa, Takahiro; Nomura, Yusuke; Biermann, Silke; Imada, Masatoshi

2016-07-01

Stabilizing superconductivity at high temperatures and elucidating its mechanism have long been major challenges of materials research in condensed matter physics. Meanwhile, recent progress in nanostructuring offers unprecedented possibilities for designing novel functionalities. Above all, thin films of cuprate and iron-based high-temperature superconductors exhibit remarkably better superconducting characteristics (for example, higher critical temperatures) than in the bulk, but the underlying mechanism is still not understood. Solving microscopic models suitable for cuprates, we demonstrate that, at an interface between a Mott insulator and an overdoped nonsuperconducting metal, the superconducting amplitude is always pinned at the optimum achieved in the bulk, independently of the carrier concentration in the metal. This is in contrast to the dome-like dependence in bulk superconductors but consistent with the astonishing independence of the critical temperature from the carrier density x observed at the interfaces of La2CuO4 and La2-x Sr x CuO4. Furthermore, we identify a self-organization mechanism as responsible for the pinning at the optimum amplitude: An emergent electronic structure induced by interlayer phase separation eludes bulk phase separation and inhomogeneities that would kill superconductivity in the bulk. Thus, interfaces provide an ideal tool to enhance and stabilize superconductivity. This interfacial example opens up further ways of shaping superconductivity by suppressing competing instabilities, with direct perspectives for designing devices.

Self-optimized superconductivity attainable by interlayer phase separation at cuprate interfaces

PubMed Central

Misawa, Takahiro; Nomura, Yusuke; Biermann, Silke; Imada, Masatoshi

2016-01-01

Stabilizing superconductivity at high temperatures and elucidating its mechanism have long been major challenges of materials research in condensed matter physics. Meanwhile, recent progress in nanostructuring offers unprecedented possibilities for designing novel functionalities. Above all, thin films of cuprate and iron-based high-temperature superconductors exhibit remarkably better superconducting characteristics (for example, higher critical temperatures) than in the bulk, but the underlying mechanism is still not understood. Solving microscopic models suitable for cuprates, we demonstrate that, at an interface between a Mott insulator and an overdoped nonsuperconducting metal, the superconducting amplitude is always pinned at the optimum achieved in the bulk, independently of the carrier concentration in the metal. This is in contrast to the dome-like dependence in bulk superconductors but consistent with the astonishing independence of the critical temperature from the carrier density x observed at the interfaces of La2CuO4 and La2−xSrxCuO4. Furthermore, we identify a self-organization mechanism as responsible for the pinning at the optimum amplitude: An emergent electronic structure induced by interlayer phase separation eludes bulk phase separation and inhomogeneities that would kill superconductivity in the bulk. Thus, interfaces provide an ideal tool to enhance and stabilize superconductivity. This interfacial example opens up further ways of shaping superconductivity by suppressing competing instabilities, with direct perspectives for designing devices. PMID:27482542

Comparison of Structural Relaxation Behavior in As-Cast and Pre-Annealed Zr-Based Bulk Metallic Glasses Just below Glass Transition

DOE PAGES

Haruyama, Osami; Yoshikawa, Kazuyoshi; Yamazaki, Yoshikatsu; ...

2015-04-25

In this paper, the α-relaxation of pre-annealed Zr 55Cu 30Ni 5Al 10 bulk metallic glasses (BMGs) was compared with that of as-cast Zr-based BMGs including Zr 55Cu 30Ni 5Al 10. The α-relaxation was investigated by volume relaxation. The relaxation behavior was well described by a stretched exponential relaxation function, Φ (t) ≈ exp [ - (t/τ α ) β α ], with the isothermal relaxation time, τ α, and the Kohlrausch exponent, β α. The β α exhibited the strong temperature dependence for the pre-annealed BMG, while the weak temperature dependence was visualized for the as-cast BMG similar to themore » dynamic relaxation. The τ α’s were modified by Moynihan and Narayanaswamy-Tool-Moynihan methods that reduce the difference in the thermal history of sample. Finally, as a result, the relaxation kinetics in the glass resembled that of a liquid deduced from the behavior of viscosity in the supercooled liquid.« less

Effect of native oxide layers on copper thin-film tensile properties: A reactive molecular dynamics study

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

Skarlinski, Michael D., E-mail: michael.skarlinski@rochester.edu; Quesnel, David J.; Department of Mechanical Engineering, University of Rochester, Rochester, New York 14627

2015-12-21

Metal-oxide layers are likely to be present on metallic nano-structures due to either environmental exposure during use, or high temperature processing techniques such as annealing. It is well known that nano-structured metals have vastly different mechanical properties from bulk metals; however, difficulties in modeling the transition between metallic and ionic bonding have prevented the computational investigation of the effects of oxide surface layers. Newly developed charge-optimized many body [Liang et al., Mater. Sci. Eng., R 74, 255 (2013)] potentials are used to perform fully reactive molecular dynamics simulations which elucidate the effects that metal-oxide layers have on the mechanical propertiesmore » of a copper thin-film. Simulated tensile tests are performed on thin-films while using different strain-rates, temperatures, and oxide thicknesses to evaluate changes in yield stress, modulus, and failure mechanisms. Findings indicate that copper-thin film mechanical properties are strongly affected by native oxide layers. The formed oxide layers have an amorphous structure with lower Cu-O bond-densities than bulk CuO, and a mixture of Cu{sub 2}O and CuO charge character. It is found that oxidation will cause modifications to the strain response of the elastic modulii, producing a stiffened modulii at low temperatures (<75 K) and low strain values (<5%), and a softened modulii at higher temperatures. While under strain, structural reorganization within the oxide layers facilitates brittle yielding through nucleation of defects across the oxide/metal interface. The oxide-free copper thin-film yielding mechanism is found to be a tensile-axis reorientation and grain creation. The oxide layers change the observed yielding mechanism, allowing for the inner copper thin-film to sustain an FCC-to-BCC transition during yielding. The mechanical properties are fit to a thermodynamic model based on classical nucleation theory. The fit implies that the oxidation of the films reduces the activation volume for yielding.« less

Changes in the Degree of Contamination of Organic Horizons of Al-Fe-Humus Podzols upon a Decrease in Aerotechnogenic Loads, the Kola Peninsula

NASA Astrophysics Data System (ADS)

Barkan, V. Sh.; Lyanguzova, I. V.

2018-03-01

Contamination levels of the organic horizon of Al-Fe-humus podzols (Albic Rustic Podzols) in the zone affected by atmospheric emissions of the Severonikel smelter (Murmansk oblast) within a 20-yearlong period are compared. The spatiotemporal changes in the total content of heavy metals in the soils in response to a decrease in aerotechnogenic loads have a complicated pattern. As the content of heavy metals in the soils varies widely, the correlation between their amount in the organic soil horizon and the distance from the contamination source is absent. In response to the ninefold decrease in the amount of atmospheric emission of Ni compounds, the bulk content of Ni in the organic horizons of podzols reliably decreased by 2.5 times. The threefold decrease in the emission of Cu compounds proved to be insufficient for a significant decrease in the Cu content in the soils. In 2016, the content of heavy metals in some sampling points even increased in comparison with the earlier periods. The Ni-to-Cu ratio in the soil samples changed significantly. In 1989-1994, bulk forms of heavy metals in the soil samples formed the sequence Ni > Cu > Co; in 2016, it changed to Cu > Ni > Co, which corresponds to the proportions of these metals in the aerial emissions. Under conditions of the continuous input of heavy metals from the atmosphere, the contamination of the organic horizons of podzols with heavy metals remains at the high or very high levels.

Innovative approach for the valorization of useful metals from waste electric and electronic equipment (WEEE)

NASA Astrophysics Data System (ADS)

Soare, V.; Burada, M.; Dumitrescu, D. V.; Constantin, I.; Soare, V.; Popescu, A.-M. J.; Carcea, I.

2016-08-01

Waste electric and electronic equipment are an important secondary source of rare and precious metals and their processing through ecological technologies constitutes a major concern in the European Union and significantly contributes to the reduction of environmental pollution and to the preservation of valuable resources of nonferrous metals. The paper presents an innovative approach for the complex valorization of useful metals contained in WEEE. The method consists in the melting of WEEE in a furnace in a microwave field at temperatures of 1000 ÷1200°C, for the complete separation of the metallic fraction from the organic components. The gases resulting from the melting process were also treated/neutralized in a microwave environment and the obtained metallic bulk (multi-component alloy) was processed through combined hydrometallurgical and electrochemical methods. The major elements in the metallic bulk (Cu, Sn, Zn, Pb) were separated/recovered by anodic dissolution, respectively by leaching in nitric acid followed by cementation using various agents, or by electrodeposition. Depending on the electrochemical parameters, cathodic deposits consisting of Cu, with a purity higher than 99.9%, or of Cu-Sn and Cu-Sn-Zn alloys were obtained. Silver was valorized by leaching/precipitation with NaCl and the gold concentrated in the anodic slime will be recovered by thiourea extraction. The experiments performed demonstrate the possibility of ecological and efficient processing of WEEE in a microwave field and the recovery of nonferrous and precious metals through combined hydrometallurgical and electrochemical methods.

Effects of CuO nanoparticles on Lemna minor.

PubMed

Song, Guanling; Hou, Wenhua; Gao, Yuan; Wang, Yan; Lin, Lin; Zhang, Zhiwei; Niu, Qiang; Ma, Rulin; Mu, Lati; Wang, Haixia

2016-12-01

Copper dioxide nanoparticles (NPs), which is a kind of important and widely used metal oxide NP, eventually reaches a water body through wastewater and urban runoff. Ecotoxicological studies of this kind of NPs effects on hydrophyte are very limited at present. Lemna minor was exposed to media with different concentrations of CuO NPs, bulk CuO, and two times concentration of Cu 2+ released from CuO NPs in culture media. The changes in plant growth, chlorophyll content, antioxidant defense enzyme activities [i.e., peroxidase (POD), catalase (CAT), superoxide dismutase (SOD) activities], and malondialdehyde (MDA) content were measured in the present study. The particle size of CuO NPs and the zeta potential of CuO NPs and bulk CuO in the culture media were also analyzed to complementally evaluate their toxicity on duckweed. Results showed that CuO NPs inhibited the plant growth at lower concentration than bulk CuO. L. minor roots were easily broken in CuO NPs media under the experimental condition, and the inhibition occurred only partly because CuO NPs released Cu 2+ in the culture media. The POD, SOD, and CAT activities of L. minor increased when the plants were exposed to CuO NPs, bulk CuO NPs and two times the concentration of Cu 2+ released from CuO NPs in culture media, but the increase of these enzymes were the highest in CuO NPs media among the three kinds of materials. The MDA content was significantly increased compared with that of the control from 50 mg L -1 CuO NP concentration in culture media. CuO NPs has more toxicity on L. minor compared with that of bulk CuO, and the inhibition occurred only partly because released Cu 2+ in the culture media. The plant accumulated more reactive oxygen species in the CuO NP media than in the same concentration of bulk CuO. The plant cell encountered serious damage when the CuO NP concentration reached 50 mg L -1 in culture media. The toxicology of CuO NP on hydrophytes must be considered because that hydrophytes are the basic of aquatic ecosystem.

Acquisition of a Modified Suction Casting Instrument for the Fabrication of Radiation Tolerant Bulk nNanostructured Metallic Materials

DTIC Science & Technology

2015-01-13

Cu/ Nb films”, Philos. Mag., 84, 1021-1028, (2004). [23] D. H. Ryan, J. M. D. Coey, “Magnetic properties of iron-rich Fe- Zr glasses”, Phys. Rev. B...2226, (1982). [26] K. Fukamichi, R. J. Gambino, T. R. McGuire, “ Electrical resistivity and Hall effect in FeZr amorphous sputtered films”, J. Appl...fabricate several bulk nanostructured metallic materials. In particular we fabricated bulk nanostructured Fe- Zr alloys via suction casting technique. The as

Interactions of trace metals with hydrogels and filter membranes used in DET and DGT techniques.

PubMed

Garmo, Oyvind A; Davison, William; Zhang, Hao

2008-08-01

Equilibrium partitioning of trace metals between bulk solution and hydrogels/filter was studied. Under some conditions, trace metal concentrations were higher in the hydrogels or filter membranes compared to bulk solution (enrichment). In synthetic soft water, enrichment of cationic trace metals in polyacrylamide hydrogels decreased with increasing trace metal concentration. Enrichment was little affected by Ca and Mg in the concentration range typically encountered in natural freshwaters, indicating high affinity but low capacity binding of trace metals to solid structure in polyacrylamide gels. The apparent binding strength decreased in the sequence: Cu > Pb > Ni approximately to Cd approximately to Co and a low concentration of cationic Cu eliminated enrichment of weakly binding trace metal cations. The polyacrylamide gels also had an affinity for fulvic acid and/or its trace metal complexes. Enrichment of cationic Cd in agarose gel and hydrophilic polyethersulfone filter was independent of concentration (10 nM to 5 microM) but decreased with increasing Ca/ Mg concentration and ionic strength, suggesting that it is mainly due to electrostatic interactions. However, Cu and Pb were enriched even after equilibration in seawater, indicating that these metals additionally bind to sites within the agarose gel and filter. Compared to the polyacrylamide gels, agarose gel had a lower affinity for metal-fulvic complexes. Potential biases in measurements made with the diffusive equilibration in thin-films (DET) technique, identified by this work, are discussed.

Influence of thin-film metallic glass coating on fatigue behavior of bulk metallic glass: Experiments and finite element modeling

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

Yu, Chia-Chi; Chu, Jinn P.; Jia, Haoling

In this paper, a coating of the Zr-based thin-film metallic glass (TFMG) was deposited on the Zr 50Cu 30Al 10Ni 10 bulk metallic glass (BMG) to investigate shear-band evolution under four-point-bend fatigue testing. The fatigue endurance-limit of the TFMG-coated samples is ~ 33% higher than that of the BMG. The results of finite-element modeling (FEM) revealed a delay in the shear-band nucleation and propagation in TFMG-coated samples under applied cyclic-loading. The FEM study of spherical indentation showed that the redistribution of stress by the TFMG coating prevents localized shear-banding in the BMG substrate. Finally, the enhanced fatigue characteristics of themore » BMG substrates can be attributed to the TFMG coatings retarding shear-band initiation at defects on the surface of the BMG.« less

Influence of thin-film metallic glass coating on fatigue behavior of bulk metallic glass: Experiments and finite element modeling

DOE PAGES

Yu, Chia-Chi; Chu, Jinn P.; Jia, Haoling; ...

2017-03-21

In this paper, a coating of the Zr-based thin-film metallic glass (TFMG) was deposited on the Zr 50Cu 30Al 10Ni 10 bulk metallic glass (BMG) to investigate shear-band evolution under four-point-bend fatigue testing. The fatigue endurance-limit of the TFMG-coated samples is ~ 33% higher than that of the BMG. The results of finite-element modeling (FEM) revealed a delay in the shear-band nucleation and propagation in TFMG-coated samples under applied cyclic-loading. The FEM study of spherical indentation showed that the redistribution of stress by the TFMG coating prevents localized shear-banding in the BMG substrate. Finally, the enhanced fatigue characteristics of themore » BMG substrates can be attributed to the TFMG coatings retarding shear-band initiation at defects on the surface of the BMG.« less

Ab initio molecular dynamics simulation of binary Cu64Zr36 bulk metallic glass: Validation of the cluster-plus-glue-atom model

NASA Astrophysics Data System (ADS)

Tian, Hua; Zhang, Chong; Wang, Lu; Zhao, JiJun; Dong, Chuang; Wen, Bin; Wang, Qing

2011-06-01

We have performed ab initio molecular dynamics simulation of Cu64Zr36 alloy at descending temperatures (from 2000 K to 400 K) and discussed the evolution of short-range order with temperature. The pair-correlation functions, coordination numbers, and chemical compositions of the most abundant local clusters have been analyzed. We found that icosahedral short-range order exists in the liquid, undercooled, and glass states, and it becomes dominant in the glass states. Moreover, we demonstrated the existence of Cu-centered Cu8Zr5 icosahedral clusters as the major local structural unit in the Cu64Zr36 amorphous alloy. This finding agrees well with our previous cluster model of Cu-Zr-based BMG as well as experimental evidences from synchrotron x ray and neutron diffraction measurements.

Interaction of atomic oxygen with thin film and bulk copper: An XPS, AES, XRD, and profilometer study

NASA Technical Reports Server (NTRS)

Raikar, Genesh N.; Gregory, John C.; Christl, Ligia C.; Peters, Palmer N.

1992-01-01

The University of Alabama in Huntsville (UAH) experiment A-0114 was designed primarily to study degradation of material surfaces due to low earth orbital (LEO) atmospheric oxygen. The experiment contained 128 one inch circular samples: metals, polymers, carbons, and semiconductors. Among metal samples, copper has shown some interesting new results. Two types of copper samples, a film sputter coated on fused silica and a bulk piece of OFHC copper, were characterized employing a variety of techniques such as X-ray and Auger electron spectroscopies, X-ray diffraction, and high resolution profilometry. Cu 2p core level spectra were used to characterize the presence of Cu2O and CuO in addition to Cu Auger LMM lines. These results are supported by our recent X-ray diffraction studies which clearly establish the presence of Cu oxides which we were unable to prove in our earlier work. Profilometry showed an increase in thickness of the film sample where exposed to 106.7 +/- 0.5 nm from an initial thickness of 74.2 +/- 1.1 nm. Further studies with SEM and ellipsometry are underway.

Disulphide linkage: To get cleaved or not? Bulk and nano copper based SERS of cystine

NASA Astrophysics Data System (ADS)

P. J., Arathi; Seemesh, Bhaskar; Rajendra Kumar Reddy, G.; Suresh Kumar, P.; Ramanathan, V.

2018-05-01

Different nano-structures of noble metals have been the conventional substrates for carrying out Surface Enhanced Raman Spectroscopy (SERS). In this paper we examine electrodeposited copper (Cu) nano-structures on pencil graphite as novel substrate to carry out SERS measurements by considering L-cystine (Cys-Cys) (dimer of the amino acid cysteine) as the probe. The formation of monolayer of the probe molecule on the substrates was confirmed using cyclic voltammetric measurements. Mode of adsorption of Cys-Cys was observed to be different on bulk Cu (taken in the wire form) and nano-structured Cu on pencil graphite. Whereas in the former the disulphide bond of Cys-Cys remained intact, it got cleaved when Cys-Cys was adsorbed on electrodeposited copper indicating the activated nature of the nano-structure compared to bulk copper. Csbnd S stretching mode of vibration underwent blue shift in Cys-Cys adsorbed on Cu on pencil graphite vis-à-vis Cys-Cys adsorbed on Cu wire. Further evidence on the cleavage of the Csbnd S bond on an activated substrate was obtained by considering a bimetallic substrate comprising of silver on copper which was electrodeposited on pencil graphite. Our studies have demonstrated that nano-copper surface is an excellent substrate for SERS giving 200 μM as lower detection limit for Cys-Cys.

Kinetics of Glass Transition and Crystallization of a Zr40Hf10Ti4Y1Al10Cu25Ni7Co2Fe1 Bulk Metallic Glass with High Mixing Entropy

NASA Astrophysics Data System (ADS)

Gong, Pan; Wang, Sibo; Li, Fangwei; Wang, Xinyun

2018-04-01

The kinetics of glass transition and crystallization of a novel Zr40Hf10Ti4Y1Al10Cu25Ni7Co2Fe1 bulk metallic glass (BMG) with high mixing entropy have been studied by differential scanning calorimetry (DSC) and X-ray diffraction (XRD). The continuous DSC curves show five stages of crystallization at lower heating rates (≤ 20 K/min). The activation energies of glass transition were determined by Moynihan and Kissinger methods, while the activation energies of crystallization were calculated utilizing Kissinger, Ozawa, and Boswell models. The crystalline phases corresponding to each crystallization step have been found out. The kinetic fragility of Zr40Hf10Ti4Y1Al10Cu25Ni7Co2Fe1 BMG has also been evaluated. Based on the isothermal DSC curves, the Avrami exponent, evaluated from the Johnson-Mehl-Avrami equation, has been analyzed in detail. The current study reveals that the crystallization behavior of Zr40Hf10Ti4Y1Al10Cu25Ni7Co2Fe1 BMG exhibits characteristics of both the high entropy BMGs and traditional BMGs with a single principal element, leading to its high glass-forming ability.

Efficient organic solar cells using copper(I) iodide (CuI) hole transport layers

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

Peng, Ying; Department of Physics and Centre for Plastic Electronics, Blackett Laboratory, Imperial College London, London SW7 2AZ; Yaacobi-Gross, Nir

We report the fabrication of high power conversion efficiency (PCE) polymer/fullerene bulk heterojunction (BHJ) photovoltaic cells using solution-processed Copper (I) Iodide (CuI) as hole transport layer (HTL). Our devices exhibit a PCE value of ∼5.5% which is equivalent to that obtained for control devices based on the commonly used conductive polymer poly(3,4-ethylenedioxythiophene): polystyrenesulfonate as HTL. Inverted cells with PCE >3% were also demonstrated using solution-processed metal oxide electron transport layers, with a CuI HTL evaporated on top of the BHJ. The high optical transparency and suitable energetics of CuI make it attractive for application in a range of inexpensive large-area optoelectronicmore » devices.« less

James C. McGroddy Prize Talk: Development and Applications of Bulk Metallic Glasses

NASA Astrophysics Data System (ADS)

Inoue, Akihisa

2009-03-01

We realized, through detailed amorphous material investigations in the 1980's, that a number of metallic glassy alloys of multi-component La-, Mg- and Zr-based systems exhibit a large supercooled-liquid region prior to crystallization. The stabilization phenomenon of these supercooled liquid should enable us to fabricate, by slow cooling processes, bulk metallic glasses (BMGs) with critical diameters larger than several millimeters. Caltech's group also succeeded the fabrication of BMG in Zr-based alloy system in 1993. Since then, much attention has been paid to BMGs because of their novel characteristics in basic science and engineering aspects and new materials science and engineering fields have emerged for BMGs. Based on knowledge obtained thus far, we have successfully developed new BMGs with technologically-important transition metals, such as Zr-, Ti-, Fe-, Co-, Ni- and Cu-based alloys. Currently, the maximum diameter for glass formation reaches 30 mm for Zr- and Cu-based systems, 12 mm for Ti-based system, 18 mm for Fe-Co-based system and 20 mm for Ni-based system, even employing the copper mold casting technique. These large size BMGs possess nearly the same fundamental properties as those of the BMGs with smaller diameters. BMGs with diameters above 10 mm can be formed in Zr-Al-Ni-Cu system with Zr compositions higher than 65 at% and they exhibit excellent properties, such as high Poisson's ratio, high ductility, high fracture toughness, high fatigue strength and high stability of mechanical properties to annealing-induced embrittlement. The new Ti-based BMGs without allergic and toxic elements should exhibit good compatibility to bio-tissues. Applications of BMGs in Fe-, Co-, Ti- and Zr-based systems have advanced many devices including the following; choke coil, power inductor, electro magnetic shielding, magnetic and position sensors, micro-geared motor, pressure sensor, Coriolis flowmeter, surface coating layer, precise polishing medium, magnetic and structural parts in electric magnetic control-type spring drive watches, medical operation instruments and so forth. A. Inoue, Acta Mater., 48(2000), 279-306.

An in-situ phosphorus source for the synthesis of Cu 3P and the subsequent conversion to Cu 3PS 4 nanoparticle clusters

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

Sheets, Erik J.; Stach, Eric A.; Yang, Wei -Chang

2015-09-20

The search for alternative earth abundant semiconducting nanocrystals for sustainable energy applications has brought forth the need for nanoscale syntheses beyond bulk synthesis routes. Of particular interest are metal phosphides and derivative I-V-VI chalcogenides including copper phosphide (Cu 3P) and copper thiophosphate (Cu 3PS 4). Herein, we report a one-pot, solution-based synthesis of Cu 3P nanocrystals utilizing an in-situ phosphorus source: phosphorus pentasulfide (P 2S 5) in trioctylphosphine (TOP). By injecting this phosphorus source into a copper solution in oleylamine (OLA), uniform and size controlled Cu 3P nanocrystals with a phosphorous-rich surface are synthesized. The subsequent reaction of the Cumore » 3P nanocrystals with decomposing thiourea forms nanoscale Cu 3PS 4 particles having p-type conductivity and an effective optical band gap of 2.36 eV.« less

SYNTHESIS OF THERMALLY STABLE CARBOXYMETHYL CELLULOSE/METAL BIODEGRADABLE NANOCOMPOSITES FOR POTENTIAL BIOLOGICAL APPLICATIONS

EPA Science Inventory

A green approach is described that generates bulk quantities of nanocomposites containing transition metals such as Cu, Ag, In and Fe at room temperature using a biodegradable polymer carboxymethyl cellulose (CMC) by reacting respective metal salts with sodium salt of CMC in aqu...

Comparative toxicity of metal oxide nanoparticles (CuO, ZnO and TiO2) to developing zebrafish embryos

NASA Astrophysics Data System (ADS)

Vicario-Parés, Unai; Castañaga, Luis; Lacave, Jose Maria; Oron, Miriam; Reip, Paul; Berhanu, Deborah; Valsami-Jones, Eugenia; Cajaraville, Miren P.; Orbea, Amaia

2014-08-01

Increasing use of nanomaterials is resulting in their release into the environment, making necessary to determine the toxicity of these materials. With this aim, the effects of CuO, ZnO and TiO2 nanoparticles (NPs) on zebrafish development were assessed in comparison with the effects caused by the ionic forms (for copper and zinc), bulk counterparts and the stabilizer used for rutile TiO2 NPs. None of the NPs caused significant embryo mortality. CuO NPs were the most toxic affecting hatching and increasing malformation prevalence (≥1 mg Cu/L), followed by ZnO NPs that affected hatching at ≥5 mg Zn/L and stabilized TiO2 NPs that caused mortality and decreased hatching at 100 mg Ti/L. Exposure to the stabilizer alone provoked the same effect. Thus, toxicity of the TiO2 NP suspension can be linked to the surfactant. For all the endpoints, the greatest effects were exerted by the ionic forms, followed by the NPs and finally by the bulk compounds. By autometallography, metal-bearing deposits were observed in embryos exposed to CuO and ZnO NPs, being more abundant in the case of embryos exposed to CuO NPs. The largest and most abundant metal-bearing deposits were detected in embryos exposed to ionic copper. In conclusion, metal oxide NPs affected zebrafish development altering hatching and increasing the prevalence of malformations. Thus, the use and release of metal oxide NPs to the environment may pose a risk to aquatic organisms as a result of the toxicity caused by NPs themselves or by the additives used in their production.

A force field for dynamic Cu-BTC metal-organic framework.

PubMed

Zhao, Lei; Yang, Qingyuan; Ma, Qintian; Zhong, Chongli; Mi, Jianguo; Liu, Dahuan

2011-02-01

A new force field that can describe the flexibility of Cu-BTC metal-organic framework (MOF) was developed in this work. Part of the parameters were obtained using density functional theory calculations, and the others were taken from other force fields. The new force field could reproduce well the experimental crystal structure, negative thermal expansion, vibrational properties as well as adsorption behavior in Cu-BTC. In addition, the bulk modulus of Cu-BTC was predicted using the new force field. We believe the new force field is useful in understanding the structure-property relationships for MOFs, and the approach can be extended to other MOFs.

ZrCuAl Bulk Metallic Glass spall induced by laser shock

NASA Astrophysics Data System (ADS)

Jodar, Benjamin; Loison, Didier; Yokoyama, Yoshihiko; Lescoute, Emilien; Berthe, Laurent; Sangleboeuf, Jean-Christophe

2017-06-01

To face High Velocity Impacts, the aerospace industry is always seeking for innovative materials usable as debris shielding components. Bulk Metallic Glasses (BMG) revealed interesting mechanical properties in case of static and quasi-static loading conditions: high elasticity, high tenacity, low density and high fracture threshold... The department of Mechanics and Glass of the Institut of Physics Rennes conducted on the ELFIE facility, laser shock experiments to study the behavior of a ternary ZrCuAl BMG under high strain rate, up-to fragmentation process. On the one hand, in-situ diagnostics were used to measure ejection velocities with PDV and debris morphologies were observed by Shadowgraphy. On the other hand, spalled areas (dimensions and features) were characterized through post-mortem analysis (optical observations, profilometry and SEM). These results are compared to experimental and numerical data on the crystalline forms of the ZrCuAl basic compounds.

Temperature rise and flow of Zr-based bulk metallic glasses under high shearing stress

NASA Astrophysics Data System (ADS)

Zhang, Weiguo; Ma, Mingzhen; Song, Aijun; Liang, Shunxing; Hao, Qiuhong; Tan, Chunlin; Jing, Qin; Liu, Riping

2011-11-01

Deformation of the bulk metallic glasses (BMGs) and the creation and propagation of the shear bands are closely interconnected. Shearing force was loaded on Zr41.2Ti13.8Cu12.5Ni10.0Be22.5(Vit.1) BMGs by cutting during the turning of the BMG rod. The temperature rise of alloy on the shear bands was calculated and the result showed that it could reach the temperature of the super-cooled liquid zone or exceed the melting point. The temperature rise caused viscous fluid flow and brought about the deformation of BMGs. This suggested that the deformation of BMGs was derived, at least to some extent, from the adiabatic shear temperature rise.

Energy of Supported Metal Catalysts: From Single Atoms to Large Metal Nanoparticles

DOE PAGES

James, Trevor E.; Hemmingson, Stephanie L.; Campbell, Charles T.

2015-08-14

It is known that many catalysts consist of late transition metal nanoparticles dispersed across oxide supports. The chemical potential of the metal atoms in these particles correlate with their catalytic activity and long-term thermal stability. This chemical potential versus particle size across the full size range between the single isolated atom and bulklike limits is reported here for the first time for any metal on any oxide. The chemical potential of Cu atoms on CeO 2(111) surfaces, determined by single crystal adsorption calorimetry of gaseous Cu atoms onto slightly reduced CeO 2(111) at 100 and 300 K is shown tomore » decrease dramatically with increasing Cu cluster size. The Cu chemical potential is ~110 kJ/mol higher for isolated Cu adatoms on stoichometric terrace sites than for Cu in nanoparticles exceeding 2.5 nm diameter, where it reaches the bulk Cu(solid) limit. In Cu dimers, Cu’s chemical potential is ~57 kJ/mol lower at step edges than on stoichiometric terrace sites. Since Cu avoids oxygen vacancies, these monomer and dimer results are not strongly influenced by the 2.5% oxygen vacancies present on this CeO 2 surface and are thus considered representative of stoichiometric CeO 2(111) surfaces.« less

Preparation and magnetic properties of phthalocyanine-based carbon materials containing transition metals

NASA Astrophysics Data System (ADS)

Honda, Z.; Sato, S.; Hagiwara, M.; Kida, T.; Sakai, M.; Fukuda, T.; Kamata, N.

2016-07-01

A simple method for the preparation of bulk quantities of magnetic carbon materials, which contain uniformly dispersed transition metals (M = Fe, Co, Ni, and Cu) as the magnetic components, is presented. By using highly chlorinated metal phthalocyanine as the building block and potassium as the coupling reagent, phthalocyanine-based carbon materials (PBCMs) containing transition metals were obtained. Our experiments demonstrate the structure of these PBCMs consists of transition metals embedded in graphitic carbon that includes a square planar MN4 magnetic core and the Fe and Co-PBCM possess spontaneous magnetization at room temperature. In addition, carbon-coated transition metal particles were obtained by the Wurtz-type reaction with excess amount of potassium coupling agent. The large transition metal surface area and magnetization of these M-PBCMs are useful for spintronic and catalytic applications.

Polyamorphism in Yb-based metallic glass induced by pressure

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

Li, Liangliang; Luo, Qiang; Li, Renfeng

2017-04-25

The Yb 62.5Zn 15Mg 17.5Cu 5 metallic glass is investigated using synchrotron x-ray total scattering method up to 38.4 GPa. The polyamorphic transformation from low density to high density with a transition region between 14.1 and 25.2 GPa is observed, accompanying with a volume collapse reflected by a discontinuousness of isothermal bulk modulus. This collapse is caused by that distortional icosahedron short range order precedes to perfect icosahedron, which might link to Yb 4f electron delocalization upon compression, and match the result of in situ electrical resistance measurement under high pressure conditions. Furthermore, this discovery in Yb-based metallic glass, combinedmore » with the previous reports on other metallic glass systems, demonstrates that pressure induced polyamorphism is the general behavior for typical lanthanide based metallic glasses.« less

First principles calculation of elastic and magnetic properties of Cr-based full-Heusler alloys

NASA Astrophysics Data System (ADS)

Aly, Samy H.; Shabara, Reham M.

2014-06-01

We present an ab-initio study of the elastic and magnetic properties of Cr-based full-Heusler alloys within the first-principles density functional theory. The lattice constant, magnetic moment, bulk modulus and density of states are calculated using the full-potential nonorthogonal local-orbital minimum basis (FPLO) code in the Generalized Gradient Approximation (GGA) scheme. Only the two alloys Co2CrSi and Fe2CrSi are half-metallic with energy gaps of 0.88 and 0.55 eV in the spin-down channel respectively. We have predicted the metallicity state for Fe2CrSb, Ni2CrIn, Cu2CrIn, and Cu2CrSi alloys. Fe2CrSb shows a strong pressure dependent, e.g. exhibits metallicity at zero pressure and turns into a half-metal at P≥10 GPa. The total and partial magnetic moments of these alloys were studied under higher pressure, e.g. in Co2CrIn, the total magnetic moment is almost unchanged under higher pressure up to 500 GPa.

Anomalous shear band characteristics and extra-deep shock-affected zone in Zr-based bulk metallic glass treated with nanosecond laser peening.

PubMed

Wei, Yanpeng; Xu, Guangyue; Zhang, Kun; Yang, Zhe; Guo, Yacong; Huang, Chenguang; Wei, Bingchen

2017-03-07

The effects of nanosecond laser peening on Zr 41 Ti 14 Cu 12.5 Ni 10 Be 22.5 metallic glass were investigated in this study. The peening treatment produced an extra-deep shock-affected zone compared to crystal metal. As opposed to the conventional shear bands, numerous arc shear bands appeared and aggregated in the vertical direction of the laser beam, forming basic units for accommodating plastic deformation. The arc shear bands exhibited short and discrete features near the surface of the material, then grew longer and fewer at deeper peened layer depths, which was closely related to the laser shock wave attenuation. An energy dissipation model was established based on Hugoniot Elastic Limit and shear band characteristics to represent the formation of an extra-deep shock-affected zone. The results presented here suggest that the bulk modification of metallic glass with a considerable affected depth is feasible. Further, they reveal that nanosecond laser peening is promising as an effective approach to tuning shear bands for improved MGs ductility.

An Innovative Electrolysis Approach for the Synthesis of Metal Matrix Bulk Nanocomposites: A Case Study on Copper-Niobium System

NASA Astrophysics Data System (ADS)

Shokrvash, Hussein; Rad, Rahim Yazdani; Massoudi, Abouzar

2018-04-01

Design and synthesis of a prototype Cu-Nb nanocomposite are presented. Oxygen-free Cu-Nb nanocomposites were prepared using an electrolysis facility with special emphasis on the cathodic deoxidation of Cu and nanometric Nb2O5 blends in a molten NaCl-CaCl2 electrolyte. The as-prepared nanocomposites were characterized by X-ray diffraction and energy-dispersive X-ray spectroscopy. The elemental analysis of the Cu matrix and Nb phase revealed the high solubility of Nb in the Cu structure (0.85 at. pct) and Cu in the Nb structure (10.59 at. pct) over short synthesis times (4-5 hours). Furthermore, precise analysis using field emission scanning electron microscopy and transmission electron microscopy confirmed the unique structure and nanocomposite morphology of the Cu-Nb nanocomposite. The successful synthesis of Cu-Nb nanocomposites offers a new conceptual and empirical outlook on the generation of bulk nanostructures of immiscible bimetals using electro-synthesis.

Impact of pyrometallurgical slags on sunflower growth, metal accumulation and rhizosphere microbial communities.

PubMed

Agnello, A C; Potysz, A; Fourdrin, C; Huguenot, D; Chauhan, P S

2018-06-05

Metallurgical exploitation originates metal-rich by-products termed slags, which are often disposed in the environment being a source of heavy metal pollution. Despite the environmental risk that this may pose for living organisms, little is known about the impact of slags on biotic components of the ecosystem like plants and rhizosphere microbial communities. In this study, metal-rich (Cu, Pb, Zn) granulated slags (GS) derived from Cu production process, were used for a leaching test in the presence of the soil pore solution, showing that soil solution enhanced the release of Cu from GS. A pot experiment was conducted using as growing substrate for sunflower (Helianthus annuus) a 50% w/w mix of an agricultural soil and GS. Bioavailability of metals in soil was, in increasing order: Pb < Zn < Cu. Sunflower was able to grow in the presence of GS and accumulated metals preferentially in above-ground tissues. Microbial diversity was assessed in rhizosphere and bulk soil using community level physiological profiling (CLPP) and 16S rRNA gene based denaturing gradient gel electrophoresis (DGGE) analyses, which demonstrated a shift in the diversity of microbial communities induced by GS. Overall, these results suggest that metallurgical wastes should not be considered inert when dumped in the soil. Implications from this study are expected to contribute to the development of sustainable practices for the management of pyrometallurgical slags, possibly involving a phytomanagement approach. Copyright © 2018 Elsevier Ltd. All rights reserved.

Coincidence of collective relaxation anomaly and specific heat peak in a bulk metallic glass-forming liquid

DOE PAGES

Jaiswal, Abhishek; Podlesynak, Andrey; Ehlers, Georg; ...

2015-07-21

The study of multicomponent metallic liquids' relaxational behavior is still the key to understanding and improving the glass-forming abilities of bulk metallic glasses. Here, we report measurements of the collective relaxation times in a melted bulk metallic glass (LM601Zr 51Cu 36Ni 4Al 9) in the kinetic regime (Q: 1.5–4.0Å –1) using quasielastic neutron scattering. The results reveal an unusual slope change in the Angell plots of this metallic liquid's collective relaxation time around 950°C, beyond the material's melting point. Measurement of specific heat capacity also reveals a peak around the same temperature. Adams-Gibbs theory is used to rationalize the coincidence,more » which motivates more careful experimental and computational studies of the metallic liquids in the future.« less

Influence of compositions on thermal stability and thermodynamic parameter in Ca-Mg-Cu bulk metallic glasses

NASA Astrophysics Data System (ADS)

Deshmukh, A. A.; Khond, A. A.; Palikundwar, U. A.

2018-05-01

In the present manuscript, influence of compositions on thermal stability (ΔTx) and thermodynamic parameter PHSS of Ca-Mg-Cu bulk metallic glasses (BMGs) is evaluated. The statistical approach of regression analysis is adopted to investigate the compositional variation with ΔTx and PHSS. It is found that calcium (Ca) and copper (Cu) content has goodlinear relationship with ΔTx and PHSS. It is observed that with increase in Ca content, ΔTx and PHSS decreases. On the other hand, increase in Cu content, both ΔTx and PHSS increases. Correlation fit of magnesium (Mg) content with both ΔTx and PHSS is very poor. A graph is also plotted to understand the relationship between ΔTx and PHSS. Result of the relationship between ΔTx and PHSS reveals that the alloy composition having more negative value of PHSS will have more stability. Therefore, compositions with more negative value of PHSS will lead to ease of BMGs formation in Ca-Mg-Cu alloy system and hence more stable it will be. It is expected that these results will be supportive in identifying the compositions having these elements for making BMGs.

Environmental monitoring and assessment of heavy metals in surface sediments at Coleroon River Estuary in Tamil Nadu, India.

PubMed

Venkatramanan, S; Chung, S Y; Ramkumar, T; Selvam, S

2015-08-01

The combined studies on grain size distribution, organic matter contents of sediments, sequential extraction and bulk concentration of heavy metals, statistical analysis, and ecological risk assessments were carried out to investigate the contamination sources and ecological risks of surface sediments at Coleroon River Estuary in Tamil Nadu, India. The sequential extraction of metals showed that a larger portion of the metals was associated with the residual phase and also in other fractions. The low concentrations of heavy metals were found in exchangeable and carbonate bounds (bioavailable phases). It revealed that sediments of Coleroon River Estuary were relatively unpolluted and were influenced mainly by natural sources. The observed order of bulk concentrations of heavy metals in the sediments was as follows: Fe > Mn > Zn > Cu > Pb > Cr > Ni > Co. Factor analyses represented that the enrichment of heavy metals was mostly resulted from lithogenic origins associated with anthropogenic sources. These sources were reconfirmed by cluster analysis. Risk assessment code (RAC) suggested that all metals were not harmful in monsoon season. However, Fe was in medium risk, and Mn and Cu were in low risk in summer. According to pollution load index (PLI) of sediments, all heavy metals were toxic. Cu might be related with adverse biological effects on the basis of sediment quality guidelines (SQG) in both seasons. These integrated approaches were very useful to identify the contamination sources and ecological risks of sediments in estuarine environment. It is expected that this research can give a useful information for the remediation of heavy metals in sediments.

Thermal activation in Au-based bulk metallic glass characterized by high-temperature nanoindentation

NASA Astrophysics Data System (ADS)

Yang, Bing; Wadsworth, Jeffrey; Nieh, Tai-Gang

2007-02-01

High-temperature nanoindentation experiments have been conducted on a Au49Ag5.5Pd2.3Cu26.9Si16.3 bulk metallic glass from 30to140°C, utilizing loading rates ranging from 0.1to100mN/s. Generally, the hardness decreased with increasing temperature. An inhomogeneous-to-homogeneous flow transition was clearly observed when the test temperature approached the glass transition temperature. Analyses of the pop-in pattern and hardness variation showed that the inhomogeneous-to-homogeneous transition temperature was loading-rate dependent. Using a free-volume model, the authors deduced the size of the basic flow units and the activation energy for the homogeneous flow. In addition, the strain rate dependency of the transition temperature was predicted.

EELS characterisation of bulk CaCu3Ti4O12 ceramics.

PubMed

Calvert, Clair C; Rainforth, W Mark; Sinclair, Derek C; West, Anthony R

2006-01-01

CaCu3Ti4O12 (CCTO) is a cubic perovskite phase and sintered ceramics exhibit high permittivity at room temperature. Electron energy-loss spectroscopy (EELS) and energy dispersive X-ray spectrometry (EDS) data have been collected from samples of CCTO to relate the observed electrical properties to the microstructure and chemistry on the nanoscale. CCTO ceramics were sintered for 24h at 1115 degrees C in air, giving a grain size of 50-300 microm. Ti L(2,3)-, Cu L(2,3)- and O K-edge EEL data were collected for bulk CCTO (within grain) and compared with well characterised Ti-oxides, CaTiO3 and BaTiO3 perovskites. The bulk metal L(2,3)-edge data for CCTO suggest that Cu is divalent and Ti is present as Ti4+. The O K-edge of CCTO shows increased near-edge structure (NES) compared to those of the simple perovskites.

Fracture Behavior of Zr-BASED Bulk Metallic Glass Under Impact Loading

NASA Astrophysics Data System (ADS)

Shin, Hyung-Seop; Kim, Ki-Hyun; Oh, Sang-Yeob

The fracture behavior of a Zr-based bulk amorphous metal under impact loading using subsize V-shaped Charpy specimens was investigated. Influences of loading rate on the fracture behavior of amorphous Zr-Al-Ni-Cu alloy were examined. As a result, the maximum load and absorbed fracture energy under impact loading were lower than those under quasi-static loading. A large part of the absorbed fracture energy in the Zr-based BMG was consumed in the process for crack initiation and not for crack propagation. In addition, fractographic characteristics of BMGs, especially the initiation and development of shear bands at the notch tip were investigated. Fractured surfaces under impact loading are smoother than those under quasi-static loading. The absorbed fracture energy appeared differently depending on the appearance of the shear bands developed. It can be found that the fracture energy and fracture toughness of Zr-based BMG are closely related with the extent of shear bands developed during fracture.

Speciation and distribution of copper in a mining soil using multiple synchrotron-based bulk and microscopic techniques.

PubMed

Yang, Jianjun; Liu, Jin; Dynes, James J; Peak, Derek; Regier, Tom; Wang, Jian; Zhu, Shenhai; Shi, Jiyan; Tse, John S

2014-02-01

Molecular-level understanding of soil Cu speciation and distribution assists in management of Cu contamination in mining sites. In this study, one soil sample, collected from a mining site contaminated since 1950s, was characterized complementarily by multiple synchrotron-based bulk and spatially resolved techniques for the speciation and distribution of Cu as well as other related elements (Fe, Ca, Mn, K, Al, and Si). Bulk X-ray absorption near-edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) spectroscopy revealed that soil Cu was predominantly associated with Fe oxides instead of soil organic matter. This agreed with the closest association of Cu to Fe by microscopic X-ray fluorescence (U-XRF) and scanning transmission X-ray microscopy (STXM) nanoanalysis, along with the non-occurrence of photoreduction of soil Cu(II) by quick Cu L3,2-edge XANES spectroscopy (Q-XANES) which often occurs when Cu organic complexes are present. Furthermore, bulk-EXAFS and STXM-coupled Fe L3,2-edge nano-XANES analysis revealed soil Cu adsorbed primarily to Fe(III) oxides by inner-sphere complexation. Additionally, Cu K-edge μ-XANES, L3,2-edge bulk-XANES, and successive Q-XANES results identified the presence of Cu2S rather than radiation-damage artifacts dominant in certain microsites of the mining soil. This study demonstrates the great benefits in use of multiple combined synchrotron-based techniques for comprehensive understanding of Cu speciation in heterogeneous soil matrix, which facilitates our prediction of Cu reactivity and environmental fate in the mining site.

Influence of the ultrasound-assisted synthesis of Cu-BTC metal-organic frameworks nanoparticles on uptake and release properties of rifampicin.

PubMed

Abbasi, Amir Reza; Rizvandi, Maryam

2018-01-01

In this work, we study uptake and release properties of rifampicin (denoted henceforth as Rif) from ultrasound-assisted synthesis Cu-BTC nanoparticles in comparison with bulk Cu-BTC and activated carbon. To explore the absorption ability of the Cu-BTC to Rif, fresh sample of Cu-BTC was immersed in an aqueous solution of Rif and were monitored in real time with UV/vis spectroscopy. Results show that the adsorbed quantity of Rif over nano Cu-BTC (denoted henceforth as I) is much higher than those over a bulk Cu-BTC (denoted henceforth as II) and activated carbon. In compound I and all of the nano-MOFs the channel length is decreased so that the amount of adsorption is increased a little. The samples were characterized with X-ray powder diffraction (XRD), Scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FT-IR), and UV/vis spectroscopy. Copyright © 2017 Elsevier B.V. All rights reserved.

An in situ neutron diffraction study of plastic deformation in a Cu 46.5Zr 46.5Al 7 bulk metallic glass composite

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

Wang, D. M.; Chen, Yan; Mu, Juan

Micro-mechanical behaviors of a Cu 46.5Zr 46.5Al 7 bulk metallic glass composite in the plastic regime were investigated by continuous in situ neutron diffraction during compression. Three stages of the plastic deformation were observed according to the work-hardening rate. Here, the underlying natures of the work hardening, correlating with the lattice/microscopic strain evolution, are revealed for the three stages: (1) the initiation of shear bands, (2) the phase load transferring from the amorphous phase to the B2 phase and (3) the accelerated martensitic transformation and the work hardening of the polycrystalline phases promoted by the rapid propagation of the shearmore » bands.« less

An in situ neutron diffraction study of plastic deformation in a Cu 46.5Zr 46.5Al 7 bulk metallic glass composite

DOE PAGES

Wang, D. M.; Chen, Yan; Mu, Juan; ...

2018-05-21

Micro-mechanical behaviors of a Cu 46.5Zr 46.5Al 7 bulk metallic glass composite in the plastic regime were investigated by continuous in situ neutron diffraction during compression. Three stages of the plastic deformation were observed according to the work-hardening rate. Here, the underlying natures of the work hardening, correlating with the lattice/microscopic strain evolution, are revealed for the three stages: (1) the initiation of shear bands, (2) the phase load transferring from the amorphous phase to the B2 phase and (3) the accelerated martensitic transformation and the work hardening of the polycrystalline phases promoted by the rapid propagation of the shearmore » bands.« less

Investigating the atomic level influencing factors of glass forming ability in NiAl and CuZr metallic glasses

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

Sedighi, Sina; Kirk, Donald Walter; Singh, Chandra Veer, E-mail: chandraveer.singh@utoronto.ca

2015-09-21

Bulk metallic glasses are a relatively new class of amorphous metal alloy which possess unique mechanical and magnetic properties. The specific concentrations and combinations of alloy elements needed to prevent crystallization during melt quenching remains poorly understood. A correlation between atomic properties that can explain some of the previously identified glass forming ability (GFA) anomalies of the NiAl and CuZr systems has been identified, with these findings likely extensible to other transition metal–transition metal and transition metal–metalloid (TM–M) alloy classes as a whole. In this work, molecular dynamics simulation methods are utilized to study thermodynamic, kinetic, and structural properties ofmore » equiatomic CuZr and NiAl metallic glasses in an attempt to further understand the underlying connections between glass forming ability, nature of atomic level bonding, short and medium range ordering, and the evolution of structure and relaxation properties in the disordered phase. The anomalous breakdown of the fragility parameter as a useful GFA indicator in TM–M alloy systems is addressed through an in-depth investigation of bulk stiffness properties and the evolution of (pseudo)Gruneisen parameters over the quench domain, with the efficacy of other common glass forming ability indicators similarly being analyzed through direct computation in respective CuZr and NiAl systems. Comparison of fractional liquid-crystal density differences in the two systems revealed 2-3 times higher values for the NiAl system, providing further support for its efficacy as a general purpose GFA indicator.« less

Excellent glass forming ability and plasticity in high entropy Zr20Ti20Hf20M20Be20 (M = Cu, Ni, Co) alloys

NASA Astrophysics Data System (ADS)

Zong, Haitao; Geng, Chenchen; Kang, Chaoyang; Cao, Guohua; Bian, Linyan; Li, Lixin; Zhang, Baoqing; Li, Ming

2018-03-01

We reported here the studies of a series of Zr20Ti20Hf20M20Be20 (M = Cu, Ni and Co) quinary high entropy bulk metallic glasses. Glasses with critical diameters (Dc) of 3 mm, 8 mm and 5 mm, respectively has been successfully fabricated by copper mold casting. Strikingly, a plastic strain of 11.6% is achieved in the Zr20Ti20Hf20Cu20Be20 metallic glass. The dynamic fragility the Zr20Ti20Hf20Cu20Be20 alloy is determined from calorimetric measurements. The excellent plasticity is explained to be attributed to relatively higher fragility.

In situ atomic-scale imaging of the metal/oxide interfacial transformation

DOE PAGES

Zou, Lianfeng; Li, Jonathan; Zakharov, Dmitri; ...

2017-08-21

Directly probing structure dynamics at metal/oxide interfaces has been a major challenge due to their buried nature.Using environmental transmission electron microscopy,here we report observations of the in-place formation of Cu 2O/Cu interfaces via the oxidation of Cu, and subsequently probe the atomic mechanisms by which interfacial transformation and grain rotation occur at the interfaces during reduction in an H 2 gas environment. The Cu 2O→Cu transformation is observed to occur initially along the Cu 2O/Cu interface in a layer-by-layer manner.The accumulation of oxygen vacancies at the Cu 2O/Cu interface drives the collapse of the Cu 2O lattice near the interfacemore » region, which results in a tilted Cu 2O/Cu interface with concomitant Cu 2O island rotation. Lastly, these results provide unprecedented microscopic detail regarding the redox reactions of supported oxides,which differs fundamentally from the reduction of bulk or isolated oxides that requires the formation of new interfaces between the parent oxide and the reduced phase.« less

Skeletal Ru/Cu catalysts prepared from crystalline and quasicrystalline ternary alloy precursors: characterization by X-ray absorption spectroscopy and CO oxidation.

PubMed

Highfield, James; Liu, Tao; Loo, Yook Si; Grushko, Benjamin; Borgna, Armando

2009-02-28

The Ru/Cu system is of historical significance in catalysis. The early development and application of X-ray absorption spectroscopy (XAS) led to the original 'bimetallic cluster" concept for highly-immiscible systems. This work explores alkali leaching of Al-based ternary crystalline and quasicrystalline precursors as a potential route to bulk Ru/Cu alloys. Single-phase ternary alloys at 3 trial compositions; Al(71)Ru(22)Cu(7), Al(70.5)Ru(17)Cu(12.5), and Al(70)Ru(10)Cu(20), were prepared by arc melting of the pure metal components. After leaching, the bimetallic residues were characterized principally by transmission XAS, "as-leached" and after annealing in H(2) (and passivation) in a thermobalance. XRD and BET revealed a nanocrystalline product with a native structure of hexagonal Ru. XPS surface analysis of Ru(22)Cu(7) and Ru(17)Cu(12.5) found only slight enrichment by Cu in the as-leached forms, with little change upon annealing. Ru(10)Cu(20) was highly segregated as-leached. XANES data showed preferential oxidation of Cu in Ru(22)Cu(7), implying that it exists as an encapsulating layer. TG data supports this view since it does not show the distinct two-stage O(2) uptake characteristic of skeletal Ru. Cu K-edge EXAFS data for Ru(22)Cu(7) were unique in showing a high proportion of Ru neighbours. The spacing, d(CuRu) = 2.65 A, was that expected from a hypothetical (ideal) solid solution at this composition, but this is unlikely in such a bulk-immiscible system and Ru K-edge EXAFS failed to confirm bulk alloying. Furthermore its invariance under annealing was more indicative of an interfacial bond between bulk components, although partial alloying with retention of local order cannot entirely be ruled out. The XAS and XPS data were reconciled in a model involving surface and bulk segregation, Cu being present at both the grain exterior and in ultra-fine internal pores. This structure can be considered as the 3-dimensional analogue of the classical type. Preliminary studies in CO and H(2) oxidation were made in a DRIFTS flow reactor with on-line MS, and their activities and selectivities were compared against skeletal Ru and Cu controls, Ru/Al(2)O(3), and Au/Fe(2)O(3). All samples were active in CO oxidation above approximately 50 degrees C, showing light-off temperatures in the range 60-70 degrees C. Ru(22)Cu(7) and Ru(17)Cu(12.5) also showed good selectivities (vs. H(2) oxidation), attributed tentatively to Ru-modified Cu surfaces of varying thickness. These compositions are promising candidates to test in a (PROX) fuel processor to supply purified (CO-free) H(2) to a PEM fuel cell.

Martensitic transformation in a B2-containing CuZr-based BMG composite revealed by in situ neutron diffraction

DOE PAGES

Song, Gian; Lee, Chanho; Hong, Sung Hwan; ...

2017-06-27

Here, CuZr-based bulk-metallic-glass (BMG) composites reinforced by a B2-type CuZr crystalline-phase (CP) have been widely studied, and exhibit that the plastic deformation of the CP induces martensitic transformation from the B2 to B19', which plays a dominant role in the deformation behavior and mechanical properties. In the present study, 2.0% Co containing CuZr-based BMG composites were investigated using in-situ neutron-diffraction technique. The in-situ neutron-diffraction results reveal the continuous load transfer from the glass matrix to B2 CP and martensitic transformation from the B2 CP to B19' during the deformation of the composite. Moreover, it was found that the martensitic transformationmore » is initiated at the applied stress higher than 1500 MPa, and is significantly suppressed during the deformation, as compared to other 0.5% Co-containing CuZr-based BMG composites. Based on these in-situ neutron-diffraction results, the martensitic transformation is strongly affected by the amount of the addition of Co, which determines the mechanical properties of CP-reinforced BMG composites, such as ductility and hardening capability.« less

Martensitic transformation in a B2-containing CuZr-based BMG composite revealed by in situ neutron diffraction

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

Song, Gian; Lee, Chanho; Hong, Sung Hwan

Here, CuZr-based bulk-metallic-glass (BMG) composites reinforced by a B2-type CuZr crystalline-phase (CP) have been widely studied, and exhibit that the plastic deformation of the CP induces martensitic transformation from the B2 to B19', which plays a dominant role in the deformation behavior and mechanical properties. In the present study, 2.0% Co containing CuZr-based BMG composites were investigated using in-situ neutron-diffraction technique. The in-situ neutron-diffraction results reveal the continuous load transfer from the glass matrix to B2 CP and martensitic transformation from the B2 CP to B19' during the deformation of the composite. Moreover, it was found that the martensitic transformationmore » is initiated at the applied stress higher than 1500 MPa, and is significantly suppressed during the deformation, as compared to other 0.5% Co-containing CuZr-based BMG composites. Based on these in-situ neutron-diffraction results, the martensitic transformation is strongly affected by the amount of the addition of Co, which determines the mechanical properties of CP-reinforced BMG composites, such as ductility and hardening capability.« less

Graphene-like Networks in the lattice of Ag, Cu and Al metals

NASA Astrophysics Data System (ADS)

Salamanca-Riba, Lourdes; Ge, Xiaoxiao; Isaacs, Romaine; Jaim, Hm Iftekar; Wuttig, Manfred; Rashkeev, Sergey; Kuklja, Maija; Hu, Lianbing; Covetics Team Team

Graphene-like networks form in the lattice of metals such as silver, copper and aluminum via an electrocharging assisted process. In this process a high current of >80A is applied to the liquid metal containing particles of activated carbon. The resulting material is called M covetic (M =Al, Ag Cu). We have previously reported that this process gives rise to carbon nanostructures with sp2 bonding embedded in the lattice of the metal. The carbon bonds to the metal as evidenced by Raman scattering and first principles simulation of the phonon density of states. With this process we have observed that graphene nanoribbons form along preferential crystalline directions and form 3D epitaxial structures with Al and Ag hosts. Bulk Cu covetic was used to deposit films by e-beam deposition and PLD. The PLD films contain higher C content and show higher transmittance (~90%) and resistance to oxidation than pure copper films of the same thickness. We compare the electrical and mechanical properties of covetics containing C in the 0 to 10 wt % and the transmittance of Cu covetic films compared to pure Cu films of the same thickness. Supported by ONR Grant N000141410042

Growth and Magnetotransport Properties of Dirac Semimetal Candidate Cu3PdN

NASA Astrophysics Data System (ADS)

Quintela, C. X.; Campbell, N.; Harris, D. T.; Shao, D. F.; Xie, L.; Pan, X. Q.; Tsymbal, E. Y.; Rzchowski, M. S.; Eom, C. B.

Since the discovery of three-dimensional Dirac semimetals (DSM) Cd3As2 and Na3Bi, many efforts have been made to identify new DSM materials. Recently, nitride antiperovskite Cu3PdN has been proposed by two different groups as a new DSM candidate. However, until now, the experimental realization of bulk Cu3PdN and the study of its electronic properties has been hindered due to the difficulty of synthesizing bulk single crystals of this material. Here, we report the first growth and magnetotransport characterization of epitaxial Cu3PdN thin films on (001) SrTiO3 substrates. Magnetotransport measurements reveal p-type metallic conduction with very low temperature coefficient of the resistance and small non-linear magnetoresistance at low temperatures. The successful growth of Cu3PdN thin films opens the path to investigating the unknown electronic properties of this material, and provides a template for further research on other antiperovskite DSM candidates such as Cu3ZnN.

Dynamic fracture instability of tough bulk metallic glass

NASA Astrophysics Data System (ADS)

Meng, J. X.; Ling, Z.; Jiang, M. Q.; Zhang, H. S.; Dai, L. H.

2008-04-01

We report the observations of a clear fractographic evolution from vein pattern, dimple structure, and then to periodic corrugation structure, followed by microbranching pattern, along the crack propagation direction in the dynamic fracture of a tough Zr41.2Ti13.8Cu12.5Ni10Be22.5 (Vit.1) bulk metallic glass (BMGs) under high-velocity plate impact. A model based on fracture surface energy dissipation and void growth is proposed to characterize this fracture pattern transition. We find that once the dynamic crack propagation velocity reaches a critical fraction of Rayleigh wave speed, the crack instability occurs; hence, crack microbranching goes ahead. Furthermore, the correlation between the critical velocity of amorphous materials and their intrinsic strength such as Young's modulus is uncovered. The results may shed new insight into dynamic fracture instability for BMGs.

Biocompatible Ni-free Zr-based bulk metallic glasses with high-Zr-content: compositional optimization for potential biomedical applications.

PubMed

Hua, Nengbin; Huang, Lu; Chen, Wenzhe; He, Wei; Zhang, Tao

2014-11-01

The present study designs and prepares Ni-free Zr60+xTi2.5Al10Fe12.5-xCu10Ag5 (at.%, x=0, 2.5, 5) bulk metallic glasses (BMGs) by copper mold casting for potential biomedical application. The effects of Zr content on the in vitro biocompatibility of the Zr-based BMGs are evaluated by investigating mechanical properties, bio-corrosion behavior, and cellular responses. It is found that increasing the content of Zr is favorable for the mechanical compatibility with a combination of low Young's modulus, large plasticity, and high notch toughness. Electrochemical measurements demonstrate that the Zr-based BMGs are corrosion resistant in a phosphate buffered saline solution. The bio-corrosion resistance of BMGs is improved with the increase in Zr content, which is attributed to the enrichment in Zr and decrease in Al concentration in the surface passive film of alloys. Regular cell responses of mouse MC3T3-E1 cells, including cell adhesion and proliferation, are observed on the Zr-Ti-Al-Fe-Cu-Ag BMGs, which reveals their general biosafety. The high-Zr-based BMGs exhibit a higher cell proliferation activity in comparison with that of pure Zr and Ti-6Al-4V alloy. The effects of Zr content on the in vitro biocompatibility can be used to guide the future design of biocompatible Zr-based BMGs. Copyright © 2014 Elsevier B.V. All rights reserved.

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

Song, Gian; Lee, Chanho; Hong, Sung Hwan

Here, CuZr-based bulk-metallic-glass (BMG) composites reinforced by a B2-type CuZr crystalline-phase (CP) have been widely studied, and exhibit that the plastic deformation of the CP induces martensitic transformation from the B2 to B19', which plays a dominant role in the deformation behavior and mechanical properties. In the present study, 2.0% Co containing CuZr-based BMG composites were investigated using in-situ neutron-diffraction technique. The in-situ neutron-diffraction results reveal the continuous load transfer from the glass matrix to B2 CP and martensitic transformation from the B2 CP to B19' during the deformation of the composite. Moreover, it was found that the martensitic transformationmore » is initiated at the applied stress higher than 1500 MPa, and is significantly suppressed during the deformation, as compared to other 0.5% Co-containing CuZr-based BMG composites. Based on these in-situ neutron-diffraction results, the martensitic transformation is strongly affected by the amount of the addition of Co, which determines the mechanical properties of CP-reinforced BMG composites, such as ductility and hardening capability.« less

Sediment quality assessment in a coastal lagoon (Ravenna, NE Italy) based on SEM-AVS and sequential extraction procedure.

PubMed

Pignotti, Emanuela; Guerra, Roberta; Covelli, Stefano; Fabbri, Elena; Dinelli, Enrico

2018-09-01

Sediments from the Pialassa Piomboni coastal lagoon (NE Italy) were studied to assess the degree of contamination and ecological risk related to trace metals by combining a geochemical characterization of bulk sediments with the assessment of the bioavailable forms of trace metals. With this purpose, sediment contamination (Cd, Cu, Hg, Ni, Pb, and Zn) was assessed by Enrichment Factors (EFs), and potential bioavailability by the Simultaneously Extracted Metals and Acid Volatile Sulfides (SEM-AVS) approach (Cd, Cu, Ni, Pb, and Zn), and by Sequential Extraction Procedure (Co, Cr, Cu, Ni, Pb, and Zn). On average, Cr and Ni exhibited no contamination (EF ≤1.5), and a predominance in the residual fraction of the sediment, indicating natural origin for these metals. Cu, Pb and Zn displayed a local contamination, which resulted in a higher proportion of Cu bound to the reducible and oxidizable fractions (~30% and ~40% as median, respectively), and Pb mostly associated with the reducible phase (~60% as median). Hence, Cu and Pb could be mobilized when environmental conditions become reducing or oxidizing. Zn resulted mainly partitioned into the reducible and residual fractions (~50% as median, in both fractions). The Risk Assessment Code (RAC) indicated that approximately 30% of samples had >10% of total Zn weakly bound to the sediment, suggesting a medium risk of exposure for aquatic organisms. RAC results were consistent with the ∑SEM-AVS findings, pointing to possible adverse effects for aquatic biota in ~30% of samples, with Zn mostly accounting for the total metal bioavailability. Hg showed a moderate to very severe enrichment, indicating that a substantial amount of this metal derives from anthropogenic sources and may pose adverse effects on the aquatic biota of the Pialassa Piomboni lagoon. Copyright © 2018 Elsevier B.V. All rights reserved.

Dynamical, structural and chemical heterogeneities in a binary metallic glass-forming liquid

NASA Astrophysics Data System (ADS)

Puosi, F.; Jakse, N.; Pasturel, A.

2018-04-01

As it approaches the glass transition, particle motion in liquids becomes highly heterogeneous and regions with virtually no mobility coexist with liquid-like domains. This complex dynamic is believed to be responsible for different phenomena including non-exponential relaxation and the breakdown of the Stokes-Einstein relation. Understanding the relationships between dynamical heterogeneities and local structure in metallic liquids and glasses is a major scientific challenge. Here we use classical molecular dynamics simulations to study the atomic dynamics and microscopic structure of Cu50Zr50 alloy in the supercooling regime. Dynamical heterogeneities are identified via an isoconfigurational analysis. We demonstrate the transition from isolated to clustering low mobility with decreasing temperature. These slow clusters, whose sizes grow upon cooling, are also associated with concentration fluctuations, characterized by a Zr-enriched phase, with a composition CuZr2 . In addition, a structural analysis of slow clusters based on Voronoi tessellation evidences an increase with respect of the bulk system of the fraction of Cu atoms having a local icosahedral order. These results are in agreement with the consolidated scenario of the relevant role played by icosahedral order in the dynamic slowing-down in supercooled metal alloys.

Towards the Better: Intrinsic Property Amelioration in Bulk Metallic Glasses

NASA Astrophysics Data System (ADS)

Sarac, Baran; Zhang, Long; Kosiba, Konrad; Pauly, Simon; Stoica, Mihai; Eckert, Jürgen

2016-06-01

Tailoring the intrinsic length-scale effects in bulk metallic glasses (BMGs) via post-heat treatment necessitates a systematic analyzing strategy. Although various achievements were made in the past years to structurally enhance the properties of different BMG alloys, the influence of short-term sub-glass transition annealing on the relaxation kinetics is still not fully covered. Here, we aim for unraveling the connection between the physical, (thermo)mechanical and structural changes as a function of selected pre-annealing temperatures and time scales with an in-house developed Cu46Zr44Al8Hf2 based BMG alloy. The controlled formation of nanocrystals below 50 nm with homogenous distribution inside the matrix phase via thermal treatment increase the material’s resistance to strain softening by almost an order of magnitude. The present work determines the design aspects of metallic glasses with enhanced mechanical properties via nanostructural modifications, while postulating a counter-argument to the intrinsic property degradation accounted for long-term annealing.

Rapid Relaxation and Embrittlement of Zr-based Bulk Metallic Glasses by Electropulsing

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

Yiu, P; Chen, Y. C.; Chu, J. P.

2013-01-01

Mechanical relaxation and embrittlement of Zr52.5Cu17.9Ni14.6Al10Ti5 bulk metallic glasses were achieved rapidly by the direct current electropulsing treatment. The temperature profile was recorded by an infrared camera and it was found to be non-uniform in the treated specimen. Specifically, temperatures below the glass transition temperature, near and above the crystallization temperature could be ach- ieved, respectively, at different locations in the same treated specimen. Two sets of nanoindentation were conducted. While the first set investigated the mechanical properties of three individually elec- tropulsed specimens with different conditions, the second set indented a single treated specimen along its temperature gradient. Bothmore » sets of indentation revealed that by Joule heating to different tempera- tures, relaxation, embrittlement, and crystallization were significantly accelerated by electrical pulses. Results suggest that electropulsing provides an opportunity to simultaneously achieve plastic forming and mechanical property control of metallic glasses.« less

Methane Oxidation to Methanol Catalyzed by Cu-Oxo Clusters Stabilized in NU-1000 Metal–Organic Framework

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

Ikuno, Takaaki; Zheng, Jian; Vjunov, Aleksei

The catalyzed conversion of shale gas-derived light hydrocarbons, e.g. methane to methanol, for further application as automotive fuels and/or bulk chemicals is especially attractive in light of improved methods of hydrocarbon extraction. MOF based catalysts have previously been demonstrated to be active for a range of catalytic reactions. In this work we used Cu-NU1000 as a methane-to-methanol oxidation catalyst. In addition to product studies, in-situ X-ray Absorption Spectroscopic (XAS) experiments are performed under catalytic conditions in order to follow the modification of the Cu-species and directly probe the structure/activity properties of the Cu-NU1000 system. The insights reported herein serve asmore » a first look at metal-organic framework materials as catalysts for methane oxidation and be the basis for development of the subsequent generations of materials.« less

High thermal stability and sluggish crystallization kinetics of high-entropy bulk metallic glasses

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

Yang, M.; Department of Mechanical Engineering, The Hong Kong Polytechnic University, Hung Hom, Kowloon; Liu, X. J.

2016-06-28

Metallic glasses are metastable and their thermal stability is critical for practical applications, particularly at elevated temperatures. The conventional bulk metallic glasses (BMGs), though exhibiting high glass-forming ability (GFA), crystallize quickly when being heated to a temperature higher than their glass transition temperature. This problem may potentially be alleviated due to the recent developments of high-entropy (or multi-principle-element) bulk metallic glasses (HE-BMGs). In this work, we demonstrate that typical HE-BMGs, i.e., ZrTiHfCuNiBe and ZrTiCuNiBe, have higher kinetic stability, as compared with the benchmark glass Vitreoy1 (Zr{sub 41.2}Ti{sub 13.8}Cu{sub 12.5}Ni{sub 10}Be{sub 22.5}) with a similar chemical composition. The measured activation energymore » for glass transition and crystallization of the HE-BMGs is nearly twice that of Vitreloy 1. Moreover, the sluggish crystallization region ΔT{sub pl-pf}, defined as the temperature span between the last exothermic crystallization peak temperature T{sub pl} and the first crystallization exothermic peak temperature T{sub pf}, of all the HE-BMGs is much wider than that of Vitreloy 1. In addition, high-resolution transmission electron microscopy characterization of the crystallized products at different temperatures and the continuous heating transformation diagram which is proposed to estimate the lifetime at any temperature below the melting point further confirm high thermal stability of the HE-BMGs. Surprisingly, all the HE-BMGs show a small fragility value, which contradicts with their low GFA, suggesting that the underlying diffusion mechanism in the liquid and the solid of HE-BMGs is different.« less

Synchrotron x-ray scattering investigations of oxygen-induced nucleation in a Zr-based glass-forming alloy.

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

Wall, J. J.; Almer, J. D.; Vogel, S. C.

The metallic glass-forming alloy VIT-105 (Zr{sub 52.5}Cu{sub 17.9}Ni{sub 14.6}Al{sub 10}Ti{sub 5}) was used to study the effect of oxygen on nucleation. Ex situ synchrotron X-ray scattering experiments performed on as-cast samples showed that oxygen leads to the formation of tetragonal and/or cubic phases, depending on oxygen content. The samples crystallized into either a primitive tetragonal phase or the so-called fcc 'big cube' phase in a glassy matrix. A subsequent discussion on the role of oxygen in heterogeneous nucleation in Zr-based bulk metallic glasses is presented.

Modeling the interaction and toxicity of Cu-Cd mixture to wheat roots affected by humic acids, in terms of cell membrane surface characteristics.

PubMed

Wang, Yi-Min; Zhou, Dong-Mei; Yuan, Xu-Yin; Zhang, Xiao-Hui; Li, Yi

2018-05-01

Responses of wheat (Triticum aestivum L.) seedling roots to the mixtures of copper (Cu), cadmium (Cd) and humic acids (HA) were investigated using the solution culture experiments, focusing on the interaction patterns between multiple metals and their influences on root proton release. A concentration-addition multiplication (CA) model was introduced into the modeling analysis. In comparison with metal ion activities in bulk-phase solutions, the incorporation of ion activities at the root cell membrane surfaces (CMs) (denoted as {Cu 2+ } 0 and {Cd 2+ } 0 ) into the CA model could significantly improve their correlation with RRE (relative root elongation) from 0.819 to 0.927. Modeling analysis indicated that the co-existence of {Cu 2+ } 0 significantly enhanced the rhizotoxicity of {Cd 2+ } 0 , while no significant effect of {Cd 2+ } 0 on the {Cu 2+ } 0 rhizotoxicity. 10 mg/L HA stimulated the root elongation even under metal stress. Although high concentration of metal ions inhibited the root proton release rate (ΔH + ), both the low concentration of metal ions and HA treatments increased the values of ΔH + . In HA-Cu-Cd mixtures, actions of metal ions on ΔH + values were varied intricately among treatments but well modeled by the CA model. We concluded from the CA models that the electrostatic effect is vitally important for explaining the effect of {Cu 2+ } 0 on the rhizotoxicity of {Cd 2+ } 0 , while it plays no unique role in understanding the influence of {Cd 2+ } 0 on the rhizotoxicity of {Cu 2+ } 0. Thus our study provide a novel way for modeling multiple metals behaviors in the environment and understanding the mechanisms of ion interactions. Copyright © 2018 Elsevier Ltd. All rights reserved.

High-resolution structural studies of ultra-thin magnetic, transition metal overlayers and two-dimensional transition metal oxides using synchrotron radiation

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

Kellar, S.A.

This thesis report the surface-structure determination of three, ultra-thin magnetic transition-metal films, Fe/Au(100), Mn/Ni(100), and Mn/Cu(100) using Angle-Resolved Photoemission Extended Fine Structure (ARPEFS) and photoelectron holography. These structural studies are the first to use non-s initial states in the ARPEFS procedure. This thesis also reports an ARPEFS surface-structure determination of a two-dimensional transition-metal oxide, [(1 x 1)O/W(110)] x 12. The authors have analyzed the ARPFES signal from the Au 4f{sub 7/5} core level of the Au(1 ML)/Fe(15 ML)/Au(100) system. The analysis shows that the Fe grows layer by layer with one monolayer of gold, acting as a surfactant, remaining onmore » top of the growing Fe layers. These surface gold atoms sit in the four-fold hollow site, 1.67 {+-} 0.02 A above the iron surface. The grown Fe layer is very much like the bulk, bcc iron, with an interlayer spacing of 1.43 {+-} 0.03 A. Analysis of the Mn 3p ARPEFS signals from c(2 x 2)Mn/Ni(100) and c(2 x 2)Mn/Cu(100) shows that the Mn forms highly corrugated surface alloys. The corrugation of the Mn/Ni(100) and Mn/Cu(100) systems are 0.24 {+-} 0.02 A and 0.30 {+-} 0.04 A respectively. In both cases the Mn is sticking above the plane of the surface substrate atoms. For the Mn/Ni(100) system the first layer Ni is contracted 4% from the bulk value. The Mn/Cu(100) system shows bulk spacing for the substrate Cu. Photoelectron holography shows that the Mn/Ni interface is very abrupt with very little Mn leaking into the second layer, while the Mn/Cu(100) case has a significant amount of Mn leaking into the second layer. A new, five-element electrostatic electron lens was developed for hemispherical electron-energy analyzers. This lens system can be operated at constant transverse or constants angular magnification, and has been optimized for use with the very small photon-spot sizes. Improvements to the hemispherical electron-energy analyzer are also discussed.« less

Effects of chemical composition and test conditions on the dynamic tensile response of Zr-based metallic glasses

NASA Astrophysics Data System (ADS)

Wang, F.; Laws, K.; Martinez, D.; Trujillo, C. P.; Brown, A. D.; Cerreta, E. K.; Hazell, P. J.; Ferry, M.; Quadir, M. Z.; Jiang, J.; Escobedo, J. P.

2017-01-01

The effects of impact velocity and temperature on the dynamic mechanical behavior of two bulk metallic (BMG) alloys with slightly different elemental compositions (Zr55Cu30Ni5Al30 and Zr46Cu38Ag8Al38) have been investigated. Bullet-shaped samples were accelerated by a gas gun to speeds in the 400˜600m/s range and tested at both room temperature and 250°C. The samples impacted steel extrusion dies which subjected the bullets to high strains at relatively high strain-rates. The extruded fragments were subsequently soft recovered by using low density foams and examined by means of optical/scanning electron microscopy and differential scanning calorimetry. It was found that shear banding was the dictating mechanism responsible for the fracture of all BMGs. At room temperature, the Zr55Cu30Ni5Al30 alloy exhibited a higher resistance to fragmentation than the Zr46Cu38Ag8Al38 alloy. At 250°C, significant melting was observed in the recovered fragments of both alloys, which indicates that the BMG glassy structure undergoes a melting process and deformation likely occurs homogeneously.

Molecular Dynamics Simulations of Grain Boundary and Bulk Diffusion in Metals.

NASA Astrophysics Data System (ADS)

Plimpton, Steven James

Diffusion is a microscopic mass transport mechanism that underlies many important macroscopic phenomena affecting the structural, electrical, and mechanical properties of metals. This thesis presents results from atomistic simulation studies of diffusion both in bulk and in the fast diffusion paths known as grain boundaries. Using the principles of molecular dynamics single boundaries are studied and their structure and dynamic properties characterized. In particular, tilt boundary bicrystal and bulk models of fcc Al and bcc alpha-Fe are simulated. Diffusion coefficients and activation energies for atomic motion are calculated for both models and compared to experimental data. The influence of the interatomic pair potential on the diffusion is studied in detail. A universal relation between the melting temperature that a pair potential induces in a simulated bulk model and the potential energy barrier height for atomic hopping is derived and used to correlate results for a wide variety of pair potentials. Using these techniques grain boundary and bulk diffusion coefficients for any fcc material can be estimated from simple static calculations without the need to perform more time-consuming dynamic simulations. The influences of two other factors on grain boundary diffusion are also studied because of the interest of the microelectronics industry in the diffusion related reliability problem known as electromigration. The first factor, known to affect the self diffusion rate of Al, is the presence of Cu impurity atoms in Al tilt boundaries. The bicrystal model for Al is seeded randomly with Cu atoms and a simple hybrid Morse potential used to model the Al-Cu interaction. While some effect due to the Cu is noted, it is concluded that pair potentials are likely an inadequate approximation for the alloy system. The second factor studied is the effect of the boundary orientation angle on the diffusion rate. Symmetric bcc Fe boundaries are relaxed to find optimal structures and their diffusion coefficients calculated. Good agreement is found with the dislocation pipe model for tilt boundary diffusion.

Controlling the Mechanical Properties of Bulk Metallic Glasses by Superficial Dealloyed Layer

PubMed Central

Wang, Chaoyang; Li, Man; Zhu, Mo; Wang, Han; Qin, Chunling; Zhao, Weimin

2017-01-01

Cu50Zr45Al5 bulk metallic glass (BMG) presents high fracture strength. For improving its plasticity and controlling its mechanical properties, superficial dealloying of the BMG was performed. A composite structure containing an inner rod-shaped Cu-Zr-Al amorphous core with high strength and an outer dealloyed nanoporous layer with high energy absorption capacity was obtained. The microstructures and mechanical properties of the composites were studied in detail. It was found, for the first time, that the mechanical properties of Cu50Zr45Al5 BMG can be controlled by adjusting the width of the buffer deformation zone in the dealloyed layer, which can be easily manipulated with different dealloying times. As a result, the compressive strength, compressive strain, and energy absorption capacity of the BMGs can be effectively modulated from 0.9 to 1.5 GPa, from 2.9% to 4.7%, and from 29.1 to 40.2 MJ/m3, respectively. The paper may open a door for developing important engineering materials with regulable and comprehensive performances. PMID:29077072

Off-plane polarization ordering in metal chalcogen diphosphates from bulk to monolayer

NASA Astrophysics Data System (ADS)

Song, Wenshen; Fei, Ruixiang; Yang, Li

2017-12-01

Vertically (off-plane) ferroelectric ordering in ultrathin films has been pursued for decades. We predict the existence of intrinsic vertical polarization orderings in ultrathin metal chalcogen-diphosphates (MCDs). Taking CuInP2Se6 as an example, the first-principles calculation and electrostatic-energy model show that, under the open-circuit boundary condition, the ground state of bulk CuInP2Se6 is ferroelectric (FE) while that of monolayer is antiferroelectric (AFE), and the critical thickness for this FE/AFE transition is around six layers. Interestingly, under the closed-circuit boundary condition, the FE state can hold even for monolayer. Particularly, because of the small energy difference but the large barrier between FE and AFE orderings, the FE state can be stabilized in a free-standing monolayer, giving rise to intrinsic, off-plane two-dimensional ferroelectrics. Applying Monte Carlo simulations, we further calculate the ferroelectric Curie temperature (Tc) and electric hysteresis.

Amorphous and nanocrystalline luminescent Si and Ge obtained via a solid-state chemical metathesis synthesis route

NASA Astrophysics Data System (ADS)

McMillan, Paul F.; Gryko, Jan; Bull, Craig; Arledge, Richard; Kenyon, Anthony J.; Cressey, Barbara A.

2005-03-01

A new solid-state metathesis synthesis route was applied to obtain bulk samples of amorphous or microcrystalline Si and Ge. The method involves reaction of Zintl phases such as NaSi or NaGe, with ammonium or metal (e.g., CuCl, CoBr 2) halides. The driving force for the solid-state reaction is provided by the formation of alkali halides and the transition metals or metal silicides, or gaseous ammonia and hydrogen. The semiconductors were purified by washing to remove other solid products. The amorphous semiconductors were obtained in bulk form from reactions carried out at 200-300 °C. Syntheses at higher temperatures gave rise to microcrystalline semiconductors, or to micro-/nanocrystalline particles contained within the amorphous material. Similar crystalline/amorphous composites were obtained after heat treatment of bulk amorphous materials.

Effects of Zr and Si on the Glass Forming Ability and Compressive Properties of Ti-Cu-Co-Sn Alloys

NASA Astrophysics Data System (ADS)

Wang, Tan; Wu, Yidong; Si, Jiajia; Hui, Xidong

2015-06-01

To succeed in finding novel Ti-based bulk metallic glasses, which are free from Be, Ni, and noble metallic elements, a comprehensive study was performed on the effects of Zr and Si on the microstructural evolution, glass-forming ability (GFA), and mechanical properties of Ti46Cu44- x Zr x Co7Sn3 ( x = 0, 5, 10, 12.5, and 16 at. pct) and Ti46Cu31.5Zr12.5- x Co7Sn3Si x ( x = 0.5, 1, and 1.5 at. pct) alloys. It is shown that with the increase of Zr, the sequence of phase formation is β-Ti + α-Ti + (Ti, Zr)3Cu4 ⇒ β-Ti + α-Ti + TiCu ⇒ β-Ti + Ti2Cu + glass ⇒ glass ⇒ β-Ti + Ti2Cu + TiCuSn. The quinary Ti-Zr-Cu-Co-Sn alloy with 12.5 pct Zr exhibits the best GFA. The addition of 1 pct Si results in the improvement of the critical size of glassy rods up to 3 mm in diameter. The yield stress and Young's modulus of Z-series alloys increases, and the plastic strain decreases with the addition of Zr. The yield stress and ultimate compression stress of Ti46Zr11.5Cu31.5Co7Sn3Si1 glassy alloy reach 2477.9 and 2623.3 MPa, respectively. It was found that the addition of Si promotes the generation and multiplication of shear bands, resulting in certain plasticity in these kinds of glassy alloys.

A Zr-based bulk metallic glass for future stent applications: Materials properties, finite element modeling, and in vitro human vascular cell response.

PubMed

Huang, Lu; Pu, Chao; Fisher, Richard K; Mountain, Deidra J H; Gao, Yanfei; Liaw, Peter K; Zhang, Wei; He, Wei

2015-10-01

Despite the prevalent use of crystalline alloys in current vascular stent technology, new biomaterials are being actively sought after to improve stent performance. In this study, we demonstrated the potential of a Zr-Al-Fe-Cu bulk metallic glass (BMG) to serve as a candidate stent material. The mechanical properties of the Zr-based BMG, determined under both static and cyclic loadings, were characterized by high strength, which would allow for the design of thinner stent struts to improve stent biocompatibility. Finite element analysis further complemented the experimental results and revealed that a stent made of the Zr-based BMG was more compliant with the beats of a blood vessel, compared with medical 316L stainless steel. The Zr-based BMG was found to be corrosion resistant in a simulated body environment, owing to the presence of a highly stable ZrO2-rich surface passive film. Application-specific biocompatibility studies were conducted using human aortic endothelial cells and smooth muscle cells. The Zr-Al-Fe-Cu BMG was found to support stronger adhesion and faster coverage of endothelial cells and slower growth of smooth muscle cells than 316L stainless steel. These results suggest that the Zr-based BMG could promote re-endothelialization and potentially lower the risk of restenosis, which are critical to improve vascular stent implantation integration. In general, findings in this study raised the curtain for the potential application of BMGs as future candidates for stent applications. Vascular stents are medical devices typically used to restore the lumen of narrowed or clogged blood vessel. Despite the clinical success of metallic materials in stent-assisted angioplasty, post-surgery complications persist due to the mechanical failures, corrosion, and in-stent restenosis of current stents. To overcome these hurdles, strategies including new designs and surface functionalization have been exercised. In addition, the development of new materials with higher performance and biocompatibility can intrinsically reduce stent failure rates. The present study demonstrates the advantages of a novel material, named bulk metallic glass (BMG), over the benchmarked 316L stainless steel through experimental methods and computational simulations. It raises the curtain of new research endeavors on BMGs as competitive alternatives for stent applications. Copyright © 2015 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

A Recyclable Metal-Organic Framework as a Dual Detector and Adsorbent for Ammonia.

PubMed

Gładysiak, Andrzej; Nguyen, Tu N; Navarro, Jorge A R; Rosseinsky, Matthew J; Stylianou, Kyriakos C

2017-10-04

Recyclable materials for simultaneous detection and uptake of ammonia (NH 3 ) are of great interest due to the hazardous nature of NH 3 . The structural versatility and porous nature of metal-organic frameworks (MOFs) make them ideal candidates for NH 3 capture. Herein, the synthesis of a water-stable and porous 3-dimensional Cu II -based MOF (SION-10) displaying a ship-in-a-bottle structure is reported; the pores of the host SION-10 framework accommodate mononuclear Cu II -complexes. SION-10 spontaneously uptakes NH 3 as a result of two concurrent mechanisms: chemisorption due to the presence of active Cu II sites and physisorption (bulk permanent porosity). The color of the material changes from green to blue upon NH 3 capture, with the shifts of the UV/Vis absorption bands clearly seen at NH 3 concentrations as low as 300 ppm. SION-10 can be recovered upon immersion of SION-10⊃NH 3 in water and can be further reused for NH 3 capture for at least three cycles. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Functional Performances of CuZnAl Shape Memory Alloy Open-Cell Foams

NASA Astrophysics Data System (ADS)

Biffi, C. A.; Casati, R.; Bassani, P.; Tuissi, A.

2018-01-01

Shape memory alloys (SMAs) with cellular structure offer a unique mixture of thermo-physical-mechanical properties. These characteristics can be tuned by changing the pore size and make the shape memory metallic foams very attractive for developing new devices for structural and functional applications. In this work, CuZnAl SMA foams were produced through the liquid infiltration of space holder method. In comparison, a conventional CuZn brass alloy was foamed trough the same method. Functional performances were studied on both bulk and foamed SMA specimens. Calorimetric response shows similar martensitic transformation (MT) below 0 °C. Compressive response of CuZnAl revealed that mechanical behavior is strongly affected by sample morphology and that damping capacity of metallic foam is increased above the MT temperatures. The shape memory effect was detected in the CuZnAl foams. The conventional brass shows a compressive response similar to that of the martensitic CuZnAl, in which plastic deformation accumulation occurs up to the cellular structure densification after few thermal cycles.

Assessment of atmospheric trace metal deposition in urban environments using direct and indirect measurement methodology and contributions from wet and dry depositions

NASA Astrophysics Data System (ADS)

Omrani, Mehrazin; Ruban, Véronique; Ruban, Gwenaël; Lamprea, Katerine

2017-11-01

Bulk Atmospheric Deposition (BAD), Wet Atmospheric Deposition (WAD) and Dry Atmospheric Deposition (DAD) were all measured within an urban residential area in Nantes (France) over a 9-month period (27 February - 10 December 2014). The objectives of this study were to compare 2 methods for measuring dry and wet atmospheric depositions in the urban environment (DAD and WAD: direct method; BAD and WAD: indirect one), and to characterize as well the variations and relative contributions of these depositions. Trace metals (As, Cd, Cr, Cu, Ni, Pt and V) were used to carry out these comparison and quantification. BAD was collected with two open polyethylene containers (72 × 54 × 21 cm), while WAD was collected by means of an automated rainwater collector and DAD was determined from both air measurements (recorded by an air sampler) and 7Be deposition velocities. The comparison based on a detailed evaluation of uncertainties showed a significant difference between the direct and indirect methods. Dry and wet depositions varied widely from one month to the next. Zn and Cu were the most abundant elements in both dry and wet depositions. The mean contribution of DAD to the bulk atmospheric deposition during this 9-month study was significant for Zn, Cu and V (about 25%) as well as for Pb (approx. 60%). For this relatively unpolluted urban residential catchment, the contribution of atmospheric deposition to global load at the catchment outlet was low, between 10% and 20% for Zn, Cu, V and Pb, 25% for Cr and about 30% for Ni. For other urban sites exhibiting high atmospheric pollution however, the atmospheric contribution to the global pollution load could be much greater. An accurate and representative estimation of DAD thus proves critical.

Cálculo del esfuerzo ideal de metales nobles mediante primeros principios en la dirección <100>

NASA Astrophysics Data System (ADS)

Bautista-Hernández, A.; López-Fuentes, M.; Pacheco-Espejel, V.; Rivas-Silva, J. F.

2005-04-01

We present calculations of the ideal strength on the < 100 > direction for noble metals (Cu, Ag and Au), by means of first principles calculations. First, we obtain the structural parameters (cell parameters, bulk modulus) for each studied metal. We deform on the < 100 > direction calculating the total energy and the stress tensor through the Hellman-Feynman theorem, by the relaxation of the unit cell in the perpendicular directions to the deformation one. The calculated cell constants differ 1.3 % from experimental data. The maximum ideal strength are 29.6, 17 and 19 GPa for Cu, Ag and Au respectively. Meanwhile, the calculated elastic modulus are 106 (Cu), 71 (Ag), and 45 GPa (Au) and are in agreement with the experimental values for polycrystalline samples. The values of maximum strength are explained by the optimum volume values due to the atomic radius size for each element.

Transport properties of Cu-doped bismuth selenide single crystals at high magnetic fields up to 60 Tesla: Shubnikov-de Haas oscillations and π-Berry phase

NASA Astrophysics Data System (ADS)

Romanova, Taisiia A.; Knyazev, Dmitry A.; Wang, Zhaosheng; Sadakov, Andrey V.; Prudkoglyad, Valery A.

2018-05-01

We report Shubnikov-de Haas (SdH) and Hall oscillations in Cu-doped high quality bismuth selenide single crystals. To increase the accuracy of Berry phase determination by means of the of the SdH oscillations phase analysis we present a study of n-type samples with bulk carrier density n ∼1019 -1020cm-3 at high magnetic field up to 60 Tesla. In particular, Landau level fan diagram starting from the value of the Landau index N = 4 was plotted. Thus, from our data we found π-Berry phase that directly indicates the Dirac nature of the carriers in three-dimensional topological insulator (3D TI) based on Cu-doped bismuth selenide. We argued that in our samples the magnetotransport is determined by a general group of carriers that exhibit quasi-two-dimensional (2D) behaviour and are characterized by topological π-Berry phase. Along with the main contribution to the conductivity the presence of a small group of bulk carriers was registered. For 3D-pocket Berry phase was identified as zero, which is a characteristic of trivial metallic states.

Petrographic and spectroscopic characterization of phosphate-stabilized mine tailings from Leadville, Colorado.

PubMed

Eusden, J D; Gallagher, L; Eighmy, T T; Crannell, B S; Krzanowski, J R; Butler, L G; Cartledge, F K; Emery, E F; Shaw, E L; Francis, C A

2002-01-01

The use of soluble PO4(3-) and lime as a heavy metal chemical stabilization agent was evaluated for mine tailings from Leadville, Colorado. The tailings are from piles associated with the Wolftone and Maid of Erin mines; ore material that was originally mined around 1900, reprocessed in the 1940s, and now requires stabilization. The dominant minerals in the tailings are galena (PbS), cerrusite (PbCO3), pyromorphite (Pb5(PO4)3Cl), plumbojarosite (Pb0.5Fe3(SO4)2(OH)6), and chalcophanites ((Pb,Fe,Zn,Mn)Mn2O5 x 2H2O). The tailings were treated with soluble PO4(3-) and lime to convert soluble heavy metals (principally Pb, Zn, Cu, Cd) into insoluble metal phosphate precipitates. The treatment process caused bulk mineralogical transformations as well as the formation of a reaction rind around the particles dominated by Ca and P. Within the mineral grains, Fe-Pb phosphosulfates, Fe-Pb sulfates (plumbojarosite), and galena convert to Fe-Ca-Pb hydroxides. The Mn-Pb hydroxides and Mn-(+/-Fe)-Pb hydroxides (chalcophanites) undergo chemical alteration throughout the grains during treatment. Bulk and surface spectroscopies showed that the insoluble reaction products in the rind are tertiary metal phosphate (e.g. (Cu,Ca2)(PO4)2) and apatite (e.g. Pb5(PO4)3Cl) family minerals. pH-dependent leaching (pH 4,6,8) showed that the treatment was able to reduce equilibrium concentrations by factors of 3 to 150 for many metals; particularly Pb2+, Zn2+, Cd2+, and Cu2+. Geochemical thermodynamic equilibrium modeling showed that apatite family and tertiary metal phosphate phases act as controlling solids for the equilibrium concentrations of Ca2+, PO4(3-) Pb2+, Zn2+, Cd2+, and Cu2+ in the leachates during pH-dependent leaching. Both end members and ideal solid solutions were seen to be controlling solids.

Characterization of crystallographic properties of thin films using X-ray diffraction

NASA Astrophysics Data System (ADS)

Zoo, Yeongseok

2007-12-01

Silver (Ag) has been recognized as one of promising candidates in Ultra-Large Scale Integrated (ULSI) applications in that it has the lowest bulk electrical resistivity of all pure metals and higher electromigration resistance than other interconnect materials. However, low thermal stability on Silicon Dioxide (Si02) at high temperatures (e.g., agglomeration) is considered a drawback for the Ag metallization scheme. Moreover, if a thin film is attached on a substrate, its properties may differ significantly from that of the bulk, since the properties of thin films can be significantly affected by the substrate. In this study, the Coefficient of Thermal Expansion (CTE) and texture evolution of Ag thin films on different substrates were characterized using various analytical techniques. The experimental results showed that the CTE of the Ag thin film was significantly affected by underlying substrate and the surface roughness of substrate. To investigate the alloying effect for Ag meatallization, small amounts of Copper (Cu) were added and characterized using theta-2theta X-ray Diffraction (XRD) scan and pole figure analysis. These XRD techniques are useful for investigating the primary texture of a metal film, (111) in this study, which (111) is the notation of a specific plane in the orthogonal coordinate system. They revealed that the (111) textures of Ag and Ag(Cu) thin films were enhanced with increasing temperature. Comparison of texture profiles between Ag and Ag(Cu) thin films showed that Cu additions enhanced (111) texture in Ag thin films. Accordingly, the texture enhancement in Ag thin films by Cu addition was discussed. Strained Silicon-On-Insulator (SSOI) is being considered as a potential substrate for Complementary Metal-Oxide-Semiconductor (CMOS) technology since the induced strain results in a significant improvement in device performance. High resolution X-ray diffraction (XRD) techniques were used to characterize the perpendicular and parallel strains in SSOI layers. XRD diffraction profiles generated from the crystalline SSOI layer provided a direct measurement of the layer's strain components. In addition, it has demonstrated that the rotational misalignment between the layer and the substrate can be incorporated within the biaxial strain equations for epitaxial layers. Based on these results, the strain behavior of the SSOI layer and the relation between strained Si and SiO2 layers are discussed for annealed samples.

Microgravity Processing of Oxide Superconductors

NASA Technical Reports Server (NTRS)

Olive, James R.; Hofmeister, William H.; Bayuzick, Robert J.; Vlasse, Marcus

1999-01-01

Considerable effort has been concentrated on the synthesis and characterization of high T(sub c) oxide superconducting materials. The YBaCuO system has received the most intense study, as this material has shown promise for the application of both thin film and bulk materials. There are many problems with the application of bulk materials- weak links, poor connectivity, small coherence length, oxygen content and control, environmental reactivity, phase stability, incongruent melting behavior, grain boundary contamination, brittle mechanical behavior, and flux creep. The extent to which these problems are intrinsic or associated with processing is the subject of controversy. This study seeks to understand solidification processing of these materials, and to use this knowledge for alternative processing strategies, which, at the very least, will improve the understanding of bulk material properties and deficiencies. In general, the phase diagram studies of the YBaCuO system have concentrated on solid state reactions and on the Y2BaCuO(x) + liquid yields YBa2Cu3O(7-delta) peritectic reaction. Little information is available on the complete melting relations, undercooling, and solidification behavior of these materials. In addition, rare earth substitutions such as Nd and Gd affect the liquidus and phase relations. These materials have promising applications, but lack of information on the high temperature phase relations has hampered research. In general, the understanding of undercooling and solidification of high temperature oxide systems lags behind the science of these phenomena in metallic systems. Therefore, this research investigates the fundamental melting relations, undercooling, and solidification behavior of oxide superconductors with an emphasis on improving ground based synthesis of these materials.

Electronic structure and glass forming ability in early and late transition metal alloys

NASA Astrophysics Data System (ADS)

Babić, E.; Ristić, R.; Figueroa, I. A.; Pajić, D.; Skoko, Ž.; Zadro, K.

2018-03-01

A correlation between the change in magnetic susceptibility (Δχexp) upon crystallisation of Cu-Zr and Hf metallic glasses (MG) with their glass forming ability (GFA) observed recently, is found to apply to Cu-Ti and Zr-Ni alloys, too. In particular, small Δχexp, which reflects similar electronic structures, ES, of glassy and corresponding crystalline alloys, corresponds to high GFA. Here, we studied Δχexp for five Cu-Ti and four Cu-Zr and Ni-Zr MGs. The fully crystalline final state of all alloys was verified from X-ray diffraction patterns. The variation of GFA with composition in Cu-Ti, Cu-Zr and Cu-Hf MGs was established from the variation of the corresponding critical casting thickness, dc. Due to the absence of data for dc in Ni-Zr MGs their GFA was described using empirical criteria, such as the reduced glass transition temperature. A very good correlation between Δχexp and dc (and/or other criteria for GFA) was observed for all alloys studied. The correlation between the ES and GFA showed up best for Cu-Zr and NiZr2 alloys where direct data for the change in ES (ΔES) upon crystallisation are available. The applicability of the Δχexp (ΔES) criterion for high GFA (which provides a simple way to select the compositions with high GFA) to other metal-metal MGs (including ternary and multicomponent bulk MGs) is briefly discussed.

Processing and characterization of Zr-based metallic glass by laser direct deposition

NASA Astrophysics Data System (ADS)

Bae, Heehun

Bulk Metallic Glass has become famous for its exceptional mechanical and corrosion properties. Especially, Zirconium has been the prominent constituent in Bulk Metallic Glass due to its superior glass forming ability, the ability to form amorphous phase with low cooling rate, thereby giving advantages in structural applications. In this study, Zirconium powder was alloyed with Aluminum, Nickel and Copper powder at an atomic ratio of 65:10:10:15, respectively. Using the ball milling process to mix the powders, Zr65Al10Ni 10Cu15 amorphous structure was manufactured by laser direct deposition. Laser power and laser scanning speed were optimized to increase the fraction of amorphous phase. X-ray Diffraction confirmed the existence of both amorphous and crystalline phase by having a wide halo peak and sharp intense peak in the spectrum. Differential Scanning Calorimetry proved the presence of amorphous phase and glass transition was observed to be around 655 K. Scanning electron microscopy showed the microstructure of the deposited sample to have repetitive amorphous and crystalline phase as XRD examined. Crystalline phase resulted from the laser reheating and remelting process due to subsequent laser scan. Laser direct deposited amorphous/crystalline composite showed Vickers Hardness of 670 Hv and exhibited improved corrosion resistance in comparison to fully-crystallized sample. The compression test showed that, due to the existence of crystalline phase, fracture strain of Zr65Al10Ni10Cu 15 amorphous composites was enhanced from less than 2% to as high as 5.7%, compared with fully amorphous metallic glass.

Effect of air humidity on the removal of carbon tetrachloride from air using Cu-BTC metal-organic framework.

PubMed

Martín-Calvo, Ana; García-Pérez, Elena; García-Sánchez, Almudena; Bueno-Pérez, Rocío; Hamad, Said; Calero, Sofia

2011-06-21

We have used interatomic potential-based simulations to study the removal of carbon tetrachloride from air at 298 K, using Cu-BTC metal organic framework. We have developed new sets of Lennard-Jones parameters that accurately describe the vapour-liquid equilibrium curves of carbon tetrachloride and the main components from air (oxygen, nitrogen, and argon). Using these parameters we performed Monte Carlo simulations for the following systems: (a) single component adsorption of carbon tetrachloride, oxygen, nitrogen, and argon molecules, (b) binary Ar/CCl(4), O(2)/CCl(4), and N(2)/CCl(4) mixtures with bulk gas compositions 99 : 1 and 99.9 : 0.1, (c) ternary O(2)/N(2)/Ar mixtures with both, equimolar and 21 : 78 : 1 bulk gas composition, (d) quaternary mixture formed by 0.1% of CCl(4) pollutant, 20.979% O(2), 77.922% N(2), and 0.999% Ar, and (e) five-component mixtures corresponding to 0.1% of CCl(4) pollutant in air with relative humidity ranging from 0 to 100%. The carbon tetrachloride adsorption selectivity and the self-diffusivity and preferential sitting of the different molecules in the structure are studied for all the systems.

AC Calorimetry and Thermophysical Properties of Bulk Glass-Forming Metallic Liquids

NASA Technical Reports Server (NTRS)

Johnson, William L.

2000-01-01

Thermo-physical properties of two bulk metallic glass forming alloys, Ti34Zr11Cu47Ni8 (VIT 101) and Zr57Nb5Ni12.6Al10CU15.4 (VIT 106), were investigated in the stable and undercooled melt. Our investigation focused on measurements of the specific heat in the stable and undercooled liquid using the method of AC modulation calorimetry. The VIT 106 exhibited a maximum undercooling of 140 K in free radiative cooling. Specific heat measurements could be performed in stable melt down to an undercooling of 80 K. Analysis of the specific heat data indicate an anomaly near the equilibrium liquidus temperature. This anomaly is also observed in y the temperature dependencies of the external relaxation time, the specific volume, and the surface tension; it is tentatively attributed to a phase separation in the liquid state. The VIT 101 specimen exhibited a small undercooling of about 50 K. Specific heat measurements were performed in the stable and undercooled melt. These various results will be combined with ground based work such as the measurement of T-T-T curves in the electrostatic levitator and low temperature viscosity and specific heat measurements for modeling the nucleation kinetics of these alloys.

Mechanical properties and microstructure of copper alloys and copper alloy-stainless steel laminates for fusion reactor high heat flux applications

NASA Astrophysics Data System (ADS)

Leedy, Kevin Daniel

A select group of copper alloys and bonded copper alloy-stainless steel panels are under consideration for heat sink applications in first wall and divertor structures of a planned thermonuclear fusion reactor. Because these materials must retain high strengths and withstand high heat fluxes, their material properties and microstructures must be well understood. Candidate copper alloys include precipitate strengthened CuNiBe and CuCrZr and dispersion strengthened Cu-Alsb2Osb3 (CuAl25). In this study, uniaxial mechanical fatigue tests were conducted on bulk copper alloy materials at temperatures up to 500sp°C in air and vacuum environments. Based on standardized mechanical properties measurement techniques, a series of tests were also implemented to characterize copper alloy-316L stainless steel joints produced by hot isostatic pressing or by explosive bonding. The correlation between mechanical properties and the microstructure of fatigued copper alloys and the interface of copper alloy-stainless steel laminates was examined. Commercial grades of these alloys were used to maintain a degree of standardization in the materials testing. The commercial alloys used were OMG Americas Glidcop CuAl25 and CuAl15; Brush Wellman Hycon 3HP and Trefimetaux CuNiBe; and Kabelmetal Elbrodur and Trefimetaux CuCrZr. CuAl25 and CuNiBe alloys possessed the best combination of fatigue resistance and microstructural stability. The CuAl25 alloy showed only minimal microstructural changes following fatigue while the CuNiBe alloy consistently exhibited the highest fatigue strength. Transmission electron microscopy observations revealed that small matrix grain sizes and high densities of submicron strengthening phases promoted homogeneous slip deformation in the copper alloys. Thus, highly organized fatigue dislocation structure formation, as commonly found in oxygen-free high conductivity Cu, was inhibited. A solid plate of CuAl25 alloy hot isostatically pressed to a 316L stainless steel plate showed the best overall mechanical properties of the studied bi-metallic bonded panels. Bond properties were nominally inferior to constituent bulk material properties and fracture toughness values, in particular, were quite low for all bonded laminates. Delamination near the copper alloy-stainless steel interface was the dominate failure mode in the bi-metallic panels. The joining processes caused microstructural alterations in the bond interfacial regions including: microporosity, new precipitate formation, existing precipitate morphology changes and interdiffusion of constituent elements.

Amorphous and nanocrystalline luminescent Si and Ge obtained via a solid-state chemical metathesis synthesis route

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

McMillan, Paul F.; Gryko, Jan; Bull, Craig

A new solid-state metathesis synthesis route was applied to obtain bulk samples of amorphous or microcrystalline Si and Ge. The method involves reaction of Zintl phases such as NaSi or NaGe, with ammonium or metal (e.g., CuCl, CoBr{sub 2}) halides. The driving force for the solid-state reaction is provided by the formation of alkali halides and the transition metals or metal silicides, or gaseous ammonia and hydrogen. The semiconductors were purified by washing to remove other solid products. The amorphous semiconductors were obtained in bulk form from reactions carried out at 200-300{sup o}C. Syntheses at higher temperatures gave rise tomore » microcrystalline semiconductors, or to micro-/nanocrystalline particles contained within the amorphous material. Similar crystalline/amorphous composites were obtained after heat treatment of bulk amorphous materials.« less

Effect of the components' interface on the synthesis of methanol over Cu/ZnO from CO2/H2: a microkinetic analysis based on DFT + U calculations.

PubMed

Tang, Qian-Lin; Zou, Wen-Tian; Huang, Run-Kun; Wang, Qi; Duan, Xiao-Xuan

2015-03-21

The elucidation of chemical reactions occurring on composite systems (e.g., copper (Cu)/zincite (ZnO)) from first principles is a challenging task because of their very large sizes and complicated equilibrium geometries. By combining the density functional theory plus U (DFT + U) method with microkinetic modeling, the present study has investigated the role of the phase boundary in CO2 hydrogenation to methanol over Cu/ZnO. The absence of hydrogenation locations created by the interface between the two catalyst components was revealed based on the calculated turnover frequency under realistic conditions, in which the importance of interfacial copper to provide spillover hydrogen for remote Cu(111) sites was stressed. Coupled with the fact that methanol production on the binary catalyst was recently believed to predominantly involve the bulk metallic surface, the spillover of interface hydrogen atoms onto Cu(111) facets facilitates the production process. The cooperative influence of the two different kinds of copper sites can be rationalized applying the Brönsted-Evans-Polanyi (BEP) relationship and allows us to find that the catalytic activity of ZnO-supported Cu catalysts is of volcano type with decrease in the particle size. Our results here may have useful implications in the future design of new Cu/ZnO-based materials for CO2 transformation to methanol.

The Applicability of the Distribution Coefficient, K D, Based on Non-Aggregated Particulate Samples from Lakes with Low Suspended Solids Concentrations

PubMed Central

Gormley-Gallagher, Aine Marie; Douglas, Richard William; Rippey, Brian

2015-01-01

Separate phases of metal partitioning behaviour in freshwater lakes that receive varying degrees of atmospheric contamination and have low concentrations of suspended solids were investigated to determine the applicability of the distribution coefficient, K D. Concentrations of Pb, Ni, Co, Cu, Cd, Cr, Hg and Mn were determined using a combination of filtration methods, bulk sample collection and digestion and Inductively Coupled Plasma-Mass Spectrometry (ICP-MS). Phytoplankton biomass, suspended solids concentrations and the organic content of the sediment were also analysed. By distinguishing between the phytoplankton and (inorganic) lake sediment, transient variations in K D were observed. Suspended solids concentrations over the 6-month sampling campaign showed no correlation with the K D (n = 15 for each metal, p > 0.05) for Mn (r 2 = 0.0063), Cu (r 2 = 0.0002, Cr (r 2 = 0.021), Ni (r 2 = 0.0023), Cd (r 2 = 0.00001), Co (r 2 = 0.096), Hg (r 2 = 0.116) or Pb (r 2 = 0.164). The results implied that colloidal matter had less opportunity to increase the dissolved (filter passing) fraction, which inhibited the spurious lowering of K D. The findings conform to the increasingly documented theory that the use of K D in modelling may mask true information on metal partitioning behaviour. The root mean square error of prediction between the directly measured total metal concentrations and those modelled based on the separate phase fractions were ± 3.40, 0.06, 0.02, 0.03, 0.44, 484.31, 80.97 and 0.1 μg/L for Pb, Cd, Mn, Cu, Hg, Ni, Cr and Co respectively. The magnitude of error suggests that the separate phase models for Mn and Cu can be used in distribution or partitioning models for these metals in lake water. PMID:26200885

Systems and Methods for Implementing Bulk Metallic Glass-Based Macroscale Compliant Mechanisms

NASA Technical Reports Server (NTRS)

Hofmann, Douglas C. (Inventor); Agnes, Gregory (Inventor)

2017-01-01

Systems and methods in accordance with embodiments of the invention implement bulk metallic glass-based macroscale compliant mechanisms. In one embodiment, a bulk metallic glass-based macroscale compliant mechanism includes: a flexible member that is strained during the normal operation of the compliant mechanism; where the flexible member has a thickness of 0.5 mm; where the flexible member comprises a bulk metallic glass-based material; and where the bulk metallic glass-based material can survive a fatigue test that includes 1000 cycles under a bending loading mode at an applied stress to ultimate strength ratio of 0.25.

Comparing WHAM 6 and MINEQL+ 4.5 for the chemical speciation of Cu2+ in the rhizosphere of forest soils.

PubMed

Cloutier-Hurteau, Benoît; Sauvé, Sébastien; Courchesne, François

2007-12-01

Metal speciation data calculated by modeling could give useful information regarding the fate of metals in the rhizospheric environment. However, no comparative study has evaluated the relative accuracy of speciation models in this microenvironment. Consequently, the present study evaluates the reliability of free Cu ion (Cu2+) activity modeled by WHAM 6 and MINEQL+ 4.5 for 18 bulk and 18 rhizospheric soil samples collected in two Canadian forested areas located near industrial facilities. The modeling of Cu speciation was performed on water extracts using pH, dissolved organic carbon (DOC), major ions, and total dissolved Al, Ca, Cu, Mg, and Zn concentrations as input data. Four scenarios representing the composition of dissolved organic substances using fulvic, humic, and acetic acids were derived from the literature and used in the modeling exercise. Different scenarios were used to contrast soil components (rhizosphere vs bulk) and soil pH levels (acidic vs neutral to alkaline). Reference Cu2+ activity values measured by an ion-selective electrode varied between 0.39 and 41 nM. The model MINEQL+ 4.5 provided good predictions of Cu2+ activities [root-mean-square residual (RMSR)= 0.37], while predictions from WHAM 6 were poor (RMSR = 1.74) because they overestimated Cu complexation with DOC. Modeling with WHAM 6 could be improved by adjusting the proportion of inert DOC and the composition of DOC (RMSR = 0.94), but it remained weaker than predictions with MINEQL+ 4.5. These results suggested that the discrepancies between speciation models were attributed to differences in the binding capacity of humic substances with Cu, where WHAM 6 appeared to be too aggressive. Therefore, we concluded that chemical interactions occurring between Cu and DOC were key factors for an accurate simulation of Cu speciation, especially in rhizospheric forest soils, where high variation of the DOC concentration and composition are observed.

Production and properties of high strength Ni free Zr-based BMGs

NASA Astrophysics Data System (ADS)

Iqbal, M.; Wang, W. H.

2014-06-01

Bulk metallic glasses (BMGs) are well known for very attractive physical, mechanical and thermal properties. Zr-based BMGs are used as structural materials in sports goods, electronics, jewelry, medical and aerospace applications. Ni free Zr48Cu36Al8M8 (M = Nb, Ti and Ta) BMGs are successfully synthesized by Cu mold casting technique. Differential scanning calorimetery (DSC) results show that the Zr48Cu36Al8Nb8 BMG have good thermal stability, wide supercooled liquid region of 80 K and contain the double stage crystallization. The alloy has fracture strength of 1.953 GPa. Shear angle was measured to be in the range of 43.5±5° for the alloy studied. Vicker's hardness of the BMGs was found to be over 500 Hv for the as cast alloy which enhanced about 11 % more by annealing up to 600 °C/20 min. Intersected shear bands were observed. The observed promising mechanical and thermal properties showed that BMG studied can be used for industrial applications.

Mineralogical and geochemical controls on the release of trace elements from slag produced by base- and precious-metal smelting at abandoned mine sites

USGS Publications Warehouse

Piatak, N.M.; Seal, R.R.; Hammarstrom, J.M.

2004-01-01

Slag collected from smelter sites associated with historic base-metal mines contains elevated concentrations of trace elements such as Cu, Zn and Pb. Weathering of slag piles, many of which were deposited along stream banks, potentially may release these trace elements into the environment. Slags were sampled from the Ely and Elizabeth mines in the Vermont copper belt, from the copper Basin mining district at Ducktown, Tennessee and from the Clayton silver mine in the Bayhorse mining district, Idaho, in the USA. Primary phases in the slags include: olivine-group minerals, glass, spinels, sulfide minerals and native metals for Vermont samples; glass, sulfide minerals and native metals for the Ducktown sample; and olivine-group minerals, clinopyroxenes, spinels, sulfide minerals, native metals and other unidentified metallic compounds for Clayton slag. Olivine-group minerals and pyroxenes are dominantly fayalitic and hedenbergitic in composition, respectively and contain up to 1.25 wt.% ZnO. Spinel minerals range between magnetite and hercynite in composition and contain Zn (up to 2.07 wt.% ZnO), Ti (up to 4.25 wt.% TiO2) and Cr (up to 1.39 wt.% Cr2O3). Cobalt, Ni, Cu, As, Ag, Sb and Pb occur in the glass phase, sulfides, metallic phases and unidentified metallic compounds. Bulk slag trace-element chemistry shows that the metals of the Vermont and Tennessee slags are dominated by Cu (1900-13,500 mg/kg) and Zn (2310-10,200 mg/kg), whereas the Clayton slag is dominated by Pb (63,000 mg/kg), Zn (19,700 mg/kg), Cu (7550 mg/kg), As (555 mg/kg), Sn (363 mg/kg) and Ag (200 mg/kg). Laboratory-based leach tests indicate metals can be released under simulated natural conditions. Leachates from most slags were found to contain elevated concentrations of Cu and Zn (up to 1800 and 470 ??g/l, respectively), well in excess of the acute toxicity guidelines for aquatic life. For the Idaho slag, the concentration of Pb in the leachate (11,000 ??g/l) is also in excess of the acute toxicity guideline. Geochemical modeling of the leachate chemistry suggests that leachates from the Vermont, Tennessee and Clayton slags are saturated with amorphous silica and Al hydroxide. Therefore, the dissolution of silicate and oxide phases, the oxidation of sulfide phases, as well as the precipitation of secondary phases may control the composition of leachate from slags. The presence of secondary minerals on slag deposits in the field is evidence that these materials are reactive. The petrographic data and results of leaching tests from this study indicate slag may be a source of potentially toxic metals at abandoned mine sites.

Development of Cu Clad Cu-Zr Based Metallic Glass and Its Solderability

NASA Astrophysics Data System (ADS)

Terajima, Takeshi; Kimura, Hisamichi; Inoue, Akihisa

Soldering is a candidate technique for joining metallic glasses. It can be processed far below the crystallization temperatures of the various metallic glasses so that there is no possibility of crystallization. However, wettability of Cu-Zr based metallic glass by Pb free solder is poor because a strong surface oxide film interferes direct contact between them. To overcome the problem, Cu thin film clad metallic glass was developed. It was preliminary produced by casting a melt of Cu36Zr48Al8Ag8 pre-alloy into Cu mold cavity, inside which Cu thin film with 2 mm in thickness was set on the wall. Cu36Zr48Al8Ag8 metallic glass, whose surface Cu thin film was welded to, was successfully produced. From the microstructure analyses, it was found that reaction layer was formed at the interface between Cu and Cu36Zr48Al8Ag8 metallic glass, however, there was no oxide in the Cu clad layer. Solderability to the metallic glass was drastically increased. The Cu clad layer played an important role to prevent the formation of surface oxide film and consequently improved the solderability.

Growth and microstructure formation of isothermally-solidified Zircaloy-4 joints brazed by a Zr-Ti-Cu-Ni amorphous alloy ribbon

NASA Astrophysics Data System (ADS)

Kim, K. H.; Lim, C. H.; Lee, J. G.; Lee, M. K.; Rhee, C. K.

2013-10-01

The microstructure and growth characteristics of Zircaloy-4 joints brazed by a Zr48Ti16Cu17Ni19 (at.%) amorphous filler metal have been investigated with regard to the controlled isothermal solidification and intermetallic formation. Two typical joints were produced depending on the isothermal brazing temperature: (1) a dendritic growth structure including bulky segregation in the central zone (at 850 °C), and (2) a homogeneous dendritic structure throughout the joint without segregation (at 890 °C). The primary α-Zr phase was solidified isothermally, nucleating to grow into a joint with a cellular or dendritic structure. Also, the continuous Zr2Ni and particulate Zr2Cu phases were formed in the segregated center zone and at the intercellular region, respectively, owing to the different solubility and atomic mobility of the solute elements (Ti, Cu, and Ni) in the α-Zr matrix. A disappearance of the central Zr2Ni phase was also rate-controlled by the outward diffusion of the Cu and Ni elements. When the detrimental Zr2Ni intermetallic phase was eliminated by a complete isothermal solidification at 890 °C, the strengths of the joints were high enough to cause yielding and fracture in the base metal, exceeding those of the bulk Zircaloy-4, at room temperature as well as at elevated temperatures (up to 400 °C).

Distribution and assessment of sediment toxicity in Tamaki Estuary, Auckland, New Zealand

NASA Astrophysics Data System (ADS)

Abrahim, G. M. S.; Parker, R. J.; Nichol, S. L.

2007-07-01

Heavy metal levels in surface sediments from Tamaki Estuary demonstrate significant up estuary increases in Cu, Pb, Zn, Cd and mud concentrations. Increased metal levels towards the head of the estuary are linked to local catchment sources reflecting the historical development, industrialisation and urbanisation of catchment areas surrounding the upper estuary. The relatively narrow constriction in the middle estuary (Panmure area), makes it susceptible to accumulation of upper estuary pollutants, since the constriction reduces circulation and extends the time required for fine waterborne sediments in the upper estuary to exchange with fresh coastal water. As a result fine fraction sediments trapped in the upper estuary facilitate capture and retention of pollutants at the head of the estuary. The increase in sandy mud poor sediments towards the mouth of the estuary is associated with generally low metal concentrations. The estuary’s geomorphic shape with a mid estuary constriction, sediment texture and mineralogy and catchment history are significant factors in understanding the overall spatial distribution of contaminants in the estuary. Bulk concentration values for Cu, Pb, Zn, and Cd in all the studied surface samples occur below ANZECC ISQG-H toxicity values. Cd and Cu concentrations are also below the ISQG-L toxicity levels for these elements. However, Pb and Zn concentrations do exceed the ISQG-L values in some of the surface bulk samples in the upper estuary proximal to long established sources of catchment pollution.

Structural and Dielectric Properties of Ionic Liquid Doped Metal Organic Framework based Polymer Electrolyte Nanocomposites

NASA Astrophysics Data System (ADS)

Dutta, Rituraj; Kumar, Ashok

2016-10-01

Metal Organic Frameworks (MOFs) are mesoporous materials that can be treated as potential hosts for trapping guest molecules in their pores. Ion conduction and phase behavior dynamics of Ionic Liquids (ILs) can be controlled by tunable interactions of MOFs with the ILs. MOFs incorporated with ionic liquid can be dispersed in the polymers to synthesize polymer electrolyte nanocomposites with high ionic conductivity, electrochemical and thermal stability for applications in energy storage and conversion devices such as rechargeable Li-ion batteries. In the present work we have synthesized Cu-based MOF [Cu3(l,3,5-benzene tricarboxylate)2(H2O)] incorporated with the ionic liquid 1-Butyl-3-methylimidazolium bromide at different weight ratios of MOF and IL. The synthesized MOF-IL composites are dispersed in Poly (ethylene oxide) (PEO). Frequency dependent behavior of permittivity and dielectric loss of the nanocomposites depict the non-Debye dielectric relaxation mechanism. The room temperature Nyquist plots reveal decreasing bulk resistance upto 189 Ω with optimum ionic conductivity of 1.3×10-3S cm-1at maximum doping concentration of IL in the nanocomposite system.

Tuning the Mechanical and Antimicrobial Performance of a Cu-Based Metallic Glass Composite through Cooling Rate Control and Annealing.

PubMed

Villapún, Victor M; Esat, F; Bull, S; Dover, L G; González, S

2017-05-06

The influence of cooling rate on the wear and antimicrobial performance of a Cu 52 Z 41 Al₇ (at. %) bulk metallic glass (BMG) composite was studied and the results compared to those of the annealed sample (850 °C for 48 h) and to pure copper. The aim of this basic research is to explore the potential use of the material in preventing the spread of infections. The cooling rate is controlled by changing the mould diameter (2 mm and 3 mm) upon suction casting and controlling the mould temperature (chiller on and off). For the highest cooling rate conditions CuZr is formed but CuZr₂ starts to crystallise as the cooling rate decreases, resulting in an increase in the wear resistance and brittleness, as measured by scratch tests. A decrease in the cooling rate also increases the antimicrobial performance, as shown by different methodologies (European, American and Japanese standards). Annealing leads to the formation of new intermetallic phases (Cu 10 Zr₇ and Cu₂ZrAl) resulting in maximum scratch hardness and antimicrobial performance. However, the annealed sample corrodes during the antimicrobial tests (within 1 h of contact with broth). The antibacterial activity of copper was proved to be higher than that of any of the other materials tested but it exhibits very poor wear properties. Cu-rich BMG composites with optimised microstructure would be preferable for some applications where the durability requirements are higher than the antimicrobial needs.

A combined arc-melting and tilt-casting furnace for the manufacture of high-purity bulk metallic glass materials.

PubMed

Soinila, E; Pihlajamäki, T; Bossuyt, S; Hänninen, H

2011-07-01

An arc-melting furnace which includes a tilt-casting facility was designed and built, for the purpose of producing bulk metallic glass specimens. Tilt-casting was chosen because reportedly, in combination with high-purity processing, it produces the best fatigue endurance in Zr-based bulk metallic glasses. Incorporating the alloying and casting facilities in a single piece of equipment reduces the amount of laboratory space and capital investment needed. Eliminating the sample transfer step from the production process also saves time and reduces sample contamination. This is important because the glass forming ability in many alloy systems, such as Zr-based glass-forming alloys, deteriorates rapidly with increasing oxygen content of the specimen. The challenge was to create a versatile instrument, in which high purity conditions can be maintained throughout the process, even when melting alloys with high affinity for oxygen. Therefore, the design provides a high-vacuum chamber to be filled with a low-oxygen inert atmosphere, and takes special care to keep the system hermetically sealed throughout the process. In particular, movements of the arc-melting electrode and sample manipulator arm are accommodated by deformable metal bellows, rather than sliding O-ring seals, and the whole furnace is tilted for tilt-casting. This performance of the furnace is demonstrated by alloying and casting Zr(55)Cu(30)Al(10)Ni(5) directly into rods up to ø 10 mm which are verified to be amorphous by x-ray diffraction and differential scanning calorimetry, and to exhibit locally ductile fracture at liquid nitrogen temperature.

Source contribution to the bulk atmospheric deposition of minor and trace elements in a Northern Spanish coastal urban area

NASA Astrophysics Data System (ADS)

Fernández-Olmo, Ignacio; Puente, Mariano; Montecalvo, Lucia; Irabien, Angel

2014-08-01

The bulk atmospheric deposition of the minor and trace elements As, Cd, Cr, Cu, Mn, Mo, Ni, Pb, Ti, V and Zn was investigated in Santander, a Northern Spanish coastal city. Bulk deposition samples were collected monthly for three years using a bottle/funnel device. Taking into account that heavy metals are bioavailable only in their soluble forms, water-soluble and water-insoluble fractions were evaluated separately for element concentration. The fluxes of the studied elements in the bulk deposition exhibited the following order: Zn > Mn ≫ Cu > Cr > Pb > V > Ni ≫ As > Mo > Cd. The fluxes of Zn and Mn were more than 10 times higher than those of the other elements, with maximum values of 554.5 and 334.1 μg m- 2 day- 1, respectively. Low solubilities (below 22%) were found for Cr, Ti and Pb, whereas the highest solubility was found for Zn (78%). With the exception of Cu, all of the studied metals in the water-soluble fraction of the atmospheric deposition showed seasonal dependence, due to the seasonal variability of precipitation. The enrichment factors (EFs) of Cu, Cd and Zn were higher than 100, indicating a clear anthropogenic origin. The EF of Mn (50) was below 100, but an exclusively industrial origin is suggested. Positive Matrix Factorisation (PMF) was used for the source apportionment of the studied minor and trace elements in the soluble fraction. Four factors were identified from PMF, and their chemical profiles were compared with those calculated from known sources that were previously identified in Santander Bay: two industrial sources, the first of which was characterised by Zn and Mn, which contributes 62.5% of the total deposition flux of the studied elements; a traffic source; and a maritime source. Zinc and Mn are considered to be the most characteristic pollutants of the studied area.

Theoretical aspects of studies of high coverage oxidation of the Cu(100) surface using low energy positrons

NASA Astrophysics Data System (ADS)

Fazleev, N. G.; Maddox, W. B.

2010-10-01

The study of adsorption of oxygen on transition metal surface is important for the understanding of oxidation, heterogeneous catalysis, and metal corrosion. The structures formed on transition metal surfaces vary from simple adlayers of chemisorbed oxygen to oxygen diffusion into the sub-surface region and the formation of oxides. In this work we present the results of an ab-initio investigation of positron surface and bulk states and annihilation probabilities of surface-trapped positrons with relevant core electrons at the oxidized Cu(100) surface under conditions of high oxygen coverage. Calculations are performed for various high coverage missing row structures ranging between 0.50 and 1.50 ML oxygen coverage. Calculations are also performed for the on-surface adsorption of oxygen on the unreconstructed Cu(001) surface for coverages up to one monolayer to use for comparison. The geometry of the surfaces with adsorbed oxygen is fully optimized. Theoretical results are compared with experimental data obtained from studies of oxidation of the Cu(100) surface using positron annihilation induced Auger electron spectroscopy.

Field trapping and magnetic levitation performances of large single-grain Gd Ba Cu O at different temperatures

NASA Astrophysics Data System (ADS)

Nariki, S.; Fujikura, M.; Sakai, N.; Hirabayashi, I.; Murakami, M.

2005-10-01

We measured the temperature dependence of the trapped field and the magnetic levitation force for c-axis-oriented single-grain Gd-Ba-Cu-O bulk samples 48 mm in diameter. Trapped magnetic field of the samples was 2.1-2.2 T at 77 K and increased with decreasing temperature and reached 4.1 T at 70 K, however the sample fractured during the measurements at lower temperatures due to a large electromagnetic force. The reinforcement by a metal ring was effective in improving the mechanical strength. The sample encapsulated in an Al ring could trap a very high magnetic field of 9.0 T at 50 K. In liquid O 2 the Gd-Ba-Cu-O bulk exhibited a trapped field of 0.42 T and a magnetic levitation force about a half value of that in liquid N 2.

Composition-dependent metallic glass alloys correlate atomic mobility with collective glass surface dynamics.

PubMed

Nguyen, Duc; Zhu, Zhi-Guang; Pringle, Brian; Lyding, Joseph; Wang, Wei-Hua; Gruebele, Martin

2016-06-22

Glassy metallic alloys are richly tunable model systems for surface glassy dynamics. Here we study the correlation between atomic mobility, and the hopping rate of surface regions (clusters) that rearrange collectively on a minute to hour time scale. Increasing the proportion of low-mobility copper atoms in La-Ni-Al-Cu alloys reduces the cluster hopping rate, thus establishing a microscopic connection between atomic mobility and dynamics of collective rearrangements at a glass surface made from freshly exposed bulk glass. One composition, La60Ni15Al15Cu10, has a surface resistant to re-crystallization after three heating cycles. When thermally cycled, surface clusters grow in size from about 5 glass-forming units to about 8 glass-forming units, evidence of surface aging without crystal formation, although its bulk clearly forms larger crystalline domains. Such kinetically stable glass surfaces may be of use in applications where glassy coatings stable against heating are needed.

Magnetic field dependence of high- T c interface superconductivity in L a 1.55 S r 0.45 Cu O 4 / L a 2 Cu O 4 heterostructures

DOE PAGES

Gasparov, V. A.; Drigo, L.; Audouard, A.; ...

2016-07-11

Heterostructures made of a layer of a cuprate insulator La 2CuO 4 on the top of a layer of a nonsuperconducting cuprate metal La 1.55Sr 0.45CuO 4 show high-T c interface superconductivity confined within a single CuO 2 plane. Given this extreme quasi-two-dimensional quantum confinement, it is of interest to find out how interface superconductivity behaves when exposed to an external magnetic field. With this motivation, we have performed contactless tunnel-diode-oscillator-based measurements in pulsed magnetic fields up to 56 T as well as measurements of the complex mutual inductance between a spiral coil and the film in static fields upmore » to 3 T. Remarkably, we observe that interface superconductivity survives up to very high perpendicular fields, in excess of 40 T. Additionally, the critical magnetic field H m(T) reveals an upward divergence with decreasing temperature, in line with vortex melting as in bulk superconducting cuprates.« less

Conocarpus biochar as a soil amendment for reducing heavy metal availability and uptake by maize plants.

PubMed

Al-Wabel, Mohammad I; Usman, Adel R A; El-Naggar, Ahmed H; Aly, Anwar A; Ibrahim, Hesham M; Elmaghraby, Salem; Al-Omran, Abdulrasoul

2015-07-01

The objective of this study was to assess the use of Concarpus biochar as a soil amendment for reducing heavy metal accessibility and uptake by maize plants (Zea mays L.). The impacts of biochar rates (0.0, 1.0, 3.0, and 5.0% w/w) and two soil moisture levels (75% and 100% of field capacity, FC) on immobilization and availability of Fe, Mn, Zn, Cd, Cu and Pb to maize plants as well as its application effects on soil pH, EC, bulk density, and moisture content were evaluated using heavy metal-contaminated soil collected from mining area. The biochar addition significantly decreased the bulk density and increased moisture content of soil. Applying biochar significantly reduced NH4OAc- or AB-DTPA-extractable heavy metal concentrations of soils, indicating metal immobilization. Conocarpus biochar increased shoot dry biomass of maize plants by 54.5-102% at 75% FC and 133-266% at 100% FC. Moreover, applying biochar significantly reduced shoot heavy metal concentrations in maize plants (except for Fe at 75% FC) in response to increasing application rates, with a highest decrease of 51.3% and 60.5% for Mn, 28% and 21.2% for Zn, 60% and 29.5% for Cu, 53.2% and 47.2% for Cd at soil moisture levels of 75% FC and 100% FC, respectively. The results suggest that biochar may be effectively used as a soil amendment for heavy metal immobilization and in reducing its phytotoxicity.

Conocarpus biochar as a soil amendment for reducing heavy metal availability and uptake by maize plants

PubMed Central

Al-Wabel, Mohammad I.; Usman, Adel R.A.; El-Naggar, Ahmed H.; Aly, Anwar A.; Ibrahim, Hesham M.; Elmaghraby, Salem; Al-Omran, Abdulrasoul

2014-01-01

The objective of this study was to assess the use of Concarpus biochar as a soil amendment for reducing heavy metal accessibility and uptake by maize plants (Zea mays L.). The impacts of biochar rates (0.0, 1.0, 3.0, and 5.0% w/w) and two soil moisture levels (75% and 100% of field capacity, FC) on immobilization and availability of Fe, Mn, Zn, Cd, Cu and Pb to maize plants as well as its application effects on soil pH, EC, bulk density, and moisture content were evaluated using heavy metal-contaminated soil collected from mining area. The biochar addition significantly decreased the bulk density and increased moisture content of soil. Applying biochar significantly reduced NH4OAc- or AB-DTPA-extractable heavy metal concentrations of soils, indicating metal immobilization. Conocarpus biochar increased shoot dry biomass of maize plants by 54.5–102% at 75% FC and 133–266% at 100% FC. Moreover, applying biochar significantly reduced shoot heavy metal concentrations in maize plants (except for Fe at 75% FC) in response to increasing application rates, with a highest decrease of 51.3% and 60.5% for Mn, 28% and 21.2% for Zn, 60% and 29.5% for Cu, 53.2% and 47.2% for Cd at soil moisture levels of 75% FC and 100% FC, respectively. The results suggest that biochar may be effectively used as a soil amendment for heavy metal immobilization and in reducing its phytotoxicity. PMID:26150758

First Principles Calculations on the Diffusion of Cu, Ag and Au Atoms or Aggregates on the Bulk and Surface of Titania

DTIC Science & Technology

2011-04-01

filament. The filament may be composed of the metal electrode which is transported into the insulator or due to the formation of sub-oxides. During the...possibility that ionic transport and red-ox processes are at the basis of the resistive switching. The idea is that the oxidation of the active metal...oxide layer and subsequent discard at the inert metal counter-electrode. This mechanism should lead to the formation of metal dendrimers inside the

Resistivity scaling due to electron surface scattering in thin metal layers

NASA Astrophysics Data System (ADS)

Zhou, Tianji; Gall, Daniel

2018-04-01

The effect of electron surface scattering on the thickness-dependent electrical resistivity ρ of thin metal layers is investigated using nonequilibrium Green's function density functional transport simulations. Cu(001) thin films with thickness d =1 -2 nm are used as a model system, employing a random one-monolayer-high surface roughness and frozen phonons to cause surface and bulk scattering, respectively. The zero-temperature resistivity increases from 9.7 ±1.0 μ Ω cm at d =1.99 nm to 18.7 ±2.6 μ Ω cm at d =0.9 0 nm, contradicting the asymptotic T =0 prediction from the classical Fuchs-Sondheimer model. At T =9 00 K, ρ =5.8 ±0.1 μ Ω cm for bulk Cu and ρ =13.4 ±1.1 and 22.5 ±2.4 μ Ω cm for layers with d =1.99 and 0.90 nm, respectively, indicating an approximately additive phonon contribution which, however, is smaller than for bulk Cu or atomically smooth layers. The overall data indicate that the resistivity contribution from surface scattering is temperature-independent and proportional to 1 /d , suggesting that it can be described using a surface-scattering mean-free path λs for 2D transport which is channel-independent and proportional to d . Data fitting indicates λs=4 ×d for the particular simulated Cu(001) surfaces with a one-monolayer-high surface roughness. The 1 /d dependence deviates considerably from previous 1 /d2 predictions from quantum models, indicating that the small-roughness approximation in these models is not applicable to very thin (<2 nm) layers, where the surface roughness is a considerable fraction of d .

Tuning the Mechanical and Antimicrobial Performance of a Cu-Based Metallic Glass Composite through Cooling Rate Control and Annealing

PubMed Central

Villapun, Victor Manuel; Esat, Faye; Bull, Steve; Dover, Lynn George; Gonzalez, Sergio

2017-01-01

The influence of cooling rate on the wear and antimicrobial performance of a Cu52Z41Al7 (at. %) bulk metallic glass (BMG) composite was studied and the results compared to those of the annealed sample (850 °C for 48 h) and to pure copper. The aim of this basic research is to explore the potential use of the material in preventing the spread of infections. The cooling rate is controlled by changing the mould diameter (2 mm and 3 mm) upon suction casting and controlling the mould temperature (chiller on and off). For the highest cooling rate conditions CuZr is formed but CuZr2 starts to crystallise as the cooling rate decreases, resulting in an increase in the wear resistance and brittleness, as measured by scratch tests. A decrease in the cooling rate also increases the antimicrobial performance, as shown by different methodologies (European, American and Japanese standards). Annealing leads to the formation of new intermetallic phases (Cu10Zr7 and Cu2ZrAl) resulting in maximum scratch hardness and antimicrobial performance. However, the annealed sample corrodes during the antimicrobial tests (within 1 h of contact with broth). The antibacterial activity of copper was proved to be higher than that of any of the other materials tested but it exhibits very poor wear properties. Cu-rich BMG composites with optimised microstructure would be preferable for some applications where the durability requirements are higher than the antimicrobial needs. PMID:28772866

In Vivo Evaluation of Bulk Metallic Glasses for Osteosynthesis Devices

PubMed Central

Imai, Kazuhiro; Hiromoto, Sachiko

2016-01-01

Bulk metallic glasses (BMGs) show higher strength and lower Young’s modulus than Ti-6Al-4V alloy and SUS 316L stainless steel. This study aimed to perform in vivo evaluations of Zr65Al7.5Ni10Cu17.5 BMGs for osteosynthesis devices. In the study for intramedullary implants, osteotomies of the femoral bones were performed in male Wistar rats and were stabilized with Zr65Al7.5Ni10Cu17.5 BMGs, Ti-6Al-4V alloy, or 316L stainless steel intramedullary nails for 12 weeks. In the study for bone surface implants, Zr65Al7.5Ni10Cu17.5 BMGs ribbons were implanted on the femur surface for 6 weeks. Local effects on the surrounding soft tissues of the implanted BMGs were assessed by histological observation. Implanted materials’ surfaces were examined using scanning electron microscopy equipped with energy dispersive X-ray spectroscopy (SEM-EDS). In the study for intramedullary implants, bone healing after osteotomy was assessed by peripheral quantitative computed tomography (QCT) and mechanical tests. Histological observation showed no findings of the biological effects. SEM-EDS showed no noticeable change on the surface of BMGs, while Ca and P deposition was seen on the Ti-6Al-4V alloy surface, and irregularities were seen on the 316L stainless steel surface. Mechanical test and peripheral QCT showed that, although there was no significant difference, bone healing of BMGs was more than that of Ti-6Al-4V alloy. The results indicated that Zr-based BMGs can lead to bone healing equal to or greater than Ti-6Al-4V alloy. Zr-based BMGs exhibited the advantage of less bone bonding and easier implant removal compared with Ti-6Al-4V alloy. In conclusion, Zr-based BMGs are promising for osteosynthesis devices that are eventually removed. PMID:28773792

Tuned critical avalanche scaling in bulk metallic glasses

DOE PAGES

Antonaglia, James; Xie, Xie; Schwarz, Gregory; ...

2014-03-17

In this study, ingots of the bulk metallic glass (BMG), Zr 64.13Cu 15.75Ni 10.12Al 10 in atomic percent (at. %), are compressed at slow strain rates. The deformation behavior is characterized by discrete, jerky stress-drop bursts (serrations). Here we present a quantitative theory for the serration behavior of BMGs, which is a critical issue for the understanding of the deformation characteristics of BMGs. The mean-field interaction model predicts the scaling behavior of the distribution, D(S), of avalanche sizes, S, in the experiments. D(S) follows a power law multiplied by an exponentially-decaying scaling function. The size of the largest observed avalanchemore » depends on experimental tuning-parameters, such as either imposed strain rate or stress. Similar to crystalline materials, the plasticity of BMGs reflects tuned criticality showing remarkable quantitative agreement with the slip statistics of slowly-compressed nanocrystals. The results imply that material-evaluation methods based on slip statistics apply to both crystalline and BMG materials.« less

Tracing metal sources in core sediments of the artificial lake An-Dong, Korea: Concentration and metal association.

PubMed

Choi, Mansik; Park, Jongkyu; Cho, Dongjin; Jang, Dongjun; Kim, Miseon; Choi, Jongwoo

2015-09-15

The concentration and source of trace metals in the artificial lake An-Dong, which has widespread abandoned mines and a Zn smelter upstream of the drainage basin, were investigated. Soils (18ea), stream waters (15ea) and sediments (15ea) in the main channel and five tributaries downstream of the Zn smelter towards the lake (~ 50 km downstream) were collected. And two core sediments were also taken from the middle of the lake. All samples were analyzed for trace metals in bulk and in a 1N HCl-leached fraction. Although the soil and stream sediments consisted mostly of sand-sized grains, concentrations of metals (Cu, Zn, Cd and Pb) were very high in all samples, including soils, stream waters and sediments at sites near the Zn smelter. However the metal concentrations decreased rapidly downstream, suggesting that the area of impact of the smelter lies within 5 km. Highly enriched metal concentrations were also found in dated core sediments from the lake; while the highest concentrations of Co, Ni, As, Cu, Zn, Cd and Pb were detected in the bottom of the sediment core (dated 1980) they decreased towards 2000, and only Cu, Zn and Cd concentrations increased again in present-day samples. Since the temporal variation in metal concentrations appeared consistent with historical variation in ore mining and Zn smelter production rates, a model combining the production rates of each was developed, which estimated 3%, 12% and 7% contributions from Zn smelter compared to ore mining production rate to levels of Cu, Cd and Zn, respectively, suggesting the different pathways by different sources. In addition, analysis of Cd/Zn and Cu/Zn ratios showed that contamination from ore mining decreased from 1980 to 2000, and smelting processes were most likely responsible for metal enrichment (Cu, Cd and Zn) from 2000 to the present. Copyright © 2015 Elsevier B.V. All rights reserved.

Al-centered icosahedral ordering in Cu46Zr46Al8 bulk metallic glass

NASA Astrophysics Data System (ADS)

Fang, H. Z.; Hui, X.; Chen, G. L.; Liu, Z. K.

2009-03-01

Icosahedral short-range order, of which Al atoms are caged in the center of icosahedra with Cu and Zr atoms being the vertices, has been evidenced in the Cu46Zr46Al8 glassy structure by ab initio molecular dynamics simulation. These Al-centered clusters distribute irregularly in the three-dimensional space and form a "backbone" structure of the Cu46Zr46Al8 glass alloy. It is suggested that this kind of local structural feature is attributed to the requirement of efficient dense packing and the chemical affinity between Zr-Zr, Zr-Al, and Cu-Zr atoms. Our calculated results are found to be in good agreement with the experimental data.

Experimental investigation of inhomogeneities, nanoscopic phase separation, and magnetism in arc melted Fe-Cu metals with equal atomic ratio of the constituents

NASA Astrophysics Data System (ADS)

Hassnain Jaffari, G.; Aftab, M.; Anjum, D. H.; Cha, Dongkyu; Poirier, Gerald; Ismat Shah, S.

2015-12-01

Composition gradient and phase separation at the nanoscale have been investigated for arc-melted and solidified with equiatomic Fe-Cu. Diffraction studies revealed that Fe and Cu exhibited phase separation with no trace of any mixing. Microscopy studies revealed that immiscible Fe-Cu form dense bulk nanocomposite. The spatial distribution of Fe and Cu showed existence of two distinct regions, i.e., Fe-rich and Cu-rich regions. Fe-rich regions have Cu precipitates of various sizes and different shapes, with Fe forming meshes or channels greater than 100 nm in size. On the other hand, the matrix of Cu-rich regions formed strips with fine strands of nanosized Fe. Macromagnetic response of the system showed ferromagnetic behavior with a magnetic moment being equal to about 2.13 μB/ Fe atom and a bulk like negligible value of coercivity over the temperature range of 5-300 K. Anisotropy constant has been calculated from various laws of approach to saturation, and its value is extracted to be equal to 1350 J/m3. Inhomogeneous strain within the Cu and Fe crystallites has been calculated for the (unannealed) sample solidified after arc-melting. Annealed sample also exhibited local inhomogeneity with removal of inhomogeneous strain and no appreciable change in magnetic character. However, for the annealed sample phase separated Fe exhibited homogenous strain.

Studies of high coverage oxidation of the Cu(100) surface using low energy positrons

NASA Astrophysics Data System (ADS)

Fazleev, N. G.; Maddox, W. B.; Weiss, A. H.

2012-02-01

The study of oxidation of single crystal metal surfaces is important in understanding the corrosive and catalytic processes associated with thin film metal oxides. The structures formed on oxidized transition metal surfaces vary from simple adlayers of chemisorbed oxygen to more complex structures which result from the diffusion of oxygen into subsurface regions. In this work we present the results of theoretical studies of positron surface and bulk states and annihilation probabilities of surface-trapped positrons with relevant core electrons at the oxidized Cu(100) surface under conditions of high oxygen coverage. Calculations are performed for various high coverage missing row structures ranging between 0.50 and 1.50 ML oxygen coverage. The results of calculations of positron binding energy, positron work function, and annihilation characteristics of surface trapped positrons with relevant core electrons as function of oxygen coverage are compared with experimental data obtained from studies of oxidation of the Cu(100) surface using positron annihilation induced Auger electron spectroscopy (PAES).

(abstract) Undercooling Studies of the Bulk Metallic Glass Forming Zr(sub 41.2)Ti(sub 13.8)Cu(sub 12.5)Ni(sub 10.0)Be(sub 22.5) Alloy During Containerless Electrostatic Levitation Processing

NASA Technical Reports Server (NTRS)

Kim, Y. J.; Busch, R.; Johnson, W. L.; Rulison, A. J.; Rhim, W. K.

1995-01-01

Bulk glass forming metallic alloys have long been desired for technological applications and for investigation into liquid undercooling, solidification processes, and thermophysical properties. A glass forming alloy Zr(sub 41.2)Ti(sub 13.8)Cu(sub 12.5)Ni(sub 10.0)Be(sub 22.5) was used to investigate the thermal treatments affecting undercooling and vitrification. The experiments were performed using the high temperature high vacuum electrostatic levitator at JPL. A sample approximately 3 mm in diameter was melted, superheated, undercooled, and solidified while levitated in high vacuum. The results show that when the sample was held above its melting temperature for a sufficient period of time to dissolve oxides and then cooled faster than a critical cooling rate, it undercooled to the glass transition temperature, T(sub g), and formed a glassy alloy. The required critical cooling rate for metallic glass formation was obtained to be between 0.9 K per second and 1.2 K per second for the 42.4 mg sample.

Trace metals solubility in rainwater: evaluation of rainwater quality at a watershed area, Istanbul.

PubMed

Başak, Bertan; Alagha, Omar

2010-08-01

In this study, 79 bulk precipitation samples were collected at two sampling sites near Büyükçekmece Lake, one of the important drinking water sources of Istanbul, for the period of October 2001 to July 2002. The study comprised the determination of trace and toxic metals concentrations in rain water. The concentrations of the metals in this study were found to be higher than those reported by other researchers around the world. The solubility of toxic metals was found in the order of Cd>Cu>V>Zn>Ni>Pb>Cr. Solubility of metals under acidic conditions (pH<5.5) was approximately five times higher than those under neutral conditions with Cd as the most soluble metal (50% soluble). Statistical evaluations including seasonal variations, crustal enrichment factors, and correlation matrix were discussed to identify the possible sources of these pollutants. The study revealed that anthropogenic elements were highly enriched especially for Cd>Cu>Pb which were found to be highly enriched. Significant portion of Cu and Pb could be increased by the effect of local sources like cement industry in the area; however, the rest of the investigated trace metals could be brought to the sampling site by long-range transport to the Büyükçekmece Lake watershed area.

Spin-memory loss due to spin-orbit coupling at ferromagnet/heavy-metal interfaces: Ab initio spin-density matrix approach

NASA Astrophysics Data System (ADS)

Dolui, Kapildeb; Nikolić, Branislav K.

2017-12-01

Spin-memory loss (SML) of electrons traversing ferromagnetic-metal/heavy-metal (FM/HM), FM/normal-metal (FM/NM), and HM/NM interfaces is a fundamental phenomenon that must be invoked to explain consistently large numbers of spintronic experiments. However, its strength extracted by fitting experimental data to phenomenological semiclassical theory, which replaces each interface by a fictitious bulk diffusive layer, is poorly understood from a microscopic quantum framework and/or materials properties. Here we describe an ensemble of flowing spin quantum states using spin-density matrix, so that SML is measured like any decoherence process by the decay of its off-diagonal elements or, equivalently, by the reduction of the magnitude of polarization vector. By combining this framework with density functional theory, we examine how all three components of the polarization vector change at Co/Ta, Co/Pt, Co/Cu, Pt/Cu, and Pt/Au interfaces embedded within Cu/FM/HM/Cu vertical heterostructures. In addition, we use ab initio Green's functions to compute spectral functions and spin textures over FM, HM, and NM monolayers around these interfaces which quantify interfacial spin-orbit coupling and explain the microscopic origin of SML in long-standing puzzles, such as why it is nonzero at the Co/Cu interface; why it is very large at the Pt/Cu interface; and why it occurs even in the absence of disorder, intermixing and magnons at the interface.

Fate and Transformation of CuO Nanoparticles in the Soil-Rice System during the Life Cycle of Rice Plants.

PubMed

Peng, Cheng; Xu, Chen; Liu, Qinglin; Sun, Lijuan; Luo, Yongming; Shi, Jiyan

2017-05-02

Agricultural soil is gradually becoming a primary sink for metal-based nanoparticles (MNPs). The uptake and accumulation of MNPs by crops may contaminate food chain and pose unexpected risks for human health. Here, we investigated the fate and transformation of CuO nanoparticles (NPs) in the soil-rice system during the rice lifecycle. The results show that at the maturation stage, 1000 mg/kg CuO NPs significantly decreased redox potential by 202.75 mV but enhanced electrical conductivity by 497.07 mS/cm compared to controls. Moreover, the bioavailability of highest CuO NPs in the soil was reduced by 69.84% along with the plant growth but then was significantly increased by 165% after drying-wetting cycles. Meanwhile, CuO and Cu combined with humic acid were transformed to Cu 2 S and Cu associated with goethite by X-ray absorption near edge structure analysis. Additionally, CuO NPs had an acute negative effect on the plant growth than bulk particles, which dramatically reduced the fresh weight of grains to 6.51% of controls. Notably, CuO NPs were found to be translocated from soil to plant especially to the chaff and promoted the Cu accumulation in the aleurone layer of rice using micro X-ray fluorescence technique, but could not reach the polished rice.

Structural and Thermal Diffusivity Studies of Polycrystalline (CuSe)1-XSeX Metal Chalcogenide Compound

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

Josephine, L. Y. C.; Talib, Z. A.; Yunus, W. M. M.

2007-05-09

This paper reports the preparation and the characterization of the (CuSe)1-xSex metal chalcogenide semiconductor compounds with different stoichiometric compositions of Se (x = 0, 0.2, 0.4, 0.5, 0.6, 0.8, 1.0) in bulk form. The (CuSe)1-xSex compounds were prepared using the solid state reaction by varying the ratio of CuSe:Se in the reaction mixture. X-ray powder diffraction analysis is used to identify and measure the mass absorption coefficient of the (CuSe)1-xSex compounds to support the thermal diffusivity behaviour. The thermal diffusivity of the polycrystalline (CuSe)1-xSex compounds were measured and analyzed for the first time, using the photoflash technique. The thermal diffusivitymore » values were determined to be in the range of 2.524 x 10-3 cm2/s to 1.125 x 10-2 cm2/s. It was found that the thermal diffusivity value tends to decrease as the parameter x increases. The relationship between the thermal diffusivity, mass absorption coefficient and density of the (CuSe)1-xSex are discussed in detail.« less

Structural, elastic and electronic properties of typical NdMgT4 (T = Co, Ni, Cu) alloys from ab initio calculation

NASA Astrophysics Data System (ADS)

Wang, Na; Zhang, Wei-bing; Tang, Bi-yu; Gao, Hai-Tao; He, En-jie; Wang, Lei

2018-07-01

The crystal structure, elastic and magnetic properties of important ternary Mg-based alloys NdMgT4 (T = Co, Ni, Cu) have been studied using reliable ab initio calculations. Both cohesive energy and charge density difference suggest that three alloys have good structural stability with the order: NdMgCo4 > NdMgNi4 > NdMgCu4. It shows that NdMgCo4 alloy has magnetic moments with the Co atoms being the main contribution, which is also in agreement with the calculated electronic structures. We find that NdMgT4 (T = Co, Ni, Cu) alloys are all ductile materials with bulk-to-shear modulus (B/G) values higher than 1.75. The trends of calculated values for the shear moduli Cs and C44 are consistent with that of shear modulus G and young's modulus E, proving that NdMgT4 (T = Co, Ni, Cu) alloys exhibit good plasticity with the trend: NdMgNi4 > NdMgCu4 > NdMgCo4. These calculated results give the basis guidance for the design of rare earth-magnesium-transition metal (R-Mg-T) alloys with improved mechanical properties.

Stability of sputter deposited cuprous oxide (Cu2O) subjected to ageing conditions for photovoltaic applications

NASA Astrophysics Data System (ADS)

Camacho-Espinosa, E.; Rimmaudo, I.; Riech, I.; Mis-Fernández, R.; Peña, J. L.

2018-02-01

Among various metal oxide p-type semiconductors, cuprous oxide (Cu2O) stands out as a nontoxic and abundant material, which also makes it a suitable candidate as a low-cost absorber for photovoltaic applications. However, the chemical stability of the absorber layer is critical for the solar cell lifetime, in particular, for Cu-based materials, concerning to its oxidation state changes. In this paper, we addressed the Cu2O stability depositing films of 170 nm by reactive radio frequency magnetron sputtering and subsequently ageing them in conditions similar to the typical accelerated life test for the solar module, in a period of time from one to five weeks. The stability of the optical, electrical, and structural properties of the Cu2O thin films was investigated using UV-VIS-near infrared transmittance, 4-probes electrical resistance characterization, high precision profilometry, X-ray photoelectron spectroscopy, and grazing incidence X-ray diffraction. Finally, we demonstrated that the aging tests affected only the surface of the films, while the bulk remained unaltered, making Cu2O a promising candidate for production of stable devices, including solar cells.

Molecular simulation investigation into the performance of Cu-BTC metal-organic frameworks for carbon dioxide-methane separations.

PubMed

Gutiérrez-Sevillano, Juan José; Caro-Pérez, Alejandro; Dubbeldam, David; Calero, Sofía

2011-12-07

We report a molecular simulation study for Cu-BTC metal-organic frameworks as carbon dioxide-methane separation devices. For this study we have computed adsorption and diffusion of methane and carbon dioxide in the structure, both as pure components and mixtures over the full range of bulk gas compositions. From the single component isotherms, mixture adsorption is predicted using the ideal adsorbed solution theory. These predictions are in very good agreement with our computed mixture isotherms and with previously reported data. Adsorption and diffusion selectivities and preferential sitings are also discussed with the aim to provide new molecular level information for all studied systems.

Pulsed laser-induced damage of metals at 492 nm.

PubMed

Marrs, C D; Faith, W N; Dancy, J H; Porteus, J O

1982-11-15

A triaxial flashlamp-pumped dye laser has been used to perform laser damage testing of metal surfaces in the blue-green spectral region. Using LD490 laser dye, the laser produces 0.18-J, 0.5-microsec pulses at 492 nm. The spatial profile of the focused beam is measured in orthogonal directions in the plane of the sample surface. The orthogonal profiles are flat-topped Gaussians with 1/e(2) widths of 270 microm. Multithreshold laser damage test results are presented for polished Mo, diamond-turned high-purity Al alloy, diamond-turned bulk Cu, and diamond-turned electrodeposits of Ag and Au on Cu. Comparisons are made between calculated and experimentally measured slip and melt thresholds.

Heavy metal remediation with Ficus microcarpa through transplantation and its environmental risks through field scale experiment.

PubMed

Luo, Jie; Cai, Limei; Qi, Shihua; Wu, Jian; Gu, Xiaowen Sophie

2018-02-01

The phytoremediation efficiency of various metals by Ficus microcarpa was evaluated through a real scale experiment in the present study. The root biomass production of the species varied significantly from 3.68 to 5.43 g because of the spatial heterogeneity of different metals. It would take 4-93 years to purify the excess Cd of the experimental site. Mercury was the most inflexible element which can barely be phytoremediated by F. microcarpa. After the species transplanted from the polluted soil to the clean site, Cd and Cu were transferred to the rhizosphere soil to different extent while the bulk soil was barely influenced. Relative to Cd and Cu, significantly fewer amounts of Pb and Hg were released. The highest concentrations of Cd, Cu, Hg and Pb in the clean soil were far below their corresponding safe thresholds for agricultural land after 3 months of the polluted plants were cultivated and metal concentrations of plant leaves were negligible, both indicated the low ecological risk of transplantation. Results from this study suggested a feasible disposal method for metal rich plants after phytoremediation. Copyright © 2017 Elsevier Ltd. All rights reserved.

The Vitrification and Determination of the Crystallization Time Scales of a Zr58.5Nb2.8Cu15.6Ni12.8Al10.3 Bulk Metallic Glass Forming Liquid

NASA Technical Reports Server (NTRS)

Hays, C. C.; Schroers, J.; Johnson, W. L.; Rathz, T. J.; Hyers, R. W.; Rogers, J. R.; Robinson, M. B.; Whitaker, Ann F. (Technical Monitor)

2001-01-01

Zr58.5Nb2.8Cul5.6Nil2.8All0.3 is the first bulk glass forming liquid that does not contain beryllium to be vitrified by purely radiative cooling in the containerless electrostatic levitation process. The measured critical cooling rate is 1.75 K/s. The sluggish crystallization kinetics enable the determination of the time-temperature-transformation (TTT) diagram between the liquidus and the glass transition temperatures. At the nose of the TTT diagram, the shortest time to reach crystallization in an isothermal experiment is 32 seconds. In contrast to other bulk metallic glasses the scatter in the crystallization onset times are small at both high and low temperatures.

Application of computational thermodynamics in the study of magnsium alloys and bulk metallic glasses

NASA Astrophysics Data System (ADS)

Cao, Hongbo

In this thesis, the application of the computational thermodynamics has been explored on two subjects, the study of magnesium alloys (Chapter 1-5) and bulk metallic glasses (BMGs) (Chapter 6-9). For the former case, a strategy of experiments coupled with the CALPHAD approach was employed to establish a thermodynamic description of the quaternary system Mg-Al-Ca-Sr focusing on the Mg-rich phase equilibria. Multicomponent Mg-rich alloys based on the MgAl-Ca-Sr system are one of the most promising candidates for the high temperature applications in the transportation industry. The Mg-Al-Ca-Sr quaternary consists of four ternaries and six binaries. Thermodynamic descriptions of all constituent binaries are available in the literature. Thermodynamic descriptions of the two key ternaries, Mg-Al-Sr and Mg-Al-Ca, were obtained by an efficient and reliable methodology, combining computational thermodynamics with key experiments. The obtained thermodynamic descriptions were validated by performing extensive comparisons between the calculations and experimental information. Thermodynamic descriptions of the other two ternaries, MgCa-Sr and Al-Ca-Sr, were obtained by extrapolation. For the later case, a computational thermodynamic strategy was formulated to obtain a minor but optimum amount of additional element into a base alloy to improve its glass forming ability (GFA). This was done through thermodynamically calculating the maximum liquidus depressions caused by various alloying addition (or replacement) schemes. The success of this approach has been examined in two multicomponent systems, Zr-based Zr-Cu-Ni-Al-Ti and Cu-rich Cu-Zr-Ti-Y. For both cases, experimental results showed conclusively that the GFA increases more than 100% from the base alloy to the one with minor but optimal elemental addition. Furthermore, a thermodynamic computational approach was employed to identify the compositions of Zr-Ti-Ni-Cu-Al alloys exhibiting low-lying liquidus surfaces, which tend to favor the BMG formation. Guided by these calculations, several series of new Zr-based alloys with excellent GFA were synthesized. The approach using the thermodynamically calculated liquidus temperatures was proved to be robust in locating BMGs and can be considered as a universal method to predict novel BMGs not only of scientific interest but also potential technological applications.

General rules for incorporating noble metal nanoparticles in organic solar cells

NASA Astrophysics Data System (ADS)

Ciesielski, A.; Switlik, D.; Szoplik, T.

2017-05-01

Over the recent years, the influence of the addition of noble metal nanoparticles (Au, Ag, Al, Cu) into the bulk heterojunction (BHJ) solar cells on their efficiency of visible sunlight absorption has been excessively studied. However, several detailed studies were focused on compounds with similar chemical structure, and thus similar optical and electric properties. Such approach provides little help when it comes to admixing metallic nanoparticles into new compound families with different properties. Moreover, theoretical approaches frequently tend to neglect the fact, that nanoparticles have different dispersion relation than bulk material, which may lead to false conclusions. In this work, we consider additional dispersion modes in the metal permittivity due to finite size of the nanoparticles. We use Maxwell-Garnet effective medium approach (EMA), combined with the transfer matrix method, as well as finite-difference time-domain (FDTD) simulations, to create a set of general rules for incorporating noble metal nanoparticles into the active layer. These principles, based on assumed basic properties of the active layer (e.g. real and imaginary part of refractive index, thickness) provide optimal material, size spectrum and fill factor of nanoparticle inclusions in order to ensure the best absorption enhancement. Our results show, that the optimal concentrations for silver nanoparticles are about 50% greater than those determined without taking into account additional components in the permittivity of the metal.

Serial Sectioning Methods for Generating 3D Characterization Data of Grain- and Precipitate-Scale Microstructures (Preprint)

DTIC Science & Technology

2010-04-01

Nielsen SF, Gundlach C, Margulies L, Huang X, Juul Jensen D (2004) Watch- ing the Growth of Bulk Grains During Recrystallization of Deformed Metals. Science...solid-solution dendrites, while the voids in the reconstruction correspond to the Pb-Sn eutectic phase (B) 3D reconstruction of an Al-Cu alloy after...a 3 week coarsening experiment. The solid corresponds to Al dendrites, while the voids in the reconstruction correspond to the Al-Cu eutectic phase

Ignition and combustion of bulk metals under elevated, normal and reduced gravity conditions

NASA Technical Reports Server (NTRS)

Abbud-Madrid, Angel; Branch, Melvyn C.; Daily, John W.

1995-01-01

This research effort is aimed at providing further insight into this multi-variable dependent phenomena by looking at the effects of gravity on the ignition and combustion behavior of metals. Since spacecraft are subjected to higher-than-1g gravity loads during launch and reentry and to zero-gravity environments while in orbit, the study of ignition and combustion of bulk metals at different gravitational potentials is of great practical concern. From the scientific standpoint, studies conducted under microgravity conditions provide simplified boundary conditions since buoyancy is removed, and make possible the identification of fundamental ignition mechanisms. The effect of microgravity on the combustion of bulk metals has been investigated by Steinberg, et al. on a drop tower simulator. However, no detailed quantitative work has been done on ignition phenomena of bulk metals at lower or higher-than-normal gravitational fields or on the combustion characteristics of metals at elevated gravity. The primary objective of this investigation is the development of an experimental system capable of providing fundamental physical and chemical information on the ignition of bulk metals under different gravity levels. The metals used in the study, iron (Fe), titanium (Ti), zirconium (Zr), magnesium (Mg), zinc (Zn), and copper (Cu) were selected because of their importance as elements of structural metals and their simple chemical composition (pure metals instead of multi-component alloys to avoid complication in morphology and spectroscopic studies). These samples were also chosen to study the two different combustion modes experienced by metals: heterogeneous or surface oxidation, and homogeneous or gas-phase reaction. The experimental approach provides surface temperature profiles, spectroscopic measurements, surface morphology, x-ray spectrometry of metals specimens and their combustion products, and high-speed cinematography of the heating, ignition and combustion stages of the metal specimen. This paper summarizes the results obtained to date from experiments conducted under normal and high-gravity conditions.

Atomic-scale bonding of bulk metallic glass to crystalline aluminum

NASA Astrophysics Data System (ADS)

Liu, K. X.; Liu, W. D.; Wang, J. T.; Yan, H. H.; Li, X. J.; Huang, Y. J.; Wei, X. S.; Shen, J.

2008-08-01

A Ti40Zr25Cu12Ni3Be20 bulk metallic glass (BMG) was welded to a crystalline aluminum by the parallel plate explosive welding method. Experimental evidence and numerical simulation show that atomic-scale bonding between the BMG and the crystalline aluminum can be achieved, and the weldment on the BMG side can retain its amorphous state without any indication of crystallization in the welding process. Nanoindentation tests reveal that the interface of the explosive joints exhibits a significant increase in hardness compared to the matrix on its two sides. The joining of BMG and crystalline materials opens a window to the applications of BMGs in engineering.

Ab initio investigation on hydrogen adsorption capability in Zn and Cu-based metal organic frameworks

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

Tanuwijaya, V. V., E-mail: viny.veronika@gmail.com; Hidayat, N. N., E-mail: avantgarde.vee@gmail.com; Agusta, M. K., E-mail: kemal@fti.itb.ac.id

2015-09-30

One of the biggest challenge in material technology for hydrogen storage application is to increase hydrogen uptake in room temperature and pressure. As a class of highly porous material, Metal-Organic Frameworks (MOF) holds great potential with its tunable structure. However, little is known about the effect of metal cluster to its hydrogen storage capability. Investigation on this matter has been carried out carefully on small cluster of Zn and Cu-based MOF using first principles method. The calculation of two distinct building units of MOFs, namely octahedral and paddle-wheel models, have been done with B3LYP density functional method using 6-31G(d,p) andmore » LANL2DZ basis sets. From geometry optimization of Zn-based MOF linked by benzene-dicarboxylate (MOF-5), it is found that hydrogen tends to keep distance from metal cluster group and stays above benzene ring. In the other hand, hydrogen molecule prefers to stay atop of the exposed Cu atom in Cu-based MOF system linked by the same linker group (Cu-bdc). Calculated hydrogen binding enthalpies for Zn and Cu octahedral cages at ZnO{sub 3} sites are 1.64kJ/mol and 2.73kJ/mol respectively, while hydrogen binding enthalpies for Zn and Cu paddle-wheel cages calculated on top of metal atoms are found to be at 6.05kJ/mol and 6.10kJ/mol respectively. Major difference between Zn-MOF-5 and Cu-bdc hydrogen uptake performance might be caused by unsaturated metal sites present in Cu-bdc system and the influence of their geometric structures, although a small difference on binding energy in the type of transition metal used is also observed. The comparison between Zn and Cu-based MOF may contribute to a comprehensive understanding of metal clusters and the importance of selecting best transition metal for design and synthesis of metal-organic frameworks.« less

In-situ ductile metal/bulk metallic glass matrix composites formed by chemical partitioning

DOEpatents

Kim, Choong Paul; Hays, Charles C.; Johnson, William L.

2004-03-23

A composite metal object comprises ductile crystalline metal particles in an amorphous metal matrix. An alloy is heated above its liquidus temperature. Upon cooling from the high temperature melt, the alloy chemically partitions, forming dendrites in the melt. Upon cooling the remaining liquid below the glass transition temperature it freezes to the amorphous state, producing a two-phase microstructure containing crystalline particles in an amorphous metal matrix. The ductile metal particles have a size in the range of from 0.1 to 15 micrometers and spacing in the range of from 0.1 to 20 micrometers. Preferably, the particle size is in the range of from 0.5 to 8 micrometers and spacing is in the range of from 1 to 10 micrometers. The volume proportion of particles is in the range of from 5 to 50% and preferably 15 to 35%. Differential cooling can produce oriented dendrites of ductile metal phase in an amorphous matrix. Examples are given in the Zr--Ti--Cu--Ni--Be alloy bulk glass forming system with added niobium.

In-situ ductile metal/bulk metallic glass matrix composites formed by chemical partitioning

DOEpatents

Kim, Choong Paul [Northridge, CA; Hays, Charles C [Pasadena, CA; Johnson, William L [Pasadena, CA

2007-07-17

A composite metal object comprises ductile crystalline metal particles in an amorphous metal matrix. An alloy is heated above its liquidus temperature. Upon cooling from the high temperature melt, the alloy chemically partitions, forming dendrites in the melt. Upon cooling the remaining liquid below the glass transition temperature it freezes to the amorphous state, producing a two-phase microstructure containing crystalline particles in an amorphous metal matrix. The ductile metal particles have a size in the range of from 0.1 to 15 micrometers and spacing in the range of from 0.1 to 20 micrometers. Preferably, the particle size is in the range of from 0.5 to 8 micrometers and spacing is in the range of from 1 to 10 micrometers. The volume proportion of particles is in the range of from 5 to 50% and preferably 15 to 35%. Differential cooling can produce oriented dendrites of ductile metal phase in an amorphous matrix. Examples are given in the Zr--Ti--Cu--Ni--Be alloy bulk glass forming system with added niobium.

Deformation behaviors of Cu29Zr32Ti15Al5Ni19 high entropy bulk metallic glass during nanoindentation

NASA Astrophysics Data System (ADS)

Fang, Qihong; Yi, Ming; Li, Jia; Liu, Bin; Huang, Zaiwang

2018-06-01

The deformation behaviors of Cu29Zr32Ti15Al5Ni19 high entropy bulk metallic glass (HE-BMG) during the nanoindentation are presented via the large-scale molecular dynamics (MD) simulations. The indentation tests are carried out using spherical rigid indenter to investigate the microstructural evolution on the mechanical properties of HE-BMGs in terms of shear strain, indentation force, and surface morphology as well as radial distribution function (RDF). Based on the Hertzian fitting the load-displacement curve, HE-BMG Cu29Zr32Ti15Al5Ni19 has the Young's modulus of 93.1 GPa and hardness of 8.8 GPa. The indentation force requiring for the continual increasing contacted area between the indenter and the substrate goes up with the increasing of indentation depth. In addition, the symmetrical distribution of atomic displacement reveals the isotropic of HE-BMG after the indentation treatment. In the deformation region, the Al element would lead to the serious fluctuation in the first peak of RDF, which is much stronger than the other elements. The severe distortion from the atomic size difference maybe reduce the activation energy to the occurrence of shear deformation in HE-BMG, leading to the transition from brittle to ductile observed by the whole sliding of the local atom group. Through the indentation load-displacement curves at various temperatures, the softening of HE-BMG at high temperatures is in qualitative agreement with the experimental findings. Moreover, this effective strategy is used to accelerate the discovery of excellent mechanical properties of HE-BMGs by means of MD simulation, as well as understand the fundamental nanoindentation response of HE-BMGs.

Study of high-Tc interface superconductivity in La1.55Sr0.45CuO4/La2CuO4 heterostructures at high magnetic fields and frequencies

NASA Astrophysics Data System (ADS)

Gasparov, V. A.; Audouard, A.; Drigo, L.; He, Xi; Bozovic, I.

2017-10-01

We have synthesized heterostructures that consist of a layer of a cuprate insulator, La2CuO4, and a layer of a nonsuperconducting cuprate metal, La1.55Sr0.45CuO4. Such bilayers show high-Tc interface superconductivity confined within a single CuO2 plane. Here, we explore the behavior of interface superconductivity at high frequencies (up to 50 MHz) under high magnetic fields (up to 56 T). We find that interface superconductivity persists up to very high perpendicular fields (exceeding 40 T). The critical magnetic field Hm(T) shows an upward divergence with decreasing temperature suggestive of vortex-lattice melting, similar to what is observed in bulk superconducting cuprates.

Theoretical aspects of studies of high coverage oxidation of the Cu(100) surface using low energy positrons

NASA Astrophysics Data System (ADS)

Fazleev, N. G.; Maddox, W. B.; Reed, J. A.

2011-03-01

The study of adsorption of oxygen on transition metal surface is important for the understanding of oxidation, heterogeneous catalysis, and metal corrosion. The structures formed on transition metal surfaces vary from simple adlayers of chemisorbed oxygen to more complex structures which results from diffusion of oxygen into the sub-surface regions. In this work we present the results of an ab-initio investigation of positron surface and bulk states and annihilation probabilities of surface-trapped positrons with relevant core electrons at the Cu(100) missing row reconstructed surface under conditions of high oxygen coverage. Calculations are performed for various surface and subsurface oxygen coverages ranging from 0.50 to 1.50 monolayers. Calculations are also performed for the on-surface adsorption of oxygen on the unreconstructed Cu(001) surface for coverages up to one monolayer to use for comparison. Estimates of the positron binding energy, positron work function, and annihilation characteristics reveal their sensitivity to atomic structure of the topmost layers of the surface and charge transfer. Theoretical results are compared with experimental data obtained from studies of oxidation of the Cu(100) surface using positron annihilation induced Auger electron spectroscopy.

On the mechanisms of cation injection in conducting bridge memories: The case of HfO{sub 2} in contact with noble metal anodes (Au, Cu, Ag)

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

Saadi, M.; CNRS, LTM, F-38000 Grenoble; El Manar University, LMOP, 2092 Tunis

Resistance switching is studied in HfO{sub 2} as a function of the anode metal (Au, Cu, and Ag) in view of its application to resistive memories (resistive random access memories, RRAM). Current-voltage (I-V) and current-time (I-t) characteristics are presented. For Au anodes, resistance transition is controlled by oxygen vacancies (oxygen-based resistive random access memory, OxRRAM). For Ag anodes, resistance switching is governed by cation injection (Conducting Bridge random access memory, CBRAM). Cu anodes lead to an intermediate case. I-t experiments are shown to be a valuable tool to distinguish between OxRRAM and CBRAM behaviors. A model is proposed to explainmore » the high-to-low resistance transition in CBRAMs. The model is based on the theory of low-temperature oxidation of metals (Cabrera-Mott theory). Upon electron injection, oxygen vacancies and oxygen ions are generated in the oxide. Oxygen ions are drifted to the anode, and an interfacial oxide is formed at the HfO{sub 2}/anode interface. If oxygen ion mobility is low in the interfacial oxide, a negative space charge builds-up at the HfO{sub 2}/oxide interface. This negative space charge is the source of a strong electric field across the interfacial oxide thickness, which pulls out cations from the anode (CBRAM case). Inversely, if oxygen ions migration through the interfacial oxide is important (or if the anode does not oxidize such as Au), bulk oxygen vacancies govern resistance transition (OxRRAM case).« less

First principles study of structural, optoelectronic and thermoelectric properties of Cu{sub 2}CdSnX{sub 4} (X = S, Se, Te) chalcogenides

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

Hussain, Sajjad; Murtaza, G., E-mail: murtaza@icp.edu.pk; Haidar Khan, Shah

2016-07-15

Highlights: • Copper based quaternary chalcogenides are important for optoelectronic devices. • The WC-GGA shows that the materials are metallic in nature. • The EV-GGA predicts better band gaps compared to WC-GGA. • Absorption peaks are high in the visible and ultraviolet energy regions. • All the semiconductors have figure of merit above 0.70. - Abstract: In this work, structural, electronic, optical and thermoelectric properties of Cu{sub 2}CdSnX{sub 4} (X = S, Se, Te) have been studied through the full potential linearized augmented plane wave method. Calculated ground state lattice parameters are in good agreement with the experimental results. Latticemore » constant and bulk moduli vary inversely by replacing the anion X from S to Te in Cu{sub 2}CdSnX{sub 4}. The WC-GGA shows that the materials are metallic in nature. The EV-GGA predicts better band gaps compared to WC-GGA. The calculated bandgap values are 1.8, 1.06 and 0.8042 for Cu{sub 2}CdSnX{sub 4}, Cu{sub 2}CdSnX{sub 4}, Cu{sub 2}CdSnX{sub 4} respectively. Cd-d, Sn-s and X-p states contribute significantly in the density of states of the compounds. Absorption peaks and optical conductivity is high in the visible and ultraviolet energy regions. All the semiconductors have figure of merit above 0.70. The optical and thermoelectric properties clearly show that Cu{sub 2}CdSnX{sub 4} are potential candidates in the fields of solar cell and thermoelectric technology.« less

In situ nanomechanical testing of twinned metals in a transmission electron microscope

DOE PAGES

Li, Nan; Wang, Jiangwei; Mao, Scott; ...

2016-04-01

This paper focuses on in situ transmission electron microscope (TEM) characterization to explore twins in face-centered-cubic and body-centered-cubic monolithic metals, and their impact on the overall mechanical performance. Taking advantage of simultaneous nanomechanical deformation and nanoscale imaging using versatile in situ TEM tools, direct correlation of these unique microscopic defects with macroscopic mechanical performance becomes possible. This article summarizes recent evidence to support the mechanisms related to strengthening and plasticity in metals, including nanotwinned Cu, Ni, Al, Au, and others in bulk, thin film, and nanowire forms.

In situ nanomechanical testing of twinned metals in a transmission electron microscope

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

Li, Nan; Wang, Jiangwei; Mao, Scott

This paper focuses on in situ transmission electron microscope (TEM) characterization to explore twins in face-centered-cubic and body-centered-cubic monolithic metals, and their impact on the overall mechanical performance. Taking advantage of simultaneous nanomechanical deformation and nanoscale imaging using versatile in situ TEM tools, direct correlation of these unique microscopic defects with macroscopic mechanical performance becomes possible. This article summarizes recent evidence to support the mechanisms related to strengthening and plasticity in metals, including nanotwinned Cu, Ni, Al, Au, and others in bulk, thin film, and nanowire forms.

Toxicity of silver and copper to Cucurbita pepo: differential effects of nano and bulk-size particles.

PubMed

Musante, Craig; White, Jason C

2012-09-01

The phytotoxicity of bulk and nanoparticle Cu and Ag was directly compared. NP Ag reduced biomass and transpiration by 66-84% when compared with bulk Ag. The Ag ion concentration was 4.4-10-times greater in NP than bulk particle solutions. The Cu ion concentration was 1.4-4.4-times greater in bulk than NP amended solutions. Humic acid (50 mg/L) decreased the ion content of bulk Cu solution by 38-42% but increased ion Cu content of NP solutions by 1.4-2.9 times. Bulk and NP Cu were highly phytotoxic; growth and transpiration were reduced by 60-70% relative to untreated controls. NP Cu phytotoxicity was unaffected by solution type, but humic acid (50 mg/L) completely alleviated phytotoxicity caused by bulk Cu. The data demonstrate differential toxicity of Ag NP relative to bulk Ag. The finding that humic acid and solution chemistry differentially impact bulk and NP behavior highlights the importance of evaluating nanoparticles under environmentally relevant conditions. Copyright © 2010 Wiley Periodicals, Inc.

Degradation of Zr-based bulk metallic glasses used in load-bearing implants: A tribocorrosion appraisal.

PubMed

Zhao, Guo-Hua; Aune, Ragnhild E; Mao, Huahai; Espallargas, Nuria

2016-07-01

Owing to the amorphous structure, Bulk Metallic Glasses (BMGs) have been demonstrating attractive properties for potential biomedical applications. In the present work, the degradation mechanisms of Zr-based BMGs with nominal compositions Zr55Cu30Ni5Al10 and Zr65Cu18Ni7Al10 as potential load-bearing implant material were investigated in a tribocorrosion environment. The composition-dependent micro-mechanical and tribological properties of the two BMGs were evaluated prior to the tribocorrosion tests. The sample Zr65-BMG with a higher Zr content exhibited increased plasticity but relatively reduced wear resistance during the ball-on-disc tests. Both BMGs experienced abrasive wear after the dry wear test under the load of 2N. The cross-sectional subsurface structure of the wear track was examined by Focused Ion Beam (FIB). The electrochemical properties of the BMGs in simulated body fluid were evaluated by means of potentiodynamic polarization and X-ray Photoelectron Spectroscopy (XPS). The spontaneous passivation of Zr-based BMGs in Phosphate Buffer Saline solution was mainly attributed to the highly concentrated zirconium cation (Zr(4+)) in the passive film. The tribocorrosion performance of the BMGs was investigated using a reciprocating tribometer equipped with an electrochemical cell. The more passive nature of the Zr65-BMG had consequently a negative influence on its tribocorrosion resistance, which induced the wear-accelerated corrosion and eventually speeded-up the degradation process. It has been revealed the galvanic coupling was established between the depassivated wear track and the surrounding passive area, which is the main degradation mechanism for the passive Zr65-BMG subjected to the tribocorrosion environment. Copyright © 2015 Elsevier Ltd. All rights reserved.

Risk assessment of trace metals in an extreme environment sediment: shallow, hypersaline, alkaline, and industrial Lake Acıgöl, Denizli, Turkey.

PubMed

Budakoglu, Murat; Karaman, Muhittin; Kumral, Mustafa; Zeytuncu, Bihter; Doner, Zeynep; Yildirim, Demet Kiran; Taşdelen, Suat; Bülbül, Ali; Gumus, Lokman

2018-02-23

The major and trace element component of 48 recent sediment samples in three distinct intervals (0-10, 10-20, and 20-30 cm) from Lake Acıgöl is described to present the current contamination levels and grift structure of detrital and evaporate mineral patterns of these sediments in this extreme saline environment. The spatial and vertical concentrations of major oxides were not uniform in the each subsurface interval. However, similar spatial distribution patterns were observed for some major element couples, due mainly to the detrital and evaporate origin of these elements. A sequential extraction procedure including five distinct steps was also performed to determine the different bonds of trace elements in the < 60-μ particulate size of recent sediments. Eleven trace elements (Ni, Fe, Cd, Pb, Cu, Zn, As, Co, Cr, Al and Mn) in nine surface and subsurface sediment samples were analyzed with chemical partitioning procedures to determine the trace element percentage loads in these different sequential extraction phases. The obtained accuracy values via comparison of the bulk trace metal loads with the total loads of five extraction steps were satisfying for the Ni, Fe, Cd, Zn, and Co. While, bulk analysis results of the Cu, Ni, and V elements have good correlation with total organic matter, organic fraction of sequential extraction characterized by Cu, As, Cd, and Pb. Shallow Lake Acıgöl sediment is characteristic with two different redox layer a) oxic upper level sediments, where trace metals are mobilized, b) reduced subsurface level, where the trace metals are precipitated.

Improvement of glass-forming ability and phase separation in Cu Ti-rich

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

Park, E S; Chang, H J; Kim, D H

2010-01-01

Present study reports improvement of glass-forming ability (GFA) and phase separation in Cu Ti-rich Cu Ti Zr Ni Si bulk metallic glasses (BMGs) by tailoring the constituent elements. The MA of metalloid element, Sn having relatively large negative enthalpy of mixing can lead to improve GFA (up to 8mm in diameter) as well as thermal stability (up toTx = 48K) by optimizing the substitution element. And the addition of elements having relatively large positive enthalpy of mixing (partial substitution of Zr or Ti with Y) can lead to the liquid state phase separation in Cu Ti Sn Zr Ni Simore » BMG, although the addition lead to drastic deterioration of the GFA.« less

An experimental investigation of silicon wafer surface roughness and its effect on the full strength of plated metals

NASA Technical Reports Server (NTRS)

Spiers, G. D.

1981-01-01

Plated silicon wafers with surface roughness ranging from 0.4 to 130 microinches were subjected to tensile pull strength tests. Electroless Ni/electroless Cu/electroplated Cu and electroless Ni/electroplated Cu were the two types of plate contacts tested. It was found that smoother surfaces had higher pull strength than rougher, chemically etched surfaces. The presence of the electroless Cu layer was found to be important to adhesion. The mode of fracture of the contact as it left the silicon was studied, and it was found that in almost all cases separation was due to fracture of the bulk silicon phase. The correlation between surface roughness and mode of contact failure is presented and interpreted.

Phosphorus-Rich Copper Phosphide Nanowires for Field-Effect Transistors and Lithium-Ion Batteries.

PubMed

Li, Guo-An; Wang, Chiu-Yen; Chang, Wei-Chung; Tuan, Hsing-Yu

2016-09-27

Phosphorus-rich transition metal phosphide CuP2 nanowires were synthesized with high quality and high yield (∼60%) via the supercritical fluid-liquid-solid (SFLS) growth at 410 °C and 10.2 MPa. The obtained CuP2 nanowires have a high aspect ratio and exhibit a single crystal structure of monoclinic CuP2 without any impurity phase. CuP2 nanowires have progressive improvement for semiconductors and energy storages compared with bulk CuP2. Being utilized for back-gate field effect transistor (FET) measurement, CuP2 nanowires possess a p-type behavior intrinsically with an on/off ratio larger than 10(4) and its single nanowire electrical transport property exhibits a hole mobility of 147 cm(2) V(-1) s(-1), representing the example of a CuP2 transistor. In addition, CuP2 nanowires can serve as an appealing anode material for a lithium-ion battery electrode. The discharge capacity remained at 945 mA h g(-1) after 100 cycles, showing a good capacity retention of 88% based on the first discharge capacity. Even at a high rate of 6 C, the electrode still exhibited an outstanding result with a capacity of ∼600 mA h g(-1). Ex-situ transmission electron microscopy and CV tests demonstrate that the stability of capacity retention and remarkable rate capability of the CuP2 nanowires electrode are attributed to the role of the metal phosphide conversion-type lithium storage mechanism. Finally, CuP2 nanowire anodes and LiFePO4 cathodes were assembled into pouch-type lithium batteries offering a capacity over 60 mA h. The full cell shows high capacity and stable capacity retention and can be used as an energy supply to operate electronic devices such as mobile phones and mini 4WD cars.

Dynamic failure in two-phase materials

DOE PAGES

Fensin, S. J.; Walker, E. K.; Cerreta, E. K.; ...

2015-12-21

Previous experimental research has shown that microstructural features such as interfaces, inclusions, vacancies, and heterogeneities can all act as voidnucleation sites. However, it is not well understood how important these interfaces are to damage evolution and failure as a function of the surrounding parentmaterials. In this work, we present results on three different polycrystallinematerials: (1) Cu, (2) Cu-24 wt. %Ag, and (3) Cu-15 wt. %Nb which were studied to probe the influence of bi-metal interfaces onvoidnucleation and growth. These materials were chosen due to the range of difference in structure and bulk properties between the two phases. The initial resultsmore » suggest that when there are significant differences between the bulk properties (for example: stacking fault energy, melting temperature, etc.) the type of interface between the two parent materials does not principally control the damage nucleation and growth process. Rather, it is the “weaker” material that dictates the dynamic spall strength of the overall two-phase material.« less

Impact of sediment characteristics on the heavy metal concentration and their ecological risk level of surface sediments of Vaigai river, Tamilnadu, India.

PubMed

Paramasivam, K; Ramasamy, V; Suresh, G

2015-02-25

The distributions of the metals (Al, Fe, Mg, Cd, Cr, Cu, Ni, Pb and Zn) were measured for the surface sediments of the Vaigai river, Tamilnadu, India. These values are compared with different standard values to assess the level of toxicity of the heavy metals in the sediments. Risk indices (CF, PLI and PER) are also calculated to understand the level of toxicity of the metals. Multivariate statistical analyses (Pearson's correlation analysis, cluster analysis and factor analysis) are carried out to know the inter-relationship between sediment characteristics and the heavy metals. From this analysis, it is confirmed that the contents of clay and organic matter play an important role to raise the level of heavy metal contents as well as PLI and PER (level of toxicity). Heavy metal concentrations of the samples (after removing silt and clay fractions from bulk samples) show decrease in their concentrations and risk indices compared to the level of bulk samples. Copyright © 2014 Elsevier B.V. All rights reserved.

Interaction of SO2 with Cu/TiC(0 0 1) and Au/TiC(0 0 1): Toward a New Family of DeSOx Catalysts

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

L Feria; J Rodriguez; T Jirsak

2011-12-31

Experiments carried out under well-controlled conditions and density functional theory (DFT)-based calculations evidence that Cu and Au nanoparticles supported on a TiC(0 0 1) surface are quite active for the dissociation of the SO{sub 2} molecule. The Cu/TiC(0 0 1) and Au/TiC(0 0 1) systems cleave both S-O bonds of SO{sub 2} at a temperature of 150 K, displaying a reactivity much larger than that of TiC(0 0 1) or extended surfaces of bulk copper and gold. The origin of the high activity of the Cu/TiC(0 0 1) and Au/TiC(0 0 1) systems lies on the interaction between the Cmore » atoms of the substrate and the metal atoms of the supported particle, which results in a large polarization of its electron density. Experiments and theory consistently indicate that the Cu/TiC system is more active toward SO{sub 2} dissociation than the Au/TiC system. This type of systems may provide alternative and efficient DeSO{sub x} catalysts.« less

Interaction of SO2 with Cu/TiC(001) and Au/TiC(001): Towards a New Family of DeSOx Catalysts

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

Rodriguez, J.A.; Feria, L.; Jirsak, T.

2011-04-25

Experiments carried out under well-controlled conditions and density functional theory (DFT)-based calculations evidence that Cu and Au nanoparticles supported on a TiC(0 0 1) surface are quite active for the dissociation of the SO{sub 2} molecule. The Cu/TiC(0 0 1) and Au/TiC(0 0 1) systems cleave both S-O bonds of SO{sub 2} at a temperature of 150 K, displaying a reactivity much larger than that of TiC(0 0 1) or extended surfaces of bulk copper and gold. The origin of the high activity of the Cu/TiC(0 0 1) and Au/TiC(0 0 1) systems lies on the interaction between the Cmore » atoms of the substrate and the metal atoms of the supported particle, which results in a large polarization of its electron density. Experiments and theory consistently indicate that the Cu/TiC system is more active toward SO{sub 2} dissociation than the Au/TiC system. This type of systems may provide alternative and efficient DeSO{sub x} catalysts.« less

Ag-Cu mixed phase plasmonic nanostructures fabricated by shadow nanosphere lithography and glancing angle co-deposition

NASA Astrophysics Data System (ADS)

Ingram, Whitney; Larson, Steven; Carlson, Daniel; Zhao, Yiping

2017-01-01

By combining shadow nanosphere lithography with a glancing angle co-deposition technique, mixed-phase Ag-Cu triangular nanopatterns and films were fabricated. They were prepared at different compositions with respect to Ag from 100% to 0% by changing the relative deposition ratio of each metal. Characterizations by ellipsometry, energy dispersive x-ray spectroscopy, and x-ray diffraction revealed that the thin films and nanopatterns were composed of small, well-mixed Ag and Cu nano-grains with a diameter less than 20 nm, and their optical properties could be described by an effective medium theory. All compositions of the nanopattern had the same shape, but showed tunable localized surface plasmon resonance (LSPR) properties. In general, the LSPR of the nanopatterns redshifted with decreasing composition. Such a relation could be fitted by an empirical model based on the bulk theory of alloy plasmonics. By changing the colloidal template and the material deposited, this fabrication technique can be used to produce other alloy plasmonic nanostructures with predicted LSPR wavelengths.

Ag-Cu mixed phase plasmonic nanostructures fabricated by shadow nanosphere lithography and glancing angle co-deposition.

PubMed

Ingram, Whitney; Larson, Steven; Carlson, Daniel; Zhao, Yiping

2017-01-06

By combining shadow nanosphere lithography with a glancing angle co-deposition technique, mixed-phase Ag-Cu triangular nanopatterns and films were fabricated. They were prepared at different compositions with respect to Ag from 100% to 0% by changing the relative deposition ratio of each metal. Characterizations by ellipsometry, energy dispersive x-ray spectroscopy, and x-ray diffraction revealed that the thin films and nanopatterns were composed of small, well-mixed Ag and Cu nano-grains with a diameter less than 20 nm, and their optical properties could be described by an effective medium theory. All compositions of the nanopattern had the same shape, but showed tunable localized surface plasmon resonance (LSPR) properties. In general, the LSPR of the nanopatterns redshifted with decreasing composition. Such a relation could be fitted by an empirical model based on the bulk theory of alloy plasmonics. By changing the colloidal template and the material deposited, this fabrication technique can be used to produce other alloy plasmonic nanostructures with predicted LSPR wavelengths.

Accumulation and chemical fractionation of heavy metals in andisols after a different, 6-year fertilization management.

PubMed

Zhao, Bingzi; Maeda, Morihiro; Zhang, Jiabao; Zhu, Anning; Ozaki, Yasuo

2006-03-01

Andisols are widespread in Japan and have some special properties such as high anion exchange capacity, low bulk density, and high organic matter content, which might influence the accumulation or chemical fractionation of heavy metals. However, few such data exist in Japanese andisols. The primary objective of this study was to investigate the distribution and chemical fractions of Cu, Zn, Ni, and Cr in the soil profiles and subsequently to assess their potential environmental hazard. Soil samples were taken from a field experiment conducted on Japanese andisols, which had received either swine compost or chemical fertilizers for 6 years. Concentrations of Cu, Zn, Ni, and Cr were determined for all of the obtained extract solutions by ICP-AES. Considerably higher total concentrations of Cu and Zn were observed in the top 20 cm layer of the compost-amended soil, relative to the unfertilized soil, while chemical fertilizers had little effect. Application of the swine compost increased the concentrations of Cu and Zn, but not Ni and Cr, in all fractions in the top 20 cm layer. The greatest increase in the organically bound fraction (OM) Cu and dilute acid-exchangeable fraction (DAEXCH) Zn was observed. This suggests that Cu and Zn are potentially bioavailable and mobile in the andisol profiles after 6-year consecutive applications of the swine compost. On the other hand, distribution of Cu, Zn, Ni and Cr among various soil fractions was generally unaffected by chemical fertilizers. We observed that 6-year consecutive applications of the swine compost led to an increase in total metals of Cu and Zn, as well as their all-chemical fractions, in the top 20 cm soil layers. Potential hazard of heavy metals, especially of Cu and Zn, as a result of the use of swine compost on andisols, must be taken into account. The long-term effect of the accumulation of heavy metals, particularly Cu and Zn, in various plant tissues and soils, as well as their potential risk to surface water via runoff and groundwater via leaching, needs to be carefully considered. Further investigations in the long-term experiments are therefore necessary.

Portulaca grandiflora as green roof vegetation: Plant growth and phytoremediation experiments.

PubMed

Vijayaraghavan, K; Arockiaraj, Jesu; Kamala-Kannan, Seralathan

2017-06-03

Finding appropriate rooftop vegetation may improve the quality of runoff from green roofs. Portulaca grandiflora was examined as possible vegetation for green roofs. Green roof substrate was found to have low bulk density (360.7 kg/m 3 ) and high water-holding capacity (49.4%), air-filled porosity (21.1%), and hydraulic conductivity (5270 mm/hour). The optimal substrate also supported the growth of P. grandiflora with biomass multiplication of 450.3% and relative growth rate of 0.038. Phytoextraction potential of P. grandiflora was evaluated using metal-spiked green roof substrate as a function of time and spiked substrate metal concentration. It was identified that P. grandiflora accumulated all metals (Al, Cd, Cr, Cu, Fe, Ni, Pb, and Zn) from metal-spiked green roof substrate. At the end of 40 days, P. grandiflora accumulated 811 ± 26.7, 87.2 ± 3.59, 416 ± 15.8, 459 ± 15.6, 746 ± 20.9, 357 ± 18.5, 565 ± 6.8, and 596 ± 24.4 mg/kg of Al, Cd, Cr, Cu, Fe, Ni, Pb and Zn, respectively. Results also indicated that spiked substrate metal concentration strongly influenced metal accumulation property of P. grandiflora with metal uptake increased and accumulation factor decreased with increase in substrate metal concentration. P. grandiflora also showed potential to translocate all the examined metals with translocation factor greater than 1 for Al, Cu, Fe, and Zn, indicating hyperaccumulation property.

Drastic influence of minor Fe or Co additions on the glass forming ability, martensitic transformations and mechanical properties of shape memory Zr-Cu-Al bulk metallic glass composites.

PubMed

González, Sergio; Pérez, Pablo; Rossinyol, Emma; Suriñach, Santiago; Dolors Baró, Maria; Pellicer, Eva; Sort, Jordi

2014-06-01

The microstructure and mechanical properties of Zr 48 Cu 48 -  x Al 4 M x (M ≡ Fe or Co, x  = 0, 0.5, 1 at.%) metallic glass (MG) composites are highly dependent on the amount of Fe or Co added as microalloying elements in the parent Zr 48 Cu 48 Al 4 material. Addition of Fe and Co promotes the transformation from austenite to martensite during the course of nanoindentation or compression experiments, resulting in an enhancement of plasticity. However, the presence of Fe or Co also reduces the glass forming ability, ultimately causing a worsening of the mechanical properties. Owing to the interplay between these two effects, the compressive plasticity for alloys with x  = 0.5 (5.5% in Zr 48 Cu 47.5 Al 4 Co 0.5 and 6.2% in Zr 48 Cu 47.5 Al 4 Fe 0.5 ) is considerably larger than for Zr 48 Cu 48 Al 4 or the alloys with x  = 1. Slight variations in the Young's modulus (around 5-10%) and significant changes in the yield stress (up to 25%) are also observed depending on the composition. The different microstructural factors that have an influence on the mechanical behavior of these composites are investigated in detail: (i) co-existence of amorphous and crystalline phases in the as-cast state, (ii) nature of the crystalline phases (austenite versus martensite content), and (iii) propensity for the austenite to undergo a mechanically-driven martensitic transformation during plastic deformation. Evidence for intragranular nanotwins likely generated in the course of the austenite-martensite transformation is provided by transmission electron microscopy. Our results reveal that fine-tuning of the composition of the Zr-Cu-Al-(Fe,Co) system is crucial in order to optimize the mechanical performance of these bulk MG composites, to make them suitable materials for structural applications.

Drastic influence of minor Fe or Co additions on the glass forming ability, martensitic transformations and mechanical properties of shape memory Zr-Cu-Al bulk metallic glass composites

NASA Astrophysics Data System (ADS)

González, Sergio; Pérez, Pablo; Rossinyol, Emma; Suriñach, Santiago; Baró, Maria Dolors; Pellicer, Eva; Sort, Jordi

2014-06-01

The microstructure and mechanical properties of Zr48Cu48 - x Al4M x (M ≡ Fe or Co, x = 0, 0.5, 1 at.%) metallic glass (MG) composites are highly dependent on the amount of Fe or Co added as microalloying elements in the parent Zr48Cu48Al4 material. Addition of Fe and Co promotes the transformation from austenite to martensite during the course of nanoindentation or compression experiments, resulting in an enhancement of plasticity. However, the presence of Fe or Co also reduces the glass forming ability, ultimately causing a worsening of the mechanical properties. Owing to the interplay between these two effects, the compressive plasticity for alloys with x = 0.5 (5.5% in Zr48Cu47.5Al4Co0.5 and 6.2% in Zr48Cu47.5Al4Fe0.5) is considerably larger than for Zr48Cu48Al4 or the alloys with x = 1. Slight variations in the Young’s modulus (around 5-10%) and significant changes in the yield stress (up to 25%) are also observed depending on the composition. The different microstructural factors that have an influence on the mechanical behavior of these composites are investigated in detail: (i) co-existence of amorphous and crystalline phases in the as-cast state, (ii) nature of the crystalline phases (austenite versus martensite content), and (iii) propensity for the austenite to undergo a mechanically-driven martensitic transformation during plastic deformation. Evidence for intragranular nanotwins likely generated in the course of the austenite-martensite transformation is provided by transmission electron microscopy. Our results reveal that fine-tuning of the composition of the Zr-Cu-Al-(Fe,Co) system is crucial in order to optimize the mechanical performance of these bulk MG composites, to make them suitable materials for structural applications.

Toward in situ x-ray diffraction imaging at the nanometer scale

NASA Astrophysics Data System (ADS)

Zatsepin, Nadia A.; Dilanian, Ruben A.; Nikulin, Andrei Y.; Gable, Brian M.; Muddle, Barry C.; Sakata, Osami

2008-08-01

We present the results of preliminary investigations determining the sensitivity and applicability of a novel x-ray diffraction based nanoscale imaging technique, including simulations and experiments. The ultimate aim of this nascent technique is non-destructive, bulk-material characterization on the nanometer scale, involving three dimensional image reconstructions of embedded nanoparticles and in situ sample characterization. The approach is insensitive to x-ray coherence, making it applicable to synchrotron and laboratory hard x-ray sources, opening the possibility of unprecedented nanometer resolution with the latter. The technique is being developed with a focus on analyzing a technologically important light metal alloy, Al-xCu (where x is 2.0-5.0 %wt). The mono- and polycrystalline samples contain crystallographically oriented, weakly diffracting Al2Cu nanoprecipitates in a sparse, spatially random dispersion within the Al matrix. By employing a triple-axis diffractometer in the non-dispersive setup we collected two-dimensional reciprocal space maps of synchrotron x-rays diffracted from the Al2Cu nanoparticles. The intensity profiles of the diffraction peaks confirmed the sensitivity of the technique to the presence and orientation of the nanoparticles. This is a fundamental step towards in situ observation of such extremely sparse, weakly diffracting nanoprecipitates embedded in light metal alloys at early stages of their growth.

First-principles calculations of stability, electronic and elastic properties of the precipitates present in 7055 aluminum alloy

NASA Astrophysics Data System (ADS)

Huang, Cheng; Shao, Hongbang; Ma, Yunlong; Huang, Yuanchun; Xiao, Zhengbing

2018-04-01

The structural stability, electronic structures and elastic properties of the strengthening precipitates, namely Al3Zr, MgZn2, Al2CuMg and Al2Cu, present in 7055 aluminum alloy were investigated by the first-principles calculations based on density functional theory (DFT). The optimized structural parameters are in good agreement with literature values available. It is found that Al3Zr has the strongest alloying ability and structural stability, while for MgZn2, its structural stability is the worst. The calculated electronic results indicate that covalent bonding is the dominant cohesion of Al3Zr, whereas the fractional ionic interactions coexisting with metallic bonding are found in MgZn2, Al2CuMg and Al2Cu. The elastic constants Cij of these precipitates were calculated, and the bulk modulus, shear modulus, Young’s modulus, Poisson’s ratio and universal elastic anisotropy were derived. It is suggested that MgZn2 is ductile, whereas Al3Zr, Al2CuMg and Al2Cu are brittle, and the elastic anisotropies of them increase in the following sequence: Al3Zr

Passivation of high temperature superconductors

NASA Technical Reports Server (NTRS)

Vasquez, Richard P. (Inventor)

1991-01-01

The surface of high temperature superconductors such as YBa2Cu3O(7-x) are passivated by reacting the native Y, Ba and Cu metal ions with an anion such as sulfate or oxalate to form a surface film that is impervious to water and has a solubility in water of no more than 10(exp -3) M. The passivating treatment is preferably conducted by immersing the surface in dilute aqueous acid solution since more soluble species dissolve into the solution. The treatment does not degrade the superconducting properties of the bulk material.

Inert anode containing base metal and noble metal useful for the electrolytic production of aluminum

DOEpatents

Ray, Siba P.; Liu, Xinghua

2000-01-01

An inert anode for production of metals such as aluminum is disclosed. The inert anode comprises a base metal selected from Cu and Ag, and at least one noble metal selected from Ag, Pd, Pt, Au, Rh, Ru, Ir and Os. The inert anode may optionally be formed of sintered particles having interior portions containing more base metal than noble metal and exterior portions containing more noble metal than base metal. In a preferred embodiment, the base metal comprises Cu, and the noble metal comprises Ag, Pd or a combination thereof.

Potential effect of CuInS2/ZnS core-shell quantum dots on P3HT/PEDOT:PSS heterostructure based solar cell

NASA Astrophysics Data System (ADS)

Jindal, Shikha; Giripunje, S. M.

2018-07-01

Nanostructured quantum dots (QDs) are quite promising in the solar cell application due to quantum confinement effect. QDs possess multiple exciton generation and large surface area. The environment friendly CuInS2/ZnS core-shell QDs were prepared by solvothermal method. Thus, the 3 nm average sized CuInS2/ZnS QDs were employed in the bulk heterojunction device and the active blend layer consisting of the P3HT and CuInS2/ZnS QDs was investigated. The energy level information of CuInS2/ZnS QDs as an electron acceptor was explored by ultra violet photoelectron spectroscopy. Bulk heterojunction hybrid device of ITO/PEDOT:PSS/P3HT: (CuInS2/ZnS QDs)/ZnO/Ag was designed by spin coating approach and its electrical characterization was investigated by solar simulator. Current density - voltage characteristics shows the enhancement in power conversion efficiency with increasing concentration of CuInS2/ZnS QDs in bulk heterojunction device.

(Zn,H)-codoped copper oxide nanoparticles via pulsed laser ablation on Cu-Zn alloy in water

PubMed Central

2012-01-01

Nanosized (5 to 10 nm) amorphous and crystalline nanocondensates, i.e., metallic α-phase of Zn-Cu alloy in face-centered cubic structure and (Zn,H)-codoped cuprite (Cu2O) with high-pressure-favored close-packed sublattice, were formed by pulsed laser ablation on bulk Cu65Zn35 in water and characterized by X-ray/electron diffractions and optical spectroscopy. The as-fabricated hybrid nanocondensates are darkish and showed photoluminescence in the whole visible region. Further dwelling of such nanocondensates in water caused progressive formation of a rice-like assembly of (Zn,H)-codoped tenorite (CuO) nanoparticles with (001), (100), and {111} preferred orientations, (111) tilt boundary, yellowish color, and minimum bandgap narrowing down to ca. 2.7 eV for potential photocatalytic applications. PMID:22647312

Computer simulation of the matrix-inclusion interphase in bulk metallic glass based nanocomposites

NASA Astrophysics Data System (ADS)

Kokotin, V.; Hermann, H.; Eckert, J.

2011-10-01

Atomistic models for matrix-inclusion systems are generated. Analyses of the systems show that interphase layers of finite thickness appear interlinking the surface of the nanocrystalline inclusion and the embedding amorphous matrix. In a first approximation, the interphase is characterized as an amorphous structure with a density slightly reduced compared to that of the matrix. This result holds for both monatomic hard sphere systems and a Cu47.5Zr47.5Al5 alloy simulated by molecular dynamics (MD). The elastic shear and bulk modulus of the interphase are calculated by simulated deformation of the MD systems. Both moduli diminish with decreasing density but the shear modulus is more sensitive against density reduction by one order of magnitude. This result explains recent observations of shear band initiation at the amorphous-crystalline interface during plastic deformation.

Two-phase quasi-equilibrium in β-type Ti-based bulk metallic glass composites

PubMed Central

Zhang, L.; Pauly, S.; Tang, M. Q.; Eckert, J.; Zhang, H. F.

2016-01-01

The microstructural evolution of cast Ti/Zr-based bulk metallic glass composites (BMGCs) containing β-Ti still remains ambiguous. This is why to date the strategies and alloys suitable for producing such BMGCs with precisely controllable volume fractions and crystallite sizes are still rather limited. In this work, a Ti-based BMGC containing β-Ti was developed in the Ti-Zr-Cu-Co-Be system. The glassy matrix of this BMGC possesses an exceptional glass-forming ability and as a consequence, the volume fractions as well as the composition of the β-Ti dendrites remain constant over a wide range of cooling rates. This finding can be explained in terms of a two-phase quasi-equilibrium between the supercooled liquid and β-Ti, which the system attains on cooling. The two-phase quasi-equilibrium allows predicting the crystalline and glassy volume fractions by means of the lever rule and we succeeded in reproducing these values by slight variations in the alloy composition at a fixed cooling rate. The two-phase quasi-equilibrium could be of critical importance for understanding and designing the microstructures of BMGCs containing the β-phase. Its implications on the nucleation and growth of the crystalline phase are elaborated. PMID:26754315

Distribution trends and influence of 4d transition metal elements (Ru, Rh and Pd) doping on mechanical properties and martensitic transformation temperature of B2-ZrCu phase

NASA Astrophysics Data System (ADS)

Guo, Fuda; Zhan, Yongzhong

2017-12-01

The prediction for distribution trends and effect of three 4d transition metal elements (Ru, Rh and Pd) on mechanical properties and martensitic transformation temperature of B2-ZrCu phase were investigated by first-principles calculations. The convex surface of formation energy suggests that the alloying elements prefer to occupy the Cu sites in B2-ZrCu phase and the dopants studied in present are able to strengthen the phase stability. The calculated results of substitutional formation energy suggest that the distribution trend of dopants in B2-ZrCu phase is Ru > Rh > Pd below the dopant concentration 9 at. %, and the distribution trend is Rh > Pd > Ru from 9 at. % to 12.5 at. %. The elastic constants and mechanical properties including bulk modulus and shear modulus were calculated and discussed. The brittleness/ductility characteristic was investigated using the B/G ratio, Poisson's ratio v and Cauchy pressure Cp. The martensitic transformation temperature (Ms) and melting point (Tm) were predicted by using two cubic elastic moduli (C‧ and C44). The prediction results suggest that only the Ms of Zr8Cu7Pd is higher than the parent. The martensitic transformation temperatures of other compounds decrease with the addition of 4d transition metal dopants. Finally, the electronic structures and electron density different were discussed to reveal the bonding characteristics.

Determination of trace metals in TSP and PM2.5 materials collected in the Metropolitan Area of Monterrey, Mexico: A characterization study by XPS, ICP-AES and SEM-EDS

NASA Astrophysics Data System (ADS)

González, Lucy T.; Longoria Rodríguez, F. E.; Sánchez-Domínguez, M.; Cavazos, Aleyda; Leyva-Porras, C.; Silva-Vidaurri, L. G.; Askar, Karim Acuña; Kharissov, B. I.; Villarreal Chiu, J. F.; Alfaro Barbosa, J. M.

2017-11-01

The concentration levels of trace metals of toxicological importance were evaluated in the total suspended particles (TSP) and particulate matter smaller than 2.5 μm (PM2.5) collected in the Metropolitan Area of Monterrey (MAM) in Mexico. Samples were characterized by inductively coupled plasma atomic emission spectroscopy (ICP-AES), X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy with an energy-dispersive spectroscopy system (SEM-EDS). In addition, the data were statistically treated by the methodology of Pearson Correlation (PC) and Principal Components Analysis (PCA) to identify the possible emitting sources. Surface analysis of the particulate matter (PM) by XPS revealed that the most abundant elements were Ca, Al, Na, Zn, Cu and Mg. The deconvolution of the Ca2p, Zn2p and Cu2p signals showed that the main contributors were CaCO3, ZnO and Cu/Cu2O, respectively. The bulk analysis of the PM by ICP-AES showed Fe, Cu and Zn as the most abundant elements. Fe-rich particles presented two different morphologies: the prismatic particles were associated with a natural origin, while the spherical particles with anthropogenic sources. The Zn and Cu were predominantly observed in the sampling stations with high vehicular traffic, and the emitting sources were associated with the burning of fuels from automobiles and the wear of the tires and brakes. The highest concentration of Pb was detected in the sampling station located near the industrial zones, and its cause was associated with the ceramic and glass industries, the burning of fuel oil in power plants and the production of lead-based batteries for automobiles.

Ground state properties of 3d metals from self-consistent GW approach

DOE PAGES

Kutepov, Andrey L.

2017-10-06

The self consistent GW approach (scGW) has been applied to calculate the ground state properties (equilibrium Wigner–Seitz radius S WZ and bulk modulus B) of 3d transition metals Sc, Ti, V, Fe, Co, Ni, and Cu. The approach systematically underestimates S WZ with average relative deviation from the experimental data of about 1% and it overestimates the calculated bulk modulus with relative error of about 25%. We show that scGW is superior in accuracy as compared to the local density approximation but it is less accurate than the generalized gradient approach for the materials studied. If compared to the randommore » phase approximation, scGW is slightly less accurate, but its error for 3d metals looks more systematic. Lastly, the systematic nature of the deviation from the experimental data suggests that the next order of the perturbation theory should allow one to reduce the error.« less

Ground state properties of 3d metals from self-consistent GW approach

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

Kutepov, Andrey L.

The self consistent GW approach (scGW) has been applied to calculate the ground state properties (equilibrium Wigner–Seitz radius S WZ and bulk modulus B) of 3d transition metals Sc, Ti, V, Fe, Co, Ni, and Cu. The approach systematically underestimates S WZ with average relative deviation from the experimental data of about 1% and it overestimates the calculated bulk modulus with relative error of about 25%. We show that scGW is superior in accuracy as compared to the local density approximation but it is less accurate than the generalized gradient approach for the materials studied. If compared to the randommore » phase approximation, scGW is slightly less accurate, but its error for 3d metals looks more systematic. Lastly, the systematic nature of the deviation from the experimental data suggests that the next order of the perturbation theory should allow one to reduce the error.« less

Zeolite-based SCR catalysts and their use in diesel engine emission treatment

DOEpatents

Narula, Chaitanya K.; Yang, Xiaofan

2016-08-02

A catalyst comprising a zeolite loaded with copper ions and at least one trivalent metal ion other than Al.sup.+3, wherein the catalyst decreases NO.sub.x emissions in diesel exhaust. The trivalent metal ions are selected from, for example, trivalent transition metal ions, trivalent main group metal ions, and/or trivalent lanthanide metal ions. In particular embodiments, the catalysts are selected from Cu--Fe-ZSM5, Cu--La-ZSM-5, Fe--Cu--La-ZSM5, Cu--Sc-ZSM-5, and Cu--In-ZSM5. The catalysts are placed on refractory support materials and incorporated into catalytic converters.

Zeolite-based SCR catalysts and their use in diesel engine emission treatment

DOEpatents

Narula, Chaitanya K; Yang, Xiaofan

2015-03-24

A catalyst comprising a zeolite loaded with copper ions and at least one trivalent metal ion other than Al.sup.+3, wherein the catalyst decreases NO.sub.x emissions in diesel exhaust. The trivalent metal ions are selected from, for example, trivalent transition metal ions, trivalent main group metal ions, and/or trivalent lanthanide metal ions. In particular embodiments, the catalysts are selected from Cu--Fe-ZSM5, Cu--La-ZSM-5, Fe--Cu--La-ZSM5, Cu--Sc-ZSM-5, and Cu--In-ZSM5. The catalysts are placed on refractory support materials and incorporated into catalytic converters.

Carbon nanotubes grown on bulk materials and methods for fabrication

DOEpatents

Menchhofer, Paul A [Clinton, TN; Montgomery, Frederick C [Oak Ridge, TN; Baker, Frederick S [Oak Ridge, TN

2011-11-08

Disclosed are structures formed as bulk support media having carbon nanotubes formed therewith. The bulk support media may comprise fibers or particles and the fibers or particles may be formed from such materials as quartz, carbon, or activated carbon. Metal catalyst species are formed adjacent the surfaces of the bulk support material, and carbon nanotubes are grown adjacent the surfaces of the metal catalyst species. Methods employ metal salt solutions that may comprise iron salts such as iron chloride, aluminum salts such as aluminum chloride, or nickel salts such as nickel chloride. Carbon nanotubes may be separated from the carbon-based bulk support media and the metal catalyst species by using concentrated acids to oxidize the carbon-based bulk support media and the metal catalyst species.

Microstructural Evolution of the Interface Between Pure Titanium and Low Melting Point Zr-Ti-Ni(Cu) Filler Metals

NASA Astrophysics Data System (ADS)

Lee, Dongmyoung; Sun, Juhyun; Kang, Donghan; Shin, Seungyoung; Hong, Juhwa

2014-12-01

Low melting point Zr-based filler metals with melting point depressants (MPDs) such as Cu and Ni elements are used for titanium brazing. However, the phase transition of the filler metals in the titanium joint needs to be explained, since the main element of Zr in the filler metals differs from that of the parent titanium alloys. In addition, since the MPDs easily form brittle intermetallics, that deteriorate joint properties, the phase evolution they cause needs to be studied. Zr-based filler metals having Cu content from 0 to 12 at. pct and Ni content from 12 to 24 at. pct with a melting temperature range of 1062 K to 1082 K (789 °C to 809 °C) were wetting-tested on a titanium plate to investigate the phase transformation and evolution at the interface between the titanium plate and the filler metals. In the interface, the alloys system with Zr, Zr2Ni, and (Ti,Zr)2Ni phases was easily changed to a Ti-based alloy system with Ti, Ti2Ni, and (Ti,Zr)2Ni phases, by the local melting of parent titanium. The dissolution depths of the parent metal were increased with increasing Ni content in the filler metals because Ni has a faster diffusion rate than Cu. Instead, slow diffusion of Cu into titanium substrate leads to the accumulation of Cu at the molten zone of the interface, which could form undesirable Ti x Cu y intermetallics. This study confirmed that Zr-based filler metals are compatible with the parent titanium metal with the minimum content of MPDs.

The characterisation of atomic structure and glass-forming ability of the Zr-Cu-Co metallic glasses studied by molecular dynamics simulations

NASA Astrophysics Data System (ADS)

Celtek, M.; Sengul, S.

2018-03-01

In the present work, the glass formation process and structural properties of Zr50Cu50-xCox (0 ≤ x ≤ 50) bulk metallic glasses were investigated by a molecular dynamics simulation with the many body tight-binding potentials. The evolution of structure and glass formation process with temperature were discussed using the coordination number, the radial distribution functions, the volume-temperature curve, icosahedral short-range order, glass transition temperature, Voronoi analysis, Honeycutt-Andersen pair analysis technique and the distribution of bond-angles. Results indicate that adding Co causes similar responses on the nature of the Zr50Cu50-xCox (0 ≤ x ≤ 50) alloys except for higher glass transition temperature and ideal icosahedral type ordered local atomic environment. Also, the differences of the atomic radii play the key role in influencing the atomic structure of these alloys. Both Cu and Co atoms play a significant role in deciding the chemical and topological short-range orders of the Zr50Cu50-xCox ternary liquids and amorphous alloys. The glass-forming ability of these alloys is supported by the experimental observations reported in the literature up to now.

Propensity of bond exchange as a window into the mechanical properties of metallic glasses

NASA Astrophysics Data System (ADS)

Jiao, W.; Wang, X. L.; Lan, S.; Pan, S. P.; Lu, Z. P.

2015-02-01

We investigated the mechanical properties of Zr-Cu-Al bulk metallic glasses, by compression experiment and molecular dynamics simulations. From the simulation, we found that the large, solvent atom, Zr, has high propensity of bond exchange compared to those of the smaller solute atoms. The difference in bond exchange is consistent with the observed disparity in mechanical behaviors: Zr-rich metallic glass exhibits low elastic modulus and large plastic strain. X-ray photoelectron spectroscopy measurements suggest that the increased propensity in bond exchange is related to the softening of Zr bonds with increasing Zr content.

Study of solid/liquid and solid/gas interfaces in Cu-isoleucine complex by surface X-ray diffraction

NASA Astrophysics Data System (ADS)

Ferrer, Pilar; Rubio-Zuazo, Juan; Castro, German R.

2013-02-01

The enzymes could be understood like structures formed by amino acids bonded with metals, which act as active sites. The research on the coordination of metal-amino acid complexes will bring light on the behavior of metal enzymes, due to the close relation existing between the atomic structure and the functionality. The Cu-isoleucine bond is considered as a good model system to attain a better insight into the characteristics of naturally occurring copper metalloproteins. The surface structure of metal-amino acid complex could be considered as a more realistic model for real systems under biologic working conditions, since the molecular packing is decreased. In the surface, the structural constrains are reduced, keeping the structural capability of surface complex to change as a function of the surrounding environment. In this work, we present a surface X-ray diffraction study on Cu-isoleucine complex under different ambient conditions. Cu(Ile)2 crystals of about 5 mm × 5 mm × 1 mm have been growth, by seeding method in a supersaturated solution, presenting a surface of high quality. The sample for the surface diffraction study was mounted on a cell specially designed for solid/liquid or solid/gas interface analysis. The Cu-isoleucine crystal was measured under a protective dry N2 gas flow and in contact with a saturated metal amino acid solution. The bulk and the surface signals were compared, showing different atomic structures. In both cases, from surface diffraction data, it is observed that the atomic structure of the top layer undergoes a clear structural deformation. A non-uniform surface relaxation is observed producing an inhomogeneous displacement of the surface atoms towards the surface normal.

Contrasting effects of photochemical and microbial degradation on Cu(II) binding with fluorescent DOM from different origins.

PubMed

Xu, Huacheng; Guan, Dong-Xing; Zou, Li; Lin, Hui; Guo, Laodong

2018-08-01

Effects of photochemical and microbial degradation on variations in composition and molecular-size of dissolved organic matter (DOM) from different sources (algal and soil) and the subsequent influence on Cu(II) binding were investigated using UV-Vis, fluorescence excitation-emission matrices coupled with parallel factor analysis, flow field-flow fractionation (FlFFF), and metal titration. The degradation processes resulted in an initial rapid decline in the bulk dissolved organic carbon and chromophoric and fluorescent DOM components, followed by a small or little decrease. Specifically, photochemical reaction decreased the aromaticity, humification and apparent molecular weights of all DOM samples, whereas a reverse trend was observed during microbial degradation. The FlFFF fractograms revealed that coagulation of both protein- and humic-like DOM induced an increase in molecular weights for algal-DOM, while the molecular weight enhancement for allochthonous soil samples was mainly attributed to the self-assembly of humic-like components. The Cu(II) binding capacity of algal-derived humic-like and fulvic-like DOM consistently increased during photo- and bio-degradation, while the soil-derived DOM exhibited a slight decline in Cu(II) binding capacity during photo-degradation but a substantial increase during microbial degradation, indicating source- and degradation-dependent metal binding heterogeneities. Pearson correlation analysis demonstrated that the Cu(II) binding potential was mostly related with aromaticity and molecular size for allochthonous soil-derived DOM, but was regulated by both DOM properties and specific degradation processes for autochthonous algal-derived DOM. This study highlighted the coupling role of inherent DOM properties and external environmental processes in regulating metal binding, and provided new insights into metal-DOM interactions and the behavior and fate of DOM-bound metals in aquatic environments. Copyright © 2018 Elsevier Ltd. All rights reserved.

Superior Electrical Conductivity in Hydrogenated Layered Ternary Chalcogenide Nanosheets for Flexible All-Solid-State Supercapacitors.

PubMed

Hu, Xin; Shao, Wei; Hang, Xudong; Zhang, Xiaodong; Zhu, Wenguang; Xie, Yi

2016-05-04

As the properties of ultrathin two-dimensional (2D) crystals are strongly related to their electronic structures, more and more attempts were carried out to tune their electronic structures to meet the high standards for the construction of next-generation smart electronics. Herein, for the first time, we show that the conductive nature of layered ternary chalcogenide with formula of Cu2 WS4 can be switched from semiconducting to metallic by hydrogen incorporation, accompanied by a high increase in electrical conductivity. In detail, the room-temperature electrical conductivity of hydrogenated-Cu2 WS4 nanosheet film was almost 10(10) times higher than that of pristine bulk sample with a value of about 2.9×10(4)  S m(-1) , which is among the best values for conductive 2D nanosheets. In addition, the metallicity in the hydrogenated-Cu2 WS4 is robust and can be retained under high-temperature treatment. The fabricated all-solid-state flexible supercapacitor based on the hydrogenated-Cu2 WS4 nanosheet film shows promising electrochemical performances with capacitance of 583.3 F cm(-3) at a current density of 0.31 A cm(-3) . This work not only offers a prototype material for the study of electronic structure regulation in 2D crystals, but also paves the way in searching for highly conductive electrodes. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

X-PEEM, XPS and ToF-SIMS characterisation of xanthate induced chalcopyrite flotation: Effect of pulp potential

NASA Astrophysics Data System (ADS)

Kalegowda, Yogesh; Chan, Yuet-Loy; Wei, Der-Hsin; Harmer, Sarah L.

2015-05-01

Synchrotron-based X-ray photoemission electron microscopy (X-PEEM), X-ray photo-electron spectroscopy (XPS), time-of-flight secondary ion mass spectrometry (ToF-SIMS) and ultraviolet visible spectroscopy were used to characterize the flotation behaviour of chalcopyrite with xanthate at different processing conditions. The flotation recovery of chalcopyrite decreased from 97% under oxidative conditions (Eh ~ 385 mV SHE, pH 4) to 41% at a reductive potential of - 100 mV SHE (at pH 9). X-PEEM images constructed from the metal L3 absorption edges were used to produce near-edge X-ray absorption fine structure (NEXAFS) spectra from regions of interest, allowing the variability in mineral surface chemistry of each mineral particle to be analysed, and the effect of pulp potential (Eh) on the flotation of chalcopyrite to be determined. XPS, ToF-SIMS and NEXAFS analyses of chalcopyrite particles at oxidative conditions show that the surface was mildly oxidised and covered with adsorbed molecular CuEX. The Cu 2p XPS and Cu L2,3 NEXAFS spectra were dominated by CuI species attributed to bulk chalcopyrite and adsorbed CuEX. At a reductive potential of - 100 mV SHE, an increase in concentration of CuI and FeIII oxides and hydroxides was observed. X-PEEM analysis was able to show the presence of a low percentage of CuII oxides (CuO or Cu(OH)2) with predominantly CuI oxide (Cu2O) which is not evident in Cu 2p XPS spectra.

Surface Plasmon Polariton Resonance of Gold, Silver, and Copper Studied in the Kretschmann Geometry: Dependence on Wavelength, Angle of Incidence, and Film Thickness

NASA Astrophysics Data System (ADS)

Takagi, Kentaro; Nair, Selvakumar V.; Watanabe, Ryosuke; Seto, Keisuke; Kobayashi, Takayoshi; Tokunaga, Eiji

2017-12-01

Surface plasmon polariton (SPP) resonance spectra for noble metals (Au, Ag, and Cu) were comprehensively studied in the Kretschmann attenuated total reflection (ATR) geometry, in the wavelength (λ) range from 300 to 1000 nm with the angle of incidence (θ) ranging from 45 to 60° and the film thickness (d) ranging from 41 to 76 nm. The experimental plasmon resonance spectra were reproduced by a calculation that included the broadening effects as follows: (1) the imaginary part of the bulk dielectric constant, (2) the thickness-dependent radiative coupling of the SPP at the metal-air interface to the prism, (3) the lack of conservation of the wavevector parallel to the interface kx(k||) caused by the surface roughness, (4) scanning λ at a fixed θ (changing both energy and kx at the same time) over the SPP dispersion relation. For Au and Ag, the experimental results were in good agreement with the calculated results using the bulk dielectric constants, showing no film thickness dependence of the plasmon resonance energy. A method to extract the true width of the plasmon resonance from raw ATR spectra is proposed and the results are rigorously compared with those expected from the bulk dielectric function given in the literature. For Au and Ag, the width increases with energy, in agreement with that expected from the relaxation of bulk free electrons including the electron-electron interaction, but there is clear evidence of extra broadening, which is more significant for thinner films, possibly due to relaxation pathways intrinsic to plasmons near the interface. For Cu, the visibility of the plasmon resonance critically depends on the evaporation conditions, and low pressures and fast deposition rates are required. Otherwise, scattering from the surface roughness causes considerable broadening of the plasmon resonance, resulting in an apparently fixed resonance energy without clear incident angle dependence. For Cu, the observed plasmon dispersion agrees well with that expected from the bulk dielectric function even with nominal oxidation of the surface, but the widths at long wavelengths are much larger than those theoretically expected.

Wear resistance of CuZr-based amorphous-forming alloys against bearing steel in 3.5% NaCl solution

NASA Astrophysics Data System (ADS)

Ji, Xiulin; Wang, Hui; Bao, Yayun; Zheng, Dingcong

2017-11-01

To investigate the amorphous-crystalline microstructure on the tribocorrosion of bulk metallic glasses (BMGs), 6 mm diameter rods of Cu46-xZr47Al7Agx (x = 0, 2, 4) amorphous-forming alloys with in situ crystalline and amorphous phases were fabricated by arc-melting and Cu-mould casting. Using a pin-on-disc tribometer, the tribo-pair composed by CuZr-based amorphous-forming alloys and AISI 52100 steel were studied in 3.5% NaCl solution. With the increase of Ag content from 0 to 4 at.%, the compressive fracture strength and the average hardness decrease firstly and then increase. Moreover, 4 at.% Ag addition increases the amount of amorphous phase obviously and inhibits the formation of brittle crystalline phase, resulting in the improvement of corrosion resistance and the corrosive wear resistance. The primary wear mechanism of the BMG composites is abrasive wear accompanying with corrosive wear. The tribocorrosion mass loss of Cu42Zr47Al7Ag4 composite is 1.5 mg after 816.8 m sliding distance at 0.75 m s-1 sliding velocity under 10 N load in NaCl solution. And the volume loss evaluated from the mass loss is about 20 times lower than that of AISI 304 SS. Thus, Cu42Zr47Al7Ag4 composite may be a good candidate in the tribology application under marine environment.

Effect of Surface Modifications of Ti40Zr10Cu38Pd12 Bulk Metallic Glass and Ti-6Al-4V Alloy on Human Osteoblasts In Vitro Biocompatibility

PubMed Central

Blanquer, Andreu; Hynowska, Anna; Nogués, Carme; Ibáñez, Elena; Sort, Jordi; Baró, Maria Dolors; Özkale, Berna; Pané, Salvador; Pellicer, Eva

2016-01-01

The use of biocompatible materials, including bulk metallic glasses (BMGs), for tissue regeneration and transplantation is increasing. The good mechanical and corrosion properties of Ti40Zr10Cu38Pd12 BMG and its previously described biocompatibility makes it a potential candidate for medical applications. However, it is known that surface properties like topography might play an important role in regulating cell adhesion, proliferation and differentiation. Thus, in the present study, Ti40Zr10Cu38Pd12 BMG and Ti6-Al-4V alloy were surface-modified electrochemically (nanomesh) or physically (microscratched) to investigate the effect of material topography on human osteoblasts cells (Saos-2) adhesion, proliferation and differentiation. For comparative purposes, the effect of mirror-like polished surfaces was also studied. Electrochemical treatments led to a highly interconnected hierarchical porous structure rich in oxides, which have been described to improve corrosion resistance, whereas microscratched surfaces showed a groove pattern with parallel trenches. Cell viability was higher than 96% for the three topographies tested and for both alloy compositions. In all cases, cells were able to adhere, proliferate and differentiate on the alloys, hence indicating that surface topography plays a minor role on these processes, although a clear cell orientation was observed on microscratched surfaces. Overall, our results provide further evidence that Ti40Zr10Cu38Pd12 BMG is an excellent candidate, in the present two topographies, for bone repair purposes. PMID:27243628

Electrical resistivity in Zr48Nb8Cu12Fe8Be24 glassy and crystallized alloys

NASA Astrophysics Data System (ADS)

Bai, H. Y.; Tong, C. Z.; Zheng, P.

2004-02-01

The electrical resistivity of Zr48Nb8Cu12Fe8Be24 bulk metallic glassy and crystallized alloys in the temperature range of 4.2-293 K is investigated. It is found that the resistivity in glassy and crystallized states shows opposite temperature coefficients. For the metallic glass, the resistivity shows a negative logarithmic dependence at temperatures below 16 K, whereas it has more normal behavior for the crystallized alloy. At higher temperatures, the resistivity in both glassy and crystallized alloys shows dependence upon both T and T2, but the signs of the T and T2 terms are opposite. The results are interpreted in terms of scattering from two-level tunneling states in glasses and the generalized Ziman diffraction model.

Stabilized Lithium-Metal Surface in a Polysulfide-Rich Environment of Lithium-Sulfur Batteries.

PubMed

Zu, Chenxi; Manthiram, Arumugam

2014-08-07

Lithium-metal anode degradation is one of the major challenges of lithium-sulfur (Li-S) batteries, hindering their practical utility as next-generation rechargeable battery chemistry. The polysulfide migration and shuttling associated with Li-S batteries can induce heterogeneities of the lithium-metal surface because it causes passivation by bulk insulating Li2S particles/electrolyte decomposition products on a lithium-metal surface. This promotes lithium dendrite formation and leads to poor lithium cycling efficiency with complicated lithium surface chemistry. Here, we show copper acetate as a surface stabilizer for lithium metal in a polysulfide-rich environment of Li-S batteries. The lithium surface is protected from parasitic reactions with the organic electrolyte and the migrating polysulfides by an in situ chemical formation of a passivation film consisting of mainly Li2S/Li2S2/CuS/Cu2S and electrolyte decomposition products. This passivation film also suppresses lithium dendrite formation by controlling the lithium deposition sites, leading to a stabilized lithium surface characterized by a dendrite-free morphology and improved surface chemistry.

Recent advances in bulk metallic glasses for biomedical applications.

PubMed

Li, H F; Zheng, Y F

2016-05-01

With a continuously increasing aging population and the improvement of living standards, large demands of biomaterials are expected for a long time to come. Further development of novel biomaterials, that are much safer and of much higher quality, in terms of both biomedical and mechanical properties, are therefore of great interest for both the research scientists and clinical surgeons. Compared with the conventional crystalline metallic counterparts, bulk metallic glasses have unique amorphous structures, and thus exhibit higher strength, lower Young's modulus, improved wear resistance, good fatigue endurance, and excellent corrosion resistance. For this purpose, bulk metallic glasses (BMGs) have recently attracted much attention for biomedical applications. This review discusses and summarizes the recent developments and advances of bulk metallic glasses, including Ti-based, Zr-based, Fe-based, Mg-based, Zn-based, Ca-based and Sr-based alloying systems for biomedical applications. Future research directions will move towards overcoming the brittleness, increasing the glass forming ability (GFA) thus obtaining corresponding bulk metallic glasses with larger sizes, removing/reducing toxic elements, and surface modifications. Bulk metallic glasses (BMGs), also known as amorphous alloys or liquid metals, are relative newcomers in the field of biomaterials. They have gained increasing attention during the past decades, as they exhibit an excellent combination of properties and processing capabilities desired for versatile biomedical implant applications. The present work reviewed the recent developments and advances of biomedical BMGs, including Ti-based, Zr-based, Fe-based, Mg-based, Zn-based, Ca-based and Sr-based BMG alloying systems. Besides, the critical analysis and in-depth discussion on the current status, challenge and future development of biomedical BMGs are included. The possible solution to the BMG size limitation, the brittleness of BMGs has been proposed. Copyright © 2016 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Insights into metals in individual fine particles from municipal solid waste using synchrotron radiation-based micro-analytical techniques.

PubMed

Zhu, Yumin; Zhang, Hua; Shao, Liming; He, Pinjing

2015-01-01

Excessive inter-contamination with heavy metals hampers the application of biological treatment products derived from mixed or mechanically-sorted municipal solid waste (MSW). In this study, we investigated fine particles of <2mm, which are small fractions in MSW but constitute a significant component of the total heavy metal content, using bulk detection techniques. A total of 17 individual fine particles were evaluated using synchrotron radiation-based micro-X-ray fluorescence and micro-X-ray diffraction. We also discussed the association, speciation and source apportionment of heavy metals. Metals were found to exist in a diffuse distribution with heterogeneous intensities and intense hot-spots of <10 μm within the fine particles. Zn-Cu, Pb-Fe and Fe-Mn-Cr had significant correlations in terms of spatial distribution. The overlapped enrichment, spatial association, and the mineral phases of metals revealed the potential sources of fine particles from size-reduced waste fractions (such as scraps of organic wastes or ceramics) or from the importation of other particles. The diverse sources of heavy metal pollutants within the fine particles suggested that separate collection and treatment of the biodegradable waste fraction (such as food waste) is a preferable means of facilitating the beneficial utilization of the stabilized products. Copyright © 2014. Published by Elsevier B.V.

Microstructure and Interfacial Shear Strength in W/(Zr55Cu30Al10Ni5)100- x Nb x Composites

NASA Astrophysics Data System (ADS)

Mahmoodan, M.; Gholamipour, R.; Mirdamadi, Sh.; Nategh, S.

2017-11-01

In the present study, (Zr55Cu30Al10Ni5)100- x Nb( x=0,1,2,3) bulk metallic glass matrix/tungsten wire composites were fabricated by a gas pressure infiltration process at temperature 950 °C for 5 min. Microstructural studies and mechanical behaviors of the materials have been investigated by scanning electron microscopy, transmission electron microscopy and pullout tests. The mechanical results showed that the interface shear strength in the composite sample with X = 2 increased more than twice compared to the composite sample with X = 0. Based on the microstructural results, the addition of two atomic percent Nb in the matrix composite causes an increase in the diffusion band thickness during the melt infiltration and change in the interface fracture mode as a result of pullout test.

Electron Scattering at Surfaces of Epitaxial Metal Layers

NASA Astrophysics Data System (ADS)

Chawla, Jasmeet Singh

In the field of electron transport in metal films and wires, the 'size effect' refers to the increase in the resistivity of the films and wires as their critical dimensions (thickness of film, width and height of wires) approach or become less than the electron mean free path lambda, which is, for example, 39 nm for bulk copper at room temperature. This size-effect is currently of great concern to the semiconductor industry because the continued downscaling of feature sizes has already lead to Cu interconnect wires in this size effect regime, with a reported 2.5 times higher resistivity for 40 nm wide Cu wires than for bulk Cu. Silver is a possible alternate material for interconnect wires and titanium nitride is proposed as a gate metal in novel field-effect-transistors. Therefore, it is important to develop an understanding of how the growth, the surface morphology, and the microstructure of ultrathin (few nanometers) Cu, Ag and TiN layers affect their electrical properties. This dissertation aims to advance the scientific knowledge of electron scattering at surfaces (external surfaces and grain boundaries), that are, the primary reasons for the size-effect in metal conductors. The effect of surface and grain boundary scattering on the resistivity of Cu thin films and nanowires is separately quantified using (i) in situ transport measurements on single-crystal, atomically smooth Cu(001) layers, (ii) textured polycrystalline Cu(111) layers and patterned wires with independently varying grain size, thickness and line width, and (iii) in situ grown interfaces including Cu-Ta, Cu-MgO, Cu-vacuum and Cu-oxygen. In addition, the electron surface scattering is also measured in situ for single-crystal Ag(001), (111) twinned epitaxial Ag(001), and single-crystal TiN(001) layers. Cu(001), Ag(001), and TiN(001) layers with a minimum continuous thickness of 4, 3.5 and 1.8 nm, respectively, are grown by ultra-high vacuum magnetron sputter deposition on MgO(001) substrates with and without thin epitaxial TiN(001) wetting layers and are studied for structure, crystalline quality, surface morphology, density and composition by a combination of x-ray diffraction theta-2theta scans, o-rocking curves, pole figures, reciprocal space mapping, Rutherford backscattering, x-ray reflectometry and transmission electron microscopy. The TiN(001) surface suppresses Cu and Ag dewetting, yielding lower defect density, no twinning, and smaller surface roughness than if grown on MgO(001). Textured polycrystalline Cu(111) layers 25-50-nm-thick are deposited on a stack of 7.5-nm-Ta on SiO2/Si(001), and subsequent in situ annealing at 350°C followed by sputter etching in Ar plasma yields Cu layers with independently variable thickness and grain size. Cu nanowires, 75 to 350 nm wide, are fabricated from Cu layers with different average grain size using a subtractive patterning process. In situ electron transport measurements at room temperature in vacuum and at 77 K in liquid nitrogen for single-crystal Cu and Ag layers is consistent with the Fuchs-Sondheimer (FS) model and indicates specular scattering at the metal-vacuum boundary with an average specularity parameter p = 0.8 and 0.6, respectively. In contrast, layers measured ex situ show diffuse surface scattering due to sub-monolayer oxidation. Also, addition of Ta atoms on Cu(001) surface perturbs the smooth interface potential and results in completely diffuse scattering at the Cu-Ta interface, and in turn, a higher resistivity of single-crystal Cu layers. In situ exposure of Cu(001) layers to O2 between 10 -3 and 105 Pa-s results in a sequential increase, decrease and increase of the electrical resistance which is attributed to specular surface scattering for clean Cu(001) and for surfaces with a complete adsorbed monolayer, but diffuse scattering at partial coverage and after chemical oxidation. Electron transport measurements for polycrystalline Cu layers and wires show a 10-15% and 7-9% decrease in resistivity, respectively, when increasing the average lateral grain size by a factor of 1.8. The maximum resistivity decrease that can be achieved by increasing the grain size of polycrystalline Cu layers with an average grain size approximately ˜2.5x the layer thickness is 20-26%.

Superconductivity at 43K in SmFeAsO1-xFx

NASA Astrophysics Data System (ADS)

Chen, X. H.; Wu, T.; Wu, G.; Liu, R. H.; Chen, H.; Fang, D. F.

2008-06-01

Since the discovery of high-transition-temperature (high-Tc) superconductivity in layered copper oxides, extensive effort has been devoted to exploring the origins of this phenomenon. A Tc higher than 40K (about the theoretical maximum predicted from Bardeen-Cooper-Schrieffer theory), however, has been obtained only in the copper oxide superconductors. The highest reported value for non-copper-oxide bulk superconductivity is Tc = 39K in MgB2 (ref. 2). The layered rare-earth metal oxypnictides LnOFeAs (where Ln is La-Nd, Sm and Gd) are now attracting attention following the discovery of superconductivity at 26K in the iron-based LaO1-xFxFeAs (ref. 3). Here we report the discovery of bulk superconductivity in the related compound SmFeAsO1-xFx, which has a ZrCuSiAs-type structure. Resistivity and magnetization measurements reveal a transition temperature as high as 43K. This provides a new material base for studying the origin of high-temperature superconductivity.

Metal-organic framework derived hollow polyhedron metal oxide posited graphene oxide for energy storage applications.

PubMed

Ramaraju, Bendi; Li, Cheng-Hung; Prakash, Sengodu; Chen, Chia-Chun

2016-01-18

A composite made from hollow polyhedron copper oxide and graphene oxide was synthesized by sintering a Cu-based metal-organic framework (Cu-MOF) embedded with exfoliated graphene oxide. As a proof-of-concept application, the obtained Cu(ox)-rGO materials were used in a lithium-ion battery and a sodium-ion battery as anode materials. Overall, the Cu(ox)-rGO composite delivers excellent electrochemical properties with stable cycling when compared to pure CuO-rGO and Cu-MOF.

Crystallization Behavior of A Bulk Amorphous Mg62Cu26Y12 Alloy

NASA Astrophysics Data System (ADS)

Wu, Shyue-Sheng; Chin, Tsung-Shune; Su, Kuo-Chang

1994-07-01

The crystallization temperature, the associated activation energy and the crystallized structure of a bulk amorphous Mg62Cu26Y12 alloy with a diameter of 2.5 mm were studied. It possesses a one-step crystallization behavior. The crystallization reaction was found to be represented by: AM(MG62Cu26Y12)→Mg2Cu+MgY+CuY+Mg, ( Tx=188°C, Eac=134 kJ/mol) where AM represents the amorphous state, T x the crystallization temperature at an infinitesimal heating rate, and E ac the associated activation energy. The amount of crystalline phases were found to be Mg2Cu:MgY:CuY=76:17:7. The Mg phase is identifiable only by high resolution electron microscopy, not by X-ray diffraction. The crystallization leads to a sharp rise in electrical resistivity which is reversed to those of iron-based amorphous alloys.

Copper-Based Metal-Organic Porous Materials for CO2 Electrocatalytic Reduction to Alcohols.

PubMed

Albo, Jonathan; Vallejo, Daniel; Beobide, Garikoitz; Castillo, Oscar; Castaño, Pedro; Irabien, Angel

2017-03-22

The electrocatalytic reduction of CO 2 has been investigated using four Cu-based metal-organic porous materials supported on gas diffusion electrodes, namely, (1) HKUST-1 metal-organic framework (MOF), [Cu 3 (μ 6 -C 9 H 3 O 6 ) 2 ] n ; (2) CuAdeAce MOF, [Cu 3 (μ 3 -C 5 H 4 N 5 ) 2 ] n ; (3) CuDTA mesoporous metal-organic aerogel (MOA), [Cu(μ-C 2 H 2 N 2 S 2 )] n ; and (4) CuZnDTA MOA, [Cu 0.6 Zn 0.4 (μ-C 2 H 2 N 2 S 2 )] n . The electrodes show relatively high surface areas, accessibilities, and exposure of the Cu catalytic centers as well as favorable electrocatalytic CO 2 reduction performance, that is, they have a high efficiency for the production of methanol and ethanol in the liquid phase. The maximum cumulative Faradaic efficiencies for CO 2 conversion at HKUST-1-, CuAdeAce-, CuDTA-, and CuZnDTA-based electrodes are 15.9, 1.2, 6, and 9.9 %, respectively, at a current density of 10 mA cm -2 , an electrolyte-flow/area ratio of 3 mL min cm -2 , and a gas-flow/area ratio of 20 mL min cm -2 . We can correlate these observations with the structural features of the electrodes. Furthermore, HKUST-1- and CuZnDTA-based electrodes show stable electrocatalytic performance for 17 and 12 h, respectively. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

First Principles Studies of Electronic and Optical Excitations in Noble Metal and Titania Clusters

NASA Astrophysics Data System (ADS)

Baishya, Kopinjol

Clusters are metastable structures that form a bridge between the atomic and the bulk phase. Due to their small size, quantum confinement effects are very important in clusters. They also have large surface to volume ratio, and as such, surface effects are also important. Due to these effects the properties of clusters are quite different from those of the bulk. When the size of a cluster is increased, its properties change from atomic to bulk values usually in nontrivial ways, often displaying interesting effects. By studying the evolution of cluster properties as a function of size one can try to understand the evolution and origin of bulk properties. This thesis concentrates on two main topics, noble-metal clusters of Ag and Cu, and TiO2 nanocrystals. I present my study of the optical properties of these systems calculated using first principles methods. Noble metal clusters have intriguing physical and chemical properties due to their electronic structure that contains a fully filled and localized d orbital energetically and spatially very close to the half filled s orbital. In Chapters 3 and 4 of this thesis, I present a detailed study of the role of d electrons on the optical properties of Ag and Cu clusters. I also show that the optical spectra of these clusters can be explained remarkably well by the classical Mie-Gans theory which uses the bulk dielectric constant of the material to predict their optical absorption spectra. The fact that the concept of the bulk dielectric constant survives up to the sub-nanometer size range is one of the main findings of this thesis. TiO2 is arguably the most studied single-crystalline material in the field of surface science of metal oxides. In chapter 5 of this thesis I present results and analyses on the electronic and optical excitations in rutile TiO2 nanocrystals. The motivation for this study stems from the following observation: In modeling optical prooperties of DSSC configurations with various organic molecules, a typical approach has been to use a finite, appropriately passivated TiO2 nanocrystal in order to limit the computational demand. In real systems on the other hand, the size of nanocrystalline TiO2 is of the order of several hundreds of nanometers, and hence, they can be considered to be essentially bulk-like. The question is then, whether finite TiO2 nanoparticles can accurately model the optical properties of bulk TiO2. I show in my thesis that the optical absorption absorption spectra of such TiO2 nanocrystals do not have the particular features seen in the imaginary part of the bulk dielectric function of TiO 2 associated with the van Hove singularities in the electronic density of states. Instead, the absorption spectra of bulk-terminated TiO2 nanocrystals can be reproduced quite well by the Mie-Gans theory.

Soil contamination in the impact zone of mining enterprises in the Bashkir Transural region

NASA Astrophysics Data System (ADS)

Opekunova, M. G.; Somov, V. V.; Papyan, E. E.

2017-06-01

The results of long-term studies of the contents of bulk forms of metals (Cu, Zn, Fe, Ni, Pb, Mn, Co, and Cd) and their mobile compounds in soils of background and human-disturbed areas within the Krasnoural'sk-Sibai-Gai copper-zinc and Baimak-Buribai mixed copper mineralization zones in the Bashkir Transural region are discussed. It is shown that soils of the region are characterized by abnormally high natural total contents of heavy metals (HMs) typomorphic for ore mineralization: Cu, Zn, and Fe for the Sibai province and Cu, Zn, and Ni for the Baimak province. In the case of a shallow depth of the ores, the concentrations of HMs in the soils are close to or higher than the tentative permissible concentration values. The concentrations of mobile HM compounds in soils of background areas and their percentage in the total HM content strongly vary from year to year in dependence on weather conditions, position in the soil catenas, species composition of vegetation, and distance from the source of technogenic contamination. The high natural variability in the content of mobile HM compounds in soils complicates the reliable determination of the regional geochemical background and necessitates annual estimation of background parameters for the purposes of the ecological monitoring of soils. The bulk content of Cu and Zn content in soils near mining enterprises exceeds the regional geochemical background values by 2-12 times and the tentative permissible concentrations of these metals by 2-4 times. Anthropogenic contamination results in a sharp rise in the content of mobile HM compounds in soils. Their highest concentrations exceed the maximum permissible concentrations by 26 times for Cu, 18 times for Zn, and 2 times for Pb. Soil contamination in the impact zone of mining enterprises is extremely dangerous or dangerous. However, because of the high temporal variability in the migration and accumulation of HMs in the soils, the recent decline in the ore mining activities, and the construction of purification facilities, no definite temporal trends in the contents of HMs in the soils have been found in the studied region for the period from 1998 to 2015.

Molecular dynamics (MD) studies on phase transformation and deformation behaviors in FCC metals and alloys

NASA Astrophysics Data System (ADS)

Qi, Yue

This thesis focused on the phase transformation and deformation behaviors in face center cubic (FCC) metals and alloys. These studies used the new quantum modified Sutton-Chen (QMSC) many-body potentials for Cu, Ni, Ag, and Au and for their alloys through simple combination rules. Various systems and processes are simulated by standard equilibrium molecular dynamics (MD), quasi-static equilibrium MD and non-equilibrium MD (NEMD), cooperated with different periodic boundary conditions. The main topics include: (1) Melting, glass formation, and crystallization processes in bulk alloys. In our simulation CuNi and pure Cu always form an FCC crystal, while Cu4Ag6 always forms glass (with Tg decreasing as the quench rate increases) due to the large atomic size difference. (2) Size effects in melting and crystallization in Ni nano clusters. There is a transition from cluster or molecular regime (where the icosahedral is the stable structure) below ˜500 atoms to a mesoscale regime (with well-defined bulk and surface properties and surface melting processes, which leads to Tm,N = Tm,B - alpha N-1/3) above ˜750 atoms. (3) The deformation behavior of metallic nanowires of pure Ni, NiCu and NiAu alloys, under high rates of uniaxial tensile strain, ranging from 5*108/s to 5*1010/s. We find that deformation proceeds through twinning and coherent slipping at low strain rate and amorphization at high strain rate. This research provides a new method, fast straining, to induce amorphization except fast cooling and disordering. (4) The calculation of the ½ <110> screw dislocation in nickel (Ni). We calculated the core energy of screw dislocation after dissociation is 0.5 eV/b, the annihilation process of opposite signed dislocations depends dramatically on the configurations of dissociation planes and the cross-slip energy barrier is 0.1eV/b. (5) Friction anisotropy on clean Ni(100)/(100) interface. We found that static friction coefficient on flat and incommensurate interface is close to zero (as analytical theory predicted), however, the calculation show the same anisotropic behavior as experiments on rough surface, thus explained the difference between theory and experiments.

Metallicity of Ca 2Cu 6P 5 with single and double copper-pnictide layers

DOE PAGES

Li, Li; Parker, David; Chi, Miaofang; ...

2016-02-16

We report thermodynamic and transport properties, and also theoretical calculations, for Cu-based compound Ca 2Cu 6P 5 and compare with CaCu 2-δP 2. Both materials have layers of edge-sharing copper pnictide tetrahedral CuP 4, similar to Fe–As and Fe–Se layers (with FeAs 4, FeSe 4) in the iron-based superconductors. Despite the presence of this similar transition-metal pnictide layer, we find that both Ca 2Cu 6P 5 and CaCu 2-δP 2 have temperature-independent magnetic susceptibility and show metallic behavior with no evidence of either magnetic ordering or superconductivity down to 1.8 K CaCu 2-δP 2 is slightly off-stoichiometric, with δ =more » 0.14. Theoretical calculations suggest that unlike Fe 3d-based magnetic materials with a large density of states (DOS) at the Fermi surface, Cu have comparatively low DOS, with the majority of the 3d spectral weight located well below Fermi level. The room-temperature resistivity value of Ca 2Cu 6P 5 is only 9 μΩ-cm, due to a substantial plasma frequency and an inferred electron-phonon coupling λ of 0.073 (significantly smaller than that of metallic Cu). Also, microscopy result shows that Cu–Cu distance along the c-axis within the double layers can be very short (2.5 Å), even shorter than metallic elemental copper bond (2.56 Å). The value of dρ/dT for CaCu 2-δP 2 at 300 K is approximately three times larger than in Ca 2Cu 6P 5, which suggests the likelihood of stronger electron-phonon coupling. Lastly, this study shows that the details of Cu–P layers and bonding are important for their transport characteristics. In addition, it emphasizes the remarkable character of the DOS of ‘122’ iron-based materials, despite much structural similarities.« less

The Effect of Copper Addition on the Properties of Sn-0.7Cu Solder Paste

NASA Astrophysics Data System (ADS)

Said, R. M.; Mohamad Johari, F. H.; Salleh, M. A. A. Mohd; Sandu, A. V.

2018-03-01

The effect of copper addition on the properties of Sn-Cu based solder paste were investigate through this study. The Sn-0.7Cu solder paste doped with different concentration of Cu were prepared using solder paste mixture. The bulk solder microstructure of assolidified solder paste was studied. Besides that, intermetallic compound (IMC) formation on Cu substrate and hardness of all solder paste also being investigated. Results shows that increasing Cu concentration cause formation of large Cu6Sn5 IMC at bulk solder and the size of the IMC grew larger at high temperature. In addition, β-Sn area reduce when Cu concentration was high. The IMC morphology for all solder paste almost remain unchanged. However, there are large Cu6Sn5 IMC form near the interfacial IMC in Sn-Cu solder paste with high amount of Cu (Sn-10Cu). The hardness value was decrease when processing temperature at 250 °C due to present of small void in the microstructure while hardness of solder material increased at high temperature.

Atomistic Modeling of Nanostructures via the BFS Quantum Approximate Method

NASA Technical Reports Server (NTRS)

Bozzolo, Guillermo; Garces, Jorge E.; Noebe, Ronald D.; Farias, D.

2003-01-01

Ideally, computational modeling techniques for nanoscopic physics would be able to perform free of limitations on the type and number of elements, while providing comparable accuracy when dealing with bulk or surface problems. Computational efficiency is also desirable, if not mandatory, for properly dealing with the complexity of typical nano-strucured systems. A quantum approximate technique, the BFS method for alloys, which attempts to meet these demands, is introduced for the calculation of the energetics of nanostructures. The versatility of the technique is demonstrated through analysis of diverse systems, including multi-phase precipitation in a five element Ni-Al-Ti-Cr-Cu alloy and the formation of mixed composition Co-Cu islands on a metallic Cu(III) substrate.

A 3D chiral metal-organic framework based on left-handed helices containing 3-amino-1 H-1,2,4-triazole ligand

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

Liu, Bing, E-mail: bliu_1203@163.com; Yang, Tian-Yi; Feng, Hui-Jun

2015-10-15

A chiral metal-organic framework, [Cu(atr)(OH)]·0.5H{sub 2}O·0.5en (1) (Hatr=3-amino-1 H-1,2,4-triazole, en=ethylenediamine), was constructed via diffusion reaction of the achiral Hatr ligand and CuSO{sub 4} as starting materials. Compound 1 crystallizes in the chiral space group P3{sub 2}21 and features a porous metal-organic framework with 44.1% solvent-accessible volume fabricated by left-handed helices with a pitch height of l{sub p}=10.442 Å. Six helices gather around in a cycle forming a large honeycomb channel with a 6.58 Å inner diameter. Cu(II) center and atr{sup ‒} ligand regarded as 3-connected nodes, compound 1 can be simplified to a 3-c uninodal (4.12{sup 2}) (qtz-h) topological network.more » A gradual decreasing in the magnetic moment depending on temperature decreasing indicates an antiferromagnetic interaction in 1. The powder XRD confirms the bulk sample is a single crystal pure phase, and the thermogravimetric analysis shows the thermal stability of 1 is up to ca. 240 °C. - Highlights: • The present 3D chiral MOF is built from achiral Hatr ligand. • Six left-handed helices gather into a honeycomb channel in chiral sp P3{sub 2}21. • Compound 1 shows a 3-c uninodal (4.12{sup 2}) or qtz-h topological network. • Compound 1 indicates an antiferromagnetic interaction.« less

Systems and Methods for Implementing Bulk Metallic Glass-Based Strain Wave Gears and Strain Wave Gear Components

NASA Technical Reports Server (NTRS)

Hofmann, Douglas C. (Inventor); Wilcox, Brian (Inventor)

2016-01-01

Bulk metallic glass-based strain wave gears and strain wave gear components. In one embodiment, a strain wave gear includes: a wave generator; a flexspline that itself includes a first set of gear teeth; and a circular spline that itself includes a second set of gear teeth; where at least one of the wave generator, the flexspline, and the circular spline, includes a bulk metallic glass-based material.

Ubiquitous long-range antiferromagnetic coupling across the interface between superconducting and ferromagnetic oxides

DOE PAGES

De Luca, G. M.; Ghiringhelli, G.; Perroni, C. A.; ...

2014-11-24

The so-called proximity effect is the manifestation, across an interface, of the systematic competition between magnetic order and superconductivity. This phenomenon has been well documented and understood for conventional superconductors coupled with metallic ferromagnets; however it is still less known for oxide materials, where much higher critical temperatures are offered by copper oxide-based superconductors. In this paper, we show that, even in the absence of direct Cu–O–Mn covalent bonding, the interfacial CuO 2 planes of superconducting La 1.85Sr 0.15CuO 4 thin films develop weak ferromagnetism associated to the charge transfer of spin-polarised electrons from the La 0.66Sr 0.33MnO 3 ferromagnet.more » Theoretical modelling confirms that this effect is general to all cuprate/manganite heterostructures and the presence of direct bonding only affects the strength of the coupling. Finally, the Dzyaloshinskii–Moriya interaction, also at the origin of the weak ferromagnetism of bulk cuprates, propagates the magnetisation from the interface CuO 2 planes into the superconductor, eventually depressing its critical temperature.« less

Study of Dielectric Behavior and Charge Conduction Mechanism of Poly(Vinyl Alcohol) (PVA)-Copper (Cu) and Gold (Au) Nanocomposites as a Bio-resorbable Material for Organic Electronics

NASA Astrophysics Data System (ADS)

Mahendia, Suman; Goyal, Parveen Kumar; Tomar, Anil Kumar; Chahal, Rishi Pal; Kumar, Shyam

2016-10-01

Poly(vinyl alcohol) (PVA) embedded with varying concentrations of chemically synthesized copper (Cu) and gold (Au) nanoparticles (NPs) were prepared using ex situ sol-gel casting method. The addition of almost the same concentration of CuNPs in PVA improves the conducting properties, while that of AuNPs improves the dielectric nature of composite films. It has been found that addition of AuNPs up to ˜0.4 wt.% concentration enhaneces the capacitive nature due to the formation of small Coulomb tunneling knots as internal capacitors. The dielectric studies suggest the Maxwell-Wagner interfacial polarization as the dominant dielectric relaxation process, whereas the I- V characteristics indicate bulk limited Poole-Frenkel emission at high voltages as the dominant charge transport mechanism operating at room temperature in all specimens. These novel features lead to the conclusion that addition of a small quantity of metal nanoparticles can help tune the properties of PVA for desired applications in bio-compatible polymer-based organic electronic devices.

High-speed electrodeposition of copper-tin-zinc stacks from liquid metal salts for Cu2ZnSnSe4 solar cells.

PubMed

Steichen, Marc; Malaquias, João C; Arasimowicz, Monika; Djemour, Rabie; Brooks, Neil R; Van Meervelt, Luc; Fransaer, Jan; Binnemans, Koen; Dale, Phillip J

2017-01-16

Cu 2 ZnSnSe 4 -based solar cells with 5.5% power conversion efficiency were fabricated from Cu/Sn/Zn stacks electrodeposited from liquid metal salts. These electrolytes allow metal deposition rates one order of magnitude higher than those of other deposition methods.

Deformation behavior, corrosion resistance, and cytotoxicity of Ni-free Zr-based bulk metallic glasses.

PubMed

Liu, L; Qiu, C L; Chen, Q; Chan, K C; Zhang, S M

2008-07-01

Two Ni-free bulk metallic glasses (BMGs) of Zr(60)Nb(5)Cu(22.5)Pd(5)Al(7.5) and Zr(60)Nb(5)Cu(20)Fe(5)Al(10) were successfully prepared by arc-melting and copper mold casting. The thermal stability and crystallization were studied using differential scanning calorimetry. It demonstrates that the two BMGs exhibit very good glass forming ability with a wide supercooled liquid region. A multi-step process of crystallization with a preferential formation of quasicrystals occurred in both BMGs under continuous heating. The deformation behavior of the two BMGs was investigated using quasi-static compression testing. It reveals that the BMGs exhibit not only superior strength but also an extended plasticity. Corrosion behaviors of the BMGs were investigated in phosphate buffered solution by electrochemical polarization. The result shows that the two BMGs exhibit excellent corrosion resistance characterized by low corrosion current densities and wide passive regions. X-ray photoelectron spectroscopy analysis revealed that the passive film formed after anodic polarization was highly enriched in zirconium, niobium, and aluminum oxides. This is attributed to the excellent corrosion resistance. Additionally, the potential cytotoxicity of the two Ni-free BMGs was evaluated through cell culture for 1 week followed by 3-(4,5-Dimethylthiazol-2-yl-)-2,5-diphenyltetrazolium bromide assay and SEM observation. The results indicate that the two Ni-free BMGs exhibit as good biocompatibility as Ti-6Al-4V alloy, and thus show a promising potential for biomedical applications. (c) 2007 Wiley Periodicals, Inc.

New Cu-Free Ti-Based Composites with Residual Amorphous Matrix

PubMed Central

Nicoara, Mircea; Locovei, Cosmin; Șerban, Viorel Aurel; Parthiban, R.; Calin, Mariana; Stoica, Mihai

2016-01-01

Titanium-based bulk metallic glasses (BMGs) are considered to have potential for biomedical applications because they combine favorable mechanical properties and good biocompatibility. Copper represents the most common alloying element, which provides high amorphization capacity, but reports emphasizing cytotoxic effects of this element have risen concerns about possible effects on human health. A new copper-free alloy with atomic composition Ti42Zr10Pd14Ag26Sn8, in which Cu is completely replaced by Ag, was formulated based on Morinaga’s d-electron alloy design theory. Following this theory, the actual amount of alloying elements, which defines the values of covalent bond strength Bo and d-orbital energy Md, situates the newly designed alloy inside the BMG domain. By mean of centrifugal casting, cylindrical rods with diameters between 2 and 5 mm were fabricated from this new alloy. Differential scanning calorimetry (DSC) and X-rays diffraction (XRD), as well as microstructural analyses using optical and scanning electron microscopy (OM/SEM) revealed an interesting structure characterized by liquid phase-separated formation of crystalline Ag, as well as metastable intermetallic phases embedded in residual amorphous phases. PMID:28773455

Effect of implanted Cu/low-density polyethylene nanocomposite on the morphology of endometrium in the mouse.

PubMed

Xia, Xianping; Xie, Changsheng; Zhu, Changhong; Cai, Shuizhou; Yang, Xiangliang

2007-08-01

To investigate the damage of endometrium caused by the implanted Cu/low-density polyethylene (LDPE) nanocomposite and the contraceptive effect of this novel copper-containing intrauterine device material. Experimental animal study. TongJi Medical College of Huazhong University of Science and Technology. Sixty healthy female mice. Twenty mice received no implants, 20 mice received the Cu/LDPE nanocomposite, and 20 mice received bulk copper. Morphologic features of the endometrium, contraceptive effect, and surface condition of the implanted implants. The contraceptive effect of both the Cu/LDPE nanocomposite and bulk copper is 100%, the damage of the endometrium caused by the Cu/LDPE nanocomposite is much less than that caused by bulk copper, and the surface of the implanted Cu/LDPE nanocomposite is much smoother and much softer than that of the implanted bulk copper. The contraceptive effect of the Cu/LDPE nanocomposite is comparable with that of bulk copper, and the damage of the endometrium caused by the Cu/LDPE nanocomposite is much less than that caused by bulk copper. The endometrium injury is related to the surface condition of the implanted intrauterine device material.

Preferential growth of short aligned, metallic-rich single-walled carbon nanotubes from perpendicular layered double hydroxide film.

PubMed

Zhao, Meng-Qiang; Tian, Gui-Li; Zhang, Qiang; Huang, Jia-Qi; Nie, Jing-Qi; Wei, Fei

2012-04-07

Direct bulk growth of single-walled carbon nanotubes (SWCNTs) with required properties, such as diameter, length, and chirality, is the first step to realize their advanced applications in electrical and optical devices, transparent conductive films, and high-performance field-effect transistors. Preferential growth of short aligned, metallic-rich SWCNTs is a great challenge to the carbon nanotube community. We report the bulk preferential growth of short aligned SWCNTs from perpendicular Mo-containing FeMgAl layered double hydroxide (LDH) film by a facile thermal chemical vapor deposition with CH(4) as carbon source. The growth of the short aligned SWCNTs showed a decreased growth velocity with an initial value of 1.9 nm s(-1). Such a low growth velocity made it possible to get aligned SWCNTs shorter than 1 μm with a growth duration less than 15 min. Raman spectra with different excitation wavelengths indicated that the as-grown short aligned SWCNTs showed high selectivity of metallic SWCNTs. Various kinds of materials, such as mica, quartz, Cu foil, and carbon fiber, can serve as the substrates for the growth of perpendicular FeMoMgAl LDH films and also the growth of the short aligned SWCNTs subsequently. These findings highlight the easy route for bulk preferential growth of aligned metallic-rich SWCNTs with well defined length for further bulk characterization and applications. This journal is © The Royal Society of Chemistry 2012

Production of Oxidation-Resistant Cu-Based Nanoparticles by Wire Explosion

PubMed Central

Kawamura, Go; Alvarez, Samuel; Stewart, Ian E.; Catenacci, Matthew; Chen, Zuofeng; Ha, Yoon-Cheol

2015-01-01

The low performance or high cost of commercially available conductive inks limits the advancement of printed electronics. This article studies the explosion of metal wires in aqueous solutions as a simple, low-cost, and environmentally friendly method to prepare metallic nanoparticles consisting of Cu and Cu alloys for use in affordable, highly conductive inks. Addition of 0.2 M ascorbic acid to an aqueous explosion medium prevented the formation of Cu2O shells around Cu nanoparticles, and allowed for the printing of conductive lines directly from these nanoparticles with no post-treatment. Cu alloy nanoparticles were generated from metal wires that were alloyed as purchased, or from two wires of different metals that were twisted together. Cu nanoparticles alloyed with 1% Sn, 5% Ag, 5% Ni and 30% Ni had electrical conductivities similar to Cu but unlike Cu, remained conductive after 24 hrs at 85 °C and 85% RH. PMID:26669447

A new RE + 011 TSIG method for the fabrication of high quality and large size single domain YBCO bulk superconductors

NASA Astrophysics Data System (ADS)

Yang, W. M.; Chen, L. P.; Wang, X. J.

2016-02-01

High quality single domain YBCO bulk superconductors, 20 mm in diameter, have been fabricated using a new top seeded infiltration and growth method (called the RE + 011 TSIG method), with a new solid phase (Y2O3 + xBaCuO2) instead of the conventional Y2BaCuO5 solid phase, x = 0, 0.5, 1.0, 1.2, 1.5, 1.8, 2.0, 2.5, 3.0. The effects of different BaCuO2 contents x on the growth morphology, microstructure, and levitation force have been investigated. The results show that the levitation force of the YBCO bulks first increases and then decreases with increasing x, and reaches maximum levitation forces of about 49.2 N (77 K, 0.5 T, with the traditional liquid phase of YBa2Cu3O y + 3 BaCuO2 + 2 CuO) and 47 N (77.3 K, 0.5 T, with the new liquid phase of Y2O3 + 10 BaCuO2 + 6 CuO) when x = 1.2, which is much higher than that of the samples fabricated with the conventional solid phases (23 N). The average Y2BaCuO5 particle size is about 1 μm, which is much smaller than the 3.4 μm in the samples prepared with the conventional Y2BaCuO5 solid phase; this means that the flux pinning force of the sample can be improved by using the new solid phase. Based on this method, single domain YBCO bulks 40 mm, 59 mm, and 93 mm in diameter have also been fabricated using the TSIG process with the new solid phases (Y2O3 + 1.2BaCuO2). These results indicate that the new TSIG process developed by our lab is a very important and practical method for the fabrication of low cost, large size, and high quality single domain REBCO bulk superconductors.

Comparative study of initial stages of copper immersion deposition on bulk and porous silicon

NASA Astrophysics Data System (ADS)

Bandarenka, Hanna; Prischepa, Sergey L.; Fittipaldi, Rosalba; Vecchione, Antonio; Nenzi, Paolo; Balucani, Marco; Bondarenko, Vitaly

2013-02-01

Initial stages of Cu immersion deposition in the presence of hydrofluoric acid on bulk and porous silicon were studied. Cu was found to deposit both on bulk and porous silicon as a layer of nanoparticles which grew according to the Volmer-Weber mechanism. It was revealed that at the initial stages of immersion deposition, Cu nanoparticles consisted of crystals with a maximum size of 10 nm and inherited the orientation of the original silicon substrate. Deposited Cu nanoparticles were found to be partially oxidized to Cu2O while CuO was not detected for all samples. In contrast to porous silicon, the crystal orientation of the original silicon substrate significantly affected the sizes, density, and oxidation level of Cu nanoparticles deposited on bulk silicon.

Copper and Zinc isotope composition of CR, CB and CH-like meteorites.

NASA Astrophysics Data System (ADS)

Russell, S.; Zhu, X.; Guo, Y.; Mullane, E.; Gounelle, M.; Mason, T.; Coles, B.

2003-04-01

Copper and zinc isotopes have recently been shown to be variable in isotopic composi-tion among terrestrial and extraterrestrial materials [1-3]. For this study, we have se-lected samples (bulk meteorite and chondrule separates) from the CR meteorite clan: Bencubbin (CB), Renazzo (CR2), NWA 801 (CR2), and HaH237 (CH-like). These meteorites were selected because meteorites from this clan have experienced very little alteration since their initial formation [4] and for their extremely high refrac-tory/volatile element ratios. The latter characteristic may allow a test of the correlation observed by [2] between element ratios and Cu isotope composition. Measurements were performed on NHM/IC Micromass Isoprobe and Oxford Nu MC-ICP-MS using techniques described elsewhere [1,5]. Each of the meteorites measured so far for Cu and Zn are isotopically light compared to the terrestrial mantle. This suggests that the terrestrial value may have been altered from the pristine solar system value, or else there were multiple early solar system components. Zinc isotopic com-positions lie on a fractionation line and range from δ66ZnNIST = -1.4±0.1ppm (bulk NWA801) to -1.9±0.1ppm (separated chondrule, NWA 801). Copper isotope compositions vary from δ65CuNIST976 = -1.5±0.1ppm (bulk Renazzo) to -3.1±0.1ppm (separated chondrule, NWA 801). Two chondrules from NWA 801 have differing Cu isotope values (-3.1±0.1 and -2.0±0.1ppm) and both are lighter than the bulk meteorite (-1.9±0.1ppm), suggesting a lack of equilibration with respect to Cu in this meteorite. The light values for the two separated chondrules, compared the bulk meteorite, hints that chondrules may be isotopically lighter than co-existing matrix, metal and sulphides with respect to Cu. The copper isotope compositions are not as isotopically light as expected for the high refractory/volatile element ratio observed in these chondrites. Thus a model to account for the Cu isotopes in chondrites may require greater com-plexity than one involving simple mixing of two primordial components. References: [1] Zhu et al., Chem. Geol. 163,139-149 (2000). [2] Luck et al., GCA 67 143 (2002). [3] Luck et al., MAPS 35 A100 (2000) [4] Krot et al., MAPS 37 1451-1490 (2002) [5] Mason et al. EOS Trans. AGU abstract V21A-0966 82 (2001)

Analysis of total copper, cadmium and lead in refuse-derived fuels (RDF): study on analytical errors using synthetic samples.

PubMed

Skutan, Stefan; Aschenbrenner, Philipp

2012-12-01

Components with extraordinarily high analyte contents, for example copper metal from wires or plastics stabilized with heavy metal compounds, are presumed to be a crucial source of errors in refuse-derived fuel (RDF) analysis. In order to study the error generation of those 'analyte carrier components', synthetic samples spiked with defined amounts of carrier materials were mixed, milled in a high speed rotor mill to particle sizes <1 mm, <0.5 mm and <0.2 mm, respectively, and analyzed repeatedly. Copper (Cu) metal and brass were used as Cu carriers, three kinds of polyvinylchloride (PVC) materials as lead (Pb) and cadmium (Cd) carriers, and paper and polyethylene as bulk components. In most cases, samples <0.2 mm delivered good recovery rates (rec), and low or moderate relative standard deviations (rsd), i.e. metallic Cu 87-91% rec, 14-35% rsd, Cd from flexible PVC yellow 90-92% rec, 8-10% rsd and Pb from rigid PVC 92-96% rec, 3-4% rsd. Cu from brass was overestimated (138-150% rec, 13-42% rsd), Cd from flexible PVC grey underestimated (72-75% rec, 4-7% rsd) in <0.2 mm samples. Samples <0.5 mm and <1 mm spiked with Cu or brass produced errors of up to 220% rsd (<0.5 mm) and 370% rsd (<1 mm). In the case of Pb from rigid PVC, poor recoveries (54-75%) were observed in spite of moderate variations (rsd 11-29%). In conclusion, time-consuming milling to <0.2 mm can reduce variation to acceptable levels, even given the presence of analyte carrier materials. Yet, the sources of systematic errors observed (likely segregation effects) remain uncertain.

Engineering the Ground State of Complex Oxides

NASA Astrophysics Data System (ADS)

Meyers, Derek Joseph

Transition metal oxides featuring strong electron-electron interactions have been at the forefront of condensed matter physics research in the past few decades due to the myriad of novel and exciting phases derived from their competing interactions. Beyond their numerous intriguing properties displayed in the bulk they have also shown to be quite susceptible to externally applied perturbation in various forms. The dominant theme of this work is the exploration of three emerging methods for engineering the ground states of these materials to access both their applicability and their deficiencies. The first of the three methods involves a relatively new set of compounds which adhere to a unique paradigm in chemical doping, a-site ordered perovskites. These compounds are iso-structural, i.e. constant symmetry, despite changing the dopant ions. We find that these materials, featuring Cu at the doped A-site, display the Zhang-Rice state, to varying degrees, found in high temperature superconducting cuprates, with the choice of B-site allowing "self-doping" within the material. Further, we find that within CaCu3Ir 4O12 the Cu gains a localized magnetic moment and leads to the experimentally observed heavy fermion state in the materials, one of only two such non-f-electron heavy fermion materials. Next, epitaxial constraint is used to modify the ground state of the rare-earth nickelates in ultra thin film form. Application of compressive (tensile) strain is found to suppress (maintain) the temperature at which the material goes through a Mott metal-insulator transition. Further, while for EuNiO3 thin films the typical bulk-like magnetic and charge ordering is found to occur, epitaxial strain is found to suppress the charge ordering in NdNiO3 thin films due to pinning to the substrate and the relatively weak tendency to monoclinically distort. Finally, the creation of superlattices of EuNiO3 and LaNiO3 was shown to not only allow the selection of the temperature at which the metal-insulator transition occurs, but through digital control the Ni site symmetry can be artificially broken leading to a previously unseen monoclinic metallic phase. Further, by creating a structure which does or does not match the bulk-like rock salt charge order pattern it was found this transition can be either strongly enhanced or removed entirely.

Investigation of thermally activated deformation in amorphous PMMA and Zr-Cu-Al bulk metallic glasses with broadband nanoindentation creep

Treesearch

J.B. Puthoff; J.E. Jakes; H. Cao; D.S. Stone

2009-01-01

The development of nanoindentation test systems with high data collection speeds has made possible a novel type of indentation creep test: broadband nanoindentation creep (BNC). Using the high density of data points generated and analysis techniques that can model the instantaneous projected indent area at all times during a constant-load indentation experiment, BNC...

Metallomics and NMR-based metabolomics of Chlorella sp. reveal the synergistic role of copper and cadmium in multi-metal toxicity and oxidative stress.

PubMed

Zhang, Wenlin; Tan, Nicole G J; Fu, Baohui; Li, Sam F Y

2015-03-01

Industrial wastewaters often contain high levels of metal mixtures, in which metal mixtures may have synergistic or antagonistic effects on aquatic organisms. A combination of metallomics and nuclear magnetic resonance spectroscopy (NMR)-based metabolomics was employed to understand the consequences of multi-metal systems (Cu, Cd, Pb) on freshwater microalgae. Morphological characterization, cell viability and chlorophyll a determination of metal-spiked Chlorella sp. suggested synergistic effects of Cu and Cd on growth inhibition and toxicity. While Pb has no apparent effect on Chlorella sp. metabolome, a substantial decrease of sucrose, amino acid content and glycerophospholipid precursors in Cu-spiked microalgae revealed Cu-induced oxidative stress. Addition of Cd to Cu-spiked cultures induced more drastic metabolic perturbations, hence we confirmed that Cu and Cd synergistically influenced photosynthesis inhibition, oxidative stress and membrane degradation. Total elemental analysis revealed a significant decrease in K, and an increase in Na, Mg, Zn and Mn concentrations in Cu-spiked cultures. This indicated that Cu is more toxic to Chlorella sp. as compared to Cd or Pb, and the combination of Cu and Cd has a strong synergistic effect on Chlorella sp. oxidative stress induction. Oxidative stress is confirmed by liquid chromatography tandem mass spectrometry analysis, which demonstrated a drastic decrease in the GSH/GSSG ratio solely in Cu-spiked cultures. Interestingly, we observed Cu-facilitated Cd and Pb bioconcentration in Chlorella sp. The absence of phytochelatins and an increment of extracellular polymeric substances (EPS) yields in Cu-spiked cultures suggested that the mode of bioconcentration of Cd and Pb is through adsorption of free metals onto the algal EPS rather than intracellular chelation to phytochelatins.

Influence of indian mustard (Brassica juncea) on rhizosphere soil solution chemistry in long-term contaminated soils: a rhizobox study.

PubMed

Kim, Kwon-Rae; Owens, Gary; Kwon, Soon-lk

2010-01-01

This study investigated the influence of Indian mustard (Brassica juncea) root exudation on soil solution properties (pH, dissolved organic carbon (DOC), metal solubility) in the rhizosphere using a rhizobox. Measurement was conducted following the cultivation of Indian mustard in the rhizobox filled four different types of heavy metal contaminated soils (two alkaline soils and two acidic soils). The growth of Indian mustard resulted in a significant increase (by 0.6 pH units) in rhizosphere soil solution pH of acidic soils and only a slight increase (< 0.1 pH units) in alkaline soils. Furthermore, the DOC concentration increased by 17-156 mg/L in the rhizosphere regardless of soil type and the extent of contamination, demonstrating the exudation of DOC from root. Ion chromatographic determination showed a marked increase in the total dissolved organic acids (OAs) in rhizosphere. While root exudates were observed in all soils, the amount of DOC and OAs in soil solution varied considerably amongst different soils, resulting in significant changes to soil solution metals in the rhizosphere. For example, the soil solution Cd, Cu, Pb, and Zn concentrations increased in the rhizosphere of alkaline soils compared to bulk soil following plant cultivation. In contrast, the soluble concentrations of Cd, Pb, and Zn in acidic soils decreased in rhizosphere soil when compared to bulk soils. Besides the influence of pH and DOC on metal solubility, the increase of heavy metal concentration having high stability constant such as Cu and Pb resulted in a release of Cd and Zn from solid phase to liquid phase.

Superconducting Thin Films for the Enhancement of Superconducting Radio Frequency Accelerator Cavities

NASA Astrophysics Data System (ADS)

Burton, Matthew C.

Bulk niobium (Nb) superconducting radio frequency (SRF) cavities are currently the preferred method for acceleration of charged particles at accelerating facilities around the world. However, bulk Nb cavities have poor thermal conductance, impose material and design restrictions on other components of a particle accelerator, have low reproducibility and are approaching the fundamental material-dependent accelerating field limit of approximately 50MV/m. Since the SRF phenomena occurs at surfaces within a shallow depth of ˜1 microm, a proposed solution to this problem has been to utilize thin film technology to deposit superconducting thin films on the interior of cavities to engineer the active SRF surface in order to achieve cavities with enhanced properties and performance. Two proposed thin film applications for SRF cavities are: 1) Nb thin films coated on bulk cavities made of suitable castable metals (such as copper or aluminum) and 2) multilayer films designed to increase the accelerating gradient and performance of SRF cavities. While Nb thin films on copper (Cu) cavities have been attempted in the past using DC magnetron sputtering (DCMS), such cavities have never performed at the bulk Nb level. However, new energetic condensation techniques for film deposition, such as High Power Impulse Magnetron Sputtering (HiPIMS), offer the opportunity to create suitably thick Nb films with improved density, microstructure and adhesion compared to traditional DCMS. Clearly use of such novel technique requires fundamental studies to assess surface evolution and growth modes during deposition and resulting microstructure and surface morphology and the correlation with RF superconducting properties. Here we present detailed structure-property correlative research studies done on Nb/Cu thin films and NbN- and NbTiN-based multilayers made using HiPIMS and DCMS, respectively.

The Melting Characteristics and Interfacial Reactions of Sn-ball/Sn-3.0Ag-0.5Cu-paste/Cu Joints During Reflow Soldering

NASA Astrophysics Data System (ADS)

Huang, J. Q.; Zhou, M. B.; Zhang, X. P.

2017-03-01

In this work, the melting characteristics and interfacial reactions of Sn-ball/Sn-3.0Ag-0.5Cu-paste/Cu (Sn/SAC305-paste/Cu) structure joints were studied using differential scanning calorimetry, in order to gain a deeper and broader understanding of the interfacial behavior and metallurgical combination among the substrate (under-bump metallization), solder ball and solder paste in a board-level ball grid array (BGA) assembly process, which is often seen as a mixed assembly using solder balls and solder pastes. Results show that at the SAC305 melting temperature of 217°C, neither the SAC305-paste nor the Sn-ball coalesce, while an interfacial reaction occurs between the SAC305-paste and Cu. A slight increase in reflow temperature (from 217°C to 218°C) results in the coalescence of the SAC305-paste with the Sn-ball. The Sn-ball exhibits premelting behavior at reflow temperatures below its melting temperature, and the premelting direction is from the bottom to the top of the Sn-ball. Remarkably, at 227°C, which is nearly 5°C lower than the melting point of pure Sn, the Sn-ball melts completely, resulting from two eutectic reactions, i.e., the reaction between Sn and Cu and that between Sn and Ag. Furthermore, a large amount of bulk Cu6Sn5 phase forms in the solder due to the quick dissolution of Cu substrate when the reflow temperature is increased to 245°C. In addition, the growth of the interfacial Cu6Sn5 layer at the SAC305-paste/Cu interface is controlled mainly by grain boundary diffusion, while the growth of the interfacial Cu3Sn layer is controlled mainly by bulk diffusion.

Meta-omic signatures of microbial metal and nitrogen cycling in marine oxygen minimum zones

PubMed Central

Glass, Jennifer B.; Kretz, Cecilia B.; Ganesh, Sangita; Ranjan, Piyush; Seston, Sherry L.; Buck, Kristen N.; Landing, William M.; Morton, Peter L.; Moffett, James W.; Giovannoni, Stephen J.; Vergin, Kevin L.; Stewart, Frank J.

2015-01-01

Iron (Fe) and copper (Cu) are essential cofactors for microbial metalloenzymes, but little is known about the metalloenyzme inventory of anaerobic marine microbial communities despite their importance to the nitrogen cycle. We compared dissolved O2, NO3−, NO2−, Fe and Cu concentrations with nucleic acid sequences encoding Fe and Cu-binding proteins in 21 metagenomes and 9 metatranscriptomes from Eastern Tropical North and South Pacific oxygen minimum zones and 7 metagenomes from the Bermuda Atlantic Time-series Station. Dissolved Fe concentrations increased sharply at upper oxic-anoxic transition zones, with the highest Fe:Cu molar ratio (1.8) occurring at the anoxic core of the Eastern Tropical North Pacific oxygen minimum zone and matching the predicted maximum ratio based on data from diverse ocean sites. The relative abundance of genes encoding Fe-binding proteins was negatively correlated with O2, driven by significant increases in genes encoding Fe-proteins involved in dissimilatory nitrogen metabolisms under anoxia. Transcripts encoding cytochrome c oxidase, the Fe- and Cu-containing terminal reductase in aerobic respiration, were positively correlated with O2 content. A comparison of the taxonomy of genes encoding Fe- and Cu-binding vs. bulk proteins in OMZs revealed that Planctomycetes represented a higher percentage of Fe genes while Thaumarchaeota represented a higher percentage of Cu genes, particularly at oxyclines. These results are broadly consistent with higher relative abundance of genes encoding Fe-proteins in the genome of a marine planctomycete vs. higher relative abundance of genes encoding Cu-proteins in the genome of a marine thaumarchaeote. These findings highlight the importance of metalloenzymes for microbial processes in oxygen minimum zones and suggest preferential Cu use in oxic habitats with Cu > Fe vs. preferential Fe use in anoxic niches with Fe > Cu. PMID:26441925

Meta-omic signatures of microbial metal and nitrogen cycling in marine oxygen minimum zones.

PubMed

Glass, Jennifer B; Kretz, Cecilia B; Ganesh, Sangita; Ranjan, Piyush; Seston, Sherry L; Buck, Kristen N; Landing, William M; Morton, Peter L; Moffett, James W; Giovannoni, Stephen J; Vergin, Kevin L; Stewart, Frank J

2015-01-01

Iron (Fe) and copper (Cu) are essential cofactors for microbial metalloenzymes, but little is known about the metalloenyzme inventory of anaerobic marine microbial communities despite their importance to the nitrogen cycle. We compared dissolved O2, NO[Formula: see text], NO[Formula: see text], Fe and Cu concentrations with nucleic acid sequences encoding Fe and Cu-binding proteins in 21 metagenomes and 9 metatranscriptomes from Eastern Tropical North and South Pacific oxygen minimum zones and 7 metagenomes from the Bermuda Atlantic Time-series Station. Dissolved Fe concentrations increased sharply at upper oxic-anoxic transition zones, with the highest Fe:Cu molar ratio (1.8) occurring at the anoxic core of the Eastern Tropical North Pacific oxygen minimum zone and matching the predicted maximum ratio based on data from diverse ocean sites. The relative abundance of genes encoding Fe-binding proteins was negatively correlated with O2, driven by significant increases in genes encoding Fe-proteins involved in dissimilatory nitrogen metabolisms under anoxia. Transcripts encoding cytochrome c oxidase, the Fe- and Cu-containing terminal reductase in aerobic respiration, were positively correlated with O2 content. A comparison of the taxonomy of genes encoding Fe- and Cu-binding vs. bulk proteins in OMZs revealed that Planctomycetes represented a higher percentage of Fe genes while Thaumarchaeota represented a higher percentage of Cu genes, particularly at oxyclines. These results are broadly consistent with higher relative abundance of genes encoding Fe-proteins in the genome of a marine planctomycete vs. higher relative abundance of genes encoding Cu-proteins in the genome of a marine thaumarchaeote. These findings highlight the importance of metalloenzymes for microbial processes in oxygen minimum zones and suggest preferential Cu use in oxic habitats with Cu > Fe vs. preferential Fe use in anoxic niches with Fe > Cu.

Beneficial Effect of Post-Deposition Treatment in High-Efficiency Cu(In,Ga)Se2 Solar Cells through Reduced Potential Fluctuations

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

Jensen, Soren A.; Glynn, Stephen; Kanevce, Ana

World-record power conversion efficiencies for Cu(In,Ga)Se2 (CIGS) solar cells have been achieved via a post-deposition treatment with alkaline metals, which increases the open-circuit voltage and fill factor. We explore the role of the potassium fluoride (KF) post-deposition treatment in CIGS by employing energy- and time-resolved photoluminescence spectroscopy and electrical characterization combined with numerical modeling. The bulk carrier lifetime is found to increase with post-deposition treatment from 255 ns to 388 ns, which is the longest charge carrier lifetime reported for CIGS, and within ~40% of the radiative limit. We find evidence that the post-deposition treatment causes a decrease in themore » electronic potential fluctuations. These potential fluctuations have previously been shown to reduce the open-circuit voltage and the device efficiency in CIGS. Additionally, numerical simulations based on the measured carrier lifetimes and mobilities show a diffusion length of ~10 um, which is ~4 times larger than the film thickness. Thus, carrier collection in the bulk is not a limiting factor for device efficiency. By considering differences in doping, bandgap, and potential fluctuations, we present a possible explanation for the voltage difference between KF-treated and untreated samples.« less

The influence of EDDS on the uptake of heavy metals in hydroponically grown sunflowers.

PubMed

Tandy, Susan; Schulin, Rainer; Nowack, Bernd

2006-03-01

Phytoextraction is an environmentally friendly in situ technique for cleaning up metal contaminated land. Unfortunately, efficient metal uptake by remediation plants is often limited by low phytoavailability of the targeted metals. Chelant assisted phytoextraction has been proposed to improve the efficiency of phytoextraction. Phytoremediation involves several subsequent steps: transfer of metals from the bulk soil to the root surfaces, uptake into the roots and translocation to the shoots. Nutrient solution experiments address the latter two steps. In this context we investigated the influence of the biodegradable chelating agent SS-EDDS on uptake of essential (Cu and Zn) and non-essential (Pb) metals by sunflowers from nutrient solution. EDDS was detected in shoots and xylem sap for the first time, proving that it is taken up into the above ground biomass of plants. The essential metals Cu and Zn were decreased in shoots in the presence of EDDS whereas uptake of the non-essential Pb was enhanced. We suggest that in the presence of EDDS all three metals were taken up by the non-selective apoplastic pathway as the EDDS complexes, whereas in the absence of EDDS essential metal uptake was primarily selective along the symplastic pathway. This shows that synthetic chelating agents do not necessarily increase uptake of heavy metals, when soluble concentrations are equal in the presence and absence of chelates.

Continuum-Scale Modeling of Shear Banding in Bulk Metallic Glass-Matrix Composites

NASA Astrophysics Data System (ADS)

Gibbons, Michael

Metallic glasses represent a relatively new class of materials that have demonstrated enormous potential for functional and structural applications due to the unique set of properties attributed to them as a result of the disordered isotropic structure with metallically bonded elements. Amorphous metals benefit from the strong nature of the metallic bonds, but lack the crystallographic structure and polycrystalline nature of traditional metals which unsurprisingly has huge implications on the material properties, as all deformation mechanisms associated with a lattice are suppressed. This results in excellent strength, a high elastic strain limit, exceptional hardness, and improved corrosion and wear resistance. "Bulk" metallic glasses (BMG) represent the amorphous metals which can be produced at the cm length-scale, thus greatly expanding their applicability for structural applications. However, due to the catastrophic nature of the failure produced upon yielding, monolithic metallic glasses are seldomly used for structural applications. Bulk metallic glass-matrix composites (BMGMCs), however, are able to combine the excellent strength, hardness, and elastic strain limit of amorphous metallic glass with a ductile crystalline phase to achieve extraordinary toughness with minimal degradation in strength. In order to explore the mechanical interactions between the amorphous and crystalline phases, a full-field micromechanical model which couples the free-volume based constitutive behavior for the matrix phase with standard rate-dependent crystal plasticity for the dendrites, and its implementation via an elastic-viscoplastic Fast-Fourier Transform (FFT) solver. The model is calibrated to macroscale stress-strain data for Ti-Zr-V-Cu-Be BMGMCs with varying composition and furthermore by comparing the deformation behavior associated with the shear bands predicted by the model, to the artifacts observed from characterization microscopy analysis on the same failed BMGMC tensile specimens in which the macroscopic composite behavior predicted by the model was validated with. The FFT-based deformation modeling is then exercised to study the nature and origin of shear bands in metallic glass composites. Synthetic 3D microstructures were produced using images of real BMGMCs, and then subjected to uniaxial tension deformation simulations. The findings indicate that in BMGMCs, local inhomogeneities in the glass phase are less influential on the mechanical performance than the contrast in individual phase properties and the spatial distribution of the microstructure. Due to the strong contrast in mechanical properties between the phases, highly heterogeneous stress fields develop, contributing to regionally confined free-volume generation, localized flow and softening in the glass. These softened regions can link and plastic flow then rapidly localizes into a thin shear band with planar like geometry. The availability of finely resolved (spatially and temporally) 3D deformation maps allow for the determination of the mechanism corresponding with these macroscopic stick-slip oscillations apparent in the stress-strain curves. In addition to shedding light on the nature of shear banding in bulk metallic glass-matrix composites, this work also demonstrates the feasibility of using a spectral-based continuum-scale model to efficiently predict the microstructure and individual phase properties that lead to new materials, superior to those found using only experimental techniques.

Copper(II)-based metal affinity chromatography for the isolation of the anticancer agent bleomycin from Streptomyces verticillus culture.

PubMed

Gu, Jiesi; Codd, Rachel

2012-10-01

The glycopeptide-based bleomycins are structurally complex natural products produced by Streptomyces verticillus used in combination therapy against testicular and other cancers. Bleomycin has a high affinity towards a range of transition metal ions with the 1:1 Fe(II) complex relevant to its mechanism of action in vivo and the 1:1 Cu(II) complex relevant to its production from culture. The affinity between Cu(II) and bleomycin was the underlying principle for using Cu(II)-based metal affinity chromatography in this work to selectively capture bleomycin from crude S. verticillus culture. A solution of standard bleomycin was retained at a binding capacity of 300 nmol mL(-1) on a 1-mL bed volume of Cu(II)-loaded iminodiacetate (IDA) resin at pH 9 via the formation of the heteroleptic immobilized complex [Cu(IDA)(bleomycin)]. Bleomycin was eluted from the resin at pH 5 as the metal-free ligand under conditions where pK(a) (IDA)

Review: mechanical behavior of metal/ceramic interfaces in nanolayered composites—experiments and modeling

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

Li, Nan; Liu, Xiang-Yang

In this study, recent experimental and modeling studies in nanolayered metal/ceramic composites are reviewed, with focus on the mechanical behaviors of metal/nitrides interfaces. The experimental and modeling studies of the slip systems in bulk TiN are reviewed first. Then, the experimental studies of interfaces, including co-deformation mechanism by micropillar compression tests, in situ TEM straining tests for the dynamic process of the co-deformation, thickness-dependent fracture behavior, and interrelationship among the interfacial bonding, microstructure, and mechanical response, are reviewed for the specific material systems of Al/TiN and Cu/TiN multilayers at nanoscale. The modeling studies reviewed cover first-principles density functional theory-based modeling,more » atomistic molecular dynamics simulations, and mesoscale modeling of nanolayered composites using discrete dislocation dynamics. The phase transformation between zinc-blende and wurtzite AlN phases in Al/AlN multilayers at nanoscale is also reviewed. Finally, a summary and perspective of possible research directions and challenges are given.« less

Review: mechanical behavior of metal/ceramic interfaces in nanolayered composites—experiments and modeling

DOE PAGES

Li, Nan; Liu, Xiang-Yang

2017-11-03

In this study, recent experimental and modeling studies in nanolayered metal/ceramic composites are reviewed, with focus on the mechanical behaviors of metal/nitrides interfaces. The experimental and modeling studies of the slip systems in bulk TiN are reviewed first. Then, the experimental studies of interfaces, including co-deformation mechanism by micropillar compression tests, in situ TEM straining tests for the dynamic process of the co-deformation, thickness-dependent fracture behavior, and interrelationship among the interfacial bonding, microstructure, and mechanical response, are reviewed for the specific material systems of Al/TiN and Cu/TiN multilayers at nanoscale. The modeling studies reviewed cover first-principles density functional theory-based modeling,more » atomistic molecular dynamics simulations, and mesoscale modeling of nanolayered composites using discrete dislocation dynamics. The phase transformation between zinc-blende and wurtzite AlN phases in Al/AlN multilayers at nanoscale is also reviewed. Finally, a summary and perspective of possible research directions and challenges are given.« less

Analysis of the heat capacity of nanoclusters of FCC metals on the example of Al, Ni, Cu, Pd, and Au

NASA Astrophysics Data System (ADS)

Gafner, Yu. Ya.; Gafner, S. L.; Zamulin, I. S.; Redel, L. V.; Baidyshev, V. S.

2015-06-01

The heat capacity of ideal nickel, copper, gold, aluminum, and palladium fcc clusters with diameter of up to 6 nm has been studied in the temperature range of 150-800 K in terms of the molecular-dynamics theory using a tight-binding potential. The heat capacity of individual metallic nanoclusters has been found to exceed that characteristic of the bulk state, but by no more than 16-20%, even in the case of very small clusters. To explain the discrepancy between the simulated data and the experimental results on the compacted metals, aluminum and palladium samples with 80% theoretical density have also been investigated. Based on the simulation results and analysis of the experimental data, it has been established that the increased heat capacity of the compacted nanomaterials does not depend on the enhanced heat capacity of the individual clusters but rather, can be due to either the disordered state of the nanomaterial or a significant content of impurities (mainly, hydrogen).

Atmospheric deposition of trace elements at urban and forest sites in central Poland - Insight into seasonal variability and sources

NASA Astrophysics Data System (ADS)

Siudek, Patrycja; Frankowski, Marcin

2017-12-01

This paper includes the results of chemical composition of bulk deposition samples collected simultaneously at urban (Poznań city) and forest (Jeziory) sites in central Poland, between April 2013 and October 2014. Rainwater samples were analyzed for trace elements (As, Zn, Ni, Pb, Cu, Cr, Cd) and physicochemical parameters. Overall, three metals, i.e. Zn, Pb and Cu were the most abundant anthropogenic constituents of rainwater samples from both locations. In Poznań city, the rainwater concentrations of trace elements did not differ significantly between spring and summer. However, they were elevated and more variable during the cold season (fall and winter), suggesting strong contribution from local high-temperature processes related to coal combustion (commercial and residential sector). In contrast to the urban site, relatively low variability in concentrations was found for Cu, Ni, Zn at the forest site, where direct impact of emission from vehicle traffic and coal-fired combustion (power plants) was much lower. The bulk deposition fluxes of Ni, As, Pb and Zn at this site exhibited a clear trend, with higher values during the cold season (fall and winter) than in spring and summer. At the urban site, the sums of total bulk deposition fluxes of Zn, Cu, Pb, Ni, As, Cr, Cd were as follows: 8460.4, 4209.2, 2247.4, 1882.1, 606.6, 281.6 and 31.4 μg m- 2. In addition, during the winter season, a significantly higher deposition fluxes of Cu and Zn were observed for rain (on average 103.8 and 129.4 μg m- 2, respectively) as compared to snow (19.7 μg Cu m- 2 and 54.1 μg Zn m- 2). This suggests that different deposition pattern of trace elements for rain, mixed and snow was probably the effect of several factors: precipitation type, changes in emission and favorable meteorological situation during rain events.

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

S Gilchrist; A Gates; E Elzinga

The abandoned Phillips sulfide mine in the critical Highlands watershed in New York has been shown to produce strongly acidic mine drainage (AMD) with anomalous metal contaminants in first-order streams that exceeded local water standards by up to several orders of magnitude (Gilchrist et al., 2009). The metal-sulfide-rich tailings also produce contaminated soils with pH < 4, organic matter < 2.5% and trace metals sequestered in soil oxides. A geochemical transect to test worst-case soil contamination showed that Cr, Co and Ni correlated positively with Mn, (r = 0.72, r = 0.89, r = 0.80, respectively), suggesting Mn-oxide sequestration andmore » that Cu and Pb correlated with Fe (r = 0.76, r = 0.83, respectively), suggesting sequestration in goethite. Ubiquitous, yellow coating on the mine wastes, including jarosite and goethite, is a carrier of the metals. Geochemical and {mu}-SXRF analyses determined Cu to be the major soil contaminant, {mu}-SXRF also demonstrated that the heterogeneous nature of the soil chemistry at the micro-meter scale is self-similar to those in the bulk soil samples. Generally metals decreased, with some fluctuations, rapidly downslope through suspension of fines and dissolution in AMD leaving the area of substantial contamination << 0.5 km from the source.« less

Removal of hazardous metals from MSW fly ash--an evaluation of ash leaching methods.

PubMed

Fedje, Karin Karlfeldt; Ekberg, Christian; Skarnemark, Gunnar; Steenari, Britt-Marie

2010-01-15

Incineration is a commonly applied management method for municipal solid waste (MSW). However, significant amounts of potentially hazardous metal species are present in the resulting ash, and these may be leached into the environment. A common idea for cleaning the ash is to use enhanced leaching with strong mineral acids. However, due to the alkalinity of the ash, large amounts of acid are needed and this is a drawback. Therefore, this work was undertaken in order to investigate some alternative leaching media (EDTA, ammonium nitrate, ammonium chloride and a number of organic acids) and to compare them with the usual mineral acids and water. All leaching methods gave a significant increase in ash specific surface area due to removal of soluble bulk (matrix) compounds, such as CaCO(3) and alkali metal chlorides. The use of mineral acids and EDTA mobilised many elements, especially Cu, Zn and Pb, whereas the organic acids generally were not very effective as leaching agents for metals. Leaching using NH(4)NO(3) was especially effective for the release of Cu. The results show that washing of MSW filter ash with alternative leaching agents is a possible way to remove hazardous metals from MSW fly ash.

Microalloying Ultrafine Grained Al Alloys with Enhanced Ductility

PubMed Central

Jiang, L.; Li, J. K.; Cheng, P. M.; Liu, G.; Wang, R. H.; Chen, B. A.; Zhang, J. Y.; Sun, J.; Yang, M. X.; Yang, G.

2014-01-01

Bulk ultrafine grained (UFG)/nanocrystal metals possess exceptional strength but normally poor ductility and thermal stability, which hinder their practical applications especially in high-temperature environments. Through microalloying strategy that enables the control of grains and precipitations in nanostructured regime, here we design and successfully produce a highly microstructure-stable UFG Al-Cu-Sc alloy with ~275% increment in ductility and simultaneously ~50% enhancement in yield strength compared with its Sc-free counterpart. Although the precipitations in UFG alloys are usually preferentially occurred at grain boundaries even at room temperature, minor Sc addition into the UFG Al-Cu alloys is found to effectively stabilize the as-processed microstructure, strongly suppress the θ-Al2Cu phase precipitation at grain boundary, and remarkably promote the θ′-Al2Cu nanoparticles dispersed in the grain interior in artificial aging. A similar microalloying strategy is expected to be equally effective for other UFG heat-treatable alloys. PMID:24398915

The importance of biomass net uptake for a trace metal budget in a forest stand in north-eastern France.

PubMed

Gandois, L; Nicolas, M; VanderHeijden, G; Probst, A

2010-11-01

The trace metal (TM: Cd, Cu, Ni, Pb and Zn) budget (stocks and annual fluxes) was evaluated in a forest stand (silver fir, Abies alba Miller) in north-eastern France. Trace metal concentrations were measured in different tree compartments in order to assess TM partitioning and dynamics in the trees. Inputs included bulk deposition, estimated dry deposition and weathering. Outputs were leaching and biomass exportation. Atmospheric deposition was the main input flux. The estimated dry deposition accounted for about 40% of the total trace metal deposition. The relative importance of leaching (estimated by a lumped parameter water balance model, BILJOU) and net biomass uptake (harvesting) for ecosystem exportation depended on the element. Trace metal distribution between tree compartments (stem wood and bark, branches and needles) indicated that Pb was mainly stored in the stem, whereas Zn and Ni, and to a lesser extent Cd and Cu, were translocated to aerial parts of the trees and cycled in the ecosystem. For Zn and Ni, leaching was the main output flux (>95% of the total output) and the plot budget (input-output) was negative, whereas for Pb the biomass net exportation represented 60% of the outputs and the budget was balanced. Cadmium and Cu had intermediate behaviours, with 18% and 30% of the total output relative to biomass exportation, respectively, and the budgets were negative. The net uptake by biomass was particularly important for Pb budgets, less so for Cd and Cu and not very important for Zn and Ni in such forest stands. Copyright © 2010 Elsevier B.V. All rights reserved.

Preparation and Thermoelectric Properties of Cu2Se Hot-Pressed from Hydrothermal Synthesis Nanopowders

NASA Astrophysics Data System (ADS)

Gao, F.; Leng, S. L.; Zhu, Z.; Li, X. J.; Hu, X.; Song, H. Z.

2018-04-01

The nanopowders of Cu2Se were synthesized by the hydrothermal method, and then were hot-pressed into bulk pellets. The effects of different preparation conditions on the structure and thermoelectric properties of Cu2Se nanocrystalline bulk alloys were investigated. The resistivity and Seebeck coefficients increase with the increment of hot-pressing temperatures, while they decrease with the increment of hot-pressing time, except for the Seebeck coefficients of the sample hot-pressed for 30 min. Based on the power factors and dimensionless thermoelectric figure-of-merit ( ZT) values, the optimum hot-pressing parameters are 700°C and 30 min.

Soldering-induced Cu diffusion and intermetallic compound formation between Ni/Cu under bump metallization and SnPb flip-chip solder bumps

NASA Astrophysics Data System (ADS)

Huang, Chien-Sheng; Jang, Guh-Yaw; Duh, Jenq-Gong

2004-04-01

Nickel-based under bump metallization (UBM) has been widely used as a diffusion barrier to prevent the rapid reaction between the Cu conductor and Sn-based solders. In this study, joints with and without solder after heat treatments were employed to evaluate the diffusion behavior of Cu in the 63Sn-37Pb/Ni/Cu/Ti/Si3N4/Si multilayer structure. The atomic flux of Cu diffused through Ni was evaluated from the concentration profiles of Cu in solder joints. During reflow, the atomic flux of Cu was on the order of 1015-1016 atoms/cm2s. However, in the assembly without solder, no Cu was detected on the surface of Ni even after ten cycles of reflow. The diffusion behavior of Cu during heat treatments was studied, and the soldering-process-induced Cu diffusion through Ni metallization was characterized. In addition, the effect of Cu content in the solder near the solder/intermetallic compound (IMC) interface on interfacial reactions between the solder and the Ni/Cu UBM was also discussed. It is evident that the (Cu,Ni)6Sn5 IMC might form as the concentration of Cu in the Sn-Cu-Ni alloy exceeds 0.6 wt.%.

N4H9Cu7S4: a hydrazinium-based salt with a layered Cu7S4- framework.

PubMed

Mitzi, David B

2007-02-05

Crystals of a hydrazinium-based copper(I) sulfide salt, N4H9Cu7S4 (1), have been isolated by an ambient temperature solution-based process. In contrast to previously reported hydrazinium salts of main-group metal chalcogenides, which consist of isolated metal chalcogenide anions, and ACu7S4 (A = NH4+, Rb+, Tl+, K+), which contains a more three-dimensional Cu7S4- framework with partial Cu-site occupancy, the structure of 1 [P21, a = 6.8621(4) A, b = 7.9851(4) A, c = 10.0983(5) A, beta = 99.360(1) degrees , Z = 2] is composed of extended two-dimensional Cu7S4- slabs with full Cu-site occupancy. The Cu7S4- slabs are separated by a mixture of hydrazinium and hydrazine moieties. Thermal decomposition of 1 into copper(I) sulfide proceeds at a significantly lower temperature than that observed for analogous hydrazinium salts of previously considered metal chalcogenides, completing the transition at temperatures as low as 120 degrees C. Solutions of 1 may be used in the solution deposition of a range of Cu-containing chalcogenide films.

Distribution and relationships of selected trace metals in molluscs and associated sediments from the Gulf of Aden, Yemen.

PubMed

Szefer, P; Ali, A A; Ba-Haroon, A A; Rajeh, A A; Gełdon, J; Nabrzyski, M

1999-09-01

Concentrations of Cd, Pb, Zn, Cu, Ni, Co, Cr, Mn and Fe in the soft tissue of Turbo coronatus, Acanthopleura haddoni, Ostrea cucullata and Pitar sp., as well as in associated surface sediments (bulk and bioavailable metal concentrations) from the Gulf of Aden, Yemen, were determined by atomic absorption spectrophotometry method. Large differences between size-classes of molluscs in metal concentrations were recorded. Significant spatial differences in metal concentrations in both the soft tissue of the molluscs and associated sediments studied were mostly identified. Statistically significant correlations (p<0.01) between concentrations of selected metals were observed. A slope of the linear regression is significantly higher than unity for Fe (9.91) and Cd (3.45) in A. haddoni and for Ni (4.15) in T. coronatus, suggesting that the bioavailability of these metals is disproportionally increased with a degree of enrichment of the sediments in Fe, Cd and Ni, respectively. A slope constant approximating to unity (1.14) for Cu in A. haddoni relative to its concentration in sediment extract implies that bioavailability of this metal proportionally increased with growing concentrations of its labile forms in the associated sediment. The degree of contamination of Gulf of Aden waters by the metals studied is discussed and the potential ability of molluscs, especially A. haddoni and T. coronatus, as biomonitors of metallic pollutants is postulated.

Ceiling (attic) dust: a "museum" of contamination and potential hazard.

PubMed

Davis, Jeffrey J; Gulson, Brian L

2005-10-01

Ceiling or attic dusts provide an indirect measure of air pollution integrated over varying time periods. We undertook an investigation into the particle-size distributions and sources and exposure pathways of metals in ceiling dusts from 38 houses in the city of Sydney, Australia. The houses ranged in age from 4 to 106 years and were grouped into three settings: industrial, semi-industrial, and non-industrial. The main roof types were terracotta tile (n=23), cement tile (n=8), and corrugated iron (n=4), with two slate and one asbestos. Soils and rocks from the Sydney area were also analyzed to provide "background" values and allow the estimation of enrichment factors. The bulk of the dusts contained particles derived from soil of crustal origin and organic plant material, with an anthropogenic component estimated at up to 25%. Particle sizes from selected dust samples showed a bimodal distribution, and the volumes of fine dusts were 50% <63 microm, 30%<38 microm, and 7%<10 microm; the highest metal concentrations were in the finest fractions. The geometric mean concentrations of important anthropogenic-derived metals from the industrial setting were 17294 microg/g Zn, 1660 microg/g Pb, 111 microg/g Cr, 261 microg/g Cu, and 26 microg/g As. The metals Cd, Cu, Pb, Sb, and Zn were consistently higher in the industrial settings than in the other settings. Median regression analyses showed that there were significant differences in the urban setting for the metals Cd, Co, Ni, Pb, and Zn. Enrichment factors for metals in the dust from the industrial site houses compared with background soils and rocks from the Sydney area were As, x 5; Cr, x2; Co, x3; Cu, x 12; Pb, x10; Sb, x 26; and Zn, 596. For the three roof types of terracotta tile, cement, and iron, median regression analyses showed that there were no significant effects with respect to age. Median regression analyses for terracotta tile, cement tile, and corrugated iron roofs showed a "roof" effect for Cu and V. Significant correlations (P0.03) were observed between most of the metals As-Cd-Cu-Pb-Sb-Zn, especially from the industrial settings. Pathways of dust exposure in this study are classified as being passive or active based upon the probable route of dust infiltration. Ceiling dusts pose a probable health hazard if the dust is disturbed and allowed to plume within the living areas of a dwelling, thereby exposing the occupants, especially children, to elevated levels of metals and fine particulates. Modeling shows that exposure to the elevated levels of Pb in dust could give rise to blood lead concentrations exceeding current guidelines for the industrial and semi-industrial areas.

Geochemistry and economic potential of massive sulfide deposits from the eastern Pacific Ocean

USGS Publications Warehouse

Bischoff, James L.; Rosenbauer, R.J.; Aruscavage, P. J.; Baedecker, P.A.; Crock, J.G.

1983-01-01

Bulk chemical analyses are performed for major and minor elements using a variety of techniques on a suite of 9 samples of sea floor massive sulfide deposits from 21?N EPR, Juan de Fuca Ridge and Galapagos Rift. Results indicate that deposits at 21?N and Juan de Fuca are very similar despite a geographic separation of 2300 km and are composed primarily of Zn, Fe, and S, with important minor concentrations of Ag, As, Cd and Ge. The Galapagos Rift massive sulfide is primarily Fe, Cu and S and with important minor contents of only Co and Mo. Au is low, ranging from below detection up to 0.17 ppm. Pt group metals are very low, and average about 0.001 ppm. Consideration of enrichment factors and relative metal abundance suggests that MORB is a sufficient source for all the metals enriched in the sea floor deposits. The economically important metals for the 21?N and Juan de Fuca deposits are primarily Zn and Ag, (97%) with potential by-products of Cu, Cd and possibly, Ge. For the Galapagos Rift, the primary value is with Cu (86%) with potential by-products of Co and Mo. The Galapagos Rift deposit is similar to, but contains about twice the Cu content, of typical ore from the Skouriotisa mine of the Troodos complex of Cyprus. The grade of the 21?N/Juan de Fuca deposits is 4 times greater than that of the Galapagos Rift and about twice that of prime deep-sea manganese nodules.

[Evaluation on environmental quality of heavy metals in soils and vegetables based on geostatistics and GIS].

PubMed

Xie, Zheng-miao; Li, Jing; Wang, Bi-ling; Chen, Jian-jun

2006-10-01

Contents of heavy metals (Pb, Zn, Cd, Cu) in soils and vegetables from Dongguan town in Shangyu city, China were studied using geostatistical analysis and GIS technique to evaluate environmental quality. Based on the evaluation criteria, the distribution of the spatial variability of heavy metals in soil-vegetable system was mapped and analyzed. The results showed that the distribution of soil heavy metals in a large number of soil samples in Dongguan town was asymmetric. The contents of Zn and Cu were lower than those of Cd and Pb. The concentrations distribution of Pb, Zn, Cd and Cu in soils and vegetables were different in spatial variability. There was a close relationship between total and available contents of heavy metals in soil. The contents of Pb and Cd in green vegetables were higher than those of Zn and Cu and exceeded the national sanitation standards for vegetables.

Trace metals in estuaries in the Russian Far East and China: case studies from the Amur River and the Changjiang.

PubMed

Shulkin, Vladimir; Zhang, Jing

2014-11-15

This paper compares the distributions of dissolved and particulate forms of Mn, Fe, Ni, Cu, Zn, Cd, and Pb in the estuaries of the largest rivers in East Asia: the Amur River and the Changjiang (Yangtze River). High suspended solid concentrations, elevated pH, and relatively low dissolved trace metal concentrations are characteristics of the Changjiang. Elevated dissolved Fe and Mn concentrations, neutral pH, and relatively low suspended solid concentrations are characteristics of the Amur River. The transfer of dissolved Fe to suspended forms is typical in the Amur River estuary, though Cd and Mn tend to mobilize to solution, and Cu and Ni are diluted in the estuarine system. Metal concentrations in suspended matter in the Amur River estuary are controlled by the ratio of terrigenous riverine material, enriched in Al and Fe, and marine biogenic particles, enriched in Cu, Mn, Cd, and in some cases Ni. The increase in dissolved forms of Mn, Fe, Ni, Cu, Cd, and Pb compared with river end-member is unique to the Changjiang estuary. Particle-solution interactions are not reflected in bulk suspended-solid metal concentrations in the Changjiang estuary due to the dominance of particulate forms of these metals. Cd is an exception in the Changjiang estuary, where the increase in dissolved Cd is of comparable magnitude to the decrease in particulate Cd. Despite runoff in the Amur River being lower than that in the Changjiang, the fluxes of dissolved Mn, Zn and Fe in the Amur River exceed those in the Changjiang. Dissolved Ni, and Cd fluxes are near equal in both estuaries, but dissolved Cu is lower in the Amur River estuary. The hydrological and physico-chemical river characteristics are dominated at the assessment of river influence on the adjoining coastal sea areas despite differences in estuarine processes. Copyright © 2014 Elsevier B.V. All rights reserved.

Transportation and Bioavailability of Copper and Zinc in a Storm Water Retention Pond

NASA Astrophysics Data System (ADS)

Camponelli, K.; Casey, R. E.; Wright, M. E.; Lev, S. M.; Landa, E. R.

2006-05-01

Highway runoff has been identified as a non-point source of metals to storm water retention ponds. Zinc and copper are major components of tires and brake pads, respectively. As these automobile parts degrade, they deposit particulates onto the roadway surface. During a storm event, these metal containing particulates are washed into a storm water retention pond where they can then accumulate over time. These metals may be available to organisms inhabiting the pond and surrounding areas. This study focuses on tracking the metals from their deposition on the roadway to their transport and accumulation into a retention pond. The retention pond is located in Owings Mills, MD and collects runoff from an adjacent four lane highway. Pond sediments, background soils, road dust samples, and storm events were collected and analyzed. Copper and zinc concentrations in the pond sediments are higher than local background soils indicating that the pond is storing anthropogenically derived metals. Storm event samples also reveal elevated levels of copper and zinc transported through runoff, along with a large concentration of total suspended solids. After looking at the particulate and dissolved fractions of both metals in the runoff, the majority of the Zn and Cu are in the particulate fraction. Changes in TSS are proportional with changes in particulate bound Zn, indicating that the solid particulates that are entering into the pond are a major contributor of the total metal loading. Sequential extractions carried out on the road dust show that the majority of zinc is extracted in the second and third fractions and could become available to organisms in the pond. There is a small amount of Cu that is being released in the more available stages of the procedure; however the bulk of the Cu is seen in the more recalcitrant steps. In the pond sediments however, both Cu and Zn are only being released from the sediments in the later steps and are most likely not highly available.

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

Zhang, Pei; Maldonis, Jason J.; Besser, M. F.

Fluctuation electron microscopy experiments combined with hybrid reverse Monte Carlo modeling show a correlation between medium-range structure at the nanometer scale and glass forming ability in two Zr–Cu–Al bulk metallic glass (BMG) alloys. Both Zr 50Cu 35Al 15 and Zr 50Cu 45Al 5 exhibit two nanoscale structure types, one icosahedral and the other more crystal-like. In Zr 50Cu 35Al 15, the poorer glass former, the crystal-like structure is more stable under annealing below the glass transition temperature, T g, than in Zr 50Cu 45Al 5. Variable resolution fluctuation microscopy of the MRO clusters show that in Zr 50Cu 35Al 15more » on sub-Tg annealing, the crystal-like clusters shrink even as they grow more ordered, while icosahedral-like clusters grow. Furthermore, the results suggest that achieving better glass forming ability in this alloy system may depend more on destabilizing crystal-like structures than enhancing non-crystalline structures.« less

Thermally activated diffusion of copper into amorphous carbon

DOE PAGES

Appy, David; Wallingford, Mark; Jing, Dapeng; ...

2017-07-11

Using x-ray photoelectron spectroscopy, the authors characterize the thermally activated changes that occur when Cu is deposited on amorphous carbon supported on Si at 300 K, then heated to 800 K. The authors compare data for Cu on the basal plane of graphite with pinning defects, where scanning tunneling microscopy reveals that coarsening is the main process in this temperature range. Coarsening begins at 500–600 K and causes moderate attenuation of the Cu photoelectron signal. For Cu on amorphous carbon, heating to 800 K causes Cu to diffuse into the bulk of the film, based on the strong attenuation ofmore » the Cu signal. Diffusion into the bulk of the amorphous carbon film is confirmed by changes in the shape of the Cu 2 p inelastic tail, and by comparison of attenuation between Cu 2 p and Cu 3 p lines. The magnitude of the photoelectron signal attenuation is compatible with Cu distributed homogeneously throughout the amorphous carbon film, and is not compatible with Cu at or below the C–Si interface under the conditions of our experiments. As a result, desorption is not significant at temperatures up to 800 K.« less

Increasing strength and conductivity of Cu alloy through abnormal plastic deformation of an intermetallic compound

PubMed Central

Han, Seung Zeon; Lim, Sung Hwan; Kim, Sangshik; Lee, Jehyun; Goto, Masahiro; Kim, Hyung Giun; Han, Byungchan; Kim, Kwang Ho

2016-01-01

The precipitation strengthening of Cu alloys inevitably accompanies lowering of their electric conductivity and ductility. We produced bulk Cu alloys arrayed with nanofibers of stiff intermetallic compound through a precipitation mechanism using conventional casting and heat treatment processes. We then successfully elongated these arrays of nanofibers in the bulk Cu alloys to 400% of original length without breakage at room temperature using conventional rolling process. By inducing such an one-directional array of nanofibers of intermetallic compound from the uniform distribution of fine precipitates in the bulk Cu alloys, the trade-off between strength and conductivity and between strength and ductility could be significantly reduced. We observed a simultaneous increase in electrical conductivity by 1.3 times and also tensile strength by 1.3 times in this Cu alloy bulk compared to the conventional Cu alloys. PMID:27488621

Investigation of noble metal substrates and buffer layers for BiSrCaCuO thin films

NASA Astrophysics Data System (ADS)

Matthiesen, M. M.; Rubin, L. M.; Williams, K. E.; Rudman, D. A.

Noble metal buffer layers and substrates for Bi2Sr2CaCu2O8 (BSCCO) films were investigated using bulk ceramic processing and thin-film techniques. Highly oriented, superconducting BSCCO films were fabricated on polycrystalline Ag substrates and on Ag/MgO and Ag/YSZ structures. Such films could not be produced on Au or Pt substrates under any annealing conditions. In addition, superconducting BSCCO films could not be produced on Ag/Al2O3, Ag/SiO2/Si, or Ag/(Haynes 230 alloy) structures using high annealing temperatures (870 C). However, oriented although poorly connected, superconducting BSCCO films were fabricated on Ag/Al2O3 structures by using lower annealing temperatures (820 C). Once lower processing temperatures are optimized, Ag may be usable as a buffer layer for BSCCO films.

A structural model for surface-enhanced stabilization in some metallic glass formers

NASA Astrophysics Data System (ADS)

Levchenko, Elena V.; Evteev, Alexander V.; Yavari, Alain R.; Louzguine-Luzgin, Dmitri V.; Belova, Irina V.; Murch, Graeme E.

2013-01-01

A structural model for surface-enhanced stabilization in some metallic glass formers is proposed. In this model, the alloy surface structure is represented by five-layer Kagomé-net-based lateral ordering. Such surface structure has intrinsic abilities to stabilize icosahedral-like short-range order in the bulk, acting as 'a cloak of liquidity'. In particular, recent experimental observations of surface-induced lateral ordering and a very high glass forming ability of the liquid alloy Au49Ag5.5Pd2.3Cu26.9Si16.3 can be united using this structural model. This model may be useful for the interpretation of surface structure of other liquid alloys with a high glass forming ability. In addition, it suggests the possibility of guiding the design of the surface coating of solid containers for the stabilization of undercooled liquids.

Transferable Force Field for Metal–Organic Frameworks from First-Principles: BTW-FF

PubMed Central

2014-01-01

We present an ab-initio derived force field to describe the structural and mechanical properties of metal–organic frameworks (or coordination polymers). The aim is a transferable interatomic potential that can be applied to MOFs regardless of metal or ligand identity. The initial parametrization set includes MOF-5, IRMOF-10, IRMOF-14, UiO-66, UiO-67, and HKUST-1. The force field describes the periodic crystal and considers effective atomic charges based on topological analysis of the Bloch states of the extended materials. Transferable potentials were developed for the four organic ligands comprising the test set and for the associated Cu, Zn, and Zr metal nodes. The predicted materials properties, including bulk moduli and vibrational frequencies, are in agreement with explicit density functional theory calculations. The modal heat capacity and lattice thermal expansion are also predicted. PMID:25574157

Shear transformation zone activation during deformation in bulk metallic glasses characterized using a new indentation creep technique

Treesearch

J.B. Puthoff; H.B. Cao; Joseph E. Jakes; P.M. Voyles; D.S. Stone

2009-01-01

We have developed a novel type of nanoindentation creep experiment, called broadband nanoindentation creep (BNC), and used it to characterize the thermal activation of shear transformation zones (STZs) in three BMGs in the Zr-Cu-Al system. Using BNC, material hardness can be determined across a wide range of strain rates (10–4 to 10 s–...

Bulk Nanocrystalline Metals: Review of the Current State of the Art and Future Opportunities for Copper and Copper Alloys

DTIC Science & Technology

2014-05-13

nanocrystalline materials using mechanical alloying, the alloy development and synthesis process for stabilizing these materials at elevated temperatures, and...the physical and mechanical properties of nanocrystalline materials with a focus throughout on nanocrystalline copper and a nanocrystalline Cu-Ta...approaches as well as experimental results for grain growth, grain boundary processes, and deformation mechanisms in nanocrystalline copper are

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

Nelson, Y.M.; DiSante, C.J.; Lion, L.W.

Toxic trace metals have been implicated as a potential cause of recent flamingo kills at Lake Nakuru, Kenya. Chromium (Cr), copper (Cu), lead (Pb), and zinc (Zn) have accumulated in the lake sediments as a result of unregulated discharges and because this alkaline lake has no natural outlet. Lesser flamingos (Phoeniconaias minor) at Lake Nakuru feed predominantly on the cyanobacterium Spirulina platensis, and because of their filter-feeding mechanism, they are susceptible to exposure to particle-bound metals. Trace metal adsorption isotherms to lake sediments and S. platensis were obtained under simulated lake conditions, and a mathematical model was developed to predictmore » metal exposure via filter feeding based on predicted trace metal phase distribution. Metal adsorption to suspended solids followed the trend Pb {much_gt} Zn > Cr > Cu, and isotherms were linear up to 60 {micro}g/L. Adsorption to S. platensis cells followed the trend Pb {much_gt} Zn > Cu > Cr and fit Langmuir isotherms for Cr, Cu and Zn and a linear isotherm for Pb. Predicted phase distributions indicated that Cr and Pb in Lake Nakuru are predominantly associated with suspended solids, whereas Cu and Zn are distributed more evenly between the dissolved phase and particulate phases of both S. platensis and suspended solids. Based on established flamingo feeding rates and particle size selection, predicted Cr and Pb exposure occurs predominantly through ingestion of suspended solids, whereas Cu and Zn exposure occurs through ingestion of both suspended solids and S. platensis. For the lake conditions at the time of sampling, predicted ingestion rates based on measured metal concentrations in lake suspended solids were 0.71, 6.2, 0.81, and 13 mg/kg-d for Cr, Cu, Pb, and Zn, respectively.« less

Zinc and copper behaviour at the soil-river interface: New insights by Zn and Cu isotopes in the organic-rich Rio Negro basin

NASA Astrophysics Data System (ADS)

Guinoiseau, Damien; Gélabert, Alexandre; Allard, Thierry; Louvat, Pascale; Moreira-Turcq, Patricia; Benedetti, Marc F.

2017-09-01

The complex behaviour of Zn and Cu at the soil-river interface was investigated in soil and riverine water samples from the Rio Negro basin, a secondary tributary of the Rio Amazonas, using their stable isotope compositions. This acidic and organic river drains two types of intensely weathered terrains: podzols in its upstream part, and lateritic soils downstream. Bulk soil particles, suspended particulate matter (SPM) as well as colloidal fractions were sampled across the whole basin during low and high water stages. In the basin, Zn and Cu are mostly exported from lateritic soils and transported by organic colloids where significant losses are observed in the downstream part of the river. The use of δ66Zn and δ65Cu measurements reveals distinct stories for these two metals in suspended sediments and colloids. In the colloids, the constant δ66Zncoll across the basin is induced by the same weak association mode between Zn and organic ligands, regardless of the origin of the water. By contrast, in SPM, the speciation of Zn and thus δ66ZnSPM differ according to the type of drained soils. Zn is associated with organic complexes in particles exported with water draining podzol whereas Zn2+ is incorporated in the structure of the remaining kaolinite clays in lateritic output. The stronger reactivity of Cu than Zn with organic ligands induces its complete complexation. Copper is controlled by refractory particulate organic matter (POM) and by reactive colloidal organic matter; the latter being enriched in 65Cu due to stronger binding interactions than in POM. While the Cu content remains constant in the upstream part of the Rio Negro, downstream, the decrease of SPM and colloidal Cu fluxes is associated with a constant δ65CuSPM and with an increase of δ65Cucoll at the Rio Negro outlet. Geochemical mass balance modelling, based on SPM, Cu and Zn fluxes in SPM and their associated isotopic signatures, confirms distinct host phases for Zn and Cu, and identifies the most probable places where losses of these two metals occur. In colloids, the observed Cu isotope fractionation (from 0.24 to 0.45‰) superimposed on the significant Cucoll loss is assumed to result from a new isotopic equilibrium in a low velocity and high productivity zone: Cu-rich colloids enriched in 63Cu aggregate and settle down, whereas the remaining heavy Cu is partially complexed on strong organic ligands secreted by phytoplankton, forming new Cu-colloids.

Analysis of scattering lengths in Co/Cu/Co and Co/Cu/Co/Cu spin-valves using a Ru barrier

NASA Astrophysics Data System (ADS)

Strijkers, G. J.; Willekens, M. M. H.; Swagten, H. J. M.; de Jonge, W. J. M.

1996-10-01

We use uncoupled Co/Cu/Co and Co/Cu/Co/Cu spin-valve structures with a Ru barrier shifted through the top Co and Cu layer, respectively, to measure the longest of the electron mean free paths in Co and Cu as originally suggested by Parkin. From semiclassical transport calculations and careful analysis of the magnetoresistance data we conclude that the exponential behavior of ΔG is uniquely related to the longest of the Co and Cu mean free paths under the condition of effective spin-dependent filtering at the interfaces or in the bulk of the Co. In this regime we have compared λlong in Co and Cu with bulk conductivities (~λshort+λlong), yielding no strong evidence for bulk spin-dependent scattering in Co.

Large H2 storage capacity of a new polyhedron-based metal-organic framework with high thermal and hygroscopic stability.

PubMed

Hong, Seunghee; Oh, Minhak; Park, Mira; Yoon, Ji Woong; Chang, Jong-San; Lah, Myoung Soo

2009-09-28

Two metal-organic frameworks (MOFs) based on metal-organic cuboctahedra were prepared using a rigid C3 symmetric ligand, where Zn polyhedron-based MOF (PMOF-2(Zn)) did not show any significant gas sorption behavior, whereas the isostructural Cu polyhedron-based MOF (PMOF-2(Cu)) showed a large surface area of approximately 4180 m2 g(-1), high hydrothermal stability, and very promising H2 sorption properties.

First-principles study of native defects in bulk Sm2CuO4 and its (001) surface structure

NASA Astrophysics Data System (ADS)

Zheng, Fubao; Zhang, Qinfang; Meng, Qiangqiang; Wang, Baolin; Song, Fengqi; Yunoki, Seiji; Wang, Guanghou

2018-04-01

Using the first-principles calculations based on the density functional theory, we have studied the bulk defect formation and surface structures of Sm2CuO4. To ensure the accuracy of calculations, the spin order of Cu atoms is rechecked and it is the well-known nearest-neighbor antiferromagnetic ground state, which can be attributed to the hole-mediated superexchange through the strong pdσ hybridization interaction between Cu dx2-y2 electron and the neighboring oxygen px (or py) electron. Under each present experimental condition, the Sm vacancy has a very high formation energy and is unlikely to be stable. The Cu vacancy is a shallow acceptor, which is preferred under O-rich conditions, whereas the O vacancy is a donor and energetically favorable under O-poor conditions. To construct its (001) surface structure, CuOO, CuO, and Cu terminated surfaces are found to be most favorable under different experimental conditions. The stable surface structures are always accompanied by significant surface atomic reconstructions and electron charge redistribution, which are intimately correlated to each other.

Microstructure and Mechanical Properties of Stainless Steel/Brass Joints Brazed by Sn-Electroplated Ag Brazing Filler Metals

NASA Astrophysics Data System (ADS)

Wang, Xingxing; Peng, Jin; Cui, Datian

2018-05-01

To develop a high-Sn-content AgCuZnSn brazing filler metal, the BAg50CuZn was used as the base filler metal and a Sn layer was electroplated upon it. Then, the 304 stainless steel and the H62 brass were induction-brazed with the Sn-plated brazing filler metals. The microstructures of the joints were examined with an optical microscope, a scanning electron microscope and an x-ray diffractometer. The corresponding mechanical properties were obtained with a universal tensile testing machine. The results indicated that the induction brazed joints consisted of the Ag phase, the Cu phase and the CuZn phase. When the content of Sn in the Sn-plated Ag brazing filler metal was 6.0 or 7.2 wt.%, the Cu5Zn8, the Cu41Sn11 and the Ag3Sn phases appeared in the brazed joint. The tensile strength of the joints brazed with the Sn-plated filler metal was higher compared to the joints with the base filler metal. When the content of Sn was 6.0 wt.%, the highest tensile strength of the joint reached to 395 MPa. The joint fractures presented a brittle mode, mixed with a low amount of ductile fracture, when the content of Sn exceeded 6.0 wt.%.

Sequestering ability to Cu2+ of a new bodipy-based dye and its behavior as in vitro fluorescent sensor.

PubMed

Papalia, Teresa; Barattucci, Anna; Barreca, Davide; Bellocco, Ersilia; Bonaccorsi, Paola; Minuti, Lucio; Nicolò, Marco Sebastiano; Temperini, Andrea; Foti, Claudia

2017-02-01

A Bodipy (4,4-difluoro-4-bora-3a,4a-diaza-s-indacene) derivative has been conceived and synthesized starting from l-aspartic acid, as a selective turn-off sensor of Cu 2+ ions. Its acid-base properties were determined to study the formation of metal/sensor complex species by titration of solutions each containing a different metal ion, such as Cu 2+ , Ca 2+ , Zn 2+ , Pb 2+ and Hg 2+ and different metal/sensor ratios. The speciation models allowed us to simulate the distribution of the metal/sensor complex species at the normal concentrations of the corresponding metals present in biological fluids. The distribution diagrams, obtained by varying the concentration of sensor 1, clearly indicate that sensor 1 responds selectively to Cu 2+ at micromolar concentrations, even in the presence of other more abundant metal cations Ca 2+ . Finally, we analyzed the cellular uptake of sensor 1 on human erythrocytes and its ability to chelate Cu 2+ in the cellular environment. Results indicate that it crosses the plasmatic membrane and colors the cells of a bright fluorescent red. Exposing the fluorescent cells to Cu 2+ results in a complete cellular photobleaching of the red fluorescence, indicating that sensor 1 is able to detect metal changes in the cytosolic environment. Copyright © 2016 Elsevier Inc. All rights reserved.

One-Step Catalytic Synthesis of CuO/Cu2O in a Graphitized Porous C Matrix Derived from the Cu-Based Metal-Organic Framework for Li- and Na-Ion Batteries.

PubMed

Kim, A-Young; Kim, Min Kyu; Cho, Keumnam; Woo, Jae-Young; Lee, Yongho; Han, Sung-Hwan; Byun, Dongjin; Choi, Wonchang; Lee, Joong Kee

2016-08-03

The hybrid composite electrode comprising CuO and Cu2O micronanoparticles in a highly graphitized porous C matrix (CuO/Cu2O-GPC) has a rational design and is a favorable approach to increasing the rate capability and reversible capacity of metal oxide negative materials for Li- and Na-ion batteries. CuO/Cu2O-GPC is synthesized through a Cu-based metal-organic framework via a one-step thermal transformation process. The electrochemical performances of the CuO/Cu2O-GPC negative electrode in Li- and Na-ion batteries are systematically studied and exhibit excellent capacities of 887.3 mAh g(-1) at 60 mA g(-1) after 200 cycles in a Li-ion battery and 302.9 mAh g(-1) at 50 mA g(-1) after 200 cycles in a Na-ion battery. The high electrochemical stability was obtained via the rational strategy, mainly owing to the synergy effect of the CuO and Cu2O micronanoparticles and highly graphitized porous C formed by catalytic graphitization of Cu nanoparticles. Owing to the simple one-step thermal transformation process and resulting high electrochemical performance, CuO/Cu2O-GPC is one of the prospective negative active materials for rechargeable Li- and Na-ion batteries.

Toxic effects of copper-based nanoparticles or compounds to lettuce (Lactuca sativa) and alfalfa (Medicago sativa).

PubMed

Hong, Jie; Rico, Cyren M; Zhao, Lijuan; Adeleye, Adeyemi S; Keller, Arturo A; Peralta-Videa, Jose R; Gardea-Torresdey, Jorge L

2015-01-01

The increased production and use of nanoparticles (NPs) has generated concerns about their impact on living organisms. In this study, nCu, bulk Cu, nCuO, bulk CuO, Cu(OH)2 (CuPRO 2005, Kocide 3000), and CuCl2 were exposed for 15 days to 10 days-old hydroponically grown lettuce (Lactuca sativa) and alfalfa (Medicago sativa). Each compound was applied at 0, 5, 10, and 20 mg L(-1). At harvest, we measured the size of the plants and determined the concentration of Cu, macro and microelements by using ICP-OES. Catalase and ascorbate peroxidase activity was also determined. Results showed that all Cu NPs/compounds reduced the root length by 49% in both plant species. All Cu NPs/compounds increased Cu, P, and S (>100%, >50%, and >20%, respectively) in alfalfa shoots and decreased P and Fe in lettuce shoot (>50% and >50%, respectively, excluding Fe in CuCl2 treatment). Biochemical assays showed reduced catalase activity in alfalfa (root and shoot) and increased ascorbate peroxidase activity in roots of both plant species. Results suggest that Cu NPs/compounds not only reduced the size of the plants but altered nutrient content and enzyme activity in both plant species.

Design Principles for Metal Oxide Redox Materials for Solar-Driven Isothermal Fuel Production.

PubMed

Michalsky, Ronald; Botu, Venkatesh; Hargus, Cory M; Peterson, Andrew A; Steinfeld, Aldo

2015-04-01

The performance of metal oxides as redox materials is limited by their oxygen conductivity and thermochemical stability. Predicting these properties from the electronic structure can support the screening of advanced metal oxides and accelerate their development for clean energy applications. Specifically, reducible metal oxide catalysts and potential redox materials for the solar-thermochemical splitting of CO 2 and H 2 O via an isothermal redox cycle are examined. A volcano-type correlation is developed from available experimental data and density functional theory. It is found that the energy of the oxygen-vacancy formation at the most stable surfaces of TiO 2 , Ti 2 O 3 , Cu 2 O, ZnO, ZrO 2 , MoO 3 , Ag 2 O, CeO 2 , yttria-stabilized zirconia, and three perovskites scales with the Gibbs free energy of formation of the bulk oxides. Analogously, the experimental oxygen self-diffusion constants correlate with the transition-state energy of oxygen conduction. A simple descriptor is derived for rapid screening of oxygen-diffusion trends across a large set of metal oxide compositions. These general trends are rationalized with the electronic charge localized at the lattice oxygen and can be utilized to predict the surface activity, the free energy of complex bulk metal oxides, and their oxygen conductivity.

Heteroepitaxial Cu 2O thin film solar cell on metallic substrates

DOE PAGES

Wee, Sung Hun; Huang, Po-Shun; Lee, Jung-Kun; ...

2015-11-06

Heteroepitaxial, single-crystal-like Cu 2O films on inexpensive, flexible, metallic substrates can potentially be used as absorber layers for fabrication of low-cost, high-performance, non-toxic, earth-abundant solar cells. Here, we report epitaxial growth of Cu 2O films on low cost, flexible, textured metallic substrates. Cu 2O films were deposited on the metallic templates via pulsed laser deposition under various processing conditions to study the influence of processing parameters on the structural and electronic properties of the films. It is found that pure, epitaxial Cu 2O phase without any trace of CuO phase is only formed in a limited deposition window of P(Omore » 2) - temperature. The (00l) single-oriented, highly textured, Cu 2O films deposited under optimum P(O 2) - temperature conditions exhibit excellent electronic properties with carrier mobility in the range of 40-60 cm 2 V -1 s -1 and carrier concentration over 10 16 cm -3. The power conversion efficiency of 1.65% is demonstrated from a proof-of-concept Cu 2O solar cell based on epitaxial Cu 2O film prepared on the textured metal substrate.« less

Heteroepitaxial Cu2O thin film solar cell on metallic substrates

PubMed Central

Wee, Sung Hun; Huang, Po-Shun; Lee, Jung-Kun; Goyal, Amit

2015-01-01

Heteroepitaxial, single-crystal-like Cu2O films on inexpensive, flexible, metallic substrates can potentially be used as absorber layers for fabrication of low-cost, high-performance, non-toxic, earth-abundant solar cells. Here, we report epitaxial growth of Cu2O films on low cost, flexible, textured metallic substrates. Cu2O films were deposited on the metallic templates via pulsed laser deposition under various processing conditions to study the influence of processing parameters on the structural and electronic properties of the films. It is found that pure, epitaxial Cu2O phase without any trace of CuO phase is only formed in a limited deposition window of P(O2) - temperature. The (00l) single-oriented, highly textured, Cu2O films deposited under optimum P(O2) - temperature conditions exhibit excellent electronic properties with carrier mobility in the range of 40–60 cm2 V−1 s−1 and carrier concentration over 1016 cm−3. The power conversion efficiency of 1.65% is demonstrated from a proof-of-concept Cu2O solar cell based on epitaxial Cu2O film prepared on the textured metal substrate. PMID:26541499

Adsorption of Cd, Cu and Zn from aqueous solutions onto ferronickel slag under different potentially toxic metal combination.

PubMed

Park, Jong-Hwan; Kim, Seong-Heon; Kang, Se-Won; Kang, Byung-Hwa; Cho, Ju-Sik; Heo, Jong-Soo; Delaune, Ronald D; Ok, Yong Sik; Seo, Dong-Cheol

2016-01-01

Adsorption characteristics of potentially toxic metals in single- and multi-metal forms onto ferronickel slag were evaluated. Competitive sorption of metals by ferronickel slag has never been reported previously. The maximum adsorption capacities of toxic metals on ferronickel were in the order of Cd (10.2 mg g(-1)) > Cu (8.4 mg g(-1)) > Zn (4.4 mg g(-1)) in the single-metal adsorption isotherm and Cu (6.1 mg g(-1)) > Cd (2.3 mg g(-1)) > Zn (0.3 mg g(-1)) in the multi-metal adsorption isotherm. In comparison with single-metal adsorption isotherm, the reduction rates of maximum toxic metal adsorption capacity in the multi-metal adsorption isotherm were in the following order of Zn (93%) > Cd (78%) > Cu (27%). The Freundlich isotherm provides a slightly better fit than the Langmuir isotherm equation using ferronickel slag for potentially toxic metal adsorption. Multi-metal adsorption behaviors differed from single-metal adsorption due to competition, based on data obtained from Freundlich and Langmuir adsorption models and three-dimensional simulation. Especially, Cd and Zn were easily exchanged and substituted by Cu during multi-metal adsorption. Further competitive adsorption studies are necessary in order to accurately estimate adsorption capacity of ferronickel slag for potentially toxic metals in natural environments.

Effects of soil properties on copper toxicity to earthworm Eisenia fetida in 15 Chinese soils.

PubMed

Duan, Xiongwei; Xu, Meng; Zhou, Youya; Yan, Zengguang; Du, Yanli; Zhang, Lu; Zhang, Chaoyan; Bai, Liping; Nie, Jing; Chen, Guikui; Li, Fasheng

2016-02-01

The bioavailability and toxicity of metals in soil are influenced by a variety of soil properties, and this principle should be recognized in establishing soil environmental quality criteria. In the present study, the uptake and toxicity of Cu to the earthworm Eisenia fetida in 15 Chinese soils with various soil properties were investigated, and regression models for predicting Cu toxicity across soils were developed. The results showed that earthworm survival and body weight change were less sensitive to Cu than earthworm cocoon production. The soil Cu-based median effective concentrations (EC50s) for earthworm cocoon production varied from 27.7 to 383.7 mg kg(-1) among 15 Chinese soils, representing approximately 14-fold variation. Soil cation exchange capacity and organic carbon content were identified as key factors controlling Cu toxicity to earthworm cocoon production, and simple and multiple regression models were developed for predicting Cu toxicity across soils. Tissue Cu-based EC50s for earthworm cocoon production were also calculated and varied from 15.5 to 62.5 mg kg(-1) (4-fold variation). Compared to the soil Cu-based EC50s for cocoon production, the tissue Cu-based EC50s had less variation among soils, indicating that metals in tissue were more relevant to toxicity than metals in soil and hence represented better measurements of bioavailability. Copyright © 2015 Elsevier Ltd. All rights reserved.

Copper toxicity and organic matter: Resiliency of watersheds in the Duluth Complex, Minnesota, USA

USGS Publications Warehouse

Piatak, Nadine; Seal, Robert; Jones, Perry M.; Woodruff, Laurel G.

2015-01-01

We estimated copper (Cu) toxicity in surface water with high dissolved organic matter (DOM) for unmined mineralized watersheds of the Duluth Complex using the Biotic Ligand Model (BLM), which evaluates the effect of DOM, cation competition for biologic binding sites, and metal speciation. A sediment-based BLM was used to estimate stream-sediment toxicity; this approach factors in the cumulative effects of multiple metals, incorporation of metals into less bioavailable sulfides, and complexation of metals with organic carbon. For surface water, the formation of Cu-DOM complexes significantly reduces the amount of Cu available to aquatic organisms. The protective effects of cations, such as calcium (Ca) and magnesium (Mg), competing with Cu to complex with the biotic ligand is likely not as important as DOM in water with high DOM and low hardness. Standard hardness-based water quality criteria (WQC) are probably inadequate for describing Cu toxicity in such waters and a BLM approach may yield more accurate results. Nevertheless, assumptions about relative proportions of humic acid (HA) and fulvic acid (FA) in DOM significantly influence BLM results; the higher the HA fraction, the higher calculated resiliency of the water to Cu toxicity. Another important factor is seasonal variation in water chemistry, with greater resiliency to Cu toxicity during low flow compared to high flow.Based on generally low total organic carbon and sulfur content, and equivalent metal ratios from total and weak partial extractions, much of the total metal concentration in clastic streambedsediments may be in bioavailable forms, sorbed on clays or hydroxide phases. However, organicrich fine-grained sediment in the numerous wetlands may sequester significant amount of metals, limiting their bioavailability. A high proportion of organic matter in waters and some sediments will play a key role in the resiliency of these watersheds to potential additional metal loads associated with future mining operations.

Thermal and magnetic characterisation of (Co0.402Fe0.201Ni0.067B0.227Si0.053Nb0.05)100-xCux bulk metallic glasses

NASA Astrophysics Data System (ADS)

Sarlar, Kagan; Kucuk, Ilker

2017-03-01

In this work, Co-based (Co0.402Fe0.201Ni0.067B0.227Si0.053Nb0.05)100-xCux bulk glassy alloys (BMG) with 2 mm diameters were formed by suction-casting method and effect of Cu in this system's thermal stability, glass forming ability and magnetic properties were also investigated. The curves of thermal analysis, obtained using differential scanning calorimetry, show that (Co0.402Fe0.201Ni0.067B0.227Si0.053Nb0.05)100-xCux (x = 0-2) has supercooled liquid region (ΔTx) of about 45 K, and reduced glass transition temperature (Tg/Tl) lies in the range from 0.663 to 0.678. The saturation magnetisation (Js) and coercivity (Hc) for as-cast BMG were in the range of 0.46 T-0.65 T and 13 A/m, respectively.

Oxidation of metals and alloys in controlled atmospheres using in situ transmission electron microscopy and Auger spectrography

NASA Technical Reports Server (NTRS)

Rao, D. B.; Heinemann, K.; Douglass, D. L.

1976-01-01

Single-crystalline thin films of copper were oxidized at an isothermal temperature of 425 C and at an oxygen partial pressure of .005 Torr in situ in a high-resolution electron microscope. The specimens were prepared by epitaxial vapor deposition onto polished 100 and 110 faces of rocksalt and mounted in a hot stage inside an ultra-high-vacuum specimen chamber of the microscope. Large amounts of sulfur, carbon, and oxygen were detected by Auger electron spectroscopy on the surface of the as-received films and were removed in situ by ion-sputter etching immediately prior to the oxidation. The nucleation and growth characteristics of Cu2O on Cu were studied. Results show that neither stacking faults nor dislocations are associated with the Cu2O nucleation sites. The growth of Cu2O nuclei is linear with time. The experimental findings, including results from oxygen dissolution experiments and from repetitive oxidation-reduction-oxidation sequences, fit well into the framework of an oxidation process involving (a) the formation of a surface-charge layer, (b) oxygen saturation in the metal and (c) nucleation, followed by surface diffusion of oxygen and bulk diffusion of copper for lateral and vertical oxide growth, respectively.

Multiplexed Paper Analytical Device for Quantification of Metals using Distance-Based Detection

PubMed Central

Cate, David M.; Noblitt, Scott D.; Volckens, John; Henry, Charles S.

2015-01-01

Exposure to metal-containing aerosols has been linked with adverse health outcomes for almost every organ in the human body. Commercially available techniques for quantifying particulate metals are time-intensive, laborious, and expensive; often sample analysis exceeds $100. We report a simple technique, based upon a distance-based detection motif, for quantifying metal concentrations of Ni, Cu, and Fe in airborne particulate matter using microfluidic paper-based analytical devices. Paper substrates are used to create sensors that are self-contained, self-timing, and require only a drop of sample for operation. Unlike other colorimetric approaches in paper microfluidics that rely on optical instrumentation for analysis, with distance-based detection, analyte is quantified visually based on the distance of a colorimetric reaction, similar to reading temperature on a thermometer. To demonstrate the effectiveness of this approach, Ni, Cu, and Fe were measured individually in single-channel devices; detection limits as low as 0.1, 0.1, and 0.05 µg were reported for Ni, Cu, and Fe. Multiplexed analysis of all three metals was achieved with detection limits of 1, 5, and 1 µg for Ni, Cu, and Fe. We also extended the dynamic range for multi-analyte detection by printing concentration gradients of colorimetric reagents using an off the shelf inkjet printer. Analyte selectivity was demonstrated for common interferences. To demonstrate utility of the method, Ni, Cu, and Fe were measured from samples of certified welding fume; levels measured with paper sensors matched known values determined gravimetrically. PMID:26009988

First-principles study of roles of Cu and Cl in polycrystalline CdTe

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

Yang, Ji-Hui; Park, Ji-Sang; Metzger, Wyatt

2016-01-28

Cu and Cl treatments are important processes to achieve high efficiency polycrystalline cadmium telluride (CdTe) solar cells, thus it will be beneficial to understand the roles they play in both bulk CdTe and CdTe grain boundaries (GBs). Using first-principles calculations, we systematically study Cu and Cl-related defects in bulk CdTe. We find that Cl has only a limited effect on improving p-type doping and too much Cl can induce deep traps in bulk CdTe, whereas Cu can enhance p-type doping of bulk CdTe. In the presence of GBs, we find that, in general, Cl and Cu will prefer to staymore » at GBs, especially for those with Te-Te wrong bonds, in agreement with experimental observations.« less

Relative contributions of copper oxide nanoparticles and dissolved copper to Cu uptake kinetics of Gulf killifish (Fundulus grandis) embryos

USGS Publications Warehouse

Jiang, Chuanjia; Castellon, Benjamin T.; Matson, Cole W.; Aiken, George R.; Hsu-Kim, Heileen

2017-01-01

The toxicity of soluble metal-based nanomaterials may be due to the uptake of metals in both dissolved and nanoparticulate forms, but the relative contributions of these different forms to overall metal uptake rates under environmental conditions are not quantitatively defined. Here, we investigated the linkage between the dissolution rates of copper(II) oxide (CuO) nanoparticles (NPs) and their bioavailability to Gulf killifish (Fundulus grandis) embryos, with the aim of quantitatively delineating the relative contributions of nanoparticulate and dissolved species for Cu uptake. Gulf killifish embryos were exposed to dissolved Cu and CuO NP mixtures comprising a range of pH values (6.3–7.5) and three types of natural organic matter (NOM) isolates at various concentrations (0.1–10 mg-C L–1), resulting in a wide range of CuO NP dissolution rates that subsequently influenced Cu uptake. First-order dissolution rate constants of CuO NPs increased with increasing NOM concentration and for NOM isolates with higher aromaticity, as indicated by specific ultraviolet absorbance (SUVA), while Cu uptake rate constants of both dissolved Cu and CuO NP decreased with NOM concentration and aromaticity. As a result, the relative contribution of dissolved Cu and nanoparticulate CuO species for the overall Cu uptake rate was insensitive to NOM type or concentration but largely determined by the percentage of CuO that dissolved. These findings highlight SUVA and aromaticity as key NOM properties affecting the dissolution kinetics and bioavailability of soluble metal-based nanomaterials in organic-rich waters. These properties could be used in the incorporation of dissolution kinetics into predictive models for environmental risks of nanomaterials.

Highly selectively monitoring heavy and transition metal ions by a fluorescent sensor based on dipeptide.

PubMed

Neupane, Lok Nath; Thirupathi, Ponnaboina; Jang, Sujung; Jang, Min Jung; Kim, Jung Hwa; Lee, Keun-Hyeung

2011-09-15

Fluorescent sensor (DMH) based on dipeptide was efficiently synthesized in solid phase synthesis. The dipeptide sensor shows sensitive response to Ag(I), Hg(II), and Cu(II) among 14 metal ions in 100% aqueous solution. The fluorescent sensor differentiates three heavy metal ions by response type; turn on response to Ag(I), ratiometric response to Hg(II), and turn off detection of Cu(II). The detection limits of the sensor for Ag(I) and Cu(II) were much lower than the EPA's drinking water maximum contaminant levels (MCL). Specially, DMH penetrated live cells and detected intracellular Ag(+) by turn on response. We described the fluorescent change, binding affinity, detection limit for the metal ions. The study of a heavy metal-responsive sensor based on dipeptide demonstrates its potential utility in the environment field. Copyright © 2011 Elsevier B.V. All rights reserved.

Predicting As, Cd, Cu, Pb and Zn levels in grasses (Agrostis sp. and Poa sp.) and stinging nettle (Urtica dioica) applying soil-plant transfer models.

PubMed

Boshoff, Magdalena; De Jonge, Maarten; Scheifler, Renaud; Bervoets, Lieven

2014-09-15

The aim of this study was to derive regression-based soil-plant models to predict and compare metal(loid) (i.e. As, Cd, Cu, Pb and Zn) concentrations in plants (grass Agrostis sp./Poa sp. and nettle Urtica dioica L.) among sites with a wide range of metal pollution and a wide variation in soil properties. Regression models were based on the pseudo total (aqua-regia) and exchangeable (0.01 M CaCl2) soil metal concentrations. Plant metal concentrations were best explained by the pseudo total soil metal concentrations in combination with soil properties. The most important soil property that influenced U. dioica metal concentrations was the clay content, while for grass organic matter (OM) and pH affected the As (OM) and Cu and Zn (pH). In this study multiple linear regression models proved functional in predicting metal accumulation in plants on a regional scale. With the proposed models based on the pseudo total metal concentration, the percentage of variation explained for the metals As, Cd, Cu, Pb and Zn were 0.56%, 0.47%, 0.59%, 0.61%, 0.30% in nettle and 0.46%, 0.38%, 0.27%, 0.50%, 0.28% in grass. Copyright © 2014 Elsevier B.V. All rights reserved.

Active biomonitoring with the moss Pseudoscleropodium purum: Comparison between different types of transplants and bulk deposition.

PubMed

Ares, A; Varela, Z; Aboal, J R; Carballeira, A; Fernández, J A

2015-10-01

Active biomonitoring with terrestrial mosses can be used to complement traditional air pollution monitoring techniques. Several studies have been carried out to compare the uptake capacity of different types of moss transplants. However, until now the relationship between the uptake of elements in devitalized moss bags and in irrigated transplants has not been explored. In this study, the final concentrations of Cd, Cu, Hg, Pb and Zn were determined in irrigated and devitalized moss transplants in the surroundings of a steelworks. The concentrations were also compared with those of the same elements in the bulk deposition to determine which type of moss transplant yields the closest correlations. Devitalized moss retained higher concentrations of all of the elements (except Hg) than the irrigated moss. Both irrigated and devitalized moss transplants appear to detect the same type of contamination (i.e. particulate matter and dissolved metals rather than gaseous forms) as significant correlations were found for Cu, Hg, Pb and Zn, whereas, neither type of the moss transplant was sensitive enough to detect changes in the soluble fraction load of bulk deposition. Further studies will be needed to a better understanding of the correlation between the concentrations of elements in moss transplants with the particulate fraction of the bulk deposition. This will enable the establishment of a more robust and accurate biomonitoring tool. Copyright © 2015 Elsevier Inc. All rights reserved.

Fostered Thermomagnetic Stabilities and Boosted Mechanical Reliability Related to High Trapped Field in Composite Bulk YBa2Cu3O(7-δ) Cryomagnets.

PubMed

Kenfaui, Driss; Sibeud, Pierre-Frédéric; Gomina, Moussa; Louradour, Eric; Chaud, Xavier; Noudem, Jacques G

2015-08-06

In the quest of YBa2Cu3O(7-δ) (Y123) bulk superconductors providing strong magnetic fields without failure, it is of paramount importance to achieve high thermal stabilities to safeguard the magnetic energy inside them during the trapping-field process, and sufficient mechanical reliability to withstand the stresses derived from the Lorenz force. Herein, we experimentally demonstrate a temperature rise induced by dissipative flux motion inside an Y123 thin-wall superconductor, and a significant thermal exchange in a composite bulk Y123 cryomagnet realized by embedding this superconductor with high thermal-conductivity metal network. It resulted in stimulating the maximum trapped field Bm, which reached 6.46 T on 15.9 mm-diameter single disk superconductor after magnetization by field cooling to 17 K under 7 T, leading to an improvement of 18% compared to the thin-wall superconductor. The composite cryomagnet particularly revealed the potential to trap stronger fields if larger magnetic activation is available. By virtue of the pore-free and crack-free microstructure of this cryomagnet, its strength σR was estimated to be 363 MPa, the largest one obtained so far for Y123 bulk superconductors, thus suggesting a striking mechanical reliability that seems to be sufficient to sustain stresses derived from trapped fields stronger than any values hitherto reported.

Fabrication of single domain GdBCO bulk superconductors by a new modified TSIG technique

NASA Astrophysics Data System (ADS)

Yang, W. M.; Zhi, X.; Chen, S. L.; Wang, M.; Li, J. W.; Ma, J.; Chao, X. X.

2014-01-01

Single domain GdBCO bulk superconductors have been fabricated with new and traditional solid phases by a top seeded infiltration and growth (TSIG) process technique. In the conventional TSIG process, three types of powders, such as Gd2BaCuO5, GdBa2Cu3O7-x and Ba3Cu5O8, must be prepared, but in our new modified TSIG technique, only BaCuO2 powders are required during the fabrication of the single domain GdBCO bulk superconductors. The solid phase used in the conventional process is Gd2BaCuO5 instead of the solid phase (Gd2O3 + BaCuO2) utilized in the new process. The liquid phase used in the conventional process is a mixture of (GdBa2Cu3O7-x + Ba3Cu5O8), and the liquid phase in the new process is a mixture of (Gd2O3 + 10BaCuO2 + 6CuO). Single domain GdBCO bulk superconductors have been fabricated with the new solid and liquid phases. The levitation force of the GdBCO bulk samples fabricated by the new solid phase is 28 N, which is slightly higher than that of the samples fabricated using the conventional solid phases (26 N). The microstructure and the levitation force of the samples indicate that this new method can greatly simplify the fabrication process, introduce nanometer-sized flux centers, improve the levitation force and working efficiency, and greatly reduce the cost of fabrication of single domain GdBCO bulk superconductors by the TSIG process.

Spectral characterization, cyclic voltammetry, morphology, biological activities and DNA cleaving studies of amino acid Schiff base metal(II) complexes

NASA Astrophysics Data System (ADS)

Neelakantan, M. A.; Rusalraj, F.; Dharmaraja, J.; Johnsonraja, S.; Jeyakumar, T.; Sankaranarayana Pillai, M.

2008-12-01

Metal complexes are synthesized with Schiff bases derived from o-phthalaldehyde (opa) and amino acids viz., glycine (gly) L-alanine (ala), L-phenylalanine (pal). Metal ions coordinate in a tetradentate or hexadentate manner with these N 2O 2 donor ligands, which are characterized by elemental analysis, molar conductance, magnetic moments, IR, electronic, 1H NMR and EPR spectral studies. The elemental analysis suggests the stoichiometry to be 1:1 (metal:ligand). Based on EPR studies, spin-Hamiltonian and bonding parameters have been calculated. The g-values calculated for copper complexes at 300 K and in frozen DMSO (77 K) indicate the presence of the unpaired electron in the d orbital. The evaluated metal-ligand bonding parameters showed strong in-plane σ- and π-bonding. X-ray diffraction (XRD) and scanning electron micrography (SEM) analysis provide the crystalline nature and the morphology of the metal complexes. The cyclic voltammograms of the Cu(II)/Mn(II)/VO(II) complexes investigated in DMSO solution exhibit metal centered electroactivity in the potential range -1.5 to +1.5 V. The electrochemical data obtained for Cu(II) complexes explains the change of structural arrangement of the ligand around Cu(II) ions. The biological activity of the complexes has been tested on eight bacteria and three fungi. Cu(II) and Ni(II) complexes show an increased activity in comparison to the controls. The metal complexes of opapal Schiff base were evaluated for their DNA cleaving activities with calf-thymus DNA (CT DNA) under aerobic conditions. Cu(II) and VO(II) complexes show more pronounced activity in presence of the oxidant.

Copper oxide nanoparticles and bulk copper oxide, combined with indole-3-acetic acid, alter aluminum, boron, and iron in Pisum sativum seeds.

PubMed

Ochoa, Loren; Zuverza-Mena, Nubia; Medina-Velo, Illya A; Flores-Margez, Juan Pedro; Peralta-Videa, José R; Gardea-Torresdey, Jorge L

2018-09-01

The interaction of CuO nanoparticles (nCuO), a potential nanopesticide, with the growth hormone indole-3-acetic acid (IAA) is not well understood. This study aimed to evaluate the nutritional components in seeds of green pea (Pisum sativum) cultivated in soil amended with nCuO at 50 or 100mgkg -1 , with/without IAA at 10 or 100μM. Similar treatments including bulk CuO (bCuO) and CuCl 2 were set as controls. Bulk CuO at 50mgkg -1 reduced seed yield (52%), compared with control. Bulk CuO at 50mgkg -1 and nCuO at 100mgkg -1 , plus IAA at 100μM, increased iron in seeds (41 and 42%, respectively), while nCuO at 50mgkg -1 , plus IAA at 100μM reduced boron (80%, respect to control and 63%, respect to IAA at 100μM). IAA, at 10μM increased seed protein (33%), compared with control (p≤0.05). At both concentrations IAA increased sugar in seeds (20%). Overall, nCuO, plus IAA at 10μM, does not affect the production or nutritional quality of green pea seeds. Copyright © 2018 Elsevier B.V. All rights reserved.

Improvement of the field-trapping capabilities of bulk Nd Ba Cu O superconductors using Ba Cu O substrates

NASA Astrophysics Data System (ADS)

Matsui, Motohide; Nariki, Shinya; Sakai, Naomichi; Iwafuchi, Kengo; Murakami, Masato

2006-07-01

We used Ba-Cu-O substrates to fabricate bulk Nd-Ba-Cu-O superconductors using a top-seeded melt-growth method. There were several advantages for the use of Ba-Cu-O substrate compared to conventional substrate materials such as MgO, ZrO2, Al2O3, RE123 and RE211 (RE = rare earth). The Ba-Cu-O did not react with the precursor and minimized liquid loss. Accordingly, the introduction of large-sized cracks was suppressed. We also found that Tc values were high at the bottom regions, which was ascribed to the beneficial effect of Ba-Cu-O in suppressing Nd/Ba substitution. As a result, we obtained bulk Nd-Ba-Cu-O superconductors that exhibited fairly good field-trapping capabilities, even at the bottom surfaces.

A superconducting conveyer system using multiple bulk Y-Ba-Cu-O superconductors and permanent magnets

NASA Astrophysics Data System (ADS)

Kinoshita, T.; Koshizuka, N.; Nagashima, K.; Murakami, M.

Developments of non-contact superconducting devices like superconducting magnetic levitation transfer and superconducting flywheel energy storage system have been performed based on the interactions between bulk Y-Ba-Cu-O superconductors and permanent magnets, in that the superconductors can stably be levitated without any active control. The performances of noncontact superconducting devices are dependent on the interaction forces like attractive forces and stiffness. In the present study, we constructed a non-contact conveyer for which the guide rails were prepared by attaching many Fe-Nd-B magnets onto an iron base plate. Along the translational direction, all the magnets were arranged as to face the same pole, and furthermore their inter-distance was made as small as possible. The guide rail has three magnet rows, for which the magnets were glued on the iron plate such that adjacent magnet rows have opposite poles like NSN. At the center row, the magnetic field at zero gap reached 0.61T, while the field strengths of two rows on the side edges were only 0.48T due to magnetic interactions among permanent magnets. We then prepared a cryogenic box made with FRP that can store several bulk Y-Ba-Cu-O superconductors 25 mm in diameter cooled by liquid nitrogen. It was found that the levitation forces and stiffness increased with increasing the number of bulk superconductors installed in the box, although the levitation force per unit bulk were almost the same. We also confirmed that these forces are dependent on the configuration of bulk superconductors.

Source and fate of inorganic soil contamination around the abandoned Phillips sulfide mine, hudson Highlands, New York

USGS Publications Warehouse

Gilchrist, S.; Gates, A.; Elzinga, E.; Gorring, M.; Szabo, Z.

2011-01-01

The abandoned Phillips sulfide mine in the critical Highlands watershed in New York has been shown to produce strongly acidic mine drainage (AMD) with anomalous metal contaminants in first-order streams that exceeded local water standards by up to several orders of magnitude (Gilchrist et al., 2009). The metal-sulfide-rich tailings also produce contaminated soils with pH < 4, organic matter < 2.5% and trace metals sequestered in soil oxides. A geochemical transect to test worst-case soil contamination showed that Cr, Co and Ni correlated positively with Mn, (r = 0.72, r= 0.89, r = 0.80, respectively), suggesting Mn-oxide sequestration and that Cu and Pb correlated with Fe (r = 0.76, r = 0.83, respectively), suggesting sequestration in goethite. Ubiquitous, yellow coating on the mine wastes, including jarosite and goethite, is a carrier of the metals. Geochemical and μ-SXRF analyses determined Cu to be the major soil contaminant. μ-SXRF also demonstrated that the heterogeneous nature of the soil chemistry at the micro-meter scale is self-similar to those in the bulk soil samples. Generally metals decreased, with some fluctuations, rapidly downslope through suspension of fines and dissolution in AMD leaving the area of substantial contamination << 0.5 km from the source.

Materials process and applications of single grain (RE)-Ba-Cu-O bulk high-temperature superconductors

NASA Astrophysics Data System (ADS)

Li, Beizhan; Zhou, Difan; Xu, Kun; Hara, Shogo; Tsuzuki, Keita; Miki, Motohiro; Felder, Brice; Deng, Zigang; Izumi, Mitsuru

2012-11-01

This paper reviews recent advances in the melt process of (RE)-Ba-Cu-O [(RE)BCO, where RE represents a rare earth element] single grain high-temperature superconductors (HTSs), bulks and its applications. The efforts on the improvement of the magnetic flux pinning with employing the top-seeded melt-growth process technique and using a seeded infiltration and growth process are discussed. Which including various chemical doping strategies and controlled pushing effect based on the peritectic reaction of (RE)BCO. The typical experiment results, such as the largest single domain bulk, the clear TEM observations and the significant critical current density, are summarized together with the magnetization techniques. Finally, we highlight the recent prominent progress of HTS bulk applications, including Maglev, flywheel, power device, magnetic drug delivery system and magnetic resonance devices.

A hydrometallurgical process for recovering total metal values from waste monolithic ceramic capacitors.

PubMed

Prabaharan, G; Barik, S P; Kumar, B

2016-06-01

A hydrometallurgical process for recovering the total metal values from waste monolithic ceramic capacitors was investigated. The process parameters such as time, temperature, acid concentration, hydrogen peroxide concentration and other reagents (amount of zinc dust and sodium formate) were optimized. Base metals such as Ba, Ti, Sn, Cu and Ni are leached out in two stages using HCl in stage 1 and HCl with H2O2 in stage 2. More than 99% of leaching efficiency for base metals (Cu, Ni, Ba, Ti and Sn) was achieved. Precious metals such as Au and Pd are leached out using aquaregia and nitric acid was used for the leaching of Ag. Base metals (Ba, Ti, Sn, Cu and Ni) are recovered by selective precipitation using H2SO4 and NaOH solution. In case of precious metals, Au and Pd from the leach solution were precipitated out using sodium metabisulphite and sodium formate, respectively. Sodium chloride was used for the precipitation of Ag from leach solution. Overall recovery for base metals and precious metals are 95% and 92%, respectively. Based on the results of the present study, a process flow diagram was proposed for commercial application. Copyright © 2016 Elsevier Ltd. All rights reserved.

Electrical wire explosion process of copper/silver hybrid nano-particle ink and its sintering via flash white light to achieve high electrical conductivity.

PubMed

Chung, Wan-Ho; Hwang, Yeon-Taek; Lee, Seung-Hyun; Kim, Hak-Sung

2016-05-20

In this work, combined silver/copper nanoparticles were fabricated by the electrical explosion of a metal wire. In this method, a high electrical current passes through the metal wire with a high voltage. Consequently, the metal wire evaporates and metal nanoparticles are formed. The diameters of the silver and copper nanoparticles were controlled by changing the voltage conditions. The fabricated silver and copper nano-inks were printed on a flexible polyimide (PI) substrate and sintered at room temperature via a flash light process, using a xenon lamp and varying the light energy. The microstructures of the sintered silver and copper films were observed using a scanning electron microscope (SEM) and a transmission electron microscope (TEM). To investigate the crystal phases of the flash-light-sintered silver and copper films, x-ray diffraction (XRD) was performed. The absorption wavelengths of the silver and copper nano-inks were measured using ultraviolet-visible spectroscopy (UV-vis). Furthermore, the resistivity of the sintered silver and copper films was measured using the four-point probe method and an alpha step. As a result, the fabricated Cu/Ag film shows a high electrical conductivity (4.06 μΩcm), which is comparable to the resistivity of bulk copper (1.68 μΩcm). In addition, the fabricated Cu/Ag nanoparticle film shows superior oxidation stability compared to the Cu nanoparticle film.

Beneficial effect of post-deposition treatment in high-efficiency Cu(In,Ga)Se{sub 2} solar cells through reduced potential fluctuations

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

Jensen, S. A., E-mail: Soren.Jensen@nrel.gov, E-mail: Darius.Kuciauskas@nrel.gov; Glynn, S.; Kanevce, A.

World-record power conversion efficiencies for Cu(In,Ga)Se{sub 2} (CIGS) solar cells have been achieved via a post-deposition treatment with alkaline metals, which increases the open-circuit voltage and fill factor. We explore the role of the potassium fluoride (KF) post-deposition treatment in CIGS by employing energy- and time-resolved photoluminescence spectroscopy and electrical characterization combined with numerical modeling. The bulk carrier lifetime is found to increase with post-deposition treatment from 255 ns to 388 ns, which is the longest charge carrier lifetime reported for CIGS, and within ∼40% of the radiative limit. We find evidence that the post-deposition treatment causes a decrease in the electronicmore » potential fluctuations. These potential fluctuations have previously been shown to reduce the open-circuit voltage and the device efficiency in CIGS. Additionally, numerical simulations based on the measured carrier lifetimes and mobilities show a diffusion length of ∼10 μm, which is ∼4 times larger than the film thickness. Thus, carrier collection in the bulk is not a limiting factor for device efficiency. By considering differences in doping, bandgap, and potential fluctuations, we present a possible explanation for the voltage difference between KF-treated and untreated samples.« less

Structural features and the microscopic dynamics of the three-component Zr{sub 47}Cu{sub 46}Al{sub 7} system: Equilibrium melt, supercooled melt, and amorphous alloy

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

Khusnutdinoff, R. M., E-mail: khrm@mail.ru; Mokshin, A. V., E-mail: anatolii.mokshin@mail.ru; Klumov, B. A.

2016-08-15

The structural and dynamic properties of the three-component Zr{sub 47}Cu{sub 46}Al{sub 7} system are subjected to a molecular dynamics simulation in the temperature range T = 250–3000 K at a pressure p = 1.0 bar. The temperature dependences of the Wendt–Abraham parameter and the translation order parameter are used to determine the glass transition temperature in the Zr{sub 47}Cu{sub 46}Al{sub 7} system, which is found to be T{sub c} ≈ 750 K. It is found that the bulk amorphous Zr{sub 47}Cu{sub 46}Al{sub 7} alloy contains localized regions with an ordered atomic structures. Cluster analysis of configuration simulation data reveals themore » existence of quasi-icosahedral clusters in amorphous metallic Zr–Cu–Al alloys. The spectral densities of time radial distribution functions of the longitudinal (C̃{sub L}(k, ω)) and transverse (C̃{sub T}(k, ω)) fluxes are calculated in a wide wavenumber range in order to study the mechanisms of formation of atomic collective excitations in the Zr{sub 47}Cu{sub 46}Al{sub 7} system. It was found that a linear combination of three Gaussian functions is sufficient to reproduce the (C̃{sub L}(k, ω)) spectra, whereas at least four Gaussian contributions are necessary to exactly describe the (C̃{sub T}(k, ω)) spectra of the supercooled melt and the amorphous metallic alloy. It is shown that the collective atomic excitations in the equilibrium melt at T = 3000 K and in the amorphous metallic alloy at T = 250 K are characterized by two dispersion acoustic-like branches related with longitudinal and transverse polarizations.« less

Dual self-organised shear banding behaviours and enhanced ductility in phase separating Zr-based bulk metallic glasses

NASA Astrophysics Data System (ADS)

Zhang, Z. Q.; Song, K. K.; Sun, B. A.; Wang, L.; Cui, W. C.; Qin, Y. S.; Han, X. L.; Xue, Q. S.; Peng, C. X.; Sarac, B.; Spieckermann, F.; Kaban, I.; Eckert, J.

2018-07-01

The multiplication and interaction of self-organised shear bands often transform to a stick-slip behaviour of a major shear band along the primary shear plane, and ultimately the major shear band becomes runaway and terminates the plasticity of bulk metallic glasses (BMGs). Here, we examined the deformation behaviours of the nanoscale phase-separating Zr65-xCu25Al10Fex (x = 5 and 7.5 at.%) BMGs. The formation of multi-step phase separation, being mainly governed by nucleation and growth, results in the microstructural inhomogeneity on a wide range of length-scales and leads to obviously macroscopic and repeatable ductility. The good deformability can be attributed to two mechanisms for stabilizing shear banding process, i.e. the mutual interaction of multiple shear bands away from the major shear band and the delaying slip-to-failure of dense fine shear bands around the major shear band, both of which show a self-organised criticality yet with different power-law exponents. The two mechanisms could come into effect in the intermediate (stable) and later plastic deformation regime, respectively. Our findings provide a possibility to enhance the shear banding stability over the whole plastic deformation through a proper design of microstructure heterogeneities.

Growth of 3-D flower/grass-like metal oxide nanoarchitectures based on catalyst-assisted oxidation method

NASA Astrophysics Data System (ADS)

Hu, Lijiao; Ju, Yang; Hosoi, Atsushi

2014-03-01

Cu2O grass-like and ZnO flower-like nanoarchitectures were fabricated directly on Cu powders and Zn powders using a novel thermal oxidation stress-induced (TOS) method based on catalyst assistance at a low temperature of 150°C under moderate humid atmosphere. The experiments of Al powder were also carried out based on TOS method. Overlapping migration (OLM) of Cu and Zn atoms and toothpaste squeezing migration (TSM) of Al atoms caused by different atom densities in metal oxide materials were studied.

Copper transport and trafficking at the host-bacterial pathogen interface.

PubMed

Fu, Yue; Chang, Feng-Ming James; Giedroc, David P

2014-12-16

CONSPECTUS: The human innate immune system has evolved the means to reduce the bioavailability of first-row late d-block transition metal ions to invading microbial pathogens in a process termed "nutritional immunity". Transition metals from Mn(II) to Zn(II) function as metalloenzyme cofactors in all living cells, and the successful pathogen is capable of mounting an adaptive response to mitigate the effects of host control of transition metal bioavailability. Emerging evidence suggests that Mn, Fe, and Zn are withheld from the pathogen in classically defined nutritional immunity, while Cu is used to kill invading microorganisms. This Account summarizes new molecular-level insights into copper trafficking across cell membranes from studies of a number of important bacterial pathogens and model organisms, including Escherichia coli, Salmonella species, Mycobacterium tuberculosis, and Streptococcus pneumoniae, to illustrate general principles of cellular copper resistance. Recent highlights of copper chemistry at the host-microbial pathogen interface include the first high resolution structures and functional characterization of a Cu(I)-effluxing P1B-ATPase, a new class of bacterial copper chaperone, a fungal Cu-only superoxide dismutase SOD5, and the discovery of a small molecule Cu-bound SOD mimetic. Successful harnessing by the pathogen of host-derived bactericidal Cu to reduce the bacterial load of reactive oxygen species (ROS) is an emerging theme; in addition, recent studies continue to emphasize the importance of short lifetime protein-protein interactions that orchestrate the channeling of Cu(I) from donor to target without dissociation into bulk solution; this, in turn, mitigates the off-pathway effects of Cu(I) toxicity in both the periplasm in Gram negative organisms and in the bacterial cytoplasm. It is unclear as yet, outside of the photosynthetic bacteria, whether Cu(I) is trafficked to other cellular destinations, for example, to cuproenzymes or other intracellular storage sites, or the general degree to which copper chaperones vs copper efflux transporters are essential for bacterial pathogenesis in the vertebrate host. Future studies will be directed toward the identification and structural characterization of other cellular targets of Cu(I) trafficking and resistance, the physical and mechanistic characterization of Cu(I)-transfer intermediates, and elucidation of the mutual dependence of Cu(I) trafficking and cellular redox status on thiol chemistry in the cytoplasm. Crippling bacterial control of Cu(I) sensing, trafficking, and efflux may represent a viable strategy for the development of new antibiotics.

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.

First-principles study of roles of Cu and Cl in polycrystalline CdTe

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

Yang, Ji -Hui; Yin, Wan -Jian; Park, Ji -Sang

2016-01-25

In this study, Cu and Cl treatments are important processes to achieve high efficiency polycrystalline cadmium telluride (CdTe) solar cells, thus it will be beneficial to understand the roles they play in both bulk CdTe and CdTe grain boundaries (GBs). Using first-principles calculations, we systematically study Cu and Cl-related defects in bulk CdTe. We find that Cl has only a limited effect on improving p-type doping and too much Cl can induce deep traps in bulk CdTe, whereas Cu can enhance ptype doping of bulk CdTe. In the presence of GBs, we find that, in general, Cl and Cu willmore » prefer to stay at GBs, especially for those with Te-Te wrong bonds, in agreement with experimental observations.« less

Competitive adsorption and selectivity sequence of heavy metals by chicken bone-derived biochar: Batch and column experiment.

PubMed

Park, Jong-Hwan; Cho, Ju-Sik; Ok, Yong Sik; Kim, Seong-Heon; Kang, Se-Won; Choi, Ik-Won; Heo, Jong-Soo; DeLaune, Ronald D; Seo, Dong-Cheol

2015-01-01

The objective of this research was to evaluate adsorption of heavy metals in single- and ternary-metal forms onto chicken bone biochar (CBB). Competitive sorption of heavy metals by CBB has never been reported previously. The maximum adsorption capacities of metals by CBB were in the order of Cu (130 mg g(-1)) > Cd (109 mg g(-1)) > Zn (93 mg g(-1)) in the single-metal adsorption isotherm and Cu (108 mg g(-1)) > Cd (54 mg g(-1)) ≥ Zn (44 mg g(-1)) in the ternary-metal adsorption isotherm. Cu was the most retained cation, whereas Zn could be easily exchanged and substituted by Cu. Batch experimental data best fit the Langmuir model rather than the Freundlich isotherms. In the column experiments, the total adsorbed amounts of the metals were in the following order of Cu (210 mg g(-1)) > Cd (192 mg g(-1)) > Zn (178) in single-metal conditions, and Cu (156) > Cd (123) > Zn (92) in ternary-metal conditions. Results from both the batch and column experiments indicate that competitive adsorption among metals increases the mobility of these metals. Especially, Zn in single-metal conditions lost it adsorption capacity most significantly. Based on the 3D simulation graphs of heavy metals, adsorption patterns under single adsorption condition were different than under competitive adsorption condition. Results from both the batch and column experiments show that competitive adsorption among metals increases the mobility of these metals. The maximum metal adsorption capacity of the metals in the column experiments was higher than that in the batch experiment indicating other metal retention mechanisms rather than adsorption may be involved. Therefore, both column and batch experiments are needed for estimating retention capacities and removal efficiencies of metals in CBB.

Toxicity of CuO nanoparticles to yeast Saccharomyces cerevisiae BY4741 wild-type and its nine isogenic single-gene deletion mutants.

PubMed

Kasemets, Kaja; Suppi, Sandra; Künnis-Beres, Kai; Kahru, Anne

2013-03-18

A suite of eight tentatively oxidative stress response-deficient Saccharomyces cerevisiae BY4741 single-gene mutants (sod1Δ, sod2Δ, yap1Δ, cta1Δ, ctt1Δ, gsh1Δ, glr1Δ, and ccs1Δ) and one copper-vulnerable mutant (cup2Δ) was used to elucidate weather the toxicity of CuO nanoparticles to S. cerevisiae is mediated by oxidative stress (OS). Specifically, sensitivity profiles of mutants' phenotypes and wild-type (wt) upon exposure to nano-CuO were compared. As controls, CuSO4 (solubility), bulk-CuO (size), H2O2, and menadione (OS) were used. Growth inhibition of wt and mutant strains was studied in rich YPD medium and cell viability in deionized water (DI). Dissolved Cu-ions were quantified by recombinant metal-sensing bacteria and chemical analysis. To wt strain nano-CuO was 32-fold more toxic than bulk-CuO: 24-h IC50 4.8 and 155 mg/L in DI and 643 and >20000 mg/L in YPD, respectively. In toxicant-free YPD medium, all mutants had practically similar growth patterns as wt. However, the mutant strains sod1Δ, sod2Δ, ccs1Δ, and yap1Δ showed up to 12-fold elevated sensitivity toward OS standard chemicals menadione and H2O2 but not to nano-CuO, indicating that CuO nanoparticles exerted toxicity to yeast cells via different mechanisms. The most vulnerable strain to all studied Cu compounds was the copper stress response-deficient strain cup2Δ (∼16-fold difference with wt), indicating that the toxic effect of CuO (nano)particles proceeds via dissolved Cu-ions. The dissolved copper solely explained the toxicity of nano-CuO in DI but not in YPD. Assumingly, in YPD nano-CuO acquired a coating of peptides/proteins and sorbed onto the yeast's outer surface, resulting in their increased solubility in the close vicinity of yeast cells and increased uptake of Cu-ions that was not registered by the assays used for the analysis of dissolved Cu-ions in the test medium. Lastly, as yeast retained its viability in DI even by 24th hour of incubation, the profiling of the acute basal toxicity of chemicals toward yeasts may be conducted in DI.

In Situ Study of Reduction Process of CuO Paste and Its Effect on Bondability of Cu-to-Cu Joints

NASA Astrophysics Data System (ADS)

Yao, Takafumi; Matsuda, Tomoki; Sano, Tomokazu; Morikawa, Chiaki; Ohbuchi, Atsushi; Yashiro, Hisashi; Hirose, Akio

2018-04-01

A bonding method utilizing redox reactions of metallic oxide microparticles achieves metal-to-metal bonding in air, which can be alternative to lead-rich high-melting point solder. However, it is known that the degree of the reduction of metallic oxide microparticles have an influence on the joint strength using this bonding method. In this paper, the reduction behavior of CuO paste and its effect on Cu-to-Cu joints were investigated through simultaneous microstructure-related x-ray diffraction and differential scanning calorimetry measurements. The CuO microparticles in the paste were gradually reduced to submicron Cu2O particles at 210-250°C. Subsequently, Cu nanoparticles were generated instantaneously at 300-315°C. There was a marked difference in the strengths of the joints formed at 300°C and 350°C. Thus, the Cu nanoparticles play a critical role in sintering-based bonding using CuO paste. Furthermore, once the Cu nanoparticles have formed, the joint strength increases with higher bonding temperature (from 350°C to 500°C) and pressure (5-15 MPa), which can exceed the strength of Pb-5Sn solder at higher temperature and pressure.

Characteristics and environmental aspects of slag: a review

USGS Publications Warehouse

Piatak, Nadine M.; Parsons, Michael B.; Seal, Robert R.

2015-01-01

The composition of ferrous slag is dominated by Ca and Si. Steel slag may contain significant Fe, whereas Mg and Al may be significant in Fe slag. Calcium-rich olivine-group silicates, melilite-group silicates that contain Al or Mg, Ca-rich glass, and oxides are the most commonly reported major phases in ferrous slag. Calcite and trace amounts of a variety of sulfides, intermetallic compounds, and pure metals are typically also present. The composition of non-ferrous slag, most commonly from base-metal production, is dominated by Fe and Si with significant but lesser amounts of Al and Ca. Silicates in the olivine, pyroxene, and melilite groups, as well as glass, spinels, and SiO2 (i.e., quartz and other polymorphs) are commonly found in non-ferrous slag. Sulfides and intermetallic compounds are less abundant than the silicates and oxides. The concentrations of some elements exceed generic USEPA soil screening levels for human contact based on multiple exposure pathways; these elements include Al, Cr, Cu, Fe, Mn, Pb, and Zn based on bulk chemical composition. Each slag type usually contains a specific suite of elements that may be of environmental concern. In general, non-ferrous slag may have a higher potential to negatively impact the environment compared to ferrous slag, and is thus a less attractive material for reuse, based on trace element chemistry, principally for base metals. However, the amount of elements released into the environment is not always consistent with bulk chemical composition. Many types of leaching tests have been used to help predict slag’s long-term environmental behavior. Overall, ferrous slags produce an alkaline leachate due to the dissolution of Ca oxides and silicates derived from compounds originally added as fluxing agents, such as lime. Ferrous slag leachate is commonly less metal-rich than leachate from non-ferrous slag generated during base metal extraction; the latter leachate may even be acidic due to the oxidation of sulfides. Because of its characteristics, ferrous slag is commonly used for construction and environmental applications, whereas both non-ferrous and ferrous slag may be reprocessed for secondary metal recovery. Both types of slag have been a source of some environmental contamination. Research into the environmental aspects of slag will continue to be an important topic whether the goal is its reuse, recycling, or remediation.

New barrierless copper-alloy film for future applications

NASA Astrophysics Data System (ADS)

Lin, Chon-Hsin Lin

2015-09-01

Since Cu metallization results in a conductivity and an electromigration resistance greater than those of Al, it has become popular for making Si-based interconnects for numerous devices in the field of microelectronics. Following the current trend of miniaturization required for most electronic components, there is a greater need for further size reduction in Si-based devices. The most critical side effect of size reduction is the increase in electronic scattering and resistivity when the barrier-layer thickness is further reduced. To explore advanced Cu-metallization methods and to develop a more economical manufacturing process for Cu-alloy films, the development of Cu materials having better quality and higher thermal stability becomes imperative for the metallization and annealing processes. For this purpose, we first fabricated Cu(GeNx) films and examined their thermal stability and electrical reliability after either cyclic or isothermal annealing. The excellent thermal and electrical properties make these new Cu-alloy films highly promising for applications that require more reliable and inexpensive copper interconnects. In this study, we fabricated Cu alloy films by doping a minute amount of Ge or GeNx, respectively, into the Cu films via barrierless Cu metallization, an inexpensive manufacturing method. Using these newly fabricated alloy films, we were able to eliminate or at least substantially reduce the detrimental interaction between the alloy and the barrierless Si substrate. The Cu(GeNx) films also exhibited high thermal stability, low resistivity and leakage current, and long time-dependent dielectric breakdown (TDDB) lifetimes, making such novel films a candidate for high-quality, economical, and more reliable Cu interconnects.

Tuning the properties of copper-based catalysts based on molecular in situ studies of model systems.

PubMed

Stacchiola, Darío J

2015-07-21

Studying catalytic processes at the molecular level is extremely challenging, due to the structural and chemical complexity of the materials used as catalysts and the presence of reactants and products in the reactor's environment. The most common materials used on catalysts are transition metals and their oxides. The importance of multifunctional active sites at metal/oxide interfaces has been long recognized, but a molecular picture of them based on experimental observations is only recently emerging. The initial approach to interrogate the surface chemistry of catalysts at the molecular level consisted of studying metal single crystals as models for reactive metal centers, moving later to single crystal or well-defined thin film oxides. The natural next iteration consisted in the deposition of metal nanoparticles on well-defined oxide substrates. Metal nanoparticles contain undercoordinated sites, which are more reactive. It is also possible to create architectures where oxide nanoparticles are deposited on top of metal single crystals, denominated inverse catalysts, leading in this case to a high concentration of reactive cationic sites in direct contact with the underlying fully coordinated metal atoms. Using a second oxide as a support (host), a multifunctional configuration can be built in which both metal and oxide nanoparticles are located in close proximity. Our recent studies on copper-based catalysts are presented here as an example of the application of these complementary model systems, starting from the creation of undercoordinated sites on Cu(111) and Cu2O(111) surfaces, continuing with the formation of mixed-metal copper oxides, the synthesis of ceria nanoparticles on Cu(111) and the codeposition of Cu and ceria nanoparticles on TiO2(110). Catalysts have traditionally been characterized before or after reactions and analyzed based on static representations of surface structures. It is shown here how dynamic changes on a catalyst's chemical state and morphology can be followed during a reaction by a combination of in situ microscopy and spectroscopy. In addition to determining the active phase of a catalyst by in situ methods, the presence of weakly adsorbed surface species or intermediates generated only in the presence of reactants can be detected, allowing in turn the comparison of experimental results with first principle modeling of specific reaction mechanisms. Three reactions are used to exemplify the approach: CO oxidation (CO + 1/2O2 → CO2), water gas shift reaction (WGSR) (CO + H2O → CO2 + H2), and methanol synthesis (CO2 + 3H2 → CH3OH + H2O). During CO oxidation, the full conversion of Cu(0) to Cu(2+) deactivates an initially outstanding catalyst. This can be remedied by the formation of a TiCuOx mixed-oxide that protects the presence of active partially oxidized Cu(+) cations. It is also shown that for the WGSR a switch occurs in the reaction mechanism, going from a redox process on Cu(111) to a more efficient associative pathway at the interface of ceria nanoparticles deposited on Cu(111). Similarly, the activation of CO2 at the ceria/Cu(111) interface allows its facile hydrogenation to methanol. Our combined studies emphasize the need of searching for optimal metal/oxide interfaces, where multifunctional sites can lead to new efficient catalytic reaction pathways.

Measurement of mechanical properties of metallic glass at elevated temperature using sonic resonance method

NASA Astrophysics Data System (ADS)

Kaluvan, Suresh; Zhang, Haifeng; Mridha, Sanghita; Mukherjee, Sundeep

2017-04-01

Bulk metallic glasses are fully amorphous multi-component alloys with homogeneous and isotropic structure down to the atomic scale. Some attractive attributes of bulk metallic glasses include high strength and hardness as well as excellent corrosion and wear resistance. However, there are few reports and limited understanding of their mechanical properties at elevated temperatures. We used a nondestructive sonic resonance method to measure the Young's modulus and Shear modulus of a bulk metallic glass, Zr41.2Ti13.8Cu12.5Ni10Be22.5, at elevated temperatures. The measurement system was designed using a laser displacement sensor to detect the sonic vibration produced by a speaker on the specimen in high-temperature furnace. The OMICRON Bode-100 Vector Network Analyzer was used to sweep the frequency and its output was connected to the speaker which vibrated the material in its flexural mode and torsional modes. A Polytec OFV-505 laser vibrometer sensor was used to capture the vibration of the material at various frequencies. The flexural and torsional mode frequency shift due to the temperature variation was used to determine the Young's modulus and Shear modulus. The temperature range of measurement was from 50°C to 350°C. The Young's modulus was found to reduce from 100GPa to 94GPa for the 300°C temperature span. Similarly, the Shear modulus decreased from 38.5GPa at 50°C to 36GPa at 350°C.

Anomalous electronic heat capacity of copper nanowires at sub-Kelvin temperatures

NASA Astrophysics Data System (ADS)

Viisanen, K. L.; Pekola, J. P.

2018-03-01

We have measured the electronic heat capacity of thin film nanowires of copper and silver at temperatures 0.1-0.3 K; the films were deposited by standard electron-beam evaporation. The specific heat of the Ag films of sub-100-nm thickness agrees with the bulk value and the free-electron estimate, whereas that of similar Cu films exceeds the corresponding reference values by one order of magnitude. The origin of the anomalously high heat capacity of copper films remains unknown for the moment. Based on the small heat capacity at low temperatures and the possibility to devise a tunnel probe thermometer on it, metal films form a promising absorber material, e.g., for microwave photon calorimetry.

Effect of sediment size on bioleaching of heavy metals from contaminated sediments of Izmir Inner Bay.

PubMed

Guven, Duyusen E; Akinci, Gorkem

2013-09-01

The effect of sediment size on metals bioleaching from bay sediments was investigated by using fine (< 45 microm), medium (45-300 microm), and coarse (300-2000 microm) size fractions of a sediment sample contaminated with Cr, Cu, Pb, and Zn. Chemical speciation of the metals in bulk and size fractions of sediment were studied before and after bioleaching. Microbial activity was provided with mixed cultures of Acidithiobacillus thiooxidans and Acidithiobacillus ferrooxidans. The bioleaching process was carried out in flask experiments for 48 days, by using 5% (W/V) of solid concentration in suspension. Bioleaching was found to be efficient for the removal of selected heavy metals from every size fraction of sediments, where the experiments with the smaller particles resulted in the highest solubilization ratios. At the end of the experimental period, Cr, Cu, Pb and Zn were solubilized to the ratios of 68%, 88%, 72%, and 91% from the fine sediment, respectively. Higher removal efficiencies can be explained by the larger surface area provided by the smaller particles. The changes in the chemical forms of metals were determined and most of the metal releases were observed from the reducible and organic fractions independent from grain size. Higher concentrations were monitored in the residual fraction after bioleaching period, suggesting they are trapped in this fraction, and cannot be solubilized under natural conditions.

Speciation and solubility of heavy metals in contaminated soil using X-ray microfluorescence, EXAFS spectroscopy, chemical extraction, and thermodynamic modeling

NASA Astrophysics Data System (ADS)

Kirpichtchikova, Tatiana A.; Manceau, Alain; Spadini, Lorenzo; Panfili, Fré; dé; ric; Marcus, Matthew A.; Jacquet, Thierry

2006-05-01

Synchrotron-based X-ray radiation microfluorescence (μ-SXRF) and micro-focused and powder extended X-ray absorption fine structure (EXAFS) spectroscopy measurements, combined with desorption experiments and thermodynamic calculations, were used to evaluate the solubility of metal contaminants (Zn, Cu, Pb) and determine the nature and fractional amount of Zn species in a near-neutral pH (6.5-7.0) truck-farming soil contaminated by sewage irrigation for one hundred years. Zn is the most abundant metal contaminant in the soil (1103 mg/kg), followed by Pb (535 mg/kg) and Cu (290 mg/kg). The extractability of Zn, Pb, and Cu with citrate, S, S-ethylenediaminedisuccinic acid (EDDS), and ethylenediaminetetraacetic acid (EDTA) was measured as a function of time (24 h, 72 h, 144 h), and also as a function of the number of applications of the chelant (5 applications each with 24 h of contact time). Fifty-three percent of the Zn was extracted after 144 h with citrate, 51% with EDDS and 46% with EDTA, compared to 69, 87, and 61% for Cu, and 24, 40, and 34% for Pb. Renewing the extracting solution removed more of the metals. Seventy-nine, 65, and 57% of the Zn was removed after five cycles with citrate, EDDS and EDTA, respectively, compared to 88, 100, and 72% for Cu, and 91, 65, and 47% for Pb. Application to the untreated soil of μ-SXRF, laterally resolved μ-EXAFS combined with principal component analysis, and bulk averaging powder EXAFS with linear least-squares combination fit of the data, identified five Zn species: Zn-sorbed ferrihydrite, Zn phosphate, Zn-containing trioctahedral phyllosilicate (modeled by the Zn kerolite, Si 4(Mg 1.65Zn 1.35)O 10(OH) 2 · nH 2O), willemite (Zn 2SiO 4), and gahnite (ZnAl 2O 4), in proportions of ˜30, 28, 24, 11, and less than 10%, respectively (precision: 10% of total Zn). In contrast to Cu and Pb, the same fractional amount of Zn was extracted after 24 h contact time with the three chelants (40-43% of the initial content), suggesting that one of the three predominant Zn species was highly soluble under the extraction conditions. Comparison of EXAFS data before and after chemical treatment revealed that the Zn phosphate component was entirely and selectively dissolved in the first 24 h of contact time. Preferential dissolution of the Zn phosphate component is supported by thermodynamic calculations. Despite the long-term contamination of this soil, about 79% of Zn, 91% of Pb, and 100% of Cu can be solubilized in the laboratory on a time scale of a few days by chemical complexants. According to metal speciation results and thermodynamic calculations, the lower extraction level measured for Zn is due to the Zn phyllosilicate component, which is less soluble than Zn phosphate and Zn ferrihydrite.

Enhanced activity of gold-supported cobalt oxide for the electrochemical evolution of oxygen.

PubMed

Yeo, Boon Siang; Bell, Alexis T

2011-04-13

Scanning electron microscopy, linear sweep voltammetry, chronoamperometry, and in situ surface-enhanced Raman spectroscopy were used to investigate the electrochemical oxygen evolution reaction (OER) occurring on cobalt oxide films deposited on Au and other metal substrates. All experiments were carried out in 0.1 M KOH. A remarkable finding is that the turnover frequency for the OER exhibited by ∼0.4 ML of cobalt oxide deposited on Au is 40 times higher than that of bulk cobalt oxide. The activity of small amounts of cobalt oxide deposited on Pt, Pd, Cu, and Co decreased monotonically in the order Au > Pt > Pd > Cu > Co, paralleling the decreasing electronegativity of the substrate metal. Another notable finding is that the OER turnover frequency for ∼0.4 ML of cobalt oxide deposited on Au is nearly three times higher than that for bulk Ir. Raman spectroscopy revealed that the as-deposited cobalt oxide is present as Co(3)O(4) but undergoes progressive oxidation to CoO(OH) with increasing anodic potential. The higher OER activity of cobalt oxide deposited on Au is attributed to an increase in fraction of the Co sites present as Co(IV) cations, a state of cobalt believed to be essential for OER to occur. A hypothesis for how Co(IV) cations contribute to OER is proposed and discussed. © 2011 American Chemical Society

Technical issues of a high-Tc superconducting bulk magnet

NASA Astrophysics Data System (ADS)

Fujimoto, Hiroyuki

2000-06-01

Superconducting magnets made of high-Tc superconductors are promising for industrial applications. It is well known that REBa2Cu3O7-x superconductors prepared by melt processes have a high critical current density, Jc, at 77 K and high magnetic fields. The materials are very promising for high magnetic field applications as a superconducting permanent/bulk magnet with liquid-nitrogen refrigeration. Light rare-earth (LRE) BaCuO bulks, compared with REBaCuO bulks, exhibit a larger Jc in high magnetic fields and a much improved irreversibility field, Hirr, at 77 K. In this study, we discuss technical issues of a high-Tc superconducting bulk magnet, namely the aspects of the melt processing for bulk superconductors, their characteristic superconducting properties and mechanical properties, and trapped field properties of a superconducting bulk magnet. One of the possible applications is a superconducting bulk magnet for the magnetically levitated (Maglev) train in the future.

Direct Observation Through In Situ Transmission Electron Microscope of Early States of Crystallization in Nanoscale Metallic Glasses

NASA Astrophysics Data System (ADS)

Xie, Y.; Sohn, S.; Schroers, J.; Cha, J. J.

2017-11-01

Crystallization is a complex process that involves multiscale physics such as diffusion of atomic species over multiple length scales, thermodynamic energy considerations, and multiple possible intermediate states. In situ crystallization experiments inside a transmission electron microscope (TEM) using nanostructured metallic glasses (MGs) provide a unique platform to study directly crystallization kinetics and pathways. Here, we study the embryonic state of eutectic growth using Pt-Ni-Cu-P MG nanorods under in situ TEM. We directly observe the nucleation and growth of a Ni-rich polymorphic phase, followed by the nucleation and slower growth of a Cu-rich phase. The suppressed growth kinetics of the Cu-rich phase is attributed to locally changing chemical compositions. In addition, we show that growth can be controlled by incorporation of an entire nucleus instead of individual atoms. Such a nucleus has to align with the crystallographic orientation of a larger grain before it can be incorporated into the crystal. By directly observing the crystallization processes, particularly the early stages of non-polymorphic growth, in situ TEM crystallization studies of MG nanostructures provide a wealth of information, some of which can be applied to typical bulk crystallization.

Transient Liquid Phase Bonding of Cu-Cr-Zr-Ti Alloy Using Ni and Mn Coatings: Microstructural Evolution and Mechanical Properties

NASA Astrophysics Data System (ADS)

Venkateswaran, T.; Ravi, K. R.; Sivakumar, D.; Pant, Bhanu; Janaki Ram, G. D.

2017-08-01

High-strength copper alloys are used extensively in the regenerative cooling parts of aerospace structures. Transient liquid phase (TLP) bonding of a Cu-Cr-Zr-Ti alloy was attempted in the present study using thin layers of elemental Ni and Mn coatings applied by electroplating. One of the base metals was given a Ni coating of 4 µm followed by a Mn coating of 15 µm, while the other base metal was given only the Ni coating (4 µm). The bonding cycle consisted of the following: TLP stage—heating to 1030 °C and holding for 15 min; homogenization stage—furnace cooling to 880 °C and holding for 2 h followed by argon quenching to room temperature. Detailed microscopy and electron probe microanalysis analysis of the brazed joints were carried out. The braze metal was found to undergo isothermal solidification within the 15 min of holding time at 1030 °C. At the end of TLP stage, the braze metal showed a composition of Cu-17Ni-9Mn (wt.%) at the center of the joint with a steep gradient in Ni and Mn concentrations from the center of the braze metal to the base metal interfaces. After holding for 2 h at 880 °C (homogenization stage), the compositional gradients were found to flatten significantly and the braze metal was found to develop a homogeneous composition of Cu-11Ni-7Mn (wt.%) at the center of the joint. In lap-shear tests, failures were always found to occur in the base metal away from the brazed region. The copper alloy base metal was found to undergo significant grain coarsening due to high-temperature exposure during brazing and, consequently, suffer considerable reduction in yield strength.

Synthesis of copper oxide nanowires and nanoporous copper via environmentally friendly transformation of bulk copper-calcium alloys.

PubMed

Zhang, X; Turcheniuk, K; Zusmann, B; Benson, J; Nelson, S; Luo, S; Magasinski, A; Yushin, G

2018-05-24

In this work, we report a novel, one-step, inexpensive and environmentally friendly synthesis of Cu nanostructures by means of chemical de-alloying of bulk Cu-Ca alloys in aqueous solutions. By controlling the synthesis conditions, we tune the morphology of the nanostructured Cu from nanoporous Cu to copper oxide nanowires.

Review of the Potential of the Ni/Cu Plating Technique for Crystalline Silicon Solar Cells

PubMed Central

Rehman, Atteq ur; Lee, Soo Hong

2014-01-01

Developing a better method for the metallization of silicon solar cells is integral part of realizing superior efficiency. Currently, contact realization using screen printing is the leading technology in the silicon based photovoltaic industry, as it is simple and fast. However, the problem with metallization of this kind is that it has a lower aspect ratio and higher contact resistance, which limits solar cell efficiency. The mounting cost of silver pastes and decreasing silicon wafer thicknesses encourages silicon solar cell manufacturers to develop fresh metallization techniques involving a lower quantity of silver usage and not relying pressing process of screen printing. In recent times nickel/copper (Ni/Cu) based metal plating has emerged as a metallization method that may solve these issues. This paper offers a detailed review and understanding of a Ni/Cu based plating technique for silicon solar cells. The formation of a Ni seed layer by adopting various deposition techniques and a Cu conducting layer using a light induced plating (LIP) process are appraised. Unlike screen-printed metallization, a step involving patterning is crucial for opening the masking layer. Consequently, experimental procedures involving patterning methods are also explicated. Lastly, the issues of adhesion, back ground plating, process complexity and reliability for industrial applications are also addressed. PMID:28788516

Review of the Potential of the Ni/Cu Plating Technique for Crystalline Silicon Solar Cells.

PubMed

Rehman, Atteq Ur; Lee, Soo Hong

2014-02-18

Developing a better method for the metallization of silicon solar cells is integral part of realizing superior efficiency. Currently, contact realization using screen printing is the leading technology in the silicon based photovoltaic industry, as it is simple and fast. However, the problem with metallization of this kind is that it has a lower aspect ratio and higher contact resistance, which limits solar cell efficiency. The mounting cost of silver pastes and decreasing silicon wafer thicknesses encourages silicon solar cell manufacturers to develop fresh metallization techniques involving a lower quantity of silver usage and not relying pressing process of screen printing. In recent times nickel/copper (Ni/Cu) based metal plating has emerged as a metallization method that may solve these issues. This paper offers a detailed review and understanding of a Ni/Cu based plating technique for silicon solar cells. The formation of a Ni seed layer by adopting various deposition techniques and a Cu conducting layer using a light induced plating (LIP) process are appraised. Unlike screen-printed metallization, a step involving patterning is crucial for opening the masking layer. Consequently, experimental procedures involving patterning methods are also explicated. Lastly, the issues of adhesion, back ground plating, process complexity and reliability for industrial applications are also addressed.

Internal versus External Dose for Describing Ternary Metal Mixture (Ni, Cu, Cd) Chronic Toxicity to Lemna minor.

PubMed

Gopalapillai, Yamini; Hale, Beverley A

2017-05-02

Simultaneous determinations of internal dose ([M] tiss ) and external doses ([M] tot , {M 2+ } in solution) were conducted to study ternary mixture (Ni, Cu, Cd) chronic toxicity to Lemna minor in alkaline solution (pH 8.3). Also, concentration addition (CA) based on internal dose was evaluated as a tool for risk assessment of metal mixture. Multiple regression analysis of dose versus root growth inhibition, as well as saturation binding kinetics, provided insight into interactions. Multiple regressions were simpler for [M] tiss than [M] tot and {M 2+ }, and along with saturation kinetics to the internal biotic ligand(s) in the cytoplasm, they indicated that Ni-Cu-Cd competed for uptake into plant, but once inside, only Cu-Cd shared a binding site. Copper inorganic complexes (hydroxides, carbonates) played a role in metal bioavailability in single metal exposure but not in mixtures. Regardless of interactions, the current regulatory approach of using CA based on [M] tot can sufficiently predict mixture toxicity (∑TU close to 1), but CA based on [M] tiss was closest to unity across a range of doses. Internal dose integrates all metal-metal interactions in solution and during uptake into the organism, thereby providing a more direct metric describing toxicity.

Aspects of forming metal-clad melt-processed Y-Ba-Cu-O tapes

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

Kozlowski, G.; Oberly, C.E.; Ho, J.

1991-03-01

This paper reports on melt-processing of Y-Ba-Cu-O superconductor in a usable form for magnet winding which requires the development of a cladding with demanding properties. Numerous recent efforts in cold forming Bi-based superconductor tapes have been successful because a silver tube can be used to constrain the ceramic material, which is sintered at much lower temperature than the Y-Ba-Cu-O. Typical high temperature metals which can be used to encase Y-Ba-Cu-O during sintering do not permit ready diffusion of oxygen as silver does. Recently, the full or partial recovery of superconductivity has been achieved in transition-metal- doped Y-Ba-Cu-O due to themore » partial-melt processing.« less

Direct in Situ Conversion of Metals into Metal-Organic Frameworks: A Strategy for the Rapid Growth of MOF Films on Metal Substrates.

PubMed

Ji, Hoon; Hwang, Sunhyun; Kim, Keonmok; Kim, CheolGi; Jeong, Nak Cheon

2016-11-30

The fabrication of metal-organic framework (MOF) films on conducting substrates has demonstrated great potential in applications such as electronic conduction and sensing. For these applications, direct contact of the film to the conducting substrate without a self-assembled monolayer (SAM) is a desired step that must be achieved prior to the use of MOF films. In this report, we propose an in situ strategy for the rapid one-step conversion of Cu metal into HKUST-1 films on conducting Cu substrates. The Cu substrate acts both as a conducting substrate and a source of Cu 2+ ions during the synthesis of HKUST-1. This synthesis is possible because of the simultaneous reaction of an oxidizing agent and a deprotonating agent, in which the former agent dissolves the metal substrate to form Cu 2+ ions while the latter agent deprotonates the ligand. Using this strategy, the HKUST-1 film could not only be rapidly synthesized within 5 min but also be directly attached to the Cu substrate. Based on microscopic studies, we propose a plausible mechanism for the growth reaction. Furthermore, we show the versatility of this in situ conversion methodology, applying it to ZIF-8, which comprises Zn 2+ ions and imidazole-based ligands. Using an I 2 -filled HKUST-1 film, we further demonstrate that the direct contact of the MOF film to the conducting substrate makes the material more suitable for use as a sensor or electronic conductor.

Distribution of heavy metals and metalloids in bulk and particle size fractions of soils from coal-mine brownfield and implications on human health.

PubMed

Li, Hongxia; Ji, Hongbing; Shi, Chunjing; Gao, Yang; Zhang, Yan; Xu, Xiangyu; Ding, Huaijian; Tang, Lei; Xing, Yuxin

2017-04-01

Heavy metals (HMs) and metalloids migrate into their surroundings, thus increasing environmental risks and threatening human health. Current studies on coal-mine brownfields, however, have not thoroughly investigated soil-associated HMs and metalloids produced by coal mining. Therefore, this study explored the spatial and particle fraction distribution and human health implications of HMs and metalloids. The soil-associated HMs and metalloids are Arsenic (As), Cadmium (Cd), Chromium (Cr), Copper (Cu), Mercury (Hg), Manganese (Mn), Nickel (Ni), Lead (Pb), Scandium (Sc), Titanium (Ti) and Zinc (Zn). Results showed that Cd, Cu, Pb, and Ni were enriched in bulk soils. Cadmium, Cu and Pb from anthropogenic source were mainly found at entrance roadsides and in sites closest to coal mines. HMs and metalloids primarily accumulated in fine fractions (<1, 1-5, and 5-10 μm). Moreover, HM and metalloid loadings substantially accumulated in the 75-250 μm and 250-1000 μm fractions. Most fine soil fractions showed moderate to strong potential ecological risks, whereas all the coarse particle fractions (50-75, 75-250, and 250-1000 μm) presented slight potential ecological risk. Exposure to soil-associated HMs and metalloids mainly occurred via ingestion. The total non-carcinogenic risks to children and adults fell below the safe level of 1, whereas the total carcinogenic risks to these individuals were higher than that of the maximum acceptable level set by the United States Environmental Protection Agency (USEPA, 1 × 10 -4 ). The total carcinogenic risk was mainly contributed by Cd and Ni through ingestion and dermal access. Therefore, hygiene and food security in areas should be emphasized. Copyright © 2017 Elsevier Ltd. All rights reserved.

Nanocrystallization in Cu-Zr-Al-Sm Bulk Metallic Glasses

NASA Astrophysics Data System (ADS)

Sikan, Fatih; Yasar, Bengisu; Kalay, Ilkay

2018-04-01

The effect of rare-earth element (Sm) microalloying on the thermal stability and crystallization kinetics of melt-spun ribbons and suction-cast rods of Zr48Cu38.4Al9.6Sm4 alloy were investigated using differential scanning calorimetry (DSC), X-ray diffraction (XRD), transmission electron microscopy (TEM), and atom probe tomography (APT). The XRD results of constant heating rate annealing indicated that amorphous Zr48Cu38.4Al9.6Sm4 melt-spun ribbons devitrifies into Cu2Sm at 673 K (400 °C). The sequence continues with the precipitation of Cu10Zr7 and then these two phases coexist. XRD and TEM studies on 1 mm diameter as suction-cast rods indicated the precipitation of 30-nm-mean size Cu2Sm crystals during solidification. TEM investigation of the isothermal crystallization sequence of melt-spun ribbons and 1-mm-diameter suction-cast rods revealed the precipitation of Cu2Sm nanocrystals at the onset of crystallization and the restriction of the growth of these nanocrystals up to 10 nm diameter with further annealing. APT analysis of 1-mm-diameter suction-cast rods showed that the limited growth of Cu2Sm nanocrystals is due to sluggish diffusion of Sm and Al-Zr pile up at the interface.

Metal concentrations in aggregate interiors, exteriors, whole aggregates, and bulk of Costa Rican soils

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

Wilcke, W.; Kretzschmar, S.; Bundt, M.

1999-10-01

In many temperate soils the preferential weathering and leaching of aggregate surfaces and the nonaggregated material between aggregates depletes geogenic metals. It also shifts metals from strongly to more weakly bound metal forms. Deposited metals are sorbed preferentially on aggregate surfaces and between aggregates. The authors examined whether preferential desilication under tropical climate causes an enrichment in the aggregate exteriors in oxidic forms of metals. They also studied where deposited metals are bound in these soils. Aggregates (2--20 mm) were selected manually from the A horizons of eight Oxisols, six Andisols, two Mollisols, and two Inceptisols in Costa Rica. Allmore » samples were fractionated into interior and exterior portions and treated with a seven-step sequence to extract Al, Cd, Cu, Fe, Mn, Pb, and Zn. Total concentrations of all metals except Zn were higher in the aggregate exteriors than in the interiors. The average Cd and Pb concentrations in easily extractable fractions were significantly higher in the aggregate exteriors. There were no significant differences in metal partitioning between interiors and exteriors except for Pb, which had higher proportions in extractable forms with NH{sub 2}OH {center{underscore}dot} HCl {gt} NH{sub 4} - acetate, pH 6.0 {gt} EDTA in the exteriors. There were few significant differences in metal concentrations and partitioning between bulk soil and whole aggregates. The results may be explained by (i) preferential desilication of the aggregate exteriors and (ii) preferential sorption of deposited heavy metals mainly in easily extractable forms.« less

Effect of physisorbed molecules and an external external fields on the metallic Shockley surface state of Cu(111): A density functional theory study

NASA Astrophysics Data System (ADS)

Berland, Kristian; Einstein, T. L.; Hyldgaard, Per

2012-02-01

To manipulate the Cu(111) partially-filled Shockley surface state, we study its response to an external fieldootnotetextKB, TLE, PH; arXiv 1109:6706 E and physisorbed PAHs and quinone molecules. We use density-functional theory calculations with periodic-boundary conditions. The van der Waals density functional version vdW-DF2 accounts for the molecular adsorption. The issue that the Kohn-Sham wave functions couple to both sides of the Cu slab is handled with a decoupling scheme based on a rotation in Hilbert space. A convergence study reveals that to obtain a proper Shockley surface state, 6 Cu layers is sufficient, while 15 is optimal. We use 6 layers for the response to the molecules and 15 to external field. We find that the surface state displays isotropic dispersion (up to order k^6), free-electron like until the Fermi wave vector but with a significant quartic component beyond. The shift in band minimum and effective mass depend linearly on E, with a smaller fractional change in the latter. Charge transfer occurs beyond the outermost copper atoms, and most of the screening is due to bulk electrons. We find that the molecular physisorption increases the band minimum, with the effect the of a quinone being much stronger than the corresponding PAH.

Synthesis and microstructural TEM investigation of CaCu 3Ru 4O 12 ceramic and thin film

NASA Astrophysics Data System (ADS)

Brizé, Virginie; Autret-Lambert, Cécile; Wolfman, Jérôme; Gervais, Monique; Gervais, François

2011-10-01

CaCu 3Ru 4O 12 (CCRO) is a conductive oxide having the same structure as CaCu 3Ti 4O 12 (CCTO) and close lattice parameters. The later compound is strongly considered for high density parallel plates capacitors application due to its so-called colossal dielectric constant. The need for an electrode inducing CCTO epitaxial growth with a clean and sharp interface is therefore necessary, and CCRO is a good potential candidate. In this paper, the synthesis of monophasic CCRO ceramic is reported, as well as pulsed laser deposition of CCRO thin film onto (001) NdCaAlO 4 substrate. Structural and physical properties of bulk CCRO were studied by transmission electron microscopy and electron spin resonance. CCRO films and ceramic exhibited a metallic behavior down to low temperature. CCRO films were (001) oriented and promoted a CCTO film growth with the same orientation.

Combined Thermodynamic-Kinetic Analysis of the Interfacial Reactions between Ni Metallization and Various Lead-Free Solders

PubMed Central

Laurila, Tomi; Vuorinen, Vesa

2009-01-01

In this paper we will demonstrate how a thermodynamic-kinetic method can be utilized to rationalize a wide range of interfacial phenomena between Sn-based lead-free solders and Ni metallizations. First, the effect of P on the interfacial reactions, and thus on the reliability, between Sn-based solders and electroless Ni/immersion Au (ENIG) metallizations, will be discussed. Next, the effect of small amounts of Cu in Sn-based solders on the intermetallic compound (IMC), which forms first on top of Ni metallization, will be covered. With the help of thermodynamic arguments a so called critical Cu concentration for the formation of (Cu,Ni)6Sn5 can be determined as a function of temperature. Then the important phenomenon of redeposition of (Au,Ni)Sn4 layer on top of Ni3Sn4 IMC will be discussed in detail. The reasons leading to this behaviour will be rationalized with the help of thermodynamic information and an explanation of why this phenomenon does not occur when an appropriate amount of Cu is present in the soldering system will be given. Finally, interfacial reaction issues related to low temperature Sn-Zn and Sn-Bi based solders and Ni metallization will be discussed.

Metal (II) Complexes Derived from Naphthofuran-2-carbohydrazide and Diacetylmonoxime Schiff Base: Synthesis, Spectroscopic, Electrochemical, and Biological Investigation

PubMed Central

Sumathi, R. B.; Halli, M. B.

2014-01-01

A new Schiff base and a new series of Co(II), Ni(II), Cu(II), Cd(II), and Hg(II) complexes were synthesized by the condensation of naphthofuran-2-carbohydrazide and diacetylmonoxime. Metal complexes of the Schiff base were prepared from their chloride salts of Co(II), Ni(II), Cu(II), Cd(II), and Hg(II) in ethanol. The ligand along with its metal complexes have been characterized on the basis of analytical data, IR, electronic, mass, 1HNMR, ESR spectral data, thermal studies, magnetic susceptibility, and molar conductance measurements. The nonelectrolytic behaviour of the complexes was assessed from the measured low conductance data. The elemental analysis of the complexes confirm the stoichiometry of the type CuL2Cl2 and MLCl2 where M = Ni(II), Co(II), Cd(II), and Hg(II) and L = Schiff base. The redox property of the Cu(II) complex was investigated by electrochemical method using cyclic voltammetry. In the light of these results, Co(II), Ni(II), and Cu(II) complexes are assigned octahedral geometry, Cd(II), and Hg(II) complexes tetrahedral geometry. In order to evaluate the effect of metal ions upon chelation, both the ligand and its metal complexes were screened for their antibacterial and antifungal activities by minimum inhibitory concentration (MIC) method. The DNA cleaving capacity of all the complexes was analysed by agarose gel electrophoresis method. PMID:24592203

Microgravity metal processing: from undercooled liquids to bulk metallic glasses

PubMed Central

Hofmann, Douglas C; Roberts, Scott N

2015-01-01

Bulk metallic glasses (BMGs) are a novel class of metal alloys that are poised for widespread commercialization. Over 30 years of NASA and ESA (as well as other space agency) funding for both ground-based and microgravity experiments has resulted in fundamental science data that have enabled commercial production. This review focuses on the history of microgravity BMG research, which includes experiments on the space shuttle, the ISS, ground-based experiments, commercial fabrication and currently funded efforts. PMID:28725709

Excellent Resistive Switching Performance of Cu-Se-Based Atomic Switch Using Lanthanide Metal Nanolayer at the Cu-Se/Al2O3 Interface.

PubMed

Woo, Hyunsuk; Vishwanath, Sujaya Kumar; Jeon, Sanghun

2018-03-07

The next-generation electronic society is dependent on the performance of nonvolatile memory devices, which has been continuously improving. In the last few years, many memory devices have been introduced. However, atomic switches are considered to be a simple and reliable basis for next-generation nonvolatile devices. In general, atomic switch-based resistive switching is controlled by electrochemical metallization. However, excess ion injection from the entire area of the active electrode into the switching layer causes device nonuniformity and degradation of reliability. Here, we propose the fabrication of a high-performance atomic switch based on Cu x -Se 1- x by inserting lanthanide (Ln) metal buffer layers such as neodymium (Nd), samarium (Sm), dysprosium (Dy), or lutetium (Lu) between the active metal layer and the electrolyte. Current-atomic force microscopy results confirm that Cu ions penetrate through the Ln-buffer layer and form thin conductive filaments inside the switching layer. Compared with the Pt/Cu x -Se 1- x /Al 2 O 3 /Pt device, the optimized Pt/Cu x -Se 1- x /Ln/Al 2 O 3 /Pt devices show improvement in the on/off resistance ratio (10 2 -10 7 ), retention (10 years/85 °C), endurance (∼10 000 cycles), and uniform resistance state distribution.

Radial metal concentration profiles in trees growing on highly contaminated soils.

PubMed

Superville, Pierre-Jean; de Winter, Niels; Phung, Anh Tuan; Proix, Nicolas; Baeyens, Willy; Gao, Yue

2017-04-01

The soil around Metaleurop, a big smelter, is heavily contaminated by Zn, Pb, Cd and Cu. In order to compare the impact of different soil amendments on the metal availability to trees, the polluted soil section was divided in a reference parcel and two others with either sulfo-calcic or silico-aluminous ash amendments. Five different tree species were planted on the parcels and the uptake of heavy metals in these trees was studied. Total and labile metal fractions were assessed in each of the 3 parcels. The mobility and assimilation of the metals was highest in the non-amended, reference soil parcel which had the lowest pH, organic matter and carbonate content. In all soils, pH decreased while organic matter content and mobility of the metals increased over time. Highest bulk concentrations of trace metals were found in white willow trees (Salix alba L.). Laser ablation-ICPMS was used to study changes in metal accumulation over a period of 10 years after planting the trees. The radial metal profiles in the trunk core samples varied between elements and tree species, however, in all willow trees the radial Cd and Zn profiles were significantly correlated. Radial pollutant concentration patterns are discussed in terms of seasonal effects, health status, tree species and metal mobility in the soil. For Cd and Zn, the profiles were influenced by their mobility in the soils. In general, periodical patterns were observed for Pb. Cu concentration profiles were decreasing over time, with the strongest decrease in the initial growth period. Copyright © 2016 Elsevier Ltd. All rights reserved.

Preparation, optical and non-linear optical power limiting properties of Cu, CuNi nanowires

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

Udayabhaskar, R.; Karthikeyan, B., E-mail: bkarthik@nitt.edu; Ollakkan, Muhamed Shafi

2014-01-06

Metallic nanowires show excellent Plasmon absorption which is tunable based on its aspect ratio and alloying nature. We prepared Cu and CuNi metallic nanowires and studied its optical and nonlinear optical behavior. Optical properties of nanowires are theoretically explained using Gans theory. Nonlinear optical behavior is studied using a single beam open aperture z-scan method with the use of 5 ns Nd: YAG laser. Optical limiting is found to arise from two-photon absorption.

Preparation, optical and non-linear optical power limiting properties of Cu, CuNi nanowires

NASA Astrophysics Data System (ADS)

Udayabhaskar, R.; Ollakkan, Muhamed Shafi; Karthikeyan, B.

2014-01-01

Metallic nanowires show excellent Plasmon absorption which is tunable based on its aspect ratio and alloying nature. We prepared Cu and CuNi metallic nanowires and studied its optical and nonlinear optical behavior. Optical properties of nanowires are theoretically explained using Gans theory. Nonlinear optical behavior is studied using a single beam open aperture z-scan method with the use of 5 ns Nd: YAG laser. Optical limiting is found to arise from two-photon absorption.

A novel series of isoreticular metal organic frameworks: realizing metastable structures by liquid phase epitaxy

PubMed Central

Liu, Jinxuan; Lukose, Binit; Shekhah, Osama; Arslan, Hasan Kemal; Weidler, Peter; Gliemann, Hartmut; Bräse, Stefan; Grosjean, Sylvain; Godt, Adelheid; Feng, Xinliang; Müllen, Klaus; Magdau, Ioan-Bogdan; Heine, Thomas; Wöll, Christof

2012-01-01

A novel class of metal organic frameworks (MOFs) has been synthesized from Cu-acetate and dicarboxylic acids using liquid phase epitaxy. The SURMOF-2 isoreticular series exhibits P4 symmetry, for the longest linker a channel-size of 3 × 3 nm2 is obtained, one of the largest values reported for any MOF so far. High quality, ab-initio electronic structure calculations confirm the stability of a regular packing of (Cu++)2- carboxylate paddle-wheel planes with P4 symmetry and reveal, that the SURMOF-2 structures are in fact metastable, with a fairly large activation barrier for the transition to the bulk MOF-2 structures exhibiting a lower, twofold (P2 or C2) symmetry. The theoretical calculations also allow identifying the mechanism for the low-temperature epitaxial growth process and to explain, why a synthesis of this highly interesting, new class of high-symmetry, metastable MOFs is not possible using the conventional solvothermal process. PMID:23213357

Linear Chains of Magnetic Ions Stacked with Variable Distance: Ferromagnetic Ordering with a Curie Temperature above 20 K.

PubMed

Friedländer, Stefan; Liu, Jinxuan; Addicoat, Matt; Petkov, Petko; Vankova, Nina; Rüger, Robert; Kuc, Agnieszka; Guo, Wei; Zhou, Wencai; Lukose, Binit; Wang, Zhengbang; Weidler, Peter G; Pöppl, Andreas; Ziese, Michael; Heine, Thomas; Wöll, Christof

2016-10-04

We have studied the magnetic properties of the SURMOF-2 series of metal-organic frameworks (MOFs). Contrary to bulk MOF-2 crystals, where Cu(2+) ions form paddlewheels and are antiferromagnetically coupled, in this case the Cu(2+) ions are connected via carboxylate groups in a zipper-like fashion. This unusual coupling of the spin 1/2 ions within the resulting one-dimensional chains is found to stabilize a low-temperature, ferromagnetic (FM) phase. In contrast to other ordered 1D systems, no strong magnetic fields are needed to induce the ferromagnetism. The magnetic coupling constants describing the interaction between the individual metal ions have been determined in SQUID experiments. They are fully consistent with the results of ab initio DFT electronic structure calculations. The theoretical results allow the unusual magnetic behavior of this exotic, yet easy-to-fabricate, material to be described in a detailed fashion. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Effect of Redox “Non-Innocent” Linker on the Catalytic Activity of Copper-Catecholate-Decorated Metal–Organic Frameworks

DOE PAGES

Zhang, Xuan; Vermeulen, Nicolaas A.; Huang, Zhiyuan; ...

2017-12-26

Two new UiO-68 type of Zr-MOFs featuring redox non-innocent catechol-based linkers of different redox activities have been synthesized through a de novo mixed-linker strategy. Also, metalation of the MOFs with Cu(II) precursors triggers the reduction of Cu(II) by the phenyl-catechol groups to Cu(I) with the concomitant formation of semiquinone radicals as evidenced by EPR and XPS characterization. The MOF-supported catalysts are selective toward the allylic oxidation of cyclohexene and it is found that the presence of in situ-generated Cu(I) species exhibits enhanced catalytic activity as compared to a similar MOF with Cu(II) metalated naphthalenyl-dihydroxy groups. Here, this work unveils themore » importance of metal-support redox interactions in the catalytic activity of MOF-supported catalysts which are not easily accessible in traditional metal oxide supports.« less

Effect of Redox “Non-Innocent” Linker on the Catalytic Activity of Copper-Catecholate-Decorated Metal–Organic Frameworks

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

Zhang, Xuan; Vermeulen, Nicolaas A.; Huang, Zhiyuan

Two new UiO-68 type of Zr-MOFs featuring redox non-innocent catechol-based linkers of different redox activities have been synthesized through a de novo mixed-linker strategy. Also, metalation of the MOFs with Cu(II) precursors triggers the reduction of Cu(II) by the phenyl-catechol groups to Cu(I) with the concomitant formation of semiquinone radicals as evidenced by EPR and XPS characterization. The MOF-supported catalysts are selective toward the allylic oxidation of cyclohexene and it is found that the presence of in situ-generated Cu(I) species exhibits enhanced catalytic activity as compared to a similar MOF with Cu(II) metalated naphthalenyl-dihydroxy groups. Here, this work unveils themore » importance of metal-support redox interactions in the catalytic activity of MOF-supported catalysts which are not easily accessible in traditional metal oxide supports.« less

Bio-corrosion and cytotoxicity studies on novel Zr 55Co 30Ti 15 and Cu 60Zr 20Ti 20 metallic glasses

DOE PAGES

Vincent, S.; Daiwile, A.; Devi, S. S.; ...

2014-09-26

Metallic glasses are a potential and compatible implant candidate for biomedical applications. In the present investigation, a comparative study between novel Zr 55Co 30Ti 15 and Cu 60Zr 20Ti 20 metallic glasses is carried out to evaluate in vitro biocompatibility using simulated body fluids. The bio-corrosion behavior of Zr- and Cu-based metallic glasses in different types of artificial body fluids such as artificial saliva solution, phosphate-buffered saline solution, artificial blood plasma solution, and Hank’s balanced saline solution is evaluated using potentiodynamic polarization studies at a constant body temperature of 310.15 K (37 °C). Surface morphology of samples after bio-corrosion experimentsmore » was observed by scanning electron microscopy. In vitro cytotoxicity test on glassy alloys were performed using human osteosarcoma cell line as per 10993-5 guidelines from International Organization for Standardization. As a result, the comparative study between Zr- and Cu-based glassy alloys provides vital information about the effect of elemental composition on biocompatibility of metallic glasses.« less

Structural characterization of multimetallic nanoparticles

NASA Astrophysics Data System (ADS)

Mukundan, Vineetha

Bimetallic and trimetallic alloy nanoparticles have enhanced catalytic activities due to their unique structural properties. Using in situ time-resolved synchrotron based x-ray diffraction, we investigated the structural properties of nanoscale catalysts undergoing various heat treatments. Thermal treatment brings about changes in particle size, morphology, dispersion of metals on support, alloying, surface electronic properties, etc. First, the mechanisms of coalescence and grain growth in PtNiCo nanoparticles supported on planar silica on silicon were examined in detail in the temperature range 400-900°C. The sintering process in PtNiCo nanoparticles was found to be accompanied by lattice contraction and L10 chemical ordering. The mass transport involved in sintering is attributed to grain boundary diffusion and its corresponding activation energy is estimated from the data analysis. Nanoscale alloying and phase transformations in physical mixtures of Pd and Cu ultrafine nanoparticles were also investigated in real time with in situ synchrotron based x-ray diffraction complemented by ex situ high-resolution transmission electron microscopy. PdCu nanoparticles are interesting because they are found to be more efficient as catalysts in ethanol oxidation reaction (EOR) than monometallic Pd catalysts. The combination of metal support interaction and reactive/non-reactive environment was found to determine the thermal evolution and ultimate structure of this binary system. The composition of the as prepared Pd:Cu mixture in this study was 34% Pd and 66% Cu. At 300°C, the nanoparticles supported on silica and carbon black intermix to form a chemically ordered CsCl-type (B2) alloy phase. The B2 phase transforms into a disordered fcc alloy at higher temperature (>450°C). The alloy nanoparticles supported on silica and carbon black are homogeneous in volume, but evidence was found of Pd surface enrichment. In sharp contrast, when supported on alumina, the two metals segregated at 300°C to produce almost pure fcc Cu and Pd phases. Upon further annealing of the mixture on alumina above 600°C, the two metals interdiffused, forming two distinct disordered alloys of compositions 30% and 90% Pd. The annealing atmosphere also plays a major role in the structural evolution of these bimetallic nanoparticles. The nanoparticles annealed in forming gas are larger than the nanoparticles annealed in helium due to reduction of the surface oxides that promotes coalescence and sintering. The nanoscale composition and structure of alloy catalysts affect heterogeneous catalysis. We also studied Pd:Cu nanoparticle mixtures of different compositions. In Pd:Cu of composition ratio 1:1, ordered B2 phase is formed during annealing at 450C. During the ramped annealing from 450°C to 750°C, the B2 phase transforms into two different alloys, one alloy rich in copper and the other rich in Pd. This structural evolution is different from that of Pd-Cu system in bulk. In the 3:1 composition, the B2 phase dominates in the isothermal anneal at 450C but a disordered alloy fcc phase is also formed. On annealing to 750°C, the disordered fcc phase grows at the expense of the B2 phase. These findings have important applications for the thermal activation of Pd-Cu nanocatalysts for EOR reactions.

Proposal of a Bulk HTSC Staggered Array Undulator

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

Kii, Toshiteru; Kinjo, Ryota; Bakr, Mahmoud A.

We proposed a new type of undulator based on bulk high-T{sub c} superconductors (HTSC) which consists of a single solenoid and a stacked array of bulk HTSC. The main advantage of this configuration is that a mechanical structure is not required to produce and control the undulator field. In order to perform a proof of principle experiment, we have developed a prototype of bulk HTSC staggered array undulator using 11 pairs of DyBaCuO bulk superconductors and a normal conducting solenoid. Experimental results obtained by using the prototype undulator and numerical results obtained by a loop current model based on themore » Bean mode for a type-II superconductor were compared.« less

Polarization Dependent Bulk-sensitive Valence Band Photoemission Spectroscopy and Density Functional Theory Calculations: Part I. 3d Transition Metals

NASA Astrophysics Data System (ADS)

Ueda, Shigenori; Hamada, Ikutaro

2017-12-01

The X-ray polarization dependent valence band HAXPES spectra of 3d transition metals (TMs) of Ti-Zn were measured to investigate the orbital resolved electronic structures by utilizing that the fact the photoionization cross-section of the atomic orbitals strongly depends on the experimental geometry. We have calculated the HAXPES spectra, which correspond to the cross-section weighted densities of states (CSW-DOSs), where the DOSs were obtained by the density functional theory calculations, and we have determined the relative photoionization cross-sections of the 4s and 4p orbitals to the 3d orbital in the 3d TMs. The experimentally obtained bulk-sensitive 3d and 4s DOSs were good agreement with the calculated DOSs in Ti, V, Cr, and Cu. In contrast, the deviations between the experimental and calculated 3d DOSs for Mn, Fe, Co, Ni were found, suggesting that the electron correlation plays an important role in the electronic structures for these materials.

Effects of minor Cu and Si additions on glass forming ability and mechanical properties of Co-Fe-Ta-B Bulk metallic glass

NASA Astrophysics Data System (ADS)

Yazici, Ziya Ozgur; Hitit, Aytekin; Yalcin, Yilmaz; Ozgul, Metin

2016-01-01

Effect of Cu and Si substitutions for Co and B on the glass forming ability (GFA) of Co(43-x)CuxFe20Ta5.5B(31.5-x)Siy (x=0-1.5 and y=5-10) were systematically investigated by X-ray diffraction, optical microscopy, scanning electron microscopy, and differential scanning calorimetry. In order to evaluate the contribution of copper and silicon, appropriate amounts of copper and silicon were individually introduced to the base alloy composition. By using the effects of copper and silicon together, significant enhancement was obtained and the critical casting thickness (CCT) of the base alloy was increased three times from 2 mm to 6 mm. Moreover, mechanical properties of the alloys were examined by compression tests and Vickers hardness measurements. The compression test results revealed that the glassy alloys having enhanced GFA shows high strength of about 3500-4000 MPa. In addition, existence of (Co,Fe)2B and (Co,Fe)20.82Ta2.18B6 crystalline phases in glassy matrix influences the hardnesses of the alloys compared to monolitic glassy structure having hardness of about 1200 Hv.

Integrated Solid/Nanoporous Copper/Oxide Hybrid Bulk Electrodes for High-performance Lithium-Ion Batteries

PubMed Central

Hou, Chao; Lang, Xing-You; Han, Gao-Feng; Li, Ying-Qi; Zhao, Lei; Wen, Zi; Zhu, Yong-Fu; Zhao, Ming; Li, Jian-Chen; Lian, Jian-She; Jiang, Qing

2013-01-01

Nanoarchitectured electroactive materials can boost rates of Li insertion/extraction, showing genuine potential to increase power output of Li-ion batteries. However, electrodes assembled with low-dimensional nanostructured transition metal oxides by conventional approach suffer from dramatic reductions in energy capacities owing to sluggish ion and electron transport kinetics. Here we report that flexible bulk electrodes, made of three-dimensional bicontinuous nanoporous Cu/MnO2 hybrid and seamlessly integrated with Cu solid current collector, substantially optimizes Li storage behavior of the constituent MnO2. As a result of the unique integration of solid/nanoporous hybrid architecture that simultaneously enhances the electron transport of MnO2, facilitates fast ion diffusion and accommodates large volume changes on Li insertion/extraction of MnO2, the supported MnO2 exhibits a stable capacity of as high as ~1100 mA h g−1 for 1000 cycles, and ultrahigh charge/discharge rates. It makes the environmentally friendly and low-cost electrode as a promising anode for high-performance Li-ion battery applications. PMID:24096928

Characterization of the interface between the bulk glass forming alloy Zr{sub 41}Ti{sub 14}Cu{sub 12}Ni{sub 10}Be{sub 23} with pure metals and ceramics

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

Schroers, Jan; Samwer, Konrad; Szuecs, Frigyes

The reaction of the bulk glass forming alloy Zr{sub 41}Ti{sub 14}Cu{sub 12}Ni{sub 10}Be{sub 23} (Vit 1) with W, Ta, Mo, AlN, Al{sub 2}O{sub 3}, Si, graphite, and amorphous carbon was investigated. Vit 1 samples were melted and subsequently solidified after different processing times on discs of the different materials. Sessile drop examinations of the macroscopic wetting of Vit 1 on the discs as a function of temperature were carried out in situ with a digital optical camera. The reactions at the interfaces between the Vit 1 sample and the different disc materials were investigated with an electron microprobe. The structuremore » and thermal stability of the processed Vit 1 samples were examined by x-ray diffraction and differential scanning calorimetry. The results are discussed in terms of possible applications for composite materials. (c) 2000 Materials Research Society.« less

CuAAC-Based Click Chemistry in Self-Healing Polymers.

PubMed

Döhler, Diana; Michael, Philipp; Binder, Wolfgang H

2017-10-17

Click chemistry has emerged as a significant tool for materials science, organic chemistry, and bioscience. Based on the initial concept of Barry Sharpless in 2001, the copper(I)-catalyzed azide/alkyne cycloaddition (CuAAC) reaction has triggered a plethora of chemical concepts for linking molecules and building blocks under ambient conditions, forming the basis for applications in autonomous cross-linking materials. Self-healing systems on the other hand are often based on mild cross-linking chemistries that are able to react either autonomously or upon an external trigger. In the ideal case, self-healing takes place efficiently at low temperatures, independent of the substrate(s) used, by forming strong and stable networks, binding to the newly generated (cracked) interfaces to restore the original material properties. The use of the CuAAC in self-healing systems, most of all the careful design of copper-based catalysts linked to additives as well as the chemical diversity of substrates, has led to an enormous potential of applications of this singular reaction. The implementation of click-based strategies in self-healing systems therefore is highly attractive, as here chemical (and physical) concepts of molecular reactivity, molecular design, and even metal catalysis are connected to aspects of materials science. In this Account, we will show how CuAAC reactions of multivalent components can be used as a tool for self-healing materials, achieving cross-linking at low temperatures (exploiting concepts of autocatalysis or internal chelation within the bulk CuAAC and systematic optimization of the efficiency of the used Cu(I) catalysts). Encapsulation strategies to separate the click components by micro- and nanoencapsulation are required in this context. Consequently, the examples reported here describe chemical concepts to realize more efficient and faster click reactions in self-healing polymeric materials. Thus, enhanced chain diffusion in (hyper)branched polymers, autocatalysis, or internal chelation concepts enable efficient click cross-linking already at 5 °C with a simultaneously reduced amount of Cu(I) catalyst and increased reaction rates, culminating in the first reported self-healing system based on click cycloaddition reactions. Via tailor-made nanocarbon/Cu(I) catalysts we can further improve the click cross-linking reaction in view of efficiency and kinetics, leading to the generation of self-healing graphene-based epoxy nanocomposites. Additionally, we have designed special CuAAC click methods for chemical reporting and visualization systems based on the detection of ruptured capsules via a fluorogenic click reaction, which can be combined with CuAAC cross-linking reactions to obtain simultaneous stress detection and self-healing within polymeric materials. In a similar concept, we have prepared polymeric Cu(I)-biscarbene complexes to detect (mechanical) stress within self-healing polymeric materials via a triggered fluorogenic reaction, thus using a destructive force for a constructive chemical response.

The Microstructural Evolution of Vacuum Brazed 1Cr18Ni9Ti Using Various Filler Metals

PubMed Central

Chen, Yunxia; Cui, Haichao; Lu, Binfeng; Lu, Fenggui

2017-01-01

The microstructures and weldability of a brazed joint of 1Cr18Ni9Ti austenitic stainless steel with BNi-2, BNi82CrSiBFe and BMn50NiCuCrCo filler metals in vacuum were investigated. It can be observed that an interdiffusion region existed between the filler metal and the base metal for the brazed joint of Ni-based filler metals. The width of the interdiffusion region was about 10 μm, and the microstructure of the brazed joint of BNi-2 filler metal was dense and free of obvious defects. In the case of the brazed joint of BMn50NiCuCrCo filler metal, there were pits, pores and crack defects in the brazing joint due to insufficient wettability of the filler metal. Crack defects can also be observed in the brazed joint of BNi82CrSiBFe filler metal. Compared with BMn50NiCuCrCo and BNi82CrSiBFe filler metals, BNi-2 filler metal is the best material for 1Cr18Ni9Ti austenitic stainless steel vacuum brazing because of its distinct weldability. PMID:28772745

Metal Immiscibility Route to Synthesis of Ultrathin Carbides, Borides, and Nitrides.

PubMed

Wang, Zixing; Kochat, Vidya; Pandey, Prafull; Kashyap, Sanjay; Chattopadhyay, Soham; Samanta, Atanu; Sarkar, Suman; Manimunda, Praveena; Zhang, Xiang; Asif, Syed; Singh, Abhisek K; Chattopadhyay, Kamanio; Tiwary, Chandra Sekhar; Ajayan, Pulickel M

2017-08-01

Ultrathin ceramic coatings are of high interest as protective coatings from aviation to biomedical applications. Here, a generic approach of making scalable ultrathin transition metal-carbide/boride/nitride using immiscibility of two metals is demonstrated. Ultrathin tantalum carbide, nitride, and boride are grown using chemical vapor deposition by heating a tantalum-copper bilayer with corresponding precursor (C 2 H 2 , B powder, and NH 3 ). The ultrathin crystals are found on the copper surface (opposite of the metal-metal junction). A detailed microscopy analysis followed by density functional theory based calculation demonstrates the migration mechanism, where Ta atoms prefer to stay in clusters in the Cu matrix. These ultrathin materials have good interface attachment with Cu, improving the scratch resistance and oxidation resistance of Cu. This metal-metal immiscibility system can be extended to other metals to synthesize metal carbide, boride, and nitride coatings. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

DFT investigation of the vibrational properties of GC Watson-Crick and Hoogsteen base pairs in the presence of Mg²⁺, Ca²⁺, and Cu²⁺ ions.

PubMed

Morari, Cristian; Muntean, Cristina M; Tripon, Carmen; Buimaga-Iarinca, Luiza; Calborean, Adrian

2014-04-01

The binding effects of Mg²⁺, Ca²⁺, and Cu²⁺ ions on the vibrational properties of guanine-cytosine base pairs have been performed using density functional theory investigations. Both Watson-Crick and Hoogsteen configurations of the base pairs were investigated. In Watson-Crick configuration, the metal was coordinated at N7 atom of guanine, while in the case of Hoogsteen configuration, the coordination is at N3 atom of guanine. We have pointed out the geometric properties of the metal-GC base pairs structure, as well as the vibrational bands that can be used to detect the presence of metallic ions in the Watson-Crick and Hoogsteen GC structures. For the geometric models used by us, the vibrational amplitudes of metallic atoms were stronger for wavenumbers lower than 500 cm⁻¹. This suggests that in the experimental studies on DNA the presence of the three metallic atoms (Mg, Ca, and Cu) can be explicitly detected at low frequencies.

Computational prediction of the electronic structure and optical properties of graphene-like β-CuN3.

PubMed

Zhang, Xu; Zhao, Xudong; Jing, Yu; Wu, Dihua; Zhou, Zhen

2015-12-21

Recently, a new polymorph of the highly energetic phase β-CuN3 has been synthesized. By hybrid density functional computations, we investigated the structural, electronic and optical properties of β-CuN3 bulk and layers. Due to the quantum confinement effect, the band gap of the monolayer (2.39 eV) is larger than that of the bulk (2.23 eV). The layer number affects the configuration and the band gap. β-CuN3 shows both ionic and covalent characters, and could be stable in the infrared and visible spectrum and would decompose under ultraviolet light. The results imply that bulk β-CuN3 could be used as an energetic material.

Novel configuration of processing bulk textured YB 2Cu 3O 7-x superconductor by seeded infiltration growth method

NASA Astrophysics Data System (ADS)

Cao, Haitao; Moutalbi, Nahed; Harnois, Christelle; Hu, Rui; Li, Jinshan; Zhou, Lian; Noudem, Jacques G.

2010-01-01

Mono-domain YBa 2Cu 3O 7-x (Y123) bulk superconductors have been processed using seeded infiltration growth technique (SIG). The combination of melt infiltrated liquid source (Ba 3Cu 5O 8) into the Y 2BaCuO 5 (Y211) pre-form and the nucleation of Y123 domain from SmBa 2Cu 3O 7 crystal seed has been investigated. The different configurations of SIG process were compared in this study. In addition, the effect of the starting Y211 particles size has been studied. The results reveal that, the Y211 particle size and different configurations strongly influence the properties of the final bulk superconductor sample.

Characterization and tailoring of porous sol-gel dielectrics for interlayer dielectric applications

NASA Astrophysics Data System (ADS)

Rogojevic, Svetlana

A new, better insulator is needed to replace SiO2 in the next generation of microelectronic devices. The dielectric constant of porous materials can be tailored by adjusting the porosity, so that their use can be extended to more than one generation of devices. Silica xerogel films with wide range of porosities (25 90%) are fabricated by varying the rate of solvent evaporation during spin-coating. Even better porosity control is achieved by using mixtures of high and low boiling point solvents, and allowing one solvent to evaporate completely during spin-coating. The quartz crystal microbalance method was employed to measure the traces of moisture adsorbed in xerogel films of varying porosities. By employing two different surface modifiers, it is demonstrated that the level of hydrophobicity is a function of surface chemistry, and can be tailored by using a suitable surface modifier. To investigate the interaction of xerogels with other materials, metallic layers were deposited on xerogel films, and subsequently annealed. When annealed in the ambient with trace amount of oxygen, Ta and Cu films undergo morphological instabilities. These morphological changes may lead to the erroneous interpretation of the Rutherford backscattering spectra as metal diffusion. When the samples are capped with a Si3N4 layer, Cu and Ta do not show diffusion through xerogel when annealed up to 650°C. Bias-temperature stressing was conducted in order to assess Cu drift through xerogel in the presence of an electric field. Contrary to what is normally observed with other dielectrics, the leakage current and C-V curve shifts were larger with an Al electrode than with a Cu electrode. This indicates that the surface modification of xerogel can contribute to the smaller charge injection from the Cu/xerogel interface, or to the inhibition of Cu diffusion, thus offering a possibility of designing future monolayer diffusion barriers for porous materials. Two possible paths of mass transfer in porous solids are identified: bulk and surface diffusion. Three driving forces are also analyzed: concentration gradient, electric field, and curvature gradient. The model of diffusion through porous solids shows the effects of the electric field, the solid network thickness, porosity, surface and bulk diffusivity. The model is a useful tool for designing and interpreting the experiments, in order to assess the role of surface diffusion in porous materials.

Environmental contamination associated with a marine landfill ('seafill') beside a coral reef.

PubMed

Jones, Ross

2010-11-01

In Bermuda, bulk waste such as scrap metal, cars, etc., and blocks of cement-stabilized incinerator ash (produced from burning garbage) are disposed of in a foreshore reclamation site, i.e., a seafill. Chemical analyses show that seawater leaching out of the dump regularly exceeds water quality guidelines for Zn and Cu, and that the surrounding sediments are enriched in multiple contaminant classes (metals, polycyclic aromatic hydrocarbons, petroleum hydrocarbons, dioxins and furans, polychlorinated biphenyls and an organochlorine pesticide), i.e., there is a halo of contamination. When compared against biological effects-based sediment quality guidelines (SQGs), numerous sediment samples exceeded the low-range values (where biological effects become possible), and for Hg and Zn exceeded the mid-range value (where they become probable). A few metres away from the edge of the 25 acre dump lies a small coral patch reef, proposed here as most contaminated coral reef in the world. Copyright © 2010 Elsevier Ltd. All rights reserved.

A model of the interfacial processes inhibiting the environmental degradation of Al-Cu alloys

NASA Astrophysics Data System (ADS)

Kearns, Jeffery Robert

A better understanding of the composition and structure of chemically treated Al alloy surfaces is necessary to devise new, more environmentally benign, coating systems for aircraft. In this work, the surface of AA2024-T3, as well as analogs for constituent intermetallic compounds (IMC), were examined at various stages of the Al alloy pretreatment and chromate conversion coating (CCC) process. A complement of techniques were used: imaging and dyanmic Secondary Ion Mass Spectroscopy (SIMS), Variable-Angle X-ray Photoelectron Spectroscopy (VA/XPS), Synchrotron Infrared Microspectroscopy (SIRS), X-ray Absorption Spectroscopy (XAS), and Electrochemical Impedance Spectroscopy (EIS). The water and hydrocarbons in commercial CCC destabilized Cr(VI) during exposure to soft x-rays. However, it was possible to prevent photochemical reduction with the ultra-clean vacuum pumping practice recently developed at Stony Brook. The type of pretreatment used prior to chromate conversion coating influenced the extent of IMC removal, Cu (re)distribution, and surface activity. Cu(I) was observed on all the chemically treated surfaces. Samples pretreated in Sanchem 1000 while galvanically coupled to a Pt mesh had a more desirable distribution of Cu for subsequent processing. Chromate reduction was not a significant factor in CCC aging over a 24-hr period, but surface dehydration and structural change were correlated and causative. Imaging SIMS revealed heterogeneities in the CCC that varied laterally with IMC in the alloy substrate. These regions were depleted in compounds containing Cr, F, and CN. Cu was found at localized sites in the CCC contact surface. Cyano groups were bound as Cr(IlI)-CNFe(H). The chromate available for CCC repair was located on matrix regions through the entire bulk of the CCC. The presence of residual contaminants (e.g. cleaning agents, metal working fluid, ink) affected the distribution of activator compounds (e.g. ferricyanide) in a CCC. The cyanide complex (Cr(Ill)-Fe-CN6) was found in the CCC bulk not just at the outermost surface. A new model for CCC on Al-Cr alloys is proposed. The model is based on the sol-gel-like nascent CCC that limits the transport of IMC dissolution products.

Influences of the third and fourth nearest neighbouring interactions on the surface anisotropy of face-centred-cubic metals

NASA Astrophysics Data System (ADS)

Luo, Yongkun; Qin, Rongshan

2014-06-01

The structure and the anisotropic properties of the surfaces of face-centred-cubic (FCC) metals have been studied using the broken-bond model while considering the third and fourth nearest neighbouring (3rd and 4th NN) interactions. The pair potential expressions are obtained using the Rose-Vinet universal potential equation. The model is suitable for calculation of the property of a surface with arbitrary crystallographic orientations and can provide absolute unrelaxed surface energy values using three input parameters, namely the lattice constant, bulk modulus and cohesive energy. These parameters are available for the majority of FCC metals. The numerical results for 7 FCC metals have been obtained and compared with these obtained from ab initio calculations and experimental measurements. Good agreement is observed between the two. Taking into account up to the 4th NN interactions, the overall surface energy anisotropy for FCC metals was found to be between 12% to 16%, and the ratio between the surface energies at (100) and (111) planes was found to be 1.05. These values are less than those reported by conventional calculations but more similar to experimental measurements. It is found that the strength of 3rd and 4th NN interactions differs from one element to another, the Ni and Cu interactions being the most significant while the Au, Pt and Pb interactions are the least significant. This suggests that the polar diagrams of the surface energy of Ni and Cu are different from those of Au, Pt and Pb by showing cusps of the unconventional {110} and high-index {210}, {311} and possibly {135} poles. This provides explanations to the recent experimental observations of the {110}, {210}, {311} and {135} facets in equilibrated Ni and Cu crystallines.

Shielding gas effect to diffusion activities of magnesium and copper on aluminum clad

NASA Astrophysics Data System (ADS)

Manurung, Charles SP; Napitupulu, Richard AM

2017-09-01

Aluminum is the second most metal used in many application, because of its corrosion resistance. The Aluminum will be damaged in over time if it’s not maintained in good condition. That is important to give protection to the Aluminums surface. Cladding process is one of surface protection methodes, especially for metals. Aluminum clad copper (Al/Cu) or copper clad aluminum (Cu/Al) composite metals have been widely used for many years. These mature protection method and well tested clad metal systems are used industrially in a variety application. The inherent properties and behavior of both copper and aluminum combine to provide unique performance advantages. In this paper Aluminum 2024 series will be covered with Aluminum 1100 series by hot rolling process. Observations will focus on diffusion activities of Mg and Cu that not present on Aluminum 1100 series. The differences of clad material samples is the use of shielding gas during heating before hot rolling process. The metallurgical characteristics will be examined by using optical microscopy. Transition zone from the interface cannot be observed but from Energy Dispersive Spectrometry it’s found that Mg and Cu are diffused from base metal (Al 2024) to the clad metal (Al 1100). Hardness test proved that base metals hardness to interface was decrease.

Toward understanding the role of individual fluorescent components in DOM-metal binding.

PubMed

Wu, Jun; Zhang, Hua; Yao, Qi-Sheng; Shao, Li-Ming; He, Pin-Jing

2012-05-15

Knowledge on the function of individual fractions in dissolved organic matter (DOM) is essential for understanding the impact of DOM on metal speciation and migration. Herein, fluorescence excitation-emission matrix quenching and parallel factor (PARAFAC) analysis were adopted for bulk DOM and chemically isolated fractions from landfill leachate, i.e., humic acids (HA), fulvic acids and hydrophilic (HyI) fraction, to elucidate the role of individual fluorescent components in metal binding (Cu(II) and Cd(II)). Three components were identified by PARAFAC model, including one humic substance (HS)-like, one protein-like and one component highly correlated with the HyI fraction. Among them, the HS-like and protein-like components were responsible for Cu(II) binding, while the protein-like component was the only fraction involved in Cd(II) complexation. It was further identified that the slight quenching effect of HA fraction by Cd(II) was induced by the presence of proteinaceous materials in HA. Fluorescent substances in the HyI fraction of landfill leachate did not play as important a role as HS did. Therefore, it was suggested that the potential risk of aged leachate (more humified) as a carrier of heavy metal should not be overlooked. Copyright © 2012 Elsevier B.V. All rights reserved.

Photo-reduced Cu/CuO nanoclusters on TiO2 nanotube arrays as highly efficient and reusable catalyst

NASA Astrophysics Data System (ADS)

Jin, Zhao; Liu, Chang; Qi, Kun; Cui, Xiaoqiang

2017-01-01

Non-noble metal nanoparticles are becoming more and more important in catalysis recently. Cu/CuO nanoclusters on highly ordered TiO2 nanotube arrays are successfully developed by a surfactant-free photoreduction method. This non-noble metal Cu/CuO-TiO2 catalyst exhibits excellent catalytic activity and stability for the reduction of 4-nitrophenol (4-NP) to 4-aminophenol (4-AP) with the presence of sodium borohydride (NaBH4). The rate constant of this low-cost Cu/CuO based catalyst is even higher than that of the noble metal nanoparticles decorated on the same TiO2 substrate. The conversion efficiency remains almost unchanged after 7 cycles of recycling. The recycle process of this Cu/CuO-TiO2 catalyst supported by Ti foil is very simple and convenient compared with that of the common powder catalysts. This catalyst also exhibited great catalytic activity to other organic dyes, such as methylene blue (MB), rhodamine B (RhB) and methyl orange (MO). This highly efficient, low-cost and easily reusable Cu/CuO-TiO2 catalyst is expected to be of great potential in catalysis in the future.

Acute Toxicity of Ternary Cd-Cu-Ni and Cd-Ni-Zn Mixtures to Daphnia magna: Dominant Metal Pairs Change along a Concentration Gradient.

PubMed

Traudt, Elizabeth M; Ranville, James F; Meyer, Joseph S

2017-04-18

Multiple metals are usually present in surface waters, sometimes leading to toxicity that currently is difficult to predict due to potentially non-additive mixture toxicity. Previous toxicity tests with Daphnia magna exposed to binary mixtures of Ni combined with Cd, Cu, or Zn demonstrated that Ni and Zn strongly protect against Cd toxicity, but Cu-Ni toxicity is more than additive, and Ni-Zn toxicity is slightly less than additive. To consider multiple metal-metal interactions, we exposed D. magna neonates to Cd, Cu, Ni, or Zn alone and in ternary Cd-Cu-Ni and Cd-Ni-Zn combinations in standard 48 h lethality tests. In these ternary mixtures, two metals were held constant, while the third metal was varied through a series that ranged from nonlethal to lethal concentrations. In Cd-Cu-Ni mixtures, the toxicity was less than additive, additive, or more than additive, depending on the concentration (or ion activity) of the varied metal and the additivity model (concentration-addition or independent-action) used to predict toxicity. In Cd-Ni-Zn mixtures, the toxicity was less than additive or approximately additive, depending on the concentration (or ion activity) of the varied metal but independent of the additivity model. These results demonstrate that complex interactions of potentially competing toxicity-controlling mechanisms can occur in ternary-metal mixtures but might be predicted by mechanistic bioavailability-based toxicity models.

The electrochemical Evaluation of a Zr-Based Bulk Metallic Glass in a Phosphate-Buffered Saline Electrolyte

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

Morrison, M. L.; Buchanan, R. A.; Leon, R. V.

2005-01-01

Bulk metallic glasses (BMGs) represent an emerging class of materials with an amorphous structure and a unique combination of properties. The objectives of this investigation were to define the electrochemical behavior of a specific Zr-based BMG alloy in a physiologically relevant environment and to compare these properties to standard, crystalline biomaterials as well as other Zr-based BMG compositions. Cyclic-anodic-polarization studies were conducted with a Zr{sub 52.5}Cu{sub 17.9}Ni{sub 14.6}Al{sub 10.0}Ti{sub 5.0} (at %) BMG in a phosphate-buffered saline electrolyte with a physiologically relevant oxygen content at 37 C. The results were compared to three common, crystalline biomaterials: CoCrMo, 316L stainless steel,more » and Ti-6Al-4V. The BMG alloy was found to have a lower corrosion penetration rate (CPR), as compared to the 316L stainless steel, and an equivalent CPR, as compared to the CoCrMo and Ti-6Al-4V alloys. Furthermore, the BMG alloy demonstrated better localized corrosion resistance than the 316L stainless steel. However, the localized corrosion resistance of the BMG alloy was not as high as those of the CoCrMo and Ti-6Al-4V alloys in the tested environment. The excellent electrochemical properties demonstrated by the BMG alloy are combined with a low modulus and unparalleled strength. This unique combination of properties dramatically demonstrates the potential for amorphous alloys as a new generation of biomaterials.« less

Silver contents and Cu/Ag ratios in Martian meteorites and the implications for planetary differentiation

NASA Astrophysics Data System (ADS)

Wang, Zaicong; Becker, Harry

2017-11-01

Silver and Cu show very similar partitioning behavior in sulfide melt-silicate melt and metal-silicate systems at low and high pressure-temperature (P-T) experimental conditions, implying that mantle melting, fractional crystallization and core-mantle differentiation have at most modest (within a factor of 3) effects on Cu/Ag ratios. For this reason, it is likely that Cu/Ag ratios in mantle-derived magmatic products of planetary bodies reflect that of the mantle and, in some circumstances, also the bulk planet composition. To test this hypothesis, new Ag mass fractions and Cu/Ag ratios in different groups of Martian meteorites are presented and compared with data from chondrites and samples from the Earth's mantle. Silver contents in lherzolitic, olivine-phyric and basaltic shergottites and nakhlites range between 1.9 and 12.3 ng/g. The data display a negative trend with MgO content and correlate positively with Cu contents. In spite of displaying variable initial Ɛ143Nd values and representing a diverse spectrum of magmatic evolution and physiochemical conditions, shergottites and nakhlites display limited variations of Cu/Ag ratios (1080 ± 320, 1 s, n = 14). The relatively constant Cu/Ag suggests limited fractionation of Ag from Cu during the formation and evolution of the parent magmas, irrespectively of whether sulfide saturation was attained or not. The mean Cu/Ag ratio of Martian meteorites thus reflects that of the Martian mantle and constrains its Ag content to 1.9 ± 0.7 ng/g (1 s). Carbonaceous and enstatite chondrites display a limited range of Cu/Ag ratios of mostly 500-2400. Ordinary chondrites show a larger scatter of Cu/Ag up to 4500, which may have been caused by Ag redistribution during parent body metamorphism. The majority of chondrites have Cu/Ag ratios indistinguishable from the Martian mantle value, indicating that Martian core formation strongly depleted Cu and Ag contents, but probably did not significantly change the Cu/Ag ratio of the mantle compared to bulk Mars. Bulk Mars is richer in moderately volatile elements than Earth, however, the Martian mantle displays a much stronger depletion of the moderately volatile elements Cu and Ag, e.g., by a factor of 15 for Cu. This observation is consistent with experimental studies suggesting that core formation at low P-T conditions on Mars led to more siderophile behavior of Cu and Ag than at high P-T conditions as proposed for Earth. In contrast, Cu/Ag ratios of the mantles of Mars and Earth (Cu/AgEarth = 3500 ± 1000) display only a difference by a factor of 3, which implies restricted fractionation of Cu and Ag even at high P-T conditions. The concentration data support the notion that siderophile element partitioning during planetary core formation scales with the size of the planetary body, which is particularly important for the differentiation of large terrestrial planets such as Earth. Collectively, the Ag and Cu data on magmatic products from the mantles of Mars and Earth and the data on chondrites confirm experimental predictions and support the limited fractionation of Cu and Ag during planetary core formation and high-temperature magmatic evolution, and probably also in early solar nebular processes.

Robust and Stable Cu Nanowire@Graphene Core-Shell Aerogels for Ultraeffective Electromagnetic Interference Shielding.

PubMed

Wu, Shiting; Zou, Mingchu; Li, Zhencheng; Chen, Daqin; Zhang, Hui; Yuan, Yongjun; Pei, Yongmao; Cao, Anyuan

2018-06-01

Cu nanowires (CuNWs) are considered as a promising candidate to develop high performance metal aerogels, yet the construction of robust and stable 3D porous structures remains challenging which severely limits their practical applications. Here, graphene-hybridized CuNW (CuNW@G) core-shell aerogels are fabricated by introducing a conformal polymeric coating and in situ transforming it into multilayered graphene seamlessly wrapped around individual CuNWs through a mild thermal annealing process. The existence of the outer graphene shell reinforces the 3D bulk structure and significantly slows down the oxidation process of CuNWs, resulting in improved mechanical property and highly stable electrical conductivity. When applied in electromagnetic interference shielding, the CuNW@G core-shell aerogels exhibit an average effectiveness of ≈52.5 dB over a wide range (from 8.2 to 18 GHz) with negligible degradation under ambient conditions for 40 d. Mechanism analysis reveals that the graphene shell with functional groups enables dual reflections on the core-shell and a multiple dielectric relaxation process, leading to enhanced dielectric loss and energy dissipation within the core-shell aerogels. The flexible core-shell-structured CuNW@G aerogels, with superior mechanical robustness and electrical stability, have potential applications in many areas such as advanced energy devices and functional composites. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Micro-PIXE study of metal loss from dental amalgam

NASA Astrophysics Data System (ADS)

Meesat, Ridthee; Sudprasert, Wanwisa; Guibert, Edouard; Wang, Liping; Chappuis, Thibault; Whitlow, Harry J.

2017-08-01

Mercury amalgams have been a topic of controversy ever since their introduction over 150 years ago as a dental material. An interesting question is if metals are released from the amalgam into the enamel and dentine tissue. To elucidate this PIXE mapping was used to investigate metal redistribution in an extracted molar tooth with a ∼30 year old high-Cu content amalgam filling. The tooth was sectioned and polished, and elemental mapping carried out on the amalgam/enamel, bulk amalgam and the wear surface of the amalgam. As expected, the amalgam was multiphase amalgam comprising of Cu-rich and Ag-rich grains with non-uniform distribution of Hg. The amalgam/dentine interface was clearly defined with amalgam elements on one side and C and P from hydroxyapatite on the other side with evidence of only slight interface corrosion. The peaks for Cu Hg and Zn were isolated from interfering signals with concentrations in the enamel tissue, observed to be at, or below the method detection limit. The proximity in energy of the Sn L α and Ca K α , peaks and the background on the Hg M α gave signal overlap which increased the MDL for these elements. Remarkably, a course grain texture in the amalgam was observed just below the biting surface of the amalgam which might be associated with tribochemical processes from mastication. This coupled with the clear absence of the amalgam metals from tooth tissue, even in close proximity to the interface, suggests that for this sample, release of Hg occurred via erosion or dissolution in saliva.

A study of the conductive properties of nanostructured metal oxide films

NASA Astrophysics Data System (ADS)

D'Olembert, Andre A.

Fuel cells which were first employed in spacecraft, producing both electricity and water for astronaut consumption during the mid-1960's, are part of the ongoing pursuit for renewable energy sources, and environmentally compatible electric power generation. Recent enhancements in design and materials might establish fuel cells in a sustainable hydrogen energy economy (SHEE) as viable alternatives to the internal combustion engine. In tune with our principal objectives, this study investigates the conductive properties of metal-oxide thin films by developing a new deposition technique called dual channel ultrasonic spray pyrolysis (DC-USP). The DC-USP process has proved to be a reliable and cost-effective method to fabricate thin films. Extending the DC-USP technique, we have created a novel mixed ionic electronic conductor (MIEC) composed of two metal-oxides: lanthanum strontium ferrite and copper-doped bismuth vanadate (LSF.40:BiCuVOx.10). When the two materials are mixed, their grain boundary regions are heavily defected because of the dissimilarity of the two crystal structures, which maintain their integrity in the formed heterogenous composite. Oxygen ion diffusion occurs as it migrates through an ionic crystal, hopping from defect site to defect site. Furthermore, a nanostructured material - with crystallite grains less than 100 nm in diameter - will improve oxygen diffusion by increasing the density of defect sites. The rate of diffusion is increased as well as the quantity of diffusion pathways. Ultimately, as the ionic current density is increased, the total efficiency (nuSOFCtotal) of the solid oxide fuel cell (SOFC) can be improved. Therefore, the LSF-40:BiCuVOx.10 material can contribute to solve the major outstanding problem of the three-phase boundary (TPB) that limits the oxygen reduction reaction to within a microscopic region near the cathode-electrolyte interface in the SOFC device. Materials were tested and analyzed using atomic force microscopy (AFM), interference microscopy (IM), x-ray diffraction (XRD), x-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), and impedance spectroscopy to elucidate their structural features and energetic properties. Results show that the total bulk electrical conductivity of LSF.40:BiCuVOx.10 increases from 0.81 to 3 S/cm at 650°C when the content of BiCuVOx.10 increases from 10 to 50 vol.%. At a lower temperature of 550°C, the average bulk resistivity value for LSF.40:BiCuVOx.10 (50:50) films was as low as 2.08 0 cm (i.e. conductivity of 0.48 S/cm).

Ultrasensitive and highly selective detection of Cu2 + ions based on a new carbazole-Schiff

NASA Astrophysics Data System (ADS)

Yin, Jun; Bing, Qijing; Wang, Lin; Wang, Guang

2018-01-01

A new chemosensor for Cu2 + based on Schiff base with high sensitivity and selectivity was designed and synthesized. The fluorescence intensity of the chemosensor in CH3CN solution was enhanced 160-fold after the addition of 10 equiv. Cu2 + over other metal ions. In addition, it also facilitates colorimetric detection for Cu2 + in CH3CN solution. The chemosensor displayed low detection limit and fast response time to Cu2 +.

Novel approach for removing brominated flame retardant from aquatic environments using Cu/Fe-based metal-organic frameworks: A case of hexabromocyclododecane (HBCD).

PubMed

Li, Xiang; Liu, Hongli; Jia, Xiaoshan; Li, Guiying; An, Taicheng; Gao, Yanpeng

2018-04-15

Cu and Fe based metal-organic frameworks (Cu-BTC and Fe-BTC) were synthesized via a simple solvothermal method and innovatively utilized to remove a typical nonionic brominated flame retardant, hexabromocyclododecane (HBCD), from aquatic environment. Results show that over 80% of HBCD was removed by Cu-BTC within 5h, which is 1.3 times higher than removal by Fe-BTC. Thermodynamic analysis confirms spontaneous adsorption of HBCD onto the metal-organic frameworks (MOFs). Furthermore, the Gibbs free energy of Cu-BTC (-9.11kJ/mol) is more negative than that of Fe-BTC (-5.04kJ/mol). Both adsorption isotherms of HBCD onto Cu-BTC and Fe-BTC followed the Langmuir model, indicating a typical monomolecular-layer adsorption mechanism. In addition, the water stability test of these MOFs shows that the collapse of the Cu-BTC crystal structure is significantly hindered in the aquatic environment due to adsorption of the hydrophobic HBCD. The proposed adsorption mechanism includes van der Waals and hydrophobic interactions. These findings demonstrate that Cu/Fe-BTC are promising adsorbents for the removal of hydrophobic organic pollutants from aquatic environments, and may further improve the understanding of MOF materials for environmental applications. Copyright © 2017 Elsevier B.V. All rights reserved.

Syntheses, structures and luminescence of three copper(I) cyanide coordination polymers based on trigonal 1,3,5-tris(1H-imidazol-1-yl)benzene ligand

NASA Astrophysics Data System (ADS)

Shao, Min; Li, Ming-Xing; Lu, Li-Ruo; Zhang, Heng-Hua

2016-09-01

Three Cu(I)-cyanide coordination polymers based on trigonal 1,3,5-tris(1H-imidazol-1-yl)benzene (tib) ligand, namely [Cu3(CN)3(tib)]n (1), [Cu4(CN)4(tib)]n (2), and [Cu2(CN)2(tib)]n (3), have been prepared and characterized by elemental analysis, IR, PXRD, thermogravimetry and single-crystal X-ray diffraction analysis. Complex 1 displays a 3D metal-organic framework with nanosized pores. Complex 2 is a 3D coordination polymer assembled by three μ2-cyanides and a μ3-cyanide with a very short Cu(I)···Cu(I) metal bond(2.5206 Å). Complex 3 is a 2D coordination polymer constructing from 1D Cu(I)-cyanide zigzag chain and bidentate tib spacer. Three Cu(I) complexes are thermally stable up to 250-350 °C. Complexes 1-3 show similar orange emission band at 602 nm originating from LMCT mechanism.

Surface and bulk effects of K in Cu 1-xK xIn 1-yGa ySe 2 solar cells

DOE PAGES

Muzzillo, Christopher P.; Anderson, Timothy J.

2017-12-29

Two strategies for enhancing photovoltaic (PV) performance in chalcopyrite solar cells were investigated: Cu 1-xK xIn 1-yGa ySe 2 absorbers with low K content (K/(K+Cu), or x ~ 0.07) distributed throughout the bulk, and CuIn 1-yGa ySe 2 absorbers with KIn 1-yGa ySe 2 grown on their surfaces. Distributing K throughout the bulk absorbers improved power conversion efficiency, open-circuit voltage (VOC) and fill factor (FF) for Ga/(Ga+In) of 0, 0.3 and 0.5. Surface KIn 1-yGa ySe 2 and bulk x ~ 0.07 Cu 1-xK xIn 1-yGa ySe 2 films with Ga/(Ga+In), or y of 0.3 and 0.5 also had improvedmore » efficiency, VOC, and FF, relative to CuIn 1-yGa ySe 2 baselines. On the other hand, y ~ 1 absorbers did not benefit from K introduction. Similar to Cu 1-xK xInSe 2, the formation of Cu 1-xK xGaSe 2 alloys was favored at low temperatures and high Na supply by the substrate, relative to the formation of mixed-phase CuGaSe 2 + KGaSe 2. KIn 1-yGa ySe 2 alloys were grown for the first time, as evidenced by X-ray diffraction and ultraviolet/visible spectroscopy. For all Ga/(Ga+In) compositions, the surface KIn 1-yGa ySe 2 absorbers had superior PV performance in buffered and buffer-free devices. However, the bulk x ~ 0.07 absorbers only outperformed the baselines in buffered devices. The data demonstrate that KIn 1-yGa ySe 2 passivates the surface of CuIn 1-yGa ySe 2 to increase efficiency, VOC, and FF, while bulk Cu 1-xK xIn 1-yGa ySe 2 absorbers with x ~ 0.07 enhance efficiency, VOC, and FF by some other mechanism.« less

Surface and bulk effects of K in Cu 1-xK xIn 1-yGa ySe 2 solar cells

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

Muzzillo, Christopher P.; Anderson, Timothy J.

Two strategies for enhancing photovoltaic (PV) performance in chalcopyrite solar cells were investigated: Cu 1-xK xIn 1-yGa ySe 2 absorbers with low K content (K/(K+Cu), or x ~ 0.07) distributed throughout the bulk, and CuIn 1-yGa ySe 2 absorbers with KIn 1-yGa ySe 2 grown on their surfaces. Distributing K throughout the bulk absorbers improved power conversion efficiency, open-circuit voltage (VOC) and fill factor (FF) for Ga/(Ga+In) of 0, 0.3 and 0.5. Surface KIn 1-yGa ySe 2 and bulk x ~ 0.07 Cu 1-xK xIn 1-yGa ySe 2 films with Ga/(Ga+In), or y of 0.3 and 0.5 also had improvedmore » efficiency, VOC, and FF, relative to CuIn 1-yGa ySe 2 baselines. On the other hand, y ~ 1 absorbers did not benefit from K introduction. Similar to Cu 1-xK xInSe 2, the formation of Cu 1-xK xGaSe 2 alloys was favored at low temperatures and high Na supply by the substrate, relative to the formation of mixed-phase CuGaSe 2 + KGaSe 2. KIn 1-yGa ySe 2 alloys were grown for the first time, as evidenced by X-ray diffraction and ultraviolet/visible spectroscopy. For all Ga/(Ga+In) compositions, the surface KIn 1-yGa ySe 2 absorbers had superior PV performance in buffered and buffer-free devices. However, the bulk x ~ 0.07 absorbers only outperformed the baselines in buffered devices. The data demonstrate that KIn 1-yGa ySe 2 passivates the surface of CuIn 1-yGa ySe 2 to increase efficiency, VOC, and FF, while bulk Cu 1-xK xIn 1-yGa ySe 2 absorbers with x ~ 0.07 enhance efficiency, VOC, and FF by some other mechanism.« less

On the use of atomistic simulations to aid bulk metallic glasses structural elucidation with solid-state NMR.

PubMed

Ferreira, Ary R; Rino, José P

2017-08-24

Solid-state nuclear magnetic resonance (ssNMR) experimental 27 Al metallic shifts reported in the literature for bulk metallic glasses (BMGs) were revisited in the light of state-of-the-art atomistic simulations. In a consistent way, the Gauge-Including Projector Augmented-Wave (GIPAW) method was applied in conjunction with classical molecular dynamics (CMD). A series of Zr-Cu-Al alloys with low Al concentrations were selected as case study systems, for which realistic CMD derived structural models were used for a short- and medium-range order mining. That initial procedure allowed the detection of trends describing changes on the microstructure of the material upon Al alloying, which in turn were used to guide GIPAW calculations with a set of abstract systems in the context of ssNMR. With essential precision and accuracy, the ab initio simulations also yielded valuable trends from the electronic structure point of view, which enabled an overview of the bonding nature of Al-centered clusters as well as its influence on the experimental ssNMR outcomes. The approach described in this work might promote the use of ssNMR spectroscopy in research on glassy metals. Moreover, the results presented demonstrate the possibility to expand the applications of this technique, with deeper insight into nuclear interactions and less speculative assignments.

Debye temperature of metallic nanowires--an experimental determination from the resistance of metallic nanowires in the temperature range 4.2 K-300 K.

PubMed

Bid, Aveek; Bora, Achyut; Raychaudhuri, A K

2007-06-01

We have studied the resistance of metallic nanowires (silver and copper) as a function of the wire diameter in the temperature range 4.2 K-300 K. The nanowires with an average diameter of 15 nm-200 nm and length 6 microm were electrochemically deposited using polycarbonate membranes as template from AgNO3 and CuSO4, respectively. The wires after growth were removed from the membranes by dissolving the polymer in dichloromethane and their crystalline nature confirmed by XRD and TEM studies. The TEM study establishes that the nanowires are single crystalline and can have twin in them. The resistivity data was fitted to Bloch-Gruneisen theorem with the values of Debye temperature and the electron-acoustic phonon coupling constant as the two fit variables. The value of the Debye temperature obtained for the Ag wires was seen to match well with that of the bulk while for Cu wires a significant reduction was observed. The observed increase in resistivity with a decrease in the wire diameter could be explained as due to diffuse surface scattering of the conduction electrons.

Effect of counterpart metals in carbon-supported Pt-based catalysts prepared using radiation chemical method

NASA Astrophysics Data System (ADS)

Okazaki, Tomohisa; Seino, Satoshi; Matsuura, Yoshiyuki; Otake, Hiroaki; Kugai, Junichiro; Ohkubo, Yuji; Nitani, Hiroaki; Nakagawa, Takashi; Yamamoto, Takao A.

2017-04-01

The process of nanoparticle formation by radiation chemical synthesis in a heterogeneous system has been investigated. Carbon-supported Pt-based bimetallic nanoparticles were synthesized using a high-energy electron beam. Rh, Cu, Ru, and Sn were used as counterpart metals. The nanoparticles were characterized by inductively coupled plasma atomic emission spectrometry, transmission electron microscopy, X-ray diffraction, and X-ray absorption spectroscopy. PtRh formed a uniform random alloy nanoparticle, while Cu partially formed an alloy with Pt and the remaining Cu existed as CuO. PtRu formed an alloy structure with a composition distribution of a Pt-rich core and Ru-rich shell. No alloying was observed in PtSn, which had a Pt-SnO2 structure. The alloy and oxide formation mechanisms are discussed considering the redox potentials, the standard enthalpy of oxide formation, and the solid solubilities of Pt and the counterpart metals.

The Removal of Cu (II) from Aqueous Solution using Sodium Borohydride as a Reducing Agent

NASA Astrophysics Data System (ADS)

Sithole, N. T.; Ntuli, F.; Mashifana, T.

2018-03-01

The removal and recovery of metals from wastewater has been a subject of significant importance due the negative impact these toxic metals have on human health and the environment as a result of water and soil pollution. Increased use of the metals and chemicals in the process industries has resulted in generation of large quantity of effluents that contains high level of toxic metals and other pollutants. The objective of this work was to recover of Cu in its elemental form as metallic powder from aqueous solution using NaBH4 as a reducing agent. Reductive precipitation was achieved in a batch reactor at 65°C using Cu powder as a seeding material. This study also investigated the effect of concentration of sodium borohydride (NaBH4) as a reducing agent. The amount of NaBH4 was varied based on mole ratios which are 1:1, 1:0.25 and 1:0.1 to recover Cu from synthetic wastewater. The results obtained showed that sodium borohydride is an effective reducing agent to recover Cu from wastewater. The optimum concentration of NaBH4 that gives the best results the 1:1 molar ratio with over 99% Cu removal.

Thiol-functionalization of metal-organic framework by a facile coordination-based postsynthetic strategy and enhanced removal of Hg2+ from water.

PubMed

Ke, Fei; Qiu, Ling-Guang; Yuan, Yu-Peng; Peng, Fu-Min; Jiang, Xia; Xie, An-Jian; Shen, Yu-Hua; Zhu, Jun-Fa

2011-11-30

The presence of coordinatively unsaturated metal centers in metal-organic frameworks (MOFs) provides an accessible way to selectively functionalize MOFs through coordination bonds. In this work, we describe thiol-functionalization of MOFs by choosing a well known three-dimensional (3D) Cu-based MOF, i.e. [Cu(3)(BTC)(2)(H(2)O)(3)](n) (HKUST-1, BTC=benzene-1,3,5-tricarboxylate), by a facile coordination-based postsynthetic strategy, and demonstrate their application for removal of heavy metal ion from water. A series of [Cu(3)(BTC)(2)](n) samples stoichiometrically decorated with thiol groups has been prepared through coordination bonding of coordinatively unsaturated metal centers in HKUST-1 with -SH group in dithioglycol. The obtained thiol-functionalized samples were characterized by powder X-ray diffraction, scanning electron microscope, energy dispersive X-ray spectroscopy, infrared spectroscopy, and N(2) sorption-desorption isothermal. Significantly, the thiol-functionalized [Cu(3)(BTC)(2)](n) exhibited remarkably high adsorption affinity (K(d)=4.73 × 10(5)mL g(-1)) and high adsorption capacity (714.29 mg g(-1)) for Hg(2+) adsorption from water, while the unfunctionalized HKUST-1 showed no adsorption of Hg(2+) under the same condition. Copyright © 2011 Elsevier B.V. All rights reserved.

Cleaning and passivation of copper surfaces to remove surface radioactivity and prevent oxide formation

NASA Astrophysics Data System (ADS)

Hoppe, E. W.; Seifert, A.; Aalseth, C. E.; Bachelor, P. P.; Day, A. R.; Edwards, D. J.; Hossbach, T. W.; Litke, K. E.; McIntyre, J. I.; Miley, H. S.; Schulte, S. M.; Smart, J. E.; Warren, G. A.

2007-08-01

High-purity copper is an attractive material for constructing ultra-low-background radiation measurement devices. Many low-background experiments using high-purity copper have indicated surface contamination emerges as the dominant background. Radon daughters plate out on exposed surfaces, leaving a residual 210Pb background that is difficult to avoid. Dust is also a problem; even under cleanroom conditions, the amount of U and Th deposited on surfaces can represent the largest remaining background. To control these backgrounds, a copper cleaning chemistry has been developed. Designed to replace an effective, but overly aggressive concentrated nitric acid etch, this peroxide-based solution allows for a more controlled cleaning of surfaces. The acidified hydrogen peroxide solution will generally target the Cu +/Cu 2+ species which are the predominant surface participants, leaving the bulk of copper metal intact. This preserves the critical tolerances of parts and eliminates significant waste disposal issues. Accompanying passivation chemistry has also been developed that protects copper surfaces from oxidation. Using a high-activity polonium surface spike, the most difficult-to-remove daughter isotope of radon, the performance of these methods are quantified.

Nonlinear electronic transport and enhanced catalytic behavior caused by native oxides on Cu nanowires

NASA Astrophysics Data System (ADS)

Hajimammadov, Rashad; Csendes, Zita; Ojakoski, Juha-Matti; Lorite, Gabriela Simone; Mohl, Melinda; Kordas, Krisztian

2017-09-01

Electrical transport properties of individual nanowires (both in axial and transversal directions) and their random networks suggest rapid oxidation when Cu is exposed to ambient conditions. The oxidation process is elucidated by thorough XRD, XPS and Raman analyzes conducted for a period of 30 days. Based on the obtained experimental data, we may conclude that first, cuprous oxide and copper hydroxide form that finally transform to cupric oxide. In electrical applications, oxidation of copper is not a true problem as long as thin films or bulk metal is concerned. However, as highlighted in our work, this is not the case for nanowires, since the oxidized surface plays quite important role in the contact formation and also in the conduction of percolated nanowire networks. On the other hand, by taking advantage of the mixed surface oxide states present on the nanowires along with their large specific surface area, we tested and found excellent catalytic activity of the oxidized nanowires in phenol oxidation, which suggests further applications of these materials in catalysis.

Source apportionment of heavy metals in agricultural soil based on PMF: A case study in Hexi Corridor, northwest China.

PubMed

Guan, Qingyu; Wang, Feifei; Xu, Chuanqi; Pan, Ninghui; Lin, Jinkuo; Zhao, Rui; Yang, Yanyan; Luo, Haiping

2018-02-01

Hexi Corridor is the most important base of commodity grain and producing area for cash crops. However, the rapid development of agriculture and industry has inevitably led to heavy metal contamination in the soils. Multivariate statistical analysis, GIS-based geostatistical methods and Positive Matrix Factorization (PMF) receptor modeling techniques were used to understand the levels of heavy metals and their source apportionment for agricultural soil in Hexi Corridor. The results showed that the average concentrations of Cr, Cu, Ni, Pb and Zn were lower than the secondary standard of soil environmental quality; however, the concentrations of eight metals (Cr, Cu, Mn, Ni, Pb, Ti, V and Zn) were higher than background values, and their corresponding enrichment factor values were significantly greater than 1. Different degrees of heavy metal pollution occurred in the agricultural soils; specifically, Ni had the most potential for impacting human health. The results from the multivariate statistical analysis and GIS-based geostatistical methods indicated both natural sources (Co and W) and anthropogenic sources (Cr, Cu, Mn, Ni, Pb, Ti, V and Zn). To better identify pollution sources of heavy metals in the agricultural soils, the PMF model was applied. Further source apportionment revealed that enrichments of Pb and Zn were attributed to traffic sources; Cr and Ni were closely related to industrial activities, including mining, smelting, coal combustion, iron and steel production and metal processing; Zn and Cu originated from agricultural activities; and V, Ti and Mn were derived from oil- and coal-related activities. Copyright © 2017 Elsevier Ltd. All rights reserved.

Corrosion behavior in high-temperature pressurized water of Zircaloy-4 joints brazed with Zr-Cu-based amorphous filler alloys

NASA Astrophysics Data System (ADS)

Lee, Jung Gu; Lee, Gyoung-Ja; Park, Jin-Ju; Lee, Min-Ku

2017-05-01

The compositional effects of ternary Zr-Cu-X (X: Al, Fe) amorphous filler alloys on galvanic corrosion susceptibility in high-temperature pressurized water were investigated for Zircaloy-4 brazed joints. Through an Al-induced microgalvanic reaction that deteriorated the overall nobility of the joint, application of the Zr-Cu-Al filler alloy caused galvanic coupling to develop readily between the Al-bearing joint and the Al-free base metal, finally leading to massive localized corrosion of the joint. Contrastingly, joints prepared with a Zr-Cu-Fe filler alloy showed excellent corrosion resistance comparable to that of the Zircaloy-4 base metal, since the Cu and Fe elements forming fine intermetallic particles with Zr did not influence the electrochemical stability of the resultant joints. The present results demonstrate that Fe is a more suitable alloying element than Al for brazing filler alloys subjected to high-temperature corrosive environments.

Continuous separation of copper ions from a mixture of heavy metal ions using a three-zone carousel process packed with metal ion-imprinted polymer.

PubMed

Jo, Se-Hee; Lee, See-Young; Park, Kyeong-Mok; Yi, Sung Chul; Kim, Dukjoon; Mun, Sungyong

2010-11-05

In this study, a three-zone carousel process based on a proper molecular imprinted polymer (MIP) resin was developed for continuous separation of Cu(2+) from Mn(2+) and Co(2+). For this task, the Cu (II)-imprinted polymer (Cu-MIP) resin was synthesized first and used to pack the chromatographic columns of a three-zone carousel process. Prior to the experiment of the carousel process based on the Cu-MIP resin (MIP-carousel process), a series of single-column experiments were performed to estimate the intrinsic parameters of the three heavy metal ions and to find out the appropriate conditions of regeneration and re-equilibration. The results from these single-column experiments and the additional computer simulations were then used for determination of the operating parameters of the MIP-carousel process under consideration. Based on the determined operating parameters, the MIP-carousel experiments were carried out. It was confirmed from the experimental results that the proposed MIP-carousel process was markedly effective in separating Cu(2+) from Mn(2+) and Co(2+) in a continuous mode with high purity and a relatively small loss. Thus, the MIP-carousel process developed in this study deserves sufficient attention in materials processing industries or metal-related industries, where the selective separation of heavy metal ions with the same charge has been a major concern. Copyright © 2010 Elsevier B.V. All rights reserved.

First principles calculations of point defect diffusion in CdS buffer layers: Implications for Cu(In,Ga)(Se,S){sub 2} and Cu{sub 2}ZnSn(Se,S){sub 4}-based thin-film photovoltaics

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

Varley, J. B.; Lordi, V.; He, X.

2016-01-14

We investigate point defects in CdS buffer layers that may arise from intermixing with Cu(In,Ga)Se{sub 2} (CIGSe) or Cu{sub 2}ZnSn(S,Se){sub 4} (CZTSSe) absorber layers in thin-film photovoltaics (PV). Using hybrid functional calculations, we characterize the migration barriers of Cu, In, Ga, Se, Sn, Zn, Na, and K impurities and assess the activation energies necessary for their diffusion into the bulk of the buffer. We find that Cu, In, and Ga are the most mobile defects in CIGS-derived impurities, with diffusion expected to proceed into the buffer via interstitial-hopping and cadmium vacancy-assisted mechanisms at temperatures ∼400 °C. Cu is predicted to stronglymore » favor migration paths within the basal plane of the wurtzite CdS lattice, which may facilitate defect clustering and ultimately the formation of Cu-rich interfacial phases as observed by energy dispersive x-ray spectroscopic elemental maps in real PV devices. Se, Zn, and Sn defects are found to exhibit much larger activation energies and are not expected to diffuse within the CdS bulk at temperatures compatible with typical PV processing temperatures. Lastly, we find that Na interstitials are expected to exhibit slightly lower activation energies than K interstitials despite having a larger migration barrier. Still, we find both alkali species are expected to diffuse via an interstitially mediated mechanism at slightly higher temperatures than enable In, Ga, and Cu diffusion in the bulk. Our results indicate that processing temperatures in excess of ∼400 °C will lead to more interfacial intermixing with CdS buffer layers in CIGSe devices, and less so for CZTSSe absorbers where only Cu is expected to significantly diffuse into the buffer.« less

Thresholds of copper phytotoxicity in field-collected agricultural soils exposed to copper mining activities in Chile.

PubMed

Verdejo, José; Ginocchio, Rosanna; Sauvé, Sébastien; Salgado, Eduardo; Neaman, Alexander

2015-12-01

It has been argued that the identification of the phytotoxic metal thresholds in soil should be based on field-collected soil rather than on artificially-contaminated soils. However, the use of field-collected soils presents several difficulties for interpretation because of mixed contamination and unavoidable covariance of metal contamination with other soil properties that affect plant growth. The objective of this study was to estimate thresholds of copper phytotoxicity in topsoils of 27 agricultural areas historically contaminated by mining activities in Chile. We performed emergence and early growth (21 days) tests (OECD 208 and ISO 11269-2) with perennial ryegrass (Lolium perenne L.). The total Cu content in soils was the best predictor of plant growth and shoot Cu concentrations, while soluble Cu and pCu(2+) did not well correlate with these biological responses. The effects of Pb, Zn, and As on plant responses were not significant, suggesting that Cu is a metal of prime concern for plant growth in soils exposed to copper mining activities in Chile. The effects of soil nutrient availability and shoot nutrient concentrations on ryegrass response were not significant. It was possible to determine EC10, EC25 and EC50 of total Cu in the soil of 327 mg kg(-1), 735 mg kg(-1) and 1144 mg kg(-1), respectively, using the shoot length as a response variable. However, the derived 95% confidence intervals for EC10, EC25 and EC50 values of total soil Cu were wide, and thus not allowing a robust assessment of metal toxicity for agricultural crops, based on total soil Cu concentrations. Thus, plant tests might need to be performed for metal toxicity assessment. This study suggests shoot length of ryegrass as a robust response variable for metal toxicity assessment in contaminated soils with different nutrient availability. Copyright © 2015 Elsevier Inc. All rights reserved.

Distribution, enrichment and accumulation of heavy metals in coastal sediments of Alang-Sosiya ship scrapping yard, India.

PubMed

Reddy, M Srinivasa; Basha, Shaik; Sravan Kumar, V G; Joshi, H V; Ramachandraiah, G

2004-06-01

Since its inception in 1982, the Alang-Sosiya yard has become the largest ship scrapping works in the world. Several hundreds of ships arrive every year. The degree of heavy metal contamination has been studied in bulk and fine sediments from the intertidal zone of this ship scrapping yard, two stations, one on either side at 5 km distance and one reference station 60 km distance near Mahuva, towards the south. The samples have been subjected to a total digestion technique and analysed for elements: Cd, Co, Cu, Cr, Fe, Mn, Ni, Pb, Zn and Al, and %TOC. The absolute metal concentrations reflected variations in BF and FF sediment samples with organic matter content. Enrichment factors (EF) and geoaccumulation indices (Igeo) have been calculated and the relative contamination levels are assessed at these sites. At Alang-Sosiya, the enrichment of heavy metals has been observed to be relatively high.

Studies on copper-yttria nanocomposites: high-energy ball milling versus chemical reduction method.

PubMed

Joshi, P B; Rehani, Bharati; Naik, Palak; Patel, Swati; Khanna, P K

2012-03-01

Oxide dispersion-strengthened copper-base composites are widely used for applications demanding high tensile strength, high hardness along with good electrical and thermal conductivity. Oxides of metals like aluminium, cerium, yttrium and zirconium are often used for this purpose as fine and uniformly distributed dispersoid particles in soft and ductile copper matrix. Such composites find applications as electrical contacts, resistance-welding tips, lead wires, continuous casting moulds, etc. In this investigation an attempt has been made to produce copper-yttria nanocomposites using two different morphologies of copper powder and two different processing routes namely, high-energy milling and in-situ chemical reduction. The synthesized powders were characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM) for their phase identification and morphological study. The nanocomposite powders in each case were subsequently processed to obtain bulk solids by classical powder metallurgy route of press-sinter-repress. The resultant bulk solid compacts were subjected to property evaluation. The study revealed that the properties of Cu-Y2O3 nanocomposites depend on the processing route used and in turn on the resultant powder morphology.

Non-conventional photocathodes based on Cu thin films deposited on Y substrate by sputtering

NASA Astrophysics Data System (ADS)

Perrone, A.; D'Elia, M.; Gontad, F.; Di Giulio, M.; Maruccio, G.; Cola, A.; Stankova, N. E.; Kovacheva, D. G.; Broitman, E.

2014-07-01

Copper (Cu) thin films were deposited on yttrium (Y) substrate by sputtering. During the deposition, a small central area of the Y substrate was shielded to avoid the film deposition and was successively used to study its photoemissive properties. This configuration has two advantages: the cathode presents (i) the quantum efficiency and the work function of Y and (ii) high electrical compatibility when inserted into the conventional radio-frequency gun built with Cu bulk. The photocathode was investigated by scanning electron microscopy to determine surface morphology. X-ray diffraction and atomic force microscopy studies were performed to compare the structure and surface properties of the deposited film. The measured electrical resistivity value of the Cu film was similar to that of high purity Cu bulk. Film to substrate adhesion was also evaluated using the Daimler-Benz Rockwell-C adhesion test method. Finally, the photoelectron performance in terms of quantum efficiency was obtained in a high vacuum photodiode cell before and after laser cleaning procedures. A comparison with the results obtained with a twin sample prepared by pulsed laser deposition is presented and discussed.

Segregation at the surfaces of CuxPd1-x alloys in the presence of adsorbed S

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

Miller, James B.; Priyadarshini, Deepika; Gellman, Andrew J.

2012-10-01

The influence of adsorbed S on surface segregation in Cu{sub x}Pd{sub 1 - x} alloys (S/Cu{sub x}Pd{sub 1 - x)} was characterized over a wide range of bulk alloy compositions (x = 0.05 to 0.95) using high-throughput Composition Spread Alloy Film (CSAF) sample libraries. Top-surface and near-surface compositions of the CSAFs were measured as functions of bulk Cu composition, x, and temperature using spatially resolved low energy ion scattering spectroscopy (LEISS) and X-ray photoemission spectroscopy (XPS). Preferential segregation of Cu to the top-surface of the S/Cu{sub x}Pd{sub 1 - x} CSAF was observed at all bulk compositions, x, but themore » extent of Cu segregation to the S/Cu{sub x}Pd{sub 1 - x} surface was lower than the Cu segregation to the surface of a clean Cu{sub x}Pd{sub 1 - x} CSAF, clear evidence of an S-induced “segregation reversal.” The Langmuir–McLean formulation of the Gibbs isotherm was used to estimate the enthalpy and entropy of Cu segregation to the top-surface, ΔH{sub seg}(x) and ΔS{sub seg}(x), at saturation sulfur coverages. While Cu segregation to the top-surface of the clean Cu{sub x}Pd{sub 1 - x} is exothermic (ΔH{sub seg} < 0) for all bulk Cu compositions, it is endothermic (ΔH{sub seg} > 0) for S/Cu{sub x}Pd{sub 1 - x}. Segregation to the S/Cu{sub x}Pd{sub 1 - x} surface is driven by entropy. Changes in segregation patterns that occur upon adsorption of S onto Cu{sub x}Pd{sub 1 - x} appear to be related to formation of energetically favored Pd{single bond}S bonds at the surface, which counterbalance the enthalpic driving forces for Cu segregation to the clean surface.« less

Thrust chamber material technology program

NASA Technical Reports Server (NTRS)

Andrus, J. S.; Bordeau, R. G.

1989-01-01

This report covers work performed at Pratt & Whitney on development of copper-based materials for long-life, reusable, regeneratively cooled rocket engine thrust chambers. The program approached the goal of enhanced cyclic life through the application of rapid solidification to alloy development, to introduce fine dispersions to strengthen and stabilize the alloys at elevated temperatures. After screening of alloy systems, copper-based alloys containing Cr, Co, Hf, Ag, Ti, and Zr were processed by rapid-solidification atomization in bulk quantities. Those bulk alloys showing the most promise were characterized by tensile testing, thermal conductivity testing, and elevated-temperature, low-cycle fatigue (LFC) testing. Characterization indicated that Cu- 1.1 percent Hf exhibited the greatest potential as an improved-life thrust chamber material, exhibiting LCF life about four times that of NASA-Z. Other alloys (Cu- 0.6 percent Zr, and Cu- 0.6 percent Zr- 1.0 percent Cr) exhibited promise for use in this application, but needed more development work to balance properties.

Minor and trace element concentrations in adjacent kamacite and taenite in the Krymka chondrite

NASA Astrophysics Data System (ADS)

Meftah, N.; Mostefaoui, S.; Jambon, A.; Guedda, E. H.; Pont, S.

2016-04-01

We report in situ NanoSIMS siderophile minor and trace element abundances in individual Fe-Ni metal grains in the unequilibrated chondrite Krymka (LL3.2). Associated kamacite and taenite of 10 metal grains in four chondrules and one matrix metal were analyzed for elemental concentrations of Fe, Ni, Co, Cu, Rh, Ir, and Pt. The results show large elemental variations among the metal grains. However, complementary and correlative variations exist between adjacent kamacite-taenite. This is consistent with the unequilibrated character of the chondrite and corroborates an attainment of chemical equilibrium between the metal phases. The calculated equilibrium temperature is 446 ± 9 °C. This is concordant with the range given by Kimura et al. (2008) for the Krymka postaccretion thermal metamorphism. Based on Ni diffusivity in taenite, a slow cooling rate is estimated of the Krymka parent body that does not exceed ~1K Myr-1, which is consistent with cooling rates inferred by other workers for unequilibrated ordinary chondrites. Elemental ionic radii might have played a role in controlling elemental partitioning between kamacite and taenite. The bulk compositions of the Krymka metal grains have nonsolar (mostly subsolar) element/Ni ratios suggesting the Fe-Ni grains could have formed from distinct precursors of nonsolar compositions or had their compositions modified subsequent to chondrule formation events.

Behaviors of heavy metals (Cd, Cu, Ni, Pb and Zn) in soil amended with composts.

PubMed

Gusiatin, Zygmunt Mariusz; Kulikowska, Dorota

2016-09-01

This study investigated how amendment with sewage sludge compost of different maturation times (3, 6, 12 months) affected metal (Cd, Cu, Ni, Pb, Zn) bioavailability, fractionation and redistribution in highly contaminated sandy clay soil. Metal transformations during long-term soil stabilization (35 months) were determined. In the contaminated soil, Cd, Ni and Zn were predominately in the exchangeable and reducible fractions, Pb in the reducible fraction and Cu in the reducible, exchangeable and oxidizable fractions. All composts decreased the bioavailability of Cd, Ni and Zn for up to 24 months, which indicates that cyclic amendment with compost is necessary. The bioavailability of Pb and Cu was not affected by compost amendment. Based on the reduced partition index (IR), metal stability in amended soil after 35 months of stabilization was in the following order: Cu > Ni = Pb > Zn > Cd. All composts were more effective in decreasing Cd, Ni and Zn bioavailability than in redistributing the metals, and increasing Cu redistribution more than that of Pb. Thus, sewage sludge compost of as little as 3 months maturation can be used for cyclic amendment of multi-metal-contaminated soil.

Comparison of the effects of platinum and CeO2 on the properties of single grain, Sm-Ba-Cu-O bulk superconductors

NASA Astrophysics Data System (ADS)

Zhao, Wen; Shi, Yunhua; Radušovská, Monika; Dennis, Anthony R.; Durrell, John H.; Diko, Pavel; Cardwell, David A.

2016-12-01

SmBa2Cu3O7-δ (Sm-123) is a light-rare-earth barium-cuprate (LRE-BCO) high-temperature superconductor (HTS) with significant potential for high field industrial applications. We report the fabrication of large, single grain bulk [Sm-Ba-Cu-O (SmBCO)] superconductors containing 1 wt% CeO2 and 0.1 wt% Pt using a top-seeded melt growth process. The performance of the SmBCO bulk superconductors containing the different dopants was evaluated based on an analysis of their superconducting properties, including critical transition temperature, T c and critical current density, J c , and on sample microstructure. We find that both CeO2 and Pt dopants refine the size of Sm2BaCuO5 (Sm-211) particles trapped in the Sm-123 superconducting phase matrix, which act as effective flux pinning centres, although the addition of CeO2 results in broadly improved superconducting performance of the fully processed bulk single grain. However, 1 wt% CeO2 is significantly cheaper than 0.1 wt% Pt, which has clear economic benefits for use in medium to large scale production processes for these technologically important materials. Finally, the use of CeO2 results generally in the formation of finer Sm-211 particles and to the generation of fewer macro-cracks and Sm-211 free regions in the sample microstructure.

Effects of exposure to nano and bulk sized TiO2 and CuO in Lemna minor.

PubMed

Dolenc Koce, Jasna

2017-10-01

Nanoparticles of TiO 2 and CuO are among most commonly used nanoparticles, and elevated concentrations of them are expected to be found in all environments, including aquatic. A standard growth inhibition test ISO/CD 20079 was used to determine the toxicity of nano sized and larger micro sized (bulk) particles in the concentrations of 0.1, 1, 10, 100 and 1000 μM CuO and TiO 2 on common duckweed (Lemna minor L.). Both nano and bulk CuO particles caused changes in the structure and function of treated plants. The number of fronds and colonies decreased by as much as 78%, the length of roots and fronds decreased by 99% and 14%, respectively. Furthermore, photochemical efficiency was reduced by up to 35%, and the activities of antioxidative enzymes guaiacol peroxidase, ascorbate peroxidase and glutathione reductase increased by more than 240%. The altered physiological state of the CuO exposed plants was also reflected in the elevated occurrence of necrosis and bleaching in the duckweed colonies. Nano sized particles of CuO proved more phytotoxic than bulk particles, and the effects of both studied CuO sizes were concentration dependent. On the other hand, both bulk and nano sized particles of TiO 2 caused no severe phytotoxic effects, there was no concentration dependence and they could be considered as non-harmful to common duckweed. Copyright © 2017 Elsevier Masson SAS. All rights reserved.

X-ray crystal structure and theoretical study of a new dinuclear Cu(II) complex with two different geometry centers bridged with an oxo group

NASA Astrophysics Data System (ADS)

Golbedaghi, Reza; Azimi, Saeid; Molaei, Atefeh; Hatami, Masoud; Notash, Behrouz

2017-10-01

A new Schiff base ligand HL, 1,3-bis(2-((Z)-(2-aminoethylimino)methyl)phenoxy)ethylene di amine, has been synthesized from the reaction of a new aldehyde and ethylenediamine. After preparation the Schiff base, a new dinuclear Cu(II) complex with two different geometry for each metal ion was synthesized. Single crystal X-ray structure analysis of the complex Cu(II) showed that the complex is binuclear and all nitrogen and oxygen atoms of ligand (N4O3) are coordinated to two Cu(II) center ions. The crystal structure studying shows, a perchlorate ion has been coordinated to the two Cu(II) metal centers as bridged and another perchlorate coordinated to the one of Cu(II) ion as terminal. However, two interesting structures square pyramidal and distorted octahedral Cu(II) ions are bridged asymmetrically by a perchlorate ion and oxygen of hydroxyl group of Schiff base ligand. In addition, we had a theoretical study to have a comparison of experimental and theoretical results we determined the HOMO and LUMO orbitals.

Evaluation of Copper-1,3,5-benzenetricarboxylate Metal-organic Framework (Cu-MOF) as a Selective Sorbent for Lewis-base Analytes

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

Harvey, Scott D.; Eckberg, Alison D.; Thallapally, Praveen K.

2011-09-01

The metal-organic framework Cu-BTC was evaluated for its ability to selectively interact with Lewis-base analytes, including explosives, by examining retention on GC columns packed with Chromosorb W HP that contained 3.0% SE-30 along with various loadings of Cu-BTC. SEM images of the support material showed the characteristic Cu-BTC crystals embedded in the SE-30 coating on the diatomaceous support. Results indicated that the Cu-BTC-containing stationary phase had limited thermal stability (220°C) and strong general retention for analytes. Kováts index calculations showed selective retention (amounting to about 300 Kováts units) relative to n-alkanes for many small Lewis-base analytes on a column thatmore » contained 0.75% Cu-BTC compared to an SE-30 control. Short columns that contained lower loadings of Cu-BTC (0.10%) were necessary to elute explosives and related analytes; however, selectivity was not observed for aromatic compounds (including nitroaromatics) or nitroalkanes. Observed retention characteristics are discussed.« less

Structural and mechanical modifications induced on Zr-based bulk metallic glass by laser shock peening

NASA Astrophysics Data System (ADS)

Zhu, Yunhu; Fu, Jie; Zheng, Chao; Ji, Zhong

2016-12-01

In this study, surface modification of a Zr41.2Ti13.8Cu12.5Ni10Be22.5 (vit1) bulk metallic glass (BMG) has been studied in an effort to improve the mechanical properties by laser shock peening (LSP) treatment. The phase structure, mechanical properties, and microstructural evolution of the as-cast and LSP treated specimens were systematically investigated. It was found that the vit1 BMG still consisted of fully amorphous structure after LSP treatment. Measurements of the heat relaxation indicate that a large amount of free volume is introduced into vit1 BMG during LSP process. LSP treatment causes a decrease of hardness attributable to generation of free volume. The plastic deformation ability of vit1 BMG was investigated under three-point bending conditions. The results demonstrate that the plastic strain of LSP treated specimen is 1.83 times as large as that of the as-cast specimen. The effect of LSP technology on the hardness and plastic deformation ability of vit1 BMG is discussed on the basis of free volume theory. The high dense shear bands on the side surface, the increase of striations and critical shear displacement on the tensile fracture region, and more uniform dimples structure on the compressive fracture region also demonstrate that the plasticity of vit1 BMG can be enhanced by LSP.

Effect of Cu addition on the martensitic transformation of powder metallurgy processed Ti–Ni alloys

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

Kim, Yeon-wook, E-mail: ywk@gw.kmu.ac.kr; Choi, Eunsoo

2014-10-15

Highlights: • M{sub s} of Ti{sub 50}Ni{sub 50} powders is 22 °C, while M{sub s} of SPS-sintered porous bulk increases up to 50 °C. • M{sub s} of Ti{sub 50}Ni{sub 40}Cu{sub 20} porous bulk is only 2 °C higher than that of the powders. • Recovered stain of porous TiNi and TiNiCu alloy is more than 1.5%. - Abstract: Ti{sub 50}Ni{sub 50} and Ti{sub 50}Ni{sub 30}Cu{sub 20} powders were prepared by gas atomization and their transformation behaviors were examined by means of differential scanning calorimetry and X-ray diffraction. One-step B2–B19’ transformation occurred in Ti{sub 50}Ni{sub 50} powders, while Ti{sub 50}Ni{submore » 30}Cu{sub 20} powders showed B2–B19 transformation behavior. Porous bulks with 24% porosity were fabricated by spark plasma sintering. The martensitic transformation start temperature (50 °C) of Ti{sub 50}Ni{sub 50} porous bulk is much higher than that (22 °C) of the as-solidified powders. However, the martensitic transformation start temperature (35 °C) of Ti{sub 50}Ni{sub 30}Cu{sub 20} porous bulk is almost the same as that (33 °C) of the powders. When the specimens were compressed to the strain of 8% and then unloaded, the residual strains of Ti{sub 50}Ni{sub 50} and Ti{sub 50}Ni{sub 30}Cu{sub 20} alloy bulks were 3.95 and 3.7%, respectively. However, these residual strains were recovered up to 1.7% after heating by the shape memory phenomenon.« less

Influence of brazing conditions on the strength of brazed joints of alumina dispersion-strengthened copper to 316 stainless steel

NASA Astrophysics Data System (ADS)

Nishi, H.; Kikuchi, K.

1998-10-01

Brazing of alumina dispersion-strengthened copper (DS Cu) to 316 stainless steel were conducted in order to investigate the influence of filler metals and brazing conditions on the joint strength. The brazing were performed with a silver-base (BAg-8) and three kinds of gold-base (BAu-2,4,11) filler metals with varying brazing joint clearance and brazing time. The filler metal had a greater effect on the joint strength than the brazing joint clearance and brazing time. The joint with BAu-2 was superior to the joint with other filler metals. The tensile strength of the joint with BAu-2 was as large as that of DS Cu, however, the Charpy and low cycle fatigue strength were lower than those of DS Cu. The DS Cu melted near the brazed zone, consequently recrystallization and agglomeration of alumina occurred in the diffusion layer for all filler metals. The grain size after the recrystallization was small in order of BAu-2, BAu-4 and BAu-11, that was in accordance with the order of the brazing temperature. The excellent fracture strength for the joint with BAu-2 was attributed to the smallest grain size.

A long-term static immersion experiment on the leaching behavior of heavy metals from waste printed circuit boards.

PubMed

Zhao, Guo-Hua; Luo, Xing-Zhang; Chen, Gui; Zhao, Yong-Jun

2014-08-01

Printed circuit boards (PCBs) are the main components of electrical and electronic equipment (EEE). Waste PCBs contain several kinds of heavy metals, including Cu, Pb and Zn. We characterize the leaching of heavy metals (Cu, Pb, Zn and Ni) from waste PCBs in a pH range of 3.0 to 5.6 using a novel approach based on batch pH-static leaching experiments in this work. The results indicate that the leaching behavior of Cu, Pb, Zn and Ni is strongly dependent on pH. Leaching behavior also varies with different pH values and leaching times. The maximum concentrations of Cu, Pb, Zn and Ni in leachate from waste PCBs were 335.00, 17.57, 2.40 and 2.33 mg L(-1), respectively. The highest Pb, Ni, and Cu concentrations leached significantly exceeded the European Union waste-acceptance limit values with respect to inert waste landfills. The leaching of metals follows the shrinking core model with surface reaction control.

Industrial grade versus scientific pure: Influence on melt properties

NASA Astrophysics Data System (ADS)

Jonas, I.; Hembree, W.; Yang, F.; Busch, R.; Meyer, A.

2018-04-01

Viscosity, density, and the undercooling ability of the Zr-based bulk glass forming melt, which was manufactured in two different degrees of purity, have been studied. Investigations have been carried out by means of Couette rheometry and electrostatic and electromagnetic levitation with the latter under microgravity conditions. We found that oxygen and impurities present in industrial grade metals do not significantly alter the melt viscosity and density, while they clearly affect the undercooling ability. Comparing container based and containerless results showed that Couette rheometry can be applied in the temperature range between 1150 K and 1375 K, where it provides reliable data, but only at a rather low oxygen content. Higher oxygen contents, as in the case of the industrial grade alloy, cause measurement artefacts. In the case of Zr59.3Cu28.8Al10.4Nb1.5 alloys, these findings allow a better localization of the key factors dominating the glass forming ability.

Effect of Atomic Layer Depositions (ALD)-Deposited Titanium Oxide (TiO2) Thickness on the Performance of Zr40Cu35Al15Ni10 (ZCAN)/TiO2/Indium (In)-Based Resistive Random Access Memory (RRAM) Structures

DTIC Science & Technology

2015-08-01

metal structures, memristors, resistive random access memory, RRAM, titanium dioxide, Zr40Cu35Al15Ni10, ZCAN, resistive memory, tunnel junction 16...TiO2 thickness ........................6 1 1. Introduction Resistive-switching memory elements based on metal-insulator-metal (MIM) diodes ...have attracted great interest due to their potential as components for simple, inexpensive, and high-density non-volatile storage devices. MIM diodes

Origin of the improved photocatalytic activity of Cu incorporated TiO2 for hydrogen generation from water

NASA Astrophysics Data System (ADS)

Hu, Qianqian; Huang, Jiquan; Li, Guojing; Jiang, Yabin; Lan, Hai; Guo, Wang; Cao, Yongge

2016-09-01

Cu incorporated TiO2 has been regarded as a low-cost photocatalyst with excellent photocatalytic performance for water splitting. Here we try to exploit the origin of its high reactivity by fabricating a series of Cu incorporated TiO2 films with the same Cu content under different atmosphere. Based on the comprehensive structure and surface characterizations, it is found that CuO is unstable and will be reduced to Cu2O or even to metallic Cu under light irradiation during the photocatalytic reaction, and Cu2O is an efficient co-catalyst that promotes the separation of photogenerated carriers while metallic Cu can further boost the photocatalytic activity. Besides, it is also noticed that the chemisorbed oxygen on the particle surface blocks the water splitting. By depositing TiO2 films under oxygen rich condition, oxygen vacancy is decreased greatly, which facilitates the removal of chemisorbed oxygen and the formation of metallic Cu during photocatalytic reaction, resulting in an ultra-high H2 evolution rate of 2.80 μmol cm-2 h-1, which is about 55 times higher than that of pure TiO2.

Immobilization of Bacillus subtilis lipase on a Cu-BTC based hierarchically porous metal-organic framework material: a biocatalyst for esterification.

PubMed

Cao, Yu; Wu, Zhuofu; Wang, Tao; Xiao, Yu; Huo, Qisheng; Liu, Yunling

2016-04-28

Bacillus subtilis lipase (BSL2) has been successfully immobilized into a Cu-BTC based hierarchically porous metal-organic framework material for the first time. The Cu-BTC hierarchically porous MOF material with large mesopore apertures is prepared conveniently by using a template-free strategy under mild conditions. The immobilized BSL2 presents high enzymatic activity and perfect reusability during the esterification reaction. After 10 cycles, the immobilized BSL2 still exhibits 90.7% of its initial enzymatic activity and 99.6% of its initial conversion.

Surface and Bulk Effects of K in Highly Efficient Cu1-xKxInSe2 Solar Cells

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

Muzzillo, Christopher; Mansfield, Lorelle M; Ramanathan, Kannan

To advance knowledge of the beneficial effects of K in Cu(In,Ga)(Se,S)2 (CIGS) photovoltaic (PV) absorbers, recent Cu-K-In-Se phase growth studies have been extended to PV performance. First, the effect of distributing K throughout bulk Cu1-xKxInSe2 absorbers at low K/(K+Cu) compositions (0 = x = 0.30) was studied. Efficiency, open-circuit voltage (VOC), and fill factor (FF) were greatly enhanced for x ~ 0.07, resulting in an officially-measured 15.0%-efficient solar cell, matching the world record CuInSe2 efficiency. The improvements were a result of reduced interface and bulk recombination, relative to CuInSe2 (x ~ 0). However, higher x compositions had reduced efficiency, short-circuitmore » current density (JSC), and FF due to greatly increased interface recombination, relative to the x ~ 0 baseline. Next, the effect of confining K at the absorber/buffer interface at high K/(K+Cu) compositions (0.30 = x = 0.92) was researched. Previous work showed that these surface layer growth conditions produced CuInSe2 with a large phase fraction of KInSe2. After optimization (75 nm surface layer with x ~ 0.41), these KInSe2 surface samples exhibited increased efficiency (officially 14.9%), VOC, and FF as a result of decreased interface recombination. The KInSe2 surfaces had features similar to previous reports for KF post-deposition treatments (PDTs) used in world record CIGS solar cells - taken as indirect evidence that KInSe2 can form during these PDTs. Both the bulk and surface growth processes greatly reduced interface recombination. However, the KInSe2 surface had higher K levels near the surface, greater lifetimes, and increased inversion near the buffer interface, relative to the champion bulk Cu1-xKxInSe2 absorber. These characteristics demonstrate that K may benefit PV performance by different mechanisms at the surface and in the absorber bulk.« less

Atomic-level deformation of CuxZr100-x metallic glasses under shock loading

NASA Astrophysics Data System (ADS)

Demaske, Brian J.; Wen, Peng; Phillpot, Simon R.; Spearot, Douglas E.

2018-06-01

Plastic deformation mechanisms in CuxZr100-x bulk metallic glasses (MGs) subjected to shock are investigated using molecular dynamics simulations. MGs with Cu compositions between 30 and 70 at. % subjected to shock waves generated via piston velocities that range from 0.125 to 2.0 km/s are considered. In agreement with prior studies, plastic deformation is initiated via formation of localized regions of high von Mises shear strain, known as shear transformation zones (STZs). At low impact velocities, but above the Hugoniot elastic limit, STZ nucleation is dispersed behind the shock front. As impact velocity is increased, STZ nucleation becomes more homogeneous, eventually leading to shock-induced melting, which is identified in this work via high atomic diffusivity. The shear stress necessary to initiate plastic deformation within the shock front is independent of composition at shock intensities near the elastic limit but increases with increasing Cu content at high shock intensities. By contrast, both the flow stress in the plastically deformed MG and the critical shock pressure associated with melting behind the shock front are found to increase with increasing Cu content over the entire range of impact velocities. The evolution of the short-range order in the MG samples during shock wave propagation is analyzed using a polydisperse Voronoi tessellation method. Cu-centered polyhedra with full icosahedral symmetry are found to be most resistant to change under shock loading independent of the MG composition. A saturation is observed in the involvement of select Cu-centered polyhedra in the plastic deformation processes at a piston velocity around 0.75 km/s.

Defect studies in copper-based p-type transparent conducting oxides

NASA Astrophysics Data System (ADS)

Ameena, Fnu

Among other intrinsic open-volume defects, copper vacancy (VCu) has been theoretically identified as the major acceptor in p-type Cu-based semiconducting transparent oxides, which has potential as low-cost photovoltaic absorbers in semi-transparent solar cells. A series of positron annihilation experiments with pure Cu, Cu2O, and CuO presented strong presence of VCu and its complexes in the copper oxides. The lifetime data also showed that the density of VCu was becoming higher as the oxidation state of Cu increased which was consistent with the decrease in the formation energy of VCu. Doppler broadening measurements further indicated that electrons with low momentum made more contribution to the contributed as pure Cu oxidizes to copper oxides. The metastable defects are known to be generated in Cu2O upon illumination and it has been known to affect the performance of Cu2O-based hetero-junctions used in solar cells. The metastable effect was studied using positron annihilation lifetime spectroscopy and its data showed the change in the defect population upon light exposure and the minimal effect of light-induced electron density increase in the bulk of materials to the average lifetime of the positrons. The change in the defect population is concluded to be related to the dissociation and association of VCu -- V Cu complexes. For example, the shorter lifetime under light was ascribed to the annihilation with smaller size vacancies, which explains the dissociation of the complexes with light illumination. Doppler broadening of the annihilation was independent of light illumination, which suggested that the chemical nature of the defects remained without change upon their dissociation and association -- only the size distribution of copper vacancies varied. The delafossite metal oxides, CuMIIIO2 are emerging wide-bandgap p-type semiconductors. In this research, the formation energies of structural vacancies are calculated using Van Vechten cavity model as an attempt to study the effect of the size of the MIII cation in the delafossites starting from Cu2O. Comparison of the formation energies between Cu2O and delafossite oxides clearly showed that the equilibrium concentration of the vacancies depended strongly on the structural parameters varied by the presence of different MIII cations. In particular, the size of the MIII cation greatly influenced the defect formation energies of VCu. It was observed from our calculations, as the size increases the formation energy decreases.

Study of the Effect of Molten Copper Chloride Immersion Test on Alloys with High Nickel Content with and without Surface Coatings

NASA Astrophysics Data System (ADS)

Siantar, Edwin

The demand for hydrogen as a clean energy carrier has increased greatly. The Cu-Cl cycle is a promising thermochemical cycle that is currently being developed to be the large-scale method of hydrogen production. The lifetime of materials for the pipes transporting molten CuCl is an important parameter for an economic design of a commercial thermochemical Cu-Cl hydrogen plant. This research is an examination of candidate materials following an immersion test in molten CuCl at 500 °C for 100 h. Two alloys, Ni based super-alloy (Inconel 625) and super austenitic stainless steel (AL6XN) were selected as the base metal. There were two types of coating applied to improve the corrosion resistance of the base metals during molten CuCl exposure. A metallic of Diamalloy 4006 and two ceramic of yttria stabilized zirconia and alumina coatings were applied to the base metal using thermal spray methods. An immersion apparatus was designed and constructed to perform an immersion test that has a condition similar to those in a hydrogen plant. After the immersion test, the materials were evaluated using an electrochemical method in combination with ex-situ surface analysis. The surface condition including elemental composition, film structure and resistivity of the materials were examined and compared. The majority of the coatings were damaged and fell off. Cracks were found in the original coated specimens indicating the sample geometry may have affected the integrity of the sprayed coating. When the coating cracked, it provided a pathway for the molten CuCl to go under the coating and react with the surface underneath the coating. Copper deposits and iron chloride that were found on the sample surfaces suggest that there were corrosion reactions that involved the metal dissolution and reduction of copper during immersion test. The results also suggest that Inconel 625 performed better than stainless steel AL6XN. Both Diamalloy 4006 and YSZ (ZrO2 18TiO2 10Y2O3) coatings seemed to provide better protection to the underlying base metal than alumina (Al2O3 3TiO2) coating.

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

Bogush, Anna; Stegemann, Julia A., E-mail: j.stegemann@ucl.ac.uk; Wood, Ian

Highlights: • 66 elements, including “critical strategic elements” were determined in UK EfW APC residues. • Metal pollutants (Zn, Pb, As, Cd, Cu, Mo, Sb, Sn, Se, Ag and In) are enriched in APC residues. • Metal pollutants were widely associated with fine deposits of highly soluble CaCl{sub x}OH{sub 2−x}. • Specific metal (Zn, Pb, Cu)-bearing minerals were also detected in APC residues. - Abstract: Air pollution control (APC) residues from energy-from-waste (EfW) are alkaline (corrosive) and contain high concentrations of metals, such as zinc and lead, and soluble salts, such as chlorides and sulphates. The EPA 3050B-extractable concentrations ofmore » 66 elements, including critical elements of strategic importance for advanced electronics and energy technologies, were determined in eight APC residues from six UK EfW facilities. The concentrations of Ag (6–15 mg/kg) and In (1–13 mg/kg), as well as potential pollutants, especially Zn (0.26–0.73 wt.%), Pb (0.05–0.2 wt.%), As, Cd, Cu, Mo, Sb, Sn and Se were found to be enriched in all APC residues compared to average crustal abundances. Results from a combination of scanning electron microscopy with energy dispersive X-ray spectroscopy and also powder X-ray diffraction, thermal analysis and Fourier transform infrared spectroscopy give an exceptionally full understanding of the mineralogy of these residues, which is discussed in the context of other results in the literature. The present work has shown that the bulk of the crystalline phases present in the investigated APC residues include Ca-based phases, such as CaCl{sub x}OH{sub 2−x}, CaCO{sub 3}, Ca(OH){sub 2}, CaSO{sub 4}, and CaO, as well as soluble salts, such as NaCl and KCl. Poorly-crystalline aragonite was identified by FTIR. Sulphur appears to have complex redox speciation, presenting as both anhydrite and hannebachite in some UK EfW APC residues. Hazardous elements (Zn and Pb) were widely associated with soluble Ca- and Cl-bearing phases (e.g. CaCl{sub x}OH{sub 2−x} and sylvite), as well as unburnt organic matter and aluminosilicates. Specific metal-bearing minerals were also detected in some samples: e.g., Pb present as cerussite; Zn in gahnite, zincowoodwardite and copper nickel zinc oxide; Cu in tenorite, copper nickel zinc oxide and fedotovite. Aluminium foil pieces were present and abundantly covered by fine phases, particularly in any cracks, probably in the form of Friedel’s salt.« less

Surface Mechanoengineering of a Zr-based Bulk Metallic Glass via Ar-Nanobubble Doping to Probe Cell Sensitivity to Rigid Materials

DOE PAGES

Huang, Lu; Tian, Mengkun; Wu, Dong; ...

2017-11-24

In this paper, a new materials platform, utilizing the amorphous microstructure of bulk metallic glasses (BMGs) and the versatility of ion implantation, was developed for the fundamental investigation of cell responses to substrate-rigidity variations in the gigapascal modulus range, which was previously unattainable with polymeric materials. The surface rigidity of a Zr-Al- Ni-Cu-Y BMG was modulated with low-energy Ar-ion implantation owing to the impartment of Ar nanobubbles into the amorphous matrix. Surface softening was achieved due to the formation of nanobubble-doped transitional zones in the Zrbased BMG substrate. Bone-forming cell studies on this newly designed platform demonstrated that mechanical cues,more » accompanied with the potential effects of other surface properties (i.e. roughness, morphology, and chemistry), contributed to modulating cell behaviors. Cell adhesion and actin filaments were found to be less established on less stiff surfaces, especially on the surface with an elastic modulus of 51 GPa. Cell growth appeared to be affected by surface mechanical properties. A lower stiffness was generally related to a higher growth rate. Findings in this study broadened our fundamental understanding concerning the mechanosensing of bone cells on stiff substrates. It also suggests that surface mechano-engineering of metallic materials could be a potential strategy to promote osseointegration of such materials for bone-implant applications. Further investigations are proposed to fine tune the ion implantation variables in order to further distinguish the surface-mechanical effect on bone-forming cell activities from the contributions of other surface properties.« less

Surface Mechanoengineering of a Zr-based Bulk Metallic Glass via Ar-Nanobubble Doping to Probe Cell Sensitivity to Rigid Materials

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

Huang, Lu; Tian, Mengkun; Wu, Dong

In this paper, a new materials platform, utilizing the amorphous microstructure of bulk metallic glasses (BMGs) and the versatility of ion implantation, was developed for the fundamental investigation of cell responses to substrate-rigidity variations in the gigapascal modulus range, which was previously unattainable with polymeric materials. The surface rigidity of a Zr-Al- Ni-Cu-Y BMG was modulated with low-energy Ar-ion implantation owing to the impartment of Ar nanobubbles into the amorphous matrix. Surface softening was achieved due to the formation of nanobubble-doped transitional zones in the Zrbased BMG substrate. Bone-forming cell studies on this newly designed platform demonstrated that mechanical cues,more » accompanied with the potential effects of other surface properties (i.e. roughness, morphology, and chemistry), contributed to modulating cell behaviors. Cell adhesion and actin filaments were found to be less established on less stiff surfaces, especially on the surface with an elastic modulus of 51 GPa. Cell growth appeared to be affected by surface mechanical properties. A lower stiffness was generally related to a higher growth rate. Findings in this study broadened our fundamental understanding concerning the mechanosensing of bone cells on stiff substrates. It also suggests that surface mechano-engineering of metallic materials could be a potential strategy to promote osseointegration of such materials for bone-implant applications. Further investigations are proposed to fine tune the ion implantation variables in order to further distinguish the surface-mechanical effect on bone-forming cell activities from the contributions of other surface properties.« less

Effects of copper excess and copper deficiency on the structural and electrical properties of bulk Cu{sub x}SnSe{sub 3} with x=1.6–2.2

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

Wubet, Walelign; Kuo, Dong-Hau, E-mail: dhkuo@mail.ntust.edu.tw

2015-03-15

Effects of the Cu variation on the morphological, structural, and electrical properties of bulk Cu{sub x}SnSe{sub 3} (CTSe) with x=1.6–2.2 have been investigated. Dense CTSe pellets with grains of 3–4 µm were obtained after sintering at 550 °C. All CTSe pellets showed a dominant p-type behavior. CTSe at x=2.0 with a hole concentration (n{sub p}) of 1.02×10{sup 18} cm{sup −3} and Hall mobility (μ) of 225 cm{sup 2}/V/s had a highest conductivity (σ) of 39 S/cm. CTSe at x=1.6 with n{sub p} of 5.0×10{sup 17} cm{sup −3} and of 11 cm{sup 2}/V/s had a lowest of 0.90 S/cm. The explanation,more » based upon vacancies and antisite defects, for the changes in electrical property with the Cu content is supported by the data from lattice parameter. The study in bulk properties of CTSe and its defects is helpful for selecting the suitable absorber composition to fabricate thin film solar cells. - Graphical abstract: Cu{sub 2}SnSe{sub 3} is an absorber candidate for solar cells. The Cu stoichiometry on electrical properties, which is important for CIGS and CZTS, is investigated and the Cu-deficiency composition is recommended. - Highlights: • Cu{sub x}SnSe{sub 3} (CTSe) bulks with 1.6≤x≤2.2 were prepared by reactive sintering. • Cu{sub 2}SnSe{sub 3} with n{sub p} of 1.02×10{sup 18} cm{sup −3} and μ of 225 cm{sup 2}/V/s had highest σ of 39 S/cm. • Cu{sub 1.6}SnSe{sub 3} with n{sub p}=5.0×10{sup 17} cm{sup −3} and μ=11 cm{sup 2}/V/s had lowest σ=0.90 S/cm. • Lower n{sub p} at CTSe at x=1.6 is related to the formation of the Sn-to-Cu defect. • The drop in n{sub p} for CTSe at x=2.2 indicates V{sub Sn}{sup 4−} dominates over Cu{sub Sn}{sup 3−} defect.« less

Decomposition of L a2 -xS rxCu O4 into several L a2O3 phases at elevated temperatures in ultrahigh vacuum inside a transmission electron microscope

NASA Astrophysics Data System (ADS)

Jeong, Jong Seok; Wu, Wangzhou; Topsakal, Mehmet; Yu, Guichuan; Sasagawa, Takao; Greven, Martin; Mkhoyan, K. Andre

2018-05-01

We report the decomposition of L a2 -xS rxCu O4 into L a2O3 and Cu nanoparticles in ultrahigh vacuum, observed by in situ heating experiments in a transmission electron microscope. The analysis of electron diffraction data reveals that the phase decomposition process starts at about 150 °C and is considerably expedited in the temperature range of 350 °C-450 °C. Two major resultant solid phases are identified as metallic Cu and L a2O3 by electron diffraction, simulation, and electron energy-loss spectroscopy (EELS) analyses. With the aid of calculations, L a2O3 phases are further identified to be derivatives of a fluorite structure—fluorite, pyrochlore, and (distorted) bixbyite—characterized by different oxygen-vacancy order. Additionally, the bulk plasmon energy and the fine structures of the O K and La M4 ,5 EELS edges are reported for these structures, along with simulated O K x-ray absorption near-edge structure. The resultant Cu nanoparticles and L a2O3 phases remain unchanged after cooling to room temperature.

A novel biodegradable β-cyclodextrin-based hydrogel for the removal of heavy metal ions.

PubMed

Huang, Zhanhua; Wu, Qinglin; Liu, Shouxin; Liu, Tian; Zhang, Bin

2013-09-12

A novel biodegradable β-cyclodextrin-based gel (CAM) was prepared and applied to the removal of Cd(2+), Pb(2+) and Cu(2+) ions from aqueous solutions. CAM hydrogel has a typical three-dimensional network structure, and showed excellent capability for the removal of heavy metal ions. The effect of different experimental parameters, such as initial pH, adsorbent dosage and initial metal ion concentration, were investigated. The adsorption isotherm data fitted well to the Freundlich model. The adsorption capacity was in the order Pb(2+)>Cu(2+)>Cd(2+) under the same experimental conditions. The maximum adsorption capacities for the metal ions in terms of mg/g of dry gel were 210.6 for Pb(2+), 116.41 for Cu(2+), and 98.88 for Cd(2+). The biodegradation efficiency of the resin reached 79.4% for Gloeophyllum trabeum. The high adsorption capacity and kinetics results indicate that CAM can be used as an alternative adsorbent to remove heavy metals from aqueous solution. Published by Elsevier Ltd.

Building thiol and metal-thiolate functions into coordination nets: Clues from a simple molecule

NASA Astrophysics Data System (ADS)

He, Jun; Yang, Chen; Xu, Zhengtao; Zeller, Matthias; Hunter, Allen D.; Lin, Jianhua

2009-07-01

The simple and easy-to-prepare bifunctional molecule 2,5-dimercapto-1,4-benzenedicarboxylic acid (H 4DMBD) interacts with the increasingly harder metal ions of Cu +, Pb 2+ and Eu 3+ to form the coordination networks of Cu 6(DMBD) 3(en) 4(Hen) 6 ( 1), Pb 2(DMBD)(en) 2 ( 2) and Eu 2(H 2DMBD) 3(DEF) 4 ( 3), where the carboxyl and thiol groups bind with distinct preference to the hard and soft metal ions, respectively. Notably, 1 features uncoordinated carboxylate groups and Cu 3 cluster units integrated via the thiolate groups into an extended network with significant interaction between the metal centers and the organic molecules; 2 features a 2D coordination net based on the mercapto and carboxylic groups all bonded to the Pb 2+ ions; 3 features free-standing thiol groups inside the channels of a metal-carboxylate-based network. This study illustrates the rich solid state structural features and potential functions offered by the carboxyl-thiol combination.

Functionalized Ni@SiO2 core/shell magnetic nanoparticles as a chemosensor and adsorbent for Cu2+ ion in drinking water and human blood.

PubMed

Park, Minsung; Seo, Sungmin; Lee, Soo Jin; Jung, Jong Hwa

2010-11-01

Fluorogenic based nitrobenzofuran-functionalized Ni@SiO(2) core/shell magnetic nanoparticles have been prepared by sol-gel grafting reaction. Their ability to detect and remove metal ions was evaluated by fluorophotometry. The nanoparticles exhibited a high affinity and selectivity for Cu(2+) over competing metal ions. Furthermore, the nanoparticles efficiently removed Cu(2+) in drinking water and human blood.

Molecular simulations for adsorption and separation of natural gas in IRMOF-1 and Cu-BTC metal-organic frameworks.

PubMed

Martín-Calvo, Ana; García-Pérez, Elena; Manuel Castillo, Juan; Calero, Sofia

2008-12-21

We use Monte Carlo simulations to study the adsorption and separation of the natural gas components in IRMOF-1 and Cu-BTC metal-organic frameworks. We computed the adsorption isotherms of pure components, binary, and five-component mixtures analyzing the siting of the molecules in the structure for the different loadings. The bulk compositions studied for the mixtures were 50 : 50 and 90 : 10 for CH4-CO2, 90 : 10 for N2-CO2, and 95 : 2.0 : 1.5 : 1.0 : 0.5 for the CH4-C2H6-N2-CO2-C3H8 mixture. We choose this composition because it is similar to an average sample of natural gas. Our simulations show that CO2 is preferentially adsorbed over propane, ethane, methane and N2 in the complete pressure range under study. Longer alkanes are favored over shorter alkanes and the lowest adsorption corresponds to N2. Though IRMOF-1 has a significantly higher adsorption capacity than Cu-BTC, the adsorption selectivity of CO2 over CH4 and N2 is found to be higher in the latter, proving that the separation efficiency is largely affected by the shape, the atomic composition and the type of linkers of the structure.

Structural and electrical properties of Si- and Ti-doped Cu{sub 2}SnSe{sub 3} bulks

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

Wubet, Walelign; Kuo, Dong-Hau, E-mail: dhkuo@mail.ntust.edu.tw

2015-07-15

Silicon-doped (Cu{sub 2}(Sn{sub 1−x}Si{sub x})Se{sub 3} and titanium-doped (Cu{sub 2}(Sn{sub 1−x}Ti{sub x})Se{sub 3} at x=0, 0.05, 0.1, 0.15, and 0.2 were prepared at 550 °C for 2 h with soluble sintering aids of volatile Sb{sub 2}S{sub 3} and Te. Defect chemistry was studied by measuring structural and electrical properties of Si-doped and Ti-doped Cu{sub 2}SnSe{sub 3} (CTSe) as a function of dopant concentration. Si-doped CTSe pellets show p-type at x=0 and 0.05 and n-type at x=0.1, 0.15, and 0.2, whereas Ti-doped CTSe pellets show p-type at x=0, 0.05 and 0.1 and n-type at x=0.15 and 0.2. The lowest hole concentrationmore » of 3.6×10{sup 17} cm{sup −3} and the highest mobility of 1525 cm{sup 2} V{sup −1} s{sup −1} were obtained for the Si-doped (Cu{sub 2}(Sn{sub 1−x}Si{sub x})Se{sub 3} bulks at x=0.1 (10% Si), while they were 3.1×10{sup 17} cm{sup −3} and 813 cm{sup 2} V{sup −1} s{sup −1} for the Ti-doped CTSe bulks at x=0.15 (15% Ti), as compared to 1.1×10{sup 18} cm{sup −3} and 209 cm{sup 2} V{sup −1} s{sup −1} for undoped one. The explanations based upon antisite defects of Si-to-Sn, Ti-to-Sn, Cu-to-Sn, and Sn-to-Cu for the changes in electrical property were declared. The study in bulk Si-doped and Ti-doped CTSe is based upon defect state and is consistent and supported by the data of electrical property and lattice parameter. - Graphical abstract: Cu{sub 2}SnSe{sub 3} (CTSe) semiconductor is interesting because of its adjustable electrical properties by extrinsic doping. Si and Ti doping in CTSe leads to high carrier mobility above 800 cm{sup 2} V{sup −1} s{sup −1}. - Highlights: • Cu{sub 2}SnSe{sub 3} (CTSe) is an interesting semiconductor because of its adjustable electrical properties. • Cu(In,Ga)Se{sub 2}, on the contrary, is difficult to change its electrical properties. • Si and Ti doping can change p-CTSe to n-CTSe. • The lowest electron concentration in doped CTSe had the highest mobility above 800 cm{sup 2} V{sup −1} s{sup −1}. • The defects of Si-to-Sn, Ti-to-Sn, Cu-to-Sn, and Sn-to-Cu in Si- and Ti-doped CTSe were proposed.« less

Lithium Assisted “Dissolution–Alloying” Synthesis of Nanoalloys from Individual Bulk Metals

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

Barkholtz, Heather M.; Gallagher, James R.; Li, Tao

2016-04-12

We report new fundamental chemistry involved in the synthesis of bimetallic nanoalloys via dissolving the pure bulk transition metals in molten lithium. It is revealed at the atomic level that when two pure bulk transition metals such as Pd and Pt are placed in molten lithium (similar to 200 degrees C), they undergo a dissolution process in which the metal-metal bonds in pure bulk transition metals are completely ruptured, which results in the existence of individual Pd and Pt atoms surrounded by lithium atoms, as is evident by synchrotron X-ray adsorption techniques. Then, upon the conversion of metal lithium tomore » LiOH in humid air, the Pd and Pt atoms undergo an alloying process to aggregate into nanoalloys. This method was further expanded to include PdZn, which is notoriously difficult to prepare via traditional nanoalloy synthesis methods due to the easily oxidizable Zn component. The constantly reducing environment of metallic Li allowed for preparation of PdZn nanoalloys with minimal Zn oxidation via dissolution-alloying of individual bulk transition metals in molten lithium. Additionally, this lithium assisted "dissolution-alloying" method bypasses many complications intrinsic to conventional ion reduction-based nanoalloy synthesis including the necessity of ligated metal ions, the use of proper reducing agents and dispersing surfactants, and the presence of segregated phases due to different reduction potentials of the constituent metal ions.« less

Effects of organic amendments on the toxicity and bioavailability of cadmium and copper in spiked formulated sediments

USGS Publications Warehouse

Besser, J.M.; Brumbaugh, W.G.; May, T.W.; Ingersoll, C.G.

2003-01-01

We evaluated the partitioning and toxicity of cadmium (Cd) and copper (Cu) spiked into formulated sediments containing two types of organic matter (OM), i.e., cellulose and humus. Amendments of cellulose up to 12.5% total organic carbon (TOC) did not affect partitioning of Cd or Cu between sediment and pore water and did not significantly affect the toxicity of spiked sediments in acute toxicity tests with the amphipod Hyalella azteca. In contrast, amendments of natural humus shifted the partitioning of both Cd and Cu toward greater concentrations in sediment and lesser concentrations in pore water and significantly reduced toxic effects of both metals. Thresholds for toxicity, based on measured metal concentrations in whole sediment, were greater for both Cd and Cu in sediments amended with a low level of humus (2.9% TOC) than in sediments without added OM. Amendments with a high level of humus (8.9% TOC) eliminated toxicity at the highest spike concentrations of both metals (sediment concentrations of 12.4 ??g Cd/g and 493 ??g Cu/g). Concentrations of Cd in pore water associated with acute toxicity were similar between sediments with and without humus amendments, suggesting that toxicity of Cd was reduced primarily by sorption to sediment OM. However, toxic effects of Cu in humus treatments were associated with greater pore-water concentrations than in controls, suggesting that toxicity of Cu was reduced both by sorption and by complexation with soluble ligands. Both sorption and complexation by OM tend to make proposed sediment quality guidelines (SQGs) based on total metal concentrations more protective for high-OM sediments. Our results suggest that the predictive ability of SQGs could be improved by models of metal interactions with natural OM in sediment and pore water.

Effects of organic amendments on the toxicity and bioavailability of cadmium and copper in spiked formulated sediments.

PubMed

Besser, John M; Brumbaugh, William G; May, Thomas W; Ingersoll, Christopher G

2003-04-01

We evaluated the partitioning and toxicity of cadmium (Cd) and copper (Cu) spiked into formulated sediments containing two types of organic matter (OM), i.e., cellulose and humus. Amendments of cellulose up to 12.5% total organic carbon (TOC) did not affect partitioning of Cd or Cu between sediment and pore water and did not significantly affect the toxicity of spiked sediments in acute toxicity tests with the amphipod Hyalella azteca. In contrast, amendments of natural humus shifted the partitioning of hoth Cd and Cu toward greater concentrations in sediment and lesser concentrations in pore water and significantly reduced toxic effects of both metals. Thresholds for toxicity, based on measured metal concentrations in whole sediment, were greater for both Cd and Cu in sediments amended with a low level of humus (2.9% TOC) than in sediments without added OM. Amendments with a high level of humus (8.9% TOC) eliminated toxicity at the highest spike concentrations of both metals (sediment concentrations of 12.4 microg Cd/g and 493 microg Cu/g). Concentrations of Cd in pore water associated with acute toxicity were similar between sediments with and without humus amendments, suggesting that toxicity of Cd was reduced primarily by sorption to sediment OM. However, toxic effects of Cu in humus treatments were associated with greater pore-water concentrations than in controls, suggesting that toxicity of Cu was reduced both by sorption and by complexation with soluble ligands. Both sorption and complexation by OM tend to make proposed sediment quality guidelines (SQGs) based on total metal concentrations more protective for high-OM sediments. Our results suggest that the predictive ability of SQGs could be improved by models of metal interactions with natural OM in sediment and pore water.

Deposition and thermal characterization of nano-structured aluminum nitride thin film on Cu-W substrate for high power light emitting diode package.

PubMed

Cho, Hyun Min; Kim, Min-Sun

2014-08-01

In this study, we developed AlN thick film on metal substrate for hybrid type LED package such as chip on board (COB) using metal printed circuit board (PCB). Conventional metal PCB uses ceramic-polymer composite as electrical insulating layer. Thermal conductivities of such type dielectric film are typically in the range of 1~4 W/m · K depending on the ceramic filler. Also, Al or Cu alloy are mainly used for metal base for high thermal conduction to dissipate heat from thermal source mounted on metal PCB. Here we used Cu-W alloy with low thermal expansion coefficient as metal substrate to reduce thermal stress between insulating layer and base metal. AlN with polyimide (PI) powder were used as starting materials for deposition. We could obtain very high thermal conductivity of 28.3 W/m · K from deposited AlN-PI thin film by AlN-3 wt% PI powder. We made hybrid type high power LED package using AlN-PI thin film. We tested thermal performance of this film by thermal transient measurement and compared with conventional metal PCB substrate.

XAFS studies of surface structures of TiO{sub 2} nanoparticles and photocatalytic reduction of metal ions.

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

Chen, L. X.; Rajh, T.; Wang, Z.

1997-01-01

To probe the origin of the unique functions of titanium dioxide (TiO{sub 2}) nanoparticles observed in photocatalytic reactions, structures of Ti atom sites in titanium dioxide (TiO{sub 2}) nanoparticles with different sizes were studied by Ti K-edge XAFS (X-ray absorption fine structure). Compared to the bulk TiO{sub 2} structure, a shorter Ti-O distance from surface TiO{sub 2} resulting from Ti-OH bonding was observed. The XAFS spectra also revealed an increasing disorder of the lattice with decreasing sizes of the nanoparticles based on a coordination number decrease for the third-shell O atoms as well as changes in relative intensities of pre-edgemore » peaks A1, A2, and A3. However, the Ti sites largely remain octahedral even in the 30 Angstrom diameter particles. These results imply that the increasing number of surface Ti sites as well as possible corner defects in small nanoparticles may be the main cause of the unique surface chemistry exhibited by nanoparticles of TiO{sub 2}. XAFS was also used in monitoring the photoreduction reaction products of Cu{sup 2+} and Hg{sup 2+} on TiO{sub 2} nanoparticle surfaces, with or without surface adsorbers, alanine (Ala) and thiolactic acid (TLA). Ala dramatically enhanced photoreduction of Cu{sup 2+} on TiO{sub 2} nanoparticle surfaces, whereas thiolactic acid did not affect or even hindered Hg{sup 2+} photoreduction. Although both surface adsorbers chelated with the metal ions in the absence of TiO{sub 2} nanoparticles, this chelation was drastically changed in the Cu-Ala complex but was largely retained in the Hg-TLA complex when TiO{sub 2} was present. This may correlate with the different effects of the adsorbers on the photoreduction of the metal. Our experimental results suggest that a proper balance between the affinities of the adsorber to the metal ions and to the surface Ti atoms of TiO{sub 2} may be one of the keys in selecting a surface adsorber for enhanced photoreduction efficiency.« less

Metal (Cu, Cd and Zn) removal and stabilization during multiple soil washing by saponin.

PubMed

Gusiatin, Zygmunt Mariusz; Klimiuk, Ewa

2012-01-01

The influence of multiple saponin washing on copper, cadmium and zinc removal and stability in three types of soils (loamy sand, loam, silty clay) was investigated. Distribution of metals and their mobility measured as the ratio of exchangeable form to the sum of all fractions in soils was differential. After single washing the highest efficiency of metal removal was obtained in loamy sand (82-90%) and loam (67-88%), whereas the lowest in silty clay (39-62%). In loamy sand and loam metals had higher mobility factors (44-61% Cu, 60-76% Cd, and 68-84% Zn) compared to silty clay (9% Cu, 28% Cd and 36% Zn). Triplicate washing led to increase both efficiency of metal removal and percentage content of their stable forms. In consequence, fractional patterns for metals before and after treatment changed visibly as a result of their redistribution. Based on the redistribution index, the most stable metal (mainly in residual and organic fractions) after triplicate washing was Cu in loamy sand and loam. For silty clay contaminated with Cd, effective metal removal and its stabilization required a higher number of washings. Copyright © 2011 Elsevier Ltd. All rights reserved.

Characterization, sorption, and exhaustion of metal oxide nanoparticles as metal adsorbents

NASA Astrophysics Data System (ADS)

Engates, Karen Elizabeth

Safe drinking water is paramount to human survival. Current treatments do not adequately remove all metals from solution, are expensive, and use many resources. Metal oxide nanoparticles are ideal sorbents for metals due to their smaller size and increased surface area in comparison to bulk media. With increasing demand for fresh drinking water and recent environmental catastrophes to show how fragile water supplies are, new approaches to water conservation incorporating new technologies like metal oxide nanoparticles should be considered as an alternative method for metal contaminant adsorbents from typical treatment methods. This research evaluated the potential of manufactured iron, anatase, and aluminum nanoparticles (Al2O3, TiO2, Fe2O3) to remove metal contaminants (Pb, Cd, Cu, Ni, Zn) in lab-controlled and natural waters in comparison to their bulk counterparts by focusing on pH, contaminant and adsorbent concentrations, particle size, and exhaustive capabilities. Microscopy techniques (SEM, BET, EDX) were used to characterize the adsorbents. Adsorption experiments were performed using 0.01, 0.1, or 0.5 g/L nanoparticles in pH 8 solution. When results were normalized by mass, nanoparticles adsorbed more than bulk particles but when surface area normalized the opposite was observed. Adsorption was pH-dependent and increased with time and solid concentration. Aluminum oxide was found to be the least acceptable adsorbent for the metals tested, while titanium dioxide anatase (TiO2) and hematite (alpha-Fe2O3) showed great ability to remove individual and multiple metals from pH 8 and natural waters. Intraparticle diffusion was likely part of the complex kinetic process for all metals using Fe2O3 but not TiO 2 nanoparticles within the first hour of adsorption. Adsorption kinetics for all metals tested were described by a modified first order rate equation used to consider the diminishing equilibrium metal concentrations with increasing metal oxides, showing faster adsorption rates for nanoparticles compared to bulk particles. Isotherms were best fit with most correlations of r=0.99 or better using the Langmuir-Freundlich equation which describes a heterogeneous surface with monolayer adsorption. Calculated rate constants and distribution coefficients (Kd) showed TiO2 nanoparticles were very good sorbents and more rapid in removing metals than other nanoparticles studied here and reported in the literature. Desorption studies concluded Pb, Cd, and Zn appear to be irreversibly sorbed to TiO2 surfaces at pH 8. TiO2 and Fe2O3 nanoparticles were capable of multiple metal loadings, with exhaustion for both adsorbents at pH 6. Exhaustion studies at pH 8 showed hematite exhausted after four consecutive cycles while anatase showed no exhaustion after 8 cycles. Their bulk counterparts exhausted in earlier cycles indicating the lack of ability to adsorb much of the multiple metals in solution. The increased surface area of TiO2 and Fe 2O3 nanoparticles, coupled with strong adsorption at the pH of most natural waters and resistance to desorption of some metals, may offer a potential remediation method for removal of metals from water in the future.

Brazing characteristics of a Zr-Ti-Cu-Fe eutectic alloy filler metal for Zircaloy-4

NASA Astrophysics Data System (ADS)

Lee, Jung G.; Lim, C. H.; Kim, K. H.; Park, S. S.; Lee, M. K.; Rhee, C. K.

2013-10-01

A Zr-Ti-Cu-Fe quaternary eutectic alloy was employed as a new Be-free brazing filler metal for Zircaloy-4 to supersede physically vapor-deposited Be coatings used conventionally with several disadvantages. The quaternary eutectic composition of Zr58Ti16Cu10Fe16 (at.%) showing a low melting temperature range from 832 °C to 853 °C was designed by a partial substitution of Zr with Ti based on a Zr-Cu-Fe ternary eutectic system. By applying an alloy ribbon with the determined composition, a highly reliable joint was obtained with a homogeneous formation of predominantly grown α-Zr phases owing to a complete isothermal solidification, exhibiting strength higher than that of Zircaloy-4. The homogenization of the joint was rate-controlled by the diffusion of the filler elements (Ti, Cu, and Fe) into the Zircaloy-4 base metal, and the detrimental segregation of the Zr2Fe phase in the central zone was completely eliminated by an isothermal holding at a brazing temperature of 920 °C for 10 min.

Synthesis, characterization and biological assay of Salicylaldehyde Schiff base Cu(II) complexes and their precursors

NASA Astrophysics Data System (ADS)

Iftikhar, Bushra; Javed, Kanwal; Khan, Muhammad Saif Ullah; Akhter, Zareen; Mirza, Bushra; Mckee, Vickie

2018-03-01

Three new Schiff base ligands were synthesized by the reaction of Salicylaldehyde with semi-aromatic diamines, prepared by the reduction of corresponding dinitro-compounds, and were further used for the formation of complexes with Cu(II) metal ion. The structural features of the synthesized compounds were confirmed by their physical properties and infrared, electronic and NMR spectroscopic techniques. The studies revealed that the synthesized Schiff bases existed as tetradentate ligands and bonded to the metal ion through the phenolic oxygen and azomethine nitrogen. One of the dinitro precursors was also analyzed by single crystal X-ray crystallography, which showed that it crystallizes in monoclinic system with space group P2/n. The thermal behavior of the Cu(II) complexes was determined by thermogravimetric analysis (TGA) and kinetic parameters were evaluated from the data. Schiff base ligands, their precursors and metal complexes were also screened for antibacterial, antifungal, antitumor, Brine shrimp lethality, DPPH free radical scavenging and DNA damage assays. The results of these analyses indicated the substantial potential of the synthesized Schiff bases, their precursors and Cu(II) complexes in biological field as future drugs.

Advanced Cu chemical displacement technique for SiO2-based electrochemical metallization ReRAM application.

PubMed

Chin, Fun-Tat; Lin, Yu-Hsien; You, Hsin-Chiang; Yang, Wen-Luh; Lin, Li-Min; Hsiao, Yu-Ping; Ko, Chum-Min; Chao, Tien-Sheng

2014-01-01

This study investigates an advanced copper (Cu) chemical displacement technique (CDT) with varying the chemical displacement time for fabricating Cu/SiO2-stacked resistive random-access memory (ReRAM). Compared with other Cu deposition methods, this CDT easily controls the interface of the Cu-insulator, the switching layer thickness, and the immunity of the Cu etching process, assisting the 1-transistor-1-ReRAM (1T-1R) structure and system-on-chip integration. The modulated shape of the Cu-SiO2 interface and the thickness of the SiO2 layer obtained by CDT-based Cu deposition on SiO2 were confirmed by scanning electron microscopy and atomic force microscopy. The CDT-fabricated Cu/SiO2-stacked ReRAM exhibited lower operation voltages and more stable data retention characteristics than the control Cu/SiO2-stacked sample. As the Cu CDT processing time increased, the forming and set voltages of the CDT-fabricated Cu/SiO2-stacked ReRAM decreased. Conversely, decreasing the processing time reduced the on-state current and reset voltage while increasing the endurance switching cycle time. Therefore, the switching characteristics were easily modulated by Cu CDT, yielding a high performance electrochemical metallization (ECM)-type ReRAM.

Piezoelectric coefficients of bulk 3R transition metal dichalcogenides

NASA Astrophysics Data System (ADS)

Konabe, Satoru; Yamamoto, Takahiro

2017-09-01

The piezoelectric properties of bulk transition metal dichalcogenides (TMDCs) with a 3R structure were investigated using first-principles calculations based on density functional theory combined with the Berry phase treatment. Values for the elastic constant Cijkl , the piezoelectric coefficient eijk , and the piezoelectric coefficient dijk are given for bulk 3R-TMDCs (MoS2, MoSe2, WS2, and WSe2). The piezoelectric coefficients of bulk 3R-TMDCs are shown to be sufficiently large or comparable to those of conventional bulk piezoelectric materials such as α-quartz, wurtzite GaN, and wurtzite AlN.

Metallic copper in ordinary chondrites

NASA Technical Reports Server (NTRS)

Rubin, Alan E.

1994-01-01

Metallic Cu of moderately high purity (approximately 985 mg/g Cu, approximately 15 mg/g Ni) occurs in at least 66% of ordinary chondrites (OC) as heterogeneously distributed, small (typically less than or equal to 20 micrometers) rounded to irregular grains. The mean modal abundance of metallic Cu in H, L and LL chondrites is low: 1.0 to 1.4 x 10(exp -4) vol%, corresponding to only 4 - 5 % of the total Cu in OC whole rocks. In more than 75% of the metallic-Cu-bearing OC, at least some metallic Cu occurs at metallic-Fe-Ni-troilite grain boundaries. In some cases it also occurs within troilite, within metallic Fe-Ni, or at the boundaries these phases form with silicates or chromite. Ordinary chondrites that contain a relatively large number of occurrences of metallic Cu/sq mm have a tendency to have experienced moderately high degrees of shock. Shock processes can cause local melting and transportation of metallic Fe-Ni and troilte; because metallic Cu is mainly associated with these phases, it also gets redistributed during shock events. In the most common petrographic assemblage containing metallic Cu, the Cu is adjacent to small irregular troilite grains surrounded by taenite plus tetrataenite; this assemblage resembles fizzed troilite and may have formed by localized shock melting or remelting of a metal-troilite assemblage.

Unique properties of ceria nanoparticles supported on metals: novel inverse ceria/copper catalysts for CO oxidation and the water-gas shift reaction.

PubMed

Senanayake, Sanjaya D; Stacchiola, Dario; Rodriguez, Jose A

2013-08-20

Oxides play a central role in important industrial processes, including applications such as the production of renewable energy, remediation of environmental pollutants, and the synthesis of fine chemicals. They were originally used as catalyst supports and were thought to be chemically inert, but now they are used to build catalysts tailored toward improved selectivity and activity in chemical reactions. Many studies have compared the morphological, electronic, and chemical properties of oxide materials with those of unoxidized metals. Researchers know much less about the properties of oxides at the nanoscale, which display distinct behavior from their bulk counterparts. More is known about metal nanoparticles. Inverse-model catalysts, composed of oxide nanoparticles supported on metal or oxide substrates instead of the reverse (oxides supporting metal nanoparticles), are excellent tools for systematically testing the properties of novel catalytic oxide materials. Inverse models are prepared in situ and can be studied with a variety of surface science tools (e.g. scanning tunneling microscopy, X-ray photoemission spectroscopy, ultraviolet photoemission spectroscopy, low-energy electron microscopy) and theoretical tools (e.g. density functional theory). Meanwhile, their catalytic activity can be tested simultaneously in a reactor. This approach makes it possible to identify specific functions or structures that affect catalyst performance or reaction selectivity. Insights gained from these tests help to tailor powder systems, with the primary objective of rational design (experimental and theoretical) of catalysts for specific chemical reactions. This Account describes the properties of inverse catalysts composed of CeOx nanoparticles supported on Cu(111) or CuOx/Cu(111) as determined through the methods described above. Ceria is an important material for redox chemistry because of its interchangeable oxidation states (Ce⁴⁺ and Ce³⁺). Cu(111), meanwhile, is a standard catalyst for reactions such as CO oxidation and the water-gas shift (WGS). This metal serves as an ideal replacement for other noble metals that are neither abundant nor cost effective. To prepare the inverse system we deposited nanoparticles (2-20 nm) of cerium oxide onto the Cu(111) surface. During this process, the Cu(111) surface grows an oxide layer that is characteristic of Cu₂O (Cu¹⁺). This oxide can influence the growth of ceria nanoparticles. Evidence suggests triangular-shaped CeO₂(111) grows on Cu₂O(111) surfaces while rectangular CeO₂(100) grows on Cu₄O₃(111) surfaces. We used the CeOx/Cu₂O/Cu(111) inverse system to study two catalytic processes: the WGS (CO + H₂O → CO₂ + H₂) and CO oxidation (2CO + O₂ → 2CO₂). We discovered that the addition of small amounts of ceria nanoparticles can activate the Cu(111) surface and achieve remarkable enhancement of catalytic activity in the investigated reactions. In the case of the WGS, the CeOx nanoparticle facilitated this process by acting at the interface with Cu to dissociate water. In the CO oxidation case, an enhancement in the dissociation of O₂ by the nanoparticles was a key factor. The strong interaction between CeOx nanoparticles and Cu(111) when preoxidized and reduced in CO resulted in a massive surface reconstruction of the copper substrate with the introduction of microterraces that covered 25-35% of the surface. This constitutes a new mechanism for surface reconstruction not observed before. These microterraces helped to facilitate a further enhancement of activity towards the WGS by opening an additional channel for the dissociation of water. In summary, inverse catalysts of CeOx/Cu(111) and CeO₂/Cu₂O/Cu(111) demonstrate the versatility of a model system to obtain insightful knowledge of catalytic processes. These systems will continue to offer a unique opportunity to probe key catalytic components and elucidate the relationship between structure and reactivity of novel materials and reactions in the future.

Facile solid-state synthesis of highly dispersed Cu nanospheres anchored on coal-based activated carbons as an efficient heterogeneous catalyst for the reduction of 4-nitrophenol

NASA Astrophysics Data System (ADS)

Wang, Shan; Gao, Shasha; Tang, Yakun; Wang, Lei; Jia, Dianzeng; Liu, Lang

2018-04-01

Coal-based activated carbons (AC) were acted as the support, Cu/AC catalysts were synthesized by a facile solid-state reaction combined with subsequent heat treatment. In Cu/AC composites, highly dispersed Cu nanospheres were anchored on AC. The catalytic activity for 4-nitrophenol (4-NP) was investigated, the effects of activation temperature and copper loading on the catalytic performance were studied. The catalysts exhibited very high catalytic activity and moderate chemical stability due to the unique characteristics of the particle-assembled nanostructures, the high surface area and the porous structure of coal-based AC and the good dispersion of metal particles. Design and preparation of non-noble metal composite catalysts provide a new direction for improving the added value of coal.

Dissolved and particulate trace metals in coastal waters of the Gulf and Western Arabian Sea

NASA Astrophysics Data System (ADS)

Fowler, S. W.; Huynh-Ngoc, L.; Fukai, R.

Concentrations of chemical species of selected heavy metals (Cu, Zn, Cd, Hg and Pb) were determined in surface waters from a series of coastal sites in Bahrain, United Arab Emirates (UAE) and the Sultanate of Oman. Analyses were carried out on bulk sea water samples as well as on suspended particulates by anodic stripping voltammetry. Heavy metal concentrations were relatively low with the exception of some "hot spots" which occurred in the vicinity of industrial and port activities. Average copper levels along the coast of UAE were generally higher than those measured in sea water from either Bahrain of Oman. Waters from the more populated and industrialised northwest coast of Oman were found to contain approximately 3 to 4-fold higher Cd and Zn (pH 4-4.5) concentrations than those from the southern coast, an undeveloped region adjacent to the more open waters of the Arabian Sea. Possible reasons for the observed regional variations in trace metal concentrations in Oman are discussed in terms of natural and anthropogenic input sources. Average concentrations in the Gulf (inside the Strait of Hormuz) were 510 ng 1 -1 (Cu), 340 ng 1 -1 (Zn), 20 ng 1 -1 (Cd), 16 ng 1 -1 (Hg) and 76 ng 1 -1 (Pb); in the western Arabian Sea along the coast of Oman concentrations averaged 290 ng 1 -1 (Cu), 180 ng 1 -1 (Zn), 37 ng 1 -1 (Cd), 11 ng 1 -1 (Hg) and 80 ng 1 -1 (Pb). Ranges of concentrations for these metals in Gulf and western Arabian Sea waters approach those which have been reported for open surface waters of the Atlantic, Pacific, Indian Oceans and the Mediterranean Sea indicating that, in general, the coastal waters of this region are not impacted by metal pollution and that the existing natural levels can be used as a point of reference for future pollutant studies.

Vacuum Brazing of WC-8Co Cemented Carbides to Carbon Steel Using Pure Cu and Ag-28Cu as Filler Metal

NASA Astrophysics Data System (ADS)

Zhang, X. Z.; Liu, G. W.; Tao, J. N.; Shao, H. C.; Fu, H.; Pan, T. Z.; Qiao, G. J.

2017-02-01

The wetting and spreading behavior of commercial pure Cu and Ag-28Cu alloy on WC-8Co cemented carbide were investigated by the sessile drop technique. The contact angle of both systems obviously decreases with moderately increasing the wetting temperature. Vacuum brazing of the WC-8Co cemented carbide to SAE1045 steel using the pure Cu or Ag-28Cu as filler metal was further carried out based on the wetting results. The interfacial interactions and joint mechanical behavior involving microhardness, shear strength and fracture were analyzed and discussed. An obvious Fe-Cu-Co transition layer is detected at the WC-8Co/Cu interface, while no obvious reaction layer is observed at the whole WC-8Co/Ag-28Cu/SAE1045 brazing seam. The microhardness values of the two interlayers and the steel substrate near the two interlayers increase more or less, while those of WC-8Co cemented carbide substrates adjacent to the two interlayers decrease. The WC-8Co/SAE1045 joints using pure Cu and Ag-28Cu alloy as filler metals obtain average shear strength values of about 172 and 136 MPa, and both of the joint fractures occur in the interlayers.

Trace metal characterization of aerosol particles and cloud water during HCCT 2010

NASA Astrophysics Data System (ADS)

Fomba, K. W.; van Pinxteren, D.; Müller, K.; Iinuma, Y.; Lee, T.; Collett, J. L., Jr.; Herrmann, H.

2015-08-01

Trace metal characterization of bulk and size-resolved aerosol and cloud water samples were performed during the Hill Cap Cloud Thuringia (HCCT) campaign. Cloud water was collected at the top of Mt. Schmücke while aerosol samples were collected at two stations upwind and downwind of Mt. Schmücke. Fourteen trace metals including Ti, V, Fe, Mn, Co, Zn, Ni, Cu, As, Sr, Rb, Pb, Cr, and Se were investigated during four full cloud events (FCEs) that fulfilled the conditions of a continuous air mass flow through the three stations. Aerosol particle trace metal concentrations were found to be lower than those observed in the same region during previous field experiments but were within a similar range to those observed in other rural regions in Europe. Fe and Zn were the most abundant elements with concentration ranges of 0.2-111.6 and 1.1-32.1 ng m-3, respectively. Fe, Mn, and Ti were mainly found in coarse mode aerosols while Zn, Pb, and As were mostly found in the fine mode. Correlation and enrichment factor analysis of trace metals revealed that trace metals such as Ti and Rb were mostly of crustal origin while trace metals such as Zn, Pb, As, Cr, Ni, V, and Cu were of anthropogenic origin. Trace metals such as Fe and Mn were of mixed origins including crustal and combustion sources. Trace metal cloud water concentration decreased from Ti, Mn, Cr, to Co with average concentrations of 9.18, 5.59, 5.54, and 0.46 μg L-1, respectively. A non-uniform distribution of soluble Fe, Cu, and Mn was observed across the cloud drop sizes. Soluble Fe and Cu were found mainly in cloud droplets with diameters between 16 and 22 μm, while Mn was found mostly in larger drops greater than 22 μm. Fe(III) was the main form of soluble Fe especially in the small and larger drops with concentrations ranging from 2.2 to 37.1 μg L-1. In contrast to other studies, Fe(II) was observed mainly in the evening hours, implying its presence was not directly related to photochemical processes. Aerosol-cloud interaction did not lead to a marked increase in soluble trace metal concentrations; rather it led to differences in the chemical composition of the aerosol due to preferential loss of aerosol particles through physical processes including cloud drop deposition to vegetative surfaces.

Trace metal characterization of aerosol particles and cloud water during HCCT 2010

NASA Astrophysics Data System (ADS)

Fomba, K. W.; van Pinxteren, D.; Müller, K.; Iinuma, Y.; Lee, T.; Collet, J., Jr.; Herrmann, H.

2015-04-01

Trace metal characterization of bulk and size resolved aerosol and cloud water samples were performed during the Hill Cap Cloud Thuringia (HCCT) campaign. Cloud water was collected at the top of Mt. Schmücke while aerosol samples were collected at two stations upwind and downwind of Mt. Schmücke. Fourteen trace metals including Ti, V, Fe, Mn, Co, Zn, Ni, Cu, As, Sr, Rb, Pb, Cr, and Se were investigated during four full cloud events (FCE) that fulfilled the conditions of a continuous air mass flow through the three stations. Aerosol particle trace metal concentrations were found to be lower than those observed in the same region during previous field experiments but were within a similar range to those observed in other rural regions in Europe. Fe and Zn were the most abundant elements with concentration ranges of 0.2-111.6 and 1.1-32.1 ng m-3, respectively. Fe, Mn and Ti were mainly found in coarse mode aerosols while Zn, Pb and As were mostly found in the fine mode. Correlation and enrichment factor analysis of trace metals revealed that trace metals such as Ti and Rb were mostly of crustal origin while trace metals such as Zn, Pb, As, Cr, Ni, V, and Cu were of anthropogenic origin. Trace metals such as Fe, Mn, were of mixed origins including crustal and combustion sources. Trace metal cloud water concentration decreased from Ti, Mn, Cr, to Co with average concentrations of 9.18, 5.59, 5.54, and 0.46 μg L-1, respectively. A non-uniform distribution of soluble Fe, Cu and Mn was observed across the cloud drop sizes. Soluble Fe and Cu were found mainly in cloud droplets with diameters between 16 and 22 μm while Mn was found mostly in larger drops greater than 22 μm. Fe (III) was the main form of soluble Fe especially in the small and larger drops with concentrations ranging from 2.2 to 37.1 μg L-1. In contrast to other studies, Fe (II) was observed mainly in the evening hours, implying its presence was not directly related to photochemical processes. Aerosol cloud interaction did not lead to a mark increase in soluble trace metal concentrations, but led to differences in the chemical composition of the aerosol due to preferential loss of aerosol particles through physical processes including cloud drop deposition to vegetative surfaces.

Epitaxial growth of CoO films on semiconductor and metal substrates by constructing a complex heterostructure

NASA Astrophysics Data System (ADS)

Entani, S.; Kiguchi, M.; Saiki, K.; Koma, A.

2003-01-01

Epitaxial growth of CoO films was studied using reflection high-energy electron diffraction (RHEED), electron energy loss spectroscopy (EELS), ultraviolet photoelectron spectroscopy (UPS) and Auger electron spectroscopy (AES). The RHEED results indicated that an epitaxial CoO film grew on semiconductor and metal substrates (CoO (0 0 1)∥GaAs (0 0 1), Cu (0 0 1), Ag (0 0 1) and [1 0 0]CoO∥[1 0 0] substrates) by constructing a complex heterostructure with two alkali halide buffer layers. The AES, EELS and UPS results showed that the grown CoO film had almost the same electronic structure as bulk CoO. We could show that use of alkali halide buffer layers was a good way to grow metal oxide films on semiconductor and metal substrates in an O 2 atmosphere. The alkali halide layers not only works as glue to connect very dissimilar materials but also prevents oxidation of metal and semiconductor substrates.

Particle Size Distribution of Heavy Metals and Magnetic Susceptibility in an Industrial Site.

PubMed

Ayoubi, Shamsollah; Soltani, Zeynab; Khademi, Hossein

2018-05-01

This study was conducted to explore the relationships between magnetic susceptibility and some soil heavy metals concentrations in various particle sizes in an industrial site, central Iran. Soils were partitioned into five fractions (< 28, 28-75, 75-150, 150-300, and 300-2000 µm). Heavy metals concentrations including Zn, Pb, Fe, Cu, Ni and Mn and magnetic susceptibility were determined in bulk soil samples and all fractions in 60 soil samples collected from the depth of 0-5 cm. The studied heavy metals except for Pb and Fe displayed a substantial enrichment in the < 28 µm. These two elements seemed to be independent of the selected size fractions. Magnetic minerals are specially linked with medium size fractions including 28-75, 75-150 and 150-300 µm. The highest correlations were found for < 28 µm and heavy metals followed by 150-300 µm fraction which are susceptible to wind erosion risk in an arid environment.

Accessing thermoplastic processing windows in metallic glasses using rapid capacitive discharge

PubMed Central

Kaltenboeck, Georg; Harris, Thomas; Sun, Kerry; Tran, Thomas; Chang, Gregory; Schramm, Joseph P.; Demetriou, Marios D.; Johnson, William L.

2014-01-01

The ability of the rapid-capacitive discharge approach to access optimal viscosity ranges in metallic glasses for thermoplastic processing is explored. Using high-speed thermal imaging, the heating uniformity and stability against crystallization of Zr35Ti30Cu7.5Be27.5 metallic glass heated deeply into the supercooled region is investigated. The method enables homogeneous volumetric heating of bulk samples throughout the entire supercooled liquid region at high rates (~105 K/s) sufficient to bypass crystallization throughout. The crystallization onsets at temperatures in the vicinity of the “crystallization nose” were identified and a Time-Temperature-Transformation diagram is constructed, revealing a “critical heating rate” for the metallic glass of ~1000 K/s. Thermoplastic process windows in the optimal viscosity range of 100–104 Pa·s are identified, being confined between the glass relaxation and the eutectic crystallization transition. Within this process window, near-net forging of a fine precision metallic glass part is demonstrated. PMID:25269892

Aluminum Cluster-Based Materials for Propulsion and Other Applications

DTIC Science & Technology

2012-04-04

CuMg8- and AuMg8- . It was shown that aromaticity, traditionally used to understand stability of organic systems , can also stabilize metallic...of arsenic and K atoms. Extensions of these to other systems is currently under study. Since 2009, 12 group publications (GP) have resulted with...CuAl22- using DFT. 9 B. Stable Aromatic Aluminum-Based Metal Clusters: Aromaticity has historically been applied to organic systems that are

Post-depositional behavior of Cu in a metal-mining polishing pond (East Lake, Canada).

PubMed

Martin, Alan J; Jambor, John L; Pedersen, Tom F; Crusius, John

2003-11-01

The post-depositional behavior of Cu in a gold-mining polishing pond (East Lake, Canada) was assessed after mine closure by examination of porewater chemistry and mineralogy. The near-surface (upper 1.5 cm) sediments are enriched in Cu, with values ranging from 0.4 to 2 wt %. Mineralogical examination revealed that the bulk of the Cu inventory is present as authigenic copper sulfides. Optical microscopy, energy-dispersion spectra, and X-ray data indicate that the main Cu sulfide is covellite (CuS). The formation of authigenic Cu-S phases is supported by the porewater data, which demonstrate that the sediments are serving as a sink for dissolved Cu below sub-bottom depths of 1-2 cm. The zone of Cu removal is consistent with the occurrence of detectable sulfide and the consumption of sulfate. The sediments can be viewed as a passive bioreactorthat permanently removes Cu as insoluble copper sulfides. This process is not unlike that which occurs in other forms of bioremediation, such as wetlands and permeable reactive barriers. Above the zone of Cu removal, dissolved Cu maxima in the interfacial porewaters range from 150 to 450 microg L(-1) and reflect the dissolution of a Cu-bearing phase in the surface sediments. The reactive phase is thought to be a component of treatment sludges delivered to the lake as part of cyanide treatment. Flux calculations indicate that the efflux of dissolved Cu from the sediments to the water column (14-51 microg cm(-2) yr(-1)) can account for the elevated levels of dissolved Cu in lake waters (approximately 50 microg L(-1)). Implications for lake recovery are discussed.

Post-Depositional Behavior of Cu in a Metal-Mining Polishing Pond (East Lake, Canada)

USGS Publications Warehouse

Martin, A.J.; Jambor, J.L.; Pedersen, Thomas F.; Crusius, John

2003-01-01

The post-depositional behavior of Cu in a gold-mining polishing pond (East Lake, Canada) was assessed after mine closure by examination of porewater chemistry and mineralogy. The near-surface (upper 1.5 cm) sediments are enriched in Cu, with values ranging from 0.4 to 2 wt %. Mineralogical examination revealed that the bulk of the Cu inventory is present as authigenic copper sulfides. Optical microscopy, energy-dispersion spectra, and X-ray data indicate that the main Cu sulfide is covellite (CuS). The formation of authigenic Cu-S phases is supported by the porewater data, which demonstrate that the sediments are serving as a sink for dissolved Cu below sub-bottom depths of 1-2 cm. The zone of Cu removal is consistent with the occurrence of detectable sulfide and the consumption of sulfate. The sediments can be viewed as a passive bioreactor that permanently removes Cu as insoluble copper sulfides. This process is not unlike that which occurs in other forms of bioremediation, such as wetlands and permeable reactive barriers. Above the zone of Cu removal, dissolved Cu maxima in the interfacial porewaters range from 150 to 450 ??g L-1 and reflect the dissolution of a Cu-bearing phase in the surface sediments. The reactive phase is thought to be a component of treatment sludges delivered to the lake as part of cyanide treatment. Flux calculations indicate that the efflux of dissolved Cu from the sediments to the water column (14-51 ??g cm-2 yr-1) can account for the elevated levels of dissolved Cu in lake waters (???50 ??g L-1). Implications for lake recovery are discussed.

Synthesis, Characterization and Biological Evaluation of Transition Metal Complexes Derived from N, S Bidentate Ligands

PubMed Central

Md Yusof, Enis Nadia; Ravoof, Thahira Begum S. A.; Tiekink, Edward R. T.; Veerakumarasivam, Abhimanyu; Crouse, Karen Anne; Mohamed Tahir, Mohamed Ibrahim; Ahmad, Haslina

2015-01-01

Two bidentate NS ligands were synthesized by the condensation reaction of S-2-methylbenzyldithiocarbazate (S2MBDTC) with 2-methoxybenzaldehyde (2MB) and 3-methoxybenzaldehyde (3MB). The ligands were reacted separately with acetates of Cu(II), Ni(II) and Zn(II) yielding 1:2 (metal:ligand) complexes. The metal complexes formed were expected to have a general formula of [M(NS)2] where M = Cu2+, Ni2+, and Zn2+. These compounds were characterized by elemental analysis, molar conductivity, magnetic susceptibility and various spectroscopic techniques. The magnetic susceptibility measurements and spectral results supported the predicted coordination geometry in which the Schiff bases behaved as bidentate NS donor ligands coordinating via the azomethine nitrogen and thiolate sulfur. The molecular structures of the isomeric S2M2MBH (1) and S2M3MBH (2) were established by X-ray crystallography to have very similar l-shaped structures. The Schiff bases and their metal complexes were evaluated for their biological activities against estrogen receptor-positive (MCF-7) and estrogen receptor-negative (MDA-MB-231) breast cancer cell lines. Only the Cu(II) complexes showed marked cytotoxicity against the cancer cell lines. Both Schiff bases and other metal complexes were found to be inactive. In concordance with the cytotoxicity studies, the DNA binding studies indicated that Cu(II) complexes have a strong DNA binding affinity. PMID:25988384

Geofractionation of heavy metals and application of indices for pollution prediction in paddy field soil of Tumpat, Malaysia.

PubMed

Sow, Ai Yin; Ismail, Ahmad; Zulkifli, Syaizwan Zahmir

2013-12-01

The present study investigates the concentration of Pb, Cd, Ni, Zn, and Cu in the paddy field soils collected from Tumpat, Kelantan. Soil samples were treated with sequential extraction to distinguish the anthropogenic and lithogenic origin of Pb, Cd, Ni, Zn, and Cu. ELFE and oxidizable-organic fractions were detected as the lowest accumulation of Pb, Cd, Ni, Zn, and Cu. Therefore, all the heavy metals examined were concentrated, particularly in resistant fraction, indicating that those heavy metals occurred and accumulated in an unavailable form. The utilization of agrochemical fertilizers and pesticides might not elevate the levels of heavy metals in the paddy field soils. In comparison, the enrichment factor and geoaccumulation index for Pb, Cd, Ni, Zn, and Cu suggest that these heavy metals have the potential to cause environmental risk, although they present abundance in resistant fraction. Therefore, a complete study should be conducted based on the paddy cycle, which in turn could provide a clear picture of heavy metals distribution in the paddy field soils.

Soil heavy metal contamination related to roasted stone coal slag: a study based on geostatistical and multivariate analyses.

PubMed

Li, De'an; Jiang, Jianguo; Li, Tianran; Wang, Jiaming

2016-07-01

Soil was examined for vanadium (V) and related metal contamination near a stone coal mine in Hubei Province, China. In total, 92 surface and vertical (0-200 cm) soil samples were collected from the site. A handheld X-ray fluorescence spectrometer was used for in situ analysis of the soil concentrations of heavy metals, including V, chromium (Cr), copper (Cu), manganese (Mn), zinc (Zn), and lead (Pb). The mean concentrations of these metals were 931, 721, 279, 223, 163, and 11 mg/kg, respectively. Based on the Chinese Environmental Quality Standard for Soils guidelines, up to 88.0, 76.1, and 56.5 % of the soil samples had single factor pollution indices >3 for V, Cr, and Cu, respectively. Furthermore, 2.2 % of samples were slightly polluted with Zn, while there was no Mn or Pb contamination. GaussAmp curve fitting was performed based on the sample frequency distribution of the Nemerow pollution index. The fitted mean was 5.99, indicating severe pollution. The heavy metals were clustered into two groups, V/Cr/Cu/Zn and Mn/Pb, based on the spatial distributions, the Pearson correlation and principal component analyses. The positive correlations within the V/Cr/Cu/Zn group suggested that they originated from roasted stone coal slag. Finally, the negative correlation between the two groups was attributed to mechanical mixing of the slag and original soil.

Adsorption of gas molecules on Cu impurities embedded monolayer MoS2: A first- principles study

NASA Astrophysics Data System (ADS)

Zhao, B.; Li, C. Y.; Liu, L. L.; Zhou, B.; Zhang, Q. K.; Chen, Z. Q.; Tang, Z.

2016-09-01

Adsorption of small gas molecules (O2, NO, NO2 and NH3) on transition-metal Cu atom embedded monolayer MoS2 was investigated by first-principles calculations based on the density-functional theory (DFT). The embedded Cu atom is strongly constrained on the sulfur vacancy of monolayer MoS2 with a high diffusion barrier. The stable adsorption geometry, charge transfer and electronic structures of these gas molecules on monolayer MoS2 embedded with transition-metal Cu atom are discussed in detail. It is found that the monolayer MoS2 with embedded Cu atom can effectively capture these gas molecules with high adsorption energy. The NH3 molecule acts as electron donor after adsorption, which is different from the other gas molecules (O2, NO, and NO2). The results suggest that MoS2-Cu system may be promising for future applications in gas molecules sensing and catalysis, which is similar to those of the transition-metal embedded graphene.

Ternary metal fluorides as high-energy cathodes with low cycling hysteresis

PubMed Central

Wang, Feng; Kim, Sung-Wook; Seo, Dong-Hwa; Kang, Kisuk; Wang, Liping; Su, Dong; Vajo, John J.; Wang, John; Graetz, Jason

2015-01-01

Transition metal fluorides are an appealing alternative to conventional intercalation compounds for use as cathodes in next-generation lithium batteries due to their extremely high capacity (3–4 times greater than the current state-of-the-art). However, issues related to reversibility, energy efficiency and kinetics prevent their practical application. Here we report on the synthesis, structural and electrochemical properties of ternary metal fluorides (M1yM21-yFx: M1, M2=Fe, Cu), which may overcome these issues. By substituting Cu into the Fe lattice, forming the solid–solution CuyFe1-yF2, reversible Cu and Fe redox reactions are achieved with surprisingly small hysteresis (<150 mV). This finding indicates that cation substitution may provide a new avenue for tailoring key electrochemical properties of conversion electrodes. Although the reversible capacity of Cu conversion fades rapidly, likely due to Cu+ dissolution, the low hysteresis and high energy suggest that a Cu-based fluoride cathode remains an intriguing candidate for rechargeable lithium batteries. PMID:25808876

Antimicrobial metallic copper surfaces kill Staphylococcus haemolyticus via membrane damage.

PubMed

Santo, Christophe Espírito; Quaranta, Davide; Grass, Gregor

2012-03-01

Recently, copper (Cu) in its metallic form has regained interest for its antimicrobial properties. Use of metallic Cu surfaces in worldwide hospital trials resulted in remarkable reductions in surface contaminations. Yet, our understanding of why microbes are killed upon contact to the metal is still limited and different modes of action have been proposed. This knowledge, however, is crucial for sustained use of such surfaces in hospitals and other hygiene-sensitive areas. Here, we report on the molecular mechanisms by which the Gram-positive Staphylococcus haemolyticus is inactivated by metallic Cu. Staphylococcus haemolyticus was killed within minutes on Cu but not on stainless steel demonstrating the antimicrobial efficacy of metallic Cu. Inductively coupled plasma mass spectroscopy (ICP-MS) analysis and in vivo staining with Coppersensor-1 indicated that cells accumulated large amounts of Cu ions from metallic Cu surfaces contributing to lethal damage. Mutation rates of Cu- or steel-exposed cells were similarly low. Instead, live/dead staining indicated cell membrane damage in Cu- but not steel-exposed cells. These findings support a model of the cellular targets of metallic Cu toxicity in bacteria, which suggests that metallic Cu is not genotoxic and does not kill via DNA damage. In contrast, membranes constitute the likely Achilles' heel of Cu surface-exposed cells.

Antimicrobial metallic copper surfaces kill Staphylococcus haemolyticus via membrane damage

PubMed Central

Santo, Christophe Espírito; Quaranta, Davide; Grass, Gregor

2012-01-01

Recently, copper (Cu) in its metallic form has regained interest for its antimicrobial properties. Use of metallic Cu surfaces in worldwide hospital trials resulted in remarkable reductions in surface contaminations. Yet, our understanding of why microbes are killed upon contact to the metal is still limited and different modes of action have been proposed. This knowledge, however, is crucial for sustained use of such surfaces in hospitals and other hygiene-sensitive areas. Here, we report on the molecular mechanisms by which the Gram-positive Staphylococcus haemolyticus is inactivated by metallic Cu. Staphylococcus haemolyticus was killed within minutes on Cu but not on stainless steel demonstrating the antimicrobial efficacy of metallic Cu. Inductively coupled plasma mass spectroscopy (ICP-MS) analysis and in vivo staining with Coppersensor-1 indicated that cells accumulated large amounts of Cu ions from metallic Cu surfaces contributing to lethal damage. Mutation rates of Cu- or steel-exposed cells were similarly low. Instead, live/dead staining indicated cell membrane damage in Cu- but not steel-exposed cells. These findings support a model of the cellular targets of metallic Cu toxicity in bacteria, which suggests that metallic Cu is not genotoxic and does not kill via DNA damage. In contrast, membranes constitute the likely Achilles’ heel of Cu surface-exposed cells. PMID:22950011

"Bulk" Nanocrystalline Metals: Review of the Current State of the Art and Future Opportunities for Copper and Copper Alloys

NASA Astrophysics Data System (ADS)

Tschopp, M. A.; Murdoch, H. A.; Kecskes, L. J.; Darling, K. A.

2014-06-01

It is a new beginning for innovative fundamental and applied science in nanocrystalline materials. Many of the processing and consolidation challenges that have haunted nanocrystalline materials are now more fully understood, opening the doors for bulk nanocrystalline materials and parts to be produced. While challenges remain, recent advances in experimental, computational, and theoretical capability have allowed for bulk specimens that have heretofore been pursued only on a limited basis. This article discusses the methodology for synthesis and consolidation of bulk nanocrystalline materials using mechanical alloying, the alloy development and synthesis process for stabilizing these materials at elevated temperatures, and the physical and mechanical properties of nanocrystalline materials with a focus throughout on nanocrystalline copper and a nanocrystalline Cu-Ta system, consolidated via equal channel angular extrusion, with properties rivaling that of nanocrystalline pure Ta. Moreover, modeling and simulation approaches as well as experimental results for grain growth, grain boundary processes, and deformation mechanisms in nanocrystalline copper are briefly reviewed and discussed. Integrating experiments and computational materials science for synthesizing bulk nanocrystalline materials can bring about the next generation of ultrahigh strength materials for defense and energy applications.

AMTEC recirculating test cell component testing and operation

NASA Technical Reports Server (NTRS)

Underwood, M. L.; Sievers, R. K.; O'Connor, D.; Williams, R. M.; Jeffries-Nakamura, B.; Bankston, C. P.

1989-01-01

Alkali metal thermoelectric converter operation in a recirculating test cell (RTC), which requires a small electromagnetic pump (EM) and a high-temperature beta-double-prime alumina-solid-electrolyte (BASE)-to-metal seal, is discussed. The design of a pump and an active metal braze seal and the initial operation of a cell using these components are described. The pump delivered 0.25 cu cm/min against a 28-psia head. A braze seal system was selected after shear strength tests of Ta or Nb brazed to BASE by a variety of fillers including TiCuNi, TiNi, and TiNiCr. The TiCuNi filler was chosen for environment cell testing and showed no failure or observable degradation after short-term tests up to 1055 K. The pump and the Nb/TiCuNi/BASE seal were used in a test that demonstrated all the operational functions of the RTC for the first time. An increase in the radiation reduction factor at constant input power was observed, indicating that the condenser was being wet by sodium resulting in an increased reflectivity.