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Sample records for ag pd cu

  1. Precipitations in a dental Ag-Pd-Cu-Au alloy.

    PubMed

    Herø, H; Jørgensen, R; Sørbrøden, E; Suoninen, E

    1982-05-01

    The structure of a dental Ag-PD-Cu-Au alloy has been studied after centrifugal casting and various heat treatments. By transmission electron microscopy, a high density of small fct particles, assumed to be PdCu, was observed, but, in addition, finely-spaced rods of approximately equal to 0.05 micrometer (500 A) diameter with an fcc structure precipitated on the [100] planes of the matrix were found. On the basis of their structure and the pertaining lattice parameter, these rods are assumed to be Cu-rich. They could also be observed by scanning electron microscopy, but not at annealing temperatures lower than 425 degrees C. PMID:6953095

  2. Enhanced hydrogenation and reduced lattice distortion in size selected Pd-Ag and Pd-Cu alloy nanoparticles

    SciTech Connect

    Sengar, Saurabh K.; Mehta, B. R.; Kulriya, P. K.; Khan, S. A.

    2013-10-21

    Important correlation between valence band spectra and hydrogenation properties in Pd alloy nanoparticles is established by studying the properties of size selected and monocrystalline Pd, Ag, Cu, Pd-Ag, and Pd-Cu nanoparticles. The X-ray photoelectron spectroscopy and elastic recoil detection analysis show that size induced Pd4d centroid shift is related to enhanced hydrogenation with H/Pd ratio of 0.57 and 0.49 in Pd-Ag and Pd-Cu nanoparticles in comparison to reported bulk values of 0.2 and 0.1, respectively. Pd-alloy nanoparticles show lower hydrogen induced lattice distortion. The reduced distortion and higher hydrogen reactivity of Pd-alloy nanoparticles is important for numerous hydrogen related applications.

  3. Size and alloying induced shift in core and valence bands of Pd-Ag and Pd-Cu nanoparticles

    SciTech Connect

    Sengar, Saurabh K.; Mehta, B. R.; Govind

    2014-03-28

    In this report, X-ray photoelectron spectroscopy studies have been carried out on Pd, Ag, Cu, Pd-Ag, and Pd-Cu nanoparticles having identical sizes corresponding to mobility equivalent diameters of 60, 40, and 20 nm. The nanoparticles were prepared by the gas phase synthesis method. The effect of size on valence and core levels in metal and alloy nanoparticles has been studied by comparing the values to those with the 60 nm nanoparticles. The effect of alloying has been investigated by comparing the valence and core level binding energies of Pd-Cu and Pd-Ag alloy nanoparticles with the corresponding values for Pd, Ag, and Cu nanoparticles of identical sizes. These effects have been explained in terms of size induced lattice contractions, alloying induced charge transfer, and hybridization effects. The observation of alloying and size induced binding energy shifts in bimetallic nanoparticles is important from the point of view of hydrogen reactivity.

  4. Sulfuration resistance of five experimental Ag-Pd-Au-Cu alloys with low Pd content of 10 or 12%.

    PubMed

    Saitoh, Setsuo; Araki, Yoshima; Taira, Masayuki

    2006-06-01

    Commercial Ag-based alloy (46Ag-20Pd-12Au-20Cu alloy) is widely used in Japan as a casting alloy. As opposed to the commercial composition, we prepared five experimental Ag-based alloys with reduced Pd content of 10 or 12%, increased Au content of 20 to 30%, and reduced Cu content of 12 to 20%. We then evaluated their sulfuration resistance by analyzing cast specimen surfaces dipped in 0.1% Na2S solution with SEM/EPMA, TF-XRD, and XPS. It became evident that all alloys were susceptible to sulfuration in the segregated Ag-rich Pd-poor phases. The degree and speed of sulfuration, however, differed among the six alloys examined. In particular, one experimental alloy (46Ag-10Pd-30Au-12Cu) possessed a sulfuration resistance equal or superior to that of commercial Ag-based alloy, while the other four experimental alloys were inferior in sulfuration resistance. Based on the results of this study, we concluded that our newly developed 46Ag-10Pd-30Au-12Cu alloy could be employed as a new sulfuration-resistant Ag-based casting alloy--which is especially useful if the price of Pd is skyrocketing again. PMID:16916236

  5. Novel PdAgCu ternary alloy: Hydrogen permeation and surface properties

    NASA Astrophysics Data System (ADS)

    Tarditi, Ana M.; Braun, Fernando; Cornaglia, Laura M.

    2011-05-01

    Dense PdAgCu ternary alloy composite membranes were synthesized by the sequential electroless plating of Pd, Ag and Cu on top of both disk and tubular porous stainless steel substrates. X-ray diffraction and scanning electron microscopy were employed to study the structure and morphology of the tested samples. The hydrogen permeation performance of these membranes was investigated over a 350-450 °C temperature range and a trans-membrane pressure up to 100 kPa. After annealing at 500 °C in hydrogen stream followed by permeation experiments, the alloy layer presented a FCC crystalline phase with a bulk concentration of 68% Pd, 7% Ag and 25% Cu as revealed by EDS. The PdAgCu tubular membrane was found to be stable during more than 300 h on hydrogen stream. The permeabilities of the PdAgCu ternary alloy samples were higher than the permeabilities of the PdCu alloy membranes with a FCC phase. The co-segregation of silver and copper to the membrane surface was observed after hydrogen permeation experiments at high temperature as determined by XPS.

  6. Corrosion of Ti-STS dissimilar joints brazed by a Ag interlayer and Ag-Cu-(Pd) alloy fillers

    NASA Astrophysics Data System (ADS)

    Lee, M. K.; Park, J. J.; Lee, G. J.; Lee, J. G.; Kim, D. W.; Lim, C. H.; Rhee, C. K.; Lee, Y. B.; Lee, J. K.; Hong, S. J.

    2011-02-01

    Corrosion behavior of dissimilar brazed joints between titanium Gr. 2 (Ti) and S31254 stainless steel (STS) was investigated. For the study, a Ag interlayer and two Ag-base eutectic alloys, 72Ag-28Cu and 66.2Ag-25.8Cu-8Pd (wt.%), were introduced as a diffusion control layer and fillers, respectively, between the base materials. The joints commonly had a layered structure of Ti(base)/TiAg/Ag solid solution/STS(base), but the one brazed by the Ag-Cu-Pd filler was slightly alloyed with the noble Pd elements over the Ag-rich solid solution region. A series of corrosion test experiments in a sea water revealed that a corrosion of TiAg layer and a stress-induced cracking at the TiAg/Ag solid solution interface were dominant due to a galvanic attack, but notably the Ti-STS dissimilar joint's resistance to corrosion was significantly improved by alloying the Pd in the joint. The corrosion behavior of such dissimilar metal joints was discussed based on galvanic corrosion effect.

  7. Formation of Ag-Pd contacts on Y-Ba-CuO ceramic and contact properties

    NASA Astrophysics Data System (ADS)

    Gartsman, K. G.; Duguzhev, Sh. M.; Parfen'eva, L. S.; Smirnov, I. A.

    1991-01-01

    Ag-Pd (30 pct Pd) contacts were formed on pellets of Y-Ba-CuO ceramic in the process of powder compaction by pressing a thin layer of Ag-Pd alloy, deposited on a 6-micron-thick organic film, to the end surfaces of the ceramic pellet. Cold pressing was followed by annealing, during which the organic substrate burned out and a bond was formed between the ceramic and the metal alloy. The resistance of the contacts produced by this method is 0.0026 ohm/sq cm, which is significantly better than that of contacts produced by using silver pastes.

  8. Structural and magnetic phase transitions in CeCu6 -xTx (T =Ag ,Pd )

    NASA Astrophysics Data System (ADS)

    Poudel, L.; de la Cruz, C.; Payzant, E. A.; May, A. F.; Koehler, M.; Garlea, V. O.; Taylor, A. E.; Parker, D. S.; Cao, H. B.; McGuire, M. A.; Tian, W.; Matsuda, M.; Jeen, H.; Lee, H. N.; Hong, T.; Calder, S.; Zhou, H. D.; Lumsden, M. D.; Keppens, V.; Mandrus, D.; Christianson, A. D.

    2015-12-01

    The structural and the magnetic properties of CeCu6 -xAgx (0 ≤x ≤0.85 ) and CeCu6 -xPdx (0 ≤x ≤0.4 ) have been studied using neutron diffraction, resonant ultrasound spectroscopy (RUS), x-ray diffraction measurements, and first principles calculations. The structural and magnetic phase diagrams of CeCu6 -xAgx and CeCu6 -xPdx as a function of Ag/Pd composition are reported. The end member, CeCu6, undergoes a structural phase transition from an orthorhombic (P n m a ) to a monoclinic (P 21/c ) phase at 240 K. In CeCu6 -xAgx , the structural phase transition temperature (Ts) decreases linearly with Ag concentration and extrapolates to zero at xS ≈0.1 . The structural transition in CeCu6 -xPdx remains unperturbed with Pd substitution within the range of our study. The lattice constant b slightly decreases with Ag/Pd doping, whereas a and c increase with an overall increase in the unit cell volume. Both systems, CeCu6 -xAgx and CeCu6 -xPdx , exhibit a magnetic quantum critical point (QCP), at x ≈0.2 and x ≈0.05 , respectively. Near the QCP, long range antiferromagnetic ordering takes place at an incommensurate wave vector (δ10 δ2), where δ1˜0.62 ,δ2˜0.25 ,x =0.125 for CeCu6 -xPdx and δ1˜0.64 ,δ2˜0.3 ,x =0.3 for CeCu6 -xAgx . The magnetic structure consists of an amplitude modulation of the Ce moments which are aligned along the c axis of the orthorhombic unit cell.

  9. The structure of a commercial dental Ag-Pd-Cu-Au casting alloy.

    PubMed

    Niemi, L; Herø, H

    1984-02-01

    The structure of a commercial dental Ag-Pd-Cu-Au casting alloy has been studied by microprobe and X-ray diffraction analyses after various heat treatments. The composition of phases in equilibrium was established. After being annealed at 400 degrees C, 500 degrees C, and 600 degrees C for seven wk, the alloy consisted of three phases: a Cu- and Pd-rich fee phase (alpha 1) with alpha = 0.372nm, a Ag-rich matrix (alpha 2) with alpha = 0.399nm, and an ordered CsCl-type bcc PdCu phase with alpha = 0.296nm. The PdCu phase was not observed above 600 degrees C, and the proportion of the alpha 1 phase decreased sharply above 700 degrees C. After being annealed at 900 degrees C, the alloy matrix was partly decomposed at the Cu-enriched grain boundaries. The decomposed areas grew into the grain interior during subsequent precipitation hardening. No segregation of Au was detected after casting, and the element was evenly distributed throughout the alloy structure after all heat treatments. PMID:6582096

  10. Nanocatalyst superior to Pt for oxygen reduction reactions: the case of core/shell Ag(Au)/CuPd nanoparticles.

    PubMed

    Guo, Shaojun; Zhang, Xu; Zhu, Wenlei; He, Kai; Su, Dong; Mendoza-Garcia, Adriana; Ho, Sally Fae; Lu, Gang; Sun, Shouheng

    2014-10-22

    Controlling the electronic structure and surface strain of a nanoparticle catalyst has become an important strategy to tune and to optimize its catalytic efficiency for a chemical reaction. Using density functional theory (DFT) calculations, we predicted that core/shell M/CuPd (M = Ag, Au) NPs with a 0.8 or 1.2 nm CuPd2 shell have similar but optimal surface strain and composition and may surpass Pt in catalyzing oxygen reduction reactions. We synthesized monodisperse M/CuPd NPs by the coreduction of palladium acetylacetonate and copper acetylacetonate in the presence of Ag (or Au) nanoparticles with controlled shell thicknesses of 0.4, 0.75, and 1.1 nm and CuPd compositions and evaluated their catalysis for the oxygen reduction reaction in 0.1 M KOH solution. As predicted, our Ag/Cu37Pd63 and Au/Cu40Pd60 catalysts with 0.75 and 1.1 nm shells were more efficient catalysts than the commercial Pt catalyst (Fuel Cells Store), with their mass activity reaching 0.20 A/mg of noble metal at -0.1 V vs Ag/AgCl (4 M KCl); this was over 3 times higher than that (0.06 A/mg Pt) from the commercial Pt. These Ag(Au)/CuPd nanoparticles are promising non-Pt catalysts for oxygen reduction reactions. PMID:25279704

  11. Pd-Cu(2)O and Ag-Cu(2)O hybrid concave nanomaterials for an effective synergistic catalyst.

    PubMed

    Li, Lingling; Chen, Xiaobin; Wu, Yuen; Wang, Dingsheng; Peng, Qing; Zhou, Gang; Li, Yadong

    2013-10-11

    Palladium and silver salts were combined with Cu2 O octadecahedra in concave heterostructures. The formation of concave faces involved selective oxidative etching of Cu2 O on the {100} faces and in situ growth of Pd/Ag on different sites. The structures showed superior catalytic activities to both single domains and their mixtures in a model Sonogashira-type organic reaction. PMID:24038721

  12. Ag-Pd-Cu alloy inserted transparent indium tin oxide electrodes for organic solar cells

    SciTech Connect

    Kim, Hyo-Joong; Seo, Ki-Won; Kim, Han-Ki; Noh, Yong-Jin; Na, Seok-In

    2014-09-01

    The authors report on the characteristics of Ag-Pd-Cu (APC) alloy-inserted indium tin oxide (ITO) films sputtered on a glass substrate at room temperature for application as transparent anodes in organic solar cells (OSCs). The effect of the APC interlayer thickness on the electrical, optical, structural, and morphological properties of the ITO/APC/ITO multilayer were investigated and compared to those of ITO/Ag/ITO multilayer electrodes. At the optimized APC thickness of 8 nm, the ITO/APC/ITO multilayer exhibited a resistivity of 8.55 × 10{sup −5} Ω cm, an optical transmittance of 82.63%, and a figure-of-merit value of 13.54 × 10{sup −3} Ω{sup −1}, comparable to those of the ITO/Ag/ITO multilayer. Unlike the ITO/Ag/ITO multilayer, agglomeration of the metal interlayer was effectively relieved with APC interlayer due to existence of Pd and Cu elements in the thin region of the APC interlayer. The OSCs fabricated on the ITO/APC/ITO multilayer showed higher power conversion efficiency than that of OSCs prepared on the ITO/Ag/ITO multilayer below 10 nm due to the flatness of the APC layer. The improved performance of the OSCs with ITO/APC/ITO multilayer electrodes indicates that the APC alloy interlayer prevents the agglomeration of the Ag-based metal interlayer and can decrease the thickness of the metal interlayer in the oxide-metal-oxide multilayer of high-performance OSCs.

  13. Solubility and Dissolution Rate of Ni Base Alloy to Molten Ag-Cu-Pd Brazing Filler

    NASA Astrophysics Data System (ADS)

    Ikeshoji, Toshi-Taka; Watanabe, Yuki; Suzumura, Akio; Yamazaki, Takahisa

    During the brazing process of the rocket engine’s nozzle skirt assembly made from Fe-Ni based super alloy pipes with Pd based brazing filler, the erosion corrosion pits were sometimes engraved on those pipes’ surface. The corrosion is considered to be assisted by the dynamic flow of the molten brazing filler. In order to estimate the amount of erosion corrosion and to prevent it, the solubility and the dissolution rate of Ni to the molten Ag-Cu-Pd brazing filler are measured experimentally. The Ni crucible poured with the Ag-Cu-Pd brazing filler was heated up to 1320K and quenched after the various keeping time. The microstructure of the solidified brazing filler part’s cross sections was observed, and the amount of the dissolved Ni was estimated using the image processing technique. The solubility was about 5.53mass%and the initial dissolution rate was 6.28 × 10-3mass%/s. Using these data, more elaborate dynamic flow simulation will be able to conduct.

  14. Transparent ITO/Ag-Pd-Cu/ITO multilayer cathode use in inverted organic solar cells

    SciTech Connect

    Kim, Hyo-Joong; Kim, Han-Ki; Lee, Hyun Hwi; Kal, Jinha; Hahn, Jungseok

    2015-10-15

    The characteristics of transparent ITO/Ag-Pd-Cu (APC)/ITO multilayer cathodes were investigated for use in inverted organic solar cells (IOSCs). The insertion of an APC interlayer into the ITO film effectively led to crystallization of the top ITO layer, unlike that in the Ag interlayer, and resulted in a low sheet resistance of 6.55 Ohm/square and a high optical transmittance of 84.14% without post annealing. In addition, the alloying of the Pd and Cu elements into Ag prevented agglomeration and oxidization of the metal interlayer and led to more stable ITO/APC/ITO films under ambient conditions. The microstructure and interfacial structure of the transparent ITO/APC/ITO cathode in the IOSCs were examined in detail by synchrotron X-ray scattering and high resolution transmission electron microscopy. Furthermore, we suggested a possible mechanism to explain the lower PCE of the IOSCs with an ITO/APC/ITO cathode than that of a reference IOSC with a crystalline ITO cathode using the external quantum efficiency of the IOSCs.

  15. Transparent ITO/Ag-Pd-Cu/ITO multilayer cathode use in inverted organic solar cells

    NASA Astrophysics Data System (ADS)

    Kim, Hyo-Joong; Lee, Hyun Hwi; Kal, Jinha; Hahn, Jungseok; Kim, Han-Ki

    2015-10-01

    The characteristics of transparent ITO/Ag-Pd-Cu (APC)/ITO multilayer cathodes were investigated for use in inverted organic solar cells (IOSCs). The insertion of an APC interlayer into the ITO film effectively led to crystallization of the top ITO layer, unlike that in the Ag interlayer, and resulted in a low sheet resistance of 6.55 Ohm/square and a high optical transmittance of 84.14% without post annealing. In addition, the alloying of the Pd and Cu elements into Ag prevented agglomeration and oxidization of the metal interlayer and led to more stable ITO/APC/ITO films under ambient conditions. The microstructure and interfacial structure of the transparent ITO/APC/ITO cathode in the IOSCs were examined in detail by synchrotron X-ray scattering and high resolution transmission electron microscopy. Furthermore, we suggested a possible mechanism to explain the lower PCE of the IOSCs with an ITO/APC/ITO cathode than that of a reference IOSC with a crystalline ITO cathode using the external quantum efficiency of the IOSCs.

  16. Microstructure and anodic polarization behavior of experimental Ag-18Cu-15Pd-12Au alloy in aqueous sulfide solution.

    PubMed

    Endo, Kazuhiko; Ohno, Hiroki; Asakura, Shukuji

    2003-05-01

    The anodic corrosion behavior of an experimental Ag-15Pd-18Cu-12Au alloy in 0.1% Na(2)S solution in relation to its microstructure was investigated using potentiodynamic and potentiostatic polarization techniques with analyses of corrosion products by X-ray diffractometry, Auger electron spectroscopy, and X-ray photoelectron spectroscopy. The role of Pd in improvement of the corrosion resistance was also investigated. In the potential/current density curve, three distinct current peaks, at -520 mV (peak I), -425 mV (peak II) and -175 mV (peak III), were observed. The Ag-rich alpha(2) matrix with coarse Cu and Pd-rich lamellae was the most corrosion-susceptible region, and this region was preferentially corroded at peak I with the formation of granular deposits of Ag(2)S. A small amount of Ag-Cu mixed sulfide deposited on the Cu and Pd-rich coarse particles and dissolution of Ag as AgO(-) might have occurred in parallel with Ag(2)S formation at peak II. Enrichment of Pd on the alloy surface occurred at peak III due to preferential dissolution of Ag and Cu. A high level of corrosion resistance was attained with the formation of a thin Pd-rich sulfide film, which enhanced the passivity of the alloy in an alkaline sulfide solution. It was found that passivity is an important phenomenon not only for base metal alloys but also for noble metal alloys to maintain high levels of resistance to corrosion and tarnishing in sulfide environments. PMID:15348446

  17. Hydrazine reduction of metal ions to porous submicro-structures of Ag, Pd, Cu, Ni, and Bi

    SciTech Connect

    Wang Yue; Shi Yongfang; Chen Yubiao; Wu Liming

    2012-07-15

    Porous submicro-structures of Ag, Pd, Cu, Ni, and Bi with high surface area have been prepared by the reduction of hydrazine in glycerol-ethanol solution at room temperature or 120-180 Degree-Sign C. Phase purity, morphology, and specific surface area have been characterized. The reactions probably undergo three different mechanisms: simple reduction for Ag and Pd, coordination-then-reduction for Cu and Ni, and hydrolysis-then-reduction for Bi. The reductant hydrazine also plays an important role to the formation of the porous submicro-structure. The reaction temperature influences the size of the constituent particles and the overall architecture of the submicro-structure so as to influence the surface area value. The as-prepared porous metals have shown the second largest surface area ever reported, which are smaller than those made by the reduction of NaBH{sub 4}, but larger than those made by hard or soft template methods. - Graphical abstract: Porous submicro-structures of Ag, Pd, Cu, Ni, and Bi with high surface area have been prepared by the reduction of hydrazine in the glycerol-ethanol solution at room temperature or 120-180 Degree-Sign C. The reactions undergo different mechanisms: simple reduction for Ag and Pd, coordination-then-reduction for Cu and Ni, and hydrolysis-then-reduction for Bi. Highlights: Black-Right-Pointing-Pointer Syntheses of porous Ag, Pd, Cu, Ni, and Bi with high surface area. Black-Right-Pointing-Pointer Ag and Pd undergo simple reduction. Black-Right-Pointing-Pointer Cu and Ni undergo coordination-then-reduction. Black-Right-Pointing-Pointer Bi undergoes hydrolysis-then-reduction. Black-Right-Pointing-Pointer The as-prepared metals have shown the second largest surface area ever reported.

  18. Tarnish resistance evaluation of experimental Pd-free Ag-Au-Pt-Cu dental alloys.

    PubMed

    Takuma, Yasuko; Shiraishi, Takanobu; Fujita, Takeshi; Hisatsune, Kunihiro

    2010-05-01

    This study evaluated the tarnish resistance of eight experimental Pd-free Ag-Au-Pt-Cu dental alloys in a 0.1% Na(2)S aqueous solution at 37 degrees C. Color measurements of the plate samples were made using a computerized spectrophotometer before and after immersion in the test solution for up to 72 hours. Tarnish discoloration was evaluated using the color difference vector, DeltaE*, in the CIELAB color space. Microstructural observation of each sample through an optical microscope revealed the matrix phase as the major constituent and second-phase small grains in the matrix phase. Selective tarnish discoloration occurred in the matrix, and fractional area of the matrix to the whole surface area was influenced by the sum of Au and Ag concentrations. The DeltaE* value significantly decreased with increasing Au/(Au+Ag) atomic ratio. In conclusion, the Au/(Au+Ag) ratio in an alloy and the fractional area of the matrix were found to be primary and auxiliary factors affecting the tarnish resistance of the experimental alloys. PMID:20495286

  19. Phase Evolution in the Pd-Ag-CuO Air Braze Filler Metal Alloy System

    SciTech Connect

    Darsell, Jens T.; Weil, K. Scott

    2006-08-01

    Palladium was added as a ternary component to a series of copper oxide-silver alloys in an effort to increase the use temperature of these materials for potential ceramic air brazing applications. Phase equilibria in the ternary Pd-Ag-CuO system were investigated via differential scanning calorimetry (DSC) and a series of quenching experiments. Presented here are the latest findings on this system and a construction of the corresponding ternary phase diagram for low-to-moderate additions of palladium. The analysis included samples with higher palladium additions than were studied in the past, as well as an analysis of the composition-temperature trends in the Ag-CuO miscibility gap with palladium addition. It was found that the addition of palladium increases the solidus and liquidus and caused three phase zones to appear as expected by the phase rule. Furthermore, the palladium additions cause the miscibility gap boundary extending from the former binary eutectic to shift to lower silver-to-copper ratios.

  20. Crystalline monolayer surface of liquid Au-Cu-Si-Ag-Pd: Metallic glass former

    SciTech Connect

    Mechler, S; Yahel, E; Pershan, P S; Meron, M; Lin, B

    2012-02-06

    It is demonstrated by means of x-ray synchrotron reflectivity and diffraction that the surface of the liquid phase of the bulk metallic glass forming alloy Au49Cu26.9Si16.3Ag5.5Pd2.3 consists of a two-dimensional crystalline monolayer phase for temperatures of up to about 50 K above the eutectic temperature. The present alloy as well as glass forming Au82Si18 and Au-Si-Ge alloys containing small amounts of Ge are the only metallic liquids to exhibit surface freezing well above the melting temperature. This suggests that the phenomena of surface freezing in metallic liquids and glass forming ability are related and probably governed by similar physical properties.

  1. Structural and magnetic phase transitions in CeCu6-xTx (T = Ag,Pd)

    DOE PAGESBeta

    Poudel, Lekhanath N.; De la cruz, Clarina; Payzant, E. Andrew; Koehler, Michael R.; May, Andrew F.; Garlea, Vasile O.; Taylor, Alice E.; Parker, David S.; Cao, Huibo B.; McGuire, Michael A.; et al

    2015-12-15

    The structural and the magnetic properties of CeCu6-xAgx (0 ≤ x ≤ 0.85) and CeCu6-xPdx (0 ≤ x ≤ 0.4) have been studied using neutron diffraction, resonant ultrasound spectroscopy (RUS), x-ray diffraction measurements, and first principles calculations. The structural and magnetic phase diagrams of CeCu6-xAgx and CeCu6-xPdx as a function of Ag/Pd composition are reported. The end member, CeCu6, undergoes a structural phase transition from an orthorhombic (Pnma) to a monoclinic (P21/c) phase at 240 K. In CeCu6-xAgx, the structural phase transition temperature (Ts) decreases linearly with Ag concentration and extrapolates to zero at xS ≈ 0.1. The structural transitionmore » in CeCu6-xPdx remains unperturbed with Pd substitution within the range of our study. The lattice constant b slightly decreases with Ag/Pd doping, whereas a and c increase with an overall increase in the unit cell volume. Both systems, CeCu6-xAgx and CeCu6-xPdx, exhibit a magnetic quantum critical point (QCP), at x ≈ 0.2 and x ≈ 0.05, respectively. Near the QCP, long range antiferromagnetic ordering takes place at an incommensurate wave vector (δ1 0 δ2), where δ1 ~ 0.62, δ2 ~ 0.25, x = 0.125 for CeCu6-xPdx and δ1 ~ 0.64, δ2 ~ 0.3, x = 0.3 for CeCu6-xAgx. As a result, the magnetic structure consists of an amplitude modulation of the Ce moments which are aligned along the c axis of the orthorhombic unit cell.« less

  2. Novel PdAgCu ternary alloy as promising materials for hydrogen separation membranes: Synthesis and characterization

    NASA Astrophysics Data System (ADS)

    Tarditi, Ana M.; Cornaglia, Laura M.

    2011-01-01

    The use of the sequential electroless plating method allowed us to obtain the PdAgCu ternary alloy on top of dense stainless steel (SS) 316 L disks. The XRD analysis indicated that initially the nucleation of the two phases of the alloy (FCC and BCC) takes place, but the FCC/BCC ratio increases with the annealing time at 500 °C in H 2 stream. After 162 h, the film contained only the FCC phase, which presents promising properties to be applied in the synthesis of hydrogen selective membranes. SEM cross-section results showed that a dense, continuous, defect-free film was deposited on top of the SS support, and the EDS data indicated that no significant gradient was present on the thickness of the film. XPS and LEIS allowed us to determine that Cu and Ag surface segregation takes place after annealing up to 500 °C/5 days. In the top-most surface layer, Ag enrichment takes place as determined by ARXPS experiments which can be the result of the lower surface tension of Ag compared to that of Cu and Pd. Increasing the annealing temperature results in an increase of the Ag surface segregation while the Cu concentration in the top-most surface layer decreases.

  3. Continuous syntheses of Pd@Pt and Cu@Ag core-shell nanoparticles using microwave-assisted core particle formation coupled with galvanic metal displacement.

    PubMed

    Miyakawa, Masato; Hiyoshi, Norihito; Nishioka, Masateru; Koda, Hidekazu; Sato, Koichi; Miyazawa, Akira; Suzuki, Toshishige M

    2014-08-01

    Continuous synthesis of Pd@Pt and Cu@Ag core-shell nanoparticles was performed using flow processes including microwave-assisted Pd (or Cu) core-nanoparticle formation followed by galvanic displacement with a Pt (or Ag) shell. The core-shell structure and the nanoparticle size were confirmed using high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) observation and EDS elemental mapping. The Pd@Pt nanoparticles with a particle size of 6.5 ± 0.6 nm and a Pt shell thickness of ca. 0.25 nm were synthesized with appreciably high Pd concentration (Pd 100 mM). This shell thickness corresponds to one atomic layer thickness of Pt encapsulating the Pd core metal. The particle size of core Pd was controlled by tuning the initial concentrations of Na2[PdCl4] and PVP. Core-shell Cu@Ag nanoparticles with a particle size of 90 ± 35 nm and an Ag shell thickness of ca. 3.5 nm were obtained using similar sequential reactions. Oxidation of the Cu core was suppressed by the coating of Cu nanoparticles with the Ag shell. PMID:24948122

  4. Copper-based alloys, crystallographic and crystallochemical parameters of alloys in binary systems Cu-Me (Me=Co, Rh, Ir, Cu, Ag, Au, Ni, Pd, Pt)

    NASA Astrophysics Data System (ADS)

    Porobova, Svetlana; Markova, Tat'jana; Klopotov, Vladimir; Klopotov, Anatoliy; Loskutov, Oleg; Vlasov, Viktor

    2016-01-01

    The article presents the results of the analysis of phase equilibrium of ordered phases in binary systems based on copper Cu- Me (where Me - Co, Rh, Ir, Ag, Au, Ni, Pd, Pt) to find correlations of crystallochemical and crystallographic factors. It is established that the packing index in disordered solid solutions in binary systems based on copper is close to the value of 0.74 against the background of an insignificant deviation of atomic volumes from the Zen's law.

  5. Structural and magnetic phase transitions in CeCu6-xTx (T = Ag,Pd)

    SciTech Connect

    Poudel, Lekhanath N.; De la cruz, Clarina; Payzant, E. Andrew; Koehler, Michael R.; May, Andrew F.; Garlea, Vasile O.; Taylor, Alice E.; Parker, David S.; Cao, Huibo B.; McGuire, Michael A.; Tian, Wei; Matsuda, Masaaki; Jeen, Hyoung Jeen; Lee, Ho Nyung; Hong, Tao; Calder, Stuart A.; Lumsden, Mark D.; Zhou, Haidong; Keppens, Veerle; Mandrus, D.; Christianson, Andrew D.

    2015-12-15

    The structural and the magnetic properties of CeCu6-xAgx (0 ≤ x ≤ 0.85) and CeCu6-xPdx (0 ≤ x ≤ 0.4) have been studied using neutron diffraction, resonant ultrasound spectroscopy (RUS), x-ray diffraction measurements, and first principles calculations. The structural and magnetic phase diagrams of CeCu6-xAgx and CeCu6-xPdx as a function of Ag/Pd composition are reported. The end member, CeCu6, undergoes a structural phase transition from an orthorhombic (Pnma) to a monoclinic (P21/c) phase at 240 K. In CeCu6-xAgx, the structural phase transition temperature (Ts) decreases linearly with Ag concentration and extrapolates to zero at xS ≈ 0.1. The structural transition in CeCu6-xPdx remains unperturbed with Pd substitution within the range of our study. The lattice constant b slightly decreases with Ag/Pd doping, whereas a and c increase with an overall increase in the unit cell volume. Both systems, CeCu6-xAgx and CeCu6-xPdx, exhibit a magnetic quantum critical point (QCP), at x ≈ 0.2 and x ≈ 0.05, respectively. Near the QCP, long range antiferromagnetic ordering takes place at an incommensurate wave vector (δ1 0 δ2), where δ1 ~ 0.62, δ2 ~ 0.25, x = 0.125 for CeCu6-xPdx and δ1 ~ 0.64, δ2 ~ 0.3, x = 0.3 for CeCu6-xAgx. As a result, the magnetic structure consists of an amplitude modulation of the Ce moments which are aligned along the c axis of the orthorhombic unit cell.

  6. Clathrates with Me = Mg, Pd, Ni, Au, Ag, Cu, Zn, Al, Sn

    NASA Astrophysics Data System (ADS)

    Wunderlich, Wilfried; Amano, Mao; Matsumura, Yoshihito

    2014-06-01

    Clathrate materials of AlSi, CuSi or NiSi type consisting of abundant elements have a realistic chance of becoming useful thermoelectrics in the near future, because the rattling effect due to their crystal cage structure provides a large figure of merit ZT even in experiments measured under large temperature gradients. In the search for better thermoelectrics, new element combinations in the clathrate type I structure with cubic space group Pm3n were calculated using VASP ab initio software. Predictions of the Seebeck coefficient were made by checking the electronic band structure and density of states for a large variety of input data. For x values around 4 to 6 in the structural formula Ba8Me x Si46- x the substituents Cu, Au, and Ag are best for good thermoelectric behavior, which is discussed in this paper as a result of the low electron-phonon interaction parameter.

  7. DFT study of Hg adsorption on M-substituted Pd(1 1 1) and PdM/γ-Al2O3(1 1 0) (M = Au, Ag, Cu) surfaces

    NASA Astrophysics Data System (ADS)

    Wang, Jiancheng; Yu, Huafeng; Geng, Lu; Liu, Jianwen; Han, Lina; Chang, Liping; Feng, Gang; Ling, Lixia

    2015-11-01

    The adsorption of Hgn (n = 1-3) on the Au-, Ag-, Cu-substituted Pd(1 1 1) surfaces as well as the PdM/γ-Al2O3(1 1 0) (M = Au, Ag, Cu) surfaces has been investigated using spin-polarized density functional theory calculations. It is found that M-substituted Pd(1 1 1) surfaces show as good Hg adsorption capacity as the perfect Pd(1 1 1) at low Hg coverage, while the Hg adsorption capacity is only slightly weakened at high Hg coverage. On the basis of stepwise adsorption energies analysis, it is concluded that M-substituted Pd(1 1 1) surfaces can contribute to the binding of Hg atom on the surfaces at high Hg coverage. The electronic properties of the second metal atoms are the main factor contributes to the Hg adsorption capacity. Gas phase Pd2 shows better Hg adsorption capacity than Pd2/γ-Al2O3, while PdM/γ-Al2O3 can adsorb Hg more efficiently than bare PdM clusters. It suggests that the γ-Al2O3 support can enhance the activity of PdM for Hg adsorption and reduces the activity of Pd2. It is also found that Pd is the main active composition responsible for the interaction of mercury with the surface for PdM/γ-Al2O3 sorbent. Taking Hg adsorption capacity and economic costs into account, Cu addition is a comparatively good candidate for Hg capture.

  8. [Study on the age-hardenable silver alloy (3 rd report). III. On the ageing process of dental Ag-Pd-Cu-Au alloy (author's transl)].

    PubMed

    Ota, M; Hisatsune, K; Yamane, M

    1975-05-01

    The precipitation hardening process of a dental silver base alloy, Ag-28 Pd-10 Cu-12 wt % Au, was studied by means of X-ray diffraction, hardness measurement and metallographic observations. After solution treatment at 900 degrees C for 30 min, specimens were subjected to anisothermal annealing at the rate of 1 degrees C/min. PdCu ordered phase and alpha2 solid solution (Ag rich phase) precipitated hetelogeneously at the grain boundaries and then grew up into each grain. Drastic increase in hardness was recognized with the spread of nodular region. Electron microscopic observation of these precipitates showed very fine lamellar structure. It is concluded that the age hardening of this alloy could be attributed to this grain boundary precipitation and the softening at the overaged stage to the second grain boundary reaction which produced very coarse lamellar structure. PMID:1058263

  9. The germanides ScTGe (T = Co, Ni, Cu, Ru, Rh, Pd, Ag, Ir, Pt, Au) - Structure and 45Sc solid state NMR spectroscopy

    NASA Astrophysics Data System (ADS)

    Heying, Birgit; Haverkamp, Sandra; Rodewald, Ute Ch; Eckert, Hellmut; Peter, Sebastian C.; Pöttgen, Rainer

    2015-01-01

    The germanides ScTGe (T = Co, Ni, Cu, Ru, Rh, Pd, Ag, Ir, Pt, Au) were obtained in X-ray pure form by arc-melting of the elements. The structures of the members with T = Co, Ni, Cu, Rh, Pd, Ag, Ir, and Pt were refined on the basis of single crystal X-ray diffractometer data. The germanides with T = Cu, Ru, Pd, Ag crystallize with the hexagonal ZrNiAl type structure, space group P 6 bar 2m and those with T = Co, Ni, Rh, Ir, Pt adopt the orthorhombic TiNiSi type. ScAuGe is isotypic with NdPtSb. All germanides exhibit single scandium sites. A simple systematization of the structure type according to the valence electron concentration is not possible. The 45Sc solid state NMR parameters (Knight shifts and nuclear electric quadrupole coupling constants) of those members crystallizing in the TiNiSi structure show systematic trends as a function of valence electron concentration number. Furthermore, within each T-group the Knight shift decreases with increasing atomic number; this correlation also includes previously published results on the isotypic silicide family. The 45Sc quadrupolar interaction tensor components are generally well-reproduced by quantum mechanical electric field gradient calculations using the WIEN2k code.

  10. Temperature, pressure, and size dependence of Pd-H interaction in size selected Pd-Ag and Pd-Cu alloy nanoparticles: In-situ X-ray diffraction studies

    SciTech Connect

    Sengar, Saurabh K.; Mehta, B. R.; Kulriya, P. K.

    2014-03-21

    In this study, in-situ X-ray diffraction has been carried out to investigate the effect of temperature and pressure on hydrogen induced lattice parameter variation in size selected Pd-Ag and Pd-Cu alloy nanoparticles. The nanoparticles of three different mobility equivalent diameters (20, 40, and 60 nm) having a narrow size distribution were prepared by gas phase synthesis method. In the present range of temperature (350 K to 250 K) and pressure (10{sup −4} to 100 millibars), no α (H/Pd ≤ 0.03) ↔ β (H/Pd ≥ 0.54) phase transition is observed. At temperature higher than 300 °C or pressure lower than 25 millibars, there is a large difference in the rate at which lattice constant varies as a function of pressure and temperature. Further, the lattice variation with temperature and pressure is also observed to depend upon the nanoparticle size. At lower temperature or higher pressure, size of the nanoparticle seems to be relatively less important. These results are explained on the basis of the relative dominance of physical absorption and diffusion of H in Pd alloy nanoparticles at different temperature and pressure. In the present study, absence of α ↔ β phase transition points towards the advantage of using Pd-alloy nanoparticles in applications requiring long term and repeated hydrogen cycling.

  11. Charge effect in S enhanced CO adsorption: A theoretical study of CO on Au, Ag, Cu, and Pd (111) surfaces coadsorbed with S, O, Cl, and Na

    NASA Astrophysics Data System (ADS)

    Gan, Li-Yong; Zhao, Yu-Jun

    2010-09-01

    The extraordinary sulfur enhanced CO adsorption on Au surface creates curiosity to many scientists in the field, and is expected to have potential applications in catalyst design. In this work, we have investigated the interactions of the coadsorption of CO and various adatoms X (X=Na, S, O, and Cl) on Au and Pd(111) surfaces and made further comparison with CO adsorption on charged Au and Pd surfaces by a first-principles study. We find out that the enhancement of CO adsorption by S on Au originates from S-induced positive polarization of Au surface. The d band of metal atoms in the positively polarized Au surface shifts up toward the Fermi level (EF) without remarkable changes of its shape and occupation. In contrast, in the negatively polarized Au(111) surface, achieved by electropositive adatom such as Na adsorption or artificially adding additional electrons to the substrate, d bands shift down relative to EF, and thus CO adsorption is weakened. Further study of CO coadsorption with X on two other noble metal (Ag and Cu) surfaces manifests that Ag shows the same behavior as Au does, while the situation of Cu is just between that on Au and Pd. It suggests that the extraordinary S-induced enhancement of CO adsorption on Au/Ag, different from other transition metals (TMs), ultimately results from the inertness of d bands buried below EF. The S-induced charge can introduce a significant d band shift on Au/Ag with respect to EF due to their narrow density of states at EF and thus strengthens CO adsorption subsequently.

  12. DEVELOPMENT OF A HIGH-TEMPERATURE CERAMIC BRAZE: ANALYSIS OF PHASE EQUILIBRIA IN THE Pd-Ag-CuOx SYSTEM

    SciTech Connect

    Weil, K. Scott; Darsell, Jens T.

    2006-01-18

    This paper describes the effects of small palladium additions on the phase equilibria in the Ag-CuOx system. Below a concentration of 5 mol%, palladium was found to increase the temperature of the eutectic reaction present in the pseudobinary system, but have little effect on a higher temperature monotectic reaction. However once enough palladium was added to increase the pseudoternary solidus temperature to that of the lower boundary for this three-phase field (~970°C), the lower boundary begins to increase in temperature as well. The addition of palladium also causes the original eutectic point to move to lower silver concentrations, which also causes a convergence of the two new three-phase fields, CuOx + L1 + L2 and CuOx + α + L1. This suggests that with higher palladium concentrations, a peritectic reaction, α + L1 + L2 → CuOx, may eventually be observed in the system.

  13. Effect of Pd Thickness on the Interfacial Reaction and Shear Strength in Solder Joints Between Sn-3.0Ag-0.5Cu Solder and Electroless Nickel/Electroless Palladium/Immersion Gold (ENEPIG) Surface Finish

    NASA Astrophysics Data System (ADS)

    Kim, Young Min; Park, Jin-Young; Kim, Young-Ho

    2012-04-01

    Intermetallic compound formation at the interface between Sn-3.0Ag-0.5Cu (SAC) solders and electroless nickel/electroless palladium/immersion gold (ENEPIG) surface finish and the mechanical strength of the solder joints were investigated at various Pd thicknesses (0 μm to 0.5 μm). The solder joints were fabricated on the ENEPIG surface finish with SAC solder via reflow soldering under various conditions. The (Cu,Ni)6Sn5 phase formed at the SAC/ENEPIG interface after reflow in all samples. When samples were reflowed at 260°C for 5 s, only (Cu,Ni)6Sn5 was observed at the solder interfaces in samples with Pd thicknesses of 0.05 μm or less. However, the (Pd,Ni)Sn4 phase formed on (Cu,Ni)6Sn5 when the Pd thickness increased to 0.1 μm or greater. A thick and continuous (Pd,Ni)Sn4 layer formed over the (Cu,Ni)6Sn5 layer, especially when the Pd thickness was 0.3 μm or greater. High-speed ball shear test results showed that the interfacial strengths of the SAC/ENEPIG solder joints decreased under high strain rate due to weak interfacial fracture between (Pd,Ni)Sn4 and (Cu,Ni)6Sn5 interfaces when the Pd thickness was greater than 0.3 μm. In the samples reflowed at 260°C for 20 s, only (Cu,Ni)6Sn5 formed at the solder interfaces and the (Pd,Ni)Sn4 phase was not observed in the solder interfaces, regardless of Pd thickness. The shear strength of the SAC/ENIG solder joints was the lowest of the joints, and the mechanical strength of the SAC/ENEPIG solder joints was enhanced as the Pd thickness increased to 0.1 μm and maintained a nearly constant value when the Pd thickness was greater than 0.1 μm. No adverse effect on the shear strength values was observed due to the interfacial fracture between (Pd,Ni)Sn4 and (Cu,Ni)6Sn5 since the (Pd,Ni)Sn4 phase was already separated from the (Cu,Ni)6Sn5 interface. These results indicate that the interfacial microstructures and mechanical strength of solder joints strongly depend on the Pd thickness and reflow conditions.

  14. Why are the 3d-5d compounds CuAu and NiPt stable, whereas the 3d-4d compounds CuAg and NiPd are not

    NASA Astrophysics Data System (ADS)

    Wang, L. G.; Zunger, Alex

    2003-03-01

    We show that the existence of stable, ordered 3d-5d intermetallics CuAu and NiPt, as opposed to the unstable 3d-4d isovalent analogs CuAg and NiPd, results from relativity. First, in shrinking the equilibrium volume of the 5d element, relativity reduces the atomic size mismatch with respect to the 3d element, thus lowering the elastic packing strain. Second, in lowering the energy of the bonding 6s,p bands and raising the energy of the 5d band, relativity enhances (diminishes) the occupation of the bonding (antibonding) bands. The raising of the energy of the 5d band also brings it closer to the energy of the 3d band, improving the 3d-5d bonding.

  15. Bimetallic Pt-Ag and Pd-Ag nanoparticles

    SciTech Connect

    Lahiri, Debdutta; Bunker, Bruce; Mishra, Bhoopesh; Zhang, Zhenyuan; Meisel, Dan; Doudna, C.M.; Bertino, M. F.; Blum, Frank D.; Tokuhiro, A.T.; Chattopadhyay, Soma; Shibata, Tomohiro; Terry, Jeff

    2005-05-01

    We report studies of bimetallic nanoparticles with 15%-16% atomic crystal parameters size mismatch. The degree of alloying was probed in a 2-nm Pt core (smallest attainable core size) of Pt-Ag nanoparticles (completely immiscible in bulk) and 20-nm-diameter Pd-Ag nanowires (completely miscible in bulk). Particles were synthesized radiolytically, and depending on the initial parameters, they assume spherical or cylindrical (nanowire) morphologies. In all cases, the metals are seen to follow their bulk alloying characteristics. Pt and Ag segregate in both spherical and wire forms, which indicates that strain due to crystallographic mismatch overcomes the excess surface free energy in the small particles. The Pd-Ag nanowires alloy similar to previously reported spherical Pd-Ag particles of similar diameter and composition.

  16. A GREENER SYNTHESIS OF CORE (FE, CU)-SHELL (AU, PT, PD AND AG) NANOCRYSTALS USING AQUEOUS VITAMIN C

    EPA Science Inventory

    A greener method to fabricate the novel core (Fe and Cu)-shell (noble metals) metal nanocrystals using aqueous ascorbic acid (vitamin C) is described. Transition metal salts such as Cu and Fe were reduced using ascorbic acid, a benign naturally available antioxidant, and then add...

  17. Atomistic Modeling of Surface and Bulk Properties of Cu, Pd and the Cu-Pd System

    NASA Technical Reports Server (NTRS)

    Bozzolo, Guillermo; Garces, Jorge E.; Noebe, Ronald D.; Abel, Phillip; Mosca, Hugo O.; Gray, Hugh R. (Technical Monitor)

    2002-01-01

    The BFS (Bozzolo-Ferrante-Smith) method for alloys is applied to the study of the Cu-Pd system. A variety of issues are analyzed and discussed, including the properties of pure Cu or Pd crystals (surface energies, surface relaxations), Pd/Cu and Cu/Pd surface alloys, segregation of Pd (or Cu) in Cu (or Pd), concentration dependence of the lattice parameter of the high temperature fcc CuPd solid solution, the formation and properties of low temperature ordered phases, and order-disorder transition temperatures. Emphasis is made on the ability of the method to describe these properties on the basis of a minimum set of BFS universal parameters that uniquely characterize the Cu-Pd system.

  18. Depletion and phase transformation of a submicron Ni(P) film in the early stage of soldering reaction between Sn-Ag-Cu and Au/Pd(P)/Ni(P)/Cu

    NASA Astrophysics Data System (ADS)

    Ho, Cheng-En; Hsieh, Wan-Zhen; Yang, Tsung-Hsun

    2015-01-01

    The early stage of soldering reaction between Sn-3Ag-0.5Cu solder and ultrathin-Ni(P)-type Au/Pd(P)/Ni(P)/Cu pad was investigated by field-emission scanning electron microscopy (FE-SEM) in conjunction with field-emission electron probe microanalysis (FEEPMA) and high-resolution transmission electron microscopy (HRTEM). FE-SEM, FE-EPMA, and HRTEM investigations showed that Ni2SnP and Ni3P were the predominant P-containing intermetallic compounds (IMCs) in the soldering reaction and that their growth behaviors strongly depended on the depletion of Ni(P). The growth of Ni3P dominated over that of Ni2SnP in the early stage of soldering, whereas the Ni3P gradually transformed into Ni2SnP after Ni(P) depletion. This Ni(P)-depletion-induced Ni2SnP growth behavior is different from the reaction mechanisms reported in the literature. Detailed analyses of the microstructural evolution of the IMC during Ni(P) depletion were conducted, and a two-stage reaction mechanism was proposed to rationalize the unique IMC growth behavior.

  19. Why are the 3d-5d compounds CuAu and NiPt stable, whereas the 3d-4d compounds CuAg and NiPd are not*

    NASA Astrophysics Data System (ADS)

    Wang, Ligen; Zunger, Alex

    2003-03-01

    Experiments indicate that the 3d-5d compounds CuAu and NiPt have negative formation enthalpies (ΔH < 0), and thus form stable ordered compounds, whereas the analogous isovalent 3d-4d compounds CuAg and NiPd, made of elements from the same columns in the periodic table, have positive formation enthalpies (ΔH > 0) and thus phase-separate. We explain this long standing puzzle according to the relativistic effect and show, via first-principles calculations, that in binary compounds of late 3d-5d intermetallics, the inter-sublattice 3d-5d coupling is dominant. First, in shrinking the equilibrium volume of the 5d element, relativity reduces the atomic size-mismatch with respect to the 3d element, thus lowering the elastic packing strain. Second, in lowering the energy of the bonding 6s,p bands and raising the energy of the 5d band, relativity enhances (diminishes) the occupation of the bonding (antibonding) bands. The raising of the energy of the 5d band also brings it closer to the energy of the 3d band, improving the 3d-5d bonding. * Supported by DOE-SC-BES-DMS

  20. Selective hydrodechlorination of 1,2-dichloroethane to ethylene over Pd-Ag/Al2O3 catalysts prepared by surface reduction

    NASA Astrophysics Data System (ADS)

    Han, Yuxiang; Gu, Guangfeng; Sun, Jingya; Wang, Wenjuan; Wan, Haiqin; Xu, Zhaoyi; Zheng, Shourong

    2015-11-01

    Alumina supported Pd-Ag and (Cu) bimetallic catalysts (denoted as sr-Pd-Ag/Al2O3 or sr-Pd-Cu/Al2O3) with varied Pd/Ag (or Cu) ratios were prepared using the surface reduction method, and the gas-phase catalytic hydrodechlorination of 1,2-dichloroethane over the catalysts were investigated. For comparison, Pd-Ag bimetallic catalysts were prepared by the conventional co-impregnation method (denoted as im-Pd-Ag/Al2O3). The catalysts were characterized by N2 adsorption, X-ray diffraction, transmission electron microscopy, X-ray photoelectron spectroscopy, and CO chemisorption. Characterization results indicated that surface reduction led to selective deposition of metallic Ag on the surface of Pd particles, while Pd and Ag just disorderly mixed in the catalyst prepared by impregnation method. Therefore, sr-Pd-Ag/Al2O3 exhibited a higher ethylene selectivity than im-Pd-Ag/Al2O3 for hydrodechlorination of 1,2-dichloroethane at a similar Ag loading amount. Moreover, among sr-Pd-Ag/Al2O3, sr-Pd-Cu/Al2O3 and im-Pd-Ag/Al2O3 catalysts, the ethylene selectivity decreased over these catalysts following the order: sr-Pd-Ag/Al2O3 > sr-Pd-Cu/Al2O3 > im-Pd-Ag/Al2O3. The present results indicate that surface reduction can be used as a potential method to synthesize catalyst with enhanced ethylene selectivity in hydrodechlorination of 1,2-dichloroethane.

  1. Reactivity of Transition Metals (Pd, Pt, Cu, Ag, Au) toward Molecular Hydrogen Dissociation: Extended Surfaces versus Particles Supported on TiC(001) or Small Is Not Always Better and Large Is Not Always Bad

    SciTech Connect

    Rodriguez, J.A.; Gomez, T.; Florez, E.; Illas, F.

    2011-05-11

    The reactivity of Pd{sub 4}, Pt{sub 4}, Cu{sub 4}, Ag{sub 4}, and Au{sub 4} clusters supported on TiC(001) toward molecular hydrogen dissociation has been studied by means of density functional based theory and periodic models and compared to that of the (111) and (001) surfaces. Pd{sub 4} and Pt{sub 4} interact rather strongly with the TiC(001) substrate, but the interaction of molecular hydrogen with the Pd{sub 4}/TiC and Pt{sub 4}/TiC systems is also very strong. As a consequence of the substantial admetal {leftrightarrow} carbide interactions, the adsorbed H{sub 2} molecule becomes more difficult to dissociate than on the corresponding extended (111) and (001) surfaces. Here, having a small supported particle does not lead to an enhanced chemical activity. On the contrary, for the Cu{sub 4}/TiC, Ag{sub 4}/TiC, and Au{sub 4}/TiC systems the combination of the small size of the particle and the polarization induced by the underlying carbide facilitates the dissociation of the hydrogen molecule with respect to the case of the extended surfaces. Here, the reduced size effectively enhances the activity of the supported particle. Thus, our results for the M(111), M(100), and M{sub 4}/TiC(001) systems show the complex interplay that can take place among the nature of the admetal, particle size effects, and support interactions.

  2. Reactivity of Transition Metals (Pd Pt Cu Ag Au) toward Molecular Hydrogen Dissociation: Extended Surfaces versus Particles Supported on TiC(001) or Small Is Not Always Better and Large Is Not Always Bad

    SciTech Connect

    Rodriguez J. A.; Gomez T.; Florez E.; Illas F.

    2011-06-16

    The reactivity of Pd{sub 4}, Pt{sub 4}, Cu{sub 4}, Ag{sub 4}, and Au{sub 4} clusters supported on TiC(001) toward molecular hydrogen dissociation has been studied by means of density functional based theory and periodic models and compared to that of the (111) and (001) surfaces. Pd{sub 4} and Pt{sub 4} interact rather strongly with the TiC(001) substrate, but the interaction of molecular hydrogen with the Pd{sub 4}/TiC and Pt{sub 4}/TiC systems is also very strong. As a consequence of the substantial admetal {leftrightarrow} carbide interactions, the adsorbed H{sub 2} molecule becomes more difficult to dissociate than on the corresponding extended (111) and (001) surfaces. Here, having a small supported particle does not lead to an enhanced chemical activity. On the contrary, for the Cu{sub 4}/TiC, Ag{sub 4}/TiC, and Au{sub 4}/TiC systems the combination of the small size of the particle and the polarization induced by the underlying carbide facilitates the dissociation of the hydrogen molecule with respect to the case of the extended surfaces. Here, the reduced size effectively enhances the activity of the supported particle. Thus, our results for the M(111), M(100), and M{sub 4}/TiC(001) systems show the complex interplay that can take place among the nature of the admetal, particle size effects, and support interactions.

  3. Electrical properties of thin-film structures formed by pulsed laser deposition of Au, Ag, Cu, Pd, Pt, W, Zr metals on n-6H-SiC crystal

    SciTech Connect

    Romanov, R. I.; Zuev, V. V.; Fominskii, V. Yu. Demin, M. V.; Grigoriev, V. V.

    2010-09-15

    Diode structures with ideality factors of 1.28-2.14 and potential barriers from 0.58 to 0.62 eV on the semiconductor side were formed by pulsed laser deposition of Au, Ag, Cu, Pd, Pt, W, and Zr metal films on n-6H-SiC crystal without epitaxial layer preparation. A high density of surface acceptor and donor states was formed at the metal-semiconductor interface during deposition of the laser-induced atomic flux, which violated the correlation between the potential barrier height and metal work function. The barrier heights determined from characteristic currents and capacitance measurements were in quite good agreement. For the used low-resistance semiconductor and contact elements, the sizes of majority carrier (electron) depletion regions were determined as 26-60 nm.

  4. Adsorbate-Induced Segregation in a PdAg Membrane Model System: Pd3Ag(1 1 1)

    SciTech Connect

    Svenum, I. H.; Herron, Jeffrey A.; Mavrikakis, Manos; Venvik, H. J.

    2012-10-15

    Thin PdAg alloy membranes with 20–25% Ag are being developed for hydrogen separation technology. Despite many investigations on such membranes as well as representative experimental and theoretical model systems, unresolved issues remain concerning the effect of the alloy surface structure and composition on adsorption and vice versa. Therefore, the interaction between hydrogen, carbon monoxide or oxygen with the surface of a PdAg model alloy was studied using periodic self-consistent density functional theory (DFT-GGA) calculations. In particular, the adsorption structure, coverage dependence and possible adsorption-induced segregation phenomena were addressed using Pd3Ag(1 1 1) model surfaces with varying degrees of surface segregation. In agreement with previous experimental and theoretical investigations, we predict Ag surface termination to be energetically favorable in vacuum. The segregation of Ag is then reversed upon adsorption of H, CO or O. For these adsorbates, the binding is strongest on Pd three-fold hollow sites, and hence complete Pd termination is favored at high coverage of H or CO, while 25% Ag may remain under oxygen because of the lower O-saturation coverage. CO adsorption provides a somewhat stronger driving force for Pd segregation when compared to H, and this may have implications with respect to permeation properties of PdAg alloy surfaces. Our predictions for high coverage are particularly relevant in underlining the importance of segregation phenomena to the hydrogen transport properties of thin PdAg alloy membranes.

  5. Screening on binary Zr-1X (X = Ti, Nb, Mo, Cu, Au, Pd, Ag, Ru, Hf and Bi) alloys with good in vitro cytocompatibility and magnetic resonance imaging compatibility.

    PubMed

    Zhou, F Y; Qiu, K J; Li, H F; Huang, T; Wang, B L; Li, L; Zheng, Y F

    2013-12-01

    In this study, the microstructures, mechanical properties, corrosion behaviors, in vitro cytocompatibility and magnetic susceptibility of Zr-1X alloys with various alloying elements, including Ti, Nb, Mo, Cu, Au, Pd, Ag, Ru, Hf and Bi, were systematically investigated to explore their potential use in biomedical applications. The experimental results indicated that annealed Zr-1X alloys consisted entirely or primarily of α phase. The alloying elements significantly increased the strength and hardness of pure Zr and had a relatively slight influence on elastic modulus. Ru was the most effective enhancing element and Zr-1Ru alloy had the largest elongation. The results of electrochemical corrosion indicated that adding various elements to Zr improved its corrosion resistance, as indicated by the reduced corrosion current density. The extracts of the studied Zr-1X alloys produced no significant deleterious effects on osteoblast-like cells (MG 63), indicating good in vitro cytocompatibility. All except for Zr-1Ag alloy showed decreased magnetic susceptibility compared to pure Zr, and Zr-1Ru alloy had the lowest magnetic susceptibility value, being comparable to that of α' phase Zr-Mo alloy and Zr-Nb alloy and far lower than that of Co-Cr alloy and Ti-6Al-4V alloy. Among the experimental Zr-1X alloys, Zr-1Ru alloy possessing high strength coupled with good ductility, good in vitro cytocompatibility and low magnetic susceptibility may be a good candidate alloy for medical devices within a magnetic resonance imaging environment. PMID:23928334

  6. Alumina supported model Pd Ag catalysts: A combined STM, XPS, TPD and IRAS study

    NASA Astrophysics Data System (ADS)

    Khan, N. A.; Uhl, A.; Shaikhutdinov, S.; Freund, H.-J.

    2006-05-01

    The bimetallic Pd-Ag model catalysts were prepared by physical vapor deposition on thin alumina films. The morphology and structure of the Pd-Ag particles were studied by STM, XPS, and by TPD and IRAS of CO. The results showed the formation of true alloy particles with Ag segregated at the surface. The addition of Ag first suppresses the most strongly bonded CO on threefold hollow sites of Pd. With further increasing Ag coverage, only isolated Pd atoms surrounded by Ag atoms are likely present on the surface. The results on CO adsorption suggest that the model Pd-Ag system mimics the structure of the real Pd-Ag catalysts.

  7. First-principles study of ferromagnetism in Pd-doped and Pd- Cu-codoped BN

    NASA Astrophysics Data System (ADS)

    Wang, Q.; Wang, S.; Dai, J. F.; Li, W. X.

    2016-07-01

    In this paper, we aimed at probing the ferromagnetism properties of Pd and Pd-Cu- codoped supercell BN based on the first-principles methods. The formation energy, lattice constants, energy band structures, spin density of state, energy difference between ferromagnetism (FM) and autiferromagnetism (AFM) orderings were calculated. Formation energy calculations showed that Pd atom tended to replace B atom in the supercell. Pd-doped BN exhibited a half-metallic ferromagnetic. And the ferromagnetism arised form the strong hybridization between the Pd4d and N2p state. Pd-Cu-codoped BN also displayed a half-metallic ferromagnetic. The incorporation of Pd and Pd-Cu induced some impurity energy differences between FM and AFM orderings. It also showed that FM state was the ground state, and room temperature ferromagnetism may be expected. These results pointed out the possibility of fabricating BN based on dilute magnetic semiconductors (DMS) by doping with Pd and Pd-Cu.

  8. Magnetic ordering and physical stability of X2Mn1+xSn1-x (X=Ru, Os, Co, Rh, Ni, Pd, Cu, and Ag) Heusler alloys from a first-principles study

    NASA Astrophysics Data System (ADS)

    Li, Chun-Mei; Hu, Qing-Miao; Yang, Rui; Johansson, Börje; Vitos, Levente

    2013-07-01

    The magnetic ordering and its effect on the physical stability of X2Mn1+xSn1-x (0≤x≤0.5, and X=Ru, Os, Co, Rh, Ni, Pd, Cu, and Ag) Heusler alloys are investigated systematically by the use of first-principles method. It is found that the ferromagnetic (FM) coupling between Mn on Mn sublattice (Mn1) and Mn on Sn sublattice (Mn2) is favorable over the antiferromagnetic (AFM) coupling for X with the number of valence electrons [Nv(X)] of 8 and 9, and vice versa for X with Nv(X)=10 and 11, originated from the competition of the exchange interactions between X-Mn2 and Mn1-Mn2. In comparison with the FM Mn1-Mn2 coupling, the AFM coupling decreases significantly the shear elastic constant C' but increases slightly C44, which results in increasing elastic anisotropy (A=C44/C') and consequently may facilitate the tetragonal shear lattice deformation. The hybridization of the minority electronic states between X d and Sn p plays a dominant role on the orientation of the magnetic coupling. The smaller change of the density of states in the Fermi level, induced by the lattice distortion for C', corresponds to the softer C' as well as the larger A in the AFM state than the FM one.

  9. Bimetallic Pt-Ag and Pd-Ag nanoparticles

    SciTech Connect

    Lahiri, Debdutta; Bunker, Bruce; Mishra, Bhoopesh; Zhang, Zhenyuan; Meisel, Dan; Doudna, C. M.; Bertino, M. F.; Blum, Frank D.; Tokuhiro, A. T.; Chattopadhyay, Soma; Shibata, Tomohiro; Terry, Jeff

    2005-04-19

    We report studies of bimetallic nanoparticles with 15%–16% atomic crystal parameters size mismatch. The degree of alloying was also probed in a 2-nm Pt core ssmallest attainable core sized of Pt–Ag nanoparticles scompletely immiscible in bulkd and 20-nm-diameter Pd–Ag nanowires scompletely miscible in bulkd. Particles were synthesized radiolytically, and depending on the initial parameters, they assume spherical or cylindrical snanowired morphologies. In all cases, the metals are seen to follow their bulk alloying characteristics. Also, Pt and Ag segregate in both spherical and wire forms, which indicates that strain due to crystallographic mismatch overcomes the excess surface free energy in the small particles. The Pd–Ag nanowires alloy similar to previously reported spherical Pd–Ag particles of similar diameter and composition

  10. EXAFS Studies of Bimetallic Ag-Pt and Ag-Pd Nanorods

    SciTech Connect

    Lahiri, D.; Chattopadhyay, S.; Bunker, B.A.; Doudna, C.M.; Bertino, M.F.; Blum, F.; Tokuhiro, A.; Terry, J.

    2008-10-30

    Nanoparticles of Ag-Pt and Ag-Pd with high aspect ratios were synthesized using a radiolysis method. Gamma rays at dose rates below 0.5 kGy/h were used for irradiation. The nanoparticles were characterized by transmission electron microscopy (TEM), optical absorption spectroscopy and x-ray Absorption Fine Structure (XAFS) spectroscopy. Bright field micrographs show that Ag-Pt nanowires are composed of large particles with diameters ranging from 20-30 nm and joined by filaments of diameter between 2-5 nm. The Ag-Pd nanowires have diameters of 20-25 nm and lengths of 1.5 {micro}m. For XAFS measurements, the Pt L3 edge (11.564 keV), Ag K-edge (25.514 keV) and Pd K-edge (24.350 keV) were excited to determine the local structure around the respective atoms in the cluster. The Ag-Pt particles were found to possess a distinct core-shell structure with Pt in the core surrounded by Ag shell, with no indication of alloy formation. However, nanorods of Ag-Pd have formed an alloy for all the alloy compositions.

  11. Controllable galvanic synthesis of triangular Ag-Pd alloy nanoframes for efficient electrocatalytic methanol oxidation.

    PubMed

    Xu, Lin; Luo, Zhimin; Fan, Zhanxi; Yu, Sijia; Chen, Junze; Liao, Yusen; Xue, Can

    2015-06-01

    Triangular Ag-Pd alloy nanoframes were successfully synthesized through galvanic replacement by using Ag nanoprisms as sacrificial templates. The ridge thickness of the Ag-Pd alloy nanoframes could be readily tuned by adjusting the amount of the Pd source during the reaction. These obtained triangular Ag-Pd alloy nanoframes exhibit superior electrocatalytic activity for the methanol oxidation reaction as compared with the commercial Pd/C catalyst due to the alloyed Ag-Pd composition as well as the hollow-framed structures. This work would be highly impactful in the rational design of future bimetallic alloy nanostructures with high catalytic activity for fuel cell systems. PMID:25925988

  12. Genetic Pd, Pt, Au, Ag, and Rh mineralogy in Noril'sk sulfide ores

    NASA Astrophysics Data System (ADS)

    Spiridonov, E. M.; Kulagov, E. A.; Serova, A. A.; Kulikova, I. M.; Korotaeva, N. N.; Sereda, E. V.; Tushentsova, I. N.; Belyakov, S. N.; Zhukov, N. N.

    2015-09-01

    The undeformed ore-bearing intrusions of the Noril'sk ore field (NOF) cut through volcanic rocks of the Late Permian-Early Triassic trap association folded in brachysynclines. Due to the nonuniform load on the roof of intrusive bodies, most sulfide melts were squeezed, up to the tops of ore-bearing intrusions; readily fusible Ni-Fe-Cu sulfide melts were almost completely squeezed. In our opinion, not only one but two stages of mineralization developed at the Noril'sk deposits: (i) syntrap magmatic and (ii) epigenetic post-trap metamorphic-hydrothermal. All platinum-group minerals (PGM) and minerals of gold are metasomatic in the Noril'sk ores. They replaced sulfide solid solutions and exsolution structures. All types of PGM and Au minerals occur in the ores, varying in composition from pyrrhotite to chalcopyrite, talnakhite, mooihoekite, and rich in galena; they are localized in the inner and outer contact zones and differ only in the quantitative proportions of ore minerals. The aureoles of PGM and Au-Ag minerals are wider than the contours of sulfide bodies and coincide with halos of fluid impact on orebodies and adjacent host rocks. The pneumatolytic PGM and Au-Ag minerals are correlated in abundance with the dimensions of sulfide bodies. Their amounts are maximal in veins of late fusible ore composed of eutectic PbS ss and iss intergrowths, as well as at their contacts. The Pd and Pt contents in eutectic sulfide ores of NOF are the world's highest. In the process of noble-metal mineral formation, the fluids supply Pd, Pt, Au, As, Sb, Sn, Bi, and a part of Te, whereas Fe, Ni, Cu, Pb, Ag, Rh, a part of Te and Pd are leached from the replaced sulfide minerals. The pneumatolytic PGM of the early stage comprises Pd and Pt intermetallic compounds enriched in Au along with Pd-Pt-Fe-Ni-Cu-Sn-Pb(As) and (Pd,Pt,Au)(Sn,Sb,Bi,Te,As) solid solutions. Pneumatolytic PGM and Au minerals of the middle stage are products of solid-phase transformation and recrystallization of

  13. Highly Active Carbon Supported Pd-Ag Nanofacets Catalysts for Hydrogen Production from HCOOH.

    PubMed

    Wang, Wenhui; He, Ting; Liu, Xuehua; He, Weina; Cong, Hengjiang; Shen, Yangbin; Yan, Liuming; Zhang, Xuetong; Zhang, Jinping; Zhou, Xiaochun

    2016-08-17

    Hydrogen is regarded as a future sustainable and clean energy carrier. Formic acid is a safe and sustainable hydrogen storage medium with many advantages, including high hydrogen content, nontoxicity, and low cost. In this work, a series of highly active catalysts for hydrogen production from formic acid are successfully synthesized by controllably depositing Pd onto Ag nanoplates with different Ag nanofacets, such as Ag{111}, Ag{100}, and the nanofacet on hexagonal close packing Ag crystal (Ag{hcp}). Then, the Pd-Ag nanoplate catalysts are supported on Vulcan XC-72 carbon black to prevent the aggregation of the catalysts. The research reveals that the high activity is attributed to the formation of Pd-Ag alloy nanofacets, such as Pd-Ag{111}, Pd-Ag{100}, and Pd-Ag{hcp}. The activity order of these Pd-decorated Ag nanofacets is Pd-Ag{hcp} > Pd-Ag{111} > Pd-Ag{100}. Particularly, the activity of Pd-Ag{hcp} is up to an extremely high value, i.e., TOF{hcp} = 19 000 ± 1630 h(-1) at 90 °C (lower limit value), which is more than 800 times higher than our previous quasi-spherical Pd-Ag alloy nanocatalyst. The initial activity of Pd-Ag{hcp} even reaches (3.13 ± 0.19) × 10(6) h(-1) at 90 °C. This research not only presents highly active catalysts for hydrogen generation but also shows that the facet on the hcp Ag crystal can act as a potentially highly active catalyst. PMID:27454194

  14. Structural characterization of bimetallic Pd-Cu vapor derived catalysts

    NASA Astrophysics Data System (ADS)

    Balerna, Antonella; Evangelisti, Claudio; Psaro, Rinaldo; Fusini, Graziano; Carpita, Adriano

    2016-05-01

    Pd-Cu bimetallic Solvated Metal Atoms (SMA) were synthesized by metal vapor synthesis technique and supported on PVPy resin. Since the catalytic activity, of the Pd-Cu system turned out to be quite high also compared to the corresponding monometallic system, a structural characterization, using electron microscopy techniques and X-ray Absorption Fine Structure spectroscopy, was performed. HRTEM analysis showed the presence of Pd particles distributed in a narrow range with a mean diameter of about 2.5 nm while the XAFS analysis, confirmed the presence of the Pd nanoparticles but revealed also some alloying with Cu atoms.

  15. Triangular Ag-Pd alloy nanoprisms: rational synthesis with high-efficiency for electrocatalytic oxygen reduction.

    PubMed

    Xu, Lin; Luo, Zhimin; Fan, Zhanxi; Zhang, Xiao; Tan, Chaoliang; Li, Hai; Zhang, Hua; Xue, Can

    2014-10-21

    We report the generation of triangular Ag-Pd alloy nanoprisms through a rationally designed synthetic strategy based on silver nanoprisms as sacrificial templates. The galvanic replacement between Ag nanoprisms and H2PdCl4 along with co-reduction of Ag(+)/Pd(2+) is responsible for the formation of final prismatic Ag-Pd alloy nanostructures. Significantly, these Ag-Pd alloy nanoprisms exhibited superior electrocatalytic activity for the oxygen reduction reaction (ORR) as compared with the commercial Pd/C catalyst. Such a high catalytic activity is attributed to not only the alloyed Ag-Pd composition but also the dominant {111} facets of the triangular Ag-Pd nanoprisms. This work demonstrates the rational design of bimetallic alloy nanostructures with control of selective crystal facets that are critical to achieve high catalytic activity for fuel cell systems. PMID:25155648

  16. Characterization of Na+- beta-Zeolite Supported Pd and Pd Ag Bimetallic Catalysts using EXAFS, TEM and Flow Reactor

    SciTech Connect

    Huang,W.; Lobo, R.; Chen, J.

    2008-01-01

    Flow reactor studies of the selective hydrogenation of acetylene in the presence of ethylene have been performed on Na+ exchanged {beta}-zeolite supported Pd, Ag and PdAg catalysts, as an extension of our previous batch reactor studies [W. Huang, J.R. McCormick, R.F. Lobo, J.G. Chen, J. Catal. 246 (2007) 40-51]. Results from flow reactor studies show that the PdAg/Na+-{beta}-zeolite bimetallic catalyst has lower activity than Pd/Na+-{beta}-zeolite monometallic catalyst, while Ag/Na+-{beta}-zeolite does not show any activity for acetylene hydrogenation. However, the selectivity for the PdAg bimetallic catalyst is much higher than that for either the Pd catalyst or Ag catalyst. The selectivity to byproduct (ethane) is greatly inhibited on the PdAg bimetallic catalyst as well. The results from the current flow reactor studies confirmed the pervious results from batch reactor studies [W. Huang, J.R. McCormick, R.F. Lobo, J.G. Chen, J. Catal. 246 (2007) 40-51]. In addition, we used transmission electron microscope (TEM), extended X-ray absorption fine structure (EXAFS), and FTIR of CO adsorption to confirm the formation of Pd-Ag bimetallic alloy in the PdAg/Na+-{beta}-zeolite catalyst.

  17. Triangular Ag-Pd alloy nanoprisms: rational synthesis with high-efficiency for electrocatalytic oxygen reduction

    NASA Astrophysics Data System (ADS)

    Xu, Lin; Luo, Zhimin; Fan, Zhanxi; Zhang, Xiao; Tan, Chaoliang; Li, Hai; Zhang, Hua; Xue, Can

    2014-09-01

    We report the generation of triangular Ag-Pd alloy nanoprisms through a rationally designed synthetic strategy based on silver nanoprisms as sacrificial templates. The galvanic replacement between Ag nanoprisms and H2PdCl4 along with co-reduction of Ag+/Pd2+ is responsible for the formation of final prismatic Ag-Pd alloy nanostructures. Significantly, these Ag-Pd alloy nanoprisms exhibited superior electrocatalytic activity for the oxygen reduction reaction (ORR) as compared with the commercial Pd/C catalyst. Such a high catalytic activity is attributed to not only the alloyed Ag-Pd composition but also the dominant {111} facets of the triangular Ag-Pd nanoprisms. This work demonstrates the rational design of bimetallic alloy nanostructures with control of selective crystal facets that are critical to achieve high catalytic activity for fuel cell systems.We report the generation of triangular Ag-Pd alloy nanoprisms through a rationally designed synthetic strategy based on silver nanoprisms as sacrificial templates. The galvanic replacement between Ag nanoprisms and H2PdCl4 along with co-reduction of Ag+/Pd2+ is responsible for the formation of final prismatic Ag-Pd alloy nanostructures. Significantly, these Ag-Pd alloy nanoprisms exhibited superior electrocatalytic activity for the oxygen reduction reaction (ORR) as compared with the commercial Pd/C catalyst. Such a high catalytic activity is attributed to not only the alloyed Ag-Pd composition but also the dominant {111} facets of the triangular Ag-Pd nanoprisms. This work demonstrates the rational design of bimetallic alloy nanostructures with control of selective crystal facets that are critical to achieve high catalytic activity for fuel cell systems. Electronic supplementary information (ESI) available. See DOI: 10.1039/c4nr03600j

  18. Ti-Ag-Pd alloy with good mechanical properties and high potential for biological applications.

    PubMed

    Zadorozhnyy, V Yu; Shi, X; Gorshenkov, M V; Kozak, D S; Wada, T; Louzguine-Luzgin, D V; Inoue, A; Kato, H

    2016-01-01

    Ti-based alloys containing Ag were produced by tilt-casting method and their properties were studied. Even in its as-cast state, Ti94Ag3Pd3 showed relatively high tensile properties, good electrochemical behavior, and good biocompatibility. The relatively good mechanical properties of the as-cast α-Ti-type Ti94Ag3Pd3 alloy (tensile strength up to 850 MPa and elongation of ~10%) can be explained by its severely deformed, fine crystalline structure. The high biocompatibility of Ti94Ag3Pd3 can be explained by the Ag-Pd interaction, which inhibits the release of Ag ions from the surface. Ag, in combination with Pd has no toxic effects and demonstrates useful antimicrobial properties. The Ti94Ag3Pd3 alloy shows a good potential to be applied as a biomedical implant alloy. PMID:27122177

  19. Cu--Pd--M hydrogen separation membranes

    DOEpatents

    Do{hacek over }an, Omer N; Gao, Michael C; Young, Rongxiang Hu; Tafen, De Nyago

    2013-12-17

    The disclosure provides an H2 separation membrane comprised of an allow having the composition Cu.Sub.(100-x-y)Pd.sub.xM.sub.y, where x is from about 35 to about 50 atomic percent and where y is from greater than 0 to about 20 atomic percent, and where M consists of magnesium, yttrium, aluminum, titanium, lanthanum, or combinations thereof. The M elements act as strong stabilizers for the B2 phase of the allow, and extend the critical temperature of the alloy for a given hydrogen concentration and pressure. Due to the phase stabilization and the greater temperature range over which a B2 phase can be maintained, the allow is well suited for service as a H2 separation membrane, particularly when applicable conditions are established or cycled above about 600.degree. C. over the course of expected operations. In certain embodiments, the B2 phase comprises at least 60 estimated volume percent of the allow at a steady-state temperature of 400.degree. C. The B2 phase stability is experimentally validated through HT-XRD.

  20. The isotopic composition of AG in meteorites and the presence of Pd-107 in protoplanets

    NASA Astrophysics Data System (ADS)

    Chen, J. H.; Wasserburg, G. J.

    1990-06-01

    Results are presented on the isotopic composition of Ag and the concentrations of Pd and Ag in metal and sulfide phases in iron meteorites Gibeon, Derrick Peak, and Mundrabilla and in schereibersite in Derrick Peak. It was found that almost all iron meteorite samples with a ratio of Pd-108/Ag-109 greater than about 400 had an excess of Ag-107. The results, in conjunction with the data of Chen and Wasserburg (1983) on IIIA-IIIB meteorites, demonstrate the widespread occurrence of excess Ag-107 in diverse types of small early planetary bodies. The excess Ag-107 is believed to be produced by the decay of Pd-107.

  1. Ag/Pd core-shell nanoparticles by a successive method: Pulsed laser ablation of Ag in water and reduction reaction of PdCl2

    NASA Astrophysics Data System (ADS)

    Mottaghi, N.; Ranjbar, M.; Farrokhpour, H.; Khoshouei, M.; Khoshouei, A.; Kameli, P.; Salamati, H.; Tabrizchi, M.; Jalilian-Nosrati, M.

    2014-02-01

    In this study Ag/Pd nanoparticles (NPs) have been fabricated by a successive method; first, colloids of Ag nanoparticles (NPs) have been prepared in water by pulsed laser ablation in liquid (PLAL) method. Then PdCl2 solution (up to 0.2 g/l) were added to the as-prepared or aged colloidal Ag NPs. Characterizations were done using UV-vis spectroscopy, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and transmissions electron microscopy (TEM) techniques. Spectroscopy data showed that surface plasmon resonance (SPR) peaks of as-prepared Ag NPs at about λ = 400 nm were completely extinguished after addition of PdCl2 solution while this effect was not observed when aged Ag NPs are used. XRD and XPS results revealed that by addition of the PdCl2 solution into the as-prepared Ag NPs, metallic palladium, and silver chloride composition products are generated. TEM images revealed that as a result of this reaction, single and core-shell nanoparticles are obtained and their average sizes are 2.4 nm (Ag) and 3.2 nm (Ag/Pd). The calculated d-spacing values form XRD data with observations on high magnification TEM images were able to explain the chemical nature of different parts of Ag/Pd NPs.

  2. Alumina-supported Pd-Ag catalysts for low-temperature CO and methanol oxidation

    NASA Technical Reports Server (NTRS)

    Mccabe, R. W.

    1987-01-01

    Pd-Ag bimetallic catalysts, supported on gamma-Al2O3, have been evaluated as exhaust catalysts for methanol-fueled vehicles. Laboratory studies have shown that a 0.01% Pd-5% Ag catalyst has greater CO and CH3OH oxidation activity than either 0.01% Pd or 5% Ag catalysts alone. Moreover, Pd and Ag interact synergistically in the bimetallic catalyst to produce greater CO and CH3OH oxidation rates and lower yields of methanol partial oxidation products than expected from a mixture of the single-component catalysts. The Pd-Ag synergism results from Pd promoting the rate of O2 adsorption and reaction with CO and CH3OH on Ag. Rate enhancement by the bimetallic catalyst is greatest at short reactor residence times where the oxygen adsorption rate limits the overall reaction rate.

  3. Enhanced formic acid oxidation on Cu-Pd nanoparticles

    NASA Astrophysics Data System (ADS)

    Dai, Lin; Zou, Shouzhong

    Developing catalysts with high activity and high resistance to surface poisoning remains a challenge in direct formic acid fuel cell research. In this work, copper-palladium nanoparticles were formed through a galvanic replacement process. After electrochemically selective dissolution of surface Cu, Pd-enriched Cu-Pd nanoparticles were formed. These particles exhibit much higher formic acid oxidation activities than that on pure Pd nanoparticles, and they are much more resistant to the surface poisoning. Possible mechanisms of catalytic activity enhancement are briefly discussed.

  4. Pd2Ag triangle supported by two micro3-amidopyridine ligands.

    PubMed

    Shen, Wei-Zheng; Costisella, Burkhard; Lippert, Bernhard

    2007-02-28

    [Pd(tmeda)(Hampy-N1)(H2O)]2+ (tmeda=N,N,N',N'-tetramethylethylenediamine; Hampy=2-aminopyridine) forms in the presence of Ag+ at pH 8-9 a triangular Pd2Ag complex containing two deprotonated ampy- ligands. It has been crystallized and structurally characterized with nitrate anions and a second co-crystallized AgNO3, [{Pd(ampy)(tmeda)}2Ag(micro-NO3)2Ag(NO3)2]. The two amidopyridine ligands are triply bridging, binding to Ag+ in a monodentate fashion viaN1, and to two PdII centres in a micro2-bridging fashion via the monodeprotonated N2 position. The resulting four-membered Pd(ampy)2Pd metallacycle is syn-planar with Pd[dot dot dot]Pd separations of 3.0878(13) A. The Pd...Ag distances are 3.0879(14) A in (isosceles triangle). In solution (D2O), the two ampy- ligand in are non-equivalent as concluded from a detailed 1H NMR spectroscopic study and confirmed by a 13C NMR spectrum. Removal of Ag+ from, as achieved by addition of Cl-, causes cluster degradation and linkage isomerization of PdII(tmeda) from the exocyclic N2 to the endocyclic N1 position. PMID:17297512

  5. Synthesis of Cu-Ag@Ag particles using hyperbranched polyester as template

    NASA Astrophysics Data System (ADS)

    Han, Wen-Song

    2015-07-01

    In this manuscript, the third-generation hyperbranched polyester was synthesized with 2, 2-dimethylol propionic acid as AB2 monomer and pentaerythrite as core molecule by using step by step polymerization process at first. Then, the Cu-Ag particles were prepared by co-reduction of silver nitrate and copper nitrate with ascorbic acid in the aqueous solution using hyperbranched polyester as template. Finally, the Cu-Ag@Ag particles were prepared by coating silver on the surface of Cu-Ag particles by reduction of silver nitrate. The synthesized hyperbranched polyester and Cu-Ag@Ag particles were characterized by Fourier transform infrared (FT-IR) spectroscopy, UV-vis spectra, x-ray diffraction, Laser light scattering, thermogravimetric analysis (TGA) and SEM. UV-vis spectra results showed that the Cu-Ag@Ag particles had a strong absorption band at around 420 nm. Laser light scattering and SEM studies confirmed that the most frequent particle sizes of Cu-Ag@Ag particles were 1.2 um. TGA results indicated that the Cu-Ag@Ag particles had good thermal stability. [Figure not available: see fulltext.

  6. Monodispersed bimetallic PdAg nanoparticles with twinned structures: Formation and enhancement for the methanol oxidation

    NASA Astrophysics Data System (ADS)

    Yin, Zhen; Zhang, Yining; Chen, Kai; Li, Jing; Li, Wenjing; Tang, Pei; Zhao, Huabo; Zhu, Qingjun; Bao, Xinhe; Ma, Ding

    2014-03-01

    Monodispersed bimetallic PdAg nanoparticles can be fabricated through the emulsion-assisted ethylene glycol (EG) ternary system. Different compositions of bimetallic PdAg nanoparticles, Pd80Ag20, Pd65Ag35 and Pd46Ag54 can be obtained via adjusting the reaction parameters. For the formation process of the bimetallic PdAg nanoparticles, there have two-stage growth processes: firstly, nucleation and growth of the primary nanoclusters; secondly, formation of the secondary nanoparticles with the size-selection and relax process via the coalescence or aggregation of the primary nanoclusters. The as-prepared PdAg can be supported on the carbon black without any post-treatment, which exhibited high electro-oxidation activity towards methanol oxidation under alkaline media. More importantly, carbon-supported Pd80Ag20 nanoparticles reveal distinctly superior activities for the methanol oxidation, even if compared with commercial Pt/C electro-catalyst. It is concluded that the enhanced activity is dependant on the unique twinning structure with heterogeneous phase due to the dominating coalescence growth in EG ternary system.

  7. Monodispersed bimetallic PdAg nanoparticles with twinned structures: Formation and enhancement for the methanol oxidation

    PubMed Central

    Yin, Zhen; Zhang, Yining; Chen, Kai; Li, Jing; Li, Wenjing; Tang, Pei; Zhao, Huabo; Zhu, Qingjun; Bao, Xinhe; Ma, Ding

    2014-01-01

    Monodispersed bimetallic PdAg nanoparticles can be fabricated through the emulsion-assisted ethylene glycol (EG) ternary system. Different compositions of bimetallic PdAg nanoparticles, Pd80Ag20, Pd65Ag35 and Pd46Ag54 can be obtained via adjusting the reaction parameters. For the formation process of the bimetallic PdAg nanoparticles, there have two-stage growth processes: firstly, nucleation and growth of the primary nanoclusters; secondly, formation of the secondary nanoparticles with the size-selection and relax process via the coalescence or aggregation of the primary nanoclusters. The as-prepared PdAg can be supported on the carbon black without any post-treatment, which exhibited high electro-oxidation activity towards methanol oxidation under alkaline media. More importantly, carbon-supported Pd80Ag20 nanoparticles reveal distinctly superior activities for the methanol oxidation, even if compared with commercial Pt/C electro-catalyst. It is concluded that the enhanced activity is dependant on the unique twinning structure with heterogeneous phase due to the dominating coalescence growth in EG ternary system. PMID:24608736

  8. Size selected cluster deposition on well characterized surfaces: Ag{sub n}/Pd(100)

    SciTech Connect

    Vandoni, G.; Felix, C.; Harbich, W.; Monot, R.; Buttet, J.; Massobrio, C.

    1997-06-20

    We study the deposition of Ag ions, and size selected Ag{sub 7} and Ag{sub 19} cluster ions on Pd(100) at total kinetic energies of 20 eV and 95 eV using Thermal Energy Atom Scattering and Molecular Dynamics simulations. We find that at all energies Ag atoms are implanted into the substrate and Pd atoms are ejected in the adlayer. The experimental results in the case of Ag{sub 7} can be understood in taking into account both implantation of Ag atoms and heavy fragmentation. In the case of Ag{sub 19} the deposition leads at low temperature to non compact structures localized around the impact point. We propose a model in which morphology changes take place between 200 K and 300 K resulting in well separated compact structures formed of Ag and Pd adatoms.

  9. Preparation of PdAg and PdAu nanoparticle-loaded carbon black catalysts and their electrocatalytic activity for the glycerol oxidation reaction in alkaline medium

    NASA Astrophysics Data System (ADS)

    Lam, Binh Thi Xuan; Chiku, Masanobu; Higuchi, Eiji; Inoue, Hiroshi

    2015-11-01

    PdAg and PdAu alloy nanoparticle catalysts for the glycerol oxidation reaction (GOR) were prepared at room temperature by a wet method. The molar ratio of the precursors controlled the bulk composition of the PdAg and PdAu alloys, and their surface composition was Ag-enriched and Pd-enriched, respectively. On PdAg-loaded carbon black (PdAg/CB) electrodes, the onset potential of GOR was 0.10-0.15 V more negative than on the Pd/CB electrode due to the electronic effect. The ratio of GOR peak current densities in the backward and forward sweeps of CVs (ib/if) was smaller because of the improved tolerance to the poisoning species. The ratio of the GOR current density at 60 and 5 min (i60/i5) for the PdAg/CB electrodes was higher for more negative potentials than the Pd/CB electrode. In contrast, the PdAu-loaded CB (PdAu/CB) electrodes had an onset potential of GOR similar to the Pd/CB electrode and a higher GOR peak current density owing to the bi-functional effect. However, the ib/if ratio was higher for PdAu/CB because of the increase in ib as the Pd surface was recovered, and the i60/i5 ratio was higher for more positive potentials, similar to the Pd/CB electrode.

  10. Leaching of Au, Ag, and Pd from waste printed circuit boards of mobile phone by iodide lixiviant after supercritical water pre-treatment

    SciTech Connect

    Xiu, Fu-Rong; Qi, Yingying; Zhang, Fu-Shen

    2015-07-15

    Highlights: • We report a novel process for recovering Au, Ag, and Pd from waste PCBs. • The effect of SCWO on the leaching of Au, Ag, and Pd in waste PCBs was studied. • SCWO was highly efficient for enhancing the leaching of Au, Ag, and Pd. • The optimum leaching parameters for Au, Ag, and Pd in iodine–iodide were studied. - Abstract: Precious metals are the most attractive resources in waste printed circuit boards (PCBs) of mobile phones. In this work, an alternative process for recovering Au, Ag, and Pd from waste PCBs of mobile phones by supercritical water oxidation (SCWO) pre-treatment combined with iodine–iodide leaching process was developed. In the process, the waste PCBs of mobile phones were pre-treated in supercritical water, then a diluted hydrochloric acid leaching (HL) process was used to recovery the Cu, whose leaching efficiency was approximately 100%, finally the resulting residue was subjected to the iodine–iodide leaching process for recovering the Au, Ag, and Pd. Experimental results indicated that SCWO pre-treatment temperature, time, and pressure had significant influence on the Au, Ag, and Pd leaching from (SCWO + HL)-treated waste PCBs. The optimal SCWO pre-treatment conditions were 420 °C and 60 min for Au and Pd, and 410 °C and 30 min for Ag. The optimum dissolution parameters for Au, Pd, and Ag in (SCWO + HL)-treated PCBs with iodine–iodide system were leaching time of 120 min (90 min for Ag), iodine/iodide mole ratio of 1:5 (1:6 for Ag), solid-to-liquid ratio (S/L) of 1:10 g/mL (1:8 g/mL for Ag), and pH of 9, respectively. It is believed that the process developed in this study is environment friendly for the recovery of Au, Ag, and Pd from waste PCBs of mobile phones by SCWO pre-treatment combined with iodine–iodide leaching process.

  11. Temperature dependent effects during Ag deposition on Cu(110)

    SciTech Connect

    Taylor, T.N.; Muenchausen, R.E.; Hoffbauer, M.A.; Denier van der Gon, A.W.; van der Veen, J.F.; FOM-Instituut voor Atoom-en Molecuulfysica, Amsterdam )

    1989-01-01

    The composition, structure, and morphology of ultrathin films grown by Ag deposition on Cu(110) were monitored as a function of temperature using low-energy electron diffraction (LEED), Auger electron spectroscopy (AES), and medium energy ion scattering (MEIS). Aligned backscattering measurements with 150 keV He ions indicate that the Ag resides on top of the Cu and there is no significant surface compound formation. Measurements with LEED show that the Ag is initially confined to the substrate troughs. Further deposition forces the Ag out of the troughs and results in a split c(2 {times} 4) LEED pattern, which is characteristic of a distorted Ag(111) monolayer template. As verified by both AES and MEIS measurements, postmonolayer deposition of Ag on Cu(110) at 300K leads to a pronounced 3-dimensional clustering. Ion blocking analysis of the Ag clusters show that the crystallites have a (110)-like growth orientation, implying that the Ag monolayer template undergoes a rearrangement. These data are confirmed by low temperature LEED results in the absence of clusters, which indicate that Ag multilayers grow from a Ag--Cu interface where the Ag is captured in the troughs. Changes observed in the film structure and morphology are consistent with a film growth mechanism that is driven by overlayer strain response to the substrate corrugation. 16 refs., 4 figs.

  12. Enhanced electrocatalytic performance of Pt monolayer on nanoporous PdCu alloy for oxygen reduction

    NASA Astrophysics Data System (ADS)

    Hou, Linxi; Qiu, Huajun

    2012-10-01

    By selectively dealloying Al from PdxCu20-xAl80 ternary alloys in 1.0 M NaOH solution, nanoporous PdCu (np-PdCu) alloys with different Pd:Cu ratios are obtained. By a mild electrochemical dealloying treatment, the np-PdCu alloys are facilely converted into np-PdCu near-surface alloys with a nearly pure-Pd surface and PdCu alloy core. The np-PdCu near-surface alloys are then used as substrates to fabricate core-shell catalysts with a Pt monolayer as shell and np-PdCu as core by a Cu-underpotential deposition-Pt displacement strategy. Electrochemical measurements demonstrate that the Pt monolayer on np-Pd1Cu1 (Pt/np-Pd1Cu1) exhibits the highest Pt surface-specific activity towards oxygen reduction, which is ˜5.8-fold that of state-of-the-art Pt/C catalyst. The Pt/np-Pd1Cu1 also shows much enhanced stability with ˜78% active surface retained after 10,000 cycles (0.6-1.2 V vs. RHE). Under the same condition, the active surface of Pt/C drops to ˜28%.

  13. Theoretical study of NH3 decomposition on Pd-Cu (1 1 1) and Cu-Pd (1 1 1) surfaces: A comparison with clean Pd (1 1 1) and Cu (1 1 1)

    NASA Astrophysics Data System (ADS)

    Jiang, Zhao; Qin, Pei; Fang, Tao

    2016-05-01

    The adsorption and successive dehydrogenation mechanisms of NH3 on Pd-Cu (1 1 1) and Cu-Pd (1 1 1) surfaces (the Pd atoms substitution of the first and second layers of Cu (1 1 1) surfaces) have been systematically investigated by density functional theory (DFT) method with a periodic slab model. All possible adsorption configurations of relevant intermediates on Pd-Cu (1 1 1) and Cu-Pd (1 1 1) surfaces are identified. It is revealed that the adsorption configurations and corresponding adsorption energies of adsorbates are slightly changed on Pd-Cu (1 1 1) and Cu-Pd (1 1 1) surfaces. The adsorption energies of NHx(x = 0-3) species exhibit the following trend: NH3 < NH2 < NH < N. Then, the minimum energy path for the complete dehydrogenation of NH3 into adsorbed N and H is identified to explore the dehydrogenation mechanisms on different surfaces. The highest energy barrier and reaction energy on Pd-Cu (1 1 1) surface are greatly reduced to 1.56 and 0.99 eV, implying that the complete dehydrogenation of NH3 on Pd-Cu (1 1 1) surface is favorable both kinetically and thermodynamically, namely, the doped-Pd atoms in the first layer are the reaction active center. Compared to that on clean Pd (1 1 1) and Cu (1 1 1) surfaces, it is found that the synergistic effect exits in different layers of catalyst surfaces. The calculated results show that the layer-substituted Pd atoms on the surface of Cu catalysts exhibit a better catalytic activity for NH3 dehydrogenation compared to the clean Cu (1 1 1) surface.

  14. Core-shell Au@Pd nanoparticles with enhanced catalytic activity for oxygen reduction reaction via core-shell Au@Ag/Pd constructions

    PubMed Central

    Chen, Dong; Li, Chengyin; Liu, Hui; Ye, Feng; Yang, Jun

    2015-01-01

    Core-shell nanoparticles often exhibit improved catalytic properties due to the lattice strain created in these core-shell particles. Herein, we demonstrate the synthesis of core-shell Au@Pd nanoparticles from their core-shell Au@Ag/Pd parents. This strategy begins with the preparation of core-shell Au@Ag nanoparticles in an organic solvent. Then, the pure Ag shells are converted into the shells made of Ag/Pd alloy by galvanic replacement reaction between the Ag shells and Pd2+ precursors. Subsequently, the Ag component is removed from the alloy shell using saturated NaCl solution to form core-shell Au@Pd nanoparticles with an Au core and a Pd shell. In comparison with the core-shell Au@Pd nanoparticles upon directly depositing Pd shell on the Au seeds and commercial Pd/C catalysts, the core-shell Au@Pd nanoparticles via their core-shell Au@Ag/Pd templates display superior activity and durability in catalyzing oxygen reduction reaction, mainly due to the larger lattice tensile effect in Pd shell induced by the Au core and Ag removal. PMID:26144550

  15. Boron induced structure modifications in Pd-Cu-B system: new Ti2Ni-type derivative borides Pd3Cu3B and Pd5Cu5B2.

    PubMed

    Sologub, Oksana; Salamakha, Leonid P; Eguchi, Gaku; Stöger, Berthold; Rogl, Peter F; Bauer, Ernst

    2016-03-21

    The formation of two distinct derivative structures of Ti2Ni-type, interstitial Pd3Cu3B and substitutive Pd5Cu5B2, has been elucidated in Pd-Cu-B alloys from analysis of X-ray single crystal and powder diffraction data and supported by SEM. The metal atom arrangement in the new boride Pd3Cu3B (space group Fd3m, W3Fe3C-type structure, a = 1.1136(3) nm) follows the pattern of atom distribution in the CdNi-type structure. Pd5Cu5B2 (space group F(4)3m, a = 1.05273(5) nm) exhibits a non-centrosymmetric substitutive derivative of the Ti2Ni-type structure. The reduction of symmetry on passing from Ti2Ni-type structure to Pd5Cu5B2 corresponds to the loss of an inversion centre delivered by an ordered occupation of the Ni position (32e) by dissimilar atoms, Cu and B. In both structures, the boron atom centers Pd forming [BPd6] octahedra in Pd3Cu3B and [BPd6] trigonal prisms in Pd5Cu5B2. Neither a perceptible homogeneity range nor mutual solid solubility was observed for two compounds at 600 °C, while in as cast conditions Pd5Cu5B2 exhibits an extended homogeneity range formed by a partial substitution of Cu atoms (in 24f) by Pd (Pd5+xCu5-xB2, 0 ≤x≤ 1). Electrical resistivity measurements performed on Pd3Cu3B as well as on Pd-poor and Pd-rich termini of Pd5+xCu5-xB2 annealed at 600 °C and in as cast conditions respectively demonstrated the absence of any phase transitions for this compounds in the temperature region from 0.3 K to 300 K. PMID:26875687

  16. Leaching of Au, Ag, and Pd from waste printed circuit boards of mobile phone by iodide lixiviant after supercritical water pre-treatment.

    PubMed

    Xiu, Fu-Rong; Qi, Yingying; Zhang, Fu-Shen

    2015-07-01

    Precious metals are the most attractive resources in waste printed circuit boards (PCBs) of mobile phones. In this work, an alternative process for recovering Au, Ag, and Pd from waste PCBs of mobile phones by supercritical water oxidation (SCWO) pre-treatment combined with iodine-iodide leaching process was developed. In the process, the waste PCBs of mobile phones were pre-treated in supercritical water, then a diluted hydrochloric acid leaching (HL) process was used to recovery the Cu, whose leaching efficiency was approximately 100%, finally the resulting residue was subjected to the iodine-iodide leaching process for recovering the Au, Ag, and Pd. Experimental results indicated that SCWO pre-treatment temperature, time, and pressure had significant influence on the Au, Ag, and Pd leaching from (SCWO+HL)-treated waste PCBs. The optimal SCWO pre-treatment conditions were 420°C and 60min for Au and Pd, and 410°C and 30min for Ag. The optimum dissolution parameters for Au, Pd, and Ag in (SCWO+HL)-treated PCBs with iodine-iodide system were leaching time of 120min (90min for Ag), iodine/iodide mole ratio of 1:5 (1:6 for Ag), solid-to-liquid ratio (S/L) of 1:10g/mL (1:8g/mL for Ag), and pH of 9, respectively. It is believed that the process developed in this study is environment friendly for the recovery of Au, Ag, and Pd from waste PCBs of mobile phones by SCWO pre-treatment combined with iodine-iodide leaching process. PMID:25802060

  17. Nanoporous Ag prepared from the melt-spun Cu-Ag alloys

    NASA Astrophysics Data System (ADS)

    Li, Guijing; Song, Xiaoping; Sun, Zhanbo; Yang, Shengchun; Ding, Bingjun; Yang, Sen; Yang, Zhimao; Wang, Fei

    2011-07-01

    Nanoporous Ag ribbons with different morphology and porosity were achieved by the electrochemical corrosion of the melt-spun Cu-Ag alloys. The Cu-rich phase in the alloys was removed, resulting in the formation of the nanopores distributed across the whole ribbon. It is found that the structures, morphology and porosity of the nanoporous Ag ribbons were dependent on the microstructures of the parent alloys. The most of ligaments presented a rod-like shape due to the formation of pseudoeutectic microstructure in the melt-spun Cu 55Ag 45 and Cu 70Ag 30 alloys. For nanoporous Ag prepared from Cu 85Ag 15 alloys, the ligaments were camber-like because of the appearance of the divorced microstructures. Especially, a novel bamboo-grove-like structure could be observed at the cross-section of the nanoporous Ag ribbons. The experiment reveals that nanoporous Ag ribbons exhibited excellent enhancement of surface-enhanced Raman scattering (SERS) effect, but a slight difference existed due to the discrepancy of their morphology.

  18. Spectroscopic and electronic structure of the CuIn, AgIn, CuGa and AgGa diatomics

    NASA Astrophysics Data System (ADS)

    Oranges, T.; Musolino, V.; Toscano, M.; Russo, N.

    1990-06-01

    Electronic, geometrical and spectroscopic properties of heteronuclear CuIn, AgIn, CuGa and AgGa diatomics have been investigated employing LCGTO-MP-LSD method. For all the molecules the ground state has been found to be the1Σ one followed by3Π,1Π and3Σ low-lying electronic state respectively. The geometric and electronic parameters are in reasonable agreement with the available experimental data. The chemical bond in the molecules has a single bond character due to the valence bond couplings between the Cu 4 s (or Ag 5 s) and the Ga 4 p (or In 5 p) electrons.

  19. Bimetallic PdAg nanoparticle arrays from monolayer films of diblock copolymer micelles

    NASA Astrophysics Data System (ADS)

    Ehret, E.; Beyou, E.; Mamontov, G. V.; Bugrova, T. A.; Prakash, S.; Aouine, M.; Domenichini, B.; Cadete Santos Aires, F. J.

    2015-07-01

    The self-assembly technique provides a highly efficient route to generate well-ordered structures on a nanometer scale. In this paper, well-ordered arrays of PdAg alloy nanoparticles on flat substrates with narrow distributions of particle size (6-7 nm) and interparticle spacing (about 60 nm) were synthesized by the block copolymer micelle approach. A home-made PS-b-P4VP diblock copolymer was prepared to obtain a micellar structure in toluene. Pd and Ag salts were then successfully loaded in the micellar core of the PS-b-P4VP copolymer. A self-assembled monolayer of the loaded micelles was obtained by dipping the flat substrate in the solution. At this stage, the core of the micelles was still loaded with the metal precursor rather than with a metal. Physical and chemical reducing methods were used to reduce the metal salts embedded in the P4VP core into PdAg nanoparticles. HRTEM and EDX indicated that Pd-rich PdAg alloy nanoparticles were synthesized by chemical or physical reduction; UV-visible spectroscopy observations confirmed that metallic PdAg nanoparticles were quickly formed after chemical reduction; XPS measurements revealed that the PdAg alloy nanoparticles were in a metallic state after a short time of exposure to O2 plasma and after hydrazine reduction.

  20. Melting curve of metals Cu, Ag and Au under pressure

    NASA Astrophysics Data System (ADS)

    Tam, Pham Dinh; Hoc, Nguyen Quang; Tinh, Bui Duc; Tan, Pham Duy

    2016-01-01

    In this paper, the dependence of the melting temperature of metals Cu, Ag and Au under pressure in the interval from 0 kbar to 40 kbar is studied by the statistical moment method (SMM). This dependence has the form of near linearity and the calculated slopes of melting curve are 3.9 for Cu, 5.7 for Ag and 6 for Au. These results are in good agreement with the experimental data.

  1. SERS monitoring of Pd-catalysed reduction processes of nitroarenes adsorbed on Ag/Pd colloidal nanoparticles

    NASA Astrophysics Data System (ADS)

    Muniz-Miranda, Maurizio; Pergolese, Barbara; Bigotto, Adriano

    2006-05-01

    The catalytic activity of palladium has been verified in Ag/Pd colloids for two different nitroarenes, 2-amino,5-nitropyridine (ANP) and 4-nitrobenzoic acid (PNBA). Palladium, deposited as nanoclusters onto the silver core, can act as catalyst for the ligands, while silver ensures the SERS enhancement, which is necessary to detect the Raman spectra of the adsorbates. The SERS measurements show that the nitrogroup of ANP is reduced to aminogroup in Ag/Pd colloids, whereas, in the case of PNBA, the azo-derivative is obtained as stable product.

  2. Bulk metallic glass formation in the Pd-Ni-P and Pd-Cu-P alloy systems

    SciTech Connect

    Schwarz, R.B.; He, Y.

    1996-12-11

    Bulk metallic glasses were prepared in the Pd-Ni-P and Pd-Cu-P systems using a fluxing technique. The formation of bulk amorphous Pd-Cu-P alloys was reported here for the first time. For both alloy systems, bulk glass formation requires maintaining the phosphorus content near 20 at.%. In the Pd-Ni-P system, 10-mm diameter amorphous Pd{sub x}Ni{sub 80{minus}x}P{sub 20} rods can be formed for 25 {le} x {le} 60. In the Pd-Cu-P system, 7-mm diameter amorphous Pd{sub x}Cu{sub 80{minus}x}P{sub 20} rods can be produced for 40 {le} x {le} 60. From all the ternary alloys studied, Pd{sub 40}Ni{sub 40}P{sub 20} has the highest glass formability, and 25-mm diameter amorphous cylinders, 50 mm in length, can be easily fabricated. The glass stability of the Pd-Ni-P system is wider than that of the Pd-Cu-P system. For most bulk Pd-Ni-P glasses, {Delta}T > 90 K. The {Delta}T values of bulk amorphous Pd-Cu-P alloys are considerably smaller, ranging from 27 to 73 K. The elastic constants of bulk amorphous Pd-Ni-P and Pd-Cu-P alloys were determined using a resonant ultrasound spectroscopy technique. The Pd-Ni-P glasses are slightly stiffer than the Pd-Cu-P glasses. Within each alloy system, the Young`s modulus and the bulk modulus show little change with alloy composition. Of all the bulk glass forming systems so far investigated, the ternary Pd-Ni-P system has the best glass formability. This alloy was one of the first bulk glasses discovered, yet it still remains the best in terms of glass formability. Upon replacing part of Ni by Cu, the critical cooling rates are expected to be further reduced.

  3. Evaluation of the catalytic activity of Pd-Ag alloys on ethanol oxidation and oxygen reduction reactions in alkaline medium

    NASA Astrophysics Data System (ADS)

    Oliveira, M. C.; Rego, R.; Fernandes, L. S.; Tavares, P. B.

    2011-08-01

    Pd-Ag alloys containing different amounts of Ag (8, 21 and 34 at.%) were prepared in order to evaluate their catalytic activity towards the ethanol oxidation (EOR) and oxygen reduction (ORR) reactions. A sequential electroless deposition of Ag and Pd on a stainless steel disc, followed by annealing at 650 °C under Ar stream, was used as the alloy electrode deposition process. From half-cell measurements in a 1.0 M NaOH electrolyte at ≅20 °C, it was found that alloying Pd with Ag leads to an increases of the ORR and EOR kinetics, relative to Pd. Among the alloys under study, the 21 at.% Ag content alloy presents the highest catalytic activity for the EOR and the lowest Ag content alloy (8 at.% Ag) shows the highest ORR activity. Moreover, it was found that the selectivity of Pd-Ag alloys towards ORR is sustained when ethanol is present in the electrolyte.

  4. Ultra-Fast Synthesis for Ag2Se and CuAgSe Thermoelectric Materials

    NASA Astrophysics Data System (ADS)

    DUAN, H. Z.; LI, Y. L.; ZHAO, K. P.; QIU, P. F.; SHI, X.; CHEN, L. D.

    2016-06-01

    Ag2Se and CuAgSe have been recently reported as promising thermoelectric materials at room temperature. The traditional melting-annealing-sintering processes are used to grow Ag2Se and CuAgSe materials with the disadvantages of high costs of energy and time. In this work, phase-pure polycrystalline Ag2Se and CuAgSe compounds were synthesized from raw elemental powders directly by manual mixing followed by spark plasma sintering (MM-SPS) in a few minutes. The influence of SPS heating rate on the phase composition, microstructure, and thermoelectric properties, including Seebeck coefficient, electrical conductivity, and thermal conductivity, were investigated. The zTs of 0.8 at 390 K and 0.6 at 450 K are obtained for Ag2Se and CuAgSe, respectively, which is comparable with the values in the materials prepared by the traditional method. Furthermore, this ultrafast sample synthesis can significantly save material synthesis time and thus has the obvious advantage for large-scale production.

  5. Effect of Pd precursor status on sonochemical surface activation in Cu electroless deposition

    NASA Astrophysics Data System (ADS)

    Kim, Kanghoon; Jin, Seonok; Kwon, Oh Joong

    2016-02-01

    Pd surface activation via a sonochemical approach was studied by varying Pd precursor status in the aqueous solution. By aging a K2PdCl6 activation solution overnight with added NH4OH, the chlorinated Pd complex was changed to an ammonia-based Pd complex. The Pd surface activation carried out with the NH4OH complexing agent resulted in improved surface condition following Cu electroless deposition. The Cu thin film deposited on a substrate sonochemically activated with the aged, ammonia-based Pd complex showed improved surface roughness and resistivity compared to that for Cu films deposited via two other precursors (chlorinated Pd complex and ammonia-based complex) without aging. In addition, nitrogen purging during sonochemical activation improved Cu film quality.

  6. Interdiffusion and stress development in single-crystalline Pd/Ag bilayers

    NASA Astrophysics Data System (ADS)

    Noah, Martin A.; Flötotto, David; Wang, Zumin; Mittemeijer, Eric J.

    2016-04-01

    Interdiffusion and stress evolution in single-crystalline Pd/single-crystalline Ag thin films were investigated by Auger electron spectroscopy sputter-depth profiling and in-situ X-ray diffraction, respectively. The concentration-dependent chemical diffusion coefficient, as well as the impurity diffusion coefficient of Ag in Pd could be determined in the low temperature range of 356 °C-455 °C. As a consequence of the similarity of the strong concentration-dependences of the intrinsic diffusion coefficients, the chemical diffusion coefficient varies only over three orders of magnitude over the whole composition range, despite the large difference of six orders of magnitude of the self-diffusion coefficients of Ag in Ag and Pd in Pd. It is shown that the Darken-Manning treatment should be adopted for interpretation of the experimental data; the Nernst-Planck treatment yielded physically unreasonable results. Apart from the development of compressive thermal stress, the development of stress in both sublayers separately could be ascribed to compositional stress (tensile in the Ag sublayer and compressive in the Pd sublayer) and dominant relaxation processes, especially in the Ag sublayer. The effect of these internal stresses on the values determined for the diffusion coefficients is shown to be negligible.

  7. THE ELECTRONIC STRUCTURE OF AG/CU(100) SURFACE ALLOYS STUDIES BY AUGER-PHOTOELECTRON COINCIDENCE SPECTROSCOPY.

    SciTech Connect

    ARENA,D.A.; BARTYNSKI,R.A.; HULBERT,S.L.

    2001-10-08

    We have measured the Ag and Pd M{sub 5}VV Auger spectrum in coincidence with Ag and Pd 4d{sub 5/2} photoelectrons for the Ag/Cu(100) and Pd/Cu(100) systems, respectively, as a function of admetal coverage. These systems form surface alloys (i.e. random substitutional alloys in the first atomic layer) for impurity concentrations in the 0.1 monolayer range. For these systems, the centroid of the impurity 4d levels is expected to shift away from the Fermi level by {approx}1 eV [Ruban et al., Journal of Molecular Catalysis. A 115 (1997) 421], an effect that should be easily seen in coincidence core-valence-valence Auger spectra. We find that the impurity Auger spectra of both systems shift in a manner that is consistent with d-band moving away from EF. However, the shift for Pd is considerably smaller than expected, and a shift almost absent for Ag. The disagreement between theory and experiment is most likely caused by the neglect of lattice relaxations in the calculations.

  8. Study of Ag-Pd bimetallic nanoparticles modified glassy carbon electrode for detection of L-cysteine

    NASA Astrophysics Data System (ADS)

    Murugavelu, M.; Karthikeyan, B.

    2014-11-01

    Ag-Pd bimetallic nanoparticles (Ag-Pd BNPs) as an enhanced sensing material with improved electronic transmission rates in the electrochemical sensing of L-cysteine (L-cys) has been reported. The morphology of Ag-Pd BNPs was characterized with X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM) and cyclic voltammetry (CV). Oxidation of L-cys on Ag-Pd BNPs is investigated in detail by discussing the effect of the structure and from the electrocatalytic oxidation of L-cys. We found that the Ag-Pd BNPs exhibited high electrocatalytic activity towards L-cys oxidation in neutral condition and could be used for the development of nonenzymatic L-cys sensor. Based on the efficient catalytic ability of Ag-Pd BNPs, the fabricated biosensor exhibited a wide linear range of responses to the L-cys with the concentration detection limit of nearly down to 2 mM with fast response time.

  9. Heat-induced spinodal decomposition of Ag-Cu nanoparticles.

    PubMed

    Sopoušek, Jiří; Zobač, Ondřej; Buršík, Jiří; Roupcová, Pavla; Vykoukal, Vít; Brož, Pavel; Pinkas, Jiří; Vřešt'ál, Jan

    2015-11-14

    Solvothermal synthesis was used for Ag-Cu nanoparticle (NP) preparation from metallo-organic precursors. The detailed NP characterization was performed to obtain information about nanoparticle microstructure and both phase and chemical compositions. The resulting nanoparticles exhibited chemical composition inside a FCC_Ag + FCC_Cu two-phase region. The microstructure study was performed by various methods of electron microscopy including high-resolution transmission electron microscopy (HRTEM) at an atomic scale. The HRTEM and X-ray diffraction studies showed that the prepared nanoparticles form the face centred cubic (FCC) crystal lattice where the silver atoms are randomly mixed with copper. The CALPHAD approach was used for predicting the phase diagram of the Ag-Cu system in both macro- and nano-scales. The predicted spinodal decomposition of the metastable Ag-Cu nanoparticles was experimentally induced by heating on an X-ray powder diffractometer (HT XRD). The nucleation of the Cu-rich phase was detected and its growth was studied. Changes in the Ag-rich phase were observed in situ by X-ray diffraction under vacuum. The heat treatment was conducted at different maximum temperatures up to 450 °C and the resulting particle product was analysed. The experiments were complemented by differential scanning calorimetry (DSC) measurements up to liquidus temperature. The start temperatures of the spinodal phase transformation and particle aggregation were evaluated. PMID:25929324

  10. Oxygen-induced Y surface segregation in a CuPdY ternary alloy

    SciTech Connect

    Tafen, D N.; Miller, J B.; Dogan, O N.; Baltrus, J P.; Kondratyuk, P

    2013-01-01

    We present a comprehensive theoretical and experimental study of the segregation behavior of the ternary alloy CuPdY in vacuum (i.e., the clean surface) and in the presence of oxygen. Theoretical prediction shows that for clean surface, yttrium will substitute first for Cu and then for Pd at the subsurface lattice site before segregating to the surface where it substitutes for Cu. XRD characterization of the surface of CuPdY indicates the presence of two major phases, B2 CuPd and Pd{sub 3}Y. In the presence of adsorbed oxygen, theory predicts that Y preferentially occupies surface sites due to its stronger oxygen affinity compared to Cu and Pd. XPS experiments confirm the computational results in the adsorbed oxygen case, showing that surface segregation of yttrium is induced by the formation of Y-oxides at the top-surface of the alloy.

  11. Size and alloying induced changes in lattice constant, core, and valance band binding energy in Pd-Ag, Pd, and Ag nanoparticles: Effect of in-flight sintering temperature

    NASA Astrophysics Data System (ADS)

    Sengar, Saurabh K.; Mehta, B. R.; Govind

    2012-07-01

    In the present study, we report the growth of size selected Pd, Ag, and Pd-Ag alloy nanoparticles by an integrated method comprising of the gas phase synthesis, electrical mobility size selection, and in-flight sintering steps. Effect of temperature during in-flight sintering on nanoparticle size, crystal structure, and electronic properties has been studied. XRD studies show lattice expansion in Pd and Ag nanoparticles and lattice contraction in Pd-Ag alloy nanoparticles on increasing the sintering temperatures. In case of Pd and Ag nanoparticles, size induced changes in lattice constants are consistent with the changes in the binding energy positions with respect to bulk values. In case of Pd-Ag alloy nanoparticles, change in nanoparticle size and composition on sintering affect the lattice constant and binding energy positions. Large changes in Pd4d valance band centroid in Pd-Ag nanoparticles are due to size and alloying effects. The results of this study are important for understanding the correlation between electronic properties and Pd-H interaction in Pd alloy nanoparticles.

  12. Pb-free Sn-Ag-Cu ternary eutectic solder

    DOEpatents

    Anderson, I.E.; Yost, F.G.; Smith, J.F.; Miller, C.M.; Terpstra, R.L.

    1996-06-18

    A Pb-free solder includes a ternary eutectic composition consisting essentially of about 93.6 weight % Sn-about 4.7 weight % Ag-about 1.7 weight % Cu having a eutectic melting temperature of about 217 C and variants of the ternary composition wherein the relative concentrations of Sn, Ag, and Cu deviate from the ternary eutectic composition to provide a controlled melting temperature range (liquid-solid ``mushy`` zone) relative to the eutectic melting temperature (e.g. up to 15 C above the eutectic melting temperature). 5 figs.

  13. Pb-free Sn-Ag-Cu ternary eutectic solder

    DOEpatents

    Anderson, Iver E.; Yost, Frederick G.; Smith, John F.; Miller, Chad M.; Terpstra, Robert L.

    1996-06-18

    A Pb-free solder includes a ternary eutectic composition consisting essentially of about 93.6 weight % Sn-about 4.7 weight % Ag-about 1.7 weight % Cu having a eutectic melting temperature of about 217.degree. C. and variants of the ternary composition wherein the relative concentrations of Sn, Ag, and Cu deviate from the ternary eutectic composition to provide a controlled melting temperature range (liquid-solid "mushy" zone) relative to the eutectic melting temperature (e.g. up to 15.degree. C. above the eutectic melting temperature).

  14. Microstructure and Corrosion Behavior of the Cu-Pd-X Ternary Alloys for Hydrogen Separation Membranes

    SciTech Connect

    O.N. Dogan; M.C. Gao; B.H. Howard

    2012-02-26

    CuPd alloys are among the most promising candidate materials for hydrogen separation membranes and membrane reactor applications due to their high hydrogen permeability and better sulfur resistance. In order to reduce the Pd content and, therefore, the cost of the membrane materials, efforts have been initiated to develop CuPdM ternary alloys having a bcc structure. The advantages of having Pd as a hydrogen separation membrane are: (1) high hydrogen selectivity; and (2) high hydrogen permeability. The disadvantages are: (1) high cost; (2) hydrogen embrittlement ({alpha} {yields} {beta} Pd hydride); and (3) sulfur poisoning. Experiments (XRD, SEM/EDS) verified that Mg, Al, La, Y and Ti are promising alloying elements to expand the B2 phase region in Cu-Pd binary system. HT-XRD showed that the B2 to FCC transition temperatures for Cu-Pd-X (X = Mg, Al, La, Y and Ti) are higher than that of Cu-Pd binary alloys. While the Cu-50Pd alloy had the highest corrosion resistance to the H2S containing syngas, the Cu-Pd-Mg alloy had a comparable resistance.

  15. Development of Pd-Cu/hematite catalyst for selective nitrate reduction.

    PubMed

    Jung, Sungyoon; Bae, Sungjun; Lee, Woojin

    2014-08-19

    A new hematite-supported Pd-Cu bimetallic catalyst (Pd-Cu/hematite) was developed in order to actively and selectively reduce nitrate (NO3(-)) to nitrogen gas (N2). Four different iron-bearing soil minerals (hematite (H), goethite (G), maghemite (M), and lepidocrocite (L)) were transformed to hematite by calcination and used for synthesis of different Pd-Cu/hematite-H, G, M, and L catalysts. Their characteristics were identified using X-ray diffraction (XRD), specific surface area (BET), temperature programed reduction (TPR), transmission electron microscopy with energy dispersive X-ray (TEM-EDX), H2 pulse chemisorption, zeta-potential, and X-ray photoelectron spectroscopy (XPS). Pd-Cu/hematite-H exhibited the highest NO3(-) removal (96.4%) after 90 min, while a lower removal (90.9, 51.1, and 30.5%) was observed in Pd-Cu/hematite-G, M, and L, respectively. The results of TEM-EDX, and TPR analysis revealed that Pd-Cu/hematite-H possessed the closest contact distance between the Cu and Pd sites on the hematite surface among the different Pd-Cu/hematite catalysts. The high removal can be also attributed to the highly active metallic sites on its positively charged surface. The XPS analysis demonstrated that the amount of hydrogen molecules can have a pivotal function on NO3(-) removal and a ratio of nitrogen to hydrogen molecule (N:H) on the Pd sites can critically determine N2 selectivity. PMID:25076058

  16. Synthesis of Cu core Ag shell nanoparticles using chemical reduction method

    NASA Astrophysics Data System (ADS)

    Chinh Trinh, Dung; Dung Dang, Thi My; Khanh Huynh, Kim; Fribourg-Blanc, Eric; Chien Dang, Mau

    2015-01-01

    A simple chemical reduction method is used to prepare colloidal bimetallic Cu-Ag core-shell (Cu@Ag) nanoparticles. Polyvinyl pyrrolidone (PVP) was used as capping agent, and ascorbic acid (C6H8O6) and sodium borohydride (NaBH4) were used as reducing agents. The obtained Cu@Ag nanoparticles were characterized by powder x-ray diffraction (XRD), transmission electron microscopy (TEM) and UV-vis spectrophotometry. The influence of [Ag]/[Cu] molar ratios on the formation of Ag coatings on the Cu particles was investigated. From the TEM results we found that the ratio [Ag+]/[Cu2+] = 0.2 is the best for the stability of Cu@Ag nanoparticles with an average size of 22 nm. It is also found out that adding ammonium hydroxide (NH4OH) makes the obtained Cu@Ag nanoparticles more stable over time when pure deionized water is used as solvent.

  17. Selective Hydrogenation of Phenylacetylene on Bimetallic Cu-Pd and Cu-Pt Catalysts

    NASA Astrophysics Data System (ADS)

    Cladaras, George

    The development of selective catalysts has become a key concept in improving the efficiency of processes. Controlling the product distribution of a reaction can result in fewer by-products and reduce energy requirements for process equipment downstream. The selective hydrogenation of alkynes to alkenes is of major importance to industrial polymerization processes where alkyne/diene impurities can poison the polymerization catalyst and have an unwanted inhibiting effect on the growth of the polymer chain. In many circumstances, bimetallic catalysts have proved to have superior catalytic properties such as greater activity, selectivity or stability compared to their monometallic analogs. A study by the Sykes group (Chemistry, Tufts) in collaboration with our group has shown that in ultra-high vacuum (UHV), the addition of Pd minority species (0.01 ML) onto an otherwise inert Cu(111) single crystal surface can activate the Cu surface for selective hydrogenation reactions. This thesis work is an extension of the surface science study to the preparation of bimetallic catalysts at the nanoscale and their testing in hydrogenation reactions at ambient reaction conditions. The overall aim of this work was to develop single atom alloy Pd-Cu and Pt-Cu catalysts which are highly active and selective for the selective hydrogenation reaction of phenylacetylene to styrene. The bimetallic catalysts were prepared by a colloidal synthesis of Cu nanoparticles immobilized on gamma-alumina support and the precious metals as a minority species were deposited by galvanic replacement. The prepared materials and synthesis technique were characterized with electron microscopy (TEM), UV-Vis spectroscopy, X-Ray diffraction (XRD), temperature programmed reduction (TPR), BET surface area measurements, chemisorption experiments and X-ray photoelectron spectroscopy (XPS). The resulting catalysts can be described as gamma-Al2O3 supported Cu nanoparticles with a narrow size distribution. The Pt/Pd

  18. Electrochemical synthesis of fractal bimetallic Cu/Ag nanodendrites for efficient surface enhanced Raman spectroscopy.

    PubMed

    Li, Da; Liu, Jingquan; Wang, Hongbin; Barrow, Colin J; Yang, Wenrong

    2016-09-21

    Here, we for the first time synthesized bimetallic Cu/Ag dendrites on graphene paper (Cu/Ag@G) using a facile electrodeposition method to achieve efficient SERS enhancement. Cu/Ag@G combined the electromagnetic enhancement of Cu/Ag dendrites and the chemical enhancement of graphene. SERS was ascribed to the rough metal surface, the synergistic effect of copper and silver nanostructures and the charge transfer between graphene and the molecules. PMID:27522964

  19. Synergic Catalysis of PdCu Alloy Nanoparticles within a Macroreticular Basic Resin for Hydrogen Production from Formic Acid.

    PubMed

    Mori, Kohsuke; Tanaka, Hiromasa; Dojo, Masahiro; Yoshizawa, Kazunari; Yamashita, Hiromi

    2015-08-17

    Highly dispersed PdCu alloy nanoparticles have been successfully prepared within a macroreticular basic resin bearing N(CH3 )2 functional groups. This previously unappreciated combination of alloy is first proven to be responsible for the efficient production of high-purity H2 from formic acid (HCOOH) dehydrogenation for chemical hydrogen storage. By the addition of Cu, the electronically promoted Pd sites show significantly higher catalytic activity as well as a better tolerance towards CO poisoning as compared to their monometallic Pd counterparts. Experimental and DFT calculation studies revealed not only the synergic alloying effect but also cooperative action by the N(CH3 )2 groups within the resin play crucial roles in achieving exceptional catalytic performances. In addition to the advantages such as, facile preparation method, free of additives, recyclable without leaching of active component, and suppression of unfavorable CO formation less than 3 ppm, the present catalytic system is cost-effective because of the superior catalytic activity compared with that of well-established precious PdAg or PdAu catalysts. The present catalytic system is particularly desirable for an ideal hydrogen vector in terms of potential industrial application for fuel cells. PMID:26178687

  20. Facile synthesis of PdAgTe nanowires with superior electrocatalytic activity

    NASA Astrophysics Data System (ADS)

    Hong, Wei; Wang, Jin; Wang, Erkang

    2014-12-01

    In this work, ultrathin Te nanowires (NWs) with high-aspect-ratio are prepared by a simple hydrothermal method. By using Te NWs as the sacrificial template, we demonstrate a facile and efficient method for the synthesis of PdAgTe NWs with high-quality through the partly galvanic replacement between Te NWs and the corresponding noble metal salts precursors in an aqueous solution. The compositions of PdAgTe NWs can be tuned by simply altering the concentration of the precursors. After cyclic voltammetry treatment, multi-component PdAgTe NW with a highly active and stable surface can be obtained. The structure and composition of the as-prepared nanomaterials are analyzed by transmission electron microscope, X-ray diffraction, energy dispersive X-ray spectroscopy, inductively coupled plasma-mass spectroscopy and X-ray photoelectron spectroscopy. Electrochemical catalytic measurement results prove that the as synthesized PdAgTe NWs present superior catalytic activity toward ethanol electrooxidation in alkaline solution than the commercial Pd/C catalyst, which making them can be used as effective catalysts for the direct ethanol fuel cells.

  1. Effect of Annealing Twins on Electromigration in Ag-8Au-3Pd Bonding Wires

    NASA Astrophysics Data System (ADS)

    Chuang, Tung-Han; Wang, Hsi-Ching; Chuang, Chien-Hsun; Lee, Jun-Der; Tsai, Hsing-Hua

    2013-03-01

    An innovative Ag-8Au-3Pd bonding wire with a high twin density has been produced. The grain size of this annealing-twinned wire changes moderately during electrical stressing, unlike that of the conventional grained wire, which increases drastically and even leads to a bamboo structure. In addition, the durability against electromigration of the annealing-twinned Ag-8Au-3Pd alloy wire is higher than that of the conventional grained wire. This higher durability can be ascribed to the surface reconstruction of a stepwise morphology and slow grain growth resulting from the abundance of annealing twins in this wire.

  2. Enhanced formic acid electro-oxidation reaction on ternary Pd-Ir-Cu/C catalyst

    NASA Astrophysics Data System (ADS)

    Chen, Jinwei; Zhang, Jie; Jiang, Yiwu; Yang, Liu; Zhong, Jing; Wang, Gang; Wang, Ruilin

    2015-12-01

    Aim to further reduce the cost of Pd-Ir for formic acid electro-oxidation (FAEO), the Cu was used to construct a ternary metallic alloy catalyst. The prepared catalysts are characterized using XRD, TGA, EDX, TEM, XPS, CO-stripping, cyclic voltammetry and chronoamperometry. It is found that the Pd18Ir1Cu6 nanoparticles with a mean size of 3.3 nm are highly dispersed on carbon support. Componential distributions on catalyst are consistent with initial contents. Electrochemical measurements show that the PdIrCu/C catalyst exhibits the highest activity for FAEO. The mass activity of Pd in Pd18Ir1Cu6/C at 0.16 V (vs. SCE) is about 1.47, 1.62 and 2.08 times as high as that of Pd18Cu6/C, Pd18Ir1/C and Pd/C, respectively. The activity enhancement of PdIrCu/C should be attributed to the weakened CO adsorption strength and the removal of adsorbed intermediates at lower potential with the addition of Cu and Ir.

  3. Pd@Ag Nanosheets in Combination with Amphotericin B Exert a Potent Anti-Cryptococcal Fungicidal Effect

    PubMed Central

    Wang, Guizhen; Fang, Wei; Ye, Chen; Hu, Hanhua; Fa, Zhenzong; Yi, Jiu; Liao, Wan-qing

    2016-01-01

    Silver nanoparticles have received considerable interest as new “nanoantibiotics” with the potential to kill drug-resistant microorganisms. Recently, a class of new core-shell nanostructures, Pd@Ag nanosheets (Pd@Ag NSs), were created using deposition techniques and demonstrated excellent inhibitory effects on various bacteria in vitro. In this study, we evaluated the antifungal activity of Pd@Ag NSs against common invasive fungal pathogens. Among these organisms, Cryptococcus neoformans complex species was most susceptible to Pd@Ag NSs, which exhibited potent antifungal activity against various molecular types or sources of cryptococcal strains including fluconazole-resistant isolates. The anticryptococcal activity of Pd@Ag NSs was significantly greater than fluconazole and similar to that of amphotericin B (AmB). At relatively high concentrations, Pd@Ag NSs exhibited fungicidal activity against Cryptococcus spp., which can likely be attributed to the disruption of cell integrity, intracellular protein synthesis, and energy metabolism. Intriguingly, Pd@Ag NSs also exhibited strong synergistic anti-cryptococcal fungicidal effects at low concentrations in combination with AmB but exhibited much better safety in erythrocytes than AmB, even at the minimal fungicidal concentration. Therefore, Pd@Ag NSs may be a promising adjunctive agent for treating cryptococcosis, and further investigation for clinical applications is required. PMID:27271376

  4. Sonogashira couplings on the surface of montmorillonite-supported Pd/Cu nanoalloys.

    PubMed

    Xu, Wei; Sun, Huaming; Yu, Bo; Zhang, Guofang; Zhang, Weiqiang; Gao, Ziwei

    2014-11-26

    To explore the true identity of palladium-catalyzed Sonogashira coupling reaction, montmorillonite (MMT)-supported transition metal nanoparticles (MMT@M, M=Pd, Cu, Fe, and Ni) were prepared, characterized, and evaluated systematically. Among all MMT@M catalysts, MMT@Pd/Cu showed the highest activity, and it was successfully extended to 20 examples with 57%-97% yields. The morphology characterization of MMT@Pd/Cu revealed that the crystalline bimetallic particles were dispersed on a MMT layer as nanoalloy with diameters ranged from 10 to 11 nm. In situ IR analysis using CO as molecular probe and XPS characterization found that the surface of Pd/Cu particles consisted of both catalytic active sites of Pd(0) and Cu(I). The experiments on the catalytic activities of MMT@M found that Pd/Cu catalyst system exhibited high activity only in nanoalloy form. Therefore, the Pd/Cu nanoalloy was identified as catalyst, on which the interatom Pd/Cu transmetalation between surfaces was proposed to be responsible for its synergistic activity. PMID:25315209

  5. Ordered PdCu-Based Nanoparticles as Bifunctional Oxygen-Reduction and Ethanol-Oxidation Electrocatalysts.

    PubMed

    Jiang, Kezhu; Wang, Pengtang; Guo, Shaojun; Zhang, Xu; Shen, Xuan; Lu, Gang; Su, Dong; Huang, Xiaoqing

    2016-07-25

    The development of superior non-platinum electrocatalysts for enhancing the electrocatalytic activity and stability for the oxygen-reduction reaction (ORR) and liquid fuel oxidation reaction is very important for the commercialization of fuel cells, but still a great challenge. Herein, we demonstrate a new colloidal chemistry technique for making structurally ordered PdCu-based nanoparticles (NPs) with composition control from PdCu to PdCuNi and PtCuCo. Under the dual tuning on the composition and intermetallic phase, the ordered PdCuCo NPs exhibit better activity and much enhanced stability for ORR and ethanol-oxidation reaction (EOR) than those of disordered PdCuM NPs, the commercial Pt/C and Pd/C catalysts. The density functional theory (DFT) calculations reveal that the improved ORR activity on the PdCuM NPs stems from the catalytically active hollow sites arising from the ligand effect and the compressive strain on the Pd surface owing to the smaller atomic size of Cu, Co, and Ni. PMID:27253520

  6. Distribution of Precious Metals (Ag, Au, Pd, Pt, and Rh) Between Copper Matte and Iron Silicate Slag

    NASA Astrophysics Data System (ADS)

    Avarmaa, Katri; Johto, Hannu; Taskinen, Pekka

    2016-02-01

    The distributions of precious metals (Ag, Au, Pd, Pt, and Rh) between copper matte and silica-saturated iron silicate slag were determined at 1523 K to 1623 K (1250 °C to 1350 °C), in controlled CO-CO2-SO2-Ar gas mixtures. The experiments were done in silica crucibles and a fixed partial pressure of sulfur dioxide for matte grades of 55, 65, and 75 wt pct Cu. High-temperature equilibration/quenching/electron probe X-ray microanalysis technique was used to obtain compositions of the equilibrated matte and slag. The technique was applied for the first time to the distributions of precious metals in simulated flash smelting conditions. The resolution of electron probe microanalysis became critical as the detection limits were insufficient to measure reliably the precious metals concentrations (except silver) in the slag. The distribution coefficient of silver, L m/s[Ag] = [wt pctAg in matte]/(wt pctAg in slag), was found to be between 200 and 300, which agrees well with the latest studies in the literature. For other precious metals, the minimum values of distribution coefficients were determined according to the detection limits in the slag. The values obtained were for gold and platinum >250, for palladium >1000, and for rhodium >900. The distribution coefficients of palladium, although locating above distribution coefficient of the detection limit, formed a clear dependency with a good repeatability as a function of the matte grade. It increased along with matte grade and was approximately 1000 at 50 pct Cu and 2000 to 3000 at 70 pct Cu. The precious metals replace metal in the matte structure and they are present as sulfides in the copper matte.

  7. Diffusion of Cu adatoms and dimers on Cu(111) and Ag(111) surfaces

    NASA Astrophysics Data System (ADS)

    Mińkowski, Marcin; Załuska-Kotur, Magdalena A.

    2015-12-01

    Diffusion of Cu adatoms and dimers on Cu(111) and Ag(111) surfaces is analyzed based on ab initio surface potentials. Single adatom diffusion is compared with dimer diffusion on both surfaces. Surface geometry makes the adatoms jump alternately between two states in the same way in both systems, whereas dimers undergo more complex diffusion process that combines translational and rotational motion. Small difference in the surface lattice constant between Cu and Ag crystals results in a completely different energy landscape for dimer jumps. As an effect the character of diffusion process changes. Homogeneous Cu dimer diffusion is more difficult and dimers rather rotate within single surface cell, whereas diffusion over Ag surface is faster and happens more smoothly. The temperature dependence of diffusion coefficient and its parameters: energy barrier and prefactor is calculated and compared for both surfaces.

  8. Facile synthesis of Cu-Pd bimetallic multipods for application in cyclohexane oxidation

    NASA Astrophysics Data System (ADS)

    Zhang, Zhuo-Qun; Huang, Jianliu; Zhang, Lan; Sun, Mei; Wang, You-Cheng; Lin, Yue; Zeng, Jie

    2014-10-01

    The synergy between Cu and Pd makes Cu-Pd bimetallic nanocrystals interesting materials for investigation. The scarcity of shapes of Cu-Pd bimetallic nanocrystals motivated us to explore highly branched structures, which may promote a wide range of applications. In this communication, we report a facile synthesis of Cu-Pd bimetallic multipods (19.2 ± 1.2 nm), on branches of which some high-index facets were exposed. Modification of reaction parameters concerning capping agents and reductant led to the formation of other shapes, including sphere-like nanocrystals (SNCs). When loaded onto TiO2, the as-prepared Cu-Pd bimetallic multipods exhibited excellent catalytic activity for the oxidation of cyclohexane by hydrogen peroxide and higher selectivity towards cyclohexanone than monometallic catalysts and SNCs/TiO2.

  9. Facile synthesis of Cu-Pd bimetallic multipods for application in cyclohexane oxidation.

    PubMed

    Zhang, Zhuo-Qun; Huang, Jianliu; Zhang, Lan; Sun, Mei; Wang, You-Cheng; Lin, Yue; Zeng, Jie

    2014-10-31

    The synergy between Cu and Pd makes Cu-Pd bimetallic nanocrystals interesting materials for investigation. The scarcity of shapes of Cu-Pd bimetallic nanocrystals motivated us to explore highly branched structures, which may promote a wide range of applications. In this communication, we report a facile synthesis of Cu-Pd bimetallic multipods (19.2 ± 1.2 nm), on branches of which some high-index facets were exposed. Modification of reaction parameters concerning capping agents and reductant led to the formation of other shapes, including sphere-like nanocrystals (SNCs). When loaded onto TiO2, the as-prepared Cu-Pd bimetallic multipods exhibited excellent catalytic activity for the oxidation of cyclohexane by hydrogen peroxide and higher selectivity towards cyclohexanone than monometallic catalysts and SNCs/TiO2. PMID:25297725

  10. Morphology and N₂ Permeance of Sputtered Pd-Ag Ultra-Thin Film Membranes.

    PubMed

    Fernandez, Ekain; Sanchez-Garcia, Jose Angel; Viviente, Jose Luis; van Sint Annaland, Martin; Gallucci, Fausto; Tanaka, David A Pacheco

    2016-01-01

    The influence of the temperature during the growth of Pd-Ag films by PVD magnetron sputtering onto polished silicon wafers was studied in order to avoid the effect of the support roughness on the layer growth. The surfaces of the Pd-Ag membrane films were analyzed by atomic force microscopy (AFM), and the results indicate an increase of the grain size from 120 to 250-270 nm and film surface roughness from 4-5 to 10-12 nm when increasing the temperature from around 360-510 K. After selecting the conditions for obtaining the smallest grain size onto silicon wafer, thin Pd-Ag (0.5-2-µm thick) films were deposited onto different types of porous supports to study the influence of the porous support, layer thickness and target power on the selective layer microstructure and membrane properties. The Pd-Ag layers deposited onto ZrO₂ 3-nm top layer supports (smallest pore size among all tested) present high N₂ permeance in the order of 10(-6) mol·m(-2)·s(-1)·Pa(-1) at room temperature. PMID:26875977

  11. Monodispersed bimetallic PdAg nanoparticles with twinned structures: formation and enhancement for the methanol oxidation.

    PubMed

    Yin, Zhen; Zhang, Yining; Chen, Kai; Li, Jing; Li, Wenjing; Tang, Pei; Zhao, Huabo; Zhu, Qingjun; Bao, Xinhe; Ma, Ding

    2014-01-01

    Monodispersed bimetallic PdAg nanoparticles can be fabricated through the emulsion-assisted ethylene glycol (EG) ternary system. Different compositions of bimetallic PdAg nanoparticles, Pd₈₀Ag₂₀, Pd₆₅Ag₃₅ and Pd₄₆Ag₅₄ can be obtained via adjusting the reaction parameters. For the formation process of the bimetallic PdAg nanoparticles, there have two-stage growth processes: firstly, nucleation and growth of the primary nanoclusters; secondly, formation of the secondary nanoparticles with the size-selection and relax process via the coalescence or aggregation of the primary nanoclusters. The as-prepared PdAg can be supported on the carbon black without any post-treatment, which exhibited high electro-oxidation activity towards methanol oxidation under alkaline media. More importantly, carbon-supported Pd₈₀Ag₂₀ nanoparticles reveal distinctly superior activities for the methanol oxidation, even if compared with commercial Pt/C electro-catalyst. It is concluded that the enhanced activity is dependant on the unique twinning structure with heterogeneous phase due to the dominating coalescence growth in EG ternary system. PMID:24608736

  12. Microstructure of Cu-Ag Uniform Nanoparticulate Films on Polyurethane 3D Catheters: Surface Properties.

    PubMed

    Rtimi, Sami; Sanjines, Rosendo; Pulgarin, Cesar; Kiwi, John

    2016-01-13

    The preparation, characterization, and antibacterial testing of Cu-Ag sputtered polyurethane (PU) catheters are addressed in this study. PU catheters with different atomic ratios Cu:Ag have been sputtered and led to different optical properties as followed by diffuse reflectance spectroscopy (DRS) and the surface redox properties were also different for different Cu-Ag ratios as observed by X-ray photoelectron spectroscopy (XPS). The surface atomic percentage concentration of the oxidized/reduced C-species originating from bacterial cultures before and after bacterial inactivation were determined on the Cu-Ag PU catheters. The crystallographic properties were determined by X-ray diffraction (XRD). The XRD-diffractogram showed the presence of Cu2O (111), Cu (200), CuO (020), and Ag (111) indicating that Cu nanoparticles present a more crystalline character compared to Ag nanoparticles. Increasing the percentage of Ag in the Cu-Ag films, bigger Ag-particle agglomerates were detected by scanning transmission electron microscopy (STEM) microanalysis confirming the results obtained by AFM. The bacterial inactivation kinetics of the sputtered Cu-Ag films on PU catheters was investigated in detail. Quasi-instantaneous bacterial inactivation kinetics was induced by the sputtered films on PU catheters after optimization of the Cu-Ag film thickness. PMID:26700113

  13. Growth of Pt/Cu(100): An Atomistic Modeling Comparison with the Pd/Cu(100) Surface Alloy

    NASA Technical Reports Server (NTRS)

    Demarco, Gustavo; Garces, Jorge E.; Bozzolo, Guillermo

    2002-01-01

    The Bozzolo, Ferrante, and Smith (BFS) method for alloys is applied to the study of Pt deposition on Cu(100). The formation of a Cu-Pt surface alloy is discussed within the framework of previous results for Pd/Cu(100). In spite of the fact that both Pd and Pt share the same basic behavior when deposited on Cu, it is seen that subtle differences become responsible for the differences in growth observed at higher cover-ages. In agreement with experiment, all the main features of Pt/Cu(100) and Pd/Cu(100) are obtained by means of a simple modeling scheme, and explained in terms of a few basic ingredients that emerge from the BFS analysis.

  14. Asymmetric AgPd-AuNR heterostructure with enhanced photothermal performance and SERS activity.

    PubMed

    Zhang, Han; Liu, Zeke; Kang, Xiaolin; Guo, Jun; Ma, Wanli; Cheng, Si

    2016-01-28

    Most as-reported nanostructures through galvanic replacement reactions are still symmetric hollow structures, until now. Asymmetric structures fabricated through a galvanic replacement reaction have been rarely reported. However, asymmetric heterostructures can generally lead to new intriguing properties through asymmetric synergistic coupling. Here, we report a simple synthesis of an asymmetric one-ended AgPd bimetal on Au nanorods (AuNR) by combining a galvanic replacement reaction with an Ostwald ripening process. The morphological evolution from a nanodumbbell to a dandelion structure is thoroughly investigated. The unique asymmetric AgPd-AuNR heterostructures possess the required plasmonic performance and avoid strong damping caused by the poor plasmonic metal Pd, resulting in a superior photothermal heating performance and enhanced SERS sensitivity for in situ monitoring of a catalytic reaction compared with the symmetric counterparts. PMID:26744075

  15. Characterization of Ag-Pd nanocomposite paste for electrochemical migration resistance.

    PubMed

    Kim, Kwang-Seok; Jung, Kwang-Ho; Park, Bum-Geun; Shin, Young-Eui; Jung, Seung-Boo

    2013-11-01

    Direct printing such as inkjet, gravure, and screen printing is an attractive approach for achieving low-cost circuitry in the printed circuit board industry. One of the challenges for direct printing technology, however, is the poor resistance to electrochemical migration (ECM), especially for silver (Ag) which has been widely used in printed electronics. We demonstrate improved resistance to Ag electrochemical migration by adding palladium (Pd) nanoparticles to the Ag nanopaste. Conductive comb-type patterns were fabricated on a bismaleimide-triazine substrate via screen printing. Their ECM characteristics were assessed by water drop test with deionized water. These results showed that the ECM time required for dendritic growth from cathode to anode to cause short-circuit failure was affected by the Pd content and applied voltages: the ECM time of Ag-15wt.% Pd nanopaste was nearly threefold that of Ag nanopaste, and the ECM time decreased by 94.22%, on average, while the applied voltage increased from 3 V to 9 V. PMID:24245303

  16. Photoluminescence of SrS:Cu,Ag and SrS 1- xSe x:Cu,Ag thin films

    NASA Astrophysics Data System (ADS)

    Poelman, D.; Wauters, D.; Van Meirhaeghe, R. L.; Cardon, F.

    2000-01-01

    The photoluminescence (PL) of SrS:Cu,Ag and SrS 1- xSe x:Cu,Ag thin films has been investigated. The influence of rapid thermal annealing conditions and Cu dopant concentration on the PL intensity has been studied. The PL emission spectrum was measured as a function of both Cu concentration and temperature. An unexpected PL intensity peak was observed around a temperature of 54 K.

  17. Recrystallization of Cu-poor CuInS{sub 2} assisted by metallic Cu or Ag

    SciTech Connect

    Rodriguez-Alvarez, Humberto; Mainz, Roland; Marsen, Bjoern; Schock, Hans-Werner

    2010-04-15

    We monitor the recrystallization of Cu-poor CuInS{sub 2} thin films assisted by pure Cu or pure Ag by means of real-time synchrotron-based polychromatic X-ray diffraction. In both cases a new microstructure is formed accompanied by an increase in grain size. In the case of Cu, the onset temperature of the thin-film recrystallization is higher than 370 deg. C. In the case of Ag, the thin-film recrystallization comes to an end at 270 deg. C. The Ag-assisted recrystallization occurs in the presence of the body-centered cubic beta-Ag{sub 2}S phase. We find that domain growth and diffusion of silver into the film occur simultaneously. - Graphical abstract Keywords: Recrystallization; Thin-film solar cells; Energy-dispersive x-ray diffraction: In-situ monitoring by means of energy-dispersive X-ray diffraction of the thin-film recrystallization of Cu-poor CuInS{sub 2} assisted by metallic Ag.

  18. Asymmetric AgPd-AuNR heterostructure with enhanced photothermal performance and SERS activity

    NASA Astrophysics Data System (ADS)

    Zhang, Han; Liu, Zeke; Kang, Xiaolin; Guo, Jun; Ma, Wanli; Cheng, Si

    2016-01-01

    Most as-reported nanostructures through galvanic replacement reactions are still symmetric hollow structures, until now. Asymmetric structures fabricated through a galvanic replacement reaction have been rarely reported. However, asymmetric heterostructures can generally lead to new intriguing properties through asymmetric synergistic coupling. Here, we report a simple synthesis of an asymmetric one-ended AgPd bimetal on Au nanorods (AuNR) by combining a galvanic replacement reaction with an Ostwald ripening process. The morphological evolution from a nanodumbbell to a dandelion structure is thoroughly investigated. The unique asymmetric AgPd-AuNR heterostructures possess the required plasmonic performance and avoid strong damping caused by the poor plasmonic metal Pd, resulting in a superior photothermal heating performance and enhanced SERS sensitivity for in situ monitoring of a catalytic reaction compared with the symmetric counterparts.Most as-reported nanostructures through galvanic replacement reactions are still symmetric hollow structures, until now. Asymmetric structures fabricated through a galvanic replacement reaction have been rarely reported. However, asymmetric heterostructures can generally lead to new intriguing properties through asymmetric synergistic coupling. Here, we report a simple synthesis of an asymmetric one-ended AgPd bimetal on Au nanorods (AuNR) by combining a galvanic replacement reaction with an Ostwald ripening process. The morphological evolution from a nanodumbbell to a dandelion structure is thoroughly investigated. The unique asymmetric AgPd-AuNR heterostructures possess the required plasmonic performance and avoid strong damping caused by the poor plasmonic metal Pd, resulting in a superior photothermal heating performance and enhanced SERS sensitivity for in situ monitoring of a catalytic reaction compared with the symmetric counterparts. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr07333b

  19. Hollow raspberry-like PdAg alloy nanospheres: High electrocatalytic activity for ethanol oxidation in alkaline media

    NASA Astrophysics Data System (ADS)

    Peng, Cheng; Hu, Yongli; Liu, Mingrui; Zheng, Yixiong

    2015-03-01

    Palladium-silver (PdAg) alloy nanospheres with unique structure were prepared using a one-pot procedure based on the galvanic replacement reaction. Their electrocatalytic activity for ethanol oxidation in alkaline media was evaluated. The morphology and crystal structure of the samples were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM) and X-ray diffraction (XRD). Electrochemical characterization techniques, including cyclic voltammetry (CV) and chronoamperometry (CA) measurements were used to analyze the electrochemical performance of the PdAg alloy nanospheres. The SEM and TEM images showed that the PdAg alloy nanospheres exhibit a hierarchical nanostructure with hollow interiors and porous walls. Compared to the commercial Pd/C catalyst, the as-prepared PdAg alloy nanospheres exhibit superior electrocatalytic activity and stability towards ethanol electro-oxidation in alkaline media, showing its potential as a new non-Pt electro-catalyst for direct alcohol fuel cells (DAFCs).

  20. Au-Ag-Cu nano-alloys: tailoring of permittivity

    NASA Astrophysics Data System (ADS)

    Hashimoto, Yoshikazu; Seniutinas, Gediminas; Balčytis, Armandas; Juodkazis, Saulius; Nishijima, Yoshiaki

    2016-04-01

    Precious metal alloys enables new possibilities to tailor materials for specific optical functions. Here we present a systematic study of the effects of a nanoscale alloying on the permittivity of Au-Ag-Cu metals at 38 different atomic mixing ratios. The permittivity was measured and analyzed numerically by applying the Drude model. X-ray diffraction (XRD) revealed the face centered cubic lattice of the alloys. Both, optical spectra and XRD results point towards an equivalent composition-dependent electron scattering behavior. Correlation between the fundamental structural parameters of alloys and the resulting optical properties is elucidated. Plasmonic properties of the Au-Ag-Cu alloy nanoparticles were investigated by numerical simulations. Guidelines for designing plasmonic response of nano- structures and their patterns are presented from the material science perspective.

  1. Au-Ag-Cu nano-alloys: tailoring of permittivity

    PubMed Central

    Hashimoto, Yoshikazu; Seniutinas, Gediminas; Balčytis, Armandas; Juodkazis, Saulius; Nishijima, Yoshiaki

    2016-01-01

    Precious metal alloys enables new possibilities to tailor materials for specific optical functions. Here we present a systematic study of the effects of a nanoscale alloying on the permittivity of Au-Ag-Cu metals at 38 different atomic mixing ratios. The permittivity was measured and analyzed numerically by applying the Drude model. X-ray diffraction (XRD) revealed the face centered cubic lattice of the alloys. Both, optical spectra and XRD results point towards an equivalent composition-dependent electron scattering behavior. Correlation between the fundamental structural parameters of alloys and the resulting optical properties is elucidated. Plasmonic properties of the Au-Ag-Cu alloy nanoparticles were investigated by numerical simulations. Guidelines for designing plasmonic response of nano- structures and their patterns are presented from the material science perspective. PMID:27118459

  2. Au-Ag-Cu nano-alloys: tailoring of permittivity.

    PubMed

    Hashimoto, Yoshikazu; Seniutinas, Gediminas; Balčytis, Armandas; Juodkazis, Saulius; Nishijima, Yoshiaki

    2016-01-01

    Precious metal alloys enables new possibilities to tailor materials for specific optical functions. Here we present a systematic study of the effects of a nanoscale alloying on the permittivity of Au-Ag-Cu metals at 38 different atomic mixing ratios. The permittivity was measured and analyzed numerically by applying the Drude model. X-ray diffraction (XRD) revealed the face centered cubic lattice of the alloys. Both, optical spectra and XRD results point towards an equivalent composition-dependent electron scattering behavior. Correlation between the fundamental structural parameters of alloys and the resulting optical properties is elucidated. Plasmonic properties of the Au-Ag-Cu alloy nanoparticles were investigated by numerical simulations. Guidelines for designing plasmonic response of nano- structures and their patterns are presented from the material science perspective. PMID:27118459

  3. Preparation and Sintering Properties of Ag27Cu2Sn Nanopaste as Die Attach Material

    NASA Astrophysics Data System (ADS)

    Liu, Xiaojian; Liu, Wei; Wang, Chunqing; Zheng, Zhen; Kong, Lingchao

    2016-06-01

    Ag27Cu2Sn nanopaste has been prepared by mixing Ag, Cu, and Sn nanoparticles with an organic solvent system. Sintering and mechanical properties of this nanopaste were characterized and investigated. Effects of sintering temperature and time on the sintered microstructure of the nanopaste and shear strength of Cu/Ag27Cu2Sn/Cu structure were analyzed. The results showed that the organic shells coated on the outside of metal nanoparticles could effectively prevent metal nanoparticles from being oxidized below 480°C. When the paste was sintered at 480°C without pressure, few voids or large particles formed within the sintered layer and distributions of Ag, Cu, and Sn were quite uniform. This sintering temperature was much lower than the eutectic temperature (779°C) of Ag-Cu bulk material. Moreover, mutual solid solubilities of Ag and Cu were increased remarkably, which may be caused by high surface activity of Ag and Cu nanoparticles and the important role of the Sn addition. Shear strength of samples with Cu/Ag27Cu2Sn/Cu structure could reach 21 MPa, which could compare with that of Ag nanopaste or conductive adhesives.

  4. Three-dimensional hyperbranched PdCu nanostructures with high electrocatalytic activity.

    PubMed

    Jiang, Bo; Li, Cuiling; Malgras, Victor; Bando, Yoshio; Yamauchi, Yusuke

    2016-01-21

    In this study, three-dimensional (3D) PdCu alloyed nanostructures, consisting of one-dimensional (1D) branches, were successfully synthesized through a facile wet-chemical method without using any seeds or organic solvent. The success of this approach relies on the use of hydrochloric acid (HCl) to control the reduction rate, and on the presence of bromide ions (Br(-)) to selectively adsorb on certain facets of the PdCu nucleus. The as-prepared 3D PdCu nanostructures exhibit a greatly enhanced catalytic activity toward formic acid oxidation, owing to a suitable electronic landscape resulting from the alloy structure and the unique morphology. PMID:26602439

  5. Comparative Study of ENIG and ENEPIG as Surface Finishes for a Sn-Ag-Cu Solder Joint

    NASA Astrophysics Data System (ADS)

    Yoon, Jeong-Won; Noh, Bo-In; Jung, Seung-Boo

    2011-09-01

    Interfacial reactions and joint reliability of Sn-3.0Ag-0.5Cu solder with two different surface finishes, electroless nickel-immersion gold (ENIG) and electroless nickel-electroless palladium-immersion gold (ENEPIG), were evaluated during a reflow process. We first compared the interfacial reactions of the two solder joints and also successfully revealed a connection between the interfacial reaction behavior and mechanical reliability. The Sn-Ag-Cu/ENIG joint exhibited a higher intermetallic compound (IMC) growth rate and a higher consumption rate of the Ni(P) layer than the Sn-Ag-Cu/ENEPIG joint. The presence of the Pd layer in the ENEPIG suppressed the growth of the interfacial IMC layer and the consumption of the Ni(P) layer, resulting in the superior interfacial stability of the solder joint. The shear test results show that the ENIG joint fractured along the interface, exhibiting indications of brittle failure possibly due to the brittle IMC layer. In contrast, the failure of the ENEPIG joint only went through the bulk solder, supporting the idea that the interface is mechanically reliable. The results from this study confirm that the Sn-Ag-Cu/ENEPIG solder joint is mechanically robust and, thus, the combination is a viable option for a Pb-free package system.

  6. Capability of defective graphene-supported Pd13 and Ag13 particles for mercury adsorption

    NASA Astrophysics Data System (ADS)

    Meeprasert, Jittima; Junkaew, Anchalee; Rungnim, Chompoonut; Kunaseth, Manaschai; Kungwan, Nawee; Promarak, Vinich; Namuangruk, Supawadee

    2016-02-01

    Reactivity of single-vacancy defective graphene (DG) and DG-supported Pdn and Agn (n = 1, 13) for mercury (Hg0) adsorption has been studied using density functional theory calculation. The results show that Pdn binds defective site of DG much stronger than the Agn, while metal nanocluster binds DG stronger than single metal atom. Metal clustering affects the adsorption ability of Pd composite while that of Ag is comparatively less. The binding strength of -8.49 eV was found for Pd13 binding on DG surface, indicating its high stability. Analyses of structure, energy, partial density of states, and d-band center (ɛd) revealed that the adsorbed metal atom or cluster enhances the reactivity of DG toward Hg adsorption. In addition, the Hg adsorption ability of Mn-DG composite is found to be related to the ɛd of the deposited Mn, in which the closer ɛd of Mn to the Fermi level correspond to the higher adsorption strength of Hg on Mn-DG composite. The order of Hg adsorption strength on Mn-DG composite are as follows: Pd13 (-1.68 eV) >> Ag13 (-0.67 eV) ∼ Ag1 (-0.69 eV) > Pd1 (-0.62 eV). Pd13-DG composite is therefore more efficient sorbent for Hg0 removal in terms of high stability and high adsorption reactivity compared to the Ag13. Further design of highly efficient carbon based sorbents should be focused on tailoring the ɛd of deposited metals.

  7. Electrocatalytic reduction of dioxygen on PdCu for polymer electrolyte membrane fuel cells

    NASA Astrophysics Data System (ADS)

    Martínez-Casillas, D. C.; Vázquez-Huerta, G.; Pérez-Robles, J. F.; Solorza-Feria, O.

    2011-05-01

    The present research is aimed to study the oxygen reduction reaction (ORR) on a PdCu electrocatalyst synthesized through reduction of PdCl2 and CuCl with NaBH4 in a THF solution. Characterization of PdCu electrocatalyst was performed by X-ray diffraction (XRD), transmission electron microscopy (TEM) and energy-dispersive X-ray (EDX) spectroscopy. Characterization results showed that the synthesis method produced spherical agglomerated nanocrystalline PdCu particles of about 10 nm size. The electrochemical activity was evaluated using cyclic voltammetry (CV), rotating disc electrode (RDE) and electrochemical impedance spectroscopy (EIS) in a 0.5 M H2SO4 electrolyte at 25 °C. The onset potential for ORR on PdCu is shifted by ca. 30 mV to more positive values and enhanced catalytic current densities were observed, compared to that of pure Pd catalyst. The synthesized PdCu electrocatalyst dispersed on a carbon black support was tested as cathode electrode in a membrane-electrode assembly (MEA) achieving a power density of 150 mW cm-2 at 0.38 V and 80 °C.

  8. Acetylene trimerization on Ag, Pd and Rh atoms deposited on MgO thin films.

    PubMed

    Judai, Ken; Wörz, Anke S; Abbet, Stéphane; Antonietti, Jean-Marie; Heiz, Ueli; Del Vitto, Annalisa; Giordano, Livia; Pacchioni, Gianfranco

    2005-03-01

    The acetylene trimerization on the group VIII transition metal atoms, Rh and Pd, as well as on Ag atoms supported on MgO thin films has been studied experimentally and theoretically. The three metal atoms with the atomic configurations 4d(8)5s1 (Rh), 4d10s0 (Pd) and 4d(10)5s1 (Ag) behave distinctly differently. The coinage metal atom silver is basically inert for this reaction, whereas Pd is active at 220 and 320 K, and Rh produces benzene in a rather broad temperature range from 350 to ca. 430 K. The origins of these differences are not only the different electronic configurations, leading to a weak interaction of acetylene with silver due to strong Pauli repulsion with the 5s electron but also the different stability and dynamics of the three atoms on the MgO surface. In particular, Rh and Pd atoms interact differently with surface defects like the oxygen vacancies (F centers) and the step edges. Pd atoms migrate already at low temperature exclusively to F centers where the cyclotrimerization is efficiently promoted. The Rh atoms on the other hand are not only trapped on F centers but also at step edges up to about 300 K. Interestingly, only Rh atoms on F centers catalyze the trimerization reaction whereas they are turned inert on the step edges due to strong steric effects. PMID:19791385

  9. Designed synthesis of Au/Ag/Pd trimetallic nanoparticle-based catalysts for Sonogashira coupling reactions.

    PubMed

    Venkatesan, P; Santhanalakshmi, J

    2010-07-20

    Pdnp and Pd containing trimetallic nanoparticles (tnp) are synthesized by chemical method with cetyltrimethylammonium bromide as the capping agent. Compositionally, four different tnp are prepared and the particle sizes are characterized by UV-vis spectra, HR-TEM, and XRD measurements. The catalytic activities of Pdnp and tnp are tested using the Sonogashira C-C coupling reaction. The product yield and recyclability of the recovered catalysts are studied. tnp (1:1:1) exhibited better catalysis than Pdnp, which may be due to the concerted electronic effects of the Au-Ag core onto the Pd shell atoms. PMID:20462280

  10. Isothermal Solid-State Transformation Kinetics Applied to Pd/Cu Alloy Membrane Fabrication

    SciTech Connect

    Pomerantz, Natalie L; Payzant, E Andrew; Ma, Yi Hua

    2010-01-01

    In this work, time-resolved, in situ high-temperature X-ray diffraction (HT-XRD) was used to study the solid-state transformation kinetics of the formation of the fcc Pd/Cu alloy from Pd/Cu bi-layers for the purpose of fabricating sulfur tolerant Pd/Cu membranes for H2 separation. Thin layers of Pd and Cu (total ~15 wt% Cu) were deposited on porous stainless steel (PSS) with the electroless deposition method and annealed in H2 at 500, 550 and 600 C. The kinetics of the annealing process were successfully described by the Avrami nucleation and growth model showing that the annealing process was diffusion controlled and one dimensional. The activation energy for the solid-state transformation was 175 kJ/mol, which was similar to the activation energy of Pd-Cu bulk interdiffusion. Furthermore, the Avrami model was able to successfully describe the changes in permeance and activation energy observed in Pd/Cu alloy membranes during characterization as they were annealed at high temperatures.

  11. [Synthesis of Cu2O-Ag-AgBr/MA visible photocatalyst and its performance in degradation of 2-chlorophenol].

    PubMed

    Wang, Ran; Zhou, Xue-feng; Hu, Xue-xiang; Hu, Chun

    2014-09-01

    Cu2O-Ag-AgBr/MA plasmon photocatalyst was prepared by the co-deposition of Cu2O and Ag-AgBr nanoparticles on mesoporous alumina (MA). The samples were characterized by means of X-ray diffraction (XRD) ,X-ray photoelectron spectroscopy (XPS) and diffuse reflectance UV-vis spectra (UV-vis DRS). The results showed that both Ag+ and Ag0 existed on the surface. The photocatalytic activity of the samples prepared were evaluated by degradation of 2-chlorophenol (2-CP) under visible light (λ >420 nm) irradiation. The results showed that the catalyst had high photocatalytic activity for the degradation of 2-CP. Meanwhile, the doping of Cu2O nanoparticles significantly inhibited the release of silver ions during the photocatalytic reaction, which improved the photostability of the catalyst. Analyses on the effects of various scavengers showed that h+ , O2- and OH radicals were the primary active species. PMID:25518659

  12. Selective Cu4Pd alloy nanoparticles anchoring on amine functionalized graphite nanosheets and their use as reusable catalysts for a C-C coupling reaction with the sacrificial role of Cu for Pd-regeneration.

    PubMed

    Chakravarty, Amrita; De, Goutam

    2016-08-01

    A facile method for the synthesis of phase selective alloy nanoparticles (NPs), Cu4Pd and their in situ anchoring on the surface of amine functionalized graphite nanosheets (AFGNS) by solvothermal process has been demonstrated. It has been seen that upon adding CuCl2·H2O and PdCl2 into the reaction medium containing AFGNS, the -NH2 group initially helps to immobilize Cu(2+) ions from CuCl2·H2O. During the solvothermal reaction in presence of N,N-dimethylformamide (DMF; solvent cum reducing agent) Pd(2+) gets reduced first due to its higher reduction potential. These Pd NPs in turn help in the reduction of Cu(2+) to Cu in an epitaxial manner. Finally at high temperature and long reaction time Cu and Pd combine to form the Cu4Pd alloy NPs along with a small fraction of Cu NPs. The conditions to obtain Cu4Pd NPs have been optimized through controlled reactions. The as prepared Cu4Pd@AFGNS composite has been successfully used for Suzuki-Miyuara C-C coupling reaction with sufficiently high yield and reusability of up to five cycles. The progress of the reaction was monitored using a fluorimeter. Interestingly, it has been observed that the small fraction of the Cu NPs present in the system played a sacrificial role in regenerating metallic Pd NPs in the first and second reaction cycles, followed by Cu from the Cu4Pd alloy itself from the third cycle onwards which played the sacrificial role to regenerate Pd(0). A probable reaction mechanism of the catalytic reaction with Cu4Pd@AFGNS has been suggested. PMID:27435633

  13. Structured Pd-Au/Cu-fiber catalyst for gas-phase hydrogenolysis of dimethyl oxalate to ethylene glycol.

    PubMed

    Zhang, Li; Han, Lupeng; Zhao, Guofeng; Chai, Ruijuan; Zhang, Qiaofei; Liu, Ye; Lu, Yong

    2015-07-01

    Galvanic co-deposition of 0.5 wt% Au and 0.1 wt% Pd on a microfibrous-structure using 8 μm Cu-fibers delivers a Pd-Au/Cu-fiber catalyst, which is highly active, selective and stable for the hydrogenolysis of dimethyl oxalate to ethylene glycol. Au and Pd synergistically promote the hydrogenolysis activity of Cu(+) sites, while Au also critically stabilizes Cu(+) sites to prevent deep reductive deactivation. PMID:26040855

  14. Hydrogenation of Acetylene-Ethylene Mixtures over Pd and Pd-Ag Alloys: First-Principles Based Kinetic Monte Carlo Simulations

    SciTech Connect

    Mei, Donghai; Neurock, Matthew; Smith, C Michael

    2009-10-22

    The kinetics for the selective hydrogenation of acetylene-ethylene mixtures over model Pd(111) and bimetallic Pd-Ag alloy surfaces were examined using first principles based kinetic Monte Carlo (KMC) simulations to elucidate the effects of alloying as well as process conditions (temperature and hydrogen partial pressure). The mechanisms that control the selective and unselective routes which included hydrogenation, dehydrogenation and C-C bond breaking pathways were analyzed using first-principle density functional theory (DFT) calculations. The results were used to construct an intrinsic kinetic database that was used in a variable time step kinetic Monte Carlo simulation to follow the kinetics and the molecular transformations in the selective hydrogenation of acetylene-ethylene feeds over Pd and Pd-Ag surfaces. The lateral interactions between coadsorbates that occur through-surface and through-space were estimated using DFT-parameterized bond order conservation and van der Waal interaction models respectively. The simulation results show that the rate of acetylene hydrogenation as well as the ethylene selectivity increase with temperature over both the Pd(111) and the Pd-Ag/Pd(111) alloy surfaces. The selective hydrogenation of acetylene to ethylene proceeds via the formation of a vinyl intermediate. The unselective formation of ethane is the result of the over-hydrogenation of ethylene as well as over-hydrogenation of vinyl to form ethylidene. Ethylidene further hydrogenates to form ethane and dehydrogenates to form ethylidyne. While ethylidyne is not reactive, it can block adsorption sites which limit the availability of hydrogen on the surface and thus act to enhance the selectivity. Alloying Ag into the Pd surface decreases the overall rated but increases the ethylene selectivity significantly by promoting the selective hydrogenation of vinyl to ethylene and concomitantly suppressing the unselective path involving the hydrogenation of vinyl to ethylidene

  15. Charge transfer, lattice distortion, and quantum confinement effects in Pd, Cu, and Pd-Cu nanoparticles; size and alloying induced modifications in binding energy

    SciTech Connect

    Sengar, Saurabh K.; Mehta, B. R.; Gupta, Govind

    2011-05-09

    In this letter, effect of size and alloying on the core and valence band shifts of Pd, Cu, and Pd-Cu alloy nanoparticles has been studied. It has been shown that the sign and magnitude of the binding energy shifts is determined by the contributions of different effects; with quantum confinement and lattice distortion effects overlapping for size induced shifts in case of core levels and lattice distortion and charge transfer effects overlapping for alloying induced shifts at smaller sizes. These results are important for understanding gas molecule-solid surface interaction in metal and alloy nanoparticles in terms of valance band positions.

  16. A cooperative Pd-Cu system for direct C-H bond arylation.

    PubMed

    Lesieur, Mathieu; Lazreg, Faïma; Cazin, Catherine S J

    2014-08-18

    A novel and efficient method for C-H arylation using well-defined Pd- and Cu-NHC systems has been developed. This process promotes the challenging construction of C-C bonds from arenes or heteroarenes using aryl bromides and chlorides. Mechanistic studies show that [Cu(OH)(NHC)] plays a key role in the C-H activation and is involved in the transmetallation with the Pd-NHC co-catalyst. PMID:24976025

  17. Hydrogen permeability of thin condensed Pd-Cu foil: Dependence on temperature and phase composition

    NASA Astrophysics Data System (ADS)

    Ievlev, V. M.; Solntsev, K. A.; Dontsov, A. I.; Maksimenko, A. A.; Kannykin, S. V.

    2016-03-01

    The hydrogen permeability of thin (about 4 μm thick) magnetron-sputtered Pd-Cu foil and structural transformations during temperature cycling (heating-cooling process) are studied. It is found that the hydrogen permeability is maximal when the content of the β-phase is 100%. Upon annealing of Pd-Cu alloy in hydrogen, the temperature range where a regular structure exists expands.

  18. Effect of Ag addition to L1{sub 0} FePt and L1{sub 0} FePd films grown by molecular beam epitaxy

    SciTech Connect

    Tokuoka, Y.; Seto, Y.; Kato, T.; Iwata, S.

    2014-05-07

    L1{sub 0} ordered FePt-Ag (5 nm) and FePd-Ag (5 nm) films were grown on MgO (001) substrate at temperatures of 250–400 °C by using molecular beam epitaxy method, and their crystal and surface structures, perpendicular magnetic anisotropies and Curie temperatures were investigated. In the case of FePt-Ag, Ag addition with the amount of 10–20 at. % was effective to promote L1{sub 0} ordering and granular growth, resulting in the increase of the perpendicular magnetic anisotropy and coercivity of the FePt-Ag films. On the other hand, in the case of FePd-Ag, Ag addition changed the surface morphology from island to continuous film associated with the reductions of its coercivity and perpendicular anisotropy. The variations of lattice constants and Curie temperature with Ag addition were significantly different between FePt-Ag and FePd-Ag. For FePd-Ag, the c and a axes lattice spacings and Curie temperature gradually changed with increasing Ag content, while they unchanged for FePt-Ag. These results suggest the possibility of the formation of FePdAg alloy in FePd-Ag, while Ag segregation in FePt-Ag.

  19. Ductility of a dental Ag-Pd-Cu-Au alloy.

    PubMed

    Syverud, M; Herø, H

    1984-02-01

    A silver-palladium type of dental alloy for fixed restorations has been investigated with regard to the ability of the material to be plastically deformed in uniaxial tensile testing after two different age-hardening treatments. A certain degree of ductility is required for the burnishing of the margins. Aged to peak hardness at 350 degrees C after solid-solution annealing at 900 degrees C, the material was found to be brittle owing to a reaction zone along the grain boundaries, promoting an intergranular fracture. When the age-hardening temperature was lowered to 275 degrees C, a less pronounced reaction zone along the grain boundaries could be observed. The accompanying mechanical properties after precipitation hardening at 275 degrees C are probably an acceptable compromise between mechanical strength and ductility. Small particles along grain boundaries and brittleness were also found after solid-solution annealing at 900 degrees C and quenching. It is suggested that the improved ductility after subsequent aging at 275 degrees C is due to a coarsening of these small particles. In the as-cast condition the alloy was softer and more ductile than in the age-hardened state. PMID:6585123

  20. High-temperature behavior of a Pd-Ag alloy for porcelain.

    PubMed

    Mackert, J R; Ringle, R D; Fairhurst, C W

    1983-12-01

    The mechanism of formation of nodular material on the surface of a Pd-Ag-based alloy for porcelain during pre-porcelainization heat treatment was investigated using scanning electron microscopy, x-ray diffraction, quantitative metallography, and Auger electron spectroscopy. The nodules were found to form by a Nabarro-Herring creep mechanism driven by the internal oxidation of tin and indium. Implications of this process with regard to porcelain bonding and discoloration are discussed. PMID:6581200

  1. Single atom alloy surface analogs in Pd0.18Cu15 nanoparticles for selective hydrogenation reactions.

    PubMed

    Boucher, Matthew B; Zugic, Branko; Cladaras, George; Kammert, James; Marcinkowski, Matthew D; Lawton, Timothy J; Sykes, E Charles H; Flytzani-Stephanopoulos, Maria

    2013-08-01

    We report a novel synthesis of nanoparticle Pd-Cu catalysts, containing only trace amounts of Pd, for selective hydrogenation reactions. Pd-Cu nanoparticles were designed based on model single atom alloy (SAA) surfaces, in which individual, isolated Pd atoms act as sites for hydrogen uptake, dissociation, and spillover onto the surrounding Cu surface. Pd-Cu nanoparticles were prepared by addition of trace amounts of Pd (0.18 atomic (at)%) to Cu nanoparticles supported on Al2O3 by galvanic replacement (GR). The catalytic performance of the resulting materials for the partial hydrogenation of phenylacetylene was investigated at ambient temperature in a batch reactor under a head pressure of hydrogen (6.9 bar). The bimetallic Pd-Cu nanoparticles have over an order of magnitude higher activity for phenylacetylene hydrogenation when compared to their monometallic Cu counterpart, while maintaining a high selectivity to styrene over many hours at high conversion. Greater than 94% selectivity to styrene is observed at all times, which is a marked improvement when compared to monometallic Pd catalysts with the same Pd loading, at the same total conversion. X-ray photoelectron spectroscopy and UV-visible spectroscopy measurements confirm the complete uptake and alloying of Pd with Cu by GR. Scanning tunneling microscopy and thermal desorption spectroscopy of model SAA surfaces confirmed the feasibility of hydrogen spillover onto an otherwise inert Cu surface. These model studies addressed a wide range of Pd concentrations related to the bimetallic nanoparticles. PMID:23793350

  2. Interplay between structural symmetry and magnetism in Ag-Cu

    NASA Astrophysics Data System (ADS)

    Yen, Tsung-Wen; Lai, S. K.

    2016-01-01

    We present first-principles theoretical calculations of the magnetic properties of bimetallic clusters Ag-Cu. The calculations proceeded by combining a previously developed state-of-the-art optimization algorithm (P.J. Hsu, S.K. Lai, J. Chem. Phys. 124 (2006) 0447110) with an empirical potential and applied this numerical scheme to determine first the lowest energy structures of pure clusters Ag38 and Cu38, and also their different atomic compositions AgnCu38-n for n=1,2,…,37. Then, we carried out the Kohn-Sham spin unrestricted density functional theory calculations on the optimized atomic structures obtained in the preceding step. Given the minimized structures from the first step as input configurations, the results of these re-optimized structures by full density functional theory calculations yield more refined electronic and atomic structures. A thorough comparison of the structural differences between these two sets of atomic geometries, one from using an empirical potential in which the electronic degrees of freedom were included approximately and another from subsequent minimization using the spin unrestricted density functional theory, sheds light on how the electronic charges disperse near atoms in clusters AgnCu38-n, and hence the distributions of electronic spin and charge densities at re-optimized sites of the cluster. These data of the electronic dispersion and the ionic configuration give clue to the mystery of the unexpected net magnetic moments which were found in some of the clusters AgnCu38-n at n=1-4, 24 as well as the two pure clusters. Possible origins for this unanticipated magnetism were explained in the context of the point group theory in much the same idea as the Clemenger-Nilsson model applied to simple metal clusters except that we draw particular attention to the atomic topologies and stress the bearing that they have on valence electrons in inducing them to disperse and occupy different molecular orbital energy levels.

  3. Characterization and device performance of (AgCu)(InGa)Se2 absorber layers

    SciTech Connect

    Hanket, Gregory; Boyle, Jonathan H.; Shafarman, William N.

    2009-06-08

    The study of (AgCu)(InGa)Se2 absorber layers is of interest in that Ag-chalcopyrites exhibit both wider bandgaps and lower melting points than their Cu counterparts. (AgCu)(InGa)Se2 absorber layers were deposited over the composition range 0 < Ag/(Ag+Cu) < 1 and 0.3 < Ga/(In+Ga) < 1.0 using a variety of elemental co-evaporation processes. Films were found to be singlephase over the entire composition range, in contrast to prior studies. Devices with Ga content 0.3 < Ga/(In+Ga) <0.5 tolerated Ag incorporation up to Ag/(Ag+Cu) = 0.5 without appreciable performance loss. Ag-containing films with Ga/(In+Ga) = 0.8 showed improved device characteristics over Cu-only control samples, in particular a 30-40% increase in short-circuit current. An absorber layer with composition Ag/(Ag+Cu) = 0.75 and Ga/(In+Ga) = 0.8 yielded a device with VOC = 890 mV, JSC = 20.5mA/cm2, fill factor = 71.3%, and η = 13.0%.

  4. Trimetallic nanostructures: the case of AgPd/Pt multiply twinned nanoparticles

    PubMed Central

    Khanal, Subarna; Bhattarai, Nabraj; Velázquez-Salazar, J. Jesús; Bahena, Daniel; Soldano, German; Ponce, Arturo; Mariscal, Marcelo M.; Mejía-Rosales, Sergio; José-Yacamán, Miguel

    2013-01-01

    We report the synthesis, structural characterization, and atomistic simulations of AgPd/Pt trimetallic (TM) nanoparticles. Two types of structure were synthesized using a relatively facile chemical method: multiply twinned core-shell, and hollow particles. The nanoparticles were small in size, with an average diameter of 11 nm and a narrow distribution, and their characterization by aberration corrected scanning transmission electron microscopy allowed us to probe the structure of the particles at atomistic level. In some nanoparticles, the formation of a hollow structure was also observed, that facilitates the alloying of Ag and Pt in the shell region and the segregation of Ag atoms in the surface, affecting the catalytic activity and stability. We also investigated the growth mechanism of the nanoparticles using grand canonical Monte Carlo simulations, and we have found that Pt regions grow at overpotentials on the AgPd nanoalloys, forming 3D islands at the early stages of the deposition process. We found very good agreement between the simulated structures and those observed experimentally. PMID:24165796

  5. Squeezing and stretching Pd thin films: A high-resolution STM study of Pd/Au(111) and Pd/Cu(111) bimetallics

    NASA Astrophysics Data System (ADS)

    Blecher, Mishan E.; Lewis, Emily A.; Pronschinske, Alex; Murphy, Colin J.; Mattera, Michael F. G.; Liriano, Melissa L.; Sykes, E. Charles H.

    2016-04-01

    Pd bimetallic alloys are promising catalysts, especially for heterogeneous reactions involving hydrogen, as they exhibit increased activity and reduced demand for expensive precious metals. Using scanning tunneling microscopy, we examine the structure of Pd thin films on Cu(111) and Au(111) and demonstrate compression and expansion, respectively, of the bulk Pd lattice constant in the film. The relative binding strength of H to the two surfaces, inferred via tip-induced diffusion barriers, suggests that the strain in these systems may alter adsorbate binding and corroborates well-known trends in d-band shifts calculated by the density functional theory. Modification to the topography and activity of Pd films based on the choice of substrate metal illustrates the value of bimetallic systems for designing less expensive, tunable catalysts.

  6. Thermoelectric properties of CuS/Ag2S nanocomposites synthesed by modified polyol method

    NASA Astrophysics Data System (ADS)

    Tarachand, Sharma, Vikash; Ganesan, V.; Okram, Gunadhor S.

    2016-05-01

    This is the report on successful synthesis of Ag doped CuS nanostructures by modified polyol method. The resulting samples were characterized by powder X-ray diffraction (XRD), energy dispersive X-ray (EDX), atomic force microscopy (AFM) and dynamic light scattering (DLS). Particle size of pure CuS nanoparticles (NPs) was 17 nm, 38 nm and 97 nm as determined from Scherrer formula, AFM and DLS, respectively. Introduction of Ag led to formation of CuS/Ag2S composites. A transition at 55 K in thermopower is ascribed to structural transformation from hexagonal to orthorhombic structure. Further, their thermoelectric properties exhibit remarkable change owing to Ag doping in CuS nanostructures. The power factor improves with increasing Ag content. They reveal that CuS/Ag2S nanocomposites are some of the potential candidates for generation of thermoelectricity in future.

  7. Modeling closure of the Pd-Ag system in iron meteorites

    NASA Astrophysics Data System (ADS)

    Van Orman, J.; Matthes, M.; Fischer-Gödde, M.; Krawczynski, M. J.; Kleine, T.

    2015-12-01

    J.A. Van Orman1, M. Matthes2, M. Fischer-Godde2, M.J. Krawczynski3, T. Kleine21 Case Western Reserve University, Cleveland, OH 44106 (james.vanorman@case.edu) 2 Westfalische Wilhelms-Universitat Muenster, 48149 Muenster, Germany 3 Washington University, St. Louis, MO 63130 The short-lived Pd-107/Ag-107 system can provide constraints on the timing of assembly and cooling of iron meteorite parent bodies, but to interpret the dates derived from this system it is necessary to understand the closure conditions. Palladium is strongly enriched in the metal phases, and sulphide (troilite) is the primary sink for radiogenic silver. Closure of the system hence depends primarily on the transfer of Ag-107 from metal to troilite. Because cation diffusion in troilite is extremely rapid, Ag-107 transfer is likely to be controlled by diffusion through the metal. Sugiura and Hoshino (2003) estimated a closure temperature of ~1100 K for the Pd/Ag system in iron meteorites under the assumption that the diffusion rate of Ag in the metal is similar to that of Ni diffusion in taenite. Here we consider the problem in more detail, utilizing constraints on Ag diffusion in taenite and kamacite from the metallurgical literature to numerically model diffusive exchange between metal and troilite with simultaneous radiogenic ingrowth. The process is complicated by exsolution of the metal into bcc kamacite and fcc taenite phases during cooling. We will discuss approaches to the treatment of this issue and their influence on the derived closure temperatures. Sugiura N., Hoshino H. (2003) Meteorit. Planet. Sci. 38, 117-143.

  8. Beet juice utilization: Expeditious green synthesis of nobel metal nanoparticles (Ag, Au, Pt, and Pd) using microwaves

    EPA Science Inventory

    Metal nanoparticles of Ag, Au, Pt, and Pd were prepared in aqueous solutions via a rapid microwave-assisted green method using beet juice, an abundant sugar-rich agricultural produce, served as both a reducing and a capping reagent. The Ag nanoparticles with capping prepared by b...

  9. Sn-Ag-Cu and Sn-Cu solders: Interfacial reactions with platinum

    NASA Astrophysics Data System (ADS)

    Kim, Tae Hyun; Kim, Young-Ho

    2004-06-01

    The interfacial reaction and intermetallic formation at the interface between tin solders containing a small amount of copper with platinum were investigated in this study. Sn-0.7Cu and Sn-1.7Cu solders were reacted with platinum by dipping Pt/Ti/Si specimens into the molten solder at 260°C. Sn-3.8Ag-0.7Cu solder was reacted with platinum by reflowing solder paste on a Pt/Ti/Si substrate at 250°C. PtSn4 intermetallic formed in all specimens while Cu6Sn5 interfacial intermetallic was not observed at the solder/platinum interfaces in any specimens. A parabolic relationship existed between the thickness of the Pt-Sn intermetallic and reaction time, which indicates the intermetallic formation in the solder/platinum interface is diffusion controlled.

  10. Effects of Annealing Twins on the Grain Growth and Mechanical Properties of Ag-8Au-3Pd Bonding Wires

    NASA Astrophysics Data System (ADS)

    Chuang, Tung-Han; Tsai, Chih-Hsin; Wang, Hsi-Ching; Chang, Che-Cheng; Chuang, Chien-Hsun; Lee, Jun-Der; Tsai, Hsing-Hua

    2012-11-01

    An innovative Ag-8Au-3Pd bonding wire containing a large amount of annealing twins has been produced. In contrast to the apparent grain growth in a conventional Ag-8Au-3Pd wire during aging at 600°C, the grain size of this annealing-twinned Ag alloy wire remains almost unchanged. The high thermal stability of the grain structure leads to a smaller heat-affected zone near the free air ball of this twinned wire. The annealing twins in this material also result in the dual merits of increased tensile strength and elongation with aging time, which is beneficial for the reliability of wire-bonded packages.

  11. Characterization of the (Ag,Cu)(In,Ga)Se2 thin film alloy system for solar cells

    NASA Astrophysics Data System (ADS)

    Boyle, Jonathan

    Energy is the underlying factor to human economic activity, and more energy is projected to be needed in the near future and photovoltaics provide a means to supply that energy. Results presented in this dissertation detail material properties of the (Ag,Cu)(In,Ga)Se2 thin film alloy system for use as a solar cell material. Structural and optical properties were determined via X-ray diffraction and UV/Vis/NIR spectrophotometry, respectively. Structural data was analyzed using JADE 2010 software and optical data was analyzed via two different methods. Results of Ag substitution into Cu(In,Ga)Se2 alloy were reconciled with the Jaffe-Wei-Zunger (JWZ) theoretical model, which relates structural and chemical properties of Cu-based ternary chalcopyrite alloys to their optical properties. Dominant phase of the alloy system was identified as chalcopyrite I-42d, Space group 122, with minor secondary phases and order defect phases. No chalcopyrite-chalcopyrite miscibility gap was present in the alloy compositional space, counter to prior literature on bulk polycrystalline materials and thermodynamic calculations performed here, indicating that Ag was successfully substituted into the chalcopyrite lattice. Lattice constant results were consistent with JWZ model, where a O lattice constant closely follows Vegard's rule, cO lattice constant changes at different rates than aO does with composition, and anion displacement is affected by cation radii. Optical results showed bandgap widening with Ag and Ga substitution across the full compositional space, with bowing parameters shown overall to be invariant with cation substitution, counter to expectations. (Ag+Cu)/(In+Ga) ratio effect on bandgap for a limited set of samples is consistent with p-d hybridization effects from JWZ model.

  12. Study on synthesis of ultrafine Cu-Ag core-shell powders with high electrical conductivity

    NASA Astrophysics Data System (ADS)

    Peng, Yu-hsien; Yang, Chih-hao; Chen, Kuan-ting; Popuri, Srinivasa R.; Lee, Ching-Hwa; Tang, Bo-Shin

    2012-12-01

    Cu-Ag composite powders with high electrical conductivity were synthesized by electroless plating of silver sulfate, copper powders with eco-friendly sodium citrate as reducing agent, dispersant and chelating agent in an aqueous system. The influences of sodium citrate/Ag ratio on Ag coatings of Cu powders were investigated. Ag was formed a dense coating on the surface of Cu powders at a molar ratio of sodium citrate/Ag = 0.07/1. SEM showed an uniformity of Ag coatings on Cu powders. SEM-EDX also revealed that Cu cores were covered by Ag shells on the whole. The surface composition analysis by XPS indicated that without Cu or Ag atoms in the surface were oxidized. The resistivity measurements of Cu-Ag paste shows that they have closer resistivity as the pure silver paste's after 250 °C for 30 min heat-treatment (2.55 × 10-4 Ω cm) and 350 °C for 30 min heat-treatment (1.425 × 10-4 Ω cm).

  13. PdAgAu alloy with high resistance to corrosion by H2S

    SciTech Connect

    Braun, Fernando; Miller, James B.; Gellman, Andrew J.; Tarditi, Ana M.; Fleutot, Benoit; Kondratyuk, Petro; Cornaglia, Laura M.

    2012-12-01

    PdAgAu alloy films were prepared on porous stainless steel supports by sequential electroless deposition. Two specific compositions, Pd83Ag2Au15 and Pd74Ag14Au12, were studied for their sulfur tolerance. The alloys and a reference Pd foil were exposed to 1000 H2S /H2 at 623 K for periods of 3 and 30 hours. The microstructure, morphology and bulk composition of both nonexposed and H2S-exposed samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and energy-dispersive X-ray spectroscopy (EDS). XRD and SEM analysis revealed time-dependent growth of a bulk Pd{sub 4}S phase on the Pd foil during H2S exposure. In contrast, the PdAgAu ternary alloys displayed the same FCC structure before and after H2S exposure. In agreement with the XRD and SEM results, sulfur was not detected in the bulk of either ternary alloy samples by EDS, even after 30 hours of H2S exposure. X-ray photoelectron spectroscopy (XPS) depth profiles were acquired for both PdAgAu alloys after 3 and 30 hours of exposure to characterize sulfur contamination near their surfaces. Very low S 2p and S 2s XPS signals were observed at the top-surfaces of the PdAgAu alloys, and those signals disappeared before the etch depth reached ~ 10 nm, even for samples exposed to H2S for 30 hours. The depth profile analyses also revealed silver and gold segregation to the surface of the alloys; preferential location of Au on the alloys surface may be related to their resistance to bulk sulfide formation. In preliminary tests, a PdAgAu alloy membrane displayed higher initial H{sub 2} permeability than a similarly prepared pure Pd sample and, consistent with resistance to bulk sulfide formation, lower permeability loss in H2S than pure Pd.

  14. Investigation of carbon supported Pd-Cu nanoparticles as anode catalysts for direct borohydride fuel cell

    NASA Astrophysics Data System (ADS)

    Behmenyar, Gamze; Akın, Ayşe Nilgün

    2014-03-01

    Carbon supported Pd and bimetallic Pd-Cu nanoparticles with different compositions are prepared by a modified polyol method and used as anode catalysts for direct borohydride fuel cell (DBFC). The physical and electrochemical properties of the as-prepared electrocatalysts are investigated by transmission electron microscopy (TEM), X-ray diffraction (XRD), ICP-AES, cyclic voltammetry (CV), chronoamperometry (CA), and fuel cell experiments. The results show that the carbon supported Pd-Cu bimetallic catalysts have much higher catalytic activity for the direct oxidation of BH4- than the carbon supported pure nanosized Pd catalyst, especially the Pd50Cu50/C catalyst presents the highest catalytic activity among all as-prepared catalysts, and the DBFC using Pd50Cu50/C as anode catalyst and Pt/C as cathode catalyst gives the best performance, and the maximum power density is 98 mW cm-2 at a current density of 223 mA cm-2 at 60 °C.

  15. Local structure order in Pd78Cu6Si16 liquid

    PubMed Central

    Yue, G. Q.; Zhang, Y.; Sun, Y.; Shen, B.; Dong, F.; Wang, Z. Y.; Zhang, R. J.; Zheng, Y. X.; Kramer, M. J.; Wang, S. Y.; Wang, C. Z.; Ho, K. M.; Chen, L. Y.

    2015-01-01

    The short-range order (SRO) in Pd78Cu6Si16 liquid was studied by high energy x-ray diffraction and ab initio molecular dynamics (MD) simulations. The calculated pair correlation functions at different temperatures agree well with the experimental results. The partial pair correlation functions from ab intio MD simulations indicate that Si atoms prefer to be uniformly distributed while Cu atoms tend to aggregate. By performing structure analysis using Honeycutt-Andersen index, Voronoi tessellation, and atomic cluster alignment method, we show that the icosahedron and face-centered cubic SRO increase upon cooling. The dominant SRO is the Pd-centered Pd9Si2 motif, namely the structure of which motif is similar to the structure of Pd-centered clusters in the Pd9Si2 crystal. The study further confirms the existence of trigonal prism capped with three half-octahedra that is reported as a structural unit in Pd-based amorphous alloys. The majority of Cu-centered clusters are icosahedra, suggesting that the presence of Cu is benefit to promote the glass forming ability. PMID:25652079

  16. Local structure order in Pd78Cu6Si16 liquid.

    PubMed

    Yue, G Q; Zhang, Y; Sun, Y; Shen, B; Dong, F; Wang, Z Y; Zhang, R J; Zheng, Y X; Kramer, M J; Wang, S Y; Wang, C Z; Ho, K M; Chen, L Y

    2015-01-01

    The short-range order (SRO) in Pd78Cu6Si16 liquid was studied by high energy x-ray diffraction and ab initio molecular dynamics (MD) simulations. The calculated pair correlation functions at different temperatures agree well with the experimental results. The partial pair correlation functions from ab intio MD simulations indicate that Si atoms prefer to be uniformly distributed while Cu atoms tend to aggregate. By performing structure analysis using Honeycutt-Andersen index, Voronoi tessellation, and atomic cluster alignment method, we show that the icosahedron and face-centered cubic SRO increase upon cooling. The dominant SRO is the Pd-centered Pd9Si2 motif, namely the structure of which motif is similar to the structure of Pd-centered clusters in the Pd9Si2 crystal. The study further confirms the existence of trigonal prism capped with three half-octahedra that is reported as a structural unit in Pd-based amorphous alloys. The majority of Cu-centered clusters are icosahedra, suggesting that the presence of Cu is benefit to promote the glass forming ability. PMID:25652079

  17. Local structure order in Pd78Cu6Si16 liquid

    DOE PAGESBeta

    Yue, G. Q.; Zhang, Y.; Sun, Y.; Shen, B.; Dong, F.; Wang, Z. Y.; Zhang, R. J.; Zheng, Y. X.; Kramer, M. J.; Wang, S. Y.; et al

    2015-02-05

    The short-range order (SRO) in Pd78Cu6Si16 liquid was studied by high energy x-ray diffraction and ab initio molecular dynamics (MD) simulations. The calculated pair correlation functions at different temperatures agree well with the experimental results. The partial pair correlation functions from ab intio MD simulations indicate that Si atoms prefer to be uniformly distributed while Cu atoms tend to aggregate. By performing structure analysis using Honeycutt-Andersen index, Voronoi tessellation, and atomic cluster alignment method, we show that the icosahedron and face-centered cubic SRO increase upon cooling. The dominant SRO is the Pd-centered Pd9Si2 motif, namely the structure of which motifmore » is similar to the structure of Pd-centered clusters in the Pd9Si2 crystal. The study further confirms the existence of trigonal prism capped with three half-octahedra that is reported as a structural unit in Pd-based amorphous alloys. The majority of Cu-centered clusters are icosahedra, suggesting that the presence of Cu is benefit to promote the glass forming ability.« less

  18. Morphology and electrochemical behavior of Ag-Cu nanoparticle-doped amalgams.

    PubMed

    Chung, Kwok-Hung; Hsiao, Li-Yin; Lin, Yu-Sheng; Duh, Jenq-Gong

    2008-05-01

    The aim of this study was to introduce Ag-Cu phase nanopowder as an additive to improve the corrosion behavior of dental amalgams. A novel Ag-Cu nanopowder was synthesized by the precipitation method. An amalgam alloy powder (World-Cap) was added and mixed with 5 wt.% and 10 wt.% of Ag-Cu nanopowders, respectively, to form experimental amalgam alloy powders. The original alloy powder was used as a control. Alloy powders were examined using X-ray diffraction, transmission electron microscopy (TEM), scanning electron microscopy and electron probe microanalysis. Amalgam disk specimens of metallurgically prepared were tested in 0.9% NaCl solution using electrochemical methods. The changes in the corrosion potential and anodic polarization characteristics were determined. Corrosion potential data were analyzed statistically (n=3, analysis of variance, Tukey's test, p<0.05). The diameters of lamellar structure Ag-Cu nanoparticles were measured to be approximately 30 nm. The composition of the Ag-Cu nanoparticles determined by TEM-energy-dispersive spectroscopy was 56.28 at.% Ag-43.72 at.% Cu. A light-shaded phase was found mixing with dark Cu-Sn reaction particles in the reaction zones of Ag-Cu nanoparticle-doped amalgams. The Ag-Cu nanoparticle-doped amalgams exhibited zero current potentials more positive than the control (p<0.05) and no current peak was observed at -325mV that related to Ag-Hg phase and Cu6Sn5 phase in anodic polarization curves. The results indicated that the corrosion resistance of high-copper single-composition amalgam could be improved by Ag-Cu nanoparticle-doping. PMID:18321799

  19. Core level shifts in Cu-Pd alloys as a function of bulk composition and structure

    NASA Astrophysics Data System (ADS)

    Boes, Jacob R.; Kondratyuk, Peter; Yin, Chunrong; Miller, James B.; Gellman, Andrew J.; Kitchin, John R.

    2015-10-01

    CuPd alloys are important materials in hydrogen purification, where they are used as dense Pd-based separation membranes. Cu is added to impart sulfur tolerance and improved mechanical properties. At intermediate compositions and T < 873 K, a BCC alloy (B2) phase occurs, which has superior separation characteristics to those of the FCC phases that form at high Cu and high Pd compositions. Identifying the composition and temperature window where the B2 phase forms is a critical need to enable the design of improved alloys. A composition spread alloy film of Cu and Pd was synthesized. The film was characterized by electron back scatter diffraction and X-ray photoelectron spectroscopy, providing the core level shifts as a function of bulk composition and bulk structure. An anomalous deviation in the Cu core level shift was observed in the composition range 0.33 < xPd < 0.55 over which the B2 phase occurs. Density functional theory calculations were used to simulate core level shifts in the FCC and B2 alloy structures. They suggest that the anomalous deviation in core level shift is due to formation of the ordered B2 phase in this composition range.

  20. High Temperature Long-Term Stability of an (Al-Ag-Cu) Three-in-One Multicell

    NASA Astrophysics Data System (ADS)

    Kim, Yong-Gyoo; Yang, Inseok; Joung, Wukchul

    2016-01-01

    In order to investigate the long-term stability of an (Al-Ag-Cu) three-in-one multicell, it was heat-treated at 1100° C, in which all metal samples were in molten state, for 1000 h. Its thermal behavior was tested using a Pt/Pd thermocouple by inducing freezes during the heat treatment. The amount by which the plateau temperature dropped after the 1000 h heat treatment were 1.62° C, 2.07° C, and 0.66° C for Al, Ag, and Cu, respectively. These degradations were suspected to be caused by self-contaminations, and to prove this, impurity concentrations in each sample of the multicell were examined. The amount of temperature dropped after the 1000 h heat treatment showed similar values to the prediction based on the impurity-induced temperature changes, and it was concluded that each cell was self-contaminated by the metallic elements from the other cells. Ag and Cu were found to be main species causing the observed degradations.

  1. Dependence of alloying and island composition on terrace width: Growth of Cu on Ag(100)

    NASA Astrophysics Data System (ADS)

    Beichert, Agnes; Zaum, Christopher; Morgenstern, Karina

    2015-07-01

    The growth of Cu on Ag(100) is investigated by low-temperature scanning tunneling microscopy. Exchange diffusion of Cu deposited onto Ag(100) leads to small pure Cu islands and larger islands consisting of a CuAg alloy in room temperature growth. The ratio of the different types of islands depends on terrace widths up to 100 nm. This surprisingly long-range dependence is correlated to the density of the surface alloy. We thus reveal that the exchange diffusion barrier is influenced by terrace widths far beyond quantum size confinement.

  2. Fabrication of Cu-Ag core-shell bimetallic superfine powders by eco-friendly reagents and structures characterization

    SciTech Connect

    Zhao Jun; Zhang Dongming; Zhao Jie

    2011-09-15

    Superfine bimetallic Cu-Ag core-shell powders were synthesized by reduction of copper sulfate pentahydrate and silver nitrate with eco-friendly ascorbic acid as a reducing agent and cyclodextrins as a protective agent in an aqueous system. The influence of Ag/Cu ratio on coatings was investigated. Ag was homogeneously distributed on the surface of Cu particles at a mole ratio of Ag/Cu=1. FE-SEM showed an uniformity of Ag coatings on Cu particles. Antioxidation of Cu particles was improved by increasing Ag/Cu ratio. TEM-EDX and UV-vis spectra also revealed that Cu cores were covered by Ag nanoshells on the whole. The surface composition analysis by XPS indicated that only small parts of Cu atoms in the surface were oxidized. It was noted that the hindrance of cyclodextrins chemisorbed on particles plays an important role in forming high quality and good dispersity Cu-Ag (Cu-Ag) core-shell powders. - Graphical abstract: Mechanism of fabricating Cu-Ag particles with good dispersibility using {beta}-CDs as a protective agent was studied because of its special structure. Highlights: > Green supramolecular {beta}-CD used as a protective agent and ascorbic acid(Vc) as a reducing agent to fabricate Cu-Ag powders. > Particles are monodisperse and the diameter is close to nanoscale(100-150 nm). > Resistance of Cu particles to oxidation was higher. > Formation mechanism explained.

  3. A comparative study on the bond strength of porcelain to the millingable Pd-Ag alloy

    PubMed Central

    Hong, Jun-Tae

    2014-01-01

    PURPOSE The porcelain fused to gold has been widely used as a restoration both with the natural esthetics of the porcelain and durability and marginal fit of metal casting. However, recently, due to the continuous rise in the price of gold, an interest towards materials to replace gold alloy is getting higher. This study compared the bond strength of porcelain to millingable palladium-silver (Pd-Ag) alloy, with that of 3 conventionally used metal-ceramic alloys. MATERIALS AND METHODS Four types of metal-ceramic alloys, castable nonprecious nickel-chrome alloy, castable precious metal alloys containing 83% and 32% of gold, and millingable Pd-Ag alloy were used to make metal specimens (n=40). And porcelain was applied on the center area of metal specimen. Three-point bending test was performed with universal testing machine. The bond strength data were analyzed with a one-way ANOVA and post hoc Scheffe's tests (α=.05). RESULTS The 3-point bending test showed the strongest (40.42 ± 5.72 MPa) metal-ceramic bond in the nonprecious Ni-Cr alloy, followed by millingable Pd-Ag alloy (37.71 ± 2.46 MPa), precious metal alloy containing 83% of gold (35.89 ± 1.93 MPa), and precious metal alloy containing 32% of gold (34.59 ± 2.63 MPa). Nonprecious Ni-Cr alloy and precious metal alloy containing 32% of gold showed significant difference (P<.05). CONCLUSION The type of metal-ceramic alloys affects the bond strength of porcelain. Every metal-ceramic alloy used in this study showed clinically applicable bond strength with porcelain (25 MPa). PMID:25352959

  4. Mechanism of Electromigration in Ag-Alloy Bonding Wires with Different Pd and Au Content

    NASA Astrophysics Data System (ADS)

    Chuang, Tung-Han; Lin, Hsin-Jung; Wang, Hsi-Ching; Chuang, Chien-Hsun; Tsai, Chih-Hsin

    2015-02-01

    The mechanism of electromigration in Ag-alloy wires containing different amounts of Pd and Au has been studied. Thinning and thickening accompanying grain growth were observed in worn bonding wire after current stress. The mean time-to-failure of bonding wires stressed with different current densities is highly dependent on their electrical resistivity, and wire temperature increases during current stress, owing to the Joule effect. An indirect method is proposed for in situ assessment of the temperatures of these fine wires under current stress. A mode of failure of these bonding wires was deduced by kinetic analysis. This mode can be correlated with atomic diffusion in the wire.

  5. Oxygen reduction reaction on Cu-doped Ag cluster for fuel-cell cathode.

    PubMed

    Ma, Wenqiang; Chen, Fuyi; Zhang, Nan; Wu, Xiaoqiang

    2014-10-01

    The development of fuel cells as clean-energy technologies is largely limited by the prohibitive cost of the noble-metal catalysts needed for catalyzing the oxygen reduction reaction (ORR) in fuel cells. A fundamental understanding of catalyst design principle that links material structures to the catalytic activity can accelerate the search for highly active and abundant bimetallic catalysts to replace platinum. Here, we present a first-principles study of ORR on Ag12Cu cluster in alkaline environment. The adsorptions of O2, OOH, and OH on Cu-doped Ag13 are stronger than on Ag13. The d-band centers of adsorption sites show the Cu-doping makes d-electrons transferred to higher energy state, and improves O2 dissociation. ORR processes on Ag12Cu and Ag13 indicate Cu-doping can strongly promote ORR, and ORR process can be better preformed on Ag12Cu than on Ag13. For four-electron transfer, the effective reversible potential is 0.401 V/RHE on Ag12Cu in alkaline medium. PMID:25227449

  6. Size effect model on kinetics of interfacial reaction between Sn-xAg-yCu solders and Cu substrate

    NASA Astrophysics Data System (ADS)

    Huang, M. L.; Yang, F.

    2014-11-01

    The downsizing of solder balls results in larger interfacial intermetallic compound (IMC) grains and less Cu substrate consumption in lead-free soldering on Cu substrates. This size effect on the interfacial reaction is experimentally demonstrated and theoretically analyzed using Sn-3.0Ag-0.5Cu and Sn-3.5Ag solder balls. The interfacial reaction between the Sn-xAg-yCu solders and Cu substrates is a dynamic response to a combination of effects of interfacial IMC growth, Cu substrate consumption and composition variation in the interface zone. A concentration gradient controlled (CGC) kinetics model is proposed to explain the combined effects. The concentration gradient of Cu at the interface, which is a function of solder volume, initial Cu concentration and reaction time, is the root cause of the size effect. We found that a larger Cu concentration gradient results in smaller Cu6Sn5 grains and more consumption of Cu substrate. According to our model, the growth kinetics of interfacial Cu6Sn5 obeys a t1/3 law when the molten solder has approached the solution saturation, and will be slower otherwise due to the interfering dissolution mechanism. The size effect introduced in this model is supported by a good agreement between theoretical and experimental results. Finally, the scope of application of this model is discussed.

  7. Size effect model on kinetics of interfacial reaction between Sn-xAg-yCu solders and Cu substrate

    PubMed Central

    Huang, M. L.; Yang, F.

    2014-01-01

    The downsizing of solder balls results in larger interfacial intermetallic compound (IMC) grains and less Cu substrate consumption in lead-free soldering on Cu substrates. This size effect on the interfacial reaction is experimentally demonstrated and theoretically analyzed using Sn-3.0Ag-0.5Cu and Sn-3.5Ag solder balls. The interfacial reaction between the Sn-xAg-yCu solders and Cu substrates is a dynamic response to a combination of effects of interfacial IMC growth, Cu substrate consumption and composition variation in the interface zone. A concentration gradient controlled (CGC) kinetics model is proposed to explain the combined effects. The concentration gradient of Cu at the interface, which is a function of solder volume, initial Cu concentration and reaction time, is the root cause of the size effect. We found that a larger Cu concentration gradient results in smaller Cu6Sn5 grains and more consumption of Cu substrate. According to our model, the growth kinetics of interfacial Cu6Sn5 obeys a t1/3 law when the molten solder has approached the solution saturation, and will be slower otherwise due to the interfering dissolution mechanism. The size effect introduced in this model is supported by a good agreement between theoretical and experimental results. Finally, the scope of application of this model is discussed. PMID:25408359

  8. Size effect model on kinetics of interfacial reaction between Sn-xAg-yCu solders and Cu substrate.

    PubMed

    Huang, M L; Yang, F

    2014-01-01

    The downsizing of solder balls results in larger interfacial intermetallic compound (IMC) grains and less Cu substrate consumption in lead-free soldering on Cu substrates. This size effect on the interfacial reaction is experimentally demonstrated and theoretically analyzed using Sn-3.0Ag-0.5Cu and Sn-3.5Ag solder balls. The interfacial reaction between the Sn-xAg-yCu solders and Cu substrates is a dynamic response to a combination of effects of interfacial IMC growth, Cu substrate consumption and composition variation in the interface zone. A concentration gradient controlled (CGC) kinetics model is proposed to explain the combined effects. The concentration gradient of Cu at the interface, which is a function of solder volume, initial Cu concentration and reaction time, is the root cause of the size effect. We found that a larger Cu concentration gradient results in smaller Cu(6)Sn(5) grains and more consumption of Cu substrate. According to our model, the growth kinetics of interfacial Cu(6)Sn(5) obeys a t(1/3) law when the molten solder has approached the solution saturation, and will be slower otherwise due to the interfering dissolution mechanism. The size effect introduced in this model is supported by a good agreement between theoretical and experimental results. Finally, the scope of application of this model is discussed. PMID:25408359

  9. Cellular Energy Allocation to Assess the Impact of Nanomaterials on Soil Invertebrates (Enchytraeids): The Effect of Cu and Ag.

    PubMed

    Gomes, Susana I L; Scott-Fordsmand, Janeck J; Amorim, Mónica J B

    2015-06-01

    The effects of several copper (Cu) and silver (Ag) nanomaterials were assessed using the cellular energy allocation (CEA), a methodology used to evaluate the energetic status and which relates with organisms' overall condition and response to toxic stress. Enchytraeus crypticus (Oligochatea), was exposed to the reproduction effect concentrations EC20/50 of several Cu and Ag materials (CuNO3, Cu-Field, Cu-Nwires and Cu-NPs; AgNO3, Ag NM300K, Ag-NPs Non-coated and Ag-NPs PVP-coated) for 7 days (0-3-7d). The parameters measured were the total energy reserves available (protein, carbohydrate and lipid budgets) and the energy consumption (Ec) integrated to obtain the CEA. Results showed that these parameters allowed a clear discrimination between Cu and Ag, but less clearly within each of the various materials. For Cu there was an increase in Ec and protein budget, while for Ag a decrease was observed. The results corroborate known mechanisms, e.g., with Cu causing an increase in metabolic rate whereas Ag induces mitochondrial damage. The various Cu forms seem to activate different mechanisms with size and shape (e.g., Cu-NPs versus Cu-Nwires), causing clearly different effects. For Ag, results are in line with a slower oxidation rate of Ag-NMs in comparison with Ag-salt and hence delayed effects. PMID:26086707

  10. Cellular Energy Allocation to Assess the Impact of Nanomaterials on Soil Invertebrates (Enchytraeids): The Effect of Cu and Ag

    PubMed Central

    Gomes, Susana I. L.; Scott-Fordsmand, Janeck J.; Amorim, Mónica J. B.

    2015-01-01

    The effects of several copper (Cu) and silver (Ag) nanomaterials were assessed using the cellular energy allocation (CEA), a methodology used to evaluate the energetic status and which relates with organisms’ overall condition and response to toxic stress. Enchytraeus crypticus (Oligochatea), was exposed to the reproduction effect concentrations EC20/50 of several Cu and Ag materials (CuNO3, Cu-Field, Cu-Nwires and Cu-NPs; AgNO3, Ag NM300K, Ag-NPs Non-coated and Ag-NPs PVP-coated) for 7 days (0-3-7d). The parameters measured were the total energy reserves available (protein, carbohydrate and lipid budgets) and the energy consumption (Ec) integrated to obtain the CEA. Results showed that these parameters allowed a clear discrimination between Cu and Ag, but less clearly within each of the various materials. For Cu there was an increase in Ec and protein budget, while for Ag a decrease was observed. The results corroborate known mechanisms, e.g., with Cu causing an increase in metabolic rate whereas Ag induces mitochondrial damage. The various Cu forms seem to activate different mechanisms with size and shape (e.g., Cu-NPs versus Cu-Nwires), causing clearly different effects. For Ag, results are in line with a slower oxidation rate of Ag-NMs in comparison with Ag-salt and hence delayed effects. PMID:26086707

  11. Sn-Ag-Cu Nanosolders: Solder Joints Integrity and Strength

    NASA Astrophysics Data System (ADS)

    Roshanghias, Ali; Khatibi, Golta; Yakymovych, Andriy; Bernardi, Johannes; Ipser, Herbert

    2016-08-01

    Although considerable research has been dedicated to the synthesis and characterization of lead-free nanoparticle solder alloys, only very little has been reported on the reliability of the respective joints. In fact, the merit of nanoparticle solders with depressed melting temperatures close to the Sn-Pb eutectic temperature has always been challenged when compared with conventional solder joints, especially in terms of inferior solderability due to the oxide shell commonly present on the nanoparticles, as well as due to compatibility problems with common fluxing agents. Correspondingly, in the current study, Sn-Ag-Cu (SAC) nanoparticle alloys were combined with a proper fluxing vehicle to produce prototype nanosolder pastes. The reliability of the solder joints was successively investigated by means of electron microscopy and mechanical tests. As a result, the optimized condition for employing nanoparticles as a competent nanopaste and a novel procedure for surface treatment of the SAC nanoparticles to diminish the oxide shell prior to soldering are being proposed.

  12. Sn-Ag-Cu Nanosolders: Solder Joints Integrity and Strength

    NASA Astrophysics Data System (ADS)

    Roshanghias, Ali; Khatibi, Golta; Yakymovych, Andriy; Bernardi, Johannes; Ipser, Herbert

    2016-05-01

    Although considerable research has been dedicated to the synthesis and characterization of lead-free nanoparticle solder alloys, only very little has been reported on the reliability of the respective joints. In fact, the merit of nanoparticle solders with depressed melting temperatures close to the Sn-Pb eutectic temperature has always been challenged when compared with conventional solder joints, especially in terms of inferior solderability due to the oxide shell commonly present on the nanoparticles, as well as due to compatibility problems with common fluxing agents. Correspondingly, in the current study, Sn-Ag-Cu (SAC) nanoparticle alloys were combined with a proper fluxing vehicle to produce prototype nanosolder pastes. The reliability of the solder joints was successively investigated by means of electron microscopy and mechanical tests. As a result, the optimized condition for employing nanoparticles as a competent nanopaste and a novel procedure for surface treatment of the SAC nanoparticles to diminish the oxide shell prior to soldering are being proposed.

  13. Accumulation of Ag and Cu in Amanita strobiliformis and characterization of its Cu and Ag uptake transporter genes AsCTR2 and AsCTR3.

    PubMed

    Beneš, Vojtěch; Hložková, Kateřina; Matěnová, Michaela; Borovička, Jan; Kotrba, Pavel

    2016-04-01

    Macrofungi can accumulate in their sporocarps remarkably high concentrations of Cu and Ag. We have previously demonstrated that the non-essential Ag is in the ectomycorrhizal, Ag-hyperaccumulating Amanita strobiliformis sequestered by 3.4-kDa metallothioneins (MTs) produced as AsMT1a, 1b and 1c isoforms. Here, we describe two populations of wild-grown A. strobiliformis sporocarps, which showed certain correlation between the concentrations of accumulated Ag (284 ± 64 and 67 ± 15 mg kg(-1)) and Cu (76 ± 13 and 30 ± 12 mg kg(-1)), suggesting that an overlap may exist in the cell biology of Ag and Cu in this species. Metal speciation analysis revealed that the intracellular Cu in the sporocarps of both populations was, like Ag, associated with the 3.4-kDa MTs. A search of A. strobiliformis transcriptome for sequences encoding proteins of the Cu transporter (CTR) family identified four AsCTR cDNAs, which were, like AsMT1s, confirmed in both populations. The predicted AsCTR proteins showed homology to vacuolar (AsCTR1 and AsCTR4) and plasma membrane (AsCTR2 and AsCTR3) CTRs. Heterologous expression of AsCTR2, AsCTR3 and their translational fusions with green fluorescent protein (GFP) in Cu uptake-deficient S. cerevisiae indicated that both AsCTRs are functional Cu and Ag uptake transporters: recombinant genes complemented growth defects and increased Cu and Ag uptake rates in yeasts and the GFP-tagged protein localized to the cell periphery. Site directed mutagenesis revealed the importance of the conserved-among-CTRs M-X3-M motif for the AsCTR2- and AsCTR3-mediated transport of both Cu and Ag. These results provide the first evidence that fungal CTRs can recognize Ag for transport. PMID:26862109

  14. Nanoscale electrical characteristics of metal (Au, Pd)-graphene-metal (Cu) contacts

    NASA Astrophysics Data System (ADS)

    Ruffino, F.; Meli, G.; Grimaldi, M. G.

    2016-01-01

    Free-standing graphene presents exceptional physical properties (as a high carrier mobility) making it the ideal candidate for the next generation nanoelectronics. However, when graphene layers are inserted in real electronics devices, metal contacting is required. The metal-graphene interaction significantly affects the graphene electrical properties, drastically changing its behavior with respect to the free-standing configuration. So, this work presents an experimental study on the nanoscale electric characteristics of metal/graphene/metal contacts. In particular, starting from single-layer graphene grown on Cu foil we deposited on the graphene surface two different metal films (Au or Pd) and the Au/graphene/Cu and Pd/graphene/Cu current-voltage characteristics are acquired, on the nanometric scale, by the conductive atomic force microscopy. Both systems presented a current voltage rectifying behavior. However, the Au/graphene/Cu system conducts significantly at negative applied bias (graphene behaves as a p-type semiconductor in a meta/semiconductor contact), while in the Pd/graphene/Cu at positive applied bias (graphene behaves as a n-type semiconductor in a metal/semiconductor contact). This difference is discussed on the basis of the band energy diagram at the metal/graphene interface and the modification of the graphene Fermi level due to the Au/graphene or Pd/graphene interaction.

  15. Charge transfer effects on the chemical reactivity of Pd(x)Cu(1-x) nanoalloys.

    PubMed

    Castegnaro, M V; Gorgeski, A; Balke, B; Alves, M C M; Morais, J

    2016-01-01

    This work reports on the synthesis and characterization of PdxCu1-x (x = 0.7, 0.5 and 0.3) nanoalloys obtained via an eco-friendly chemical reduction method based on ascorbic acid and trisodium citrate. The average size of the quasi-spherical nanoparticles (NPs) obtained by this method was about 4 nm, as observed by TEM. The colloids containing different NPs were then supported on carbon in order to produce powder samples (PdxCu1-x/C) whose electronic and structural properties were probed by different techniques. XRD analysis indicated the formation of crystalline PdCu alloys with a nanoscaled crystallite size. Core-level XPS results provided a fingerprint of a charge transfer process between Pd and Cu and its dependency on the nanoalloy composition. Additionally, it was verified that alloying was able to change the NP's reactivity towards oxidation and reduction. Indeed, the higher the amount of Pd in the nanoalloy, less oxidized are both the Pd and the Cu atoms in the as-prepared samples. Also, in situ XANES experiments during thermal treatment under a reducing atmosphere showed that the temperature required for a complete reduction of the nanoalloys depends on their composition. These results envisage the control at the atomic level of novel catalytic properties of such nanoalloys. PMID:26647173

  16. Solid Effect Between Quadrupolar Transitions in Dilute Cu-Pd Alloys

    NASA Astrophysics Data System (ADS)

    Konzelmann, K.; Majer, G.; Seeger, A.

    1996-06-01

    The paper investigates the Dynamic Solid Effect (DSE) in Nuclear Quadrupole Double Reso-nance (NQDOR) on a system (dilute alloys of CuPd with 8, 42, 210, or 1000 at.ppm Pd) chosen for its simplicity and the possibility to test the theoretical concepts on which the experimental tech-niques (in particular the so-called Berthier-Minier technique for exhibiting the DSE) are based. NQDOR allows to observe the transitions between the Cu nuclear energy levels split by the quadrupolar interaction with the electric field gradients generated by nearby Pd atoms even in dilute alloys, in which the fraction of Cu nuclei experiencing a given field gradient is very small. The DSE permits transitions at frequencies corresponding to the sums or differences of quadrupolar level splittings at neighbouring nuclei and thus gives access to information on the spatial correlation of nuclei accessible to NQDOR studies. The DSE information is shown to be in full accord with the conclusions drawn earlier, on the basis of line-intensity arguments, on the assignment of quadrupo-lar transitions to the first four shells of Cu nuclei surrounding isolated Pd atoms but, in addition, allows to identify the low-frequency NQDOR lines associated with Cu nuclei in the fifth and sixth shells.

  17. Surface mobility of Ag on Pd(100) measured by specular helium scattering

    NASA Astrophysics Data System (ADS)

    Félix, C.; Vandoni, G.; Harbich, W.; Buttet, J.; Monot, R.

    1996-12-01

    We study the deposition and the very first steps of nucleation and growth of Ag on Pd(100) with thermal energy atom scattering. This technique is a very sensitive and nonperturbing probe to surface point defects, which permits an in situ and in-time monitoring of the deposition. The intention of this paper is to give a detailed description of the approach used in our work. The form of the specularly reflected helium signal as a function of coverage and surface temperature is compared to a theoretical curve, which is computed by solving a system of rate equations that describe the formation and destruction of clusters during the deposition process. The analysis of the experimental data gives two main results. The diffusion parameters (activation barrier Ed=0.37+/-0.03 eV and preexponential factor ν0=8×109 s-1) have been extracted for the system Ag on Pd(100). We find furthermore that all silver atoms impinging on a zone of 6.1 Å around an adatom on the surface are captured by it at surface temperatures well below the onset of thermally activated mobility. The origin of this phenomenon is discussed and tentatively assigned to a combined effect of transient and neighbor driven mobility.

  18. EFFECT OF IMPURITIES ON THE PERFORMANCE OF A Pd-Ag DIFFUSER

    SciTech Connect

    Morgan, G.

    2010-12-16

    A commercially fabricated diffuser purchased from Johnson-Matthey, Inc. was evaluated for performance characterization testing at the Savannah River National Laboratory (SRNL). Different impurities are often present in the feed streams of the process diffusers, but the effect of these impurities on the diffuser performance is currently unknown. Various impurities were introduced into the feed stream of the diffuser at various levels ranging from 0.5% to 10% of the total flow in order to determine the effect that these impurities have on the permeation of hydrogen through the palladium-silver membrane. The introduction of various impurities into the feed stream of the diffuser had a minimal effect on the overall permeation of hydrogen through the Pd-Ag membrane. Of the four impurities introduced into the feed stream, carbon monoxide (CO) was the only impurity that showed any evidence of causing a reduction in the amount of hydrogen permeating through the Pd-Ag membrane. The hydrogen permeation returned to its baseline level after the CO was removed from the feed stream. There were no lasting effects of the CO exposure on the ability of the membrane to effectively separate hydrogen from the non-hydrogen species in the gas stream under the conditions tested.

  19. Magnetic properties of ZnS doped with noble metals (X = Ru, Rh, Pd, and Ag)

    NASA Astrophysics Data System (ADS)

    Tan, Zhiyun; Xiao, Wenzhi; Wang, Lingling; Yang, Youchang

    2012-12-01

    Density functional theory calculations are carried out to study the electronic structures and magnetic properties in zinc-blende structure ZnS doped with nonmagnetic noble metals (X = Ru, Rh, Pd, and Ag). Results show robust magnetic ground states for X-doped ZnS. The total magnetic moments are about 2.0, 3.0, and 2.0 μB per supercell for the Ru-, Rh-, and Pd-doped ZnS, respectively. As the atomic number of X element increases, the local magnetic moment tends toward delocalize and the hybridization between X-4d and S-3p states become stronger. This trend is strongly related to the difference in electronegativity between the substitutional X and the cation in the ZnS host. For Ag-doped ZnS, both non-spin- and spin-polarized calculations yield nearly equal total energy. The substitution of Zn in ZnS parent material by the nonmagnetic 4d transition-metals may lead to half-metallic ferromagnetism which stems from the hybridization between X-4d and S-3p states and could be attributed to a double-exchange mechanism. Curie temperature values are estimated using mean-field approximation.

  20. Pd/Ag coated fiber Bragg grating sensor for hydrogen monitoring in power transformers.

    PubMed

    Ma, G M; Jiang, J; Li, C R; Song, H T; Luo, Y T; Wang, H B

    2015-04-01

    Compared with conventional DGA (dissolved gas analysis) method for on-line monitoring of power transformers, FBG (fiber Bragg grating) hydrogen sensor represents marked advantages over immunity to electromagnetic field, time-saving, and convenience to defect location. Thus, a novel FBG hydrogen sensor based on Pd/Ag (Palladium/Silver) along with polyimide composite film to measure dissolved hydrogen concentration in large power transformers is proposed in this article. With the help of Pd/Ag composite coating, the enhanced performance on mechanical strength and sensitivity is demonstrated, moreover, the response time and sensitivity influenced by oil temperature are solved by correction lines. Sensitivity measurement and temperature calibration of the specific hydrogen sensor have been done respectively in the lab. And experiment results show a high sensitivity of 0.055 pm/(μl/l) with instant response time about 0.4 h under the typical operating temperature of power transformers, which proves a potential utilization inside power transformers to monitor the health status by detecting the dissolved hydrogen concentration. PMID:25933889

  1. Surface mobility of Ag on Pd(100) measured by specular helium scattering

    SciTech Connect

    Felix, C.; Vandoni, G.; Harbich, W.; Buttet, J.; Monot, R.

    1996-12-01

    We study the deposition and the very first steps of nucleation and growth of Ag on Pd(100) with thermal energy atom scattering. This technique is a very sensitive and nonperturbing probe to surface point defects, which permits an {ital in} {ital situ} and in-time monitoring of the deposition. The intention of this paper is to give a detailed description of the approach used in our work. The form of the specularly reflected helium signal as a function of coverage and surface temperature is compared to a theoretical curve, which is computed by solving a system of rate equations that describe the formation and destruction of clusters during the deposition process. The analysis of the experimental data gives two main results. The diffusion parameters (activation barrier {ital E}{sub {ital d}}=0.37{plus_minus}0.03 eV and preexponential factor {nu}{sub 0}=8{times}10{sup 9} s{sup {minus}1}) have been extracted for the system Ag on Pd(100). We find furthermore that all silver atoms impinging on a zone of 6.1 A around an adatom on the surface are captured by it at surface temperatures well below the onset of thermally activated mobility. The origin of this phenomenon is discussed and tentatively assigned to a combined effect of transient and neighbor driven mobility. {copyright} {ital 1996 The American Physical Society.}

  2. Pd/Ag coated fiber Bragg grating sensor for hydrogen monitoring in power transformers

    NASA Astrophysics Data System (ADS)

    Ma, G. M.; Jiang, J.; Li, C. R.; Song, H. T.; Luo, Y. T.; Wang, H. B.

    2015-04-01

    Compared with conventional DGA (dissolved gas analysis) method for on-line monitoring of power transformers, FBG (fiber Bragg grating) hydrogen sensor represents marked advantages over immunity to electromagnetic field, time-saving, and convenience to defect location. Thus, a novel FBG hydrogen sensor based on Pd/Ag (Palladium/Silver) along with polyimide composite film to measure dissolved hydrogen concentration in large power transformers is proposed in this article. With the help of Pd/Ag composite coating, the enhanced performance on mechanical strength and sensitivity is demonstrated, moreover, the response time and sensitivity influenced by oil temperature are solved by correction lines. Sensitivity measurement and temperature calibration of the specific hydrogen sensor have been done respectively in the lab. And experiment results show a high sensitivity of 0.055 pm/(μl/l) with instant response time about 0.4 h under the typical operating temperature of power transformers, which proves a potential utilization inside power transformers to monitor the health status by detecting the dissolved hydrogen concentration.

  3. PdCuPt Nanocrystals with Multibranches for Enzyme-Free Glucose Detection.

    PubMed

    Fu, Shaofang; Zhu, Chengzhou; Song, Junhua; Engelhard, Mark; Xia, Haibing; Du, Dan; Lin, Yuehe

    2016-08-31

    By carefully controlling the synthesis condition, branched PtCu bimetallic templates were synthesized in aqueous solution. After the galvanic replacement reaction between PtCu templates and the Pt precursors, PdCuPt trimetallic nanocrystals with branched structures were obtained. Owing to the open structure and the optimized composition, the electrochemical experimental results reveal that the PdCuPt trimetallic nanocrystals possess high electrocatalytic activity, selectivity and stability for the oxidation of glucose in alkaline solution. In detail, a detection limit of 1.29 μM and a sensitivity of 378 μA/mM/cm(2) are achieved. The good electrocatalytic performance should be attributed to the unique branched nanostructure as well as the synergistic effect among metals. The superior catalytic properties suggest that these nanocrystals are promising for enzyme-free detection of glucose. PMID:27494365

  4. Microstructural aspects of Cu-Ag produced by the Taylor wire method

    SciTech Connect

    Han, K.; Embury, J.D.; Petrovic, J.J.; Weatherly, G.C.

    1998-08-10

    The microstructure and phase transformations of Cu-16 at.% Ag fabricated by the Taylor wire technique of drawing molten metals in a glass tube have been studied. As the diameter of the wire becomes smaller and the cooling rate increases, the scale of the microstructure is refined. Nano-crystals of supersaturated solid solution with a 10 nm grain size were observed when the wire diameter was less than 10{micro}m. When the diameter of the wire was larger than 20 {micro}m, proeutectic Cu and the Cu + Ag eutectic were found. In the region where the Cu-Ag eutectic was formed, a (111) twin orientation relationship was found between Cu and Ag.

  5. Effects of the crystallographic orientation of Sn on the electromigration of Cu/Sn-Ag-Cu/Cu ball joints

    SciTech Connect

    Lee, Kiju; Kim, Keun-Soo; Tsukada, Yutaka; Suganuma, Katsuaki; Yamanaka, Kimihiro; Kuritani, Soichi; Ueshima, Minoru

    2011-11-17

    Electromigration behavior and fast circuit failure with respect to crystallographic orientation of Sn grains were examined. The test vehicle was Cu/Sn-3.0 wt% Ag-0.5 wt% Cu/Cu ball joints, and the applied current density was 15 kA/cm2 at 160 °C. The experimental results indicate that most of the solder bumps show different microstructural changes with respect to the crystallographic orientation of Sn grains. Fast failure of the bump occurred due to the dissolution of the Cu circuit on the cathode side caused by the fast interstitial diffusion of Cu atoms along the c-axis of the Sn grains when the c-axis was parallel to the electron flow. Slight microstructural changes were observed when the c-axis was perpendicular to the electron flow. In addition, Cu6Sn5 intermetallic compound (IMC) was formed along the direction of the c-axis of the Sn grains instead of the direction of electron flow in all solder ball joints.

  6. A LEED study of c(2 × 2) Cu and Ag/Mo(100)

    NASA Astrophysics Data System (ADS)

    Cerdá, J. R.; Soria, F.; Palomares, F. J.; de Andres, P. L.

    1992-05-01

    We have performed a low-energy electron diffraction (LEED) analysis of the novel structures c(2 × 2) Cu/Mo(100), and c(2 × 2) Ag/Mo(100). Both adsorbates sit in the hollow site, at a higher of 1.22 ± 0.08 Å for Cu atoms and 1.78 ± 0.10 Å for the Ag. Also, the typical inwards relaxation of Mo(100)(1.48Å) is released to a value near the bulk (1.575Å) for Cu, while this effect is not seen for Ag.

  7. Preparation and optical properties of silica@Ag Cu alloy core-shell composite colloids

    NASA Astrophysics Data System (ADS)

    Zhang, Jianhui; Liu, Huaiyong; Wang, Zhenlin; Ming, Naiben

    2007-04-01

    The silica@Ag-Cu alloy core-shell composite colloids have been successfully synthesized by an electroless plating approach to explore the possibility of modifying the plasmon resonance at the nanoshell surface by varying the metal nanoshell composition for the first time. The surface plasmon resonance of the composite colloids increases in intensity and shifts towards longer, then shorter wavelengths as the Cu/Ag ratio in the alloy shell is increased. The variations in intensity of the surface plasmon resonance with the Cu/Ag ratio obviously affect the Raman bands of the silica colloid core. The report here may supply a new technique to effectively modify the surface plasmon resonance.

  8. Plasmon-enhanced photocatalytic properties of nano Ag@AgBr on single-crystalline octahedral Cu2O (1 1 1) microcrystals composite photocatalyst

    NASA Astrophysics Data System (ADS)

    Liu, Li; Lin, Shuanglong; Hu, Jinshan; Liang, Yinghua; Cui, Wenquan

    2015-03-01

    A new composite photocatalyst Ag@AgBr/Cu2O was prepared by loading Ag@AgBr on (1 1 1) facts of octahedral Cu2O substrate via a facile precipitation in situ photoreduction method and characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy dispersive X-ray spectroscopy (EDX), ultraviolet-visible diffuse reflectance spectroscopy (UV-vis), nitrogen sorption and the photoelectrochemical measurements. The results show that Ag@AgBr nanoparticles are well-dispersed on Cu2O nanoparticles with narrow size distributions and controllable sizes from 10 to 30 nm. TEM results of the as-synthesized Ag@AgBr/Cu2O nanocomposite revealed that Ag@AgBr nanoparticles were attached to the surface of octahedral Cu2O. Photocatalytic degradation of methylene blue (MB) was carried out to evaluate the photocatalytic activity of Ag@AgBr/Cu2O under visible-light irradiation. The Ag@AgBr/Cu2O composite showed stronger visible light absorption capacity and higher photocatalytic activity than pure Cu2O. The Ag@AgBr (15 wt.%)/Cu2O sample presented the best photocatalytic activity, degrading 93.28% MB after irradiation for 90 min, due to their high surface area (18.499 m2 g-1), the Crystal effect of Cu2O and surface plasmon resonance of Ag NPs. Meanwhile, phenol was degraded to further prove the degradation ability of Ag@AgBr/Cu2O. In addition, the quenching effect was examined in the photocatalytic reaction process of MB. Active h+, Br0 and the resulting rad O2- played the major roles for the dye degradation, while rad OH was verified to be insignificant. Based on the experimental results, a photocatalytic mechanism for organics degradation over Ag@AgBr/Cu2O photocatalysts was proposed. The electronic interactions were systematically studied and confirmed by the photoelectrochemical measurements.

  9. Sulfur Tolerant Pd/Cu and Pd/Au Alloy Membranes for H2 Separation with High Pressure CO2 for Sequestration

    SciTech Connect

    Yi Hua Ma; Natalie Pomerantz; Chao-Huang Chen

    2008-09-30

    The effect of H{sub 2}S poisoning on Pd, Pd/Cu, and Pd/Au alloy composite membranes prepared by the electroless deposition method on porous Inconel supports was investigated to provide a fundamental understanding of the durability and preparation of sulfur tolerant membranes. X-ray photoelectron spectroscopy (XPS) studies showed that the exposure of pure Pd to 50 ppm H{sub 2}S/H{sub 2} mixtures caused bulk sulfide formation at lower temperatures and surface sulfide formation at higher temperatures. Lower temperatures, longer exposure times, and higher H{sub 2}S concentrations resulted in a higher degree of sulfidation. In a Pd membrane, the bulk sulfide formation caused a drastic irrecoverable H{sub 2} permeance decline and an irreparable loss in selectivity. Pd/Cu and Pd/Au alloy membranes exhibited permeance declines due to surface sulfide formation upon exposure to 50 ppm H{sub 2}S/H{sub 2} gas mixtures. However in contrast to the pure Pd membrane, the permeances of the Pd/Cu and Pd/Au alloy membranes were mostly recovered in pure H{sub 2} and the selectivity of the Pd alloy layers remained essentially intact throughout the characterization in H{sub 2}, He and H{sub 2}S/H{sub 2} mixtures which lasted several thousand hours. The amount of irreversible sulfur poisoning decreased with increasing temperature due to the exothermicity of H{sub 2}S adsorption. Longer exposure times increased the amount of irreversible poisoning of the Pd/Cu membrane but not the Pd/Au membrane. Pd/Au coupon studies of the galvanic displacement method showed that higher Au{sup 3+} concentrations, lower pH values, higher bath temperatures and stirring the bath at a rate of 200 rpm yielded faster displacement rates, more uniform depositions, and a higher Au content within the layers. While 400 C was found to be sufficient to form a Pd/Au alloy on the surface, high temperature X-ray diffraction (HTXRD) studies showed that even after annealing between 500-600 C, the Pd/Cu alloys could have

  10. A green method to prepare Pd-Ag nanoparticles supported on reduced graphene oxide and their electrochemical catalysis of methanol and ethanol oxidation

    NASA Astrophysics Data System (ADS)

    Li, Lingzhi; Chen, Mingxi; Huang, Guanbo; Yang, Nian; Zhang, Li; Wang, Huan; Liu, Yu; Wang, Wei; Gao, Jianping

    2014-10-01

    Bimetallic palladium-silver nanoparticles (NPs) supported on reduced oxide graphene (RGO) with different Pd/Ag ratios (Pd-Ag/RGO) were prepared by an easy green method which did not use any additional reducing agents or a dispersing agent. During the process, simultaneous redox reactions between AgNO3, K2PdCl4 and graphene oxide (GO) led to bimetallic Pd-Ag NPs. The morphology and composition of the Pd-Ag/RGO were characterized by transmission electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy, thermogravimetric analysis and Raman spectroscopy. Cyclic voltammetry and chronoamperometry were used to investigate the electrochemical activities and stabilities of these Pd-Ag/RGO catalysts for the electro-oxidation of methanol and ethanol in alkaline media. Among the different Pd/Ag ratios, the Pd-Ag (1:1)/RGO had the best catalytic activities and stability. So it is a promising catalyst for direct alcohol fuel cell applications.

  11. Electrocatalytic hydrodehalogenation of atrazine in aqueous solution by Cu@Pd/Ti catalyst.

    PubMed

    Chen, Ya-Li; Xiong, Lu; Song, Xiang-Ning; Wang, Wei-Kang; Huang, Yu-Xi; Yu, Han-Qing

    2015-04-01

    Electrocatalytic hydrodehalogenation is a cost-effective approach to degrade halogenated organic pollutants in groundwater, and Pd-based catalysts have been found to be an efficient cathode material for this purpose. In this work, a novel Cu@Pd bimetallic catalyst loaded on Ti plate was prepared via combined electrodeposition and galvanic replacement for electrocatalytic hydrodehalogenation of atrazine, a typical halogenated pollutant. The obtained bimetallic catalyst with uniformly dispersed Pd nanoparticles possessed a large electrochemically active surface area of 572 cm2. The Cu@Pd/Ti cathode exhibited a higher electrocatalytic efficiency towards atrazine reduction than the individual Pd/Ti or Cu/Ti cathodes, and achieved up to 91.5% within 120 min under a current density of 1 mA cm(-2). Such an electrocatalytic reduction followed pseudo-first-order kinetics with a rate constant of 0.0214 min(-1). Atrazine was selectively transformed to dechlorinated atrazine, and its degradation pathway was identified. Current density was found to have a critical influence on the atrazine reduction due to the competitive hydrogen evolution reaction at a higher current density. The fabricated bimetallic catalyst also exhibited a good stability. This work provides an efficient and stable electrocatalyst for chlorinated contaminate removal and groundwater remediation. PMID:25697805

  12. Deviations from one-electron behavior in the Ag and Pd M4,5-VV Auger spectra of AgcPd1-c alloys

    NASA Astrophysics Data System (ADS)

    Mariot, J.-M.; Hague, C. F.; Dufour, G.

    1981-04-01

    A systematic investigation of the Ag and Pd M4,5-VV Auger spectra in the pure metals and in the AgcPd1-c(0.1<=c<=0.9) alloys is presented. The shape of the Auger spectra is discussed in relation to the values of the effective Coulomb interaction Ueff between the two holes present in the final state of the Auger transition and of the width W of the one-electron local densities of states as obtained from Lβ2,15 soft-x-ray emission bands. The Auger spectra of Ag in the metal and the alloys have a pronounced quasiatomic character, as can be expected from the Ueff2W ratio which is found to be close to unity. The Auger spectrum of pure Pd (Ueff2W~0.4) can be explained in terms of an atomic model in which strong band effects are present. For alloys with low-Pd content where Pd forms an impurity state, it is shown that final states other than the localized [4d2] two-hole state have to be invoked to explain the line shape.

  13. Characterization of Cu3P phase in Sn3.0Ag0.5Cu0.5P/Cu solder joints

    NASA Astrophysics Data System (ADS)

    Chen, Jian-xun; Zhao, Xing-ke; Zou, Xu-chen; Huang, Ji-hua; Hu, Hai-chun; Luo, Hai-lian

    2014-01-01

    This article reports the effects of phosphorus addition on the melting behavior, microstructure, and mechanical properties of Sn3.0Ag0.5Cu solder. The melting behavior of the solder alloys was determined by differential scanning calorimetry. The interfacial microstructure and phase composition of solder/Cu joints were studied by scanning electron microscopy and energy dispersive spectrometry. Thermodynamics of Cu-P phase formation at the interface between Sn3.0Ag0.5Cu0.5P solder and the Cu substrate was characterized. The results indicate that P addition into Sn3.0Ag0.5Cu solder can change the microstructure and cause the appearance of rod-like Cu3P phase which is distributed randomly in the solder bulk. The Sn3.0Ag0.5Cu0.5P joint shows a mixture of ductile and brittle fracture after shear testing. Meanwhile, the solidus temperature of Sn3.0Ag0.5Cu solder is slightly enhanced with P addition.

  14. Differential Responsivity of the Organic-Inorganic Ag/n-GaAs/p-CuPc/Ag Photoelectric Sensor

    NASA Astrophysics Data System (ADS)

    Karimov, Kh. S.; Qazi, I.; Fedorov, M. I.; Moiz, S. A.; Khan, T. A.; Senin, H. B.

    2007-05-01

    A thin film of copper phthalocynanine (CuPc) as p-type semiconductor was deposited by vacuum evaporation on an n-type GaAs single-crystal semiconductor substrate. Then semitransparent Ag thin film having gradient of thickness was deposited on CuPc film by thermal evaporation in vacuum to fabricate Ag/n-GaAs/p-CuPc/Ag sensor. Due to gradient of thickness, 6% and 10% of the incident light can be transmitted through the silver film in the edge and in the center of the sample respectively. Open circuit voltage and short circuit current were measured by exposing only a small area of the sensor to light i.e. in differential mode of operation. It was observed that open-circuit voltage and short-circuit current depends on position of the exposed area of the sensor to light. In differential mode of operation the open-circuit voltage and short circuit current versus intensity of illumination showed less non linearity as compared to integral mode of operation. On the basis of experimental data, an equivalent circuit of the sensor was designed and its computer simulation was carried out. The simulated data matched reasonably with the experimental curves. It was found that in differential mode of operation the Ag/n-GaAs/p-CuPc/Ag sensor's output voltage and current depends on the position of light beam probe. Due to this the sensor may be used as a photoelectric displacement transducer.

  15. Electronic structure of disordered CuPd alloys by positron-annihilation 2D-ACAR

    SciTech Connect

    Smedskjaer, L.C.; Benedek, R.; Siegel, R.W.; Legnini, D.G.; Stahulak, M.D.; Bansil, A.

    1988-01-01

    We report 2D-ACAR experiments and KKR CPA calculations on alpha-phase single-crystal Cu/sub 1-x/Pd/sub x/ in the range x less than or equal to 0.25. The flattening of the Fermi surface near (110) with increasing x predicted by theory is confirmed by our experimental results. 16 refs., 2 figs.

  16. Highly efficient hydrogen generation from methanolysis of ammonia borane on CuPd alloy nanoparticles

    NASA Astrophysics Data System (ADS)

    Li, Pengyao; Xiao, Zhengli; Liu, Zhaoyan; Huang, Jiale; Li, Qingbiao; Sun, Daohua

    2015-01-01

    A low-cost and facile route has been developed for the synthesis of monodisperse CuPd nanoparticles with tunable composition. (Scanning transmission electron microscopy-energy-dispersive x-ray spectroscopy) STEM-EDX results verified the structure of the alloy for the obtained nanoparticles. These CuPd nanoparticles supported on carbon were active catalysts for hydrogen generation from the methanolysis of ammonia borane (AB) at room temperature, and their activities were closely related with the compositions. Cu48Pd52 NPs exhibited the highest activity among the tested catalysts. Moreover, their activity can be further improved by thermal annealing at 300 °C under nitrogen flow, with a very high total turnover frequency value of 53.2 min-1. The reusability test indicated that the Cu48Pd52/C catalyst retains 86% of its initial activity and 100% conversion after 8 cycles. The catalyst, which features lost cost and high efficiency, may help move forward the practical application of AB as a sustainable hydrogen storage material.

  17. Cu-Ag core-shell nanoparticles with enhanced oxidation stability for printed electronics

    NASA Astrophysics Data System (ADS)

    Lee, Changsoo; Kim, Na Rae; Koo, Jahyun; Jong Lee, Yung; Lee, Hyuck Mo

    2015-11-01

    In this work, we synthesized uniform Cu-Ag core-shell nanoparticles using a facile two-step process that consists of thermal decomposition and galvanic displacement methods. The core-shell structure of these nanoparticles was confirmed through characterization using transmission electron microscopy, energy-dispersive spectroscopy, and x-ray diffraction. Furthermore, we investigated the oxidation stability of the Cu-Ag core-shell nanoparticles in detail. Both qualitative and quantitative x-ray photoelectron spectroscopy analyses confirm that the Cu-Ag core-shell nanoparticles have considerably higher oxidation stability than Cu nanoparticles. Finally, we formulated a conductive ink using the synthesized nanoparticles and coated it onto glass substrates. Following the sintering process, we compared the resistivity of the Cu-Ag core-shell nanoparticles with that of the Cu nanoparticles. The results of this study clearly show that the Cu-Ag core-shell nanoparticles can potentially be used as an alternative to Ag nanoparticles because of their superior oxidation stability and electrical properties.

  18. Thermoelectric Properties of CuAgSe doped with Co, Cr

    NASA Astrophysics Data System (ADS)

    Czajka, Peter; Yao, Mengliang; Opeil, Cyril

    Thermoelectric materials represent one way that reliable cooling below the boiling point of nitrogen can be realized. Current materials do not exhibit sufficiently high efficiencies at cryogenic temperatures, but significant progress is being made. One material that has generated significant interest recently is CuAgSe. It has been demonstrated (Ishiwata et al., Nature Mater. 2013) that doping CuAgSe with 10% Ni at the Cu sites increases the material's thermoelectric figure of merit (ZT) at 100 K from 0.02 to 0.10. This is intriguing not just because of the dramatic effect that the Ni doping produces, but also because CuAgSe is a semimetal and semimetals are not usually able to exhibit the kind of asymmetric carrier activation necessary for strong thermoelectric performance. In order to further investigate the unusual nature of thermoelectricity in CuAgSe and its strong dependence on chemical composition, we have synthesized and measured the thermoelectric properties of a series of CuAgSe samples doped with Co and Cr. Temperature-dependent magnetic and thermoelectric transport properties of CuAgSe as a function of Co and Cr doping will be discussed. This work is supported by the Department of Defense, AFOSR, MURI Program Contract # FA9550-10-1-0533 and the Trustees of Boston College.

  19. Photoelectron spectroscopic and computational study of (M-CO2)- anions, M = Cu, Ag, Au

    NASA Astrophysics Data System (ADS)

    Zhang, Xinxing; Lim, Eunhak; Kim, Seong K.; Bowen, Kit H.

    2015-11-01

    In a combined photoelectron spectroscopic and computational study of (M-CO2)-, M = Au, Ag, Cu, anionic complexes, we show that (Au-CO2)- forms both the chemisorbed and physisorbed isomers, AuCO 2- and Au-(CO2), respectively; that (Ag-CO2)- forms only the physisorbed isomer, Ag-(CO2); and that (Cu-CO2)- forms only the chemisorbed isomer, CuCO 2- . The two chemisorbed complexes, AuCO 2- and CuCO 2- , are covalently bound, formate-like anions, in which their CO2 moieties are significantly reduced. These two species are examples of electron-induced CO2 activation. The two physisorbed complexes, Au-(CO2) and Ag-(CO2), are electrostatically and thus weakly bound.

  20. New bulk glassy alloys in Cu-Zr-Ag ternary system prepared by casting and milling

    NASA Astrophysics Data System (ADS)

    Janovszky, D.; Tomolya, K.; Sveda, M.; Solyom, J.; Roosz, A.

    2009-01-01

    The thermal stability, crystallization behaviour and glass forming ability of Cu-Zr-Ag system have been investigated on the basis of a ternary phase diagram. We altered the concentration of the alloys from the Cu58Zr42 to the concentration of the deep eutectic point of the Cu-Zr-Ag ternary system and we calculated the glass forming ability parameters. This paper summerises the results of the procedure during which Cu-Zr-Ag amorphous alloys with different Ag content (0-25%) were prepared by casting and ball-milling. Wedge-shaped samples were prepared from the ingots by centrifugal casting into copper mold. The supercooled liquid region (ΔTx) exceeded 75K. Following the characterization of the cast alloys, master alloys of identical composition were milled in a Fritsch Pulverisette 2 ball-mill. The powders, milled for various periods of time were analysed by XRD in order to define the amorphous fraction.

  1. Structural and magnetic properties of Cu-alloyed FePd films

    NASA Astrophysics Data System (ADS)

    Polit, A.; Makarov, D.; Brombacher, C.; Krupinski, M.; Perzanowski, M.; Zabila, Y.; Albrecht, M.; Marszałek, M.

    2015-05-01

    Multilayer films [Cu(d Å)/Fe(9 Å)/Pd(11 Å)]5 were deposited at room temperature on Si(001)/SiO2(400 nm) substrates. In order to induce chemical L10 ordering, the as-deposited samples were post-annealed by rapid thermal annealing (RTA) at 600 °C for 90 s followed additionally by heating in ultra-high vacuum (UHV) at 700 °C up to several hours. In this study the impact of post-annealing on the structural and magnetic properties of FePdCu alloy films in dependence on the Cu content was investigated. It was found that the addition of Cu to the FePd alloy has a strong influence on the chemical ordering process and the (001) texture formation. After the RTA treatment only an isotropic distribution of the easy axis of magnetization with coercive fields in the range of a few hundred mT was observed. In contrast, samples which were additionally heated for 1 h at 700 °C revealed an out-of-plane easy axis of magnetization with an effective magnetic anisotropy of about 2×105 J/m3 for the sample containing 10 at% of Cu.

  2. Understanding the enhanced catalytic activity of Cu1@Pd3(111) in formic acid dissociation, a theoretical perspective

    NASA Astrophysics Data System (ADS)

    He, Feng; Li, Kai; Xie, Guangyou; Wang, Ying; Jiao, Menggai; Tang, Hao; Wu, Zhijian

    2016-06-01

    The bimetallic Cu1@Pd3(111) catalyst has been synthesized recently and exhibits better catalytic activity and durability compared with pure Pd(111) as anode catalyst in direct formic acid fuel cells (DFAFCs). In this work, we studied the reaction mechanism of formic acid dissociation on both Pd(111) and Cu1@Pd3(111) by using the density functional method. Our calculations showed that the surface adsorption of the poisoning species CO on Cu1@Pd3(111) is weakened mainly by the strain effect rather than the Cusbnd Pd ligand effect. The Cu1@Pd3(111) can effectively promote the catalytic activity for formic acid dissociation by decreasing the barrier of CO2 formation from the preferential trans-COOH intermediate and increasing the barrier of CO formation from the reduction of CO2. We found that the H atom accumulation, electron accumulation and low electrode potential could accelerate the catalyst deactivation due to the contamination of the poisoning species CO. Furthermore, under low anode potential, the Cu1@Pd3(111) has better durability than pure Pd(111), which can be attributed to the unfavorable CO formation and the favorable CO desorption.

  3. A highly sensitive non-enzymatic glucose sensor based on bimetallic Cu-Ag superstructures.

    PubMed

    Li, Hua; Guo, Chun-Yan; Xu, Cai-Ling

    2015-01-15

    Bimetallic Cu-Ag superstructures were successfully fabricated for the first time by using the natural leaves as reducing agent through a facile one-step hydrothermal process. Morphology, structure and composition of the Cu-Ag superstructures were characterized by field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), X-ray photoelectron spectra (XPS) and inductively coupled plasma-optical emission spectroscopy (ICP-OES), respectively. The results reveal that the Cu-Ag superstructure is bimetallic nanocomposite constructed by nanoparticles with low Ag content and shows a rough surface and porous flexural algae-like microstructure. By using a three-dimensional nickel foam as the scaffold, a novel non-enzymatic glucose sensor based on Cu-Ag nanocomposites has been fabricated and applied to non-enzymatic glucose detection. The as-prepared Cu-Ag nanocomposites based glucose sensor displays distinctly enhanced electrocatalytic activity compared to those obtained with pure Cu nanomaterials prepared with a similar procedure, revealing a synergistic effect of the matrix Cu and the doped Ag. Cyclic voltammetry, chronoamperometry and electrochemical impedance spectroscopy indicate that the Cu-Ag superstructures based glucose sensor displays a fascinating sensitivity up to 7745.7 μA mM(-1) cm(-2), outstanding detection limit of 0.08 μM and fast amperometric response (<2 s) for glucose detection. Furthermore, the sensor also exhibits significant selectivity, excellent stability and reproducibility, as well as attractive feasibility for real sample analysis. Because of its excellent electrochemical performance, low cost and easy preparation, this novel electrode material is a promising candidate in the development of non-enzymatic glucose sensor. PMID:25113052

  4. A green approach to ethyl acetate: quantitative conversion of ethanol through direct dehydrogenation in a Pd-Ag membrane reactor.

    PubMed

    Zeng, Gaofeng; Chen, Tao; He, Lipeng; Pinnau, Ingo; Lai, Zhiping; Huang, Kuo-Wei

    2012-12-01

    Pincers do the trick: The conversion of ethanol to ethyl acetate and hydrogen was achieved using a pincer-Ru catalyst in a Pd-Ag membrane reactor. Near quantitative conversions and yields could be achieved without the need for acid or base promoters or hydrogen acceptors (see scheme). PMID:23136053

  5. Green Synthesis of Ag and Pd Nanospheres, Nanowires, and Nanorods Using Vitamin B2: Catalytic Polymerisation of Aniline and Pyrrole

    EPA Science Inventory

    For the first time, we report green chemistry approach using vitamin B2 in the synthesis of silver (Ag) and palladium (Pd), nanospheres, nanowires and nanorods at room temperature without using any harmful reducing agents, such as sodium borohydride (NaBH4) or hydroxylamine hydro...

  6. H2 dissociation on γ-Al2O3 supported Cu/Pd atoms: A DFT investigation

    NASA Astrophysics Data System (ADS)

    Wang, Hongtao; Chen, Lijuan; Lv, Yongkang; Ren, Ruipeng

    2014-01-01

    The density functional theory (DFT) was applied to investigate the promotion effects of single Cu and Pd atoms deposition on γ-Al2O3 surface for the adsorption and dissociation of H2 molecule, which is of importance for many catalysis reactions. Due to its strong Lewis acidity, the tri-coordinated surface Al site was identified to be the most preferable site for both Cu and Pd location. The inner surface electrons rearrangement from O to Al of alumina was found to be a key factor to stabilize the Cu/Pd adsorption configurations, rather than the total electrons transfer between Cu/Pd and the surface. It was found that the supported Cu and Pd atoms are more active for H2 dissociation than the clean γ-Al2O3 surface. The supported Pd is more active than Cu for H2 dissociation. In addition, the metal-support interaction of the γ-Al2O3 supported Cu/Pd atoms are more favored than the metal-metal interaction of the metal clusters for the H2 dissociated adsorption.

  7. Ti/Pd/Ag Contacts to n-Type GaAs for High Current Density Devices

    NASA Astrophysics Data System (ADS)

    Huo, Pengyun; Rey-Stolle, Ignacio

    2016-06-01

    The metallization stack Ti/Pd/Ag on n-type Si has been readily used in solar cells due to its low metal/semiconductor specific contact resistance, very high sheet conductance, bondability, long-term durability, and cost-effectiveness. In this study, the use of Ti/Pd/Ag metallization on n-type GaAs is examined, targeting electronic devices that need to handle high current densities and with grid-like contacts with limited surface coverage (i.e., solar cells, lasers, or light emitting diodes). Ti/Pd/Ag (50 nm/50 nm/1000 nm) metal layers were deposited on n-type GaAs by electron beam evaporation and the contact quality was assessed for different doping levels (from 1.3 × 1018 cm-3 to 1.6 × 1019 cm-3) and annealing temperatures (from 300°C to 750°C). The metal/semiconductor specific contact resistance, metal resistivity, and the morphology of the contacts were studied. The results show that samples doped in the range of 1018 cm-3 had Schottky-like I- V characteristics and only samples doped 1.6 × 1019 cm-3 exhibited ohmic behavior even before annealing. For the ohmic contacts, increasing annealing temperature causes a decrease in the specific contact resistance ( ρ c,Ti/Pd/Ag ~ 5 × 10-4 Ω cm2). In regard to the metal resistivity, Ti/Pd/Ag metallization presents a very good metal conductivity for samples treated below 500°C ( ρ M,Ti/Pd/Ag ~ 2.3 × 10-6 Ω cm); however, for samples treated at 750°C, metal resistivity is strongly degraded due to morphological degradation and contamination in the silver overlayer. As compared to the classic AuGe/Ni/Au metal system, the Ti/Pd/Ag system shows higher metal/semiconductor specific contact resistance and one order of magnitude lower metal resistivity.

  8. The influence of hydrogen sulfide-to-hydrogen partial pressure ratio on the sulfidization of Pd and 70 mol% Pd-Cu membranes

    SciTech Connect

    Iyoha, O.; Enick, R.M.; Killmeyer, R.P.; Morreale, B.D.

    2007-11-15

    The influence of H2S-to-H2 partial pressure ratio on the sulfidization of Pd and 70 mol% Pd–Cu membrane alloys was studied using various H2S-containing gas mixtures. The Pd membranes exposed to various H2S mixtures were in very good agreement with the thermodynamic calculations used in this study, resisting sulfidization when exposed to H2S-to-H2 ratios below the equilibrium value predicted for Pd4S formation, and experiencing sulfidization when exposed to ratios above the equilibrium values. The 70 mol% Pd–Cu membranes, however, exhibited deviations from the predicted values, resisting sulfidization at some conditions close to the equilibrium values at which sulfidization was expected, and experiencing sulfidization at some conditions at which resistance was expected. This phenomenon was attributed to deviations of the Pd–Cu alloy from ideality, probably due to Cu segregation at the membrane surface.

  9. Mechanical Properties and Electrochemical Corrosion Behavior of Al/Sn-9Zn- xAg/Cu Joints

    NASA Astrophysics Data System (ADS)

    Huang, M. L.; Huang, Y. Z.; Ma, H. T.; Zhao, J.

    2011-03-01

    The effect of Ag content on the wetting behavior of Sn-9Zn- xAg on aluminum and copper substrates during soldering, as well as the mechanical properties and electrochemical corrosion behavior of Al/Sn-9Zn- xAg/Cu solder joints, were investigated in the present work. Tiny Zn and coarsened dendritic AgZn3 regions were distributed in the Sn matrix in the bulk Sn-9Zn- xAg solders, and the amount of Zn decreased while that of AgZn3 increased with increasing Ag content. The wettability of Sn-9Zn-1.5Ag solder on Cu substrate was better than those of the other Sn-9Zn- xAg solders but worse than that of Sn-9Zn solder. The wettability of Sn-9Zn-1.5Ag on the Al substrate was also better than those of the other Sn-9Zn- xAg solders, and even better than that of Sn-9Zn solder. The Al/Sn-9Zn/Cu joint had the highest shear strength, and the shear strength of the Al/Sn-9Zn- xAg/Cu ( x = 0 wt.% to 3 wt.%) joints gradually decreased with increasing Ag content. The corrosion resistance of the Sn-9Zn- xAg solders in Al/Sn-9Zn- xAg/Cu joints in 5% NaCl solution was improved compared with that of Sn-9Zn. The corrosion potential of Sn-9Zn- xAg solders continuously increased with increasing Ag content from 0 wt.% to 2 wt.% but then decreased for Sn-9Zn-3Ag. The addition of Ag resulted in the formation of the AgZn3 phase and in a reduction of the amount of the eutectic Zn phase in the solder matrix; therefore, the corrosion resistance of the Al/Sn-9Zn- xAg/Cu joints was improved.

  10. Effect of Synthesis Techniques on Crystallization and Optical Properties of Ag-Cu Bimetallic Nanoparticles

    NASA Astrophysics Data System (ADS)

    Xiong, Ziye; Qin, Fen; Huang, Po-Shun; Nettleship, Ian; Lee, Jung-Kun

    2016-04-01

    Silver (Ag)-copper (Cu) bimetallic nanoparticles (NPs) were synthesized by the reduction of silver nitrate and copper (II) acetate monohydrate using ethylene glycol in a microwave (MW) heating system with controlled reaction times ranging from 5 min to 30 min. The molar ratio Ag/Cu was varied from 1:1 to 1:3. The effect of reaction conditions on the bimetallic NPs structures and compositions were characterized by x-ray photoelectron spectroscopy, x-ray diffraction and transmission electron microscopy. The average particle size was approximately 150 nm. The surface plasmon resonance (SPR) of Ag-Cu bimetallic NPs was investigated by monitoring the SPR band peak behavior via UV/Vis spectrophotometry. The resonance peak positions and peak widths varied due to the different structures of the bimetallic NPs created under the synthesis conditions. In the MW heating method, the reduction of Cu was increased and Cu was inhomogeneously deposited over the Ag cores. As the composition of Cu becoming higher in the Ag-Cu bimetallic NPs, the absorption between 400 nm to 600 nm was greatly enhanced.

  11. Fabrication of Cu-Ag core-shell bimetallic superfine powders by eco-friendly reagents and structures characterization

    NASA Astrophysics Data System (ADS)

    Zhao, Jun; Zhang, Dongming; Zhao, Jie

    2011-09-01

    Superfine bimetallic Cu-Ag core-shell powders were synthesized by reduction of copper sulfate pentahydrate and silver nitrate with eco-friendly ascorbic acid as a reducing agent and cyclodextrins as a protective agent in an aqueous system. The influence of Ag/Cu ratio on coatings was investigated. Ag was homogeneously distributed on the surface of Cu particles at a mole ratio of Ag/Cu=1. FE-SEM showed an uniformity of Ag coatings on Cu particles. Antioxidation of Cu particles was improved by increasing Ag/Cu ratio. TEM-EDX and UV-vis spectra also revealed that Cu cores were covered by Ag nanoshells on the whole. The surface composition analysis by XPS indicated that only small parts of Cu atoms in the surface were oxidized. It was noted that the hindrance of cyclodextrins chemisorbed on particles plays an important role in forming high quality and good dispersity Cu-Ag (Cu@Ag) core-shell powders.

  12. Microstructural investigation of the oxidation behavior of Cu in Ag-coated Cu films using a focused ion beam transmission electron microscopy technique

    NASA Astrophysics Data System (ADS)

    Kim, Ji Hwan; Lee, Jong-Hyun

    2016-06-01

    With the aim of elucidating a detailed mechanism for the oxidation behavior in submicron Cu particles coated with a thin Ag layer, the dewetting of Ag and the oxidation behavior of Cu in Ag-coated Cu films upon heating were investigated with a focused ion beam transmission electron microscopy technique. A slight dewetting of the Ag layer began at approximately 200 °C and aggregates of Cu2O particles were formed on the Ag layer, indicating that the initial Cu2O phase was formed on the thin Ag layer. Voids were formed in the Cu layer because of Cu atoms diffusing through the thin Ag layer to be oxidized in the upper Cu2O aggregates. After being heated to 250 °C, the Ag layer became more irregular, and in some regions, it disappeared because of intensive dewetting. The number and average size of the voids also increased. At 300 °C, a hollow structure with a Cu2O shell was formed. Pillar-like structures of unoxidized Cu and large voids were found under the Cu2O layer.

  13. Cu-Au, Ag-Au, Cu-Ag, and Ni-Au intermetallics: First-principles study of temperature-composition phase diagrams and structures

    NASA Astrophysics Data System (ADS)

    Ozoliņš, V.; Wolverton, C.; Zunger, Alex

    1998-03-01

    The classic metallurgical systems-noble-metal alloys-that have formed the benchmark for various alloy theories are revisited. First-principles fully relaxed general-potential linearized augmented plane-wave (LAPW) total energies of a few ordered structures are used as input to a mixed-space cluster expansion calculation to study the phase stability, thermodynamic properties, and bond lengths in Cu-Au, Ag-Au, Cu-Ag, and Ni-Au alloys. (i) Our theoretical calculations correctly reproduce the tendencies of Ag-Au and Cu-Au to form compounds and Ni-Au and Cu-Ag to phase separate at T=0 K. (ii) Of all possible structures, Cu3Au (L12) and CuAu (L10) are found to be the most stable low-temperature phases of Cu1-xAux with transition temperatures of 530 K and 660 K, respectively, compared to the experimental values 663 K and ~670 K. The significant improvement over previous first-principles studies is attributed to the more accurate treatment of atomic relaxations in the present work. (iii) LAPW formation enthalpies demonstrate that L12, the commonly assumed stable phase of CuAu3, is not the ground state for Au-rich alloys, but rather that ordered (100) superlattices are stabilized. (iv) We extract the nonconfigurational (e.g., vibrational) entropies of formation and obtain large values for the size-mismatched systems: 0.48 kB/atom in Ni0.5Au0.5 (T=1100 K), 0.37 kB/atom in Cu0.141Ag0.859 (T=1052 K), and 0.16 kB/atom in Cu0.5Au0.5 (T=800 K). (v) Using 8 atom/cell special quasirandom structures we study the bond lengths in disordered Cu-Au and Ni-Au alloys and obtain good qualitative agreement with recent extended x-ray-absorption fine-structure measurements.

  14. Kinetics of CO adsorption on epitaxial (111)Cu on (111)Pd thin films

    SciTech Connect

    Oral, B.; Kothari, R.; Vook, R.W.

    1989-05-01

    CO adsorption has been studied on (111)Cu/Pd thin-film surfaces grown epitaxially on mica in UHV of base pressure 5 x 10/sup -11/ Torr. Auger electron spectroscopy investigations of the growth of Cu on (111)Pd films showed that layer growth occurred. The Kelvin probe, work function method was used to monitor the CO adsorption at 298 K as a function of Cu overlayer thickness. It was found that very thin Cu overlayers had a drastic effect on saturation CO coverage: one monolayer of copper reduced the saturation CO coverage by /similar to/95%. For the pure (111)Pd thin-film surface, the data showed that the rate of CO adsorption changes when the CO fractional coverage approaches /similar to/0.4. This result is most likely due to the previously reported change in CO superlattice structure that occurs with increasing coverage. The kinetic adsorption data for various bilayers were interpreted in terms of a first-order Kisliuk mobile precursor model.

  15. Electronic structure of transition metal dichalcogenides PdTe2 and Cu0.05PdTe2 superconductors obtained by angle-resolved photoemission spectroscopy

    NASA Astrophysics Data System (ADS)

    Liu, Yan; Zhao, Jian-Zhou; Yu, Li; Lin, Cheng-Tian; Hu, Cheng; Liu, De-Fa; Peng, Ying-Ying; Xie, Zhuo-Jin; He, Jun-Feng; Chen, Chao-Yu; Feng, Ya; Yi, He-Mian; Liu, Xu; Zhao, Lin; He, Shao-Long; Liu, Guo-Dong; Dong, Xiao-Li; Zhang, Jun; Chen, Chuang-Tian; Xu, Zu-Yan; Weng, Hong-Ming; Dai, Xi; Fang, Zhong; Zhou, Xing-Jiang

    2015-06-01

    The layered transition metal chalcogenides have been a fertile land in solid state physics for many decades. Various MX2-type transition metal dichalcogenides, such as WTe2, IrTe2, and MoS2, have triggered great attention recently, either for the discovery of novel phenomena or some extreme or exotic physical properties, or for their potential applications. PdTe2 is a superconductor in the class of transition metal dichalcogenides, and superconductivity is enhanced in its Cu-intercalated form, Cu0.05PdTe2. It is important to study the electronic structures of PdTe2 and its intercalated form in order to explore for new phenomena and physical properties and understand the related superconductivity enhancement mechanism. Here we report systematic high resolution angle-resolved photoemission (ARPES) studies on PdTe2 and Cu0.05PdTe2 single crystals, combined with the band structure calculations. We present in detail for the first time the complex multi-band Fermi surface topology and densely-arranged band structure of these compounds. By carefully examining the electronic structures of the two systems, we find that Cu-intercalation in PdTe2 results in electron-doping, which causes the band structure to shift downwards by nearly 16 meV in Cu0.05PdTe2. Our results lay a foundation for further exploration and investigation on PdTe2 and related superconductors. Project supported by the National Natural Science Foundation of China (Grant No. 11190022), the National Basic Research Program of China (Grant Nos. 2011CB921703 and 2011CBA00110), and the Strategic Priority Research Program (B) of the Chinese Academy of Sciences (Grant No. XDB07020300).

  16. Surface modification of oleylamine-capped Ag-Cu nanoparticles to fabricate low-temperature-sinterable Ag-Cu nanoink.

    PubMed

    Kim, Na Rae; Lee, Yung Jong; Lee, Changsoo; Koo, Jahyun; Lee, Hyuck Mo

    2016-08-26

    By treating oleylamine (OA)-capped Ag-Cu nanoparticles with tetramethylammonium hydroxide (TMAH), we obtained metal nanoparticles that are suspended in polar solvents and sinterable at low temperatures. The simple process with ultra sonication enables synthesis of monodispersed and high purity nanoparticles in an organic base, where the resulting nanoparticles are dispersible in polar solvents such as ethanol and isopropyl alcohol. To investigate the surface characteristics, we conducted Fourier-transform infrared and zeta-potential analyses. After thermal sintering at 200 °C, which is approximately 150 °C lower than the thermal decomposition temperature of OA, an electrically conductive thin film was obtained. Electrical resistivity measurements of the TMAH-treated ink demonstrate that surface modified nanoparticles have a low resistivity of 13.7 × 10(-6) Ω cm. These results confirm the prospects of using low-temperature sinterable nanoparticles as the electrode layer for flexible printed electronics without damaging other stacked polymer layers. PMID:27454465

  17. Synthesis and anti-bacterial activity of Cu, Ag and Cu-Ag alloy nanoparticles: A green approach

    SciTech Connect

    Valodkar, Mayur; Modi, Shefaly; Pal, Angshuman; Thakore, Sonal

    2011-03-15

    Research highlights: {yields} Synthesis of novel nanosized copper-silver alloys of different compositions. {yields} Completely green approach for synthesis of water soluble bimetallic nanoparticle. {yields} Interesting anti-bacterial activity of as synthesized metal and alloy nanoparticle. -- Abstract: Metallic and bimetallic nanoparticles of copper and silver in various proportions were prepared by microwave assisted chemical reduction in aqueous medium using the biopolymer, starch as a stabilizing agent. Ascorbic acid was used as the reducing agent. The silver and copper nanoparticles exhibited surface plasmon absorption resonance maxima (SPR) at 416 and 584 nm, respectively; while SPR for the Cu-Ag alloys appeared in between depending on the alloy composition. The SPR maxima for bimetallic nanoparticles changes linearly with increasing copper content in the alloy. Transmission electron micrograph (TEM) showed monodispersed particles in the range of 20 {+-} 5 nm size. Both silver and copper nanoparticles exhibited emission band at 485 and 645 nm, respectively. The starch-stabilized nanoparticles exhibited interesting antibacterial activity with both gram positive and gram negative bacteria at micromolar concentrations.

  18. Atmospheric Corrosion of Ag and Cu with Ozone, UV and NaCl

    NASA Astrophysics Data System (ADS)

    Lin, Huang

    Ag and Cu are both used for electronics and are susceptible to atmospheric corrosion. They are also good corrosivity monitors used to evaluate aggressiveness of the environment. Unfortunately, laboratory exposure testing does not always represent field environments very well. Discrepancies between lab and field exposure tests are not uncommon. For example, Ag does not corrode in salt spray exposure during ASTM B117 test, while it corrodes everywhere outdoor. This suggests that new laboratory exposure test for Ag needs to be designed and studied. A full factorial experiment was carried out with three factors: ozone, UV intensity and relative humidity (RH). NaCl was loaded by fast evaporation of NaCl/ethanol solution before exposure. After exposure, corrosion products were identified by XRD and quantified by galvanostatic reduction technique. For lab exposure samples, AgCl was identified as the only corrosion product in high RH (87%) environments, while Ag2O and AgO formed as well during exposures at low RH. This result derived a qualitative prediction on corrosion behavior of Ag in field. It predicts that less stable silver compounds such as oxide and sulfate are possible corrosion products in field even silver chloride is the dominant corrosion product forming in field. This prediction was confirmed by analysis of field exposed Ag samples. By quantification of corrosion products, it is determined that UV has two contravening effects on atmospheric corrosion of Ag: photolysis of ozone to generate stronger oxidizing species such as atomic O and photodecomposition of Ag corrosion products by UV radiation. Following its success in Ag corrosion research, the environment of UV, ozone and NaCl was extended to study Cu corrosion. It is determined that UV alone can double Cu corrosion rate by generation of electron-hole pairs in n-type cuprous oxide. It is also found that ozone alone is not as aggressive on Ag as on Cu because protection of naturally formed cuprous oxide

  19. Green Synthesis of Ag and Pd Nanospheres, Nanowires, and Nanorods Using Vitamin B 2 : Catalytic Polymerisation of Aniline and Pyrrole

    DOE PAGESBeta

    Nadagouda, Mallikarjuna N.; Varma, Rajender S.

    2008-01-01

    Formore » the first time, we report green chemistry approach using vitamin B 2 in the synthesis of silver (Ag) and palladium (Pd), nanospheres, nanowires, and nanorods at room temperature without using any harmful reducing agents, such as sodium borohydride ( NaBH 4 ) or hydroxylamine hydrochloride and any special capping or dispersing agent. Vitamin B 2 was used as reducing agent as well as capping agent due to its high-water solubility, biodegradability, and low-toxicity compared with other reducing agents. The average particle size of nanoprticle was found to be Ag (average size 6.1 ± 0.1 nm) and Pd (average size 4.1 ± 0.1 nm) nanoparticles in ethylene glycol and Ag (average size 5.9 ± 0.1 nm, and average size 6.1 ± 0.1) nanoparticles in acetic acid and NMP, respectively. The formation of noble multiple shape nanostructures and their self assembly were dependent on the solvent employed for the preparation. When water was used as solvent media, Ag and Pd nanoparticles started to self-assemble into rod-like structures and in isopropanol Ag and Pd nanoparticles yielded wire-like structures with a thickness in the range of 10 to 20 nm and several hundred microns in length. In acetone and acetonitrile medium, the Ag and Pd nanoparticles are self-assembled into a regular pattern making nanorod structures with thicknesses ranging from 100 to 200 nm and lengths of a few microns. The so-synthesized nanostructures were characterized using scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy dispersive X-ray (EDX) analysis, and UV spectroscopy. The ensuing Ag and Pd nanoparticles catalyzed the reactions of aniline and pyrrole to generate polyaniline and polypyrrole nanofibers and may find various technological and biological applications. This single-step greener approach is general and can be extended to other noble metals and transition metal oxides.« less

  20. Electron correlation and relativistic effects in the coinage metal compounds. II. Heteronuclear dimers: CuAg, CuAu, and AgAu

    NASA Astrophysics Data System (ADS)

    Kellö, Vladimir; Sadlej, Andrzej J.

    1995-08-01

    Electric properties of heteronuclear dimers of the coinage metals are calculated at the level of the CCSD(T) approximation applied to 38 electrons of the valence and next-to-valence atomic shells. The relativistic effects are accounted for by using the scalar approximation to the Pauli hamiltonian. Both the pure relativistic and mixed relativistic-correlation contributions to energies and electric properties are computed. All calculations have been carried out by using the recently developed first-order polarized basis sets of the coinage metal atoms. In the non-relativistic approximation all studied dimers show only a moderate degree of polarity; the non-relativistic CuAg turns out to be the most polar dimer with the Cu(-)Ag(+) polarity. The relativistic effects considerably reduce the negative value of the CuAg dipole moment, change the sign of the CuAu dipole moment, and make the AgAu molecule the most polar species in the series. Simultaneously, the parallel component of the dipole polarizability shows only a small relativistic contraction. The calculated quasirelativistic interaction potentials have a correct behavior in the vicinity of their minima and give the Re and ωe values in complete agreement with experiment. Much less satisfactory are the dissociation energy data which seem to suffer from the single reference configuration approximation.

  1. Kinetic trapping through coalescence and the formation of patterned Ag-Cu nanoparticles

    NASA Astrophysics Data System (ADS)

    Grammatikopoulos, Panagiotis; Kioseoglou, Joseph; Galea, Antony; Vernieres, Jerome; Benelmekki, Maria; Diaz, Rosa E.; Sowwan, Mukhles

    2016-05-01

    In recent years, due to its inherent flexibility, magnetron-sputtering has been widely used to synthesise bi-metallic nanoparticles (NPs) via subsequent inert-gas cooling and gas-phase condensation of the sputtered atomic vapour. Utilising two separate sputter targets allows for good control over composition. Simultaneously, it involves fast kinetics and non-equilibrium processes, which can trap the nascent NPs into metastable configurations. In this study, we observed such configurations in immiscible, bi-metallic Ag-Cu NPs by scanning transmission electron microscopy (S/TEM) and electron energy-loss spectroscopy (EELS), and noticed a marked difference in the shape of NPs belonging to Ag- and Cu-rich samples. We explained the formation of Janus or Ag@Cu core/shell metastable structures on the grounds of in-flight mixed NP coalescence. We utilised molecular dynamics (MD) and Monte Carlo (MC) computer simulations to demonstrate that such configurations cannot occur as a result of nanoalloy segregation. Instead, sintering at relatively low temperatures can give rise to metastable structures, which eventually can be stabilised by subsequent quenching. Furthermore, we compared the heteroepitaxial diffusivities along various surfaces of both Ag and Cu NPs, and emphasised the differences between the sintering mechanisms of Ag- and Cu-rich NP compositions: small Cu NPs deform as coherent objects on large Ag NPs, whereas small Ag NPs dissolve into large Cu NPs, with their atoms diffusing along specific directions. Taking advantage of this observation, we propose controlled NP coalescence as a method to engineer mixed NPs of a unique, patterned core@partial-shell structure, which we refer to as a ``glass-float'' (ukidama) structure.In recent years, due to its inherent flexibility, magnetron-sputtering has been widely used to synthesise bi-metallic nanoparticles (NPs) via subsequent inert-gas cooling and gas-phase condensation of the sputtered atomic vapour. Utilising two

  2. Interfacial Phenomena in Al/Al, Al/Cu, and Cu/Cu Joints Soldered Using an Al-Zn Alloy with Ag or Cu Additions

    NASA Astrophysics Data System (ADS)

    Pstruś, Janusz; Gancarz, Tomasz

    2014-05-01

    The studies of soldered joints were carried out in systems: Al/solder/Al, Al/solder/Cu, Cu/solder/Cu, where the solder was (Al-Zn)EUT, (Al-Zn)EUT with 0.5, 1.0, and 1.5 at.% of Ag and (Al-Zn)EUT with 0.5, 1.0, and 1.5 at.% of Cu addition. Brazing was performed at 500 °C for 3 min. The EDS analysis indicated that the composition of the layers starting from the Cu pad was CuZn, Cu5Zn8, and CuZn4, respectively. Wetting tests were performed at 500 °C for 3, 8, 15, and 30 min, respectively. Thickness of the layers and their kinetics of growth were measured based on the SEM micrographs. The formation of interlayers was not observed from the side of Al pads. On the contrary, dissolution of the Al substrate and migration of Al-rich particles into the bulk of the solder were observed.

  3. The interaction of Ag with Bi-Pb-Sr-Ca-Cu-O superconductor

    NASA Astrophysics Data System (ADS)

    Dou, S. X.; Song, K. H.; Liu, H. K.; Sorrell, C. C.; Apperley, M. H.; Gouch, A. J.; Savvides, N.; Hensley, D. W.

    1989-10-01

    Bi-Pb-Sr-Ca-Cu-O superconductor compounds have been doped with up to 30 wt% Ag, sintered under variable oxygen partial pressure, and characterised in terms of the electrical and crystallographic behaviour. In contrast to previous reports that claim that Ag is the only metal non-poisoning to the superconductivity of Bi-Sr-Ca-Cu-O (BSCCO), it has been found that Ag additions to Bi-Pb-Sr-Ca-Cu-O depress Tc and Jc drastically and cause a large decrease in lattice parameters when samples are treated in air or pure oxygen. However, the lattice parameters, Tc and Jc remain unaffected by Ag additions when samples are heat treated in 0.030-0.067 atm oxygen. It is clear that the Ag reacts with and destabilises the superconducting phase when the samples are treated in air or pure oxygen while, when the samples are heat treated in low oxygen partial pressures, the Ag remains as an isolated inert metal phase that improves the weak links between the grains. This discovery clearly shows the feasibility of Ag-clad superconductor wire. For Ag-clad superconductor tape of 0.1 mm 2 cross sectional area heat treated in air, Jc was measured to be 54 A/cm 2. The same specimen sintered in 0.067 atm oxygen showed that the Jc increased to 2078 A/cm 2.

  4. Nano-Nucleation Characteristic of Cu-Ag Alloy Directly Electrodeposited on W Diffusion Barrier for Microelectronic Device Interconnect.

    PubMed

    Kim, Kang O; Kim, Sunjung

    2016-05-01

    Cu-Ag alloy interconnect is promising for ultra-large-scale integration (ULSI) microelectronic system of which device dimension keeps shrinking. In this study, seedless electrodeposition of Cu-Ag alloy directly on W diffusion barrier as interconnect technology is presented in respect of nano-nucleation control. Chemical equilibrium state of electrolyte was fundamentally investigated according to the pH of electrolyte because direct nano-nucleation of Cu-Ag alloy on W surface is challenging. Chelation behavior of Cu2+ and Ag+ ions with citrate (Cit) and ammonia ligands was dependent on the pH of electrolyte. The amount and kind of Cu- and Ag-based complexes determine the deposition rate, size, elemental composition, and surface morphology of Cu-Ag alloy nano-nuclei formed on W surface. PMID:27483895

  5. Ag- and Cu-doped multifunctional bioactive nanostructured TiCaPCON films

    NASA Astrophysics Data System (ADS)

    Shtansky, D. V.; Batenina, I. V.; Kiryukhantsev-Korneev, Ph. V.; Sheveyko, A. N.; Kuptsov, K. A.; Zhitnyak, I. Y.; Anisimova, N. Yu.; Gloushankova, N. A.

    2013-11-01

    A key property of multicomponent bioactive nanostructured Ti(C,N)-based films doped with Ca, P, and O (TiCaPCON) that can be improved further is their antibacterial effect that should be achieved without compromising the implant bioactivity and biocompatibility. The present work is focused on the study of structure, chemical, mechanical, tribological, and biological properties of Ag- and Cu-doped TiCaPCON films. The films with Ag (0.4-4 at.%) and Cu (13 at.%) contents were obtained by simultaneous sputtering of a TiC0.5-Ca3(PO4)2 target and either an Ag or a Cu target. The film structure was studied using X-ray diffraction, transmission and scanning electron microscopy, energy dispersive X-ray spectroscopy, glow discharge optical emission spectroscopy, and Raman-shift and IR spectroscopy. The films were characterized in terms of their hardness, elastic modulus, dynamic impact resistance, friction coefficient and wear rate (both in air and normal saline), surface wettability, electrochemical behavior and Ag or Cu ion release in normal saline. Particular attention was paid to the influence of inorganic bactericides (Ag and Cu ions) on the bactericidal activity against unicellular yeast fungus Saccharomyces cerevisiae and gram-positive bacteria Lactobacillus acidophilus, as well as on the attachment, spreading, actin cytoskeleton organization, focal adhesions, and early stages of osteoblastic cell differentiation. The obtained results show that the Ag-doped films are more suitable for the protection of metallic surfaces against bacterial infection compared with their Cu-doped counterpart. In particular, an excellent combination of mechanical, tribological, and biological properties makes Ag-doped TiCaPCON film with 1.2 at.% of Ag very attractive material for bioengineering and modification of load-bearing metal implant surfaces.

  6. High glass-forming ability correlated with fragility of Mg-Cu(Ag)-Gd alloys

    NASA Astrophysics Data System (ADS)

    Zheng, Qiang; Xu, Jian; Ma, Evan

    2007-12-01

    We report bulk metallic glasses with critical diameter (Dc) in the 20-27mm range over a relatively wide composition range in the Mg-Cu-Ag-Gd quaternary system. Such an extraordinary glass-forming ability is correlated with the relatively strong liquid behavior of these alloys in terms of Angell's [Science 267, 1924 (1995)] fragility concept. The relaxation time of the ternary Mg61Cu28Gd11 and quaternary Mg59.5Cu22.9Ag6.6Gd11 alloys was measured. In terms of the fragility parameter D*, the Mg59.5Cu22.9Ag6.6Gd11 alloy with a critical diameter of 27mm under copper mold casting has a D* of 25, higher than all the bulk metallic glass-forming alloys reported so far. The implications of these findings are discussed.

  7. Kinetic trapping through coalescence and the formation of patterned Ag-Cu nanoparticles.

    PubMed

    Grammatikopoulos, Panagiotis; Kioseoglou, Joseph; Galea, Antony; Vernieres, Jerome; Benelmekki, Maria; Diaz, Rosa E; Sowwan, Mukhles

    2016-05-14

    In recent years, due to its inherent flexibility, magnetron-sputtering has been widely used to synthesise bi-metallic nanoparticles (NPs) via subsequent inert-gas cooling and gas-phase condensation of the sputtered atomic vapour. Utilising two separate sputter targets allows for good control over composition. Simultaneously, it involves fast kinetics and non-equilibrium processes, which can trap the nascent NPs into metastable configurations. In this study, we observed such configurations in immiscible, bi-metallic Ag-Cu NPs by scanning transmission electron microscopy (S/TEM) and electron energy-loss spectroscopy (EELS), and noticed a marked difference in the shape of NPs belonging to Ag- and Cu-rich samples. We explained the formation of Janus or Ag@Cu core/shell metastable structures on the grounds of in-flight mixed NP coalescence. We utilised molecular dynamics (MD) and Monte Carlo (MC) computer simulations to demonstrate that such configurations cannot occur as a result of nanoalloy segregation. Instead, sintering at relatively low temperatures can give rise to metastable structures, which eventually can be stabilised by subsequent quenching. Furthermore, we compared the heteroepitaxial diffusivities along various surfaces of both Ag and Cu NPs, and emphasised the differences between the sintering mechanisms of Ag- and Cu-rich NP compositions: small Cu NPs deform as coherent objects on large Ag NPs, whereas small Ag NPs dissolve into large Cu NPs, with their atoms diffusing along specific directions. Taking advantage of this observation, we propose controlled NP coalescence as a method to engineer mixed NPs of a unique, patterned core@partial-shell structure, which we refer to as a "glass-float" (ukidama) structure. PMID:27119383

  8. Study of tribological behavior of Cu-MoS2 and Ag-MoS2 nanocomposite lubricants.

    PubMed

    An, V; Anisimov, E; Druzyanova, V; Burtsev, N; Shulepov, I; Khaskelberg, M

    2016-01-01

    Tribological behavior of Cu-MoS2 and Ag-MoS2 nanocomposite lubricant was studied. Cu nanoparticles produced by electrical explosion of copper wires and Ag nanoparticles prepared by electrospark erosion were employed as metal cladding modifiers of MoS2 nanolamellar particles. The tribological tests showed Cu-MoS2 and Ag-MoS2 nanocomposite lubricants changed the friction coefficient of the initial grease and essentially improved its wear resistance. PMID:26837277

  9. Distribution of Ag in Cu-sulfides in Kupferschiefer deposit, SW Poland

    NASA Astrophysics Data System (ADS)

    Kozub, Gabriela A.

    2014-05-01

    The Cu-Ag Kupferschiefer deposit located at the Fore-Sudetic Monocline (SW Poland) is a world class deposit of stratabound type. The Cu-Ag mineralization in the deposit occurs in the Permian sedimentary rocks (Rotliegend and Zechstein) in three lithological types of ore: the dolomite, the black shale and the sandstone. Silver, next to copper, is the most important element in the Kupferschiefer deposit (Salamon 1979; Piestrzyński 2007; Pieczonka 2011). Although occurrence of the Ag-minerals such as native silver, silver amalgams, stromeyerite, jalpaite and mckinstryite, silver is mainly present in the deposit due to isomorphic substitutions in Cu-minerals such as chalcocite, bornite, tennantite, covellite and chalcopyrite. The aim of the study was to define distribution of silver in Cu-minerals and correlate occurrence of Ag-enriched Cu-sulfides with native silver and silver amalgams. Identification of minerals and textural observation were performed using field emission scanning electron microscope. Analyzes of chemical composition of Cu-sulfides were performed utilizing electron microprobe. Silver concentration in Cu sulfides ranges from 0.1 to 10.4 wt.% in chalcocite, 0.2-15.8 wt.% in bornite, 0.1-2.9 wt.% in tennantite, 0.05-0.3 wt.% in chalcopyrite and ca. 0.4 wt.% in covellite. In general, distribution of silver in Cu-minerals is irregular, as indicated by high variations of Ag concentration in each mineral. Content of Ag in Cu-sulphides, in samples where native silver and silver amalgams are not found, is lower than in samples, where native silver and silver amalgams are noted. The chemical analyzes of Ag-bearing Cu-minerals indicate decrease of Cu content in minerals with high Ag concentration. In such case, decrease of Fe content is also noted in bornite. Lack of micro-inclusions of the native silver or silver amalgams in the Cu-minerals indicates that presence of Ag is mainly related to the isomorphic substitutions. This is in agreement with previous

  10. Luminescent Ag i-Cu i heterometallic hexa-, octa-, and hexadecanuclear alkynyl complexes.

    PubMed

    Wei, Qiao-Hua; Yin, Gang-Qiang; Zhang, Li-Yi; Shi, Lin-Xi; Mao, Zong-Wan; Chen, Zhong-Ning

    2004-05-31

    A series of Ag(I)-Cu(I) heteronuclear alkynyl complexes were prepared by reaction of polymeric (MCCC(6)H(4)R-4)(n)() (M = Cu(I) or Ag(I); R = H, CH(3), OCH(3), NO(2), COCH(3)) with [M'(2)(mu-Ph(2)PXPPh(2))(2)(MeCN)(2)](ClO(4))(2) (M' = Ag(I) or Cu(I); X = NH or CH(2)). Heterohexanuclear complexes [Ag(4)Cu(2)(mu-Ph(2)PNHPPh(2))(4)(CCC(6)H(4)R-4)(4)](ClO(4))(2) (R = H, 1; CH(3), 2) were afforded when X = NH, and heterooctanuclear complexes [Ag(6)Cu(2)(micro-Ph(2)PCH(2)PPh(2))(3)(CCC(6)H(4)R-4)(6)(MeCN)](ClO(4))(2) (R = H, 3; CH(3), 4; OCH(3), 5; NO(2), 6) were isolated when X = CH(2). Self-assembly reaction between (MCCC(6)H(4)COCH(3)-4)(n) and [M'(2)(mu-Ph(2)PCH(2)PPh(2))(2)(MeCN)(2)](ClO(4))(2), however, gave heterohexadecanuclear complex [Ag(6)Cu(2)(micro-Ph(2)PCH(2)PPh(2))(3)(CCC(6)H(4)COCH(3)-4)(6)](2)(ClO(4))(4) (7). The heterohexanuclear complexes 1 and 2 show a bicapped cubic skeleton (Ag(4)Cu(2)C(4)) consisting of four Ag(I) and two Cu(I) atoms and four acetylide C donors. The heterooctanuclear complexes 3-6 exhibit a waterwheel-like structure that can be regarded as two Ag(3)Cu(CCC(6)H(5))(3) components put together by three bridging Ph(2)PCH(2)PPh(2) ligands. The heterohexadecanuclear complex 7 can be viewed as a dimer of heterooctanuclear complex [Ag(6)Cu(2)(micro-Ph(2)PCH(2)PPh(2))(3)(CCC(6)H(4)COCH(3)-4)(6)](ClO(4))(2) through the silver and acetyl oxygen (Ag-O = 2.534 (4) A) linkage between two waterwheel-like Ag(6)Cu(2) units. All of the complexes show intense luminescence in the solid states and in fluid solutions. The microsecond scale of lifetimes in the solid state at 298 K reveals that the emission is phosphorescent in nature. The emissive state in compounds 1-5 is likely derived from a (3)LMCT (CCC(6)H(4)R-4 --> Ag(4)Cu(2) or Ag(6)Cu(2)) transition, mixed with a metal cluster-centered (d --> s) excited state. The lowest lying excited state in compounds 6 and 7 containing electron-deficient 4-nitrophenylacetylide and 4-acetylphenylacetylide

  11. Characterization of CeO2-Supported Cu-Pd Bimetallic Catalyst for the Oxygen-Assisted Water-Gas Shift Reaction

    SciTech Connect

    Fox, Elise; Velu, Subramani; Engelhard, Mark H.; Chin, Ya-Huei; Miller, Jeffrey T.; Kropf, Jeremy; Song, Chunshan

    2008-12-10

    This study was focused to investigate the roles of Cu and Pd in CuPd/CeO2 bimetallic catalysts containing 20-30 wt% Cu and 0.5-1 wt% Pd used in the oxygen-assisted water-gas shift (OWGS) reaction employing a combined bulk and surface characterization techniques such as XRD, TPR, CO chemisorption, and in-situ XPS. The catalytic activity for CO conversion and the stability of catalyst during on-stream operation increased by the addition of Cu to Pd/CeO2 or Pd to Cu/CeO2 monometallic catalysts, especially when the OWGS reaction was performed under low temperatures, below 200oC. The bimetallic catalyst after leaching with nitric acid retained about 60% of its original activity. The TPR of monometallic Cu/CeO2 showed reduction of CuO supported on CeO2 in two distinct regions, around 150 and 250oC. The high temperature peak disappeared and reduction occurred in a single step around 150oC upon Pd addition. The Pd dispersion decreased from 38.5% for Pd/CeO2 to below 1% for CuPd/CeO2 bimetallic catalyst. In-situ XPS studies showed a shift in Cu 2p peaks toward lower binding energy (BE) with concommitant shift in the Pd 3d peaks toward higher BE. Addition of Pd decreased the surface Cu concentration while the concentration of Pd remained unaltered. All these observations indicated the formation of Cu-Pd surface alloy. The valence band XP spectra collected below 10 eV corroborated the core level XP spectra and indicated that Cu is mainly involved in the catalytic reaction. The improved catalytic activity and stability of CuPd/CeO2 bimetallic catalyst was attributed to the alloy formation.

  12. (Ag,Cu)-Ta-O ternaries as high-temperature solid-lubricant coatings.

    PubMed

    Gao, Hongyu; Otero-de-la-Roza, Alberto; Gu, Jingjing; Stone, D'Arcy; Aouadi, Samir M; Johnson, Erin R; Martini, Ashlie

    2015-07-22

    Ternary oxides have gained increasing attention due to their potential use as solid lubricants at elevated temperatures. In this work, the tribological properties of three ternary oxides-AgTaO3, CuTaO3, and CuTa2O6-were studied using a combination of density-functional theory (DFT), molecular dynamics (MD) simulations with newly developed empirical potential parameters, and experimental measurements (AgTaO3 and CuTa2O6 only). Our results show that the MD-predicted friction force follows the trend AgTaO3 < CuTaO3 < CuTa2O6, which is consistent with the experimentally measured coefficients of friction. The wear performance from both MD and experiment exhibits the opposite trend, with CuTa2O6 providing the best resistance to wear. The sliding mechanisms are investigated using experimental characterization of the film composition after sliding, quantification of Ag or Cu cluster formation at the interface during the evolution of the film in MD, and DFT energy barriers for atom migration on the material surface. All our observations are consistent with the hypothesis that the formation of metal (or metal oxide) clusters on the surface are responsible for the friction and wear behavior of these materials. PMID:26106877

  13. Nanoalloying and phase transformations during thermal treatment of physical mixtures of Pd and Cu nanoparticles

    NASA Astrophysics Data System (ADS)

    Mukundan, Vineetha; Yin, Jun; Joseph, Pharrah; Luo, Jin; Shan, Shiyao; Zakharov, Dmitri N.; Zhong, Chuan-Jian; Malis, Oana

    2014-04-01

    Nanoscale alloying and phase transformations in physical mixtures of Pd and Cu ultrafine nanoparticles are investigated in real time with in situ synchrotron-based x-ray diffraction complemented by ex situ high-resolution transmission electron microscopy. 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. 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 annealing in helium due to reduction of the surface oxides that promotes coalescence and sintering.

  14. Asymmetric Hydroarylation of Vinylarenes Using a Synergistic Combination of CuH and Pd Catalysis.

    PubMed

    Friis, Stig D; Pirnot, Michael T; Buchwald, Stephen L

    2016-07-13

    Detailed in this Communication is the enantioselective synthesis of 1,1-diarylalkanes, a structure found in a range of pharmaceutical drug agents and natural products, through the employment of copper(I) hydride and palladium catalysis. Judicious choice of ligand for both Cu and Pd enabled this hydroarylation protocol to work for an extensive array of aryl bromides and styrenes, including β-substituted vinylarenes and six-membered heterocycles, under relatively mild conditions. PMID:27346525

  15. Size-Dependent Disorder-Order Transformation in the Synthesis of Monodisperse Intermetallic PdCu Nanocatalysts.

    PubMed

    Wang, Chenyu; Chen, Dennis P; Sang, Xiahan; Unocic, Raymond R; Skrabalak, Sara E

    2016-06-28

    The high performance of Pd-based intermetallic nanocatalysts has the potential to replace Pt-containing catalysts for fuel-cell reactions. Conventionally, intermetallic particles are obtained through the annealing of nanoparticles of a random alloy distribution. However, this method inevitably leads to sintering of the nanoparticles and generates polydisperse samples. Here, monodisperse PdCu nanoparticles with the ordered B2 phase were synthesized by seed-mediated co-reduction using PdCu nanoparticle seeds with a random alloy distribution (A1 phase). A time-evolution study suggests that the particles must overcome a size-dependent activation barrier for the ordering process to occur. Characterization of the as-prepared PdCu B2 nanoparticles by electron microscopy techniques revealed surface segregation of Pd as a thin shell over the PdCu core. The ordered nanoparticles exhibit superior activity and durability for the oxygen reduction reaction in comparison with PdCu A1 nanoparticles. This seed-mediated co-reduction strategy produced monodisperse nanoparticles ideally suited for structure-activity studies. Moreover, the study of their growth mechanism provides insights into the size dependence of disorder-order transformations of bimetallic alloys at the nanoscale, which should enable the design of synthetic strategies toward other intermetallic systems. PMID:27214313

  16. CO oxidation over sonochemically synthesized Pd-Cu/Al2O3 nanocatalyst used in hydrogen purification: effect of Pd loading and ultrasound irradiation time.

    PubMed

    Estifaee, Pooya; Haghighi, Mohammad; Mohammadi, Nima; Rahmani, Farhad

    2014-05-01

    The bimetallic Pd-Cu nanocatalysts with different Pd loadings and ultrasonic irradiation times were sonochemically synthesized and their activities toward CO oxidation were investigated. XRD, FESEM, TEM, BET, FTIR and TG-DTG techniques were employed in nanocatalysts characterization. XRD data confirmed formation of CuAl2O4 spinel with an average crystallite size of 4.9 nm. FESEM images revealed more uniform pattern and also fewer agglomerations were observed by increasing ultrasonic irradiation time. In agreement with FESEM result, TEM images depicted nanoparticles and uniform dispersion of active phase over alumina. BET surface analysis showed that increasing the Pd loading has no significant effect on surface area; whereas by increasing irradiation time the surface area increases slightly. Catalytic performance tests of synthesized samples showed that Pd(1.5%)-Cu(20%)/Al2O3 with 95 min ultrasonic irradiation time had the best activity over the course of reaction. In addition, increasing CO at feed composition revealed that among synthesized nanocatalysts with 0.5%, 1% and 1.5% of Pd, synthesized sample with 1.5% of Pd had the best low-temperature activity. PMID:24369903

  17. Atomic-scale investigation of interface-facilitated deformation twinning in severely deformed Ag-Cu nanolamellar composites

    SciTech Connect

    An, X. H. E-mail: xiaozhou.liao@sydenye.edu.au; Cao, Y.; Liao, X. Z. E-mail: xiaozhou.liao@sydenye.edu.au; Zhu, S. M.; Nie, J. F.; Kawasaki, M.; Ringer, S. P.; Langdon, T. G.; Zhu, Y. T.

    2015-07-06

    We report an atomic-scale investigation of interface-facilitated deformation twinning behaviour in Ag-Cu nanolamellar composites. Profuse twinning activities in Ag supply partial dislocations to directly transmit across the Ag-Cu lamellar interface that promotes deformation twinning in the neighbouring Cu lamellae although the interface is severely deformed. The trans-interface twin bands change the local structure at the interface. Our analysis suggests that the orientation relationship and interfacial structure between neighbouring Ag-Cu lamellae play a crucial role in such special interface-facilitated twinning behaviour.

  18. The Reliability of Microalloyed Sn-Ag-Cu Solder Interconnections Under Cyclic Thermal and Mechanical Shock Loading

    NASA Astrophysics Data System (ADS)

    Mattila, Toni T.; Hokka, Jussi; Paulasto-Kröckel, Mervi

    2014-11-01

    In this study, the performance of three microalloyed Sn-Ag-Cu solder interconnection compositions (Sn-3.1Ag-0.52Cu, Sn-3.0Ag-0.52Cu-0.24Bi, and Sn-1.1Ag-0.52Cu-0.1Ni) was compared under mechanical shock loading (JESD22-B111 standard) and cyclic thermal loading (40 ± 125°C, 42 min cycle) conditions. In the drop tests, the component boards with the low-silver nickel-containing composition (Sn-Ag-Cu-Ni) showed the highest average number of drops-to-failure, while those with the bismuth-containing alloy (Sn-Ag-Cu-Bi) showed the lowest. Results of the thermal cycling tests showed that boards with Sn-Ag-Cu-Bi interconnections performed the best, while those with Sn-Ag-Cu-Ni performed the worst. Sn-Ag-Cu was placed in the middle in both tests. In this paper, we demonstrate that solder strength is an essential reliability factor and that higher strength can be beneficial for thermal cycling reliability but detrimental to drop reliability. We discuss these findings from the perspective of the microstructures and mechanical properties of the three solder interconnection compositions and, based on a comprehensive literature review, investigate how the differences in the solder compositions influence the mechanical properties of the interconnections and discuss how the differences are reflected in the failure mechanisms under both loading conditions.

  19. BRAZING OF POROUS ALUMINA TO MONOLITHIC ALUMINA WITH Ag-CuO and Ag-V2O5 ALLOYS

    SciTech Connect

    Lamb, M. C.; Camardello, Sam J.; Meier, Alan; Weil, K. Scott; Hardy, John S.

    2005-01-31

    The feasibility of joining porous alumina (Al{sub 2}O{sub 3}) bodies to monolithic Al{sub 2}O{sub 3} using Ag-CuO and Ag-V{sub 2}O{sub 5} alloys via reactive air brazing (RAB) was examined for a nanoporous filter application. Brazing for these systems is complicated by the conflicting requirements of satisfactory wetting to fill the braze gap, while minimizing the infiltration of the porous body. By varying the firing time, temperature, and initial powder size, porous bodies with a range of pore microstructures were fabricated. The wettability was evaluated via sessile drop testing on monolithic substrates and porous body infiltration. Porous Al{sub 2}O{sub 3}/monolithic Al{sub 2}O{sub 3} brazed samples were fabricated, and the microstructures were evaluated. Both systems exhibited satisfactory wetting for brazing, but two unique types of brazing behavior were observed. In the Ag-CuO system, the braze alloy infiltrated a short distance into the porous body. For these systems, the microstructures indicated satisfactory filling of the brazed gap and a sound joint regardless of the processing conditions. The Ag-V{sub 2}O{sub 5} alloys brazed joints exhibited a strong dependence on the amount of V{sub 2}O{sub 5} available. For Ag-V{sub 2}O{sub 5} alloys with large V{sub 2}O{sub 5} additions, the braze alloy aggressively infiltrated the porous body and significantly depleted the Ag from the braze region resulting in poor bonding and large gaps within the joint. With small additions of V{sub 2}O{sub 5}, the Ag infiltrated the porous body until the V{sub 2}O{sub 5} was exhausted and the Ag remaining at the braze interlayer bonded with the Al{sub 2}O{sub 3}. Based on these results, the Ag-CuO alloys have the best potential for brazing porous Al{sub 2}O{sub 3} to monolithic Al{sub 2}O{sub 3}.

  20. Evidence for highly anharmonic low-frequency vibrational modes in bulk amorphous Pd40Cu40P20

    NASA Astrophysics Data System (ADS)

    Safarik, D. J.; Schwarz, R. B.

    2009-09-01

    We have measured the elastic constants of amorphous Pd40Cu40P20 (isotropic, two independent elastic constants), single crystal Pd40Cu40P20 (tetragonal, six elastic constants), and single crystal Pd50Cu50 (fcc, three elastic constants) over the range 3.9Pd40Cu40P20 and Pd50Cu50 are well described by C(T)=C(0)-BT2+ΔCLat(T) , where BT2 gives the electronic contribution and ΔCLat(T) is the contribution due to the anharmonicity of the lattice vibrations. The temperature dependence of the shear modulus of amorphous Pd40Cu40P20 includes an additional contribution, ΔCE(T) , which becomes dominant for T<20K : C(T)=C(0)-BT2+ΔCLat(T)+ΔCE(T) . The ΔCE(T) contribution can be explained by the presence of a small number of low-frequency, highly anharmonic vibrational modes, which we characterize as Einstein oscillators with temperature θE≈12K and Grüneisen parameter γEC'≫2 . Theory and computer modeling suggest that these modes involve the collective vibration of stringlike arrays of atoms.

  1. Energetics of the formation of Cu-Ag core–shell nanoparticles

    SciTech Connect

    Chandross, Michael

    2014-10-06

    Our work presents molecular dynamics and Monte Carlo simulations aimed at developing an understanding of the formation of core–shell Cu-Ag nanoparticles. The effects of surface and interfacial energies were considered and used to form a phenomenological model that calculates the energy gained upon the formation of a core–shell structure from two previously distinct, non-interacting nanoparticles. In most cases, the core–shell structure was found to be energetically favored. Specifically, the difference in energy as a function of the radii of the individual Cu and Ag particles was examined, with the assumption that a core–shell structure forms. In general, it was found that the energetic gain from forming such a structure increased with increasing size of the initial Ag particle. This result was interpreted as a result of the reduction in surface energy. Moreover, for two separate particles, both Cu and Ag contribute to the surface energy; however, for a core–shell structure, the only contribution to the surface energy is from the Ag shell and the Cu contribution is changed to a Cu–Ag interfacial energy, which is always smaller.

  2. Energetics of the formation of Cu-Ag core–shell nanoparticles

    DOE PAGESBeta

    Chandross, Michael

    2014-10-06

    Our work presents molecular dynamics and Monte Carlo simulations aimed at developing an understanding of the formation of core–shell Cu-Ag nanoparticles. The effects of surface and interfacial energies were considered and used to form a phenomenological model that calculates the energy gained upon the formation of a core–shell structure from two previously distinct, non-interacting nanoparticles. In most cases, the core–shell structure was found to be energetically favored. Specifically, the difference in energy as a function of the radii of the individual Cu and Ag particles was examined, with the assumption that a core–shell structure forms. In general, it was foundmore » that the energetic gain from forming such a structure increased with increasing size of the initial Ag particle. This result was interpreted as a result of the reduction in surface energy. Moreover, for two separate particles, both Cu and Ag contribute to the surface energy; however, for a core–shell structure, the only contribution to the surface energy is from the Ag shell and the Cu contribution is changed to a Cu–Ag interfacial energy, which is always smaller.« less

  3. Processing of nanoporous Ag layers by potential-controlled displacement (PCD) of Cu.

    PubMed

    Viyannalage, L T; Liu, Y; Dimitrov, N

    2008-08-01

    A cementation-like process taking place under potential control and introduced in this work as a "potential-controlled displacement" (PCD) is developed as a new method for processing of nanoporous Ag structures with controlled roughness (porosity) length scales. Most of the development work is done in a deoxygenated electrolyte containing 1 x 10(-3) M AgClO(4 )+ 5 x 10(-2) M CuSO(4) + 1 x 10(-1) M HClO(4) using a copper rotating disk electrode at 50 rpm. At this electrolyte concentration, the Ag deposition is under diffusion limitations whereas the Cu dissolution displays a typical Butler-Volmer anodic behavior. Thus, a careful choice of the operational current density enables strict control of the ratio between the dissolving and depositing metals as ascertained independently by atomic absorption spectrometry (AAS). The roughness length scale of the resulting surfaces is controlled by a careful selection of the current density applied. The highest surface area and finest morphology is obtained when the atomic ratio of Ag deposition and Cu dissolution becomes 1:1. Preseeding of uniform Ag clusters on the Cu surface made by pulse plating of Ag along with complementary plating and stripping of Pb monolayer is found to yield finer length scale resulting in up to a 67% higher surface area. An electrochemical technique using as a reference value the charge of an underpotentially deposited Pb layer on a flat Ag surface is used for measuring the real surface area. Scanning electron microscopy (SEM) studies are conducted to examine and characterize the deposit morphology of Ag grown by PCD on Cu substrates. PMID:18613704

  4. [Fatigue properties of dental alloys. 12% Au-Pd-Ag alloy and type III gold alloy].

    PubMed

    Kato, H

    1989-12-01

    Usually the mechanical properties of dental alloys are determined from the values obtained through static tests of their tensile strength, hardness, etc. Generally, high tensile strength and ductility are preferred. However, when small stresses within proportional limits are applied repeatedly (even though not amounting to destructive forces in static tests), they may cause rupture in the alloy or, at least, cause it to lose its original mechanical properties. This phenomenon is called metal fatigue. It is estimated that the intraoral stress loads received by dental restorations during mastication or during insertion and removal of appliances are repeated more than 3 x 10(5) times/year. From this standpoint, it may be more appropriate to estimate the fracture strength of such dental alloys based on the fatigue properties of the restorative materials used for clasps, bars, and fixed bridges. For this reason, it is necessary to obtain data through fatigue tests on the fatigue strength and the fatigue endurance limits of dental alloys, and it is important to find a correlation between these data and the static data on tensile strengths and ductility obtained by tensile tests. Two alloys are used in these experiments. Both wrought specimens and cast specimens of 12% Au-Pd-Ag and Type III gold alloy were prepared for the fatigue tests. The size of the rectangular wrought specimens was 3 x 4 x 110 mm. The 12% Au-Pd-Ag alloy was heated to 800 degrees C for 15 minutes, quenched, and reheated to 400 degrees C for 20 minutes and quenched again according to the manufacturer's instructions for heat treatment. The Type III gold alloy was heated to 700 degrees C for 10 minutes, quenched, and reheated to 350 degrees C for 20 minutes and quenched again. The cylindrical cast specimens were 60 mm long and 2 mm in diameter. They were invested by conventional methods and cast in a centrifugal casting machine, Thermotrol Model 2500. The four point bending test for the wrought specimen

  5. Noble metals (Ag, Au) nanoparticles addition effects on superconducting properties of CuTl-1223 phase

    NASA Astrophysics Data System (ADS)

    Jabbar, Abdul; Mumtaz, Muhammad; Nadeem, Kashif

    2015-03-01

    Low anisotropic (Cu0.5Tl0.5) Ba2Ca2Cu3O10 - δ (CuTl-1223) high temperature superconducting phase was synthesized by solid-state reaction, silver (Ag) nanoparticles were prepared by sol-gel method and gold (Au) nanoparticles were extracted from colloidal solution. We added Ag and Au nanoparticles in CuTl-1223 matrix separately with same concentration during the final sintering process to get (M)x/CuTl-1223; M = Ag nanoparticles or Au nanoparticles (x = 0 and 1.0 wt.%) nano-superconductor composites. We investigated and compared the effects of these noble metals nanoparticles addition on structural, morphological and superconducting transport properties of CuTl-1223 phase. The crystal structure of the host CuTl-1223 superconducting phase was not affected significantly after the addition of these nanoparticles. The enhancement of superconducting properties was observed after the addition of both Ag and Au nanoparticles, which is most probably due to improved inter-grains weak-links and reduction of defects such as oxygen deficiencies, etc. The reduction of normal state room temperature resistivity is the finger prints of the reduction of barriers and facilitation to the carriers transport across the inter-crystallite sites due to improved inter-grains weak-links. The greater improvement of superconducting properties in Ag nanoparticles added samples is attributed to the higher conductivity of silver as compared to gold, which also suits for practical applications due to lower cost and easy synthesis of Ag nanoparticles as compared to Au nanoparticles.

  6. Effect of copper content on Pt-Pd-CuO/{gamma}-alumina catalysts for motorcycle soot conversion

    SciTech Connect

    Chien, C.C.; Huang, T.J.

    1995-06-01

    Catalytic combustion of motorcycle soot particulates over {gamma}-alumina-supported CuO, Pt, Pd, Pt-CuO, and Pd-CuO catalysts was studied. The catalyst coated with motorcycle soots was placed in a flow reactor to perform temperature-programmed oxidation. Results indicated that the CuO catalyst was quite effective for the catalytic combustion. The high activity of the CuO catalyst could be illustrated by a redox mechanism and an induced particle-motion mechanism. A higher copper content enhanced the reducibility of the copper oxide and induced a higher activity for catalytic combustion until the copper oxide content reached 5 wt%. A redispersion phenomenon of the CuO species was observed and was consistent with the induced particle-motion mechanism. Additionally, the effect of the noble metal additive was to promote the activity of the CuO species by a mechanism including dissociative adsorption and spillover of oxygen.

  7. Investigation of thermal, mechanical and magnetic behaviors of the Cu-11%Al alloy with Ag and Mn additions

    SciTech Connect

    Silva, R.A.G.; Paganotti, A.; Gama, S.; Adorno, A.T.; Carvalho, T.M.; Santos, C.M.A.

    2013-01-15

    The investigation of thermal, mechanical and magnetic behaviors of the Cu-11%Al, Cu-11%Al-3%Ag, Cu-11%Al-10%Mn and Cu-11%Al-10%Mn-3%Ag alloys was made using microhardness measurements, differential scanning calorimetry, X-ray diffractometry, scanning electron microscopy, energy dispersion X-ray spectroscopy and magnetic moment change with applied field measurement. The results indicated that the Mn addition changes the phase stability range, the microhardness values and makes undetectable the eutectoid reaction in annealed Cu-11%Al and Cu-11%Al-3%Ag alloys while the presence of Ag does not modify the phase transformation sequence neither microhardness values of the annealed Cu-11%Al and Cu-11%Al-10%Mn alloys, but it increases the magnetic moment of this latter at about 2.7 times and decreases the rates of eutectoid and peritectoid reactions of the former. - Highlights: Black-Right-Pointing-Pointer The microstructure of Cu-Al alloy is modified in the Ag presence. Black-Right-Pointing-Pointer ({alpha} + {gamma}) phase is stabilized down to room temperature when Ag is added to Cu-Al alloy. Black-Right-Pointing-Pointer Ag-rich phase modifies the magnetic characteristics of Cu-Al-Mn alloy.

  8. Amperometric biosensor of SnO2 thin film modified by Pd, In and Ag nanostructure synthesized by CSP method

    NASA Astrophysics Data System (ADS)

    Hassan, Marwa Abdul Muhsien; Hateef, Areej Adnan; Majeed, Aseel Mustafa Abdul; Al-Jabiry, Ali Jasim Mohammed; Jameel, Sabah; Hussian, Haidar Abdul Razaq Abdul

    2013-10-01

    Palladium, Indium and Silver-doped SnO2 thin film was deposited by chemical spray pyrolysis on ITO and porous silicon substrates to be a fast MgSO4·7H2O amperometric biosensor. The prepared SnO2 films were doped by dipping in palladium chloride PdCl2, indium chloride, InCl3 and silver nitrides AgNO3 dissolved in ethanol C2H5OH. The structural and optical properties of the prepared films were studied. The sensitivity behaviors of SnO2, SnO2: Pd, SnO2: In and SnO2: Ag based on the amperometric biosensor to MgSO4·7H2O salts were investigated at room temperature with different doping.

  9. Synthesis of Ag/Pd nanoparticles via reactive micelles as templates and its application to electroless copper deposition.

    PubMed

    Yang, Chia-Cheng; Wan, Chi-Chao; Wang, Yung-Yun

    2004-11-15

    Ag/Pd nanoparticles have been synthesized with a reactive alcohol-type surfactant, sodium dodecyl sulfate (SDS), without the presence of an external reducing agent. Both UV-vis absorption spectra and X-ray diffraction patterns for the bimetallic and physical mixtures of individual nanoparticles revealed the formation of a bimetallic structure. Based on this method, an ordered 3D grapelike nanostructure was formed, possibly due to transformation of the liquid crystal phase of the micelles. Data from the energy-dispersive X-ray analysis show that the composition of bimetallic nanoparticle is approximately equal to the feeing solution. Furthermore, the Ag/Pd nanoparticles exhibit distinct catalyst for electroless copper deposition and may be a substitute for the conventional palladium system, which is expensive and unstable in operation. PMID:15464808

  10. Fabrication of Pd/Pd-Alloy Films by Surfactant Induced Electroless Plating for Hydrogen Separation from Advanced Coal Gasification Processes

    SciTech Connect

    Ilias, Shamsuddin; Kumar, Dhananjay

    2012-07-31

    Dense Pd, Pd-Cu and Pd-Ag composite membranes on microporous stainless steel substrate (MPSS) were fabricated by a novel electroless plating (EP) process. In the conventional Pd-EP process, the oxidation-reduction reactions between Pd-complex and hydrazine result in an evolution of NH{sub 3} and N{sub 2} gas bubbles. When adhered to the substrate surface and in the pores, these gas bubbles hinder uniform Pd-film deposition which results in dendrite growth leading to poor film formation. This problem was addressed by introducing cationic surfactant in the electroless plating process known as surfactant induced electroless plating (SIEP). The unique features of this innovation provide control of Pd-deposition rate, and Pd-grain size distribution. The surfactant molecules play an important role in the EP process by tailoring grain size and the process of agglomeration by removing tiny gas bubbles through adsorption at the gas-liquid interface. As a result surfactant can tailor a nanocrystalline Pd, Cu and Ag deposition in the film resulting in reduced membrane film thickness. Also, it produces a uniform, agglomerated film structure. The Pd-Cu and Pd-Ag membranes on MPSS support were fabricated by sequential deposition using SIEP method. The pre- and post-annealing characterizations of these membranes (Pd, Pd-Cu and Pd-Ag on MPSS substrate) were carried out by SEM, EDX, XRD, and AFM studies. The SEM images show significant improvement of the membrane surface morphology, in terms of metal grain structures and grain agglomeration compared to the membranes fabricated by conventional EP process. The SEM images and helium gas-tightness studies indicate that dense and thinner films of Pd, Pd-Cu and Pd-Ag membranes can be produced with shorter deposition time using surfactant. H{sub 2} Flux through the membranes fabricated by SIEP shows large improvement compared to those by CEP with comparable permselectivity. Pd-MPSS composite membrane was subjected to test for long term

  11. The growth, structure, and thermal stability of vapor deposited ultra-thin metal films: Rh on Ag(100), Au on Pd(110), and Pt on Pd(110)

    SciTech Connect

    Schmitz, P.

    1990-09-21

    The growth, structure, and thermal stability of ultra-thin metal films (Rh on Ag(100); Au on Pd(110) and Pt on Pd(110)) is investigated using surface sensitive techniques. The three systems studied present a variety of differing characteristics which can contribute to the growth mode, two-dimensional structure, and thermal stability of the films. The main factors contributing to the differing properties of the three systems presented here are: (1) the different substrate morphologies; (2) the differences in surface free energies between the overlayer and the substrate; (3) the degree of lattice mismatch for a particular system; and (4) the extent of miscibility of the two metals. 200 refs., 38 figs.

  12. PdCu Nanoalloy Electrocatalysts in Oxygen Reduction Reaction: Role of Composition and Phase State in Catalytic Synergy.

    PubMed

    Wu, Jinfang; Shan, Shiyao; Luo, Jin; Joseph, Pharrah; Petkov, Valeri; Zhong, Chuan-Jian

    2015-11-25

    The catalytic synergy of nanoalloy catalysts depends on the nanoscale size, composition, phase state, and surface properties. This report describes findings of an investigation of their roles in the enhancement of electrocatalytic activity of PdCu alloy nanoparticle catalysts for oxygen reduction reaction (ORR). Pd(n)Cu(100-n) nanoalloys with controlled composition and subtle differences in size and phase state were synthesized by two different wet chemical methods. Detailed electrochemical characterization was performed to determine the surface properties and the catalytic activities. The atomic-scale structures of these catalysts were also characterized by high-energy synchrotron X-ray diffraction coupled with atomic pair distribution function analysis. The electrocatalytic activity and stability were shown to depend on the size, composition, and phase structure. With Pd(n)Cu(100-n) catalysts from both methods, a maximum ORR activity was revealed at Pd/Cu ratio close to 50:50. Structurally, Pd50Cu50 nanoalloys feature a mixed phase consisting of chemically ordered (body-centered cubic type) and disordered (face-centered cubic type) domains. The phase-segregated structure is shown to change to a single phase upon electrochemical potential cycling in ORR condition. While the surface Cu dissolution occurred in PdCu catalysts from the two different synthesis methods, the PdCu with a single-phase character is found to exhibit a tendency of a much greater dissolution than that with the phase segregation. Analysis of the results, along theoretical modeling based on density functional theory calculation, has provided new insights for the correlation between the electrocatalytic activity and the catalyst structures. PMID:26569372

  13. Constraints on Variable Ag:Au:Cu Ore-Metal Ratios in Felsic Arc-Magmas

    NASA Astrophysics Data System (ADS)

    Piccoli, P.; Englander, L.; Candela, P.

    2004-12-01

    Silver:gold:copper ratios are variable in porphyry-type ore systems. In an attempt to better understand why, we have employed experimental techniques to determine how silver and copper, and gold from previous experiments, are sequestered in felsic magmas. To this end, we are performing sealed silica tube experiments on the equilibria among pyrrhotite-magnetite-silver alloy at 800C and at vapor pressure. Run times for the preliminary experiments were 144 hours; runs had magnetite/pyrrhotite ratio of 4. The source of silver in the runs was AgCl. Analysis of reconnaissance experiments demonstrates the stability of magnetite, pyrrhotite and a silver sulfide solid solution under the conditions of the experiments. Equilibrium concentrations of ore metals in the run products are ~3000 ppm Ag and 3500 ppm Cu in the pyrrhotite. However, the concentrations in magnetite are significantly different: 100 ppm Ag and ~20 ppm Cu. Like copper and gold (Jugo et al., 1999; Lithos), silver is concentrated in pyrrhotite relative to magnetite. The equilibrium Ag-sulfide composition in the run products is Ag53Fe8Cu3S36, with a mole fraction of Ag2S of 0.74. The log fS2 is approximated as ~ -4. The mole fraction of Ag in an ideal metal solid solution in equilibrium with an ideal model Ag2S solid solution, and a log fS2 of -4, is ~0.4. By analogy with Au, the substitution of Ag into pyrrhotite may occur as an AgFeS2 component. The substitutional mechanism for Ag in magnetite is not clear: silver may substitute as AgFe(3+)(Fe(2+))-2, but may also be present in defects in the magnetite structure. The partition coefficient (D(po/mt)) for approximately 30 for Ag. The partition coefficient for Au is higher (~120) based on the data of Simon et al. (2003; Am. Min,) and Jugo et al. (1999; Lithos). These data can be combined with data on the solubility of Ag in silicate melts to calculate mineral-melt partition coefficients. These data suggest that the role of pyrrhotite crystallization in felsic

  14. Study of the state of Ag and Pd in silver-palladium catalysts on a titanium dioxide substrate by IR spectroscopy of adsorbed CO

    NASA Astrophysics Data System (ADS)

    Kovalenko, N. A.; Sen'ko, T. L.; Petkevich, T. S.; Egiazarov, Yu. G.

    2007-01-01

    We have used IR spectroscopy of adsorbed CO to study the effect of the method for preparation of silver-palladium catalysts on a TiO2 substrate and exposure to an oxidizing or reducing gaseous atmosphere on the state of Ag and Pd centers. We have shown that as a result of the metal-support interaction, the reducibility of the Ag and Pd particles is increased, which leads to a change in their adsorption and catalytic properties.

  15. Mechanical properties of Sm-Ba-Cu-O/Ag bulk superconductors

    NASA Astrophysics Data System (ADS)

    Sakai, N.; Mase, A.; Ikuta, H.; Seo, S.-J.; Mizutani, U.; Murakami, M.

    2000-06-01

    We studied the mechanical properties of melt-processed, single-grain, Ag-doped, Sm-Ba-Cu-O bulks with different densities. The tensile strength of the dense sample was 48.0 MPa and about 1.3 times larger than that of the porous sample with Ag and twice as large as that of the sample without Ag doping. The bending strength of the dense sample was estimated to be 137 MPa based on the Weibull distribution function and the effective volume of the samples. It was found that a reduction in the pore density and Ag addition were effective in increasing the mechanical strength of the Sm-Ba-Cu-O bulk.

  16. Preparation of Ag/Cu Janus nanowires: Electrodeposition in track-etched polymer templates

    NASA Astrophysics Data System (ADS)

    Zhu, X. R.; Wang, C. M.; Fu, Q. B.; Jiao, Z.; Wang, W. D.; Qin, G. Y.; Xue, J. M.

    2015-08-01

    Bimetal (Janus) nanowire has been widely used as a promising nanoscale motor. In this paper we present a highly controllable method to fabricate Ag/Cu Janus nanowires using track-etched polymer templates. Ag/Cu Janus nanowires with uniform size and stabilized structure have been successfully fabricated by electrodepositing Ag nanowires, and subsequently Cu nanowires in track-etched polymer templates. The pore size of nanopores prepared by this template is uniform and continuously controlled, so aperture of achieved nanowires are uniform and can be regulated. This polymer template can dissolve inorganic solvents that do not react with the nanowires, making it is easy to release the nanowires into solution. The nanopore shape in the track-etched templates is adjustable (e.g. conical), nanowires with more special shapes could be fabricated. Thus, these features make this simple and inexpensive method very suitable for the preparation of Janus nanowire.

  17. Study on deposition technique and properties of Pd/Ag alloy film sensor supported on ceramic substrate

    NASA Astrophysics Data System (ADS)

    Geng, Z. T.; He, Q.; Jin, C. G.

    2016-07-01

    Developing high-quality hydrogen sensitive material is the core part of hydrogen sensor, whose performance is determined by the sensitive response, reproducibility and recovery of hydrogen material etc. In order to overcome the defects of hydrogen embrittlement in previous hydrogen sensor which were based on the pure palladium, sliver as the second component added to the palladium was studied. Using photochemical etching technology to produce a bent metal mask, the mask is put on the ceramic substrate. Firstly, the thin film of Ta2O5 as a transition layer grew on the ceramic substrate. Then, a series of Pd/Ag alloy film sensors were prepared, and each performance characterization of Pd/Ag alloy film was studied. Testing results indicated that the thin film had a good linear output performance at 0∼⃒30% hydrogen concentration range, and demonstrates a high responsiveness and good repeatability. With temperature increasing, the strength of the responsive signal of the Pd/Ag alloy film decreases and its responsive time was also shortened.

  18. Oxygen chemisorption effects on the spatial atomic distribution of CuNi, CuPd and NiPt nanostructures

    NASA Astrophysics Data System (ADS)

    Montejano-Carrizales, J. M.; Morán-López, J. L.

    1993-05-01

    The spatial atomic distribution in cubo-octahedral CuNi, CuPd and NiPt clusters with a total number of atoms, N = 147, in the presence of chemisorbed oxygen, is studied. The equilibrium atomic configuration is obtained by calculating the free energy within the regular solution model and by assuming that the surface of the cluster is covered by oxygen atoms. Depending on the interaction between oxygen and the cluster components, the atomic distribution in the cluster can be completely modified as compared to the case of clusters with a clean surface. We present result for the temperature dependence of the concentration at the different shells around the central atom.

  19. Oxidation Behavior of a Pd43Cu27Ni10P20 Bulk Metallic Glass and Foam in Dry Air

    NASA Astrophysics Data System (ADS)

    Kai, W.; Ren, I. F.; Barnard, B.; Liaw, P. K.; Demetriou, M. D.; Johnson, W. L.

    2010-07-01

    The oxidation behavior of both Pd43Cu27Ni10P20 bulk metallic glass (Pd4-BMG) and its amorphous foam containing 45 pct porosity (Pd4-AF) was investigated over the temperature range of 343 K (70 °C) to 623 K (350 °C) in dry air. The results showed that virtually no oxidation occurred in the Pd4-BMG at T < 523 K (250 °C), revealing the alloy’s favorable oxidation resistance in this temperature range. In addition, the oxidation kinetics at T ≥ 523 K (250 °C) followed a parabolic-rate law, and the parabolic-rate constants ( k p values) generally increased with temperature. It was found that the oxidation k p values of the Pd4-AF are slightly lower than those of the Pd4-BMG, indicating that the porous structure contributes to improving the overall oxidation resistance. The scale formed on the alloys was composed exclusively of CuO at T ≥ 548 K (275 °C), whose thickness gradually increased with increasing temperature. In addition, the amorphous structure remained unchanged at T ≤ 548 K (275 °C), while a triplex-phase structure developed after the oxidation at higher temperatures, consisting of Pd2Ni2P, Cu3P, and Pd3P.

  20. Nanoparticles of Ag with a Pt and Pd rich surface supported on carbon as a new catalyst for the oxygen electroreduction reaction (ORR) in acid electrolytes: Part 1

    NASA Astrophysics Data System (ADS)

    Pech-Pech, I. E.; Gervasio, Dominic F.; Godínez-Garcia, A.; Solorza-Feria, O.; Pérez-Robles, J. F.

    2015-02-01

    Silver (Ag) nanoparticles enriched with platinum (Pt) and palladium (Pd) on their surfaces (Ag@Pt0.1Pd0.1) are supported on Vulcan XC-72 carbon (C) to form a new catalyst (Ag@Pt0.1Pd0.1/C) for the oxygen reduction reaction (ORR) in acid electrolytes. This catalyst is prepared in one pot by reducing Ag and then Pt and Pd metal salts with sodium borohydride in the presence of trisodium citrate then adding XC-72 while applying intense ultrasound. The metallic Ag@Pt0.1Pd0.1 nanoparticles contain 2 weight percent of Pt, are spherical and have an average size less than 10 nm as determined by X-ray diffraction (XRD) and transmission electron microscopy (TEM). At the ORR potentials, Ag nanoparticles on carbon (Ag/C) rapidly lose Ag by dissolution and show no more catalytic activity for the ORR than the carbon support, whereas Ag@Pt0.1Pd0.1/C is a stable catalyst and exhibits 1.4 and 1.6 fold greater specific activity, also 3.6 and 2.8 fold greater mass activity for ORR in 0.5 M H2SO4 solution than comparable Pt/C and Pt0.5Pd0.5/C catalysts with the same Pt loading as determined for thin-films of these catalysts on a rotating-disk electrode (TF-RDE). Using silver nanoparticles increases Pt utilization and therefore decreases Pt-loading and cost of a catalyst for a proton exchange membrane fuel cell (PEMFC) electrode.

  1. Effect of electronic structures on catalytic properties of CuNi alloy and Pd in MeOH-related reactions

    SciTech Connect

    Tsai, An-Pang; Kimura, Tomofumi; Suzuki, Yukinori; Kameoka, Satoshi; Shimoda, Masahiko; Ishii, Yasushi

    2013-04-14

    We investigated the catalytic properties of a CuNi solid solution and Pd for methanol-related reactions and associated valence electronic structures. Calculations and X-ray photoelectron spectroscopy measurements revealed that the CuNi alloy has a similar valence electronic structure to Pd and hence they exhibited similar CO selectivities in steam reforming of methanol and decomposition of methanol. Samples prepared by various processes were found to have similar CO selectivities. We conjecture that alloying of Cu and Ni dramatically alters the valence electronic structures, making it similar to that of Pd so that the alloy exhibits similar catalytic properties to Pd. First-principles slab calculations of surface electronic structures support this conjecture.

  2. Single CuO nanowires decorated with size-selected Pd nanoparticles for CO sensing in humid atmosphere

    NASA Astrophysics Data System (ADS)

    Steinhauer, Stephan; Singh, Vidyadhar; Cassidy, Cathal; Gspan, Christian; Grogger, Werner; Sowwan, Mukhles; Köck, Anton

    2015-05-01

    We report on conductometric gas sensors based on single CuO nanowires and compare the carbon monoxide (CO) sensing properties of pristine as well as Pd nanoparticle decorated devices in humid atmosphere. Magnetron sputter inert gas aggregation combined with a quadrupole mass filter for cluster size selection was used for single-step Pd nanoparticle deposition in the soft landing regime. Uniformly dispersed, crystalline Pd nanoparticles with size-selected diameters around 5 nm were deposited on single CuO nanowire devices in a four point configuration. During gas sensing experiments in humid synthetic air, significantly enhanced CO response for CuO nanowires decorated with Pd nanoparticles was observed, which validates that magnetron sputter gas aggregation is very well suited for the realization of nanoparticle-functionalized sensors with improved performance.

  3. Single CuO nanowires decorated with size-selected Pd nanoparticles for CO sensing in humid atmosphere.

    PubMed

    Steinhauer, Stephan; Singh, Vidyadhar; Cassidy, Cathal; Gspan, Christian; Grogger, Werner; Sowwan, Mukhles; Köck, Anton

    2015-05-01

    We report on conductometric gas sensors based on single CuO nanowires and compare the carbon monoxide (CO) sensing properties of pristine as well as Pd nanoparticle decorated devices in humid atmosphere. Magnetron sputter inert gas aggregation combined with a quadrupole mass filter for cluster size selection was used for single-step Pd nanoparticle deposition in the soft landing regime. Uniformly dispersed, crystalline Pd nanoparticles with size-selected diameters around 5 nm were deposited on single CuO nanowire devices in a four point configuration. During gas sensing experiments in humid synthetic air, significantly enhanced CO response for CuO nanowires decorated with Pd nanoparticles was observed, which validates that magnetron sputter gas aggregation is very well suited for the realization of nanoparticle-functionalized sensors with improved performance. PMID:25854640

  4. Enhanced Selectivity to H2 Formation in Decomposition of HCOOH on the Ag19@Pd60 Core-Shell Nanocluster from First-Principles.

    PubMed

    Cho, Jinwon; Lee, Sangheon; Han, Jonghee; Yoon, Sung Pil; Nam, Suk Woo; Choi, Sun Hee; Hong, Seong-Ahn; Lee, Kwan-Young; Ham, Hyung Chul

    2015-10-01

    In this study, using spin-polarized density functional theory calculation we examined the origin of enhanced catalytic activity toward H2 production from HCOOH in Ag19@Pd60 core-shell nanoclusters (a 79-atom truncated octahedral cluster models). First, we find that the Pd monolayer shell on the Ag core can greatly enhance the selectivity to H2 formation via HCOOH decomposition compared to the pure Pd79 cluster by substantially reducing the binding energy of key intermediate HCOO and in turn the barrier for dehydrogenation. This activity enhancement is related to the modification of d states in the Pd monolayer shell by the strong ligand effect between Ag core and Pd shell, rather than the tensile strain effect by Ag core. In particular, the absence of dz2-r2 density of states near the Fermi level in the Pd monolayer shell (which originated from the substantial charge transfer from Ag to Pd) is the main reason for the increased H2 production from HCOOH decomposition. PMID:26726494

  5. Effects of Pd substitution on the thermoelectric and electronic properties of delafossite Cu{sub 1−x}Pd{sub x}FeO{sub 2} (x=0.01, 0.03 and 0.05)

    SciTech Connect

    Ruttanapun, Chesta

    2014-07-01

    Cu{sub (1−x)}Pd{sub (x)}FeO{sub 2} (x=0.01, 0.03 and 005) delafossite was prepared by solid state reactions and was calcined/sintered at 1050 °C. The effect of Pd{sup 2+} substitution for the Cu{sup 1+} sites on the thermoelectric and electronic properties of Cu{sub (1−x)}Pd{sub (x)}FeO{sub 2} were investigated. The crystal structure, oxygen decomposition, thermoelectric and electronic properties were characterized by X-ray diffraction, thermogravimetric analysis, X-ray photoelectron spectroscopy (XPS), Seebeck coefficient, electrical conductivity and thermal conductivity measurements. The characterization showed that Cu{sub (1−x)}Pd{sub (x)}FeO{sub 2} formed a hexagonal delafossite structure with R3−m symmetry. The existence of Pd{sup 2+}, Cu{sup 1+}, Cu{sup 2+}, Fe{sup 3+}, Fe{sup 4+} and O was revealed from the XPS results. Confirmation of Pd{sup 2+} substitution for the Cu{sup 1+} sites occurred by increasing the c-axis in the lattice parameter with a Pd content. The O content intercalated at the center of the triangular Cu acted as a support to produce Cu{sup 2+} ions and was reduced with an increasing Pd content. The mixed valencies of Cu{sup 1+}/Cu{sup 2+} and Cu{sup 1+}/Pd{sup 2+} in the Cu layer changed the electrical conductivity and the Fe{sup 3+}/Fe{sup 4+} mixed valencies in the FeO{sub 6} layer caused the Seebeck coefficient to increase. Both the electrical conductivity and Seebeck coefficient for Pd contents of x=0.01 and 0.03 were higher than that of non-doped CuFeO{sub 2}. The low thermal conductivity of Cu{sub (1−x)}Pd{sub (x)}FeO{sub 2} resulted from the substitution of Pd, which has a large atomic mass, into structure. The Jonker plot indicated that the electronic properties displayed a degenerate density of states and that Cu{sub (1−x)}Pd{sub (x)}FeO{sub 2} was a semiconductor. A high ZT value of 0.055 was obtained for a Pd content of 0.03 at 950 K. The Pd{sup 2+} substitution for the Cu{sup 1+} sites influenced the thermoelectric

  6. Co-deposited thin films of YBa 2Cu 3O 7-δ-Ag

    NASA Astrophysics Data System (ADS)

    Moshfegh, A. Z.; Wang, Y. Q.; Sun, Y. Y.; Mesarwi, A.; Hor, P. H.; Ignatiev, A.

    1993-12-01

    The fabrication of high-temperature superconducting YBa 2Cu 3O 7-δ-Ag thin films has been investigated using a high-pressure Ag coevaporation-DC sputtering technique. Various analytical techniques including X-ray diffraction (XRD), Auger electron spectroscopy (AES), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), electron probe microanalysis (EPMA), energy dispersive X-ray analysis (EDX), and Tc measurement have been utilized for characterization of the films. Highly reproducible c-oriented (00 l) films have been prepared in-situ at a relatively low growth temperature (≃670°C) by this technique. The transition temperatures Tc gradually decreased with added Ag from 90 K (0 at.% Ag) to 72 K (22.3 at.% Ag) for the films deposited on MgO (100) substrates. X-ray diffraction indicated that the Ag is in the metallic state as a separate phase with respect to the YBCO and that the c-lattice parameter of the grown films remained unchanged with Ag addition. Surface morphology of the YBCO-Ag films exhibited a particulate-type structure with the grain size increasing as the Ag content increased. The temperature coefficient of the normalized resistance, d R( T)/ R(280 K)/d T, was also noticed to decrease for the Ag- containing samples as compared to Ag-free YBCO films. AES depth profiling identified Ag residing mainly at the YBCO/MgO interface. The effect of Ag addition to the films has been described by a particle growth model.

  7. Cluster reaction of [Ag8]-/[Cu8]- with chlorine: Evidence for the harpoon mechanism?

    NASA Astrophysics Data System (ADS)

    Luo, Zhixun; Berkdemir, Cüneyt; Smith, Jordan C.; Castleman, A. W.

    2013-09-01

    To examine the question whether the harpoon mechanism can account for the reactive behavior of microscopic charged systems, we have investigated the reactivity of coinage metal clusters in gas phase. Our studies reveal that the reactivity between [Cu8]-/[Ag8]- and chlorine gas is consistent with the harpoon mechanism. An increased reactive cross section is noted through our theoretical estimation based on two methods, ascribed to a long-range transfer of valence electrons from the [Cu8]-/[Ag8]- cluster to chlorine. Insights into this reactivity will be of interest to other researchers working on obtaining a better understanding of the reaction mechanisms of such superatomic species.

  8. Oxygen reduction on Ni, Ag, and Cu meniscus electrodes in molten carbonate

    SciTech Connect

    Ogura, Hiroyuki; Shirogami, Tamotsu

    1994-12-31

    The oxygen reduction pathways in molten carbonates have been investigated by analyzing the charge transfer resistances of the i-V curves on the meniscus electrodes of Ni, Cu, and Ag screens at 550 C. The electrochemical reduction pathways of oxygen at the meniscus electrode were found to be different depending on the electrode materials. For the Ni meniscus electrode system, the reactive material of charge transfer is the lithium doped nickel oxide, for the Ag system that is the silver oxide ion, and for the Cu system that is peroxide ion, respectively.

  9. Interface stress development in the Cu/Ag nanostructured multilayered film during the tensile deformation

    SciTech Connect

    Su, R.; Nie, Z. H.; Zhang, Q. H.; Li, X. J.; Li, L. E-mail: ydwang@mail.neu.edu.cn; Zhou, X. T.; Wang, Y. D. E-mail: ydwang@mail.neu.edu.cn; Wu, Y. D.; Hui, X. D.; Wang, M. G.

    2014-12-01

    Cu/Ag nanostructured multilayered films (NMFs) with different stacking sequences were investigated by synchrotron X-ray diffraction during the tensile deformations for interface stress study. The lattice strains were carefully traced and the stress partition, which usually occurs in the multiphase bulk metallic materials during plastic deformations, was first quantitatively analyzed in the NMFs here. The interface stress of the Cu/Ag NMFs was carefully analyzed during the tensile deformation and the results revealed that the interface stress was along the loading direction and exhibited three-stage evolution. This tensile interface stress has a detrimental effect on the deformation, leading to the early fracture of the NMFs.

  10. Determination of the compositions of the DIGM zone in nanocrystalline Ag/Au and Ag/Pd thin films by secondary neutral mass spectrometry.

    PubMed

    Molnár, Gábor Y; Shenouda, Shenouda S; Katona, Gábor L; Langer, Gábor A; Beke, Dezső L

    2016-01-01

    Alloying by grain boundary diffusion-induced grain boundary migration is investigated by secondary neutral mass spectrometry depth profiling in Ag/Au and Ag/Pd nanocrystalline thin film systems. It is shown that the compositions in zones left behind the moving boundaries can be determined by this technique if the process takes place at low temperatures where solely the grain boundary transport is the contributing mechanism and the gain size is less than the half of the grain boundary migration distance. The results in Ag/Au system are in good accordance with the predictions given by the step mechanism of grain boundary migration, i.e., the saturation compositions are higher in the slower component (i.e., in Au or Pd). It is shown that the homogenization process stops after reaching the saturation values and further intermixing can take place only if fresh samples with initial compositions, according to the saturation values, are produced and heat treated at the same temperature. The reversal of the film sequence resulted in the reversal of the inequality of the compositions in the alloyed zones, which is in contrast to the above theoretical model, and explained by possible effects of the stress gradients developed by the diffusion processes itself. PMID:27335738

  11. Determination of the compositions of the DIGM zone in nanocrystalline Ag/Au and Ag/Pd thin films by secondary neutral mass spectrometry

    PubMed Central

    Molnár, Gábor Y; Shenouda, Shenouda S; Katona, Gábor L; Langer, Gábor A

    2016-01-01

    Summary Alloying by grain boundary diffusion-induced grain boundary migration is investigated by secondary neutral mass spectrometry depth profiling in Ag/Au and Ag/Pd nanocrystalline thin film systems. It is shown that the compositions in zones left behind the moving boundaries can be determined by this technique if the process takes place at low temperatures where solely the grain boundary transport is the contributing mechanism and the gain size is less than the half of the grain boundary migration distance. The results in Ag/Au system are in good accordance with the predictions given by the step mechanism of grain boundary migration, i.e., the saturation compositions are higher in the slower component (i.e., in Au or Pd). It is shown that the homogenization process stops after reaching the saturation values and further intermixing can take place only if fresh samples with initial compositions, according to the saturation values, are produced and heat treated at the same temperature. The reversal of the film sequence resulted in the reversal of the inequality of the compositions in the alloyed zones, which is in contrast to the above theoretical model, and explained by possible effects of the stress gradients developed by the diffusion processes itself. PMID:27335738

  12. Surface structure and reaction property of CuCl2-PdCl2 bimetallic catalyst in methanol oxycarbonylation: A DFT approach

    NASA Astrophysics Data System (ADS)

    Meng, Qingsen; Wang, Shengping; Shen, Yongli; Yan, Bing; Wu, Yuanxin; Ma, Xinbin

    2014-02-01

    Surface structure of CuCl2-PdCl2 bimetallic catalyst (Wacker-type catalyst) was built employing density functional theory (DFT) calculations, and the reaction mechanism of methanol oxycarbonylation over the CuCl2-PdCl2 surfaces was also investigated. On the CuCl2-PdCl2 surface, the active site for methanol oxidation was confirmed as Cu-Cl-Cu (Pd). Comparing with pure CuCl2 surface, the introduction of Pd atom causes the electron repopulation on the surface and lowers the energy barrier for methanol oxidation, but the number of the active site decreases with the increasing of Pd doping volume. Agreed with previous experimental results, the Pd site is most favorable for the CO insertion, indicated by the lowest activation barrier for the formation of COOCH3 on Pd atom. The lowest energy barrier for the formation of DMC appears when COOCH3 species adsorbed on Pd atom and methoxyl adsorbed on Cu atoms, which is 0.42 eV. Finally, the reconstruction of the unsaturated surface is a spontaneous and exothermic process. Comparing with other surfaces, the rate-limiting step, methanol oxidation, on CuCl2-PdCl2 surface with Pd/Cu = 1:17 has the lowest energy barrier, which is agreed with the experimental observation that PdCl2-CuCl2 catalyst with Pd/Cu = 1:20 has the favorable activity. The adsorbed methoxyl will further lower the activation barrier of methanol oxidation, which is agreed with experimental observation that the Wacker-type catalysts have an induction period in the methanol oxidative carbonylation system.

  13. Global optimization and oxygen dissociation on polyicosahedral Ag32Cu6 core-shell cluster for alkaline fuel cells

    NASA Astrophysics Data System (ADS)

    Zhang, N.; Chen, F. Y.; Wu, X. Q.

    2015-07-01

    The structure of 38 atoms Ag-Cu cluster is studied by using a combination of a genetic algorithm global optimization technique and density functional theory (DFT) calculations. It is demonstrated that the truncated octahedral (TO) Ag32Cu6 core-shell cluster is less stable than the polyicosahedral (pIh) Ag32Cu6 core-shell cluster from the atomistic models and the DFT calculation shows an agreeable result, so the newfound pIh Ag32Cu6 core-shell cluster is further investigated for potential application for O2 dissociation in oxygen reduction reaction (ORR). The activation energy barrier for the O2 dissociation on pIh Ag32Cu6 core-shell cluster is 0.715 eV, where the d-band center is -3.395 eV and the density of states at the Fermi energy level is maximal for the favorable absorption site, indicating that the catalytic activity is attributed to a maximal charge transfer between an oxygen molecule and the pIh Ag32Cu6 core-shell cluster. This work revises the earlier idea that Ag32Cu6 core-shell nanoparticles are not suitable as ORR catalysts and confirms that Ag-Cu nanoalloy is a potential candidate to substitute noble Pt-based catalyst in alkaline fuel cells.

  14. Global optimization and oxygen dissociation on polyicosahedral Ag32Cu6 core-shell cluster for alkaline fuel cells

    PubMed Central

    Zhang, N.; Chen, F. Y.; Wu, X.Q.

    2015-01-01

    The structure of 38 atoms Ag-Cu cluster is studied by using a combination of a genetic algorithm global optimization technique and density functional theory (DFT) calculations. It is demonstrated that the truncated octahedral (TO) Ag32Cu6 core-shell cluster is less stable than the polyicosahedral (pIh) Ag32Cu6 core-shell cluster from the atomistic models and the DFT calculation shows an agreeable result, so the newfound pIh Ag32Cu6 core-shell cluster is further investigated for potential application for O2 dissociation in oxygen reduction reaction (ORR). The activation energy barrier for the O2 dissociation on pIh Ag32Cu6 core-shell cluster is 0.715 eV, where the d-band center is −3.395 eV and the density of states at the Fermi energy level is maximal for the favorable absorption site, indicating that the catalytic activity is attributed to a maximal charge transfer between an oxygen molecule and the pIh Ag32Cu6 core-shell cluster. This work revises the earlier idea that Ag32Cu6 core-shell nanoparticles are not suitable as ORR catalysts and confirms that Ag-Cu nanoalloy is a potential candidate to substitute noble Pt-based catalyst in alkaline fuel cells. PMID:26148904

  15. H2 production from simulated coal syngas containing H2S in multi-tubular Pd and 80 wt% Pd-20 wt% Cu membrane reactors

    SciTech Connect

    Iyoha, O.; Enick, R.M.; Killmeyer, R.P.; Howard, B.H.; Ciocco, M.V.; Morreale, B.

    2007-12-01

    99.7% conversion of CO in a simulated syngas feed containing 53% CO, 35% H2 and 12% CO2 was achieved via the water–gas shift (WGS) reaction in a counter-current Pd multi-tube membrane reactor (MR) at 1173 K and 2 s residence time. This conversion is significantly greater than the 32% equilibrium conversion associated with a conventional (non-membrane) reactor primarily due to the high rate of H2 extraction from the reaction zone through the Pd membranes at elevated temperatures. Furthermore, nearly complete H2 recovery was attained in the permeate, resulting in the simultaneous production of a high-pressure CO2 (>99%) retentate stream after condensation of the steam. When Pd80 wt%Cu tubes were used in the reactor, a significantly lower CO conversion of 68% was attained at comparable residence times, probably due to the lower H2 permeance of the alloy. When H2S was added to the syngas feed and the H2S-to-H2 ratio was maintained below the threshold required for thermodynamically stable sulfides to form, the Pd and Pd80 wt%Cu MRs retained their mechanical integrity and H2 selectivity, but a precipitous drop in CO conversion was observed due to deactivation of the catalytic surface. The Pd and Pd80 wt%Cu MRs were observed to fail within minutes after increasing the H2S-to-H2 ratio to levels above that expected for thermodynamically stable sulfides to form, as evidenced by rupturing of the membrane tubes. SEM–EDS analyses of the membranes suggested that at high H2S-to-H2 ratios, the H2S compromised the mechanical integrity of the MRs by preferentially attacking the grain boundary region.

  16. Effect of Ag addition on the thermal characteristics and structural evolution of Ag-Cu-Ni ternary alloy nanoclusters: Atomistic simulation study

    NASA Astrophysics Data System (ADS)

    Subbaraman, Ram; Sankaranarayanan, Subramanian K. R. S.

    2011-08-01

    Atomic-scale compositional variation in Ag contents across Ag-Cu-Ni alloy upon being subjected to repeated annealing cycles is shown to result in significant differences in the structure and the thermal stability of ternary alloy nanoclusters. Molecular dynamics (MD) simulations employing quantum Sutton-Chen potentials were used to investigate the effect of Ag addition on the thermal characteristics of Ag-Cu-Ni ternary alloy nanoclusters of 4-nm diameter. The initial configurations were generated using Monte Carlo simulations and comprise surface-segregated structures with the lowest surface energy component, Ag, occupying low coordination sites such as corners, edges, and faces. A compositional oscillation between the Cu and Ni atoms was observed for layers beneath the surface which transitions into a bulk alloy composition at the core. We find that the Cu-Ni binary alloys on being subjected to annealing schedules demonstrated an increase in thermal stability, as indicated by the increase in melting points. The annealed configurations of the Ag-Cu-Ni ternary alloy, on the other hand, showed a nonmonotonic behavior. For Ag compositions less than 20%, we observe an initial increase in melting point followed by a decrease in the third cycle. For higher Ag compositions (>20%), we observe a decrease in melting point with annealing; the rate of decrease is strongly correlated to the Ag composition in the alloy. Cu-Ni nanoclusters having 50% Cu showed a transition from an initial icosahedral to a cuboctahedron-like structure whereas Ag-rich Ag-Cu-Ni ternary alloys showed a transition from icosahedral to an amorphous structure. Compositional analysis based on radial distribution functions and density profiles indicate that these transitions were dependent on the distribution of the alloying elements in the nanocluster. Calculated root-mean-square displacements and diffusion coefficients indicate that the rate of mixing of Ag increases with Ag content in the Ag-Cu

  17. Active phase of a Pd-Cu/ZSM-5 catalyst for benzene hydroxylation: In-situ XAFS studies

    NASA Astrophysics Data System (ADS)

    Cho, Kye-Sung; Lee, Yong-Kul

    2012-07-01

    The gas-phase hydroxylation of benzene by using a mixture of oxygen and hydrogen has been carried out over Cu/ZSM-5 catalysts modified with palladium. In-situ X-ray absorption studies employed in the course of H2-tempereature programmed reduction (H2-TPR) followed by benzene hydroxylation confirmed that the oxidic phase of Cu2+ was transformed to Cu+ during the reaction. The addition of Pd to Cu/ZSM-5 noticeably improved the reducibility of the oxidic Cu phase, which resulted in an increase in the activity of the reaction.

  18. Sensitive and selective detection of Hg2+ and Cu2+ ions by fluorescent Ag nanoclusters synthesized via a hydrothermal method

    NASA Astrophysics Data System (ADS)

    Liu, Jing; Ren, Xiangling; Meng, Xianwei; Fang, Zheng; Tang, Fangqiong

    2013-09-01

    An easily prepared fluorescent Ag nanoclusters (Ag NCs) probe for the sensitive and selective detection of Hg2+ and Cu2+ ions was developed here. The Ag NCs were synthesized by using polymethacrylic acid sodium salt as a template via a convenient hydrothermal process. The as-prepared fluorescent Ag NCs were monodispersed, uniform and less than 2 nm in diameter, and can be quenched in the presence of mercury (Hg2+) or copper (Cu2+) ions. Excellent linear relationships existed between the quenching degree of the Ag NCs and the concentrations of Hg2+ or Cu2+ ions in the range of 10 nM to 20 μM or 10 nM to 30 μM, respectively. By using ethylenediaminetetraacetate (EDTA) as the masking agent of Cu2+, Hg2+ was exclusively detected in coexistence with Cu2+ with high sensitivity (LOD = 10 nM), which also provided a reusable detection method for Cu2+. Furthermore, the different quenching phenomena caused by the two metals ions such as changes in visible colour, shifts of UV absorbance peaks and changes in size of Ag NCs make it easy to distinguish between them. Therefore the easily synthesized fluorescent Ag NCs may have great potential as Hg2+ and Cu2+ ions sensors.An easily prepared fluorescent Ag nanoclusters (Ag NCs) probe for the sensitive and selective detection of Hg2+ and Cu2+ ions was developed here. The Ag NCs were synthesized by using polymethacrylic acid sodium salt as a template via a convenient hydrothermal process. The as-prepared fluorescent Ag NCs were monodispersed, uniform and less than 2 nm in diameter, and can be quenched in the presence of mercury (Hg2+) or copper (Cu2+) ions. Excellent linear relationships existed between the quenching degree of the Ag NCs and the concentrations of Hg2+ or Cu2+ ions in the range of 10 nM to 20 μM or 10 nM to 30 μM, respectively. By using ethylenediaminetetraacetate (EDTA) as the masking agent of Cu2+, Hg2+ was exclusively detected in coexistence with Cu2+ with high sensitivity (LOD = 10 nM), which also provided a

  19. Synthesis and characterization of Ag@Cu nano/microstructure ordered arrays as SERS-active substrates

    NASA Astrophysics Data System (ADS)

    Zhang, Pinhua; Cui, Guangliang; Xiao, Chuanhai; Zhang, Mingzhe; Chen, Li; Shi, Changmin

    2016-06-01

    We fabricated an Ag decorated Cu (Ag@Cu) nano/microstructure ordered array by facile template-free 2D electrodeposition combined with a galvanic reduction method for SERS applications. The Cu nano/microstructure ordered arrays were first synthesized by a 2D electrodeposition method, then Ag nanocubes were decorated on the arrays by galvanic reduction without any capping agent. The pollution-free surface and edge-to-face heterostructure of Ag nanocubes and Cu nano/microstructure arrays provide the powerful field-enhancements for SERS performance. The results verified that the Ag@Cu nano/microstructure ordered arrays have excellent activity for 4-Mercaptopyridine, and the sensitivity limit is as low as 10‑8 M. Therefore, this facile route provides a useful platform for the fabrication of a SERS substrate based on nano/microstructure ordered arrays.

  20. First principles investigation of the diffusion of interstitial Cu, Ag and Au in ZnTe

    NASA Astrophysics Data System (ADS)

    Chen, Li An; Zhu, Xing Feng; Chen, Ling Fu

    2015-07-01

    The diffusion is of great significance in many applications when the impurities are employed to tune the semiconductor's electrical or optical properties. It is necessary to understand how dopant defects diffuse in semiconductors. Using first-principles calculations, we consider interstitial diffusion mechanisms and calculate the migration barrier energies of interstitial Cu, Ag and Au atoms in II-VI compounds ZnTe. We find that the relative size of dopant and bulk atoms is an important factor which affects the diffusion behavior. The high symmetry Tc site, which is tetrahedrally coordinated by four cation atoms, is the global minimum energy location for Ag and Au interstitials. The size of Cu adatom is small, so Cu is more stable when it locates at the Ta site which is tetrahedrally coordinated by four anion atoms. But the global minimum energy location for Cu interstitials is M site which is of smaller space than Ta. Cu adatoms show an asymmetric curve of energy diffusion barrier with two energetically distinct extremum in the pathway. Ag diffuses along nearly straight line paths along [111] or equivalent directions. Diffusion for Cu or Au deviates from the straight line paths along <111> avoiding high symmetric sites.

  1. Isothermal nucleation and growth kinetics of Pd/Ag alloy phase via in-situ time-resolved high-temperature x-ray diffraction (HTXRD) analysis

    SciTech Connect

    Ayturk, Mahmut Engin; Payzant, E Andrew; Speakman, Scott A; Ma, Yi Hua

    2008-01-01

    Among several different approaches to form Pd/Ag alloys for hydrogen separation applications, ex-situ studies carried by conventional X-ray point scanning detectors might fail to reveal the key aspects of the phase transformation between Pd and Ag metals. In this respect, in-situ time-resolved high temperature X-ray diffraction (HTXRD) was employed to study the Pd/Ag alloy phase nucleation and growth kinetics. By the use of linear position sensitive detectors, advanced optics and profile fitting with the use of JADE-6.5 software, isothermal phase evolution of the Pd/Ag alloy at 500 C, 550 C and 600 C under hydrogen atmosphere were quantified to elucidate the mechanistic details of the Pd/Ag alloy phase nucleation and growth pattern. Analysis of the HTXRD data by the Avrami model indicated that the nucleation of the Pd/Ag alloy phase was instantaneous where the growth mechanism was through diffusion-controlled one-dimensional thickening of the Pd/Ag alloy layer. The value of the Avrami exponent, n, was found to increase with temperature with the values of 0.34, 0.39 and 0.67 at 500oC, 550oC and 600oC, respectively. In addition, parabolic rate law analysis suggested that the nucleation of the Pd/Ag alloy phase was through a heterogeneous nucleation mode, in which the nucleation sites were defined as the non-equilibrium defects. The cross-sectional SEI micrographs indicated that the Pd/Ag alloy phase growth was strongly dependent upon the deposition morphology of the as-synthesized Pd and Ag layers formed by the electroless plating. Based on the Avrami model and the parabolic rate law, the estimated activation energies for the phase transformation were 236.5 and 185.6 kJ/mol and in excellent agreement with the literature values (183-239.5 kJ/mol).

  2. Local structure order in Pd78Cu6Si16 liquid

    SciTech Connect

    Yue, G. Q.; Zhang, Y.; Sun, Y.; Shen, B.; Dong, F.; Wang, Z. Y.; Zhang, R. J.; Zheng, Y. X.; Kramer, M. J.; Wang, S. Y.; Wang, C. Z.; Ho, K. M.; Chen, L. Y.

    2015-02-05

    The short-range order (SRO) in Pd78Cu6Si16 liquid was studied by high energy x-ray diffraction and ab initio molecular dynamics (MD) simulations. The calculated pair correlation functions at different temperatures agree well with the experimental results. The partial pair correlation functions from ab intio MD simulations indicate that Si atoms prefer to be uniformly distributed while Cu atoms tend to aggregate. By performing structure analysis using Honeycutt-Andersen index, Voronoi tessellation, and atomic cluster alignment method, we show that the icosahedron and face-centered cubic SRO increase upon cooling. The dominant SRO is the Pd-centered Pd9Si2 motif, namely the structure of which motif is similar to the structure of Pd-centered clusters in the Pd9Si2 crystal. The study further confirms the existence of trigonal prism capped with three half-octahedra that is reported as a structural unit in Pd-based amorphous alloys. The majority of Cu-centered clusters are icosahedra, suggesting that the presence of Cu is benefit to promote the glass forming ability.

  3. Multi-functional ultrathin PdxCu1-x and Pt~PdxCu1-x one-dimensional nanowire motifs for various small molecule oxidation reactions

    SciTech Connect

    Liu, Haiqing; Wong, Stanislaus S.; Adzic, Radoslav R.

    2015-11-18

    Developing novel electrocatalysts for small molecule oxidation processes, including formic acid oxidation (FAOR), methanol oxidation reaction (MOR), and ethanol oxidation reaction (EOR), denoting the key anodic reactions for their respective fuel cell configurations, is a significant and relevant theme of recent efforts in the field. Herein, in this report, we demonstrated a concerted effort to couple and combine the benefits of small size, anisotropic morphology, and tunable chemical composition in order to devise a novel “family” of functional architectures. In particular, we have fabricated not only ultrathin 1-D Pd1–xCux alloys but also Pt-coated Pd1–xCux (i.e., Pt~Pd1–xCux; herein the ~ indicates an intimate association, but not necessarily actual bond formation, between the inner bimetallic core and the Pt outer shell) core–shell hierarchical nanostructures with readily tunable chemical compositions by utilizing a facile, surfactant-based, wet chemical synthesis coupled with a Cu underpotential deposition technique. Our main finding is that our series of as-prepared nanowires are functionally flexible. More precisely, we demonstrate that various examples within this “family” of structural motifs can be tailored for exceptional activity with all 3 of these important electrocatalytic reactions. In particular, we note that our series of Pd1–xCux nanowires all exhibit enhanced FAOR activities as compared with not only analogous Pd ultrathin nanowires but also commercial Pt and Pd standards, with Pd9Cu representing the “optimal” composition. Moreover, our group of Pt~Pd1–xCux nanowires consistently outperformed not only commercial Pt NPs but also ultrathin Pt nanowires by several fold orders of magnitude for both the MOR and EOR reactions in alkaline media. As a result, the variation of the MOR and EOR performance with

  4. Nitrate reduction over a Pd-Cu/MWCNT catalyst: application to a polluted groundwater.

    PubMed

    Soares, Olivia Salomé G P; Orfão, José J M; Gallegos-Suarez, Esteban; Castillejos, Eva; Rodríguez-Ramos, Inmaculada; Pereira, Manuel Fernando R

    2012-01-01

    The influence of the presence of inorganic and organic matter during the catalytic reduction of nitrate in a local groundwater over a Pd-Cu catalyst supported on carbon nanotubes was investigated. It was observed that the catalyst performance was affected by the groundwater composition. The nitrate conversion attained was higher in the experiment using only deionized water as solvent than in the case of simulated or real groundwater. With exception of sulphate ions, all the other solutes evaluated (chloride and phosphate ions and natural organic matter) had a negative influence on the catalytic activity and selectivity to nitrogen. PMID:23393977

  5. 3D Epitaxy of Graphene nanostructures in the Matrix of Ag, Al and Cu

    NASA Astrophysics Data System (ADS)

    Salamanca-Riba, Lourdes; Isaacs, Romaine; Wuttig, Manfred; Lemieux, Melburne; Hu, Liangbing; Iftekhar, Jaim; Rashkeev, Sergey; Kukla, Maija; Rabin, Oded; Mansour, Azzam

    2015-03-01

    Graphene nanostructures in the form ribbons were embedded in the lattice of metals such as Ag, Cu, and Al in concentrations up to 36.4 at.%, 21.8 at% and 10.5 at.%, respectively. These materials are called covetics. Raman scattering from Ag and Al covetics indicate variations in the intensity of peaks at ~ 1,300 cm-1 and 1,600 cm-1 with position on the sample. These peaks are associated with the D (defects) and G (graphite E2g mode) peaks of graphitic carbon with sp2 bonding and reveal various degrees of imperfections in the graphene layers. First principles calculations of the dynamic matrix of Ag and Al covetics show bonding between C and the metal. EELS mapping of the C-K edge and high resolution lattice images show that the graphene-like regions form ribbons with epitaxial orientation with the metal lattice of Ag and Al. The temperature dependences of the resistivites of Ag and Cu covetics are similar to those of the pure metals with only slight increase in resistivity. Films of Cu covetic deposited by e-beam evaporation and PLD show higher transmittance and resistance to oxidation than pure metal films of the same thickness indicating that copper covetic films can be used for transparent electrodes. Funded by DARPA/ARL Grant No. W911NF-13-1-0058, and ONR Award No N000141410042.

  6. Growth Behavior of Intermetallic Compounds in Cu/Sn3.0Ag0.5Cu Solder Joints with Different Rates of Cooling

    NASA Astrophysics Data System (ADS)

    Yang, Linmei; Zhang, Z. F.

    2015-01-01

    The growth behavior of intermetallic compounds (IMC) in Cu/Sn3.0Ag0.5Cu solder joints, including the interfacial Cu6Sn5 layer and Ag3Sn, and Cu6Sn5 in the solder, were investigated when different cooling methods—quenched water, cooling in air, and cooling in a furnace after reflow—were used. For the solder joint quenched in water, no obvious Cu6Sn5 or Ag3Sn was detected in the solder, and the thickness of interfacial Cu6Sn5 layer was slightly thinner than that of the joint cooled in air. On the basis of results from scanning electron microscopy and energy-dispersive spectrometry, a mechanism is proposed for growth of IMC in Sn3.0Ag0.5Cu solder during solidification. The rate of cooling has a substantial effect on the morphology and size of Ag3Sn, which evolved into large plate-like shapes when the joint was cooled slowly in a furnace. However, the morphology of Ag3Sn was branch-like or particle-like when the joint was cooled in air. This is attributed to re-growth of Ag3Sn grains via substantial atomic diffusion during the high-temperature stage of furnace cooling.

  7. THE TWO-DIMENSIONAL VALENCE ELECTRONIC STRUCTURE OF A MONOLYAER OF Ag ON Cu(00l)

    SciTech Connect

    Tobin, J.G.; Robey, S.W.; Shirley, D.A.

    1985-05-01

    The metal overlayer system c(10x2)Ag/Cu(001) was studied at coverages near one monolayer with angle-resolved photoemission. The observed spectroscopic features indicate a two-dimensional d-band electronic structure that can be interpreted using a model with planar, hexagonal symmetry in which crystal field effects dominate over spin-orbit effects.

  8. ZnO-(Cu/Ag)TCNQ heterostructure network over flexible platform for enhanced cold cathode application

    NASA Astrophysics Data System (ADS)

    Pal, Shreyasi; Maiti, Soumen; Narayan Maiti, Uday; Chattopadhyay, Kalyan Kumar

    2016-07-01

    Multistage field emitters consisting of organic/inorganic hybrid nanostructures with branched geometry are designed via a two-step protocol: a simple wet chemical method followed by a vapor-solid-phase technique. (Cu/Ag)TCNQ (copper/silver-7,7,8,8-tetracyanoquinodimethane) nanowires (NWs) were grown hierarchically on zinc oxide (ZnO) nanorods (NRs) to form ZnO-(Cu/Ag)TCNQ heterostructure assemblies. By monitoring the metallic Cu and Ag coating thickness on ZnO NRs, precise control over the morphology and orientations of the secondary organic NWs is achieved. In-depth analysis of electron field emission (FE) behavior of the ZnO-(Cu/Ag)TCNQ-based hierarchy suggests highest emission performance with low turn-on as well as threshold fields of 1.15 and 3.75 V μm‑1 respectively from the morphology-optimized hierarchy. Beneficial orientation of the branched organic NWs ensures sequential electric field enhancement in the consecutive stem and branches whereas its low work function eases electron emission; these aspects combined together render an overall enhancement in the emission behavior of the hybrid system. As compared to individual building units, the heterostructures show improved field electron emission. Additionally, successful construction of this novel hybrid over a fabric platform displays great potential in opening up new pathways in the highly-anticipated field of flexible electronics.

  9. Potential energy curves for the ground and low-lying excited states of CuAg

    SciTech Connect

    Alizadeh, Davood; Shayesteh, Alireza E-mail: ashayesteh@ut.ac.ir; Jamshidi, Zahra E-mail: ashayesteh@ut.ac.ir

    2014-10-21

    The ground and low-lying excited states of heteronuclear diatomic CuAg are examined by multi-reference configuration interaction (MRCI) method. Relativistic effects were treated and probed in two steps. Scalar terms were considered using the spin-free DKH Hamiltonian as a priori and spin-orbit coupling was calculated perturbatively via the spin-orbit terms of the Breit-Pauli Hamiltonian based on MRCI wavefunctions. Potential energy curves of the spin-free states and their corresponding Ω components correlating with the separated atom limits {sup 2}S(Cu) + {sup 2}S(Ag) and {sup 2}D(Cu) + {sup 2}S(Ag) are obtained. The results are in fine agreement with the experimental measurements and tentative conclusions for the ion-pair B0{sup +} state are confirmed by our theoretical calculations. Illustrative results are presented to reveal the relative importance and magnitude of the scalar and spin-orbit effects on the spectroscopic properties of this molecule. Time dependent density functional theory calculations, using the LDA, BLYP, B3LYP, and SAOP functionals have been carried out for CuAg and the accuracy of TD-DFT has been compared with ab initio results.

  10. Single naphthalene and anthracene molecular junctions using Ag and Cu electrodes in ultra high vacuum

    NASA Astrophysics Data System (ADS)

    Fujii, Shintaro; Kaneko, Satoshi; Chenyang, Liu; Kiguchi, Manabu

    2015-11-01

    We present a charge transport study on single naphthalene and anthracene molecular junctions wired into Ag and Cu electrodes using mechanically controllable break junction technique at 100 K under ultra-high vacuum condition. In particular we focus on effect of metal-π interaction on the formation probability of the molecular junctions. We found that the single molecular junctions of the acene molecules (e.g. naphthalene and anthracene) exhibit highly conductive character below 0.2 G0 (G0 = 2e2/h). The acene molecular junctions displayed formation probability of ca. 20% for Ag system and >40% for Cu system. The high formation probability of the molecular junctions with respect to benzene/Au junctions can be qualitatively explained by size effect, in which larger molecules of the naphthalene and anthracene can effectively bridge the gap between metal electrodes compared with small molecule such as benzene. The acene/Cu junctions displayed higher formation probability than the acene/Ag junctions. This result demonstrated that not only the size effect but the degree of the metal-π interaction have to be taken into account to quantitatively evaluate the formation probability of the molecular junctions for Ag and Cu system.

  11. ZnO-(Cu/Ag)TCNQ heterostructure network over flexible platform for enhanced cold cathode application.

    PubMed

    Pal, Shreyasi; Maiti, Soumen; Maiti, Uday Narayan; Chattopadhyay, Kalyan Kumar

    2016-07-01

    Multistage field emitters consisting of organic/inorganic hybrid nanostructures with branched geometry are designed via a two-step protocol: a simple wet chemical method followed by a vapor-solid-phase technique. (Cu/Ag)TCNQ (copper/silver-7,7,8,8-tetracyanoquinodimethane) nanowires (NWs) were grown hierarchically on zinc oxide (ZnO) nanorods (NRs) to form ZnO-(Cu/Ag)TCNQ heterostructure assemblies. By monitoring the metallic Cu and Ag coating thickness on ZnO NRs, precise control over the morphology and orientations of the secondary organic NWs is achieved. In-depth analysis of electron field emission (FE) behavior of the ZnO-(Cu/Ag)TCNQ-based hierarchy suggests highest emission performance with low turn-on as well as threshold fields of 1.15 and 3.75 V μm(-1) respectively from the morphology-optimized hierarchy. Beneficial orientation of the branched organic NWs ensures sequential electric field enhancement in the consecutive stem and branches whereas its low work function eases electron emission; these aspects combined together render an overall enhancement in the emission behavior of the hybrid system. As compared to individual building units, the heterostructures show improved field electron emission. Additionally, successful construction of this novel hybrid over a fabric platform displays great potential in opening up new pathways in the highly-anticipated field of flexible electronics. PMID:27188388

  12. Effects of Li content on precipitation in Al-Cu-(Li)-Mg-Ag-Zr alloys

    SciTech Connect

    Huang, B.P.; Zheng, Z.Q.

    1998-01-06

    Although much attention has been paid to Al-Cu-Li-Mg-Ag-Zr alloys, there are sparse reports about the influence of Li on precipitation in these alloys. The aim of the present study is to determine the effects of Li on modifying precipitation in a baseline aluminum alloy 2195 and the accompanying variants with 0--1.6 wt.% Li.

  13. Electronic structure of CeNi{sub 1{minus}x}Pd{sub x}Sn and LaMSn (M=Ni,Cu,Pd)

    SciTech Connect

    Slebarski, A.; Jezierski, A.; Maehl, S.; Neumann, M.; Borstel, G.

    1997-09-01

    The electronic structure of CeNi{sub 1{minus}x}Pd{sub x}Sn has been studied by photoemission spectroscopy. CeNiSn belongs to the class of Kondo insulating materials. The gap formed at the Fermi level is strongly suppressed by substituting Pd for Ni. The x-ray photoemission spectroscopy (XPS) valence band spectra can be compared with {ital ab initio} electronic-structure calculations using the linearized muffin-tin orbital (LMTO) method. We have found a small indirect gap and a low density of states at the Fermi energy for CePdSn. The 3d XPS spectra and LMTO calculations indicate a strong hybridization of the f orbitals with conduction band and the interatomic hybridization which causes the large charge transfer between atoms. We have also observed the correlation between the electronic structure near Fermi energy and the crystallographic properties of the alloyed CeNiSn. We also present the electronic structures of LaNiSn, LaCuSn, and LaPdSn. These compounds are good reference for CeNiSn. At Fermi energy a relatively low density of states is found, for LaCuSn an indirect gap is formed. The metallic samples show a relatively high resistivity at room temperature, the largest for LaCuSn, which demonstrates the influence of the gap on the electric transport properties. {copyright} {ital 1997} {ital The American Physical Society}

  14. Fabrication of nanoporous silver by de-alloying Cu-Zr-Ag amorphous alloys

    NASA Astrophysics Data System (ADS)

    Wang, Hui; Xiao, Shang-gang; Zhang, Tao

    2016-07-01

    Nanoporous silver (NPS) with a ligament size ranging from 15 to 40 nm was fabricated by de-alloying (Cu50Zr50)100- x Ag x ( x = 10at%, 20at%, 30at%, and 40at%) amorphous ribbons in a mixed aqueous solution of hydrofluoric (HF) acid and nitric acid under free corrosion conditions. Nanoporous silver ligaments and pore sizes were able to be fine-tuned through tailoring the chemical composition, corrosion conditions, and de-alloying time. The ligament size increases with an increase in Ag content and de-alloying time, but decreases with an increase in HF concentration. This phenomenon may be attributed to the dissolution of Zr/Cu and the diffusion, aggregation, nucleation, and recrystallization of Ag, leading to an oriented attachment of adjacent nanocrystals as revealed by TEM analysis.

  15. Abundances of Ag and Cu in mantle peridotites and the implications for the behavior of chalcophile elements in the mantle

    NASA Astrophysics Data System (ADS)

    Wang, Zaicong; Becker, Harry

    2015-07-01

    Silver abundances in mantle peridotites and the behavior of Ag during high temperature mantle processes have received little attention and, as a consequence, the abundance of Ag in the bulk silicate Earth (BSE) has been poorly constrained. In order to better understand the processes that fractionate Ag and other chalcophile elements in the mantle, abundances of Ag and Cu in mantle peridotites from different geological settings (n = 68) have been obtained by isotope dilution ICP-MS methods. In peridotite tectonites and in a few suites of peridotite xenoliths which display evidence for variable extents of melt depletion and refertilization by silicate melts, Ag and Cu abundances show positive correlations with moderately incompatible elements such as S, Se, Te and Au. The mean Cu/Ag in fertile peridotites (3500 ± 1200, 1s, n = 38) is indistinguishable from the mean Cu/Ag of mid ocean ridge basalts (MORB, 3600 ± 400, 1s, n = 338) and MORB sulfide droplets. The constant mean Cu/Ag ratios indicate similar behavior of Ag and Cu during partial melting of the mantle, refertilization and magmatic fractionation, and thus should be representative of the Earth's upper mantle. The systematic fractionation of Cu, Ag, Au, S, Se and Te in peridotites and basalts is consistent with sulfide melt-silicate melt partitioning with apparent partition coefficients of platinum group elements (PGE) > Au ⩾ Te > CuAg > Se ⩾ S. Because of the effects of secondary processes, the abundances of chalcophile elements, notably S, Se, but also Cu and the PGE in many peridotite xenoliths are variable and lower than in peridotite massifs. Refertilization of peridotite may change abundances of chalcophile and lithophile elements in peridotite massifs, however, this seems to mostly occur in a systematic way. Correlations with lithophile and chalcophile elements and the overlapping mean Cu/Ag ratios of peridotites and ocean ridge basalts are used to constrain abundances of Ag and Cu in the BSE

  16. Facile Synthesis of Ag Nanorods with No Plasmon Resonance Peak in the Visible Region by Using Pd Decahedra of 16 nm in Size as Seeds.

    PubMed

    Luo, Ming; Huang, Hongwen; Choi, Sang-Il; Zhang, Chao; da Silva, Robson Rosa; Peng, Hsin-Chieh; Li, Zhi-Yuan; Liu, Jingyue; He, Zhike; Xia, Younan

    2015-10-27

    This article describes a seed-mediated approach to the synthesis of Ag nanorods with thin diameters and tunable aspect ratios. The success of this method is built upon our recent progress in the synthesis of Pd decahedra as uniform samples, together with controllable sizes. When used as a seed, the Pd decahedron could direct the deposition of Ag atoms along the 5-fold axis to generate a nanorod, with its diameter being determined by the lateral dimension of the seed. We were able to generate Ag nanorods with uniform diameters down to 20 nm. Under the conditions we used for growth, symmetry breaking occurred as the Ag atoms were only deposited along one side of the Pd decahedral seed to generate a Ag nanorod with the Pd seed being positioned at one of its two ends. We also systematically investigated the localized surface plasmon resonance (LSPR) properties of the Ag nanorods. With the transverse mode kept below 400 nm, the longitudinal mode could be readily tuned from the visible to the near-infrared region by varying the aspect ratio. As an important demonstration, we obtained Ag nanorods with no LSPR peak in the visible spectrum (400-800 nm), which are attractive for applications related to the fabrication of touchscreen displays, solar films, and energy-saving smart windows. PMID:26372854

  17. Pd-grafted open metal site copper-benzene-1,4-dicarboxylate metal organic frameworks (Cu-BDC MOF's) as promising interfacial catalysts for sustainable Suzuki coupling.

    PubMed

    Rostamnia, Sadegh; Alamgholiloo, Hassan; Liu, Xiao

    2016-05-01

    In this work, open metal site metal-organic framework of Cu-BDC was selected as a support for the multi-step grafting of palladium. The palladium ions was coordinated onto the Schiff base-decorated Cu-BDC pore cage, that this bifunctional Pd@Cu-BDC/Py-SI catalyst was successfully applied for Suzuki cross-coupling reaction. Recyclability test for the Pd@Cu-BDC/Py-SI catalyst showed a successful reusability for 7 runs. PMID:26897567

  18. Elevated temperature fracture toughness of Al-Cu-Mg-Ag sheet: Characterization and modeling

    SciTech Connect

    Haynes, M.J.; Gangloff, R.P.

    1997-09-01

    The plane-strain initiation fracture toughness (K{sub JlCi}) and plane-stress crack growth resistance of two Al-Cu-Mg-Ag alloy sheets are characterized as a function of temperature by a J-integral method. For AA2519 + Mg + Ag, K{sub JlCi} decreases from 32.5 MPa {radical}m at 250 C to 28.5 MPa {radical}m at 175 C, while K{sub JlCi} for a lower Cu variant increases from 34.2 MPa {radical}m at 25 C to 36.0 Mpa {radical}m at 150 C. Crack-tip damage in AA2519 + Mg + Ag evolves by nucleation and growth of voids from large undissolved Al{sub 2}Cu particles, but fracture resistance is controlled by void sheeting coalescence associated with dispersoids. Quantitative fractography, three-dimensional (3-D) reconstruction of fracture surfaces, and metallographic crack profiles indicate that void sheeting is retarded as temperature increases from 25 C to 150 C, consistent with a rising fracture resistance. Primary microvoids nucleate from smaller constituent particles in the low Cu alloy, and fracture strain increases. A strain-controlled micromechanical model accurately predicts K{sub JlCi} as a function of temperature, but includes a critical distance parameter (l*) that is not definable a priori. Nearly constant initiation toughness for AA2519 + Mg + Ag is due to rising fracture strain with temperature, which balances the effects of decreasing flow strength, work hardening, and elastic modulus on the crack-tip strain distribution. Ambient temperature toughnesses of the low Cu variant are comparable to those of AA2519 + Mg + Ag, despite increased fracture strain, because of reduced constituent spacing and l*.

  19. Investigation on the interaction of nanoAg with Cu-Zn SOD.

    PubMed

    Zhang, Bin; Yu, Lei; Zhang, Ruijing; Liu, Yang; Liu, Rutao

    2015-12-01

    Silver nanoparticles (nanoAg) are used more and more widely, particularly because of their antimicrobial properties. The effect of exposure to nanoAg on the structure of superoxide dismutase (SOD) was thoroughly investigated using fluorescence measurements, synchronous fluorescence spectroscopy, steady-state and time-resolved fluorescence quenching measurements, UV/Vis absorption spectroscopy, resonance light scattering (RLS), circular dichroism (CD), isothermal titration calorimetry (ITC) and high-resolution transmission electron microscopy (HRTEM). Through van der Waal's force, nanoAg interacted with Cu-Zn SOD and influenced the active site by inducing structural changes, which influenced the function of SOD. The fluorescence studies show that both static and dynamic quenching processes occur. This paper provides reference data for toxicological studies of nanoAg, which are important in the future development of nanotechnology. PMID:25754791

  20. Sensitive and selective detection of Hg2+ and Cu2+ ions by fluorescent Ag nanoclusters synthesized via a hydrothermal method.

    PubMed

    Liu, Jing; Ren, Xiangling; Meng, Xianwei; Fang, Zheng; Tang, Fangqiong

    2013-10-21

    An easily prepared fluorescent Ag nanoclusters (Ag NCs) probe for the sensitive and selective detection of Hg(2+) and Cu(2+) ions was developed here. The Ag NCs were synthesized by using polymethacrylic acid sodium salt as a template via a convenient hydrothermal process. The as-prepared fluorescent Ag NCs were monodispersed, uniform and less than 2 nm in diameter, and can be quenched in the presence of mercury (Hg(2+)) or copper (Cu(2+)) ions. Excellent linear relationships existed between the quenching degree of the Ag NCs and the concentrations of Hg(2+) or Cu(2+) ions in the range of 10 nM to 20 μM or 10 nM to 30 μM, respectively. By using ethylenediaminetetraacetate (EDTA) as the masking agent of Cu(2+), Hg(2+) was exclusively detected in coexistence with Cu(2+) with high sensitivity (LOD = 10 nM), which also provided a reusable detection method for Cu(2+). Furthermore, the different quenching phenomena caused by the two metals ions such as changes in visible colour, shifts of UV absorbance peaks and changes in size of Ag NCs make it easy to distinguish between them. Therefore the easily synthesized fluorescent Ag NCs may have great potential as Hg(2+) and Cu(2+) ions sensors. PMID:24056730

  1. First-principles investigation of the structural stability and electronic properties of Pd doped monoclinic Cu6Sn5 intermetallic compounds

    NASA Astrophysics Data System (ADS)

    Shao, Wei-Quan; Lu, Wen-Cai; Chen, Sha-Ou

    2014-12-01

    Tri-layer Au/Pd/Ni(P) films have been widely used as surface finish over the Cu pads in high-end packaging applications. It was found that a thin (Cu,Pd)6Sn5 IMC layer was beneficial in effective reducing inter-diffusion between a Cu substrate and a solder, and therefore the growth of the IMC layer and the EM (electromigration) processes. In this study, the structural properties and phase stability of monoclinic Cu6Sn5-based structures with Pd substitutions were studied by using the first-principles method. The (Cu,Pd)6Sn5 structure with the 4e site substituted by Pd has the lowest heat of formation and is the most stable among (Cu,Pd)6Sn5 structures. Hybridization of Pd-d and Sn-p states is a dominant factor for stability improvement. Moreover, Pd atoms concentration corresponding to the most stable structure of (Cu,Pd)6Sn5 was found to be 1.69 %, which is consistent with the experimental results.

  2. Electronic Properties of MoSi2-Type Hf2X Intermetallic Compounds (X=Pd, Ag, Cd)

    NASA Astrophysics Data System (ADS)

    Yaar, I.; Maytal-Beck, S.; Berant, Z.

    2001-11-01

    The Hf z coordinate and the value of the electric field gradient (efg) main component (V zz ), were calculated for three Hf2X compounds (X = Pd, Ag, Cd) on a first-principle basis, using the full potential linear augmented plane wave (LAPW) method. Exchange and correlation effects were treated either by the local spine density approximation (LSDA) or by the more advanced generalized gradient approximation (GGA). The calculated V zz values, in the Hf site, were in very good agreement with available 181Hf TDPAC experimental results.

  3. Investigation of nanostructured Pd-Ag/n-ZnO thin film based Schottky junction for methane sensing

    NASA Astrophysics Data System (ADS)

    Roy, S.; Das, S.; Sarkar, C. K.

    2016-07-01

    Undoped nanocrystalline n-type ZnO thin film was deposited by chemical deposition technique on a thermally oxidized p-Si (~5 Ω cm resistivity and <100> orientation) substrate. Formation of stable zinc oxide thin film was confirmed by two-dimensional X-Ray Diffraction (XRD) and EDX analysis. The average crystallite size of the ZnO sample was evaluated as ~50 nm. The surface was characterized by Field Emission Scanning Electron Microscopy (FESEM) and Atomic Force Microscopy (AFM) that confirm the formation of nanocrystalline (grain size ~50 nm) ZnO thin film with surface roughness of ~100 nm. Good conversion of precursor into ZnO thin film in the chemical deposition method was evident by Fourier Transform Infrared Spectroscopy (FTIR). A small peak at 479 cm-1was observed in the FTIR spectrum confirming the formation of quartzite structure of the ZnO. The band gap (~3.44 eV) of the material was calculated from the optical absorption spectroscopy. To prepare Pd-Ag/n-ZnO Schottky junction, Pd-Ag contacts were taken by electron beam evaporation method. I-V characteristics of the junction were studied at different temperatures in inert and reducing ambient (N2 and N2 + CH4) with turn on voltage of around 0.2 V. The parameters like ideality factor ( η), saturation current ( I 0), series resistance ( Rs), and barrier height ( Φ BO) of the junction were calculated in the temperature range 50-200 °C in N2 as well as in 1 % CH4 + N2 ambient. It was observed that the ideality factor decreases in the temperature range 50-200 °C ( η = 12.34 at 50 °C and η = 1.52 at 200 °C) in N2 ambient and η = 1.18 in N2 +CH4 ambient at 200 °C. Schottky Barrier Height ( Φ BO) of the Pd-Ag/n-ZnO junction was found to increase with temperature. A close observation of Pd-Ag/n-ZnO junction in the presence of methane was performed to appreciate its application as methane sensor. The sensing mechanism was illustrated by a simplified energy band diagram.

  4. Investigation of nanostructured Pd-Ag/n-ZnO thin film based Schottky junction for methane sensing

    NASA Astrophysics Data System (ADS)

    Roy, S.; Das, S.; Sarkar, C. K.

    2016-07-01

    Undoped nanocrystalline n-type ZnO thin film was deposited by chemical deposition technique on a thermally oxidized p-Si (~5 Ω cm resistivity and <100> orientation) substrate. Formation of stable zinc oxide thin film was confirmed by two-dimensional X-Ray Diffraction (XRD) and EDX analysis. The average crystallite size of the ZnO sample was evaluated as ~50 nm. The surface was characterized by Field Emission Scanning Electron Microscopy (FESEM) and Atomic Force Microscopy (AFM) that confirm the formation of nanocrystalline (grain size ~50 nm) ZnO thin film with surface roughness of ~100 nm. Good conversion of precursor into ZnO thin film in the chemical deposition method was evident by Fourier Transform Infrared Spectroscopy (FTIR). A small peak at 479 cm-1was observed in the FTIR spectrum confirming the formation of quartzite structure of the ZnO. The band gap (~3.44 eV) of the material was calculated from the optical absorption spectroscopy. To prepare Pd-Ag/n-ZnO Schottky junction, Pd-Ag contacts were taken by electron beam evaporation method. I-V characteristics of the junction were studied at different temperatures in inert and reducing ambient (N2 and N2 + CH4) with turn on voltage of around 0.2 V. The parameters like ideality factor (η), saturation current (I 0), series resistance (Rs), and barrier height (Φ BO) of the junction were calculated in the temperature range 50-200 °C in N2 as well as in 1 % CH4 + N2 ambient. It was observed that the ideality factor decreases in the temperature range 50-200 °C (η = 12.34 at 50 °C and η = 1.52 at 200 °C) in N2 ambient and η = 1.18 in N2 +CH4 ambient at 200 °C. Schottky Barrier Height (Φ BO) of the Pd-Ag/n-ZnO junction was found to increase with temperature. A close observation of Pd-Ag/n-ZnO junction in the presence of methane was performed to appreciate its application as methane sensor. The sensing mechanism was illustrated by a simplified energy band diagram.

  5. New constraints on the origin of the Skaergaard intrusion Cu-Pd-Au mineralization: Insights from high-resolution X-ray computed tomography

    NASA Astrophysics Data System (ADS)

    Godel, Bélinda; Rudashevsky, Nikolay S.; Nielsen, Troels F. D.; Barnes, Stephen J.; Rudashevsky, Vladimir N.

    2014-03-01

    This contribution presents the first detailed three-dimensional (3D) in situ analysis of samples from the Platinova Reef using high-resolution X-ray computed tomography (HRXCT) and 3D image processing and quantification coupled with microscopic and mineralogical investigations. Our HRXCT analyses reveal the complex textural relationships between Cu-rich sulfides (bulk composition close to bornite), skaergaardite (PdCu), Au-rich phases, silicates and Fe-Ti oxides and provide unequivocal textural evidences, not observed previously. The association in 3D between Cu-rich sulfide globules, PdCu alloy and ilmenite is inconsistent with a hydrothermal origin of the Cu-Pd mineralization. In contrast, our results combined with phase diagrams strongly support a primary magmatic origin for the Cu-Pd mineralization where Cu and Pd-rich, Fe-poor sulfide liquid represents a cumulus phase that forms by in-situ nucleation. These sulfide droplets and attached skaergaardite grains were trapped during the formation and crystallization of the Fe-Ti oxides. Subsequent, post-cumulus processes led to the partial to total dissolution of the sulfide not entirely enclosed by the Fe-Ti oxides (i.e., not protected from reaction) leading to the observed variability in Cu and Pd composition at the aggregate (sulfide + PdCu) scale and to the occurrence of free PdCu alloys. In contrast to the PdCu alloy, gold-bearing minerals are never observed entirely enclosed within the Fe-Ti oxide. Two hypotheses can be envisaged for the formation of the gold enriched layer in the upper part of the section. Gold may have either precipitated from high-temperature late magmatic Cl-rich fluids. Alternatively, gold may have been enriched during fractional crystallization after sulfide had been suppressed from the liquidus after the Pd layer crystallized and then deposited along redox barriers.

  6. Absorption vs. redox reduction of Pd2+ and Cu2+ on triboelectrically and naturally charged dielectric polymers.

    PubMed

    Piperno, Silvia; Cohen, Hagai; Bendikov, Tatyana; Lahav, Meir; Lubomirsky, Igor

    2012-04-28

    It has recently been reported that Teflon and polyethylene (PE) if rubbed by polymethylmethacrylate (PMMA) or Nylon as well as non-rubbed PMMA and Nylon induce "redox" reactions, including those of the reduction of Pd(+2) and Cu(+2) ions. On this basis, it was deduced that these dielectric materials may hold ≅10(13)-10(14) of "hidden" electrons cm(-2), a value at least three orders of magnitude higher than the charge that a dielectric surface can accumulate without being discharged in air. The "hidden" electrons were termed "cryptoelectrons". In variance to these reports, we offer here an alternative interpretation. Our model is supported by X-ray photoelectron spectroscopy, contact angle and vibrating electrode (modified Kelvin probe) measurements performed on representative examples. Rubbing of the polymers was found to transfer polymer fragments between the rubbed surfaces altering their physical properties. The transferred polymer fragments promote adsorption of Cu(2+) and Pd(2+) ions. It was found that Teflon and PE rubbed with PMMA and Nylon, and non-rubbed PMMA and non-rubbed Nylon do not induce "redox" reactions of Cu(2+) and Pd(2+) ions but adsorb these ions on their surfaces. Furthermore, the earlier reported reduction of Pd(2+) to Pd(0) by electrons, as detected by catalytic activity of Pd(0) in a Cu-plating bath, can be alternatively explained by reduction of adsorbed Pd(2+) by the reducing agents of the bath itself. Based on these findings, we support the hypothesis that charging of dielectric polymers is due to ions or free radicals rather than electrons and there is no evidence to invoke a hypothesis of "cryptoelectrons". PMID:22398656

  7. Active Brazing of C/C Composite to Copper by AgCuTi Filler Metal

    NASA Astrophysics Data System (ADS)

    Zhang, Kexiang; Xia, Lihong; Zhang, Fuqin; He, Lianlong

    2016-05-01

    Brazing between the carbon-fiber-reinforced carbon composite (C/C composite) and copper has gained increasing interest because of its important application in thermal management systems in nuclear fusion reactors and in the aerospace industry. In order to examine the "interfacial shape effect" on the mechanical properties of the joint, straight and conical interfacial configurations were designed and machined on the surface of C/C composites before joining to copper using an Ag-68.8Cu-4.5Ti (wt pct) alloy. The microstructure and interfacial microchemistry of C/C composite/AgCuTi/Cu brazed joints were comprehensively investigated by using high-resolution transmission electron microscopy. The results indicate that the joint region of both straight and conical joints can be described as a bilayer. Reaction products of Cu3Ti3O and γ-TiO were formed near the copper side in a conical interface joint, while no reaction products were found in the straight case. The effect of Ag on the interfacial reaction was discussed, and the formation mechanism of the joints during brazing was proposed. On the basis of the detailed microstructure presented, the mechanical performance of the brazed joints was discussed in terms of reaction and morphology across the joint.

  8. High temperature phase equilibria studies in the Bi-Sr-Ca-Cu-O-Ag system

    SciTech Connect

    Margulies, Lawrence

    1999-11-08

    A variety of experimental techniques were utilized to examine the high temperature phase equilibria in the Bi-Sr-Ca-Cu-O-Ag system. Quenching studies were used to determine the liquid solubility of Ag in the Bi{sub 2}Sr{sub 2}CaCu{sub 2}O{sub 8} (Bi2212) melt and the details of the peritectic decomposition pathway of Bi2212 as a function on Ag content and oxygen partial pressure (PO{sub 2}). A liquid immiscibility region between oxide and Ag liquids in the 8--98 at% range was found above 900 C. Two eutectics were found in the Bi2212-Ag pseudobinary. On the oxide rich side, a eutectic exists at approximately 4 at% Ag. On the Ag rich side, a eutectic exists at approximately 98 at% Ag at a temperature of 15 C below the melting point of pure Ag. Six distinct solid phases were found to be in equilibrium with the partial melt within the Ag content and PO{sub 2} range studied. The stability of these solid phases were found to be highly sensitive to PO{sub 2}, and to a much lesser extent Ag content. High temperature x-ray diffraction (HTXRD) studies of this system are in conflict with these results. It is suggested that these discrepancies are due to experimental artifacts caused by the significant thermal gradients and lack of full bulk sampling which is inherent in conventional HTXRD designs. In part 2, a new furnace design compatible with synchrotron radiation sources is introduced to address these problems. This design allows for full bulk sampling in a low thermal gradient environment using Debye-Scherrer transmission geometry. Sample spinning is also introduced in the design to eliminate preferred orientation and incomplete powder averaging and allow for quantitative phase analysis and structural refinement. Studies on model systems are presented to demonstrate the capabilities for high resolution structural studies (Al{sub 2}O{sub 3}) and time resolved phase transformation studies (SrCO{sub 3}). Finally, the Bi2212 system is examined to confirm the quenching results

  9. Evaluation of the microstructure of Al-Cu-Li-Ag-Mg Weldalite (tm) alloys, part 4

    NASA Technical Reports Server (NTRS)

    Pickens, Joseph R.; Kumar, K. S.; Brown, S. A.; Gayle, Frank W.

    1991-01-01

    Weldalite (trademark) 049 is an Al-Cu-Li-Ag-Mg alloy designed to have ultrahigh strength and to serve in aerospace applications. The alloy displays significantly higher strength than competitive alloys in both naturally aged and artificially aged tempers. The strengthening phases in such tempers have been identified to, in part, explain the mechanical properties attained. In general, the alloy is strengthened by delta prime Al3Li and Guinier-Preston (GP) zones in the naturally aged tempers. In artificially aged tempers in slightly underaged conditions, strengthening is provided by several phases including GP zones, theta prime Al2Cu, S prime Al2CuMg, T(sub 1) Al2CuLi, and possibly a new phase. In the peak strength artificially aged tempers, T(sub 1) is the predominant strengthening phase.

  10. DFT study of the adsorption properties of single Pt, Pd, Ag, In and Sn on the γ-Al2O3 (1 1 0) surface

    NASA Astrophysics Data System (ADS)

    Gao, Hongwei

    2016-07-01

    GGA/PW91 exchange-correlation functional within periodic density functional theory (DFT) has been used to investigate the adsorption properties of different metal atoms (Pt, Pd, Ag, Sn and In) on the O-terminated and Al-terminated γ-Al2O3 (1 1 0) surface. The predicted adsorption energies follow the order Sn > In > Ag > Pd > Pt. It is found that O-bridge position is the most favorable site for single Pt, Pd, Ag, Sn and In adsorption on the O-terminated γ-Al2O3 (1 1 0) surface. It is found that the most favorable site on the Al-terminated γ-Al2O3 (1 1 0) surface is O-top position.

  11. High resolution electron microscopy study of a high Cu variant of Weldalite (tm) 049 and a high strength Al-Cu-Ag-Mg-Zr alloy

    NASA Technical Reports Server (NTRS)

    Herring, R. A.; Gayle, Frank W.; Pickens, Joseph R.

    1991-01-01

    Weldalite (trademark) 049 is an Al-Cu-Li-Ag-Mg alloy that is strengthened in artificially aged tempers primarily by very thin plate-like precipitates lying on the set of (111) matrix planes. This precipitate might be expected to be the T(sub 1) phase, Al2CuLi, which has been observed in Al-Cu-Li alloys. However, in several ways this precipitate is similar to the omega phase which also appears as the set of (111) planes plates and is found in Al-Cu-Ag-Mg alloys. The study was undertaken to identify the set of (111) planes precipitate or precipitates in Weldalite (trademark) 049 in the T8 (stretched and artificially aged) temper, and to determine whether T(sub 1), omega, or some other phase is primarily responsible for the high strength (i.e., 700 MPa tensile strength) in this Al-Cu-Li-Ag-Mg alloy.

  12. Impacts of Pristine and Transformed Ag and Cu Engineered Nanomaterials on Surficial Sediment Microbial Communities Appear Short-Lived.

    PubMed

    Moore, Joe D; Stegemeier, John P; Bibby, Kyle; Marinakos, Stella M; Lowry, Gregory V; Gregory, Kelvin B

    2016-03-01

    Laboratory-based studies have shown that many soluble metal and metal oxide engineered nanomaterials (ENM) exert strong toxic effects on microorganisms. However, laboratory-based studies lack the complexity of natural systems and often use "as manufactured" ENMs rather than more environmentally relevant transformed ENMs, leaving open the question of whether natural ligands and seasonal variation will mitigate ENM impacts. Because ENMs will accumulate in subaquatic sediments, we examined the effects of pristine and transformed Ag and Cu ENMs on surficial sediment microbial communities in simulated freshwater wetlands. Five identical mesocosms were dosed through the water column with either Ag(0), Ag2S, CuO or CuS ENMs (nominal sizes of 4.67 ± 1.4, 18.1 ± 3.2, 31.1 ± 12, and 12.4 ± 4.1, respectively) or Cu(2+). Microbial communities were examined at 0, 7, 30, 90, 180, and 300 d using qPCR and high-throughput 16S rRNA gene sequencing. Results suggest differential short-term impacts of Ag(0) and Ag2S, similarities between CuO and CuS, and differences between Cu ENMs and Cu(2+). PICRUSt-predicted metagenomes displayed differential effects of Ag treatments on photosynthesis and of Cu treatments on methane metabolism. By 300 d, all metrics pointed to reconvergence of ENM-dosed mesocosm microbial community structure and composition, suggesting that the long-term microbial community impacts from a pulse of Ag or Cu ENMs are limited. PMID:26841726

  13. Effect of Additional 3d Elements M (M = Fe and Ni) on Atomic Ordered Structure in Cu-M-Pd alloy

    NASA Astrophysics Data System (ADS)

    Ahmad, Naseeb; Takahashi, Miwako; Bashir Ziya, Amer; Ohshima, Ken-ichi

    X-ray diffraction measurements were performed to elucidate the effect of ternary addition of Fe and Ni elements to Cu-rich Cu-Pd binary alloy system on the structure and an atomic ordering. X-ray polycrystalline diffraction patterns of the specimens quenched from 900 °C have shown that a single phase with face-centered cubic (fcc) structure is formed in all the specimens for Ni system and in specimens with Pd composition xPd (at. %) more than 10 for Fe system. After appropriate heat treatment, the Fe system a fcc single phase forms fcc-based Cu3Au-type ordered structure for xPd around 20, and body-centered-cubic based CsCl-type ordered structure xPd for around 40. Assuming that Fe atoms simply substitute for Cu atoms in the ordered structures, the atomic phase coincides well with that of Cu-Pd alloys for the Cu3Au-type structure, but there is a discrepancy for the CsCl-type structure on that it does not appear as a single phase in Cu-Fe-Pd alloys. As for Ni system, no ordered structures are formed except for the alloys with xPd more than 35, in which fcc and CsCl-type structures are found to coexist.

  14. Nanoparticles of Ag with a Pt and Pd rich surface supported on carbon as a new catalyst for the oxygen electroreduction reaction (ORR) in acid electrolytes: Part 2

    NASA Astrophysics Data System (ADS)

    Pech-Pech, I. E.; Gervasio, Dominic F.; Pérez-Robles, J. F.

    2015-02-01

    In the first part of this work, the feasibility of developing a catalyst with high activity for the oxygen electroreduction reaction (ORR) in acid media and with low Pt loading was demonstrated by over coating a silver (Ag) nanoparticle with a shell of platinum (Pt) and palladium (Pd) [7]. The results show that best activity is not directly related to a higher PtPd loading on the surface of the Ag. The best catalyst in a series of this type of catalyst is found with Ag@Pt0.3Pd0.3/C which gives a specific activity for oxygen reduction, jk (in units of mA cm-2 of real area), of 0.07 mA cm-2 at 0.85 V vs. NHE, as compared to 0.04 mA cm-2 when with a commercial Pt on carbon catalyst (Pt20/C) is used in an identical electrode except for the catalyst. The mass activity, jm (in units of mA μg-1 of Pt), for Ag@Pt0.3Pd0.3/C is 0.04 mA μg-1 of Pt at 0.85 V vs. NHE, whereas that for the Pt20/C gives 0.02 mA μg-1 of Pt, showing Ag@Pt0.3Pd0.3/C is a lower-cost catalyst, because using a Ag core and Pd with Pt in the shell gives the highest catalytic activity using less Pt.

  15. Scanning tunneling microscope-induced modification of Cu(100) surfaces and Ag nanowire arrays

    NASA Astrophysics Data System (ADS)

    Leibsle, Fred; York, Mike; Aurongzeb, Deeder

    2001-03-01

    We have used scanning tunneling microscopy to selectively modify areas of Cu(100) surfaces. By scanning repeatedly over areas with extremely low bias voltages and high tunneling currents, we can create nanometer-scale pits several layers deep. The atoms removed from these pits form nearby islands. The evolution of these pits and islands is also studied with images showing changes in shape, coalescence and both rapid and gradual decay. We also demonstrate how we can selectively modify segments of Ag nanowire arrays grown on atomic nitrogen-modified Cu(100) surfaces.

  16. Effect of Surplus Phase on the Microstructure and Mechanical Properties in Al-Cu-Mg-Ag Alloys with High Cu/Mg Ratio

    NASA Astrophysics Data System (ADS)

    Xu, Xiaofeng; Zhao, Yuguang; Wang, Xudong; Zhang, Ming; Ning, Yuheng

    2015-11-01

    In order to examine the effect of surplus phase on the microstructure and mechanical properties, different compositions with high Cu/Mg ratio of the T6-temper extruded Al-Cu-Mg-Ag alloys were studied in this investigation. The results show that the Al-5.6Cu-0.56Mg-0.4Ag alloy obtains superior mechanical properties at room temperature, while the yield strength of Al-6.3Cu-0.48Mg-0.4Ag alloy is 378 MPa at 200 °C, which is 200 MPa higher than that of Al-5.6Cu-0.56Mg-0.4Ag alloy. Although the excessive Cu content causes the slight strength loss and elongation decrease in the Al-6.3Cu-0.48Mg-0.4Ag alloy at room temperature, the surplus phases and recrystallized microstructure will play an effective role in strengthening the alloy at elevated temperature.

  17. Characterization of Binary Ag-Cu Ion Mixtures in Zeolites: Their Reduction Products and Stability to Air Oxidation

    SciTech Connect

    Fiddy, Steven; Petranovskii, Vitalii; Ogden, Steve; Iznaga, Inocente Rodriguez

    2007-02-02

    A series of Ag+-Cu2+ binary mixtures with different Ag/Cu ratios were supported on mordenite with different Si/Al ratios and were subsequently reduced under hydrogen in the temperature range 323K - 473K. Ag and Cu K-edge X-ray Absorption Spectroscopy (XAS) was conducted on these systems in-situ to monitor the reduction species formed and the kinetics of their reduction. In-situ XANES clearly demonstrates that the formation of silver particles is severely impeded by the addition of copper and that the copper is converted from Cu(II) to Cu(I) during reduction and completely reverts back to Cu(II) during cooling. There are no indications at any stage of the formation of bimetallic Ag-Cu clusters. Interestingly, the Ag/Cu ratio appears to have no influence of the reduction kinetics and reduction products formed with only the highest Si/Al ratio (MR = 128) investigated during this study having an influence on the reduction and stability to air oxidation.

  18. Nucleation and Growth of Cu-Al Intermetallics in Al-Modified Sn-Cu and Sn-Ag-Cu Lead-Free Solder Alloys

    NASA Astrophysics Data System (ADS)

    Reeve, Kathlene N.; Anderson, Iver E.; Handwerker, Carol A.

    2015-03-01

    Lead-free solder alloys Sn-Cu (SC) and Sn-Ag-Cu (SAC) are widely used by the microelectronics industry, but enhanced control of the microstructure is needed to improve solder performance. For such control, nucleation and stability of Cu-Al intermetallic compound (IMC) solidification catalysts were investigated by variation of the Cu (0.7-3.0 wt.%) and Al (0.0-0.4 wt.%) content of SC + Al and SAC + Al alloys, and of SAC + Al ball-grid array (BGA) solder joints. All of the Al-modified alloys produced Cu-Al IMC particles with different morphologies and phases (occasionally non-equilibrium phases). A trend of increasing Cu-Al IMC volume fraction with increasing Al content was established. Because of solidification of non-equilibrium phases in wire alloy structures, differential scanning calorimetry (DSC) experiments revealed delayed, non-equilibrium melting at high temperatures related to quenched-in Cu-Al phases; a final liquidus of 960-1200°C was recorded. During cooling from 1200°C, the DSC samples had the solidification behavior expected from thermodynamic equilibrium calculations. Solidification of the ternary alloys commenced with formation of ternary β and Cu-Al δ phases at 450-550°C; this was followed by β-Sn, and, finally, Cu6Sn5 and Cu-Al γ1. Because of the presence of the retained, high-temperature phases in the alloys, particle size and volume fraction of the room temperature Cu-Al IMC phases were observed to increase when the alloy casting temperature was reduced from 1200°C to 800°C, even though both temperatures are above the calculated liquidus temperature of the alloys. Preliminary electron backscatter diffraction results seemed to show Sn grain refinement in the SAC + Al BGA alloy.

  19. Development of Pd-Ag Compostie Membrane for Separation of Hydrogen at Elevated Temperature

    SciTech Connect

    Shamsuddin Ilias

    2009-02-28

    Pd-based membrane reactor offers the possibility of combining reaction and separation in a single operation at high temperatures to overcome the equilibrium limitations experienced in conventional reactor configurations. In this project to develop a defect-free and hermally-stable Pd-film on microporous stainless steel (MPSS) support for H2-separation and membrane reactor applications, the electroless plating process was revisited with an aim to improve the membrane morphology. Specifically, this study includes; (a) an improvement f activation step using Pulse Laser Deposition (PLD), (b) development of a novel surfactant induced electroless plating (SIEP) for depositing robust Pd-film on microporous support, and (c) application of Pd-membrane as membrane reactor in steam methanol reforming (SMR) reactions.

  20. Electrochemical aptasensor for the detection of adenosine by using PdCu@MWCNTs-supported bienzymes as labels.

    PubMed

    Wu, Dan; Ren, Xiang; Hu, Lihua; Fan, Dawei; Zheng, Yang; Wei, Qin

    2015-12-15

    A highly sensitive electrochemical adenosine aptasensor was fabricated by covalently immobilizing 3'-NH2-terminated capture probe (SSDNA1) and thionine (TH) on Au-GS modified glassy carbon electrode. 3'-SH-terminated adenosine aptamer (SSDNA2) was adsorbed onto palladium/copper alloyed supported on MWCNTs (PdCu@MWCNTs)-conjugated multiple bienzymes, glucose oxidase (GOx), and horseradish peroxidase (HRP) (SSDNA2/PdCu@MWCNTs/HRP/GOx). Then, it was immobilized onto the electrode surface through the hybridization between the adenosine aptamer and the capture probe. The signal was amplified based on the gradual electrocatalytic reduction of GOx-generated hydrogen peroxide by the multiple HRP through the mediating ability of the loaded multiple TH. However, the peak current of TH decreased in the presence of adenosine because the interaction between adenosine and its aptamer made SSDNA2/PdCu@MWCNTs/HRP/GOx release from the modified electrode. Various experimental parameters have been optimized for the detection of adenosine and tests for selectivity, reproducibility and stability have also been performed. Under the optimal condition, the proposed aptasensor displayed a wide linear range (10-400 nM) with the low detection limit (2.5 nM), which has been applied in human serum samples with satisfactory results. Thus, the combination of Au-GS as a sensor platform and PdCu@MWCNTs/HRP/GOx as labels can be a promising amplification strategy for highly sensitive adenosine detection. PMID:26164010

  1. Pd-Catalyzed, Cu(I)-Mediated Cross-Couplings of Bisarylthiocyclobutenediones with Boronic Acids and Organostannanes

    PubMed Central

    Aguilar-Aguilar, Angélica; Liebeskind, Lanny S.; Peña-Cabrera, Eduardo

    2009-01-01

    Bisarylthiocyclobutenedione 7 reacted smoothly with a variety of both organostannanes and (hetero)aryl boronic acids in the presence of a catalytic amount of Pd and a stoichiometric amount of CuTC, to produce symmetrical disubstituted cyclobutenediones in yields that range from 37 to 94% (18 examples). PMID:17892299

  2. Pd/Cu-cocatalyzed aerobic oxidative carbonylative homocoupling of arylboronic acids and CO: a highly selective approach to diaryl ketones.

    PubMed

    Ren, Long; Jiao, Ning

    2014-09-01

    A highly selective Pd/Cu-cocatalyzed aerobic oxidative carbonylative homocoupling of arylboronic acids has been developed. This method employs a simple catalytic system, readily available boronic acids as the substrates, molecular oxygen as the oxidant, and 1 atm of CO/O2 , which makes this method practical for further applications. PMID:24990473

  3. Efficient enhancement of hydrogen production by Ag/Cu2O/ZnO tandem triple-junction photoelectrochemical cell

    NASA Astrophysics Data System (ADS)

    Liu, Ying; Ren, Feng; Shen, Shaohua; Fu, Yanming; Chen, Chao; Liu, Chang; Xing, Zhuo; Liu, Dan; Xiao, Xiangheng; Wu, Wei; Zheng, Xudong; Liu, Yichao; Jiang, Changzhong

    2015-03-01

    Highly efficient semiconductor photoelectrodes for solar hydrogen production through photocatalytic water splitting are a promising and challenge solution to solve the energy problems. In this work, Ag/Cu2O/ZnO tandem triple-junction photoelectrode was designed and prepared. An increase of 11 times of photocurrent is achieved in the Ag/Cu2O/ZnO photoelectrode comparing to that of the Cu2O film. The high performance of the Ag/Cu2O/ZnO film is due to the optimized design of the tandem triple-junction structure, where the localized surface Plasmon resonance of Ag and the hetero-junctions efficiently absorb solar energy, produce, and separate electron-hole pairs in the photocathode.

  4. Ag-Cu nanoalloyed film as a high-performance cathode electrocatalytic material for zinc-air battery

    NASA Astrophysics Data System (ADS)

    Lei, Yimin; Chen, Fuyi; Jin, Yachao; Liu, Zongwen

    2015-04-01

    A novel Ag50Cu50 film electrocatalyst for oxygen reduction reaction (ORR) was prepared by pulsed laser deposition (PLD) method. The electrocatalyst actually is Ag-Cu alloyed nanoparticles embedded in amorphous Cu film, based on transmission electron microscopy (TEM) characterization. The rotating disk electrode (RDE) measurements provide evidence that the ORR proceed via a four-electron pathway on the electrocatalysts in alkaline solution. And it is much more efficient than pure Ag catalyst. The catalytic layer has maximum power density of 67 mW cm-2 and an acceptable cell voltage at 0.863 V when current densities increased up to 100 mA cm-2 in the Ag50Cu50-based primary zinc-air battery. The resulting rechargeable zinc-air battery exhibits low charge-discharge voltage polarization of 1.1 V at 20 mAcm-2 and high durability over 100 cycles in natural air.

  5. Nanostructured YbAgCu4 for potentially cryogenic thermoelectric cooling.

    PubMed

    Koirala, Machhindra; Wang, Hui; Pokharel, Mani; Lan, Yucheng; Guo, Chuanfei; Opeil, Cyril; Ren, Zhifeng

    2014-09-10

    We have studied the thermoelectric properties of nanostructured YbAgCu4 materials. A high power factor of ∼131 μW cm(-1) K(-2) has been obtained at 22 K for nanostructured samples prepared by ball milling the arc melted ingot into nanopowder and hot pressing the nanopowder. The implementation of nanostructuring method decreased the thermal conductivity at 42 K by 30-50% through boundary scattering comparing with the previously reported value of polycrystalline YbAgCu4. A peak dimensionless thermoelectric figure-of-merit, ZT, of 0.11 has been achieved at 42 K, which may find potential applications for cryogenic cooling below 77 K. The nanostructuring approach can be extended to other heavy Fermion materials to achieve high power factor and low thermal conductivity and ultimately higher ZT. PMID:25079115

  6. Possible Mesozoic age of Ellenville Zn-Pb-Cu(Ag) deposit, Shawangunk Mountains, New York

    USGS Publications Warehouse

    Friedman, J.D.; Conrad, J.E.; McKee, E.H.; Mutschler, F.E.; Zartman, R.E.

    1994-01-01

    Ore textures, epithermal open-space filling of Permian structures of the Alleghanian orogeny, and largely postorogenic mineralization of the Ellenville, New York, composite Zn-Pb-Cu(Ag) vein system, provide permissive evidence for post-Permian mineralization. Isochron ages determined by 40Ar/39Ar laser-fusion techniques for K-bearing liquid inclusions in main-stage quartz from the Ellenville deposit additionally suggest a Mesozoic time of mineralization, associated with extensional formation of the Newark basin. The best 40Ar/39Ar total-fusion age range is 165 ?? 30 to 193 ?? 35 Ma. The Mesozoic 40Ar/39Ar age agrees with that of many other dated northern Appalachian Zn-Pb-Cu(Ag) deposits with near-matching lead isotope ratios, and adds new evidence of Jurassic tectonism and mineralization as an overprint to Late Paleozoic tectonism at least as far north as Ellenville (lat. 41??43???N). ?? 1994 Springer-Verlag.

  7. Formation of M-C≡C-Cl (m = ag or Cu) and Characterization by Rotational Spectroscopy

    NASA Astrophysics Data System (ADS)

    Zaleski, Daniel P.; Tew, David Peter; Walker, Nick; Legon, Anthony

    2015-06-01

    The new linear molecule Ag-C≡C-Cl has been detected and characterized by means of rotational spectroscopy. It was synthesized by laser ablation of a slver rod in the presence of a gaseous sample containing a low concentration of CCl4 in argon, cooled to a rotational temperature approaching 2 K through supersonic expansion and analyzed by chirped pulse Fourier transform microwave spectroscopy. Substitution coordinates are available for the silver and chlorine positions and will be compared to ab initio calculations at the CCSD(T)/aug-cc-pV5Z level of theory. The Ag-13C≡13C-Cl isotopologue was also observed using a similar gas mixture containing 13CCl4. The Cu analogue Cu-C≡C-Cl was similarly identified and characterized.

  8. Gold and palladium minerals (including empirical PdCuBiSe3) from the former Roter Bär mine, St. Andreasberg, Harz Mountains, Germany: a result of low-temperature, oxidising fluid overprint

    NASA Astrophysics Data System (ADS)

    Cabral, Alexandre Raphael; Ließmann, Wilfried; Lehmann, Bernd

    2015-10-01

    At Roter Bär, a former underground mine in the polymetallic deposits of St. Andreasberg in the middle-Harz vein district, Germany, native gold and palladium minerals occur very locally in clausthalite-hematite pockets of few millimetres across in carbonate veinlets. The native gold is a Au-Ag intermetallic compound and the palladium minerals are characterised as mertieite-II [Pd8(Sb,As)3] and empirical PdCuBiSe3 with some S. The latter coexists with bohdanowiczite (AgBiSe2), a mineral that is stable below 120 °C. The geological setting of Roter Bär, underneath a post-Variscan unconformity, and its hematite-selenide-gold association suggest that oxidising hydrothermal brines of low temperature were instrumental to the Au-Pd mineralisation. The Roter Bär Au-Pd mineralisation can be explained by Permo-Triassic, red-bed-derived brines in the context of post-Variscan, unconformity-related fluid overprint.

  9. Surface segregation in a polycrystalline Pd70Cu30 alloy hydrogen purification membrane

    SciTech Connect

    Miller, J.B.; Matranga, C.; Gellman, A.J.

    2008-01-01

    X-ray photoelectron spectroscopy (XPS) and low energy ion scattering spectroscopy (LEISS) have been used to study the effects of various surface preparations and thermal treatments on the composition of the near-surface region (~7 atomic layers) and the topmost atomic layer of a polycrystalline Pd70Cu30 alloy. Palladium enrichment (relative to the bulk composition) is observed in the XPS-accessible near-surface region, but copper enrichment is observed in the topmost atomic layer. At temperatures above ~800 K, where the bulk, the near-surface region and the topmost atomic layer are likely in thermodynamic equilibrium, segregation to the top layer can be described in terms of a simple thermodynamic model. Temperature programmed desorption (TPD) of H2 and CO from the annealed surfaces illustrates the impact of segregation and atomic distribution in the top layer on surface chemical activity.

  10. Surface Segregation in a PdCu Alloy Hydrogen Separation Membrane

    SciTech Connect

    Miller, J.B.; Matranga, C.S.; Gellman, A.J.

    2007-06-01

    Separation of hydrogen from mixed gas streams is an important step for hydrogen generation technologies, including hydrocarbon reforming and coal/biomass gasification. Dense palladium-based membranes have received significant attention for this application because of palladium’s ability to dissociatively adsorb molecular hydrogen at its surface for subsequent transport of hydrogen atoms through its bulk. Alloying palladium with minor components, like copper, has been shown to improve both the membrane’s structural characteristics and resistance to poisoning of its catalytic surface [1]. Surface segregation—a composition difference between the bulk material and its surface—is common in alloys and can affect important surface processes. Rational design of alloy membranes requires that surface segregation be understood, and possibly controlled. In this work, we examine surface segregation in a polycrystalline Pd70Cu30 hydrogen separation membrane as a function of thermal treatment and adsorption of hydrogen sulfide.

  11. Microstructure-property relationships in Al-Cu-Li-Ag-Mg Weldalite (tm) alloys, part 2

    NASA Technical Reports Server (NTRS)

    Langan, T. J.; Pickens, J. R.

    1991-01-01

    The microstructure and mechanical properties of the ultrahigh strength Al-Cu-Li-Ag-Mg alloy, Weldalite (tm) 049, were studied. Specifically, the microstructural features along with tensile strength, weldability, Young's modulus and fracture toughness were studied for Weldalite (tm) 049 type alloys with Li contents ranging from 1.3 to 1.9 wt. pct. The tensile properties of Weldalite 049 and Weldalite 049 reinforced with TiB2 particles fabricated using the XD (tm) process were also evaluated at cryogenic, room, and elevated temperatures. In addition, an experimental alloy, similar in composition to Weldalite 049 but without the Ag+Mg, was fabricated. The microstructure of this alloy was compared with that of Weldalite 049 in the T6 condition to assess the effect of Ag+Mg on nucleation of strengthening phases in the absence of cold work.

  12. Cu-In-Te and Ag-In-Te colloidal nanocrystals with tunable composition and size.

    PubMed

    Yarema, Olesya; Yarema, Maksym; Lin, Weyde M M; Wood, Vanessa

    2016-09-18

    We synthesize stable colloids of Cu-In-Te and Ag-In-Te nanocrystals using an amide-promoted technique, which enables independent size and composition control, and report the dependence of structural and optical properties on composition and size. Comparison to the synthesis of other ternary I-III-VI nanocrystals gives insight into the reaction mechanism and the generalizability of the amide-promote approach. PMID:27530620

  13. Growth of Nucleation Sites on Pd-doped Bi_2Sr_2Ca1 Cu_2O_8+δ

    NASA Astrophysics Data System (ADS)

    Kouzoudis, D.; Finnemore, D. K.; Xu, Ming; Balachandran

    1996-03-01

    Enviromental Scanning Electron Microscope has shown evidence that during the growth of Bi_2Sr_2Ca_2Cu_3O_10+δ from mixed powders of Pb-doped Bi_2Sr_2Ca_1Cu_2O_8+δ and other oxides, a dense array of hillocks or mesas grow at the interface between an Ag overlay and Pb doped Bi_2Sr_2Ca_1Cu_2O_8+δ grains. These hillocks develop a texture that looks like ''chicken pox'' during the ramp up to the reaction temperature starting at about 700^circ C and they are about 500 to 1000 nm across and are spaced at about 500 to 1000 nm. If there is no Ag, this texture does not develop. Preliminary measurments indicate that the hillocks are re-crystallization of (Bi,Pb)_2Sr_2Ca_1Cu_2O_8+δ and are definetely not a Pb rich phase

  14. Electromigration induced Kirkendall void growth in Sn-3.5Ag/Cu solder joints

    SciTech Connect

    Jung, Yong; Yu, Jin

    2014-02-28

    Effects of electric current flow on the Kirkendall void formation at solder joints were investigated using Sn-3.5Ag/Cu joints specially designed to have localized nucleation of Kirkendall voids at the Cu{sub 3}Sn/Cu interface. Under the current density of 1 × 10{sup 4} A/cm{sup 2}, kinetics of Kirkendall void growth and intermetallic compound thickening were affected by the electromigration (EM), and both showed the polarity effect. Cu{sub 6}Sn{sub 5} showed a strong susceptibility to the polarity effect, while Cu{sub 3}Sn did not. The electromigration force induced additional tensile (or compressive) stress at the cathode (or anode), which accelerated (or decelerated) the void growth. From the measurements of the fraction of void at the Cu{sub 3}Sn/Cu interface on SEM micrographs and analysis of the kinetics of void growth, the magnitude of the local stress induced by EM was estimated to be 9 MPa at the anode and −7 MPa at the cathode.

  15. Overcoming the "oxidant problem": strategies to use O2 as the oxidant in organometallic C-H oxidation reactions catalyzed by Pd (and Cu).

    PubMed

    Campbell, Alison N; Stahl, Shannon S

    2012-06-19

    Oxidation reactions are key transformations in organic chemistry because they can increase chemical complexity and incorporate heteroatom substituents into carbon-based molecules. This principle is manifested in the conversion of petrochemical feedstocks into commodity chemicals and in the synthesis of fine chemicals, pharmaceuticals, and other complex organic molecules. The utility and function of these molecules correlate directly with the presence and specific placement of oxygen and nitrogen heteroatoms and other functional groups within the molecules. Methods for selective oxidation of C-H bonds have expanded significantly over the past decade, and their role in the synthesis of organic chemicals will continue to increase. Our group's contributions to this field are linked to our broader interest in the development and mechanistic understanding of aerobic oxidation reactions. Molecular oxygen (O(2)) is the ideal oxidant. Its low cost and lack of toxic byproducts make it a highly appealing reagent that can address key "green chemistry" priorities in industry. With strong economic and environmental incentives to use O(2), the commmodity chemicals industry often uses aerobic oxidation reactions. In contrast, O(2) is seldom used to prepare more-complex smaller-volume chemicals, a limitation that reflects, in part, the limited synthetic scope and utility of existing aerobic reactions. Pd-catalyzed reactions represent some of the most versatile methods for selective C-H oxidation, but they often require stoichiometric transition-metal or organic oxidants, such as Cu(II), Ag(I), or benzoquinone. This Account describes recent strategies that we have identified to use O(2) as the oxidant in these reactions. In Pd-catalyzed C-H oxidation reactions that form carbon-heteroatom bonds, the stoichiometric oxidant is often needed to promote difficult reductive elimination steps in the catalytic mechanism. To address this challenge, we have identified new ancillary ligands for

  16. Combinatorial development of antibacterial Zr-Cu-Al-Ag thin film metallic glasses

    NASA Astrophysics Data System (ADS)

    Liu, Yanhui; Padmanabhan, Jagannath; Cheung, Bettina; Liu, Jingbei; Chen, Zheng; Scanley, B. Ellen; Wesolowski, Donna; Pressley, Mariyah; Broadbridge, Christine C.; Altman, Sidney; Schwarz, Udo D.; Kyriakides, Themis R.; Schroers, Jan

    2016-05-01

    Metallic alloys are normally composed of multiple constituent elements in order to achieve integration of a plurality of properties required in technological applications. However, conventional alloy development paradigm, by sequential trial-and-error approach, requires completely unrelated strategies to optimize compositions out of a vast phase space, making alloy development time consuming and labor intensive. Here, we challenge the conventional paradigm by proposing a combinatorial strategy that enables parallel screening of a multitude of alloys. Utilizing a typical metallic glass forming alloy system Zr-Cu-Al-Ag as an example, we demonstrate how glass formation and antibacterial activity, two unrelated properties, can be simultaneously characterized and the optimal composition can be efficiently identified. We found that in the Zr-Cu-Al-Ag alloy system fully glassy phase can be obtained in a wide compositional range by co-sputtering, and antibacterial activity is strongly dependent on alloy compositions. Our results indicate that antibacterial activity is sensitive to Cu and Ag while essentially remains unchanged within a wide range of Zr and Al. The proposed strategy not only facilitates development of high-performing alloys, but also provides a tool to unveil the composition dependence of properties in a highly parallel fashion, which helps the development of new materials by design.

  17. Combinatorial development of antibacterial Zr-Cu-Al-Ag thin film metallic glasses.

    PubMed

    Liu, Yanhui; Padmanabhan, Jagannath; Cheung, Bettina; Liu, Jingbei; Chen, Zheng; Scanley, B Ellen; Wesolowski, Donna; Pressley, Mariyah; Broadbridge, Christine C; Altman, Sidney; Schwarz, Udo D; Kyriakides, Themis R; Schroers, Jan

    2016-01-01

    Metallic alloys are normally composed of multiple constituent elements in order to achieve integration of a plurality of properties required in technological applications. However, conventional alloy development paradigm, by sequential trial-and-error approach, requires completely unrelated strategies to optimize compositions out of a vast phase space, making alloy development time consuming and labor intensive. Here, we challenge the conventional paradigm by proposing a combinatorial strategy that enables parallel screening of a multitude of alloys. Utilizing a typical metallic glass forming alloy system Zr-Cu-Al-Ag as an example, we demonstrate how glass formation and antibacterial activity, two unrelated properties, can be simultaneously characterized and the optimal composition can be efficiently identified. We found that in the Zr-Cu-Al-Ag alloy system fully glassy phase can be obtained in a wide compositional range by co-sputtering, and antibacterial activity is strongly dependent on alloy compositions. Our results indicate that antibacterial activity is sensitive to Cu and Ag while essentially remains unchanged within a wide range of Zr and Al. The proposed strategy not only facilitates development of high-performing alloys, but also provides a tool to unveil the composition dependence of properties in a highly parallel fashion, which helps the development of new materials by design. PMID:27230692

  18. Combinatorial development of antibacterial Zr-Cu-Al-Ag thin film metallic glasses

    PubMed Central

    Liu, Yanhui; Padmanabhan, Jagannath; Cheung, Bettina; Liu, Jingbei; Chen, Zheng; Scanley, B. Ellen; Wesolowski, Donna; Pressley, Mariyah; Broadbridge, Christine C.; Altman, Sidney; Schwarz, Udo D.; Kyriakides, Themis R.; Schroers, Jan

    2016-01-01

    Metallic alloys are normally composed of multiple constituent elements in order to achieve integration of a plurality of properties required in technological applications. However, conventional alloy development paradigm, by sequential trial-and-error approach, requires completely unrelated strategies to optimize compositions out of a vast phase space, making alloy development time consuming and labor intensive. Here, we challenge the conventional paradigm by proposing a combinatorial strategy that enables parallel screening of a multitude of alloys. Utilizing a typical metallic glass forming alloy system Zr-Cu-Al-Ag as an example, we demonstrate how glass formation and antibacterial activity, two unrelated properties, can be simultaneously characterized and the optimal composition can be efficiently identified. We found that in the Zr-Cu-Al-Ag alloy system fully glassy phase can be obtained in a wide compositional range by co-sputtering, and antibacterial activity is strongly dependent on alloy compositions. Our results indicate that antibacterial activity is sensitive to Cu and Ag while essentially remains unchanged within a wide range of Zr and Al. The proposed strategy not only facilitates development of high-performing alloys, but also provides a tool to unveil the composition dependence of properties in a highly parallel fashion, which helps the development of new materials by design. PMID:27230692

  19. Hot Electron Attenuation Length Measurements of Cu and Ag using BEEM

    NASA Astrophysics Data System (ADS)

    Garramone, John; Abel, Joseph; Sitnitsky, Ilona; Zhao, Lai; Appelbaum, Ian; Labella, Vincent

    2010-03-01

    33.4˜2.9 nm 1.0 eV Understanding electron transport and scattering in nanoscale Cu and Ag structures is important for modern integrated circuit technology and futuristic applications such as spintronics and hydrogen sensing footnotetextHuang et al., Rev. Lett. 99 177209 (2007)^,footnotetextNienhaus et at., Appl. Phys. Lett. 74 4046 (1999). In this study we will report on hot electron attenuation length measurements of nanometer thick films of Cu and Ag on the Si substrate utilizing ballistic electron emission microscopy (BEEM). BEEM is a three terminal scanning tunneling microcopy (STM) based technique where electrons are injected from a STM tip into a grounded metal base of a Schottky diode. The electrons that transverse the metal overlayer and surmount the Schottky barrier are measured as the BEEM current by a backside contact to the semiconductor. The attenuation length is extracted by measuring the falloff in BEEM current as a function of metal film thickness. The hot electron attenuation length for Cu of is measured at a tip bias of and a temperature of 80 K. Results for Ag will also be presented as well as models used to extract the relative contribution of elastic and inelastic electron scattering in the metal films as a function of electron energy.

  20. Hydrothermal ethanol conversion on Ag, Cu, Au/TiO2

    NASA Astrophysics Data System (ADS)

    Mai, Do Tkhyui; Mikhalenko, I. I.; Pylinina, A. I.

    2014-10-01

    The effect UV irradiation and silver, copper, and gold ions (M z+) supported on titania (anatase) have on the activity of M/TiO2 samples in ethanol conversion at 150-400°C is examined. After UV irradiation, the yields of acetaldehyde and ethylene increase for TiO2 and Ag/TiO2 samples, while the activity of Cu2+/TiO2 decreases. The activation energy of ethanol dehydration declines in the order TiO2 > Au3+ > Cu2+ > Ag+ and correlates linearly with a reduction in the radius of M z+ in crystal. The number of acidic sites on a M/TiO2 surface titrated via pyridine adsorption grows upon the introduction of M. Unlike Cu2+/TiO2, these sites are not activated after the irradiation of TiO2, Ag+/TiO2, and Au3+/TiO2. According to IR spectral data on adsorbed pyridine, all samples contain Lewis and Brönsted acidic sites.

  1. Ag 2CuMnO 4: A new silver copper oxide with delafossite structure

    NASA Astrophysics Data System (ADS)

    Muñoz-Rojas, David; Subías, Gloria; Oró-Solé, Judith; Fraxedas, Jordi; Martínez, Benjamín; Casas-Cabanas, Montse; Canales-Vázquez, Jesús; Gonzalez-Calbet, Jose; García-González, Ester; Walton, Richard I.; Casañ-Pastor, Nieves

    2006-12-01

    The use of hydrothermal methods has allowed the synthesis of a new silver copper mixed oxide, Ag 2CuMnO 4, the first example of a quaternary oxide containing both elements. It crystallizes with the delafossite 3 R structure, thus being the first delafossite to contain both Ag and Cu. Synthesis conditions affect the final particle size (30-500 nm). Powder X-ray diffraction Rietveld refinement indicates a trigonal structure (R3¯m) and cell parameters a=2.99991 Å and c=18.428 Å, where Cu and Mn are disordered within the octahedral B positions in the plane and linearly coordinated Ag occupies de A position between layers. X-ray absorption near edge spectroscopy (XANES) for copper and manganese, and XPS for silver evidence +2, +4, and +1 oxidation states. The microstructure consists of layered particles that may form large twins showing 5 nm nanodomains. Finally, magnetic measurements reveal the existence of ferromagnetic coupling yielding in-plane moments that align antiferromagnetically at lower temperatures. The singularity of the new phase resides on the fact that is an example of a bidimensional arrangement of silver and copper in an oxide that also shows clear bidimensionality in its physical properties. That is of special relevance to the field of high Tc superconducting oxides, while the ferromagnetic coupling in a bidimensional system deserves itself special attention.

  2. Tunable Catalysis of Water to Peroxide with Anionic, Cationic, and Neutral Atomic Au, Ag, Pd, Rh, and Os

    NASA Astrophysics Data System (ADS)

    Suggs, K.; Kiros, F.; Tesfamichael, A.; Felfli, Z.; Msezane, A. Z.

    2015-05-01

    Fundamental anionic, cationic, and neutral atomic metal predictions utilizing density functional theory calculations validate the recent discovery identifying the interplay between Regge resonances and Ramsauer-Townsend minima obtained through complex angular momentum analysis as the fundamental atomic mechanism underlying nanoscale catalysis. Here we investigate the optimization of the catalytic behavior of Au, Ag, Pd, Rh, and Os atomic systems via polarization effects and conclude that anionic atomic systems are optimal and therefore ideal for catalyzing the oxidation of water to peroxide, with anionic Os being the best candidate. The discovery that cationic systems increase the transition energy barrier in the synthesis of peroxide could be important as inhibitors in controlling and regulating catalysis. These findings usher in a fundamental and comprehensive atomic theoretical framework for the generation of tunable catalytic systems. The ultimate aim is to design giant atomic catalysts and sensors, in the context of the recently synthesized tri-metal Ag@Au@Pt and bimetal Ag@Au nanoparticles for greatly enhanced plasmonic properties and improved chemical stability for chemical and biological sensing. Research was supported by U.S. DOE Office of Basic Energy Sciences.

  3. Pd@Cu(II)-MOF-Catalyzed Aerobic Oxidation of Benzylic Alcohols in Air with High Conversion and Selectivity.

    PubMed

    Chen, Gong-Jun; Wang, Jing-Si; Jin, Fa-Zheng; Liu, Ming-Yang; Zhao, Chao-Wei; Li, Yan-An; Dong, Yu-Bin

    2016-03-21

    A new 3D porous Cu(II)-MOF (1) was synthesized based on a ditopic pyridyl substituted diketonate ligand and Cu(OAc)2 in solution, and it features a 3D NbO motif which is determined by the X-ray crystallography. Furthermore, the Pd NPs-loaded hybrid material Pd@Cu(II)-MOF (2) was prepared based on 1 via solution impregnation, and its structure was confirmed by HRTEM, SEM, XRPD, gas adsorption-desorption, and ICP measurement. 2 exhibits excellent catalytic activity (conversion, 93% to >99%) and selectivity (>99% to benzaldehydes) for various benzyl alcohol substrates (benzyl alcohol and its derivatives with electron-withdrawing and electron-donating groups) oxidation reactions in air. In addition, 2 is a typical heterogeneous catalyst, which was confirmed by hot solution leaching experiment, and it can be recycled at least six times without significant loss of its catalytic activity and selectivity. PMID:26959340

  4. Characterization of Al-Cu-Mg-Ag Alloy RX226-T8 Plate

    NASA Technical Reports Server (NTRS)

    Lach, Cynthia L.; Domack, Marcia S.

    2003-01-01

    Aluminum-copper-magnesium-silver (Al-Cu-Mg-Ag) alloys that were developed for thermal stability also offer attractive ambient temperature strength-toughness combinations, and therefore, can be considered for a broad range of airframe structural applications. The current study evaluated Al-Cu-Mg-Ag alloy RX226-T8 in plate gages and compared performance with sheet gage alloys of similar composition. Uniaxial tensile properties, plane strain initiation fracture toughness, and plane stress tearing resistance of RX226-T8 were examined at ambient temperature as a function of orientation and thickness location in the plate. Properties were measured near the surface and at the mid-plane of the plate. Tensile strengths were essentially isotropic, with variations in yield and ultimate tensile strengths of less than 2% as a function of orientation and through-thickness location. However, ductility varied by more than 15% with orientation. Fracture toughness was generally higher at the mid-plane and greater for the L-T orientation, although the differences were small near the surface of the plate. Metallurgical analysis indicated that the microstructure was primarily recrystallized with weak texture and was uniform through the plate with the exception of a fine-grained layer near the surface of the plate. Scanning electron microscope analysis revealed Al-Cu-Mg second phase particles which varied in composition and were primarily located on grain boundaries parallel to the rolling direction. Fractography of toughness specimens for both plate locations and orientations revealed that fracture occurred predominantly by transgranular microvoid coalescence. Introduction High-strength, low-density Al-Cu-Mg-Ag alloys were initially developed to replace conventional 2000 (Al-Cu-Mg) and 7000 (Al-Zn-Cu-Mg) series aluminum alloys for aircraft structural applications [1]. During the High Speed Civil Transport (HSCT) program, improvements in thermal stability were demonstrated for candidate

  5. Influence of alloying effect on X-ray fluorescence parameters of Co and Cu in CoCuAg alloy films

    NASA Astrophysics Data System (ADS)

    Aylikci, Nuray Kup; Tiraşoğlu, Engin; Apaydin, Gökhan; Cengiz, Erhan; Aylikci, Volkan; Bakkaloğlu, Ömer Faruk

    2009-06-01

    In this study, K β/K α X-ray intensity ratios, σ, σ production cross-sections and ωK fluorescence yields of Co and Cu and L β/L α X-ray intensity ratios, σ, σ production cross-sections and ϖ average fluorescence yields of Ag in pure metals and in different alloy compositions were measured. In this study, alloying effects on the σ production cross-sections of Co and Cu were investigated and changes interpreted according to the rearrangement of valance state electrons and the charge transfer process between the 3d elements (Co and Cu) and Ag.

  6. 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

  7. Optical behavior and structural property of CuAlS₂ and AgAlS₂ wide-bandgap chalcopyrites.

    PubMed

    Ho, Ching-Hwa; Pan, Chia-Chi

    2014-08-01

    Single crystals of CuAlS₂ and AgAlS₂ were grown by chemical vapor transport method using ICl₃ as the transport. The as-grown CuAlS₂ crystals reveal transparent and light-green color. Most of them possess a well-defined (112) surface. The AgAlS₂ crystals essentially show transparent and white color in vacuum. As the AgAlS₂ was put into the atmosphere, the crystal surface gradually darkened and became brownish because of the surface reaction with humidity or hydrogen gas. After a long-term chemical reaction process, the AgAlS₂ will transform into a AgAlO₂ oxide with yellow color. From x-ray diffraction measurements, both CuAlS₂ and AgAlS₂ as-grown crystals show single-phase and isostructural to a chalcopyrite structure. The (112) face is more preferable for the formation of the chalcopyrite crystals. The energies of interband transitions of the CuAlS₂ and AgAlS₂ were determined accurately by thermoreflectance measurements in a wide energy range of 2-6 eV. The valence-band electronic structures of CuAlS₂ and AgAlS₂ have been detailed and characterized using polarized-thermoreflectance measurements in the temperature range between 30 and 300 K. The band-edge transitions belonging to the E(∥) and E(⊥) polarizations have been, respectively, identified. The band edge of AgAlS₂ is near 3.2 eV while that of AgAlS₂ is about 3.5 eV. On the basis of the experimental analyses, optical and sensing behaviors of the chalcopyrite crystals have been realized. PMID:25090358

  8. Associations of Pd, U and Ag in the SiC layer of neutron-irradiated TRISO fuel

    SciTech Connect

    Lillo, Thomas; Rooyen, Isabella Van

    2015-05-01

    Knowledge of the associations and composition of fission products in the neutron irradiated SiC layer of high-temperature gas reactor TRISO fuel is important to the understanding of various aspects of fuel performance that presently are not well understood. Recently, advanced characterization techniques have been used to examine fuel particles from the Idaho National Laboratory’s AGR-1 experiment. Nano-sized Ag and Pd precipitates were previously identified in grain boundaries and triple points in the SiC layer of irradiated TRISO nuclear fuel. Continuation of this initial research is reported in this paper and consists of the characterization of a relatively large number of nano-sized precipitates in three areas of the SiC layer of a single irradiated TRISO nuclear fuel particle using standardless EDS analysis on focused ion beam-prepared transmission electron microscopy samples. Composition and distribution analyses of these precipitates, which were located on grain boundaries, triple junctions and intragranular precipitates, revealed low levels, generally <10 atomic %, of palladium, silver and/or uranium with palladium being the most common element found. Palladium by itself, or associated with either silver or uranium, was found throughout the SiC layer. A small number of precipitates on grain boundaries and triple junctions were found to contain only silver or silver in association with palladium while uranium was always associated with palladium but never found by itself or in association with silver. Intergranular precipitates containing uranium were found to have migrated ~23 μm along a radial direction through the 35 μm thick SiC coating during the AGR-1 experiment while silver-containing intergranular precipitates were found at depths up to ~24 μm in the SiC layer. Also, Pd-rich, nano-precipitates (~10 nm in diameter), without evidence for the presence of either Ag or U, were revealed in intragranular regions throughout the SiC layer. Because not all

  9. Associations of Pd, U and Ag in the SiC layer of neutron-irradiated TRISO fuel

    NASA Astrophysics Data System (ADS)

    Lillo, T. M.; van Rooyen, I. J.

    2015-05-01

    Knowledge of the associations and composition of fission products in the neutron irradiated SiC layer of high-temperature gas reactor TRISO fuel is important to the understanding of various aspects of fuel performance that presently are not well understood. Recently, advanced characterization techniques have been used to examine fuel particles from the Idaho National Laboratory's AGR-1 experiment. Nano-sized Ag and Pd precipitates were previously identified in grain boundaries and triple points in the SiC layer of irradiated TRISO nuclear fuel. Continuation of this initial research is reported in this paper and consists of the characterization of a relatively large number of nano-sized precipitates in three areas of the SiC layer of a single irradiated TRISO nuclear fuel particle using standardless EDS analysis on focused ion beam-prepared transmission electron microscopy samples. Composition and distribution analyses of these precipitates, which were located on grain boundaries, triple junctions and intragranular precipitates, revealed low levels, generally <10 atomic %, of palladium, silver and/or uranium with palladium being the most common element found. Palladium by itself, or associated with either silver or uranium, was found throughout the SiC layer. A small number of precipitates on grain boundaries and triple junctions were found to contain only silver or silver in association with palladium while uranium was always associated with palladium but never found by itself or in association with silver. Intergranular precipitates containing uranium were found to have migrated ∼23 μm along a radial direction through the 35 μm thick SiC coating during the AGR-1 experiment while silver-containing intergranular precipitates were found at depths up to ∼24 μm in the SiC layer. Also, Pd-rich, nano-precipitates (∼10 nm in diameter), without evidence for the presence of either Ag or U, were revealed in intragranular regions throughout the SiC layer. Because not

  10. ⁶⁴Cu-Doped PdCu@Au Tripods: A Multifunctional Nanomaterial for Positron Emission Tomography and Image-Guided Photothermal Cancer Treatment.

    PubMed

    Pang, Bo; Zhao, Yongfeng; Luehmann, Hannah; Yang, Xuan; Detering, Lisa; You, Meng; Zhang, Chao; Zhang, Lei; Li, Zhi-Yuan; Ren, Qiushi; Liu, Yongjian; Xia, Younan

    2016-03-22

    This article reports a facile synthesis of radiolabeled PdCu@Au core-shell tripods for use in positron emission tomography (PET) and image-guided photothermal cancer treatment by directly incorporating radioactive (64)Cu atoms into the crystal lattice. The tripod had a unique morphology determined by the PdCu tripod that served as a template for the coating of Au shell, in addition to well-controlled specific activity and physical dimensions. The Au shell provided the nanostructure with strong absorption in the near-infrared region and effectively prevented the Cu and (64)Cu atoms in the core from oxidization and dissolution. When conjugated with D-Ala1-peptide T-amide (DAPTA), the core-shell tripods showed great enhancement in targeting the C-C chemokine receptor 5 (CCR5), a newly identified theranostic target up-regulated in triple negative breast cancer (TNBC). Specifically, the CCR5-targeted tripods with an arm length of about 45 nm showed 2- and 6-fold increase in tumor-to-blood and tumor-to-muscle uptake ratios, respectively, relative to their nontargeted counterpart in an orthotopic mouse 4T1 TNBC model at 24 h postinjection. The targeting specificity was further validated via a competitive receptor blocking study. We also demonstrated the use of these targeted, radioactive tripods for effective photothermal treatment in the 4T1 tumor model as guided by PET imaging. The efficacy of treatment was confirmed by the significant reduction in tumor metabolic activity revealed through the use of (18)F-fluorodeoxyglucose PET/CT imaging. Taken together, we believe that the (64)Cu-doped PdCu@Au tripods could serve as a multifunctional platform for both PET imaging and image-guided photothermal cancer therapy. PMID:26824412

  11. Quasi-Instantaneous Bacterial Inactivation on Cu-Ag Nanoparticulate 3D Catheters in the Dark and Under Light: Mechanism and Dynamics.

    PubMed

    Rtimi, Sami; Sanjines, Rosendo; Pulgarin, Cesar; Kiwi, John

    2016-01-13

    The first evidence for Cu-Ag (50%/50%) nanoparticulate hybrid coatings is presented leading to a complete and almost instantaneous bacterial inactivation in the dark (≤5 min). Dark bacterial inactivation times on Cu-Ag (50%/50%) were observed to coincide with the times required by actinic light irradiation. This provides the evidence that the bimetal Cu-Ag driven inactivation predominates over a CuO/Cu2O and Ag2O oxides inducing a semiconductor driven behavior. Cu- or Ag-coated polyurethane (PU) catheters led to bacterial inactivation needing about ∼30 min. The accelerated bacterial inactivation by Cu-Ag coated on 3D catheters sputtered was investigated in a detailed way. The release of Cu/Ag ions during bacterial inactivation was followed by inductively coupled plasma mass-spectrometry (ICP-MS) and the amount of Cu and Ag-ions released were below the cytotoxicity levels permitted by the sanitary regulations. By stereomicroscopy the amount of live/dead cells were followed during the bacterial inactivation time. By Fourier transform infrared spectroscopy (FTIR), the systematic shift of the -(CH2) band stretching of the outer lipo-polysaccharide bilayer (LPS) was followed to monitor the changes leading to cell lysis. A hydrophobic to hydrophilic transformation of the Cu-Ag PU catheter surface under light was observed within 30 min followed concomitantly to a longer back transformation to the hydrophobic initial state in the dark. Physical insight is provided for the superior performance of Cu-Ag films compared to Cu or Ag films in view of the drastic acceleration of the bacterial inactivation observed on bimetal Cu-Ag films coating PU catheters. A mechanism of bacterial inactivation is suggested that is consistent with the findings reported in this study. PMID:26699928

  12. Newly-designed complex ternary Pt/PdCu nanoboxes anchored on three-dimensional graphene framework for highly efficient ethanol oxidation.

    PubMed

    Hu, Chuangang; Cheng, Huhu; Zhao, Yang; Hu, Yue; Liu, Yong; Dai, Liming; Qu, Liangti

    2012-10-23

    Newly-designed ternary Pt/PdCu nanoboxes on three-dimensional graphene framework (Pt/PdCu/3DGF) have been fabricated via a dual solvothermal strategy. This structurally well-defined Pt/PdCu/3DGF system possesses an approximately 4-fold improvement in catalytic activity for ethanol oxidation in alkaline media over the commercial 20% Pt/C catalyst as normalized by the total mass of active metals, showing the great potential for direct fuel cell applications. PMID:22886893

  13. Anodic behavior of carbon supported Cu@Ag core-shell nanocatalysts in direct borohydride fuel cells

    NASA Astrophysics Data System (ADS)

    Duan, Donghong; Liu, Huihong; You, Xiu; Wei, Huikai; Liu, Shibin

    2015-10-01

    Carbon-supported Cu@Ag core-shell nanoparticles are prepared by a successive reduction method in an aqueous solution and are used as an anode electrocatalyst for the direct borohydride-hydrogen peroxide fuel cell (DBHFC). The physical and electrochemical properties of the as-prepared electrocatalysts are investigated by transmission electron microscopy (TEM), X-ray diffraction (XRD), cyclic voltammetry (CV), chronopotentiometry (CP), and fuel cell tests. In situ Fourier transform infrared (FTIR) spectroscopy is employed in 2 M NaOH/0.1 M NaBH4 to understand the borohydride oxidation reaction (BOR) mechanism by studying the intermediate reactions occurring on the Cu@Ag/C electrode. The TEM images show that the average size of the Cu1@Ag1/C particles is approximately 18 nm. Among the as-prepared catalysts, the Cu2@Ag1/C catalyst presents the highest catalytic activity. As shown by in situ FTIR, the oxidation reaction mechanism of BH4- is similar to that of Ag/C: BHn(OH)4-n- + 2OH- → BHn-1(OH)5-n- +H2 O + 2e . At 25 °C, the DBHFC with Cu2@Ag1/C as the anode electrocatalyst and Pt mesh (1 cm2) as the cathode electrode exhibits a maximum anodic power density of 17.27 mW mg-1 at a discharge current density of 27.8 mA mg-1.

  14. Semiempirical calculation of radiative constants in the spectra of nickel-like ions Kr IX, Sr XI, Y XII, Ru XVII, Pd XIX, and Ag XX

    NASA Astrophysics Data System (ADS)

    Loginov, A. V.

    2015-03-01

    The probabilities of the electric-dipole transitions 3 d 94 p, 3 d 94 f-3 d 10, 3 d 94 s, and 3 d 94 d in the spectra of nickel-like ions Kr IX, Sr XI, Y XII, Ru XVII, Pd XIX, and Ag XX are calculated semiempirically with the use of published energy levels.

  15. Phase constitution and interface structure of nano-sized Ag-Cu/AlN multilayers: Experiment and ab initio modeling

    SciTech Connect

    Pigozzi, Giancarlo; Janczak-Rusch, Jolanta; Passerone, Daniele; Antonio Pignedoli, Carlo; Patscheider, Joerg; Jeurgens, Lars P. H.; Antusek, Andrej; Parlinska-Wojtan, Magdalena; Bissig, Vinzenz

    2012-10-29

    Nano-sized Ag-Cu{sub 8nm}/AlN{sub 10nm} multilayers were deposited by reactive DC sputtering on {alpha}-Al{sub 2}O{sub 3}(0001) substrates. Investigation of the phase constitution and interface structure of the multilayers evidences a phase separation of the alloy sublayers into nanosized grains of Ag and Cu. The interfaces between the Ag grains and the quasi-single-crystalline AlN sublayers are semi-coherent, whereas the corresponding Cu/AlN interfaces are incoherent. The orientation relationship between Ag and AlN is constant throughout the entire multilayer stack. These observations are consistent with atomistic models of the interfaces as obtained by ab initio calculations.

  16. Bidirectional threshold switching in engineered multilayer (Cu{sub 2}O/Ag:Cu{sub 2}O/Cu{sub 2}O) stack for cross-point selector application

    SciTech Connect

    Song, Jeonghwan; Prakash, Amit; Lee, Daeseok; Woo, Jiyong; Cha, Euijun; Lee, Sangheon; Hwang, Hyunsang

    2015-09-14

    In this study, we achieved bidirectional threshold switching (TS) for selector applications in a Ag-Cu{sub 2}O-based programmable-metallization-cell device by engineering the stack wherein Ag was intentionally incorporated in the oxide (Cu{sub 2}O) layer by a simple approach comprising co-sputtering and subsequent optimized annealing. The distribution of the Ag was directly confirmed by transmission electron microscopy and energy dispersive spectroscopy line profiling. The observed TS occurred because of the spontaneous self-rupturing of the unstable Ag filament that formed in the oxide layer.

  17. Polymer-supported CuPd nanoalloy as a synergistic catalyst for electrocatalytic reduction of carbon dioxide to methane.

    PubMed

    Zhang, Sheng; Kang, Peng; Bakir, Mohammed; Lapides, Alexander M; Dares, Christopher J; Meyer, Thomas J

    2015-12-29

    Developing sustainable energy strategies based on CO2 reduction is an increasingly important issue given the world's continued reliance on hydrocarbon fuels and the rise in CO2 concentrations in the atmosphere. An important option is electrochemical or photoelectrochemical CO2 reduction to carbon fuels. We describe here an electrodeposition strategy for preparing highly dispersed, ultrafine metal nanoparticle catalysts on an electroactive polymeric film including nanoalloys of Cu and Pd. Compared with nanoCu catalysts, which are state-of-the-art catalysts for CO2 reduction to hydrocarbons, the bimetallic CuPd nanoalloy catalyst exhibits a greater than twofold enhancement in Faradaic efficiency for CO2 reduction to methane. The origin of the enhancement is suggested to arise from a synergistic reactivity interplay between Pd-H sites and Cu-CO sites during electrochemical CO2 reduction. The polymer substrate also appears to provide a basis for the local concentration of CO2 resulting in the enhancement of catalytic current densities by threefold. The procedure for preparation of the nanoalloy catalyst is straightforward and appears to be generally applicable to the preparation of catalytic electrodes for incorporation into electrolysis devices. PMID:26668386

  18. Hydrogen FBG sensor using Pd/Ag film with application in propulsion system fuel tank model of aerospace vehicle

    NASA Astrophysics Data System (ADS)

    Saad, Said; Hassine, Lotfi; Elfahem, Wassim

    2014-09-01

    The high efficiency hydrogen fiber Bragg grating (FBG) sensor is presented. The sensitive film was a new alliance of palladium-silver (Pd-Ag). In addition, the titanium (Ti) layer was used as the adhesive layer. The presented sensor showed the resolution of more than 60 pm/1% H2, and a fast response time of 4 s-5 s was guaranteed in the 0.1% H2-4% H2 range. Moreover, the life time of the sensor was investigated. The obtained results showed that the sensor had an enhanced life time. Furthermore, the sensor was applied in the propulsion system fuel tank model of the aerospace vehicle. The obtained results indicated that it is a prevention system against the disaster aerospace due to hydrogen leakage.

  19. Intermetallic compounds formed at the interface between Cu substrate and an Sn-9Zn-0.5Ag lead-free solder

    SciTech Connect

    Chang, T.-C.; Hon, M.-H.; Wang, M.-C

    2003-04-30

    The intermetallic compounds (IMCs) formed at the interface between Cu substrate and an Sn-9Zn-0.5Ag lead-free solder alloy have been investigated by X-ray diffraction (XRD), transmission electron microscopy (TEM) and electron diffraction (ED). The XRD patterns show that the main IMCs formed at the interface of Sn-9Zn-0.5Ag/Cu are {gamma}-Cu{sub 5}Zn{sub 8} and {eta}'-Cu{sub 6}Sn{sub 5}. The Ag{sub 3}Sn IMC with orthorhombic structure was also observed at the Sn-9Zn-0.5Ag/Cu interface by TEM and ED analyses. The interfacial adhesion strength between the Cu substrate and Sn-9Zn-0.5Ag lead-free solder alloy is higher than that of the Sn-9Zn alloy due to the formation of Ag{sub 3}Sn IMC at the interface.

  20. Bactericidal effect of graphene oxide/Cu/Ag nanoderivatives against Escherichia coli, Pseudomonas aeruginosa, Klebsiella pneumoniae, Staphylococcus aureus and Methicillin-resistant Staphylococcus aureus.

    PubMed

    Jankauskaitė, V; Vitkauskienė, A; Lazauskas, A; Baltrusaitis, J; Prosyčevas, I; Andrulevičius, M

    2016-09-10

    A systematic analysis of antibacterial activity of individual nanoderivatives, e.g. GO nanosheets, Ag and Cu nanoparticles (NPs), as well as combinations of Cu-Ag NPs, and GO-Cu-Ag nanocomposites against Escherichia coli, Pseudomonas aeruginosa, Staphylococcus aureus, Klebsiella pneumoniae and Methicillin-resistant Staphylococcus aureus (MRSA) was performed. Chemical properties of the GO, Cu and Ag NPs were determined employing X-ray photoelectron spectroscopy and X-Ray-excited Auger electron spectroscopy. Morphology of corresponding nanoderivatives was studied employing transmission electron microscopy and scanning electron microscopy. It was shown that combination of Cu and Ag NPs, as well as GO-Cu-Ag nanocomposite material possess enhanced antibacterial activity through a possible synergy between multiple toxicity mechanisms. MRSA showed highest resistance in all cases. PMID:27370911

  1. Bonding of Cf/SiC composite to Invar alloy using an active cement, Ag-Cu eutectic and Cu interlayer

    NASA Astrophysics Data System (ADS)

    Lei, Zhao; Xiaohong, Li; Jinbao, Hou; Qiang, Sun; Fuli, Zhang

    2012-10-01

    The interfacial microstructures and mechanical properties of the joints formed by active cement added brazing in vacuum of Cf/SiC composite to Invar alloy, using Ag-Cu eutectic alloy and pure copper foil as braze alloy and interlayer respectively, were investigated. CuTi, Cu4Ti3, Fe2Ti and the reaction layer of TiC and Si were the predominant components at the joint interface. The maximum shear strength of the joint was 77 MPa for brazing at 850 °C for 15 min. The results show that active cement added brazing in vacuum using Ag-Cu eutectic alloy and Cu interlayer can be used successfully for joining Cf/SiC composites to Invar alloy.

  2. Clean Synthesis of an Economical 3D Nanochain Network of PdCu Alloy with Enhanced Electrocatalytic Performance towards Ethanol Oxidation.

    PubMed

    Liu, Jiawei; Huang, Zhao; Cai, Kai; Zhang, Huan; Lu, Zhicheng; Li, Tingting; Zuo, Yunpeng; Han, Heyou

    2015-12-01

    A one-pot method for the fast synthesis of a 3D nanochain network (NNC) of PdCu alloy without any surfactants is described. The composition of the as-prepared PdCu alloy catalysts can be precisely controlled by changing the precursor ratio of Pd to Cu. First, the Cu content changes the electronic structure of Pd in the 3D NNC of PdCu alloy. Second, the 3D network structure offers large open pores, high surface areas, and self-supported properties. Third, the surfactant-free strategy results in a relatively clean surface. These factors all contribute to better electrocatalytic activity and durability towards ethanol oxidation. Moreover, the use of copper in the alloy lowers the price of the catalyst by replacing the noble metal palladium with non-noble metal copper. The composition-optimized Pd80 Cu20 alloy in the 3D NNC catalyst shows an increased electrochemically active surface area (80.95 m(2)  g(-1) ) and a 3.62-fold enhancement of mass activity (6.16 A mg(-1) ) over a commercial Pd/C catalyst. PMID:26472208

  3. Photocatalytic comparison of Cu- and Ag-doped TiO2/GF for bioaerosol disinfection under visible light

    NASA Astrophysics Data System (ADS)

    Pham, Thanh-Dong; Lee, Byeong-Kyu

    2015-12-01

    Photocatalysts, TiO2/glass fiber (TiO2/GF), Cu-doped TiO2/glass fiber (Cu-TiO2/GF) and Ag-doped TiO2/glass fiber (Ag-TiO2/GF), were synthesized by a sol-gel method. They were then used to disinfect Escherichia coli (E. coli) and Staphylococcus aureus (S. aureus) in bioaerosols under visible light irradiation. TiO2/GF did not show any significant disinfection effect. Both Cu and Ag acted as intermediate agents to enhance separation efficiency of electron-hole pairs of TiO2, leading to improved photocatalytic activity of Cu-TiO2/GF and Ag-TiO2/GF under visible light. Cu in Cu-TiO2/GF acted as a defective agent, increasing the internal quantum efficiency of TiO2, while Ag in Ag-TiO2/GF acted as a sensitive agent, enhancing the transfer efficiency of the electrons generated. The highest disinfection efficiencies of E. coli and S. aureus by Cu-TiO2/GF were 84.85% and 65.21%, respectively. The highest disinfection efficiencies of E. coli and S. aureus by Ag-TiO2/GF were 94.46% and 73.12%, respectively. Among three humidity conditions - 40±5% (dry), 60±5% (moderate), and 80±5% (humid) - the moderate humidity condition showed the highest disinfection efficiency for both E. coli and S. aureus. This study also showed that a Gram-negative bacterium (E. coli) were more readily disinfected by the photocatalysts than a Gram-positive bacterium (S. aureus).

  4. The effect of palladium additions on the solidus/liquidus temperatures and wetting properties of Ag-CuO based air brazes

    SciTech Connect

    Darsell, Jens T.; Weil, K. Scott

    2007-01-01

    A new ceramic brazing technique referred to as reactive air brazing (RAB) has recently been developed for potential applications in high temperature devices such as gas concentrators, solid oxide fuel cells, gas turbines, and combustion engines. At present, the technique utilizing a silver-copper oxide system is of great interest. The maximum operating temperature of this system is limited by its eutectic temperature of ~945°C, although in practice the operating temperature will need to be lower. An obvious strategy that can be employed to increase the maximum operating temperature of the braze material is to add a higher melting noble alloying element. In this paper, we report the effects of palladium addition on the melting characteristics of the Ag-CuO system and on the wetting properties of the resulting braze with respect to alumina. It was found that the addition of Pd will cause an increase in the melting temperature of the Ag-CuO braze but possibly at a sacrifice of wetting properties depending on composition.

  5. Experimental and theoretical determination of cross sections and rate constants for charge transfer population of some excited Ag+, I+, and Cu+ levels

    NASA Astrophysics Data System (ADS)

    Temelkov, K. A.; Vuchkov, N. K.; Sabotinov, N. V.

    2007-04-01

    Cross-sections and rate constants for thermal energy charge transfer into some Ag+, I+, and Cu+ excited states are theoretically and experimentally obtained for a gas discharge in the He-CuBr, Ne-CuBr, He-AgI, and Ne-AgI mixtures. Besides the pumping process the formation of the inversion population is determined by the radiative transitions, which populate or depopulate the upper and lower laser levels.

  6. Monolayer magnetism of 3d transition metals in Ag, Au, Pd, and Pt hosts: Systematics of local moment variation

    NASA Astrophysics Data System (ADS)

    McHenry, M. E.; MacLaren, J. M.; Clougherty, D. P.

    1991-11-01

    Electronic and magnetic properties of T/Aun, T/Agn (T=Cr, Mn, Fe, Co, and Ni), Fe/Pdn and Fe/Ptn multilayers and sandwiches have been computed using the layer Korringa-Kohn-Rostoker (LKKR) band-structure technique. Enhanced (as compared with bulk) 2D T magnetism is observed in all Cr, Mn, and Fe/host configurations, consistent with weak coupling between Cr, Mn, and Fe d bands and those of the noble metal (NM) hosts and consequently d bandwidths which are exceeded by the exchange splitting. Fe and Cr moments vary systematically with the number of mediating Ag or Au planes and the Fermi energy of the system. These systematics are explained by considering the variation of the Fermi energy (EF) with composition as well as constraints of charge neutrality and strong (single-band) ferromagnetism. For Fe in Pt and Pd hosts, d-d hybridization leads to a nearly invariant Fe moment as a function of the number of mediating Pd or Pt planes but with large induced moments on the host.

  7. Synthesis, surface and optical properties of Ag2Cu(VO3)4 and Cu(VO3)2 vanadates

    NASA Astrophysics Data System (ADS)

    Qiao, Xuebin; Wan, Yingpeng; Li, Yuze; Qin, Lin; Seo, Hyo Jin

    2016-04-01

    Ag2Cu(VO3)4 and Cu(VO3)2 were prepared via the sol-gel chemical synthesis. The phase formation was confirmed by X-ray powder polycrystalline diffraction (XRD) measurements. The surface properties were measured with the scanning electron microscope (SEM), energy dispersive spectra (EDS), transmission electron microscopy (TEM), and nitrogen adsorption-desorption isotherms. The optical properties and the band-gap structures were investigated. The vanadates have efficient optical absorption in the UV to visible wavelength region with an indirect allowed transition. Ag2Cu(VO3)4 has smaller band gap (1.85 eV) than that of Cu(VO3)2 (2.03 eV). The narrowed band gap is due to the hybridization between the Ag-4d and O-2p in the valence band. The photocatalysis was investigated by photodegradation of methylene blue (MB) solutions excited by the light with wavelength longer than 420 nm. Correspondingly Ag2Cu(VO3)4 has more efficient photocatalytic activity on MB photodegradation than that of Cu(VO3)2. The photocatalytic mechanisms were suggested according to the band positions and the trapping experiments.

  8. AgCuVO4 : A quasi-one-dimensional S=(1)/(2) chain compound

    NASA Astrophysics Data System (ADS)

    Möller, A.; Schmitt, M.; Schnelle, W.; Förster, T.; Rosner, H.

    2009-09-01

    We present a joint experimental and computational study of the recently synthesized spin 1/2 system silver-copper-orthovanadate AgCuVO4 [A. Möller and J. Jainski, Z. Anorg. Allg. Chem. 634, 1669 (2008)] exhibiting chains of trans corner-sharing [CuO4] plaquettes. The static magnetic susceptibility and specific heat measurements of AgCuVO4 can be described to a good approximation by the Bonner-Fisher spin-chain model with Jintra≈330K . Evidence for a Néel-type of order at ˜2.5K is obtained from the specific heat and corroborated by ESR studies. To independently obtain a microscopically based magnetic model, density functional electronic structure calculations were performed. In good agreement with the experimental data, we find pronounced one-dimensional magnetic exchange along the corner-sharing chains with small interchain couplings. The difference between the experimentally observed and the calculated ordering temperature can be assigned to a sizable interchain frustration derived from the calculations.

  9. Effect of cooling rate on the microstructure and microhardness of the CuZrAgAl alloy

    SciTech Connect

    Liu, Y.; Blandin, J.J.; Suery, M.; Kapelski, G.

    2012-08-15

    The effect of cooling rate on the microstructure and microhardness of the Cu{sub 40}Zr{sub 44}Ag{sub 8}Al{sub 8} (at.%) alloy has been studied. The crystalline phases were characterized by X-ray diffraction, optical microscopy and scanning electron microscopy with energy dispersive X-ray spectroscopy, and identified as AlCu{sub 2}Zr, Cu{sub 10}Zr{sub 7} and CuZr{sub 2}. The solidification sequence was established as following: the Cu{sub 10}Zr{sub 7} phase forms first in the periphery of the rod, then following with AlCu{sub 2}Zr phase in the rod center and finally CuZr{sub 2} crystals in Cu-depleted areas. The effect of crystals on the mechanical properties of the Cu{sub 40}Zr{sub 44}Ag{sub 8}Al{sub 8} alloy was also estimated through the microhardness. According to the value of microhardness, inhomogeneous structure of the amorphous matrix is more easily formed for the alloy in the low cooling rate (i.e., 9 mm) as compared with the alloy with fully amorphous state in the large cooling rate (i.e., 3 mm). This inhomogeneous structure was attributed to the composition change of amorphous matrix arising from the forming of crystalline phases due to the low cooling rate. - Highlights: Black-Right-Pointing-Pointer The crystalline phases in the Cu{sub 40}Zr{sub 44}Ag{sub 8}Al{sub 8} alloy were identified. Black-Right-Pointing-Pointer The solidification sequence of Cu{sub 40}Zr{sub 44}Ag{sub 8}Al{sub 8} alloy was verified. Black-Right-Pointing-Pointer The softening and hardening of alloy could be observed due to the crystallization.

  10. Photoconversion in n-ZnO:Al/PdPc/p-CuIn{sub 3}Se{sub 5} Structures

    SciTech Connect

    Bodnar', I.V.; Dmitrieva, E.S.; Nikitin, S.E.; Rud', Yu.V.; Terukov, E.I.; Rud', V.Yu.

    2005-04-01

    n-ZnO:Al/PdPc/p-CuIn{sub 3}Se{sub 5} photosensitive structures have been proposed and fabricated for the first time by vacuum sublimation of palladium phthalocyanine on the surface of wafers of the ternary semiconductor compound CuIn{sub 3}Se{sub 5} and by magnetron sputtering of n-ZnO:Al films on the surface of palladium phthalocyanine films. The current-voltage characteristics and spectra of the photoconversion quantum efficiency of the obtained structures are investigated. It is shown that these structures can be used as multiband white-light converters.

  11. Investigating Quantum Oscillations in the Thermal Coefficient of Resistivity of Ultra-thin Ag Capping Layers on Cu for IC Interconnect Applications

    NASA Astrophysics Data System (ADS)

    Tatem, Elroy

    As the semiconductor industry continues to scale feature sizes, scattering from phonons, surfaces, and grain boundaries result in an increase of metal interconnect resistivity in state-of-the-art integrated circuits (ICs). The interconnect chapter of the 2011 International Technology Roadmap for Semiconductors (ITRS) stated that there are currently no manufacturable solutions in the near term for suitable Cu replacements. Previous studies of thin Ag films deposited on Cu demonstrated oscillations in the electron-phonon interactions within the bilayer system. This thesis investigates oscillations in the resistive properties of the Ag/Cu bilayer system and discusses the applicability of these oscillations to the resistivity challenges facing metal-based IC interconnects. Ag/Cu bilayer films were prepared by physical vapor deposition (PVD). The films were characterized by measuring the electrical resistance of the films at various temperatures and calculating the thermal coefficient of resistance (TCR) for various Ag capping layer thicknesses. Films were further characterized by atomic force microscopy (AFM), Rutherford backscattering (RBS), and scanning electron microscopy (SEM). Patterned Ag-capped Cu lines were fabricated, which exhibited resistive behavior similar to that of the Ag/Cu films. Compared to bare Cu, the resistances of Ag-capped Cu lines and films were lower and exhibited a reduced dependence on temperature. Smaller thermal coefficients of resistivity were also observed for Ag-capped Cu films and patterned lines when compared to Cu alone.

  12. Relationship between morphologies and orientations of Cu{sub 6}Sn{sub 5} grains in Sn3.0Ag0.5Cu solder joints on different Cu pads

    SciTech Connect

    Tian, Yanhong Zhang, Rui; Hang, Chunjin; Niu, Lina; Wang, Chunqing

    2014-02-15

    The morphologies and orientations of Cu{sub 6}Sn{sub 5} intermetallic compounds in the Sn3.0Ag0.5Cu solder joints both on polycrystalline and single crystal Cu pads under different peak reflow temperatures and times above liquids were investigated. The relationship between Cu{sub 6}Sn{sub 5} grain orientations and morphologies was clarified. At the interface of Sn3.0Ag0.5Cu/polycrystalline Cu pad, scalloped Cu{sub 6}Sn{sub 5} intermetallic compounds formed at 250 °C and roof shape Cu{sub 6}Sn{sub 5} formed at 300 °C. Both scalloped Cu{sub 6}Sn{sub 5} and roof shape Cu{sub 6}Sn{sub 5} had a preferred orientation of (0001) plane being parallel to polycrystalline Cu pad surface. Besides, the percentage of large angle grain boundaries increased as the peak reflow temperature rose. At the interface of Sn3.0Ag0.5Cu/(111) single crystal Cu pad, the Cu{sub 6}Sn{sub 5} intermetallic compounds were mainly scallop-type at 250 °C and were prism type at 300 °C. The prismatic Cu{sub 6}Sn{sub 5} grains grew along the three preferred directions with the inter-angles of 60° on (111) single crystal Cu pad while along two perpendicular directions on (100) single crystal Cu pad. The orientation relationship between Cu{sub 6}Sn{sub 5} grains and the single crystal Cu pads was investigated by electron backscatter diffraction technology. In addition, two types of hollowed Cu{sub 6}Sn{sub 5} intermetallic compounds were found inside the joints of polycrystalline Cu pads. The long hexagonal Cu{sub 6}Sn{sub 5} strips were observed in the joints reflowing at 250 °C while the hollowed Cu{sub 6}Sn{sub 5} strips with the ‘▪’ shape cross-sections appeared at 300 °C, which was attributed to the different grain growth rates of different Cu{sub 6}Sn{sub 5} crystal faces. - Highlights: • The orientation of interfacial Cu{sub 6}Sn{sub 5} grains was obtained by EBSD technology. • Two types of hollowed Cu{sub 6}Sn{sub 5} strips were found at different temperatures. • The formation

  13. One-Step Solvothermal Method to Prepare Ag/Cu2O Composite With Enhanced Photocatalytic Properties.

    PubMed

    Deng, Xiaolong; Wang, Chenggang; Zhou, E; Huang, Jinzhao; Shao, Minghui; Wei, Xianqi; Liu, Xiaojing; Ding, Meng; Xu, Xijin

    2016-12-01

    Ag/Cu2O microstructures with diverse morphologies have been successfully synthesized with different initial reagents of silver nitrate (AgNO3) by a facile one-step solvothermal method. Their structural and morphological characteristics were carefully investigated by means of X-ray diffraction (XRD), scanning electron microscopy (SEM), and transmission electron microscopy (TEM), and the experimental results showed that the morphologies transformed from microcubes for pure Cu2O to microspheres with rough surfaces for Ag/Cu2O. The photocatalytic activities were evaluated by measuring the degradation of methyl orange (MO) aqueous solution under visible light irradiation. The photocatalytic efficiencies of MO firstly increased to a maximum and then decreased with the increased amount of AgNO3. The experimental results revealed that the photocatalytic activities were significantly influenced by the amount of AgNO3 during the preparation process. The possible reasons for the enhanced photocatalytic activities of the as-prepared Ag/Cu2O composites were discussed. PMID:26781287

  14. One-Step Solvothermal Method to Prepare Ag/Cu2O Composite With Enhanced Photocatalytic Properties

    NASA Astrophysics Data System (ADS)

    Deng, Xiaolong; Wang, Chenggang; Zhou, E.; Huang, Jinzhao; Shao, Minghui; Wei, Xianqi; Liu, Xiaojing; Ding, Meng; Xu, Xijin

    2016-01-01

    Ag/Cu2O microstructures with diverse morphologies have been successfully synthesized with different initial reagents of silver nitrate (AgNO3) by a facile one-step solvothermal method. Their structural and morphological characteristics were carefully investigated by means of X-ray diffraction (XRD), scanning electron microscopy (SEM), and transmission electron microscopy (TEM), and the experimental results showed that the morphologies transformed from microcubes for pure Cu2O to microspheres with rough surfaces for Ag/Cu2O. The photocatalytic activities were evaluated by measuring the degradation of methyl orange (MO) aqueous solution under visible light irradiation. The photocatalytic efficiencies of MO firstly increased to a maximum and then decreased with the increased amount of AgNO3. The experimental results revealed that the photocatalytic activities were significantly influenced by the amount of AgNO3 during the preparation process. The possible reasons for the enhanced photocatalytic activities of the as-prepared Ag/Cu2O composites were discussed.

  15. Phonons, nature of bonding, and their relation to anomalous thermal expansion behavior of M2O (M = Au, Ag, Cu)

    NASA Astrophysics Data System (ADS)

    Gupta, M. K.; Mittal, R.; Chaplot, S. L.; Rols, S.

    2014-03-01

    We report a comparative study of the dynamics of Cu2O, Ag2O, and Au2O (i.e., M2O with M = Au, Ag, and Cu) using first principle calculations based on the density functional theory. Here, for the first time, we show that the nature of chemical bonding and open space in the unit cell are directly related to the magnitude of thermal expansion coefficient. A good match between the calculated phonon density of states and that derived from inelastic neutron scattering measurements is obtained for Cu2O and Ag2O. The calculated thermal expansions of Ag2O and Cu2O are negative, in agreement with available experimental data, while it is found to be positive for Au2O. We identify the low energy phonon modes responsible for this anomalous thermal expansion. We further calculate the charge density in the three compounds and find that the magnitude of the ionic character of the Ag2O, Cu2O, and Au2O crystals is in decreasing order, with an Au-O bond of covalent nature strongly rigidifying the Au4O tetrahedral units. The nature of the chemical bonding is also found to be an important ingredient to understand the large shift of the phonon frequencies of these solids with pressure and temperature. In particular, the quartic component of the anharmonic term in the crystal potential is able to account for the temperature dependence of the phonon modes.

  16. Activity of calcined Ag,Cu,Au/TiO2 catalysts in the dehydrogenation/dehydration of ethanol

    NASA Astrophysics Data System (ADS)

    Mai, Do Tkhyui; Pylinina, A. I.; Mikhailenko, I. I.

    2015-07-01

    The catalytic activity of the anatase TiO2 and M z+/TiO2 with supported ions M z+ = Ag+, Cu2+, Au3+ in vapor phase conversions of ethanol is investigated at temperatures of 100-400°C. It is shown that the yields of acetaldehyde and ethylene decline for the most active catalyst Cu2+/TiO2 but increase for TiO2 and Ag/TiO2. The drop in the activation energy of the dehydrogenation reaction over calcined samples is linearly correlated with the one in the reduction potential of M z+ to Cu+, Au+, Ag0 and the ionic radius of M z+ in the crystal. The energies of activation for ethylene formation change in the series TiO2 > Au3+ > Cu2+ >Ag+ and TiO2 ≈ Cu2+ ≈ Ag+ > Au3+ for the calcined samples. The rate of pyridine adsorption, considered as an indicator of the activity of acid sites, is a linear function of ion charge + z = 1, 2, 3, and slows by two-thirds after calcination.

  17. Assessing the effect of surface roughness on the wetting of Cu and Pd by Sn/Pb solder

    SciTech Connect

    O`Toole, E.J.; Yost, F.G.; Roberts, J.L.

    1996-12-31

    Artificially enhancing the solder ability of a surface can at times prove to be advantageous. As chip packaging geometries become increasingly complex, the issue of solder wettability becomes significantly more important. Here, the authors examine the effect of varying substrate surface roughness on solder wettability (area of spread) and the time required to reach terminal area of spread. Results are given for solder wetting experiments that were performed on copper (Cu) substrates having chemically etched surfaces, as well as, Alumina (Al{sub 2}O{sub 3}) substrates electroplated with various thicknesses of palladium (Pd). The effect of etching on the Al{sub 2}O{sub 3}/Pd specimens was also examined as related to surface roughness and solder spread. These surface treatments were found to significantly alter wettability. Substantial improvements were observed in both solder wettability and time to wet with the uniformly etched Cu surfaces used in this study. For the Cu substrates, the average terminal area of spread is shown to be directly related to the substrates root mean square (RMS) surface roughness. The rate of wetting of the Cu surfaces is also shown to increase when chemical surface treatment is used. Maximum wetting on the Al{sub 2}O{sub 3}/Pd specimens was found to be directly related to surface smoothness. The average terminal area of spread of Al{sub 2}O{sub 3}/Pd specimens is inversely related to the vertical distance from the highest surface peak to the deepest surface valley (i.e., peak-to-peak variation).

  18. Natural water as the test medium for Ag and CuO nanoparticle hazard evaluation: An interlaboratory case study.

    PubMed

    Heinlaan, Margit; Muna, Marge; Knöbel, Melanie; Kistler, David; Odzak, Niksa; Kühnel, Dana; Müller, Josefine; Gupta, Govind Sharan; Kumar, Ashutosh; Shanker, Rishi; Sigg, Laura

    2016-09-01

    Engineered nanoparticles (NPs) have realistic potential of reaching natural waterbodies and of exerting toxicity to freshwater organisms. The toxicity may be influenced by the composition of natural waters as crucial NP properties are influenced by water constituents. To tackle this issue, a case study was set up in the framework of EU FP7 NanoValid project, performing an interlaboratory hazard evaluation of NPs in natural freshwater. Ag and CuO NPs were selected as model NPs because of their potentially high toxicity in the freshwater. Daphnia magna (OECD202) and Danio rerio embryo (OECD236) assays were used to evaluate NP toxicity in natural water, sampled from Lake Greifen and Lake Lucerne (Switzerland). Dissolution of the NPs was evaluated by ultrafiltration, ultracentrifugation and metal specific sensor bacteria. Ag NP size was stable in natural water while CuO NPs agglomerated and settled rapidly. Ag NP suspensions contained a large fraction of Ag(+) ions and CuO NP suspensions had low concentration of Cu(2+) ions. Ag NPs were very toxic (48 h EC50 1-5.5 μg Ag/L) to D. magna as well as to D. rerio embryos (96 h EC50 8.8-61 μg Ag/L) in both standard media and natural waters with results in good agreement between laboratories. CuO NP toxicity to D. magna differed significantly between the laboratories with 48 h EC50 0.9-11 mg Cu/L in standard media, 5.7-75 mg Cu/L in Lake Greifen and 5.5-26 mg Cu/L in Lake Lucerne. No toxicity of CuO NP to zebrafish embryos was detected up to 100 mg/L independent of the medium used. The results show that Ag and CuO NP toxicity may be higher in natural water than in the standard media due to differences in composition. NP environmental hazard evaluation can and should be carried out in natural water to obtain more realistic estimates on the toxicity. PMID:27357482

  19. Effect of Yttrium on the Fracture Strength of the Sn-1.0Ag-0.5Cu Solder Joints

    NASA Astrophysics Data System (ADS)

    Choi, Hyelim; Kaplan, Wayne D.; Choe, Heeman

    2016-04-01

    This is a preliminary investigation on the mechanical properties of Pb-free Sn-1.0Ag-0.5Cu solder joints containing 0.02 wt.% to 0.1 wt.% Y under a range of thermal aging and reflow conditions. Despite the significantly thicker intermetallic compound (IMC) formed at the solder joint, the 0.1 wt.% Y-doped joint exhibited a higher fracture strength than its baseline Sn-1.0Ag-0.5Cu counterpart under most aging and reflow conditions. This may be associated with the formation of Y-Cu IMCs formed at the interface between the solder and the Cu substrate, because the Y-Cu IMCs have recently been referred to as relatively `ductile' IMCs.

  20. Effect of Yttrium on the Fracture Strength of the Sn-1.0Ag-0.5Cu Solder Joints

    NASA Astrophysics Data System (ADS)

    Choi, Hyelim; Kaplan, Wayne D.; Choe, Heeman

    2016-07-01

    This is a preliminary investigation on the mechanical properties of Pb-free Sn-1.0Ag-0.5Cu solder joints containing 0.02 wt.% to 0.1 wt.% Y under a range of thermal aging and reflow conditions. Despite the significantly thicker intermetallic compound (IMC) formed at the solder joint, the 0.1 wt.% Y-doped joint exhibited a higher fracture strength than its baseline Sn-1.0Ag-0.5Cu counterpart under most aging and reflow conditions. This may be associated with the formation of Y-Cu IMCs formed at the interface between the solder and the Cu substrate, because the Y-Cu IMCs have recently been referred to as relatively `ductile' IMCs.

  1. Dirac and Weyl Semimetal in XYBi (X = Ba, Eu; Y = Cu, Ag and Au).

    PubMed

    Du, Yongping; Wan, Bo; Wang, Di; Sheng, Li; Duan, Chun-Gang; Wan, Xiangang

    2015-01-01

    Weyl and Dirac semimetals recently stimulate intense research activities due to their novel properties. Combining first-principles calculations and effective model analysis, we predict that nonmagnetic compounds BaYBi (Y = Au, Ag and Cu) are Dirac semimetals. As for the magnetic compound EuYBi, although the time reversal symmetry is broken, their long-range magnetic ordering cannot split the Dirac point into pairs of Weyl points. However, we propose that partially substitute Eu ions by Ba ions will realize the Weyl semimetal. PMID:26399742

  2. Photoelectron diffraction studies of Cu on Pd(111) random surface alloys

    SciTech Connect

    Siervo, A. de; Landers, R.; Soares, E. A.; Kleiman, G.G.

    2005-03-15

    The study of surface alloys is motivated by their use in many applications of different segments of industry, such as in the search for new catalysts and sensors, in surface protection against corrosion, in lowering friction, and in testing electronic devices. An important aspect of surface alloys studies is that of the precise quantification of segregation and diffusion processes as well as the determination of surface structure. In this paper we report a combined low-energy electron diffraction and photoelectron diffraction (PED) (using synchrotron radiation) study of surface alloy formation when Cu ultrathin films are evaporated onto Pd(111) single-crystal surfaces. We present results for two different coverages (1 and 3 ML) and three annealing temperatures (300, 600, and 800 K). For these preparation conditions, a random alloy phase with different concentrations seems to form in the first few layers. Through the analysis of PED data performed using a multiple scattering formalism and the average T-matrix approximation it was possible to determine the atomic structure and the atomic concentration of the first three layers.

  3. Shock melting method to determine melting curve by molecular dynamics: Cu, Pd, and Al

    SciTech Connect

    Liu, Zhong-Li; Zhang, Xiu-Lu; Cai, Ling-Cang

    2015-09-21

    A melting simulation method, the shock melting (SM) method, is proposed and proved to be able to determine the melting curves of materials accurately and efficiently. The SM method, which is based on the multi-scale shock technique, determines melting curves by preheating and/or prepressurizing materials before shock. This strategy was extensively verified using both classical and ab initio molecular dynamics (MD). First, the SM method yielded the same satisfactory melting curve of Cu with only 360 atoms using classical MD, compared to the results from the Z-method and the two-phase coexistence method. Then, it also produced a satisfactory melting curve of Pd with only 756 atoms. Finally, the SM method combined with ab initio MD cheaply achieved a good melting curve of Al with only 180 atoms, which agrees well with the experimental data and the calculated results from other methods. It turned out that the SM method is an alternative efficient method for calculating the melting curves of materials.

  4. Oxidation-induced spin reorientation in Co adatoms and CoPd dimers on Ni/Cu(100)

    NASA Astrophysics Data System (ADS)

    Chen, K.; Beeck, T.; Fiedler, S.; Baev, I.; Wurth, W.; Martins, M.

    2016-04-01

    Ultrasmall magnetic clusters and adatoms are of strong current interest because of their possible use in future technological applications. Here, we demonstrate that the magnetic coupling between the adsorbates and the substrate can be significantly changed through oxidation. The magnetic properties of Co adatoms and CoPd dimers deposited on a remanently magnetized Ni/Cu(100) substrate have been investigated by x-ray absorption and x-ray magnetic circular dichroism spectroscopy at the Co L2 ,3 edges. Using spectral differences, pure and oxidized components are distinguished, and their respective magnetic moments are determined. The Co adatoms and the CoPd dimers are coupled ferromagnetically to the substrate, while their oxides, Co-O and CoPd-O, are coupled antiferromagnetically to the substrate. Along with the spin reorientation from the pure to the oxidized state, the magnetic moment of the adatom is highly reduced from Co to Co-O. In contrast, the magnetic moment of the dimer is of similar order for CoPd and CoPd-O.

  5. An analytical electron microscopic investigation of precipitation in an Al-Cu-Zn-Mg-Ag alloy.

    PubMed

    Hasan, F; Lorimer, G W

    1993-03-01

    The distribution, morphology, chemistry, and crystallography of the precipitates formed during aging of an Al-Cu-Zn-Mg-Ag alloy have been studied using analytical transmission electron microscopy. The first precipitates to appear during aging at 150 degrees C were thin hexagonal-shaped plate-like precipitates which formed on the (111)Al planes. These precipitates had a face-centred orthorhombic crystal structure and their composition was essentially CuAl2 although they contained a trace of silver. At peak hardness the microstructure consisted of the plate-like precipitates on (111)Al planes and theta' precipitates on (100)Al planes. Overaging resulted in the precipitation of equilibrium theta, CuAl2, which exhibited a lath morphology and an orientation-relationship with the matrix (210)Al magnitude of (110)gamma; (001)Al misoriented from (001)gamma by approximately 6 degrees. Prolonged overaging at 250 degrees C resulted in the formation of cuboid-shaped Al5(Cu,Zn)6Mg2 precipitates which had a cubic crystal structure and a cube:cube orientation-relationship with the matrix. PMID:8513176

  6. Dynamical effects in dissociative adsorption: Quantum state-resolved studies of H(2) scattering from Pd and Cu

    NASA Astrophysics Data System (ADS)

    Gostein, Michael

    The effects of molecular rotation and vibration in the dynamics of H2 scattering from Pd(111) and Cu(110) were studied using molecular beam and laser spectroscopy techniques. These studies test state-of-the- art theoretical simulations of molecule-surface interactions, a fundamental understanding of which is relevant to diverse fields in science and technology. Experiments on the rotational state dependence of H2 dissociation on Pd(111) were motivated by recent theoretical results concerning the concept of dynamical steering. This concept has been invoked to explain the enhancement of sticking at low translational energy for H2 incident on certain metals. It suggests that sticking should also be enhanced for low rotational energy in these systems. The experiments presented here qualitatively confirm this prediction. For incident translational energies from 31- 95 meV, the H2/Pd(111) sticking coefficient goes down as the rotational quantum number J is raised from 0 to 3. It then increases for J = 4 and 5, which is consistent with rotational energy also helping directly overcome the activation barrier. A fraction of the scattered H2 molecules are also rotationally excited. This occurs directly upon scattering but is activated by the surface temperature, not the incident translational energy. This behavior is not explained by current theoretical treatments and requires further exploration. Experiments on the vibrational state dependence of H2 scattering from Cu(110) and Pd(111) were motivated by continued considerations of activation barriers to dissociative adsorption, since vibrational energy assists in surmounting barriers which occur 'late' along the reaction path. The survival probability of H2 in the rovibrational state (v = 1, J = 1), prepared by stimulated Raman scattering, was measured for scattering from each surface. In both cases the (v = 1, J = 1) survival probability is smaller than that of the ground vibrational state, in accord with expectations for a

  7. Mechanical, structural and thermal properties of Ag-Cu and ZnO reinforced polylactide nanocomposite films.

    PubMed

    Ahmed, Jasim; Arfat, Yasir Ali; Castro-Aguirre, Edgar; Auras, Rafael

    2016-05-01

    Plasticized polylactic acid (PLA) based nanocomposite films were prepared by incorporating polyethylene glycol (PEG) and two selected nanoparticles (NPs) [silver-copper (Ag-Cu) alloy (<100 nm) and zinc oxide (ZnO) (<50 and <100 nm)] through solvent casting method. Incorporation of Ag-Cu alloy into the PLA/PEG matrix increased the glass transition temperature (Tg) significantly. The crystallinity of the nanocomposites (NCs) was significantly influenced by NP incorporation as evidenced from differential scanning calorimetry (DSC) and X-ray diffraction (XRD) analysis. The PLA nanocomposite reinforced with NPs exhibited much higher tensile strength than that of PLA/PEG blend. Melt rheology of NCs exhibited a shear-thinning behavior. The mechanical property drastically reduced with a loading of NPs, which is associated with degradation of PLA. SEM micrographs exhibited that both Ag-Cu alloy and ZnO NPs were dispersed well in the PLA film matrix. PMID:26893045

  8. Self-organized metal networks at ion-etched Cu/Si and Ag/Si interfaces

    SciTech Connect

    Stepanova, M.; Dew, S.K.; Karpuzov, D.S.

    2005-04-15

    We report self-organized metal nanopatterns on Si substrates produced by ion beam etching. We have deposited thin layers of metal such as Cu or Ag on Si substrates and then etched the deposited layers by a 1-5 keV Ar{sup +} ion beam at room temperature. At the stage when the metal-Si interface is reached, we have observed networks of metal clusters on the Si substrate with the characteristic size of 30-60 nm for Cu and 100-200 nm for Ag. The Cu patterns are sensitive to the ion energy. At 1 keV energy, we observe a well-defined Cu network, whereas at 3-5 keV energy, the Cu pattern becomes fuzzy without clear boundaries. To systematize and explain our results, we have suggested a kinetic model that combines ion etching and coarsening of the metal clusters on Si substrates. From our kinetic Monte Carlo simulations, we have found that the cooperative effect of coarsening and etching has a regime when the size of metal clusters can be approximated by the expression a(4D/aR){sup 1/3}, where D is the surface diffusivity of metal adatoms on the Si substrate, R is the etch rate, and a is the interatomic distance. Our synergistic model of coarsening and sputtering explains the observed difference in Cu and Ag cluster sizes and predicts the fuzzy Cu patterns at elevated ion energies.

  9. Electrochemical depositions of fluorohydroxyapatite doped by Cu2+, Zn2+, Ag+ on stainless steel substrates

    NASA Astrophysics Data System (ADS)

    Bir, F.; Khireddine, H.; Touati, A.; Sidane, D.; Yala, S.; Oudadesse, H.

    2012-07-01

    Fluoridated hydroxyapatite (FHA, Ca10(PO4)6(OH)2-xFx where 0 < x < 2 is the degree of fluoridation) and inorganic ions (Zn2+, Cu2+, Ag+) substituted fluoridated hydroxyapatite coatings (M-FHA) were deposited on the surface of medical grade 316L stainless steel samples by electrochemical deposition technique. The FHA coatings were co-substituted with antibacterial ions (Zn2+, Cu2+ or Ag+) by co-precipitation and ion-exchange methods. Characterization studies of coatings from X-ray diffraction (XRD), Scanning electron microscopy (SEM) and Energy dispersive X-ray spectroscopy (EDX) showed that the obtained layers are monophase crystals FHA and did not contain any discernible crystalline impurity. The particles of all samples are of nano size that gives thin layers. The surface morphology, microstructure and Ca/P atomic ratio of the FHA coatings can be regulated by varying electrolyte temperature. This later affects the porosity of the coating surface and the chemical compositions of the deposits. Quantitative elemental analysis indicates that the copper, zinc and silver ions are incorporated into the Fluorohydroxyapatite. The antimicrobial effects of doped fluorohydroxyapatite coatings against pathogen bacterial strains Staphylococcus aureus were tested in liquid media. The results are promising and demonstrated that all doped FHA samples exhibit excellent antimicrobial activity "in vitro" against the microorganism, so the antimicrobial properties of the coatings developed are improved.

  10. HRLEED study of the roughening transitions in Cu(110), Ni(110) and Ag(110) surfaces

    SciTech Connect

    Wang, K.; Montano, P.A. |

    1996-12-01

    The authors present the results of High Resolution Low Energy Electron Diffraction (HRLEED) measurements of the thermal roughening transition on Cu(110), Ag(110) and Ni(110) surfaces. They performed careful spot profile intensity measurements as a function of temperature. They observed a proliferation of steps along the (110) and (001) directions. In addition a strong deviation from a Debye model was observed in the scattered intensity of the Bragg reflections. This deviation from the harmonic approximation occurs well below the roughening transition temperature. The behavior of the three metal surfaces is qualitatively similar except for the transition temperatures. Ni shows the highest transition temperature (1,300 K), Cu is intermediate (1,000 K) and Ag has the lowest temperature (730 K). Analyzing the behavior of the (00) reflection intensity, and the evolution of the line shape as a function of the temperature, they found clear evidence of a roughening transition at the (110) surface. A lineshape analysis of the (00) reflection shows the transition from a Lorentzian lineshape to a power law. They also proved, based on the experimental data and a recent theoretical model, that there is a tremendous increase in step density and a decrease in the average terrace size as the temperature increases. They used STM to corroborate the HRLEED results at room temperature. They found excellent agreement.

  11. Hot Deformation Characteristics and Processing Maps of the Cu-Cr-Zr-Ag Alloy

    NASA Astrophysics Data System (ADS)

    Zhang, Yi; Chai, Zhe; Volinsky, Alex A.; Sun, Huili; Tian, Baohong; Liu, Ping; Liu, Yong

    2016-03-01

    The hot deformation behavior of the Cu-Cr-Zr-Ag alloy has been investigated by hot compressive tests in the 650-950 °C temperature and 0.001-10 s-1 strain rate ranges using Gleeble-1500D thermo-mechanical simulator. The microstructure evolution of the alloy during deformation was characterized using optical and transmission electron microscopy. The flow stress decreases with the deformation temperature and increases with the strain rate. The apparent activation energy for hot deformation of the alloy was 343.23 kJ/mol. The constitutive equation of the alloy based on the hyperbolic-sine equation was established to characterize the flow stress as a function of the strain rate and the deformation temperature. The processing maps were established based on the dynamic material model. The optimal processing parameters for hot deformation of the Cu-Cr-Zr-Ag alloy are 900-950 °C and 0.001-0.1 s-1 strain rate. The evolution of DRX microstructure strongly depends on the deformation temperature and the strain rate.

  12. Containerless electromagnetic levitation melting of Cu-Fe and Ag-Ni alloys

    NASA Technical Reports Server (NTRS)

    Abbaschian, G. J.; Ethridge, E. C.

    1983-01-01

    The feasibility of producing silver or copper alloys containing finely dispersed nickel or iron particles, respectively, by utilizing containerless electromagnetic levitation casting techniques was investigated. A levitation coil was designed to successfully levitate and melt a variety of alloys including Nb-Ge, Cu-Fe, Fe-C, and Ag-Ni. Samples of 70 Cu-30 Fe and 80 Ag-20 Ni (atomic %), prepared by mechanical pressing of the constituent powders, were levitated and heated either to the solid plus liquid range of the alloys or to the fully liquid region. The samples were then solidified by passing helium gas into the bell jar or they were dropped into a quenching oil. The structure of the samples which were heated to the solid plus liquid range consists of uniform distribution of Fe or Ni particle in their respective matrices. A considerable amount of entrapped gas bubbles were contained. Upon heating for longer periods or to higher temperatures, the bubbles coalesced and burst, causing the samples to become fragmented and usually fall out of the coil.

  13. Two Liquid Phases Separation of Fe-Cu-B and Fe-Cu-Ag-B systems at 1873 and 1523 K

    NASA Astrophysics Data System (ADS)

    Ono-Nakazato, Hideki; Yamaguchi, Katsuhiro; Agawa, Shingo; Taguchi, Kenji; Usui, Tateo

    In recycling of steel scraps, the accumulation of tramp element in steel has been one of serious problems. Because copper in steel causes hot-shortness, the copper content of steel scraps is strictly adjusted under the upper limiting value in steelmaking process. In addition, recycling of steel scrap is necessary for energy savings and to realize a recycling-oriented society. In the present study,it was found that addition of boron could separate a single liquid in Fe-Cu system into Fe-rich and Cu-rich phases. Equilibrium experiments in Fe-Cu-B ternary system at 1873 and 1523 K showed that the copper content in Fe-rich phase decreased to 4.3 mass%. Subsequently, equilibrium experiments in Fe-Cu-Ag-B system were carried out and the copper was observed to be distributed between Fe-B and Ag phases. The distribution ratio of [mass%Cu](in Ag) / [mass%Cu](in Fe) was about 6 at 1873 K, regardless of copper content. It was found that the copper content of iron could be decreased by using silver as the solvent.

  14. Mechanical Behavior of Sn-3.0Ag-0.5Cu/Cu Solder Joints After Isothermal Aging

    NASA Astrophysics Data System (ADS)

    Nguyen, Van Luong; Chung, Chin-Sung; Kim, Ho-Kyung

    2016-01-01

    The tensile impact behavior of lead-free Sn-3Ag-0.5Cu/Cu solder joints aged at 413 K and 453 K for times ranging from 24 h to 1000 h has been investigated in this study. The activation energy for growth of the intermetallic compound (IMC) layer was estimated and compared with literature values. Additionally, the tensile strength of solder joints with IMC thickness of 17.6 μm was found to be more sensitive to the strain rate as compared with solder joints with thinner IMC layers. Equations representing the relationships among the effective stress, strain rate, aging time, and aging temperature as well as IMC thickness were established using matrix laboratory (MATLAB) software. These equations show that the tensile strength decreases with increase in the IMC thickness to about 8 μm, after which it becomes nearly constant when the IMC thickness is between approximately 8 μm and 14 μm, before decreasing significantly when the IMC thickness exceeds 14 μm. The main reason for these characteristics was excessive increase in the IMC thickness of solder joints, causing a change in the stress concentration of the tensile load from the protruding region to the inside of the IMC layer at the same tested strain rate.

  15. A colorimetric assay for measuring iodide using Au@Ag core-shell nanoparticles coupled with Cu(2+).

    PubMed

    Zeng, Jingbin; Cao, Yingying; Lu, Chun-Hua; Wang, Xu-Dong; Wang, Qianru; Wen, Cong-Ying; Qu, Jian-Bo; Yuan, Cunguang; Yan, Zi-Feng; Chen, Xi

    2015-09-01

    Au@Ag core-shell nanoparticles (NPs) were synthesized and coupled with copper ion (Cu(2+)) for the colorimetric sensing of iodide ion (I(-)). This assay relies on the fact that the absorption spectra and the color of metallic core-shell NPs are sensitive to their chemical ingredient and dimensional core-to-shell ratio. When I(-) was added to the Au@Ag core-shell NPs-Cu(2+) system/solution, Cu(2+) can oxidize I(-) into iodine (I2), which can further oxidize silver shells to form silver iodide (AgI). The generated Au@AgI core-shell NPs led to color changes from yellow to purple, which was utilized for the colorimetric sensing of I(-). The assay only took 10 min with a lowest detectable concentration of 0.5 μM, and it exhibited excellent selectivity for I(-) over other common anions tested. Furthermore, Au@Ag core-shell NPs-Cu(2+) was embedded into agarose gels as inexpensive and portable "test strips", which were successfully used for the semi-quantitation of I(-) in dried kelps. PMID:26388386

  16. Tuning of Ag doped core-shell ZnO NWs/Cu2O grown by electrochemical deposition

    NASA Astrophysics Data System (ADS)

    Makhlouf, Houssin; Messaoudi, Olfa; Souissi, Ahmed; Ben Assaker, Ibtissem; Oueslati, Mihrez; Bechelany, Mikhael; Chtourou, Radhouane

    2015-09-01

    ZnO nanowires (NWs)/Cu2O-Ag core-shell nanostructures (NSs) have been synthesized by electrochemical deposition method on ITO-coated glass substrates in order to improve the efficiency of the type-II transition of core-shell ZnO NWs/Cu2O-Ag NSs. The morphologies of the obtained NSs were studied by scanning electron microscopy confirming the presence of core-shell NSs. The crystalline proprieties were analyzed by x-ray diffraction and micro-Raman measurement: wurtzite ZnO and cuprit Cu2O phase were founded. The presence of Ag content in core-shell NS was detected by EDX. Optical measurement reveals an additional contribution δE at about 1.72 eV attributed to the type-II interfacial transition between the valance band of cuprit-Cu2O and the conduction band of W-ZnO. The effect of the Ag doping into the type-II transition was investigated. A red shift of the type-II transition was detected according to the Ag concentration. These materials could have potential applications in photocatalytic and photovoltaic fields.

  17. Structural and optical properties of (Ag,Cu)(In,Ga)Se{sub 2} polycrystalline thin film alloys

    SciTech Connect

    Boyle, J. H.; Shafarman, W. N.; Birkmire, R. W.; McCandless, B. E.

    2014-06-14

    The structural and optical properties of pentenary alloy (Ag,Cu)(In,Ga)Se{sub 2} polycrystalline thin films were characterized over the entire compositional range at a fixed (Cu + Ag)/(In + Ga) ratio. Films deposited at 550 °C on bare and molybdenum coated soda-lime glass by elemental co-evaporation in a single-stage process with constant incident fluxes exhibit single phase chalcopyrite structure, corresponding to 122 spacegroup (I-42d) over the entire compositional space. Unit cell refinement of the diffraction patterns show that increasing Ag substitution for Cu, the refined a{sub o} lattice constant, (Ag,Cu)-Se bond length, and anion displacement increase in accordance with the theoretical model proposed by Jaffe, Wei, and Zunger. However, the refined c{sub o} lattice constant and (In,Ga)-Se bond length deviated from theoretical expectations for films with mid-range Ag and Ga compositions and are attributed to influences from crystallographic bond chain ordering or cation electronegativity. The optical band gap, derived from transmission and reflection measurements, widened with increasing Ag and Ga content, due to influences from anion displacement and cation electronegativity, as expected from theoretical considerations for pseudo-binary chalcopyrite compounds.

  18. Variability in the fractionation of Cu, Ag, and Zn among cytosolic proteins in the bivalve Macoma balthica

    USGS Publications Warehouse

    Johansson, C.; Cain, Daniel J.; Luoma, Samuel N.

    1986-01-01

    Gel filtration chromatographs of cytosols from the clam Macorna balthica analysed from both field and laboratory treated specimens showed that uptake of Cu, Ag, and Zn in the metallothionein-like protein (MLP) pool follows exposure both in nature and in the laboratory. Specimens collected from San Francisco Bay over 18 mo showed strong temporal variability in the fractionation of the metals among cytosolic proteins. A marked increase in Cu, Ag, and Zn in a very low molecular weight pool occurred when concentrations were highest In the MLP pool. The correlation between total cytosollc metal and MLP-metal also appeared to approach a hyperbolic character at the highest concentrations.

  19. M-Au/TiO2 (M = Ag, Pd, and Pt) nanophotocatalyst for overall solar water splitting: role of interfaces.

    PubMed

    Melvin, Ambrose A; Illath, Kavya; Das, Tanmay; Raja, Thirumalaiswamy; Bhattacharyya, Somnath; Gopinath, Chinnakonda S

    2015-08-28

    M-Au/TiO2 (M = Ag, Pd, Pt) composites were prepared through a facile one-pot photodeposition synthesis and evaluated for solar water splitting (SWS) with and without a sacrificial agent. The M-Au combination exhibits a dominant role in augmenting the H2 generation activity by forming a bi-metallic system. Degussa P25 was used as a TiO2 substrate to photodeposit Au followed by Au + M (M = Ag/Pd/Pt). The SWS activity of the M-Au/TiO2 was determined through photocatalytic H2 production in the presence of methanol as a sacrificial agent under one sun conditions with an AM1.5 filter. The highest H2 yield was observed for Pt0.5-Au1/TiO2 and was around 1.3 ± 0.07 mmol h(-1) g(-1), with an apparent quantum yield (AQY) of 6.4%. Pt0.5-Au1/TiO2 also demonstrated the same activity for 25 cycles of five hours each for 125 h. Critically, the same Pt0.5-Au1/TiO2 catalyst was active in overall SWS (OSWS) without any sacrificial agent, with an AQY = 0.8%. The amount of Au and/or Pt was varied to obtain the optimum composition and it was found that the Pt0.5-Au1/TiO2 composition exhibits the best activity. Detailed characterization by physico-chemical, spectral and microscopy measurements was carried out to obtain an in-depth understanding of the origin of the photocatalytic activity of Pt0.5-Au1/TiO2. These in-depth studies show that gold interacts predominantly with oxygen vacancies present on titania surfaces, and Pt preferentially interacts with gold for an effective electron-hole pair separation at Pt-Au interfaces and electron storage in metal particles. The Pt in Pt0.5-Au1/TiO2 is electronically and catalytically different from the Pt in Pt/TiO2 and it is predicted that the former suppresses the oxygen reduction reaction. PMID:26199221

  20. Comparison of Extensive Thermal Cycling Effects on Microstructure Development in Micro-alloyed Sn-Ag-Cu Solder Joints

    SciTech Connect

    Anderson, Iver E.; Boesenberg, Adam; Harringa, Joel; Riegner, David; Steinmetz, Andrew; Hillman, David

    2011-09-28

    Pb-free solder alloys based on the Sn-Ag-Cu (SAC) ternary eutectic have promise for widespread adoption across assembly conditions and operating environments, but enhanced microstructural control is needed. Micro-alloying with elements such as Zn was demonstrated for promoting a preferred solidification path and joint microstructure earlier in simple (Cu/Cu) solder joints studies for different cooling rates. This beneficial behavior now has been verified in reworked ball grid array (BGA) joints, using dissimilar SAC305 (Sn-3.0Ag-0.5Cu, wt.%) solder paste. After industrial assembly, BGA components joined with Sn-3.5Ag-0.74Cu-0.21Zn solder were tested in thermal cycling (-55 C/+125 C) along with baseline SAC305 BGA joints beyond 3000 cycles with continuous failure monitoring. Weibull analysis of the results demonstrated that BGA components joined with SAC + Zn/SAC305 have less joint integrity than SAC305 joints, but their lifetime is sufficient for severe applications in consumer, defense, and avionics electronic product field environments. Failure analysis of the BGA joints revealed that cracking did not deviate from the typical top area (BGA component side) of each joint, in spite of different Ag3Sn blade content. Thus, SAC + Zn solder has not shown any advantage over SAC305 solder in these thermal cycling trials, but other characteristics of SAC + Zn solder may make it more attractive for use across the full range of harsh conditions of avionics or defense applications.

  1. Improved galvanic replacement growth of Ag microstructures on Cu micro-grid for enhanced SERS detection of organic molecules.

    PubMed

    Guo, Tian-Long; Li, Ji-Guang; Sun, Xudong; Sakka, Yoshio

    2016-04-01

    Galvanic growth of Ag nano/micro-structures on Cu micro-grid was systematically studied for surface-enhanced Raman scattering (SERS) applications. Detailed characterizations via FE-SEM and HR-TEM showed that processing parameters, (reaction time, Ag(+) concentration, and PVP addition) all substantially affect thermodynamics/kinetics of the replacement reaction to yield substrates of significantly different microstructures/homogeneities and thus varied SERS performances (sensitivity, enhancement factor, and reproducibility) of the Ag substrates in the detection of R6G analyte. PVP as an additive was shown to notably alter nucleation/growth behaviors of the Ag crystals and promote the deposition of dense and uniform Ag films of nearly monodisperse polyhedrons/nanoplates through suppressing dendrites crystallization. Under optimized synthesis (50mM of Ag(+), 30s of reaction, and 700 wt.% of PVP), Ag substrates exhibiting a high Raman signal enhancement factor of ~1.1 × 10(6) and a low relative standard deviation of ~0.13 in the repeated detection of 10 μM R6G were obtained. The facile deposition and excellent performance reported in this work may allow the Ag microstructures to find wider SERS applications. Moreover, growth mechanisms of the different Ag nano/micro-structures were discussed based on extensive FE-SEM and HR-TEM analysis. PMID:26838829

  2. Cu/Pd-Catalyzed, Three-Component Click Reaction of Azide, Alkyne, and Aryl Halide: One-Pot Strategy toward Trisubstituted Triazoles.

    PubMed

    Wei, Fang; Li, Haoyu; Song, Chuanling; Ma, Yudao; Zhou, Ling; Tung, Chen-Ho; Xu, Zhenghu

    2015-06-01

    A Cu/Pd-catalyzed, three-component click reaction of azide, alkyne, and aryl halide has been developed. By using this Cu/Pd transmetalation relay catalysis, a variety of 1,4,5-trisubstituted 1,2,3-triazoles were quickly assembled in one step in high yields with complete regioselectivity, just like assembling Lego bricks. Notably, different from the well-established CuAAC click reactions only working on terminal alkynes, this reaction offers an alternative solution for the problem of the click reaction of internal alkynes. PMID:26000564

  3. Chemical Stability of (Ag,Cu)2Se: a Historical Overview

    NASA Astrophysics Data System (ADS)

    Brown, David R.; Day, Tristan; Caillat, Thierry; Snyder, G. JeffREY

    2013-07-01

    Recent work on Cu2- x Se has caused strong interest in this material due to its high reported peak zT (1.5) and the reduction of thermal conductivity through the mechanism of liquid-like suppression of heat capacity. In the 1960s, 3M patented Cu1.97Ag0.03Se as "TPM-217." Over the following decade it was tested and developed by the 3M Corporation, at the National Aeronautics and Space Administration (NASA) Jet Propulsion Laboratory, Teledyne Energy Systems, and the General Atomics Corporation for use as a next-generation thermoelectric material. During these tests, extreme problems with material loss through Se vaporization and chemical reactions between the material and the device contacts were found. These problems were especially severe while operating under conditions of high iL/A. As a result, the material system was abandoned. The results of these reports are discussed. A simple test of degradation of Cu2Se under conditions of applied current and thermal gradient was performed and showed results compatible with the work done by General Atomics.

  4. Microstructural evolution during aging of an Al-Cu-Li-Ag-Mg-Zr alloy

    NASA Technical Reports Server (NTRS)

    Kumar, K. S.; Brown, S. A.; Pickens, Joseph R.

    1991-01-01

    Alloys in the Al-Cu-Li Ag-Mg subsystem were developed that exhibit desirable combinations of strength and ductility. These Weldalite (trademark) alloys, are unique for Al-Cu-Li alloys in that with or without a prior cold stretching operation, they obtain excellent strength-ductility combinations upon natural and artificial aging. This is significant because it enables complex, near-net shape products such as forgings and super plastically formed parts to be heat treated to ultra-high strengths. On the other hand, commercial extrusions, rolled plates and sheets of other Al-Cu-Li alloys are typically subjected to a cold stretching operation before artificial aging to the highest strength tempers to introduce dislocations that provide low-energy nucleation sites for strengthening precipitates such as the T(sub 1) phase. The variation in yield strength (YS) with Li content in the near-peak aged condition for these Weldalite (trademark) alloys and the associated microstructures were examined, and the results are discussed.

  5. Exchange interaction between magnetic impurities on surfaces of Cu(x)Pd(1-x) and Cu(x)Au(1-x) random substitutional alloys.

    PubMed

    Ujfalussy, B; Simon, E

    2014-07-01

    We present fully relativistic first principles calculations of the exchange interactions between magnetic impurities deposited on the (1 1 1) surfaces of CuxPd1-x and CuxAu1-x random substitutional alloys, described using the coherent potential approximation. We show that as with pure surfaces of Cu and Au, where Shockley-type surface states mediate an RKKY-type interaction, a surface state and its dispersion can be obtained from studying the Bloch spectral function. In the second part of the paper we show how the details of the interaction are determined by the properties and dispersion of the surface states of the host material. We find an extra exponential decay in the range of the interactions compared to the 1/R(2) decay on surfaces of pure metals. The similar topology of the Fermi surface of Cu and Au allows us to scale the spin-orbit coupling and to study the Bychkov-Rashba splitting. Alternatively, the entirely different topology of the Cu and Pd Fermi surfaces allows us to study changes in the surface-state dispersion of the RKKY interaction between surface impurities. PMID:24934437

  6. The influence of hydrogen sulfide-to-hydrogen partial pressure ratio on the sulfidization of Pd and 70 mol% Pd–Cu membranes

    SciTech Connect

    Iyoha, O.; Enick, R.M.; Killmeyer, R.P.; Morreale, B.

    2007-11-15

    The influence of H2S-to-H2 partial pressure ratio on the sulfidization of Pd and 70 mol% Pd–Cu membrane alloys was studied using various H2Scontaining gas mixtures. The Pd membranes exposed to various H2S mixtures were in very good agreement with the thermodynamic calculations used in this study, resisting sulfidization when exposed to H2S-to-H2 ratios below the equilibrium value predicted for Pd4S formation, and experiencing sulfidization when exposed to ratios above the equilibrium values. The 70 mol% Pd–Cu membranes, however, exhibited deviations from the predicted values, resisting sulfidization at some conditions close to the equilibrium values at which sulfidization was expected, and experiencing sulfidization at some conditions at which resistance was expected. This phenomenon was attributed to deviations of the Pd–Cu alloy from ideality, probably due to Cu segregation at the membrane surface.

  7. Bis(thiosemicarbazonato) chelates of Co(II), Ni(II), Cu(II), Pd(II) and Pt(II)

    NASA Astrophysics Data System (ADS)

    Chandra, Sulekh; Singh, R.

    1985-01-01

    Bis chelates of Co(II), Ni(II), Cu(II), Pd(II) and Pt(II) with the enolic form of diethyl ketone and methyl n-propyl thiosemicarbazones were synthesized and characterized by elemental analyses, magnetic moments, i.r. and electronic and electron spin resonance spectral studies. All the complexes were found to have the composition ML 2 [where M = Co(II), Ni(II), Cu(II), Pd(ii) and Pt(II) and L = thiosemicarbazones of diethyl ketone and methyl n-propyl ketone]. Co(II) and Cu(II) complexes are paramagnetic and may have polymeric six-coordinate octahedral and square planar geometries, respectively. The Ni(II), Pd(II) and Pt(II) complexes are diamagnetic and may have square planar geometries. Pyridine adducts (ML 2·2Py) of Ni(II) and Cu(II) complexes were also prepared and characterized.

  8. Quantitative description of short-range order and its influence on the electronic structure in Ag-Pd alloys.

    PubMed

    Hoffmann, M; Marmodoro, A; Ernst, A; Hergert, W; Dahl, J; Lång, J; Laukkanen, P; Punkkinen, M P J; Kokko, K

    2016-08-01

    We investigate the effect of short-range order (SRO) on the electronic structure in alloys from the theoretical point of view using density of states (DOS) data. In particular, the interaction between the atoms at different lattice sites is affected by chemical disorder, which in turn is reflected in the fine structure of the DOS and, hence, in the outcome of spectroscopic measurements. We aim at quantifying the degree of potential SRO with a proper parameter. The theoretical modeling is done with the Korringa-Kohn-Rostoker Green's function method. Therein, the extended multi-sublattice non-local coherent potential approximation is used to include SRO. As a model system, we use the binary solid solution Ag c Pd1-c at three representative concentrations c  =  0.25, 0.5 and 0.75. The degree of SRO is varied from local ordering to local segregation through an intermediate completely uncorrelated state. We observe some pronounced features, which change over the whole energy range of the valence bands as a function of SRO in the alloy. These spectral variations should be traceable in modern photoemission experiments. PMID:27269809

  9. Quantitative description of short-range order and its influence on the electronic structure in Ag-Pd alloys

    NASA Astrophysics Data System (ADS)

    Hoffmann, M.; Marmodoro, A.; Ernst, A.; Hergert, W.; Dahl, J.; Lång, J.; Laukkanen, P.; Punkkinen, M. P. J.; Kokko, K.

    2016-08-01

    We investigate the effect of short-range order (SRO) on the electronic structure in alloys from the theoretical point of view using density of states (DOS) data. In particular, the interaction between the atoms at different lattice sites is affected by chemical disorder, which in turn is reflected in the fine structure of the DOS and, hence, in the outcome of spectroscopic measurements. We aim at quantifying the degree of potential SRO with a proper parameter. The theoretical modeling is done with the Korringa–Kohn–Rostoker Green’s function method. Therein, the extended multi-sublattice non-local coherent potential approximation is used to include SRO. As a model system, we use the binary solid solution Ag c Pd1‑c at three representative concentrations c  =  0.25, 0.5 and 0.75. The degree of SRO is varied from local ordering to local segregation through an intermediate completely uncorrelated state. We observe some pronounced features, which change over the whole energy range of the valence bands as a function of SRO in the alloy. These spectral variations should be traceable in modern photoemission experiments.

  10. Novel Galvanic Nanostructures of Ag and Pd for Efficient Laser Desorption/Ionization of Low Molecular Weight Compounds

    NASA Astrophysics Data System (ADS)

    Silina, Yuliya E.; Meier, Florian; Nebolsin, Valeriy A.; Koch, Marcus; Volmer, Dietrich A.

    2014-05-01

    A simple approach for synthesis of palladium and silver nanostructures with readily adjustable morphologies was developed using galvanic electrochemical deposition, for application to surface-assisted laser desorption/ionization (SALDI) of small biological molecules. A range of fatty acids, triglycerides, carbohydrates, and antibiotics were investigated to assess the performance of the new materials. Intense analyte cations were generated from the galvanic surfaces upon UV laser irradiation such as potassium adducts for a film thickness <100 nm (originating from impurities of the electrolyte solution) and Pd and Ag cluster ions for films with a thickness >120 nm. Possible laser desorption/ionization mechanisms of these galvanic structures are discussed. The films exhibited self-organizing abilities and adjustable morphologies by changing electrochemical parameters. They did not require any stabilizing agents and were inexpensive and very easy to produce. SALDI analysis showed that the materials were stable under ambient conditions and analytical results with excellent measurement reproducibility and detection sensitivity similar to MALDI were obtained. Finally, we applied the galvanic surfaces to fast screening of natural oils with minimum sample preparation.

  11. Hardening by cooling rate control and post-firing heat treatment in Pd-Ag-Sn alloy for bonding porcelain.

    PubMed

    Yu, Young-Jun; Seol, Hyo-Joung; Cho, Mi-Hyang; Kim, Hyung-Il; Kwon, Yong Hoon

    2016-01-01

    The aim of this study was to determine the hardening effect by controlling the cooling rate during the porcelain firing process and performing an additional post-firing heat treatment in a Pd-Ag-Sn alloy. The most effective cooling rate for alloy hardening was determined by cooling the specimens at various cooling rates after oxidation treatment. A subsequent porcelain firing simulation followed by cooling at the selected cooling rate was performed. A post-firing heat treatment was then done at 600°C in a porcelain furnace. The hardening mechanism was characterized by a hardness test, X-ray diffraction, field emission scanning electron microscopy and energy dispersive X-ray spectroscopy. Alloy softening occurred during the porcelain firing process followed by cooling at a controlled cooling rate. A post-firing heat treatment allowed apparent precipitation hardening. It is advisable to perform a postfiring heat treatment at 600°C in a porcelain furnace by annealing metal substructure after porcelain fusing. PMID:27041022

  12. Sn-Ag-Cu to Cu joint current aging test and evolution of resistance and microstructure

    NASA Astrophysics Data System (ADS)

    Xu, Di Erick; Chow, Jasper; Mayer, Michael; Jung, Jae Pil; Yoon, Jong Hyun

    2015-11-01

    SAC 305 solder bump with 800 μm diameter were produced and soldered to a custom substrate with Cu lines as leads that allow for resistance measurement during current aging. The measured joint resistance values (leads plus solder bump) before aging are 7.7 ± 1.8 mΩ and 11.8 ± 2.8 mΩ at room temperature and 160°C, respectively. In general, the resistance of the solder joint increases instantly by about 1 mΩ, when subjected to a 2.2 A aging current at 160°C. The increase is gradual in the following hours of aging and more drastic as it approaches the final failure. Four stages are identified in the resistance signal curve and compared with observations from cross sections. The stages are IMC growth, crack formation and propagation, intermittent crack healing-forming, and final failure resulting in an open connection at the cathode. Recently a periodical drop and rise behavior was reported for the resistance signal. This behavior is reproduced and attributed to the intermittent crack healing-forming stage. The healing events observed are faster than the sampling time. Possibly, as current is concentrated when bypassing interfacial cracks, local melting occurs partially filling cracks before resolidifying. [Figure not available: see fulltext.

  13. Electron configuration and charge state of electrically active Cu, Ag and Au ions in ZnSe

    NASA Astrophysics Data System (ADS)

    Nedeoglo, N. D.; Sirkeli, V. P.; Nedeoglo, D. D.; Laiho, R.; Lähderanta, E.

    2006-08-01

    The Hall effect, electrical conductivity and electron mobility are investigated at temperatures between 55 and 500 K in n-ZnSe crystals doped with Cu, Ag or Au. The presence of a small amount of Cu atoms leads to an inversion of the sign of the Hall coefficient at temperatures above 300 K. Anomalous temperature dependence of the electron mobility is observed in the samples with low Cu concentration (<0.3 at.% in the melt). Different characters of the temperature dependences of kinetic coefficients are found for n-ZnSe doped with Ag and Au. These curves are typical for crystals having several donor levels at different energetic depths. Immediately after doping, silver behaves like a usual compensating acceptor impurity while gold shows amphoteric properties. We propose a model that explains the anomalies of the temperature dependences of the kinetic coefficients in Cu-doped crystals and the lack of the anomalies in Ag-doped and Au-doped crystals. In accordance with this model and our experimental data, copper in n-ZnSe has two charge states, CuZn+ (d10) and CuZn2+ (d9), and two acceptor levels near the valence band. Silver and gold exist in single-charged states AgZn+ and AuZn+ with d10 electron configuration forming single energy levels near the valence band. Au atoms form mainly interstitial Aui donors at low doping concentrations and substitutional AuZn and AuZn-based acceptors at high doping concentrations. Time stimulation of the amphoteric properties of Ag is discussed.

  14. The Electronic and Optical Properties of X-Doped SrTiO3 (x = Rh, Pd, Ag): a First-Principles Calculations

    NASA Astrophysics Data System (ADS)

    Qiu, Bo; Yan, Xin-Guo; Huang, Wei-Qing; Huang, Gui-Fang; Jiao, Chao; Zhan, Si-Qi; Long, Jin-Ping; Yang, Zheng-Mei; Wan, Zhuo; Peng, P.

    2014-12-01

    The electronic and optical properties of X-doped (X = Rh, Pd, Ag) cubic SrTiO3 in perovskite structure are investigated using first-principles calculations. The strength of the Ti-O bonds near the substitutional X impurity is found to be weakened by the shorter X-O bonds. Three types of electronic characteristics due to X-doping are demonstrated. X-doping decreases the band gap of SrTiO3, extending the optical absorption edge to visible light. Although Pd-doped SrTiO3 has the greatest absorption in the visible light region, its photocatalytic activity is lower than that of Rh-doped SrTiO3, because the intermediate bands from the 4d orbitals of the Pd dopant act as recombination centers. The theoretical results coincide with the available experimental results.

  15. Five-fold twinned Pd2NiAg nanocrystals with increased surface Ni site availability to improve oxygen reduction activity.

    PubMed

    Liu, Suli; Zhang, Qinghua; Li, Yafei; Han, Min; Gu, Lin; Nan, Cewen; Bao, Jianchun; Dai, Zhihui

    2015-03-01

    The synthesis of highly active oxygen reduction reaction (ORR) catalysts with good durability and low cost is highly desirable but still remains a significant challenge. In this work, we present the synthesis of five-fold twinned Pd2NiAg nanocrystals (NCs) with a Ni-terminal surface which exhibit excellent electrocatalytic performance for ORR in alkaline media, even better than the performance of the commercial Pt/C catalyst. Using high-angle annular-dark-field imaging together with density functional theory calculations, it is found that the surfaces of the five-fold twinned Pd2NiAg NCs exhibit an unusual valence electron density. The maximum catalytic activity originates from the increased availability of surface Ni sites in five-fold twinned Pd2NiAg NCs and the features of twinned structural defects. This study provides an explanation of the enhanced ORR from the special structure of this novel material, which opens up new avenues for the design of novel classes of electrocatalysts for fuel cells and metal-air batteries. PMID:25626352

  16. Polymer-supported CuPd nanoalloy as a synergistic catalyst for electrocatalytic reduction of carbon dioxide to methane

    PubMed Central

    Zhang, Sheng; Kang, Peng; Bakir, Mohammed; Lapides, Alexander M.; Dares, Christopher J.; Meyer, Thomas J.

    2015-01-01

    Developing sustainable energy strategies based on CO2 reduction is an increasingly important issue given the world’s continued reliance on hydrocarbon fuels and the rise in CO2 concentrations in the atmosphere. An important option is electrochemical or photoelectrochemical CO2 reduction to carbon fuels. We describe here an electrodeposition strategy for preparing highly dispersed, ultrafine metal nanoparticle catalysts on an electroactive polymeric film including nanoalloys of Cu and Pd. Compared with nanoCu catalysts, which are state-of-the-art catalysts for CO2 reduction to hydrocarbons, the bimetallic CuPd nanoalloy catalyst exhibits a greater than twofold enhancement in Faradaic efficiency for CO2 reduction to methane. The origin of the enhancement is suggested to arise from a synergistic reactivity interplay between Pd–H sites and Cu–CO sites during electrochemical CO2 reduction. The polymer substrate also appears to provide a basis for the local concentration of CO2 resulting in the enhancement of catalytic current densities by threefold. The procedure for preparation of the nanoalloy catalyst is straightforward and appears to be generally applicable to the preparation of catalytic electrodes for incorporation into electrolysis devices. PMID:26668386

  17. The Effects of Adding Elements of Zinc and Magnesium on Ag-Cu Eutectic Alloy for Warming Acupuncture

    PubMed Central

    Park, Il Song; Kim, Keun Sik; Lee, Min Ho

    2013-01-01

    The warming acupuncture for hyperthermia therapy is made of STS304. However, its needle point cannot be reached to a desirable temperature due to heat loss caused by low thermal conductivity, and the quantification of stimulation condition and the effective standard establishment of warming acupuncture are required as a heat source. Accordingly, in this study, after Ag-Cu alloys with different composition ratios were casted and then mixed with additives to improve their physical and mechanical properties, the thermal conductivity and biocompatibility of the alloy specimens were evaluated for selecting suitable material. Ag-Cu binary alloys and ternary alloys added 5 wt% Zn or 2 wt% Mg were casted and then cold drawn to manufacture needles for acupuncture, and their physical properties, thermal conductivity, and biocompatibility were evaluated for their potential use in warming acupuncture. The results of this study showed that the physical and mechanical properties of the Ag-Cu alloys were improved by additives and that the thermal conductivity, machinability, and biocompatibility of the Ag-Cu alloys were improved by Mg addition. PMID:24078827

  18. Ag-Cu nanoalloyed film as a high-performance cathode electrocatalytic material for zinc-air battery.

    PubMed

    Lei, Yimin; Chen, Fuyi; Jin, Yachao; Liu, Zongwen

    2015-01-01

    A novel Ag50Cu50 film electrocatalyst for oxygen reduction reaction (ORR) was prepared by pulsed laser deposition (PLD) method. The electrocatalyst actually is Ag-Cu alloyed nanoparticles embedded in amorphous Cu film, based on transmission electron microscopy (TEM) characterization. The rotating disk electrode (RDE) measurements provide evidence that the ORR proceed via a four-electron pathway on the electrocatalysts in alkaline solution. And it is much more efficient than pure Ag catalyst. The catalytic layer has maximum power density of 67 mW cm(-2) and an acceptable cell voltage at 0.863 V when current densities increased up to 100 mA cm(-2) in the Ag50Cu50-based primary zinc-air battery. The resulting rechargeable zinc-air battery exhibits low charge-discharge voltage polarization of 1.1 V at 20 mAcm(-2) and high durability over 100 cycles in natural air. PMID:25977668

  19. Localized surface plasmon behavior of Ag-Cu alloy nanoparticles stabilized by rice-starch and gelatin

    SciTech Connect

    Singh, Manish Kumar; Mandal, R. K.; Manda, Premkumar; Singh, A. K.

    2015-10-15

    The purpose of this communication was to understand localized surface plasmon behavior of a series of Ag-Cu alloy nanoparticles capped by rice-starch and gelatin. The structures of dried powders were investigated with the help of X-ray diffraction. The analysis revealed Ag-rich and Cu-rich phases with maximum solid solubility of Cu ∼9 atom per cent; 8 atom per cent and Ag ∼ 16 atom per cent; 14 atom per cent in rice-starch and gelatin capped samples respectively. Transmission electron microscope was used for knowing the particle size as well as to supplement FCC phase formations of Ag-rich and Cu-rich solid phases arrived at based on X-ray diffraction studies. The UV-Vis spectra of sols were examined for the formation and stability of alloy nanoparticles. The temporal evolution of LSPR curves gave us to assert that the sol is stable for more than two months. Small angle X-ray scattering in the sol state was extensively utilized to understand nature of suspensions in terms of fractals. Such a study is important for having a correlation between LSPR behaviors with those of nanoparticle dispersion in aqueous media. It is believed that this work will be a contribution to the emerging field of plasmonics that include applications in the area of photophysical processes and photochemical reactions.

  20. Localized surface plasmon behavior of Ag-Cu alloy nanoparticles stabilized by rice-starch and gelatin

    NASA Astrophysics Data System (ADS)

    Singh, Manish Kumar; Manda, Premkumar; Singh, A. K.; Mandal, R. K.

    2015-10-01

    The purpose of this communication was to understand localized surface plasmon behavior of a series of Ag-Cu alloy nanoparticles capped by rice-starch and gelatin. The structures of dried powders were investigated with the help of X-ray diffraction. The analysis revealed Ag-rich and Cu-rich phases with maximum solid solubility of Cu ˜9 atom per cent; 8 atom per cent and Ag ˜ 16 atom per cent; 14 atom per cent in rice-starch and gelatin capped samples respectively. Transmission electron microscope was used for knowing the particle size as well as to supplement FCC phase formations of Ag-rich and Cu-rich solid phases arrived at based on X-ray diffraction studies. The UV-Vis spectra of sols were examined for the formation and stability of alloy nanoparticles. The temporal evolution of LSPR curves gave us to assert that the sol is stable for more than two months. Small angle X-ray scattering in the sol state was extensively utilized to understand nature of suspensions in terms of fractals. Such a study is important for having a correlation between LSPR behaviors with those of nanoparticle dispersion in aqueous media. It is believed that this work will be a contribution to the emerging field of plasmonics that include applications in the area of photophysical processes and photochemical reactions.

  1. Facile solvothermal synthesis of highly active and robust Pd1.87Cu0.11Sn electrocatalyst towards direct ethanol fuel cell applications

    NASA Astrophysics Data System (ADS)

    Jana, Rajkumar; Dhiman, Shikha; Peter, Sebastian C.

    2016-08-01

    Ordered intermetallic Pd1.87Cu0.11Sn ternary electrocatalyst has been synthesized by sodium borohydride reduction of precursor salts Pd(acac)2, CuCl2.2H2O and SnCl2 using one-pot solvothermal synthesis method at 220 °C with a reaction time of 24 h. To the best of our knowledge, here for the first time we report surfactant free synthesis of a novel ordered intermetallic ternary Pd1.87Cu0.11Sn nanoparticles. The ordered structure of the catalyst has been confirmed by powder x-ray diffraction, transmission electron microscopy (TEM). Composition and morphology of the nanoparticles have been confirmed through field emission scanning electron microscopy, energy-dispersive spectrometry and TEM. The electrocatalytic activity and stability of the ternary electrocatalyst towards ethanol oxidation in alkaline medium was investigated by cyclic voltammetry and chronoamperometry techniques. The catalyst is proved to be highly efficient and stable upto 500th cycle and even better than commercially available Pd/C (20 wt%) electrocatalysts. The specific and mass activity of the as synthesized ternary catalyst are found to be ∼4.76 and ∼2.9 times better than that of commercial Pd/C. The enhanced activity and stability of the ordered ternary Pd1.87Cu0.11Sn catalyst can make it as a promising candidate for the alkaline direct ethanol fuel cell application.

  2. Integration of Kinetic Control and Lattice Mismatch To Synthesize Pd@AuCu Core-Shell Planar Tetrapods with Size-Dependent Optical Properties.

    PubMed

    Meng, Min; Fang, Zhicheng; Zhang, Chao; Su, Hongyang; He, Rong; Zhang, Renpeng; Li, Hongliang; Li, Zhi-Yuan; Wu, Xiaojun; Ma, Chao; Zeng, Jie

    2016-05-11

    Planar nanocrystals with multiple branches exhibit unique localized surface plasmon resonance properties and great promise in optical applications. Here, we report an aqueous synthesis of Pd@AuCu core-shell planar tetrapods through preferential overgrowth on Pd cubic seeds. The large lattice mismatch between the Pd core and the AuCu shell is the key to induce the formation of branches under sluggish reduction kinetics. Meanwhile, the capping effect of cetyltrimethylammonium chloride on the {100} facets of Pd cubes with an aspect ratio of 1.2 can determine the growth direction of AuCu branches to form a planar structure. Through simply varying the amounts of Pd cubic seeds, the sizes of products can be well-controlled in the range from 33 to 70 nm. With the manipulation of sizes, the peak position of in-plane dipole resonance can be adjusted from visible to near-infrared region. Due to the presence of tips and edges in the branches, planar tetrapods exhibited excellent surface-enhanced Raman scattering performance with an enhancement factor up to 9.0 × 10(3) for 70 nm Pd@AuCu planar tetrapods. PMID:27074129

  3. General synthesis of noble metal (Au, Ag, Pd, Pt) nanocrystal modified MoS2 nanosheets and the enhanced catalytic activity of Pd-MoS2 for methanol oxidation

    NASA Astrophysics Data System (ADS)

    Yuwen, Lihui; Xu, Fei; Xue, Bing; Luo, Zhimin; Zhang, Qi; Bao, Biqing; Su, Shao; Weng, Lixing; Huang, Wei; Wang, Lianhui

    2014-05-01

    A general and facile method for water-dispersed noble metal (Au, Ag, Pd, Pt) nanocrystal modified MoS2 nanosheets (NM-MoS2 NSs) has been developed. By using sodium carboxymethyl cellulose as a stabilizer, well-dispersed NM-MoS2 NSs with homogeneously deposited noble metal nanocrystals (NM NCs) can be synthesized in aqueous solutions. Due to the transition from the semiconducting 2H phase to the metallic 1T phase, the chemically exfoliated MoS2 (ce-MoS2) NSs have improved electrochemical activity. The partially metallic nature of the ce-MoS2 NSs and the catalytic activity of the NM NCs synergistically make NM-MoS2 NSs a potential electrochemical catalyst. For the first time, Pd-MoS2 NSs were used as an electrocatalyst for methanol oxidation in alkaline media. The results showed that Pd-MoS2 NSs have enhanced catalytic activity with 2.8-fold anodic peak current mass density compared to a commercial Pd/C catalyst, suggesting potential for application in direct methanol fuel cells (DMFCs).A general and facile method for water-dispersed noble metal (Au, Ag, Pd, Pt) nanocrystal modified MoS2 nanosheets (NM-MoS2 NSs) has been developed. By using sodium carboxymethyl cellulose as a stabilizer, well-dispersed NM-MoS2 NSs with homogeneously deposited noble metal nanocrystals (NM NCs) can be synthesized in aqueous solutions. Due to the transition from the semiconducting 2H phase to the metallic 1T phase, the chemically exfoliated MoS2 (ce-MoS2) NSs have improved electrochemical activity. The partially metallic nature of the ce-MoS2 NSs and the catalytic activity of the NM NCs synergistically make NM-MoS2 NSs a potential electrochemical catalyst. For the first time, Pd-MoS2 NSs were used as an electrocatalyst for methanol oxidation in alkaline media. The results showed that Pd-MoS2 NSs have enhanced catalytic activity with 2.8-fold anodic peak current mass density compared to a commercial Pd/C catalyst, suggesting potential for application in direct methanol fuel cells (DMFCs

  4. Electrochemical performance and carbon deposition resistance of M-BaZr₀.₁Ce₀.₇Y₀.₁Yb₀.₁O₃₋δ (M = Pd, Cu, Ni or NiCu) anodes for solid oxide fuel cells.

    PubMed

    Li, Meng; Hua, Bin; Pu, Jian; Chi, Bo; Jian, Li

    2015-01-01

    Pd-, Cu-, Ni- and NiCu-BaZr₀.₁Ce₀.₇Y₀.₁Yb₀.₁O₃₋δ anodes, designated as M-BZCYYb, were prepared by impregnating M-containing solution into BZCYYb scaffold, and investigated in the aspects of electrocatalytic activity for the reactions of H₂ and CH₄ oxidation and the resistance to carbon deposition. Impregnation of Pd, Ni or NiCu significantly reduced both the ohmic (RΩ) and polarization (RP) losses of BZCYYb anode exposed to H₂ or CH₄, while Cu impregnation decreased only RΩ in H₂ and the both in CH4. Pd-, Ni- and NiCu-BZCYYb anodes were resistant to carbon deposition in wet (3 mol. % H₂O) CH₄ at 750°C. Deposited carbon fibers were observed in Pd- and Ni-BZCYYb anodes exposed to dry CH4 at 750°C for 12 h, and not observed in NiCu-BZCYYb exposed to dry CH₄ at 750°C for 24 h. The performance of a full cell with NiCu-BZCYYb anode, YSZ electrolyte and La₀.₆Sr₀.₄Co₀.₂Fe₀.₈O₃₋δ-Gd doped CeO₂ (LSCF-GDC) cathode was stable at 750°C in wet CH₄ for 130 h, indicating that NiCu-BZCYYb is a promising anode for direct CH₄ solid oxide fuel cells (SOFCs). PMID:25563843

  5. Surface plasmon resonance enhancement of the magneto-optical Kerr effect in Cu/Co/Ag/SnO2 structure

    NASA Astrophysics Data System (ADS)

    Ghanaatshoar, Majid; Moradi, Mehrdad; Tohidi, Parsis

    2014-10-01

    In this paper, an Ag ultra thin layer was deposited on the Cu/Co film by thermal evaporation technique in the vacuum. The atomic force microscopy confirms that nanoparticles of Ag were formed on the Co magnetic layer, and subsequently, the longitudinal Kerr signal of Cu/Co/Ag was amplified more than 2 times. This enhancement is resulting from the overlap of the surface plasmon resonance in the silver with the electronic transition in the Co layer. Furthermore, we investigated the effect of transparent semiconductor SnO2 as a cap layer on the magnitude of longitudinal Kerr signal. To obtain the optimal thickness of cap layer, a numerical analysis was carried out using a 4 × 4 characteristic matrix, which takes into account multiple reflections from interfaces within the medium and light transmission through the layers.

  6. Isotopic Ag-Cu-Pb record of silver circulation through 16th-18th century Spain.

    PubMed

    Desaulty, Anne-Marie; Telouk, Philippe; Albalat, Emmanuelle; Albarède, Francis

    2011-05-31

    Estimating global fluxes of precious metals is key to understanding early monetary systems. This work adds silver (Ag) to the metals (Pb and Cu) used so far to trace the provenance of coinage through variations in isotopic abundances. Silver, copper, and lead isotopes were measured in 91 coins from the East Mediterranean Antiquity and Roman world, medieval western Europe, 16th-18th century Spain, Mexico, and the Andes and show a great potential for provenance studies. Pre-1492 European silver can be distinguished from Mexican and Andean metal. European silver dominated Spanish coinage until Philip III, but had, 80 y later after the reign of Philip V, been flushed from the monetary mass and replaced by Mexican silver. PMID:21606351

  7. Development of a new Pb-free solder: Sn-Ag-Cu

    SciTech Connect

    Miller, C.M.

    1995-02-10

    With the ever increasing awareness of the toxicity of Pb, significant pressure has been put on the electronics industry to get the Pb out of solder. This work pertains to the development and characterization of an alloy which is Pb-free, yet retains the proven positive qualities of current Sn-Pb solders while enhancing the shortcomings of Sn-Pb solder. The solder studied is the Sn-4.7Ag-1.7Cu wt% alloy. By utilizing a variety of experimental techniques the alloy was characterized. The alloy has a melting temperature of 217{degrees}C and exhibits eutectic melting behavior. The solder was examined by subjecting to different annealing schedules and examining the microstructural stability. The effect of cooling rate on the microstructure of the solder was also examined. Overall, this solder alloy shows great promise as a viable alternative to Pb-bearing solders and, as such, an application for a patent has been filed.

  8. Atomic Mobilities in the Ag-Cu-Sn Face-Centered Cubic Lattice

    NASA Astrophysics Data System (ADS)

    Gierlotka, W.; Chen, Y. H.; Haque, M. A.; Rahman, M. A.

    2012-12-01

    Knowledge of atomic mobilities is necessary to predict the evolution of microstructure. The theoretical description of atomic mobilities is connected to the chemical potentials of the components in a given phase. A new thermodynamic description of the quaternary Ag-Cu-In-Sn system was recently published, and it is clear that a new description of the mobilities is also necessary. Based on the available literature and using Dictra software, optimization of the mobility parameters of silver, copper, and tin in the face-centered cubic phase was carried out. The results were compared with relevant data from literature as well as with our own experimental results. Good agreement between calculations and experiment was obtained.

  9. Low-energy electron elastic scattering from Mn, Cu, Zn, Ni, Ag, and Cd atoms

    SciTech Connect

    Felfli, Z.; Msezane, A. Z.; Sokolovski, D.

    2011-05-15

    Electron elastic total cross sections (TCSs) for ground and excited Mn, Cu, Zn, Ni, Ag, and Cd atoms have been investigated in the electron-impact energy range 0 {<=}E{<=} 1 eV. The near-threshold TCSs for both the ground and excited states of these atoms are found to be characterized by Ramsauer-Townsend minima, shape resonances, and extremely sharp resonances corresponding to the formation of stable bound negative ions. The recently developed Regge-pole methodology where the crucial electron-electron correlations are embedded is employed for the calculations. From close scrutiny of the imaginary parts of the complex angular momenta, we conclude that these atoms form stable weakly bound ground and excited negative ions as Regge resonances through slow electron collisions. The extracted electron binding energies from the elastic TCSs of these atoms are contrasted with the available experimental and theoretical values.

  10. Site preference of ternary alloying additions to NiTi: Fe, Pt, Pd, Au, Al, Cu, Zr and Hf

    NASA Technical Reports Server (NTRS)

    Bozzolo, Guillermo; Noebe, Ronald D.; Mosca, Hugo O.

    2004-01-01

    Atomistic modeling of the site substitution behavior of Pd in NiTi (J. Alloys and Comp. (2004), in press) has been extended to examine the behavior of several other alloying additions, namely, Fe, Pt, Au, Al, Cu, Zr and Hf in this important shape memory alloy. It was found that all elements, to a varying degree, displayed absolute preference for available sites in the deficient sublattice. How- ever, the energetics of the different substitutional schemes, coupled with large scale simulations indicate that the general trend in all cases is for the ternary addition to want to form stronger ordered structures with Ti.

  11. A general Pd/Cu-catalyzed C-H heteroarylation of 3-bromoquinolin-2(1H)-ones.

    PubMed

    Bruneau, Alexandre; Brion, Jean-Daniel; Messaoudi, Samir; Alami, Mouad

    2014-11-14

    3-(Heteroaryl)quinolin-2(1H)-ones were synthesized in good to excellent yields using a bimetallic catalytic system through the C-H heteroarylation strategy. Starting from 3-bromoquinolin-2(1H)-ones, various azoles have been successfully used. In all cases, the reactions take place rapidly in dioxane and efficiently proceed in the presence of a bimetallic Pd(OAc)2/CuI as the catalyst, PPh3 as the ligand and LiOtBu or KOAc as the base. PMID:25237986

  12. The Low-Lying States of AlCu and AlAg

    NASA Technical Reports Server (NTRS)

    Bauschlicher, Charles W., Jr.; Langhoff, Stephen R.; Partridge, Harry

    1994-01-01

    The singlet and triplet states of AlCu and AlAg below about 32 000/cm are studied using the internally contracted multireference configuration-interaction method. A more elaborate study of the X(sup 1)Sum(sup +) ground state of AlCu is undertaken using extended Gaussian basis sets, including the effect of inner-shell correlation and including a perturbational estimate of relativistic effects. Our best estimate of the spectroscopic constants (r(sub 0), DeltaG(sub 1/2), and D(sub 0)) for the X(sup 1)Sum(sup+) state with the experimental values in parentheses are: 4.416(4.420) a(sub 0), 295 (294) /cm, and 2.318 (2.315) eV. The calculations definitively assign the upper state in the observed transition at 14 892/cm to the lowest (sup 1)Prod state. The calculated spectroscopic constants and radiative lifetime for the (sup 1)Prod state are in good agreement with experiment. The calculations support the tentative assignments of Behm et al. for three band systems observed in the visible region between 25 000 and 28 000 / cm. However, the computed spectroscopic constants are in very poor agreement with those deduced from an analysis of the spectra. Analogous theoretical results for AlAg suggest that the (2)(sup 3)Prod, (3)(sup 3)Prod, and (3)(sup 1)Sum(sup +) states account for the bands observed, but not assigned, by Duncan and co-workers.

  13. Ligand field spectroscopy of Cu(II) and Ag(II) complexes in the gas phase: theory and experiment.

    PubMed

    Puskar, Ljiljana; Cox, Hazel; Goren, Alan; Aitken, Georgina D C; Stace, Anthony J

    2003-01-01

    Ligand field spectra have been recorded in the gas phase for the two series of complexes containing either Cu(II) or Ag(II) in association with pyridine. Where comparisons are possible, the gas phase spectra match those recorded in the condensed phase; however, for Ag(II) systems the results differ in interpretation. The Ag(II) data are attributed to a ligand-to-metal charge transfer process, and the Cu(II) data (spectral region and extinction coefficient) match the characteristics of a d-d transition. A detailed theoretical analysis of two complexes. [Cu(py)4]2+ and [Ag(py)4]2+ provides evidence of a minimum energy, D4h structure and two less stable D2h and D2d structures within approximately 60 kJ mol(-1). From these structures it is possible to identify a range of optically and vibronically allowed transitions that could contribute to spectra observed in the gas phase. In the case of calculations on [Ag(py)4]2+ there is strong evidence of an electronic transition that would account for the observation of charge transfer in the experiments. Less detailed calculations on [Cu(py)6]2+ and [Ag(py)6]2+ show structural evidence of extensive Jahn Teller distortion. Taken together with incremental binding energies calculated for complexes containing between two and six pyridine molecules, these results show that the level of theory adopted is capable of providing a semi-quantitative understanding of the experimental data. PMID:14527220

  14. Influence of nanoparticle addition on the formation and growth of intermetallic compounds (IMCs) in Cu/Sn-Ag-Cu/Cu solder joint during different thermal conditions

    NASA Astrophysics Data System (ADS)

    Tan, Ai Ting; Tan, Ai Wen; Yusof, Farazila

    2015-06-01

    Nanocomposite lead-free solders are gaining prominence as replacements for conventional lead-free solders such as Sn-Ag-Cu solder in the electronic packaging industry. They are fabricated by adding nanoparticles such as metallic and ceramic particles into conventional lead-free solder. It is reported that the addition of such nanoparticles could strengthen the solder matrix, refine the intermetallic compounds (IMCs) formed and suppress the growth of IMCs when the joint is subjected to different thermal conditions such as thermal aging and thermal cycling. In this paper, we first review the fundamental studies on the formation and growth of IMCs in lead-free solder joints. Subsequently, we discuss the effect of the addition of nanoparticles on IMC formation and their growth under several thermal conditions. Finally, an outlook on the future growth of research in the fabrication of nanocomposite solder is provided.

  15. Mechanical Deformation Behavior of Sn-Ag-Cu Solders with Minor Addition of 0.05 wt.% Ni

    NASA Astrophysics Data System (ADS)

    Hammad, A. E.; El-Taher, A. M.

    2014-11-01

    The aim of the present work is to develop a comparative evaluation of the microstructural and mechanical deformation behavior of Sn-Ag-Cu (SAC) solders with the minor addition of 0.05 wt.% Ni. Test results showed that, by adding 0.05Ni element into SAC solders, generated mainly small rod-shaped (Cu,Ni)6Sn5 intermetallic compounds (IMCs) inside the β-Sn phase. Moreover, increasing the Ag content and adding Ni could result in the change of the shape and size of the IMC precipitate. Hence, a significant improvement is observed in the mechanical properties of SAC solders with increasing Ag content and Ni addition. On the other hand, the tensile results of Ni-doped SAC solders showed that both the yield stress and ultimate tensile strengths decrease with increasing temperature and with decreasing strain rate. This behavior was attributed to the competing effects of work hardening and dynamic recovery processes. The Sn-2.0Ag-0.5Cu-0.05Ni solder displayed the highest mechanical properties due to the formation of hard (Cu,Ni)6Sn5 IMCs. Based on the obtained stress exponents and activation energies, it is suggested that the dominant deformation mechanism in SAC (205)-, SAC (0505)- and SAC (0505)-0.05Ni solders is pipe diffusion, and lattice self-diffusion in SAC (205)-0.05Ni solder. In view of these results, the Sn-2.0Ag-0.5Cu-0.05Ni alloy is a more reliable solder alloy with improved properties compared with other solder alloys tested in the present work.

  16. In vitro chemical and biological effects of Ag, Cu and Cu + Zn adjunction in 46S6 bioactive glasses

    NASA Astrophysics Data System (ADS)

    Bunetel, L.; Wers, E.; Novella, A.; Bodin, A.; Pellen-Mussi, P.; Oudadesse, H.

    2015-09-01

    Three bioactive glasses belonging to the system SiO2-CaO- Na2O-P2O5 elaborated by conventional melt-quenching techniques were doped with silver, copper and copper + zinc. They were characterized using the usual physical methods. Human osteoblast cells Saos-2 and human endothelial cells EAhy926 were used for viability assays and to assess the metallic ions, self toxicity. Human monocyte cells THP-1 were used to measure interleukins IL1β and IL6 release. Glass chemical structures did not vary much on introduction of metal ions. A layer of hydroxyapatite was observed on every glass after 30 days of SBF immersion. A proliferative action was seen on Saos-2 after 24 h of incubation, EAhy926 growth was not affected. For both cell lines, a moderate cytotoxicity was found after 72 h. Dose-dependent toxic effects of Ag, Cu and Zn ions were observed on Saos-2 and EAhy926 cells. Measured CD50 of silver against these two cell lines were 8 to 20 fold lower than copper and zinc’s. Except undoped control glass, all doped glasses tested showed anti-inflammatory properties by preventing IL1β and IL6 excretion by differentiated THP-1. In conclusion, strictly monitored adjunction of metal ions to bioglasses ensures good anti-inflammatory properties without altering their biocompatibility.

  17. Orthogonal Cu- and Pd-Based Catalyst Systems for the O- and N-Arylation of Aminophenols

    PubMed Central

    Maiti, Debabrata; Buchwald, Stephen L.

    2009-01-01

    O- or N-arylated aminophenol products constitute a common structural motif in various potentially useful therapeutic agents and/or drug candidates. We have developed a complementary set of Cu- and Pd-based catalyst systems for the selective O- and N-arylation of unprotected aminophenols using aryl halides. Selective O-arylation of 3- and 4-aminophenols is achieved with copper-catalyzed methods employing picolinic acid or CyDMEDA, trans-N,N′-dimethyl-1,2-cyclohexanediamine, respectively, as the ligand. The selective formation of N-arylated products of 3- and 4-aminophenols can be obtained with BrettPhos precatalyst, a biarylmonophosphine-based palladium catalyst. 2-Aminophenol can be selectively N-arylated with CuI, although no system for the selective O-arylation could be found. Coupling partners with diverse electronic properties and a variety of functional groups can be selectively transformed under these conditions. PMID:19899753

  18. Cu, Pt, and Pd complexes of the 3-deoxy-1,2-bis(thiosemicarbazone) derived from D-glucose.

    PubMed

    Horton, D; Varela, O

    2000-09-22

    3-Deoxy-D-erythro-hexos-2-ulose bis(thiosemicarbazone) (1) acts as a tetradentate ligand of the N2S2 type which forms stable coordination complexes with metal(II) cations. The Cu(II), Pt(II), and Pd(II) chelates (2, 4, and 6, respectively) of 1 were synthesized and characterized by elemental analysis and NMR spectroscopy. The NMR spectra of the Pt complex (4) showed the coupling of H-1 and C-1, C-2 of the bis(thiosemicarbazone) with 195Pt (33.7% naturally occurring), which supports the structure proposed for the chelate. The complexes 2, 4, and 6 were acetylated to give the corresponding tri-O-acetyl derivatives 3, 5, and 7. Elimination of Cu(II) from 3 with hydrogen sulfide afforded 8, the tri-O-acetyl derivative of 1. Preliminary studies have shown antiviral activity of chelates 2, 4, and 6 against poliovirus type 1. PMID:11072850

  19. Comparative modular analysis of two complex sulfosalt structures: sterryite, Cu(Ag,Cu)3Pb19(Sb,As)22(As-As)S56, and parasterryite, Ag4Pb20(Sb,As)24S58.

    PubMed

    Moëlo, Yves; Guillot-Deudon, Catherine; Evain, Michel; Orlandi, Paolo; Biagioni, Cristian

    2012-10-01

    The crystal structures of two very close, but distinct complex minerals of the lead sulfosalt group have been solved: sterryite, Cu(Ag,Cu)(3)Pb(19)(Sb,As)(22)(As-As)S(56), and parasterryite, Ag(4)Pb(20)(Sb,As)(24)S(58). They are analyzed and compared according to modular analysis. The fundamental building block is a complex column centred on a Pb(6)S(12) triangular prismatic core, with two additional long and short arms. The main chemical and topological differences relate to the short arm, which induces a relative a/4 shift (~2 Å along the elongation parameter) of the constitutive rod layers, as illustrated by distinct cell settings within the same space group (P2(1)/n and P2(1)/c, respectively). Selection of the shortest (i.e. strongest) (Sb,As)-S bonds permitted to enhance the polymeric organization of (Sb,As) atoms with triangular pyramidal coordination. These two quasi-homeotypic structures are expanded derivatives of owyheeite, Ag(3)Pb(10)Sb(11)S(28). The hierarchy of organization levels from zero- to three-dimensional entities is subordinated to building operators, which appear as the driving force for the construction of such complex structures. Minor cations (Ag, Cu) or the As-As pair in sterryite secure the final locking, which favours the formation of one or the other compound. PMID:22992793

  20. Ni-free Zr-Cu-Al-Nb-Pd bulk metallic glasses with different Zr/Cu ratios for biomedical applications.

    PubMed

    Huang, Lu; Yokoyama, Yoshihiko; Wu, Wei; Liaw, Peter K; Pang, Shujie; Inoue, Akihisa; Zhang, Tao; He, Wei

    2012-08-01

    Zr-based bulk metallic glasses (BMGs) possess attractive properties for prospective biomedical applications. The present study designs Ni-free Zr-Cu-Al-Nb-Pd BMGs and investigates their in vitro biocompatibility by studying mechanical properties, bio-corrosion resistance, and cellular responses. The Ti-6Al-4V alloy is used as a reference material. It is found that the Zr-based BMGs exhibit good mechanical properties, including high strengths above 1600 MPa, high hardness over 4700 MPa, and low elastic moduli of 85-90 GPa. The Zr-based BMGs are corrosion resistant in a simulated body environment, as revealed by wide passive regions, low passive current densities, and high pitting overpotentials. The formation of ZrO(2)-rich surface passive films of the Zr-based BMGs contributes to their high corrosion resistance, whereas their pitting corrosion in the phosphate buffered saline solution can be attributed to the sensitivity of the ZrO(2) films to the chloride ion. The general biosafety of the Zr-based BMGs is revealed by normal cell adhesions and cell morphologies. Moreover, the Zr/Cu content ratio in the alloy composition affects the biocompatibility of the Zr-based BMGs, by increasing their corrosion resistance and surface wettability with the increase of the Zr/Cu ratio. Effects of Zr/Cu ratios can be used to guide the future design of biocompatible Zr-based BMGs. PMID:22689253

  1. Bi2Sr2CaCu2O8 + x round wires with Ag/Al oxide dispersion strengthened sheaths: microstructure-properties relationships, enhanced mechanical behavior and reduced Cu depletion

    NASA Astrophysics Data System (ADS)

    Kajbafvala, Amir; Nachtrab, William; Wong, Terence; Schwartz, Justin

    2014-09-01

    Ag/Al alloys with various Al content (0.50 wt%, 0.75 wt%, 1.00 wt%, and 1.25 wt%) are made by powder metallurgy and used as the outer sheath material for Bi2Sr2CaCu2O8 + x (Bi2212)/Ag/AgAl multifilamentary round wires (RW). Bi2212/Ag/AgAl RW microstructural, mechanical and electrical properties are studied in various conditions, including as-drawn, after internal oxidation, and after partial melt processing (PMP). The results are compared with the behavior of a Bi2212/Ag/Ag0.20Mg wire of the same geometry. The grains in as-drawn Ag/Al alloys are found to be ˜25% smaller than those in the corresponding Ag/0.20 wt%Mg, but after PMP, the Ag/Al and Ag/0.20 wt%Mg grain sizes are comparable. Tensile tests show that Bi2212/Ag/AgAl green wires have yield strength (YS) of ˜115 MPa, nearly 65% higher than that of Bi2212/Ag/Ag0.20Mg. After PMP, the Bi2212/Ag/AgAl YS is about 35% greater than that of Bi2212/Ag/Ag0.20Mg. Furthermore, Bi2212/Ag/AgAl wires exhibit higher ultimate tensile strength and modulus and twice the elongation-to-failure. Atomic resolution high-angle annular dark-field scanning transmission electron microscopy, high resolution transmission electron microscopy and energy dispersive spectroscopy demonstrate the formation of nanosize MgO and Al2O3 precipitates via internal oxidation. Large spherical MgO precipitates are observed on the Ag grain boundaries of Ag/0.20 wt%Mg alloy, whereas the Al2O3 precipitates are distributed homogenously in the dispersion-strengthened (DS) Ag/Al alloy. Furthermore, it is found that less Cu diffused from the Bi2212 filaments in the Bi2212/Ag/Ag0.75Al wire during PMP than from the filaments in the Bi2212/Ag/Ag0.20Mg wire. These results show that DS Ag/Al alloy is a strong candidate for improved Bi2212 wire.

  2. K-shell ionization cross section for Ti, Fe, Cu, Zr, and Ag

    SciTech Connect

    Benka, O.; Geretschlager, M.

    1981-04-01

    Absolute K-shell ionisation cross sections have been measured for thin targets of Ti, Fe, Cu, Zr and Ag for protons in the energy range 85-790 keV and for thin targets of Ti, Fe and Cu for He ions in the energy range 190-750 keV. In addition the relative variation of the cross sections with energy has been determined with high accuracy. The experimental values are compared to the perturbed stationary state approximation (CPSSR) and the semiclassical approximation (SCA). The CPSSR theory provides the best overall agreement with experimental cross sections. For higher scaled energies the CPSSR theory predicts the energy dependence of the cross sections very well but in the lower energy range it overpredicts the cross sections by as much as a factor of two and this overprediction seems to increase with Z/sub 2/ at a fixed scaled energy y. The SCA theory predicts slightly too large ionisation cross sections except for the lowest pounds values. The relative variation of the cross sections with energy is not well described in either energy range.

  3. Composition and anisotropy in Al-Cu-Li-Ag-Mg-Zr alloys

    SciTech Connect

    Gayle, F.W. . Metallurgy Div.); Tack, W.T.; Swanson, G. ); Heubaum, F.H.; Pickens, J.R. )

    1994-03-15

    Aluminum-lithium alloys that have been hot worked generally suffer from an anisotropy of mechanical properties, both through thickness (surface to centerline) and in plane (from longitudinal to 45[degree] to transverse). Although such anisotropy is present in all tempers, it is more pronounced in the commercially-important, high strength, artificially aged conditions. Yield strength differences between the longitudinal and long transverse orientations ([Delta]YS) of up to 240 MPa for Al-Cu-Li alloy 2090 have been reported. Since minimum properties in all orientations must be considered in applications design, mechanical property anisotropy can limit the use of an alloy. To investigate the role composition plays in the development of mechanical property anisotropy, the authors have examined a range of compositions in the Weldalite[reg sign] 049 alloy family as well as certain model alloys. This novel approach is in contrast to most attempts to reduce anisotropy which have been based on established alloys of relatively narrow composition ranges. In the present study, a baseline aluminum alloy 2195 (4.0 Cu-0.95 Li-0.4 Ag-0.4 Mg-0.14 Zr, in wt.%) with accompanying experimental variants containing 0 to 1.4% Li and 0.4 and 1.2% Mg, were evaluated for tensile property anisotropy, fracture toughness, and microstructure.

  4. Site-specific growth of AgPd nanodendrites on highly purified Au bipyramids with remarkable catalytic performance

    NASA Astrophysics Data System (ADS)

    Zhou, Lin; Liu, Zeke; Zhang, Han; Cheng, Si; Fan, Li-Juan; Ma, Wanli

    2014-10-01

    Au nanorods have been extensively explored in various applications as the template for heterogeneous metallic nanostructures. However, Au bipyramids (AuBPs) have been paid much less attention although they possess an intriguing crystalline structure and extremely superior plasmonic properties which are absent in AuNRs. The state-of-the-art synthesis cannot produce pure AuBPs, which has become a major barrier to their various applications like catalysis since purity is often critical for achieving the desired performance. Herein, we have shown a facile approach to obtain large-scale high-purity AuBPs. The purity of AuBPs can be improved from 30 to 50% for the as-synthesized AuBP solution to over 95% for the purified solution. Site-specific growth of AgPd nanodendrites on multiply twinned AuBPs from core-shell to tipped nanostructures was achieved for the first time by coupling a galvanic replacement with a co-reduction process, which show remarkable catalytic activity in the reduction reaction of 4-nitrophenol (4-NP) by NaBH4. The use of ascorbic acid (AA) as a reductant in the co-reduction process and the intriguing crystalline structure of AuBPs play a critical role in forming these unique structures. We believe that this work would provide a general strategy to prepare high-purity AuBP based trimetallic nanostructures, which offers the opportunity for AuBPs to be widely used in catalysis or other plasmonic-effect related applications in the near future.Au nanorods have been extensively explored in various applications as the template for heterogeneous metallic nanostructures. However, Au bipyramids (AuBPs) have been paid much less attention although they possess an intriguing crystalline structure and extremely superior plasmonic properties which are absent in AuNRs. The state-of-the-art synthesis cannot produce pure AuBPs, which has become a major barrier to their various applications like catalysis since purity is often critical for achieving the desired

  5. Cu(II) and Pd(II) complexes of water soluble O-carboxymethyl chitosan Schiff bases: Synthesis, characterization.

    PubMed

    Baran, Talat; Menteş, Ayfer

    2015-08-01

    This study reports the synthesis of two new water soluble O-carboxymethyl chitosan Schiff bases (OCMCS-5 and OCMCS-6a) and their Cu(II) and Pd(II) complexes. Characterizations of these complexes were carried out with FTIR, elemental analysis, (13)C CPMAS, UV-vis, magnetic moment and molar conductivity techniques. The degrees of substitution (DS) for OCMCS-5a and OCMCS-6a were determined to be 0.48 and 0.44 in elemental analysis. The solubility test revealed that OCMCS-5a and OCMCS-6a dissolved thoroughly in water. The surface morphologies of chitosan (CS), OCMCS-5a, OCMCS-6a and their complexes were studied with SEM-EDAX. Thermal stability of the synthesized compounds was evaluated by TG/DTG and their crystallinity values were investigated with powder X-ray diffraction. Cu(II) and Pd(II) contents of the complexes were estimated with ICP-OES. The characterization studies demonstrated that the thermal stability and crystallinity values of the OCMCS-5a and OCMCS-6a were lower than those of CS. PMID:26021275

  6. A GREEN CHEMISTRY APPROACH TO PREPARATION OF CORE (FE OR CU)-SHELL (NOBLE METALS) NANOCOMPOSITES USING AQUEOUS ASCORBIC ACID

    EPA Science Inventory

    A greener method to fabricate novel core (Fe or Cu)-shell (noble metals) nanocomposites of transition metals such as Fe and Cu and noble metals such as Au, Pt, Pd, and Ag using aqueous ascorbic acid is described. Transition metal salts such as Cu and Fe were reduced using ascor...

  7. Photocatalytic removal of M(2+) (Ni(2+), Cu(2+), Zn(2+), Cd(2+), Hg(2+) and Ag(+)) over new catalyst CuCrO(2).

    PubMed

    Ketir, W; Bouguelia, A; Trari, M

    2008-10-30

    The metal ions M(2+) (Ni(2+), Cu(2+), Zn(2+), Cd(2+), Hg(2+) and Ag(+)) are potentially toxic. Their electro deposition has been carried out in aqueous air-equilibrated CuCrO(2) suspension upon visible illumination. The delafossite CuCrO(2) is p-type semiconductor characterized by a low band gap (1.28 eV) and a long-term chemical stability. The corrosion rate is found to be 10(-2) micromol m(-2)month(-1) in aqua regia. The oxide has been elaborated through nitrate route where the specific surface area is increased via the surface/bulk ratio. A correlation exists between the dark M(2+) adsorption, the redox potential of M(2+/0) couple and the conduction band of CuCrO(2) positioned at -1.06 V(SCE). Ag(+) cannot be photoreduced because of its positive potential located far above the valence band. By contrast, Zn(2+) is efficiently deposited due to the large driving force at the interface. The improved photoactivity of copper with a deposition percentage (90%) is attributed to the strong dark adsorption onto the surface catalyst. The results indicate a competitive effect with the water reduction; it has been observed that the M(2+) deposition goes parallel with the hydrogen evolution. Such behavior is attributed to the low H(2) over voltage when ultra fine aggregate of M islands are photodeposited onto CuCrO(2) substrate. PMID:18384943

  8. Accelerated Bonding of Magnesium and Aluminum with a CuNi/Ag/CuNi Sandwich Interlayer by Plasma-Activated Sintering

    NASA Astrophysics Data System (ADS)

    Wang, Yiyu; Rao, Mei; Li, Leijun; Luo, Guoqiang; Shen, Qiang; Zhang, Lianmeng

    2016-02-01

    Plasma-activated sintering (PAS) has been applied, for the first time, to join magnesium and aluminum using a CuNi/Ag/CuNi sandwich structural interlayer. A cleaning effect and high efficient plasma heating mode in PAS have contributed to forming a strong interfacial diffusion bond under low temperature 673 K (400 °C) and short dwell time (0.6 ks). The designed interlayer provides a diffusion barrier effect and an enhanced physical contact between the interfaces. Strong bonding has been achieved without forming the brittle Mg-Al intermetallics.

  9. Combined promoting effects of low-Pd-containing and Cu-doped LaCoO3 perovskite supported on cordierite for the catalytic combustion of benzene.

    PubMed

    Chen, Y W; Li, B; Niu, Q; Li, L; Kan, J W; Zhu, S M; Shen, S B

    2016-08-01

    The catalytic activities for benzene oxidation and resistance to SO2 poisoning were tested for a series of Pd/La-Cu-Co-O/cordierite catalysts, which were prepared using a multiple-step impregnation method. The XRD, SEM, and IR characterization techniques were performed to investigate the relationship between the catalytic performance and its physicochemical properties. When Pd/La-Cu-Co-O/cordierite catalysts with Pd loadings of 0.06 and 0.08 % were prepared at a calcination temperature of 500 °C for 5 h, they exhibited similar catalytic activity and sulfur resistance. When the concentration of benzene was 1500 ppm and the GHSV was 20000 h(-1), the benzene conversion was above 95 % at a reaction temperature of 350 °C in SO2 existing at 100 ppm. These results were mainly attributed to the cooperation between La-Cu-Co-O perovskite and the noble metal Pd. Specifically, the addition of copper can strengthen the catalytic activity of La-Co-O/cordierite catalysts by decreasing the crystalline size of the active ingredients. A moderate Pd addition can drastically improve the sulfur resistance and further improve the catalytic activity of the La-Cu-Co-O/cordierite catalyst. PMID:27094280

  10. Effects of Cooling Rate on the Microstructure and Morphology of Sn-3.0Ag-0.5Cu Solder

    NASA Astrophysics Data System (ADS)

    Lee, Hwa-Teng; Huang, Kuo-Chen

    2016-01-01

    This study explored the effect of the cooling rate on the microstructure and morphology of Sn-3.0Ag-0.5Cu (SAC305) lead-free solder. In the experiments, rapid cooling (P1: 63.17°C/s) of SAC305 solder resulted in high tensile strength (60.8 MPa) with no significant loss in ductility (strain >40%) due to the formation of fine-grained primary β-Sn (average size ˜14 μm) surrounded by a network-like fine eutectic structure consisting of β-Sn and particle-like Ag3Sn compound. As the cooling rate was reduced, the morphology of the Ag3Sn compound evolved progressively from a particle- to a needle-like form and finally to a leaf- or plate-like form. The cooling rate significantly affected the β-Sn grain size and the morphology of the Ag3Sn compound. Water cooling (at the fastest cooling rate of 100°C/s) of a solder sample resulted in a microstructure consisting of the finest structure of Ag3Sn and β-Sn with no Cu6Sn5, consequently exhibiting the highest hardness of the various specimens. By contrast, after cooling at the slowest rate of 0.008°C/s, the sample exhibited a coarse eutectic structure consisting of large plate-like Ag3Sn compound and isolated long rod-like Cu6Sn5 precipitates. This coarse structure resulted in both lower hardness and poorer tensile strength.

  11. Hydrogen evolution from water using Ag(x)Cu(1-x)GaSe2 photocathodes under visible light.

    PubMed

    Zhang, Li; Minegishi, Tsutomu; Kubota, Jun; Domen, Kazunari

    2014-04-01

    Photoelectrochemical (PEC) water splitting using CuGaSe2 (CGSe) thin film photocathodes modified by partial substitution of Cu with Ag was investigated. The AgxCu1-xGaSe2 (ACGSe) thin films were deposited onto Mo-coated soda-lime glass substrates by means of co-evaporation using a molecular beam epitaxy (MBE) system. The valence band maximum (VBM) potential of ACGSe is deeper than that of CGSe, and its grain size is greatly increased compared to that of CGSe. A Pt and CdS modified ACGSe electrode (Pt/CdS/ACGSe) with a Ag/(Cu + Ag) ratio of about 5% showed a cathodic photocurrent of 8.1 mA cm(-2) at 0 VRHE and an onset potential of 0.70 VRHE (defined as a cathodic photocurrent of 0.05 mA cm(-2)) under simulated sunlight in a 0.1 M Na2SO4 solution (pH 9.5). Moreover, Pt/CdS/ACGSe exhibited a stable cathodic photocurrent for over 55 h, with no clear decrease. PMID:24562096

  12. Nanocelluloses and their phosphorylated derivatives for selective adsorption of Ag(+), Cu(2+) and Fe(3+) from industrial effluents.

    PubMed

    Liu, Peng; Borrell, Pere Ferrer; Božič, Mojca; Kokol, Vanja; Oksman, Kristiina; Mathew, Aji P

    2015-08-30

    The potential of nanoscaled cellulose and enzymatically phosphorylated derivatives as bio-adsorbents to remove metal ions (Ag(+), Cu(2+) and Fe(3+)) from model water and industrial effluents is demonstrated. Introduction of phosphate groups onto nanocelluloses significantly improved the metal sorption velocity and sorption capacity. The removal efficiency was considered to be driven by the high surface area of these nanomaterials as well as the nature and density of functional groups on the nanocellulose surface. Generally, in the solutions containing only single types of metal ions, the metal ion selectivity was in the order Ag(+)>Cu(2+)>Fe(3+), while in the case of mixtures of ions, the order changed to Ag(+)>Fe(3+)>Cu(2+), irrespective of the surface functionality of the nanocellulose. In the case of industrial effluent from the mirror making industry, 99% removal of Cu(2+) and Fe(3+) by phosphorylated nanocellulose was observed. The study showed that phosphorylated nanocelluloses are highly efficient biomaterials for scavenging multiple metal ions, simultaneously, from industrial effluents. PMID:25867590

  13. CO₂ electroreduction at bare and Cu-decorated Pd pseudomorphic layers: catalyst tuning by controlled and indirect supporting onto Au(111).

    PubMed

    Januszewska, Aneta; Jurczakowski, Rafal; Kulesza, Pawel J

    2014-12-01

    We report here the results of electrochemical studies on CO2 electroreduction at multilayered catalyst composed of the monatomic layer of copper covering palladium overlayers (0.8-10 monolayers) deposited on the well-defined Au(111) surface. These multilayered systems were obtained by successive underpotential deposition steps: Pd on Au(111) as well as Cu on Pd/Au(111). Low index orientation of Au substrate was chosen to compare Pd overlayers with bulk Pd(111), which is known to reduce CO2 to CO adsorbates in acidic solutions. The process of CO2 electroreduction was studied by using classical transient electrochemical methods. Catalytic activity of bare Pd layers was investigated in acidic and neutral solutions. In the latter case, much higher activity of Pd overlayers was observed. The results showed that the palladium layer thickness significantly changed the catalytic activities of both bare Pd overlayers and the one Cu monolayer covered electrodes toward CO2 electroreduction. Results show that catalytic activity can be finely tuned by using the multilayered near-surface-alloy approach. PMID:25350872

  14. High-temperature phase equilibria studies in the Bi-Sr- Ca-Cu-O-Ag system

    NASA Astrophysics Data System (ADS)

    Margulies, Lawrence

    A variety of experimental techniques were utilized to examine the high temperature phase equilibria in the Bi- Sr-Ca-Cu-O-Ag system. Quenching studies were used to determine the liquid solubility of Ag in the Bi2Sr 2CaCu2O8 (Bi2212) melt and the details of the peritectic decomposition pathway of Bi2212 as a function on Ag content and oxygen partial pressure (PO2). A liquid immiscibility region between oxide and Ag liquids in the 8-98 at% range was found above 900°C. Two eutectics were found in the Bi2212-Ag pseudo-binary. On the oxide rich side, a eutectic exists at approximately 4 at% Ag. On the Ag rich side, a eutectic exists at approximately 98 at% Ag at a temperature of 15°C below the melting point of pure Ag. Six distinct solid phases were found to be in equilibrium with the partial melt within the Ag content and PO2 range studied. The stability of these solid phases were found to be highly sensitive to PO2, and to a much lesser extent Ag content. High temperature x-ray diffraction (HTXRD) studies of this system are in conflict with these results. It is suggested that these discrepancies are due to experimental artifacts caused by the significant thermal gradients and lack of full bulk sampling which is inherent in conventional HTXRD designs. In part II, a new furnace design compatible with synchrotron radiation sources is introduced to address these problems. This design allows for full bulk sampling in a low thermal gradient environment using Debye- Scherrer transmission geometry. Sample spinning is also introduced in the design to eliminate preferred orientation and incomplete powder averaging and allow for quantitative phase analysis and structural refinement. Studies on model systems are presented to demonstrate the capabilities for high resolution structural studies (Al 2O3) and time resolved phase transformation studies (SrCO 3). Finally, the Bi2212 system is examined to confirm the quenching results of part I, and to demonstrate the degree to which

  15. Properties of the Ti40Zr10Cu36Pd14 BMG Modified by Sn and Nb Additions

    NASA Astrophysics Data System (ADS)

    Sypien, Anna; Stoica, Mihail; Czeppe, Tomasz

    2016-03-01

    The results of investigation of the influence of additions of 2 and 3 at.% of Sn and simultaneously of Sn and 3 at.% Nb on microstructure and properties of the bulk metallic glasses of composition (Ti40Cu36- x Zr10Pd14Sn x )100- y Nb y are reported. It was found that the additions of Sn increased the temperatures of glass transition (T g), primary crystallization (T x ), melting, and liquidus as well as supercooled liquid range (Δ T) and glass forming ability (GFA). The nanohardness and elastic modulus decreased in alloys with 2 and 3 at.% Sn additions, revealing similar values. The 3 at.% Nb addition to the Sn-containing amorphous phase decreased as well all the T g, T x , T L, and T m temperatures as Δ T and GFA; however, relatively larger values of this parameters in alloys containing larger Sn content were preserved. In difference to the previously published results, in the case of the amorphous alloys containing small Nb and Sn additions, a noticeable amount of the quenched-in crystalline phases was not confirmed, at least of the micrometric sizes. In the case of the alloys containing Sn or both Sn and Nb, two slightly different amorphous phase compositions were detected, suggesting separation in the liquid phase. Phase composition of the alloys determined after amorphous phase crystallization was similar for all compositions. The phases Cu8Zr3, CuTiZr, and Pd3Zr were mainly identified in the proportions dependent on the alloy compositions.

  16. The mechanism of N-Ag bonding determined tunability of surface-enhanced Raman scattering of pyridine on MAg (M = Cu, Ag, Au) diatomic clusters.

    PubMed

    Chen, Lei; Gao, Yang; Xu, Haoran; Wang, Zhigang; Li, Zhengqiang; Zhang, Rui-Qin

    2014-10-14

    Binary coinage metal clusters can show a significantly different enhancement in surface-enhanced Raman scattering (SERS) from that of pure element clusters, owing to their tunable surface plasmon resonance energies affected by the composition and atomic ordering. Yet, the tunability by composition requires a deep understanding in order to further optimize the SERS-based detection technique. Here, to fill this deficiency, we conducted detailed analyses of the SERS of pyridine adsorbed through N-Ag bonding on the homonuclear diatomic metal cluster Ag2 and heteronuclear diatomic metal clusters of AuAg and CuAg, as well as the involved charge transfer under an intracluster excitation, based on calculations using time-dependent density functional theory with a short-time approximation for the Raman cross-section. We find that although the SERS enhancements for all complexes can reach the order of 10(3)-10(4), the corresponding wavelengths used for SERS excitation are significantly different. Our molecular orbital analysis reveals that the complexes based on heteronuclear metal clusters can produce varied electronic transitions owing to the polarization between different metal atoms, which tune the SERS enhancements with altered optical properties. Our analyses are expected to provide a theoretical basis for exploring the multi-composition SERS substrates applicable for single molecular detection, nanostructure characterization, and biological molecular identification. PMID:25157565

  17. Interfacial Reactions of Sn-3.0Ag-0.5Cu Solder with Cu-Mn UBM During Aging

    NASA Astrophysics Data System (ADS)

    Tseng, Chien-Fu; Wang, Kai-Jheng; Duh, Jenq-Gong

    2010-12-01

    Cu under bump metallurgy (UBM) has been widely used in flip-chip technology. The major disadvantages of Cu UBM are fast consumption of copper, rapid growth of intermetallic compounds (IMCs), and easy formation of Kirkendall voids. In this study we added two different contents of Mn (2 at.% and 10 at.%) to Cu UBM by sputtering to modify the conventional Cu metallization. For the higher Mn concentration in the Cu-Mn UBM, a new Sn-rich phase formed between Cu6Sn5 and the Cu-Mn UBM, and cracks formed after aging. For the lower Mn concentration, growth of Cu3Sn and Kirkendall voids was significantly suppressed after thermal aging. Kinetic analysis and x-ray elemental mapping provided evidence that Mn diffusion into Cu3Sn slowed diffusion of Cu in the Cu3Sn layer. The Mn-enriched Cu3Sn layer may serve as a diffusion barrier to reduce the interfacial reaction rate and Kirkendall void formation. These results suggest that Cu-Mn UBM with low Mn concentration is beneficial in terms of retarding Cu pad consumption in solder joints.

  18. Efficient enhancement of hydrogen production by Ag/Cu{sub 2}O/ZnO tandem triple-junction photoelectrochemical cell

    SciTech Connect

    Liu, Ying; Ren, Feng Chen, Chao; Liu, Chang; Xing, Zhuo; Liu, Dan; Xiao, Xiangheng; Wu, Wei; Zheng, Xudong; Liu, Yichao; Jiang, Changzhong; Shen, Shaohua; Fu, Yanming

    2015-03-23

    Highly efficient semiconductor photoelectrodes for solar hydrogen production through photocatalytic water splitting are a promising and challenge solution to solve the energy problems. In this work, Ag/Cu{sub 2}O/ZnO tandem triple-junction photoelectrode was designed and prepared. An increase of 11 times of photocurrent is achieved in the Ag/Cu{sub 2}O/ZnO photoelectrode comparing to that of the Cu{sub 2}O film. The high performance of the Ag/Cu{sub 2}O/ZnO film is due to the optimized design of the tandem triple-junction structure, where the localized surface Plasmon resonance of Ag and the hetero-junctions efficiently absorb solar energy, produce, and separate electron-hole pairs in the photocathode.

  19. XRD (x-ray diffraction) and HREM (high resolution electron microscopy) studies of nanocrystalline Cu and Pd

    SciTech Connect

    Nieman, G.W.; Weertman, J.R. . Dept. of Materials Science and Engineering); Siegel, R.W. )

    1990-12-01

    Consolidated powders of nanocrystalline Cu and Pd have been studied by x-ray diffraction (XRD) and high resolution electron microscopy (HREM) as part of an investigation of the mechanical behavior of nanocrystalline pure metals. XRD line broadening measurements were made to estimate grain size, qualitative grain size distribution and average long range strains in a number of samples. Mean grain sizes range from 4--60 nm and have qualitatively narrow grain size distributions. Long range lattice strains are of the order of 0.2--3% in consolidated samples. These strains apparently persist and even increase in Cu samples after annealing at 0.35 Tm (498K) for 2h, accompanied by an apparent increase in grain size of {ge}2x. Grain size, grain size distribution width and internal strains vary somewhat among samples produced under apparently identical processing conditions. HREM studies show that twins, stacking faults and low-index facets are abundant in as-consolidated nanocrystalline Cu samples. Methodology, results, and analysis of XRD and HREM experiments are presented. 17 refs., 2 figs., 2 tabs.

  20. Lattice-matched bimetallic CuPd-graphene nanocatalysts for facile conversion of biomass-derived polyols to chemicals.

    PubMed

    Jin, Xin; Dang, Lianna; Lohrman, Jessica; Subramaniam, Bala; Ren, Shenqiang; Chaudhari, Raghunath V

    2013-02-26

    A bimetallic nanocatalyst with unique surface configuration displays extraordinary performance for converting biomass-derived polyols to chemicals, with potentially much broader applications in the design of novel catalysts for several reactions of industrial relevance. The synthesis of nanostructured metal catalysts containing a large population of active surface facets is critical to achieve high activity and selectivity in catalytic reactions. Here, we describe a new strategy for synthesizing copper-based nanocatalysts on reduced graphene oxide support in which the catalytically active {111} facet is achieved as the dominant surface by lattice-match engineering. This method yields highly active Cu-graphene catalysts (turnover frequency = 33-114 mol/g atom Cu/h) for converting biopolyols (glycerol, xylitol, and sorbitol) to value-added chemicals, such as lactic acid and other useful co-products consisting of diols and linear alcohols. Palladium incorporation in the Cu-graphene system in trace amounts results in a tandem synergistic system in which the hydrogen generated in situ from polyols is used for sequential hydrogenolysis of the feedstock itself. Furthermore, the Pd addition remarkably enhances the overall stability of the nanocatalysts. The insights gained from this synthetic methodology open new vistas for exploiting graphene-based supports to develop novel and improved metal-based catalysts for a variety of heterogeneous catalytic reactions. PMID:23297693

  1. Photochemical synthesis of noble metal (Ag, Pd, Au, Pt) on graphene/ZnO multihybrid nanoarchitectures as electrocatalysis for H2O2 reduction.

    PubMed

    Gu, Hui; Yang, Yan; Tian, Jixiang; Shi, Guoyue

    2013-07-24

    For the first time, a series of noble metal (Ag, Au, Pd, and Pt) nanoparticles (NPs) based on new functional graphene were successfully achieved via UV-assisted photocatalytic reduction by ZnO nanorods. The whole preparation strategy for constructing noble metal deposited graphene sheets/ZnO (GS/ZnO) was elucidated in detail in this work. First, graphene oxide based two-dimensional carbon nanostructures served as a support to disperse ZnO nanorods through a hydrothermal route. The ZnO nanorods were self-assembled onto the surface of graphene sheets, forming GS/ZnO nanocomposite, and the graphene oxide was reduced, yielding reduced graphene sheets in this synthetic procedure. Second, the GS/ZnO films were further employed as supporting materials for the dispersion of metal nanoparticles. Photogenerated electrons from UV-irradiated ZnO were transported across GS to stepwise and respectively reduce v μL metal ions (Ag(+), Pd(2+), AuCl4(-), PtCl6(2-), 20 mg/mL) into metal (Ag, Pd, Au, Pt) NPs at a location distinct from the ZnO anchored site, forming five graphene-based hybrid nanocomposites designated as GS/ZnO, GS/ZnO@Agv, GS/ZnO@Pdv, GS/ZnO@Auv, GS/ZnO@Ptv, respectively. The obtained mutihybrid nanoarchitectured materials were clearly characterized by transmission electron microscopy (TEM) and X-ray diffraction (XRD). According to the diameters and distribution, the four metal NPs on GS/ZnO were divided into two categories: Ag&Au and Pd&Pt. Their difference was rooted in the rival abilities of gathering electron between graphene and different metal islands in the photochemical reduction process. The electrochemical behaviors of the five resultant hybrid nanocomposites were investigated in H2O2 as well as in potassium ferricyanide (Fe(CN)6(3-/4-)) and displayed distinct electrocatalytic activity. PMID:23790187

  2. Studies on mass attenuation coefficients, effective atomic numbers and electron densities for CoCuAg alloy thin film

    NASA Astrophysics Data System (ADS)

    Apaydın, G.; Cengiz, E.; Tıraşoğlu, E.; Aylıkcı, V.; Bakkaloğlu, Ö. F.

    2009-05-01

    The mass attenuation coefficients for the elements Co, Cu and Ag and a thin film of CoCuAg alloy were measured in the energy range 4.029-38.729 keV. Effective atomic numbers and electron densities were calculated by using these coefficients. The energies were obtained by using secondary targets that were irradiated with gamma-ray photons of 241Am. The x-rays were counted by using a Canberra Ultra-LEGe detector with a resolution of 150 eV at 5.9 keV. The results were compared with theoretical calculated values and fairly good agreement was found between them within an average experimental error. The mass attenuation coefficients, effective atomic numbers and electron densities were plotted versus photon energy.

  3. Experimental partitioning studies near the Fe-FeS eutectic, with an emphasis on elements important to iron meteorite chronologies (Pb, Ag, Pd, and Tl)

    NASA Technical Reports Server (NTRS)

    Jones, J. H.; Hart, S. R.; Benjamin, T. M.

    1993-01-01

    Partitioning coefficients for metal/sulfide liquid, troilite/sulfide liquid, and schreibersite/sulfide liquid were determined for Ag, Au, Mo, Ni, Pd, and Tl (using EMPA and proton-induced X-ray microprobe and ion microprobe analyses) in order to understand the chronometer systems of iron meteorites. In general, the obtained schreibersite/metal and troilite/metal partition coefficients for 'compatible' elements were quite similar to those inferred from natural assemblages, reinforcing an earlier made conclusion that there is a class of elements for which experimental troilite/metal and schreibersite/metal partition coefficients approximate those inferred from natural samples. The consistency between experimental and natural assemblages, however, was not observed for Ag, Pb, and Tl, indicating that the abundances of these elements determined in 'metal' and 'troilite' separates from iron meteorites are influenced by trace minerals that concentrate incompatible elements.

  4. Precipitation Hardening and Statistical Modeling of the Aging Parameters and Alloy Compositions in Al-Cu-Mg-Ag Alloys

    NASA Astrophysics Data System (ADS)

    Al-Obaisi, A. M.; El-Danaf, E. A.; Ragab, A. E.; Soliman, M. S.

    2016-04-01

    The addition of Ag to Al-Cu-Mg systems has been proposed to replace the existing high-strength 2xxx and 7xxx Al alloys. The aged Al-Cu-Mg-Ag alloys exhibited promising properties, due to special type of precipitates named Ω, which cooperate with other precipitates to enhance the mechanical properties significantly. In the present investigation, the effect of changing percentages of alloying elements, aging time, and aging temperature on the hardness values was studied based on a factorial design. According to this design of experiments (DOE)—23 factorial design, eight alloys were cast and hot rolled, where (Cu, Mg, and Ag) were added to aluminum with two different levels for each alloying element. These alloys were aged at different temperatures (160, 190, and 220 °C) over a wide range of time intervals from 10 min. to 64 h. The resulting hardness data were used as an input for Minitab software to model and relate the process variables with hardness through a regression analysis. Modifying the alloying elements' weight percentages to the high level enhanced the hardness of the alloy with about 40% as compared to the alloy containing the low level of all alloying elements. Through analysis of variance (ANOVA), it was figured out that altering the fraction of Cu had the greatest effect on the hardness values with a contribution of about 49%. Also, second-level interaction terms had about 21% of impact on the hardness values. Aging time, quadratic terms, and third-level interaction terms had almost the same level of influence on hardness values (about 10% contribution). Furthermore, the results have shown that small addition of Mg and Ag was enough to improve the mechanical properties of the alloy significantly. The statistical model formulated interpreted about 80% of the variation in hardness values.

  5. Growth of periodic nano-layers of nano-crystals of Au, Ag, Cu by ion beam

    NASA Technical Reports Server (NTRS)

    Smith, Cydale C.; Zheng, B.; Muntele, C. I.; Muntele, I. C.; Ila, D.

    2005-01-01

    Multilayered thin films of SiO2/AU+ SiO2/, SiO2/Ag+ SiO2/, and SiO2/Cu+ SiO2/, were grown by deposition. We have previously shown that MeV ion Bombardment of multi-nano-layers of SiO2/AU+ SiO2/ produces Au nanocrystals in the AU+ SiO2 layers. An increased number of nano-layers followed by MeV ion bombardment produces a wide optical absorption band, of which its FWHM depends on the number of nano-layers of SiO2/AU+ SiO2/. We have successfully repeated this process for nano-layers of SiO2/Ag+ SiO2/, and SiO2/Cu+ SiO2/. In this work we used 5 MeV Si as the post deposition bombardment ion and monitored the location as well as the optical absorption's FWHM for each layered structure using Optical Absorption Photospectrometry. The concentration and location of the metal nano-crystals were measured by Rutherford Backscattering Spectrometry. We will report on the results obtained for nano-layered structures produced by post deposition bombardment of SiO2/AU+ SiO2/, SiO2/Ag+ SiO2/, and SiO2/Cu+ SiO2/ layered systems as well as the results obtained from a system containing a periodic combination of SiO2/AU+ SiO2/, SiO2/Ag+ SiO2/, and SiO2/Cu+ SiO2/.

  6. Precipitation Hardening and Statistical Modeling of the Aging Parameters and Alloy Compositions in Al-Cu-Mg-Ag Alloys

    NASA Astrophysics Data System (ADS)

    Al-Obaisi, A. M.; El-Danaf, E. A.; Ragab, A. E.; Soliman, M. S.

    2016-06-01

    The addition of Ag to Al-Cu-Mg systems has been proposed to replace the existing high-strength 2xxx and 7xxx Al alloys. The aged Al-Cu-Mg-Ag alloys exhibited promising properties, due to special type of precipitates named Ω, which cooperate with other precipitates to enhance the mechanical properties significantly. In the present investigation, the effect of changing percentages of alloying elements, aging time, and aging temperature on the hardness values was studied based on a factorial design. According to this design of experiments (DOE)—23 factorial design, eight alloys were cast and hot rolled, where (Cu, Mg, and Ag) were added to aluminum with two different levels for each alloying element. These alloys were aged at different temperatures (160, 190, and 220 °C) over a wide range of time intervals from 10 min. to 64 h. The resulting hardness data were used as an input for Minitab software to model and relate the process variables with hardness through a regression analysis. Modifying the alloying elements' weight percentages to the high level enhanced the hardness of the alloy with about 40% as compared to the alloy containing the low level of all alloying elements. Through analysis of variance (ANOVA), it was figured out that altering the fraction of Cu had the greatest effect on the hardness values with a contribution of about 49%. Also, second-level interaction terms had about 21% of impact on the hardness values. Aging time, quadratic terms, and third-level interaction terms had almost the same level of influence on hardness values (about 10% contribution). Furthermore, the results have shown that small addition of Mg and Ag was enough to improve the mechanical properties of the alloy significantly. The statistical model formulated interpreted about 80% of the variation in hardness values.

  7. The creation, manipulation and evolution of nanometer-scale structures in the Ag/Cu(111) system

    NASA Astrophysics Data System (ADS)

    York, Mike; Leibsle, Fred; Goedken, Aaron

    2001-03-01

    We demonstrate how we can use scanning tunneling microscopy to create nanometer-scale pits several layers deep on Ag(111) films grown on a Cu(111) substrate. The creation of these pits is accompanied by the formation of multilayer high islands. We also demonstrate the ability to manipulate small one-layer deep pits. In addition, the evolution of the islands and pits is also studied. Images show island and pit coalescence and instances of rapid and gradual decay.

  8. Distributions of dissolved trace metals (Cd, Cu, Mn, Pb, Ag) in the southeastern Atlantic and the Southern Ocean

    NASA Astrophysics Data System (ADS)

    Boye, M.; Wake, B. D.; Lopez Garcia, P.; Bown, J.; Baker, A. R.; Achterberg, E. P.

    2012-08-01

    Comprehensive synoptic datasets (surface water down to 4000 m) of dissolved cadmium (Cd), copper (Cu), manganese (Mn), lead (Pb) and silver (Ag) are presented along a section between 34° S and 57° S in the southeastern Atlantic Ocean and the Southern Ocean to the south off South Africa. The vertical distributions of Cu and Ag display nutrient-like profiles similar to silicic acid, and of Cd similar to phosphate. The distribution of Mn shows a subsurface maximum in the oxygen minimum zone, whereas Pb concentrations are rather invariable with depth. Dry deposition of aerosols is thought to be an important source of Pb to surface waters close to South Africa, and dry deposition and snowfall may have been significant sources of Cu and Mn at the higher latitudes. Furthermore, the advection of water masses enriched in trace metals following contact with continental margins appeared to be an important source of trace elements to the surface, intermediate and deep waters in the southeastern Atlantic Ocean and the Antarctic Circumpolar Current. Hydrothermal inputs may have formed a source of trace metals to the deep waters over the Bouvet Triple Junction ridge crest, as suggested by relatively enhanced dissolved Mn concentrations. The biological utilization of Cu and Ag was proportional to that of silicic acid across the section, suggesting that diatoms formed an important control over the removal of Cu and Ag from surface waters. However, uptake by dino- and nano-flagellates may have influenced the distribution of Cu and Ag in the surface waters of the subtropical Atlantic domain. Cadmium correlated strongly with phosphate (P), yielding lower Cd / P ratios in the subtropical surface waters where phosphate concentrations were below 0.95 μM. The greater depletion of Cd relative to P observed in the Weddell Gyre compared to the Antarctic Circumpolar Current could be due to increase Cd uptake induced by iron-limiting conditions in these high-nutrient-low-chlorophyll waters

  9. Distributions of dissolved trace metals (Cd, Cu, Mn, Pb, Ag) in the southeastern Atlantic and the Southern Ocean

    NASA Astrophysics Data System (ADS)

    Boye, M.; Wake, B. D.; Lopez Garcia, P.; Bown, J.; Baker, A. R.; Achterberg, E. P.

    2012-03-01

    Comprehensive synoptic datasets (surface water down to 4000 m) of dissolved cadmium (Cd), copper (Cu), manganese (Mn), lead (Pb) and silver (Ag) are presented along a section between 34° S and 57° S in the southeastern Atlantic Ocean and the Southern Ocean to the south off South Africa. The vertical distributions of Cu, Ag, and of Cd display nutrient-like profiles similar to silicic acid, and phosphate, respectively. The distribution of Mn shows a subsurface maximum in the oxygen minimum zone, whereas Pb concentrations are rather invariable with depth. Dry deposition of aerosols is thought to be an important source of Pb to surface waters close to South Africa, and dry deposition and snowfall may have been significant sources of Cu and Mn at the higher latitudes. Furthermore, the advection of water-masses enriched in trace metals following contact with continental margins appeared to be an important source of trace elements to the surface, intermediate and deep waters in the southeastern Atlantic Ocean and the Antarctic Circumpolar Current. Hydrothermal inputs appeared to have formed a source of trace metals to the deep waters over the Bouvet Triple Junction ridge crest, as suggested by relatively enhanced dissolved Mn concentrations. The biological utilization of Cu and Ag was proportional to that of silicic acid across the section, suggesting that diatoms formed an important control over the removal of Cu and Ag from surface waters. However uptake by dino- and nano-flagelattes may have influenced the distribution of Cu and Ag in the surface waters of the subtropical Atlantic domain. Cadmium correlated strongly with phosphate (P), yielding lower Cd/P ratios in the subtropical surface waters where phosphate concentrations were below 0.95 μM. The greater depletion of Cd relative to P observed in the Weddell Gyre compared to the Antarctic Circumpolar Current could be due to increase Cd-uptake induced by iron-limiting conditions in these High-Nutrient Low

  10. Ag{sub 2}CuMnO{sub 4}: A new silver copper oxide with delafossite structure

    SciTech Connect

    Munoz-Rojas, David; Subias, Gloria; Fraxedas, Jordi; Martinez, Benjamin; Casas-Cabanas, Montse; Canales-Vazquez, Jesus; Gonzalez-Calbet, Jose; Garcia-Gonzalez, Ester; Walton, Richard I.; Casan-Pastor, Nieves . E-mail: nieves@icmab.es

    2006-12-15

    The use of hydrothermal methods has allowed the synthesis of a new silver copper mixed oxide, Ag{sub 2}CuMnO{sub 4}, the first example of a quaternary oxide containing both elements. It crystallizes with the delafossite 3R structure, thus being the first delafossite to contain both Ag and Cu. Synthesis conditions affect the final particle size (30-500nm). Powder X-ray diffraction Rietveld refinement indicates a trigonal structure (R3-bar m) and cell parameters a=2.99991A and c=18.428A, where Cu and Mn are disordered within the octahedral B positions in the plane and linearly coordinated Ag occupies de A position between layers. X-ray absorption near edge spectroscopy (XANES) for copper and manganese, and XPS for silver evidence +2, +4, and +1 oxidation states. The microstructure consists of layered parts that may form large twins showing 5nm nanodomains. Finally, magnetic measurements reveal the existence of ferromagnetic coupling yielding in-plane moments that align antiferromagnetically at lower temperatures. The singularity of the new phase resides on the fact that is an example of a bidimensional arrangement of silver and copper in an oxide that also shows clear bidimensionality in its physical properties. That is of special relevance to the field of high T{sub c} superconducting oxides, while the ferromagnetic coupling in a bidimensional system deserves itself special attention.

  11. A DFT investigation of the adsorption of iodine compounds and water in H-, Na-, Ag-, and Cu- mordenite

    NASA Astrophysics Data System (ADS)

    Chibani, Siwar; Chebbi, Mouheb; Lebègue, Sébastien; Bučko, Tomáš; Badawi, Michael

    2016-06-01

    The potential use of some cation-exchanged mordenite (H+, Na+, Cu+, and Ag+) as a selective adsorbent for volatile iodine species (ICH3 and I2), which can be released during a nuclear accident together with a steam carrier gas, is investigated using density functional theory. It is found that in the case of Cu-MOR and Ag-MOR, the absolute values of interaction energies of ICH3 and I2 are higher than that of water which indicates that these forms of zeolite could be suitable for selective adsorption of iodine species. In contrast, the H-MOR and Na-MOR are found to be unsuitable for this purpose. A systematic investigation of all adsorption sites allowed us to analyze the structural effects affecting the adsorption behavior. For the Ag-MOR and Cu-MOR zeolites, the iodine compounds are adsorbed preferentially in the large channel of mordenite (main channel) while water prefers the small channel or the side pocket where it forms stronger hydrogen bonds. The factors governing the interaction energies between the cationic sites and the different molecules are analyzed and the important role of van der Waals interactions in these systems is highlighted.

  12. The effect of Zn, Ag and Au substitution for Cu in Finemet on the crystallization and magnetic properties

    NASA Astrophysics Data System (ADS)

    Chau, N.; Hoa, N. Q.; The, N. D.; Vu, L. V.

    2006-08-01

    Soft magnetic ribbons of Finemet compound with Zn, Ag and Au substituted for Cu: Fe 73.5Si 13.5B 9Nb 3Cu 1-xM x (M=Zn, Ag, Au; x=0.5, 1.0) have been fabricated by rapid quenching technique with wheel speeds of 10, 25 and 30 m/s, respectively. The crystallization evolution of samples examined by DSC measurements showed that the high cooling rates make the ribbons in amorphous state whereas the samples with M=Zn; x=0.5, 1.0 showed to be partly crystallized when they fabricated by the wheel speed of 10 m/s. In the case of Zn ( x=0.5, 1.0) and Ag ( x=1.0) substitution there is a sharp peak in the DSC curve corresponding to crystallization of α-Fe(Si) phase. However, the role of Au is similar to that of Cu. Hysteresis loops of as-cast samples exhibited square form which relates to the pinning centers in domain wall displacement. After appropriate annealing, the ultrasoft magnetic properties of studied ribbons are obtained.

  13. Wet chemical synthesis, structural and spectroscopic studies of CuSe-Ag hierarchical sphere and drum-like microporous structure.

    PubMed

    Kumar, Pushpendra; Singh, Jai; Pandey, Mukesh Kumar

    2013-06-01

    Nanostructural self-assembly has become field of intense research activities from both fundamental and technological standpoints to understanding the mechanism of driving forces and finding artificial methods of assembling them into continuous structures without any obstructions. Various exciting and refined examples of nanostructured self-assembly are well documented. In the present manuscript the crystallization process and optical properties of self assembled CuSe-Ag hierarchical microporous sphere and drum-like structures, synthesized by wet chemical method has been investigated. Thus formed structures are accumulated by numerous polyhedral rod-like subunits, and each unit seems to be an incomplete structure of a randomly grown rod. Phase analysis, purity and morphology of the product have been well studied by X-ray diffraction (XRD), photo-luminescent spectroscopy (PL), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and high resolution transmission electron microscopy (HRTEM). Due to their microporous structures CuSe-Ag could be potential building blocks to construct functional devices like sensing and several other applications. A possible reaction mechanism for the formation of CuSe-Ag has also been proposed. PMID:23557774

  14. A DFT investigation of the adsorption of iodine compounds and water in H-, Na-, Ag-, and Cu- mordenite.

    PubMed

    Chibani, Siwar; Chebbi, Mouheb; Lebègue, Sébastien; Bučko, Tomáš; Badawi, Michael

    2016-06-28

    The potential use of some cation-exchanged mordenite (H(+), Na(+), Cu(+), and Ag(+)) as a selective adsorbent for volatile iodine species (ICH3 and I2), which can be released during a nuclear accident together with a steam carrier gas, is investigated using density functional theory. It is found that in the case of Cu-MOR and Ag-MOR, the absolute values of interaction energies of ICH3 and I2 are higher than that of water which indicates that these forms of zeolite could be suitable for selective adsorption of iodine species. In contrast, the H-MOR and Na-MOR are found to be unsuitable for this purpose. A systematic investigation of all adsorption sites allowed us to analyze the structural effects affecting the adsorption behavior. For the Ag-MOR and Cu-MOR zeolites, the iodine compounds are adsorbed preferentially in the large channel of mordenite (main channel) while water prefers the small channel or the side pocket where it forms stronger hydrogen bonds. The factors governing the interaction energies between the cationic sites and the different molecules are analyzed and the important role of van der Waals interactions in these systems is highlighted. PMID:27369531

  15. Influence of High- G Mechanical Shock and Thermal Cycling on Localized Recrystallization in Sn-Ag-Cu Solder Interconnects

    NASA Astrophysics Data System (ADS)

    Lee, Tae-Kyu; Kim, Choong-Un; Bieler, Thomas R.

    2014-01-01

    The impact of isothermal aging and recrystallized grain structure distribution on mechanical shock and thermal cycling performance of solder joints with 1% and 3% silver content Sn-Ag-Cu interconnects were investigated. Localized recrystallized grain structure distributions were analyzed to identify correlations between the microstructure evolution and shock performance. The results reveal that the shock tolerance depends on the amount of shock energy that can be absorbed during each shock cycle, which depends on microstructural features. Based on the recrystallized grain distribution, additional isothermal aging in 1% silver Sn-Ag-Cu interconnects shows improved shock performance, whereas degraded shock performance was observed in 3% Sn-Ag-Cu interconnects. Using the same grain boundary distribution analysis on thermally cycled samples, relationships between the particle size distribution, localized recrystallized grain structure development, shock, and thermomechanical performance were identified: finer particle spacing is beneficial for thermal cycling as it resists grain boundary generation, while conversely, wider particle spacing facilitates recrystallization and grain boundary mobility that allows Sn to absorb shock energy.

  16. Investigation on NOx adsorption in [M‧]-MAPO-5 (M = Si, Ti; M‧ = Ag, Cu) by density functional theory calculation

    NASA Astrophysics Data System (ADS)

    Liu, Jiexiang; Zhang, Xiaoguang

    2013-01-01

    NO, N2O and NO2 adsorption in [M‧]-MAPO-5 (M = Si, Ti; M‧ = Ag, Cu) models of the modified aluminophosphate molecular sieves was investigated by density functional theory (DFT) method. The equilibrium structural parameters and adsorption energies were obtained and compared. The structural parameters of NO and NO2 in the adsorbed state had a distinct change than that of N2O compared to their free gas state. [M‧]-MAPO-5 was more effective for the activation of NOx molecule compared to [M‧]-AlMOR (M‧ = Ag, Cu) models of the modified mordenite in our previous studies. The adsorption energies data indicated that adsorption strength of NOx followed the decreasing order of NO2 > NO > N2O. And adsorption complexes in η1-N mode were much stabler than that in η1-O mode, which was similar to that in [M‧]-AlMOR. [Cu]-MAPO-5 had a much stronger adsorption for NOx than [Ag]-MAPO-5. And [M‧]-SiMOR had a little stronger adsorption for NOx than [M‧]-TiMOR. Furthermore, the resistance capabilities of [M‧]-MAPO-5 to SO2, H2O and O2 were studied and analyzed. The interaction mechanism of NOx adsorption in [M‧]-MAPO-5 was also discussed by natural bond orbital (NBO) analysis, which was in reasonable agreement with the adsorption interaction strengths.

  17. Two-dimensional topological insulators in group-11 chalcogenide compounds: M2Te (M =Cu ,Ag )

    NASA Astrophysics Data System (ADS)

    Ma, Yandong; Kou, Liangzhi; Dai, Ying; Heine, Thomas

    2016-06-01

    Two-dimensional (2D) topological insulators (TIs) are recently recognized states of quantum matter that are highly interesting for lower-power-consuming electronic devices owing to their nondissipative transport properties protected from backscattering. So far, only few 2D TIs, suffering from small bulk band gap (<10 meV ), have been experimentally confirmed. Here, through first-principles calculations, we propose a family of 2D TIs in group-11 chalcogenide 2D crystals, M2Te (M =Cu ,Ag ) . The nontrivial topological states in C u2Te and A g2Te 2D crystals, identified by topological invariant and edge state calculations, exhibit sizeable bulk gaps of 78 and 150 meV, respectively, suggesting that they are candidates for room-temperature applications. Moreover, strain engineering leads to effective control of the nontrivial gaps of C u2Te and A g2Te , and a topological phase transition can be realized in C u2Te , while the nontrivial phase in A g2Te is stable against strain. Their dynamic and thermal stabilities are further confirmed by employing phonon calculations and ab initio molecular dynamic simulations.

  18. Dihydrogen bond interactions as a result of H2 cleavage at Cu, Ag and Au centres.

    PubMed

    Grabowski, Sławomir J; Ruipérez, Fernando

    2016-05-14

    A quantum chemical study of H2 activation at fluorides of coinage metals, MF (M = Cu, Ag and Au), and its splitting was performed. The following reaction path was analyzed: FMH2→ FHHM → HMFH, where both the molecular complexes and the corresponding transition states have been characterized at the CCSD(T)/aug-cc-pVQZ//MP2/aug-cc-pVQZ level of theory. Further single-point CASSCF/CASPT2 calculations, including spin-orbit coupling effects, were also performed to analyze the role of non-dynamic correlation. The scalar relativistic effects are included via aug-cc-pVQZ-PP basis sets used for the metals. The dihydrogen-bonded copper (FHHCu) and silver (FHHAg) complexes are observed as a result of H2 cleavage, while the corresponding FHHAu gold complex is not found but the HAuHF arrangement is observed, instead. The energetic and geometrical parameters of the complexes have been analyzed and both the Quantum Theory of Atoms in Molecules approach and the Natural Bond Orbitals method were additionally applied to analyze the intermolecular interactions. PMID:27101741

  19. Ternary eutectic growth of Ag-Cu-Sb alloy within ultrasonic field

    NASA Astrophysics Data System (ADS)

    Zhai, Wei; Hong, Zhenyu; Wei, Bingbo

    2007-08-01

    The liquid to solid transformation of ternary Ag42.4Cu21.6Sb36 eutectic alloy was accomplished in an ultrasonic field with a frequency of 35 kHz, and the growth mechanism of this ternary eutectic was examined. Theoretical calculations predict that the sound intensity in the liquid phase at the solidification interface increases gradually as the interface moves up from the sample bottom to its top. The growth mode of ( ɛ + θ + Sb) ternary eutectic exhibits a transition of “divorced eutectic—mixture of anomalous and regular structures—regular eutectic” along the sample axis due to the inhomogeneity of sound field distribution. In the top zone with the highest sound intensity, the cavitation effect promotes the three eutectic phases to nucleate independently, while the acoustic streaming efficiently suppresses the coupled growth of eutectic phases. In the meantime, the ultrasonic field accelerates the solute transportation at the solid-liquid interface, which reduces the solute solubility of eutectic phases.

  20. Electronic structure and conductivity of nanocomposite metal (Au,Ag,Cu,Mo)-containing amorphous carbon films

    SciTech Connect

    Endrino, Jose L.; Horwat, David; Gago, Raul; Andersson, Joakim; Liu, Y.S.; Guo, Jinghua; Anders, Andre

    2008-05-14

    In this work, we study the influence of the incorporation of different metals (Me = Au, Ag, Cu, Mo) on the electronic structure of amorphous carbon (a-C:Me) films. The films were produced at room temperature using a novel pulsed dual-cathode arc deposition technique. Compositional analysis was performed with secondary neutral mass spectroscopy whereas X-ray diffraction was used to identify the formation of metal nanoclusters in the carbon matrix. The metal content incorporated in the nanocomposite films induces a drastic increase in the conductivity, in parallel with a decrease in the band gap corrected from Urbach energy. The electronic structure as a function of the Me content has been monitored by x-ray absorption near edge structure (XANES) at the C K-edge. XANES showed that the C host matrix has a dominant graphitic character and that it is not affected significantly by the incorporation of metal impurities, except for the case of Mo, where the modifications in the lineshape spectra indicated the formation of a carbide phase. Subtle modifications of the spectral lineshape are discussed in terms of nanocomposite formation.

  1. Chemical elements diffusion in the stainless steel components brazed with Cu-Ag alloy

    NASA Astrophysics Data System (ADS)

    Voiculescu, I.; Geanta, V.; Vasile, I. M.; Binchiciu, E. F.; Winestoock, R.

    2016-06-01

    The paper presents the study of diffusion of chemical elements through a brazing joint, between two thin components (0.5mm) made of stainless steel 304. An experimental brazing filler material has been used for brazing stainless steel component and then the diffusion phenomenon has been studied, in terms of chemical element displacement from the brazed separation interface. The filler material is in the form of a metal rod coated with ceramic slurry mixture of minerals, containing precursors and metallic powders, which can contribute to the formation of deposit brazed. In determining the distance of diffusion of chemical elements, on both sides of the fusion line, were performed measurements of the chemical composition using electron microscopy SEM and EDX spectrometry. Metallographic analysis of cross sections was performed with the aim of highlight the microstructural characteristics of brazed joints, for estimate the wetting capacity, adherence of filler metal and highlight any imperfections. Analyzes performed showed the penetration of alloying elements from the solder (Ag, Cu, Zn and Sn) towards the base material (stainless steel), over distances up to 60 microns.

  2. Synthesis and thermal behavior of tin-based alloy (Sn-Ag-Cu) nanoparticles.

    PubMed

    Roshanghias, Ali; Yakymovych, Andriy; Bernardi, Johannes; Ipser, Herbert

    2015-03-19

    The prominent melting point depression of nanoparticles has been the subject of a considerable amount of research. For their promising applications in electronics, tin-based nano-alloys such as near-eutectic Sn-Ag-Cu (SAC) alloys have been synthesized via various techniques. However, due to issues such as particle aggregation and oxidation or introduced impurities, the application of these nano-size particles has been confined or aborted. For instance, thermal investigations by DTA/DSC in a large number of studies revealed exothermic peaks in the range of 240-500 °C, i.e. above the melting point of SAC nanoparticles, with different and quite controversial explanations for this unclear phenomenon. This represents a considerable drawback for the application of nanoparticles. Correspondingly, in the current study, the thermal stability of SAC nanoparticles has been investigated via electron microscopy, XRD, FTIR, and DSC/TG analysis. It was found that the nanoparticles consist mainly of a metallic β-Sn core and an amorphous tin hydroxide shell structure. The SnO crystalline phase formation from this amorphous shell has been associated with the exothermic peaks on the first heating cycle of the nanoparticles, followed by a disproportionation reaction into metallic Sn and SnO₂.The results also revealed that the surfactant and reducing agent cannot only affect the size and size distribution of the nanoparticles, they might also alter the ratio between the amorphous shell and the crystalline core in the structure of particles. PMID:25757694

  3. Authenticity determination of Ag-Cu Lebanese coins using combined PIXE and RBS techniques

    NASA Astrophysics Data System (ADS)

    Roumie, M.; Nsouli, B.; Assafiri, Y.

    2012-07-01

    A set of silver-copper coins were investigated for their stochiometry in order to check any possible counterfeit. The studied coins are 50 Lebanese Piastres and are relatively recent, minted in 1952. They are supposed to have nominal concentration of 60 wt.% Ag and 40 wt.% Cu. In this work, it is shown the utility and capability of combining PIXE (particle induced X-ray emission) and RBS (Rutherford backscattering spectrometry) techniques to determine the elemental content and check the presence, if any, of surface layer. For this aim, 3 MeV proton beam and Al funny filter, used as x-ray absorber, were used to determine the elemental composition, based on the emission and detection of the characteristic x-rays of the corresponding elements. The first PIXE results of the supposed bulky coins showed an excess of silver composition vs. copper. In addition, the experimental protocol was checked by analyzing some other coins of known composition, such as 1-euro and 2-euro coins.

  4. Alkali and transition metal (Ag, Cu) salts of bridged 5-nitrotetrazole derivatives for energetic applications.

    PubMed

    Klapötke, Thomas M; Sabaté, Carles Miró; Rasp, Matthias

    2009-03-14

    A family of energetic salts based on the novel 5-(5-nitrotetrazole-2-ylmethyl)-tetrazolate anion (NTTz(-)) with alkali metals (Li(+), Na(+), K(+), Rb(+) and Cs(+)) were synthesized by the reaction of the free acid 5-(5-nitrotetrazole-2-ylmethyl)-tetrazole with a suitable alkali metal base (bicarbonate or carbonate) in alcohol or water. The sodium salt () was, in turn, used to form salts containing the NTTz(-) anion and Ag(+) () or Cu(2+) (, and ) cations. The new compounds were characterized by IR, Raman and NMR spectroscopy, mass spectroscopy, elemental analysis and differential scanning calorimetry (DSC). In addition, the solid-state structure of the NTTz(-) anion was determined by diffraction methods using X-ray analysis. We also assessed the energetic properties of the compounds using standardized (BAM) tests. Interestingly, the silver and copper salts are easily and safely initiated by the laser beam generated by a Raman machine and some of the compounds reported here have promising properties for applications as a new class of nitrogen-rich, more environmentally-friendly energetic materials. PMID:19240918

  5. Dehydrocyclization of peripheral alkyl groups in porphyrins at Cu(100) and Ag(111) surfaces

    NASA Astrophysics Data System (ADS)

    Williams, Christopher G.; Wang, Miao; Skomski, Daniel; Tempas, Christopher D.; Kesmodel, Larry L.; Tait, Steven L.

    2016-11-01

    The self-assembly of organic and metal-organic species at metal surfaces is a topic of high interest for applications that can benefit from tunable surface functionalization through organic building block design. As the complexity of molecular building blocks increases to direct ordering and function, thermal stability of the adsorbate often increases opening up new surface-catalyzed reaction pathways. We report dehydrocyclization of octaethylporphyrin to tetrabenzoporphyrin on the Cu(100) and Ag(111) surfaces at 500-600 K. Dehydrocyclization of smaller species is not typically observed on these surfaces at low pressure due to short adsorption lifetimes. The dehydrocyclization of peripheral ethyl groups forms benzo groups which then undergo additional dehydrogenation. The reaction products are characterized by high resolution electron energy loss spectroscopy (HREELS), scanning tunneling microscopy (STM), and X-ray photoelectron spectroscopy (XPS). These results extend our understanding of reaction pathways that may be encountered as molecular building blocks increase in size and complexity on relatively inert surfaces.

  6. Effect of Board Thickness on Sn-Ag-Cu Joint Interconnect Mechanical Shock Performance

    NASA Astrophysics Data System (ADS)

    Lee, Tae-Kyu; Xie, Weidong

    2014-12-01

    The mechanical stability of solder joints with Sn-Ag-Cu alloy joints on various board thicknesses was investigated with a high G level shock environment. A test vehicle with three different board thicknesses was used for board drop shock performance tests. These vehicles have three different strain and shock level condition couples per board, and are used to identify the joint stability and failure modes based on the board responses. The results revealed that joint stability is sensitive to board thickness. The board drop shock test showed that the first failure location shifts from the corner location near the standoff to the center with increased board thickness due to the shock wave response. From analysis of the thickness variation and failure cycle number, the strain rate during the pulse strain cycle is the dominant factor, which defines the life cycle number per board thickness, and not the maximum strain value. The failure location shift and the shock performance differentiation are discussed from the perspective of maximum principal strain, cycle frequency and strain rate per cycle.

  7. Thermal Cycling Reliability of Sn-Ag-Cu Solder Interconnections. Part 1: Effects of Test Parameters

    NASA Astrophysics Data System (ADS)

    Hokka, Jussi; Mattila, Toni. T.; Xu, Hongbo; Paulasto-Kröckel, Mervi

    2013-06-01

    The work presented in part 1 of this study focuses on identifying the effects of thermal cycling test parameters on the lifetime of ball grid array (BGA) component boards. Detailed understanding about the effects of the thermal cycling parameters is essential because it provides means to develop more efficient and meaningful methods of reliability assessment for electronic products. The study was carried out with a single package type (BGA with 144 solder balls), printed wiring board (eight-layer build-up FR4 structure), and solder interconnection composition (Sn-3.1Ag-0.5Cu) to ensure that individual test results would be comparable with each other. The effects of (i) temperature difference (Δ T), (ii) lower dwell temperature and lower dwell time, (iii) mean temperature, (iv) dwell time, and (v) ramp rate were evaluated. Based on the characteristic lifetimes, the thermal cycling profiles were categorized into three lifetime groups: (i) highly accelerated conditions, (ii) moderately accelerated conditions, and (iii) mildly/nonaccelerated conditions. Thus, one might be tempted to use the highly accelerated conditions to produce lifetime statistics as quickly as possible. However, to do this one needs to know that the failure mechanisms do not change from one lifetime group to another and that the failure mechanisms correlate with real-use failures. Therefore, in part 2 the observed differences in component board lifetimes will be explained by studying the failure mechanisms that take place in the three lifetime groups.

  8. A bamboo-inspired hierarchical nanoarchitecture of Ag/CuO/TiO2 nanotube array for highly photocatalytic degradation of 2,4-dinitrophenol.

    PubMed

    Zhang, Xuhong; Wang, Longlu; Liu, Chengbin; Ding, Yangbin; Zhang, Shuqu; Zeng, Yunxiong; Liu, Yutang; Luo, Shenglian

    2016-08-01

    The optimized geometrical configuration of muitiple active materials into hierarchical nanoarchitecture is essential for the creation of photocatalytic degradation system that can mimic natural photosynthesis. A bamboo-like architecture, CuO nanosheets and Ag nanoparticles co-decorated TiO2 nanotube arrays (Ag/CuO/TiO2), was fabricated by using simple solution-immersion and electrodeposition process. Under simulated solar light irradiation, the 2,4-dinitrophenol (2,4-DNP) photocatalytic degradation rate over Ag/CuO/TiO2 was about 2.0, 1.5 and 1.2 times that over TiO2 nanotubes, CuO/TiO2 and Ag/TiO2, respectively. The enhanced photocatalytic activity of ternary Ag/CuO/TiO2 photocatalyst was ascribed to improved light absorption, reduced carrier recombination and more exposed active sites. Moreover, the excellent stability and reliability of the Ag/CuO/TiO2 photocatalyst demonstrated a promising application for organic pollutant removal from water. PMID:27107324

  9. Effect of Graphene Nanoplatelets on Wetting, Microstructure, and Tensile Characteristics of Sn-3.0Ag-0.5Cu (SAC) Alloy

    NASA Astrophysics Data System (ADS)

    Sharma, Ashutosh; Sohn, Heung-Rak; Jung, Jae Pil

    2016-01-01

    The effect of graphene nanoplatelets (GNPs) on the wettability, microstructure, and tensile properties of Sn-3.0Ag-0.5Cu (SAC 305) was studied using melting and casting route. The microstructure of the bulk solder is observed with a scanning electron microscope and transmission electron microscope, and the intermetallic compound (IMC) phases are identified by electron probe micro-analyzer. The solderability of the samples is assessed by spreading and wetting tests on a Cu substrate. The experimental results indicate that an addition of 0.05 wt pct GNPs in Sn-3Ag-0.5Cu solder improves the spreading and wettability significantly compared to monolithic SAC. It is also revealed that the thickness of the Ag3Sn IMCs is reduced as compared to the monolithic SAC alloy. Tensile results show that the composite solder exhibits the 13.9 pct elongation and 17 pct increase in the ultimate tensile strength when 0.05 wt pct GNPs in Sn-3Ag-0.5Cu alloy are added. This may be due to the refinement of the IMCs in composite solders compared to the same in Sn-3Ag-0.5Cu alloy brought about by the uniform dispersion of graphene nanoplatelets. It is suggested in this study that the amount of GNPs in Sn-3Ag-0.5Cu alloy should not exceed 0.05 wt pct as it may degrade the desired properties due to the agglomeration of GNPs.

  10. Catalytic reduction of nitrate in secondary effluent of wastewater treatment plants by Fe(0) and Pd-Cu/γ-Al2O3.

    PubMed

    Yun, Yupan; Li, Zifu; Chen, Yi-Hung; Saino, Mayiani; Cheng, Shikun; Zheng, Lei

    2016-01-01

    Total nitrogen, in which NO3(-) is dominant in the effluent of most wastewater treatment plants, cannot meet the requirements of the Chinese wastewater discharge standard (<15 mg/L), making nitrate (NO3(-)) elimination attract considerable attention. In this study, reductant iron (Fe(0)) and γ-Al2O3 supported palladium-copper bimetallic catalysts (Pd-Cu/γ-Al2O3) were innovatively used for the chemical catalytic reduction of nitrate in wastewater. A series of specific operational conditions (such as mass ratio of Pd:Cu, catalyst amounts, reaction time and pH of solution) were optimized for nitrate reduction in the artificial solution, and then the selected optimal conditions were further applied for investigating the nitrate elimination of secondary effluent of a wastewater treatment plant in Beijing, China. Results indicated that a better catalytic performance (74% of nitrate removal and 62% of N2 selectivity) could be obtained under the optimal condition: 5 g/L Fe(0), 3:1 mass ratio (Pd:Cu), 4 g/L catalyst, 2 h reaction time and pH 5.1. It is noteworthy to point out that nitrogen gas (N2) predominated in the byproducts without another system to treat ammonium and nitrite. Therefore, the chemical catalytic reduction combining Fe(0) with Pd-Cu/γ-Al2O3 could be regarded as a better alternative for nitrate removal in wastewater treatment. PMID:27232406

  11. Development of Sn-Ag-Cu-X Solders for Electronic Assembly by Micro-Alloying with Al

    SciTech Connect

    Boesenberg, Adam; Anderson, Iver; Harringa, Joel

    2012-03-10

    Of Pb-free solder choices, an array of solder alloys based on the Sn-Ag-Cu (SAC) ternary eutectic (T eut = 217°C) composition have emerged with potential for broad use, including ball grid array (BGA) joints that cool slowly. This work investigated minor substitutional additions of Al (<0.25 wt.%) to Sn-3.5Ag-0.95Cu (SAC3595) solders to promote more consistent solder joint microstructures and to avoid deleterious product phases, e.g., Ag3Sn “blades,” for BGA cooling rates, since such Al additions to SAC had already demonstrated excellent thermal aging stability. Consistent with past work, blade formation was suppressed for increased Al content (>0.05Al), but the suppression effect faded for >0.20Al. Undercooling suppression did not correlate specifically with blade suppression since it became significant at 0.10Al and increased continuously with greater Al to 0.25Al. Surprisingly, an intermediate range of Al content (0.10 wt.% to 0.20 wt.% Al) promoted formation of significant populations of 2-μm to 5-μm faceted Cu-Al particles, identified as Cu33Al17, that clustered at the top of the solder joint matrix and exhibited extraordinary hardness. Clustering of Cu33Al17 was attributed to its buoyancy, from a lower density than Sn liquid, and its early position in the nucleation sequence within the solder matrix, permitting unrestricted migration to the top interface. Joint microstructures and implications for the full nucleation sequence for these SAC + Al solder joints are discussed, along with possible benefits from the clustered particles for improved thermal cycling resistance.

  12. Elastic properties of Pd40Cu30Ni10P20 bulk glass in supercooled liquid region

    NASA Astrophysics Data System (ADS)

    Nishiyama, N.; Inoue, A.; Jiang, J. Z.

    2001-04-01

    In situ ultrasonic measurements for the Pd40Cu30Ni10P20 bulk glass in three states: Glassy solid, supercooled liquid, and crystalline, have been performed. It is found that velocities of both longitudinal and transverse waves and elastic moduli (shear modulus, bulk modulus, Young's modulus, and Lamé parameter), together with Debye temperature, gradually decrease with increasing temperature through the glass transition temperature as the Poisson's ratio increases. The behavior of the velocity of transverse wave vs. temperature in the supercooled liquid region could be explained by viscosity flow, rather than the two different crystallization processes in the region, suggested in the literature. No decomposition was detected at a temperature only 5 K below the crystallization temperature.

  13. Surface segregation in a polycrystalline Pd70Cu30 alloy hydrogen purification membrane

    SciTech Connect

    Miller, James B.; Matranga, Christopher; Gellman, Andrew J.

    2008-01-01

    X-ray photoelectron spectroscopy (XPS) and low energy ion scattering spectroscopy (LEISS) have been used to study the effects of various surface preparations and thermal treatments on the composition of the near-surface region (~7 atomic layers) and the topmost atomic layer of a polycrystalline Pd70Cu30 alloy. Palladium enrichment (relative to the bulk composition) is observed in the XPS-accessible near-surface region, but copper enrichment is observed in the topmost atomic layer. At temperatures above similar to 800 K, where the bulk, the near-surface region and the topmost atomic layer are likely in thermodynamic equilibrium, segregation to the top layer can be described in terms of a simple thermodynamic model. Temperature programmed desorption (TPD) of H2 and CO from the annealed surfaces illustrates the impact of segregation and atomic distribution in the top layer on surface chemical activity.

  14. Internally consistent database for sulfides and sulfosalts in the system Ag 2S-Cu 2S-ZnS-Sb 2S 3-As 2S 3

    NASA Astrophysics Data System (ADS)

    Sack, Richard O.

    2000-11-01

    An updated thermodynamic database for Ag 2S-Cu 2S-ZnS-Sb 2S 3-As 2S 3 sulfides and sulfosalts applicable to temperatures above 119°C is developed to calculate phase relations for polybasite-pearceite- and fahlore-bearing assemblages. It is based on pre-existing and new constraints on activity-composition, Ag-Cu and As-Sb partitioning, and other relations, and on experiments (200-300°C, evacuated silica tubes) conducted to define the stability of the polybasite-pearceite [(Ag 1- x,Cu x) 16(Sb 1- y,As y) 2S 11] + ZnS sphalerite assemblage with respect to assemblages containing (Ag,Cu) 2S sulfides coexisting with (Cu, Ag) 10Zn 2(Sb,As) 4S 13 fahlore sulfosalts. It was found that the thermodynamics of mixing of bcc- and hcp-(Ag,Cu) 2S solutions, which are fast-ion conductors, may be described by using site multiplicities of metals α Ag,Cu > 2 and temperature-dependent regular solution parameters. We obtained estimates for the Gibbs energies of formation for Ag 16Sb 2S 11 and Cu 16Sb 2S 11 polybasite endmembers from the simple sulfides (Ag 2S, Cu 2S, and Sb 2S 3) of -30.79 and -4.07 kJ/gfw at 200°C, and -32.04 and -0.59 kJ/gfw at 400°C, respectively, that are about one half kJ/gfw more positive and about 6 kJ/gfw more negative than those estimated by Harlov and Sack (1995b). The corresponding estimates for formation energies of Ag 10Zn 2Sb 4S 13 and Cu 10Zn 2Sb 4S 13 fahlores (-20.29 and -105.29 kJ/gfw at 200°C and -23.72 and -105.76 kJ/gfw at 400°C) are comparable to, and roughly 110 kJ/gfw more positive than, the corresponding estimates of Ebel and Sack (1994). We also determined that the Gibbs energies of the As-Sb exchange reactions: 1/4Ag 10Zn2Sb4S13+1/2Ag 16As2S11=1/2Ag 16Sb2S11+1/4Ag 10Zn2As4S13Sb-fahlorepearceitepolybasiteAs-fahlore and Ag3SbS3+1/2Ag 16As2S11=1/2Ag 16Sb2S11+Ag3AsS3pyrargyritepearceitepolybasiteproustite are, respectively, 8.75 and 0.40 kJ/gfw in the range 150-350°C, and these predictions are consistent with As-Sb partitioning relations

  15. Nonlinear optical properties and surface-plasmon enhanced optical limiting in Ag-Cu nanoclusters co-doped in SiO{sub 2} Sol-Gel films

    SciTech Connect

    Kiran, P. Prem; Shivakiran Bhaktha, B.N.; Rao, D. Narayana; De, Goutam

    2004-12-01

    The nonlinear optical properties and the role of the surface-plasmon resonance (SPR) on optical limiting (OL) properties of Ag-Cu nanoclusters co-doped in SiO{sub 2} matrix prepared using the sol-gel technique with a Cu/Ag molar ratio of 1, 2 and 3, respectively, are presented. The studies were made using the second harmonic of high-power nanosecond and picosecond Nd:YAG lasers. These films show a self-defocusing nonlinearity with both nanosecond and picosecond pulses and a good nonlinear absorption behavior with the nanosecond pulse excitation. The nonlinear refractive index decreased with decreasing particle size, whereas the nonlinear absorption increased with an increase in Cu concentration. The observed nonlinear absorption is explained by taking into account the cumulative effect of both the intraband and interband mechanisms. The excitation near the SPR of Cu resulted in an enhanced OL behavior with increasing Cu concentration. No such concentration dependence is observed when the excitation is near the SPR of Ag, however, the limiting threshold is reduced approximately 10-17 times. Excitation at wavelengths far below the SPR of Ag and Cu has not shown any OL behavior. The major contribution toward OL is observed to be from the interband absorption and from a possible energy transfer within the higher unoccupied states of Cu and Ag. Although nonlinear scattering is observed at higher intensities, its contribution is found to be much less than that of the nonlinear absorption assisted by an energy transfer.

  16. Transient Liquid Phase Diffusion Bonding of 6061Al-15 wt.% SiC p Composite Using Mixed Cu-Ag Powder Interlayer

    NASA Astrophysics Data System (ADS)

    Roy, Pallab; Pal, Tapan Kumar; Maity, Joydeep

    2016-06-01

    Microstructure and shear strength of transient liquid phase diffusion bonded (560 °C, 0.2 MPa) 6061Al-15 wt.% SiCp extruded composite using a 50-µm-thick mixed Cu-Ag powder interlayer have been investigated. During isothermal solidification that took 2 h for completion, a ternary liquid phase formed due to diffusion of Cu and Ag in Al. Subsequent cooling formed a ternary phase mixture (α-Al + CuAl2 + Ag2Al) upon eutectic solidification. With mixed Cu-Ag powder interlayer, isothermal solidification was faster than for pure Al joints made using a 50-µm-thick Cu foil interlayer and for the composite joints made using a 50-µm-thick Cu foil/powder interlayer under similar conditions. The presence of brittle eutectic phase mixture (CuAl2 + Ag2Al) led to poor joint strength at short TLP bonding times. The mixture disappeared upon isothermal solidification with a 2-h hold yielding improved joint strength even with solidification shrinkage in the joint. Increased holding time (6 h) erased shrinkage via solid state diffusion and yielded the highest joint strength (87 MPa) and fair joint efficiency (83%).

  17. Shear and Pull Testing of Sn-3.0Ag-0.5Cu Solder with Ti/Ni(V)/Cu Underbump Metallization During Aging

    NASA Astrophysics Data System (ADS)

    Wang, Kai-Jheng; Duh, Jenq-Gong

    2009-12-01

    Ti/Ni(V)/Cu underbump metallization (UBM) is widely used in flip-chip technology today. The advantages of Ti/Ni(V)/Cu UBM are a low reaction rate with solder and the lack of a magnetic effect during sputtering. Sn atoms diffuse into the Ni(V) layer to form a Sn-rich phase, the so-called Sn-patch, during reflow and aging. In this study, the relationship between interfacial reaction and mechanical properties of the solder joints with Ti/Ni(V)/Cu UBM was evaluated. Sn-3.0Ag-0.5Cu solder was reflowed on sputtered Ti/Ni(V)/Cu UBM, and then the reflowed samples were aged at 125°C and 200°C, respectively. (Cu,Ni)6Sn5 was formed and grew gradually at the interface of the solder joints during aging at 125°C. The Sn-patch replaced the Ni(V) layer, and (Ni,Cu)3Sn4 was thus formed between (Cu,Ni)6Sn5 and the Sn-patch at 200°C. The Sn-patch, composed of Ni and V2Sn3 after reflow, was transformed to V2Sn3 and amorphous Sn during aging. Shear and pull tests were applied to evaluate the solder joints under various heat treatments. The shear force of the solder joints remained at 421 mN, yet the pull force decreased after aging at 125°C. Both the shear and pull forces of the solder joints decreased during aging at 200°C. The effects of aging temperature on the mechanical properties of solder joint were investigated and discussed.

  18. Effect of a prior stretch on the aging response of an Al-Cu-Li-Ag-Mg-Zr alloy

    NASA Technical Reports Server (NTRS)

    Kumar, K. S.; Brown, S. A.; Pickens, Joseph R.

    1991-01-01

    Recently, a family of Al-Cu-Li alloys containing minor amounts of Ag, Mg, and Zr and having desirable combinations of strength and toughness were developed. The Weldalite (trademark) alloys exhibit a unique characteristic in that with or without a prior stretch, they obtain significant strength-ductility combinations upon natural and artificial aging. The ultra-high strength (approximately 690 MPa yield strength) in the peak-aged tempers (T6 and T8) were primarily attributed to the extremely fine T(sub 1) (Al2CuLi) or T(sub 1)-type precipitates that occur in these alloys during artificial aging, whereas the significant natural aging response observed is attributed to strengthening from delta prime (Al3Li) and GP zones. In recent work, the aging behavior of an Al-Cu-Li-Ag-Mg alloy without a prior stretch was followed microstructurally from the T4 to the T6 condition. Commercial extrusions, rolled plates, and sheets of Al-Cu-Li alloys are typically subjected to a stretching operation before artificial aging to straighten the extrusions and, more importantly, introduce dislocations to simulate precipitation of strengthening phases such as T(sub 1) by providing relatively low-energy nucleation sites. The goals of this study are to examine the microstructure that evolves during aging of an alloy that was stretch after solution treatment and to compare the observations with those for the unstretched alloy.

  19. Synthesis of {beta}-phase Ag{sub 1-x}Cu{sub x}I (x = 0-0.5) solid solutions nanocrystals

    SciTech Connect

    Liu, Xianli; Zhang, Jinghong; Zhang, Guilan; Jiang, Zhonghao; Jin, Dezhen

    2011-06-15

    Research highlights: {yields} Wet-chemical-chelating reaction processing has been used to synthesized A series of single {beta}-phase nano-Ag{sub 1-x}Cu{sub x}I (x = 0-0.5) solid solutions powders. {yields} Citric acid as complexing agent takes part in the process of chemical reaction and the chemical reactions can be described in this paper. {yields} The lattice parameters have been ascertained by the results of XRD. {yields} Crystalline sizes, which decrease with copper iodide concentration increasing, have been demonstrated by XRD and TEM. -- Abstract: A series of single {beta}-phase nano-Ag{sub 1-x}Cu{sub x}I (x = 0-0.5) solid solutions powders were synthesized by wet-chemical-chelating reaction processing and citric acid used as complexing agent. The Ag{sub 1-x}Cu{sub x}I powders were determined by X-ray diffraction and transmission electron microscopy. It was demonstrated that the crystalline size and lattice parameter of the Ag{sub 1-x}Cu{sub x}I powders decrease with an increase in the amount of CuI substitution. The copper in the lattice of the Ag{sub 1-x}Cu{sub x}I can effectively prevent the crystalline growth of the Ag{sub 1-x}Cu{sub x}I powders and citrate used in the Ag{sub 1-x}Cu{sub x}I powders synthesized process can accelerate single {beta}-phase crystalline structure formation.

  20. Time-temperature-transformation diagram and microstructures of bulk glass forming Pd{sub 40}Cu{sub 30}Ni{sub 10}P{sub 20}

    SciTech Connect

    Loeffler, Joerg F.; Schroers, Jan; Johnson, William L.

    2000-07-31

    Isothermal crystallization studies were performed on the bulk glass forming alloy Pd{sub 40}Cu{sub 30}Ni{sub 10}P{sub 20} in the undercooled liquid region between the glass transition and liquidus temperature, resulting in a complete time-temperature-transformation (TTT) diagram for crystallization. The TTT diagram shows a typical ''C'' shape with the nose at 50 s and 680 K. Assuming steady state nucleation and a diffusion-controlled growth rate, the TTT diagram was successfully fit over the entire range of the measurement. The microstructure after isothermal crystallization shows a modulation in Cu and P for all degrees of undercooling. The primary solidified phase is Cu{sub 3}Pd, which forms distinct dendrites at low undercooling. From additional constant cooling experiments, the critical cooling rate to bypass crystallization was determined to be 0.33 K/s. (c) 2000 American Institute of Physics.