Reflectance properties of one-dimensional metal-dielectric ternary photonic crystal

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

Pandey, G. N., E-mail: gnpandey2009@gmail.com; Kumar, Narendra; Thapa, Khem B.

2016-05-06

Metallic photonic crystal has a very important application in absorption enhancement in solar cells. It has been found that an ultra-thin metallic layer becomes transparent due to internal scattering of light through the each interface of the dielectric and metal surfaces. The metal has absorption due to their surface plasmon and the plasmon has important parameters for changing optical properties of the metal. We consider ternary metallic-dielectric photonic crystal (MDPC) for having large probabilities to change the optical properties of the MDPC and the photonic crystals may be changed by changing dimensionality, symmetry, lattice parameters, Filling fraction and effective refractivemore » index refractive index contrast. In this present communication, we try to show that the photonic band gap in ternary metal-dielectric photonic crystal can be significantly enlarged when air dielectric constant is considered. All the theoretical analyses are made based on the transfer matrix method together with the Drude model of metal.« less

Work Function of Oxide Ultrathin Films on the Ag(100) Surface.

PubMed

Sementa, Luca; Barcaro, Giovanni; Negreiros, Fabio R; Thomas, Iorwerth O; Netzer, Falko P; Ferrari, Anna Maria; Fortunelli, Alessandro

2012-02-14

Theoretical calculations of the work function of monolayer (ML) and bilayer (BL) oxide films on the Ag(100) surface are reported and analyzed as a function of the nature of the oxide for first-row transition metals. The contributions due to charge compression, charge transfer and rumpling are singled out. It is found that the presence of empty d-orbitals in the oxide metal can entail a charge flow from the Ag(100) surface to the oxide film which counteracts the decrease in the work function due to charge compression. This flow can also depend on the thickness of the film and be reduced in passing from ML to BL systems. A regular trend is observed along first-row transition metals, exhibiting a maximum for CuO, in which the charge flow to the oxide is so strong as to reverse the direction of rumpling. A simple protocol to estimate separately the contribution due to charge compression is discussed, and the difference between the work function of the bare metal surface and a Pauling-like electronegativity of the free oxide slabs is used as a descriptor quantity to predict the direction of charge transfer.

Dispersion relation of a surface wave at a rough metal-air interface

DOE PAGES

Kotelnikov, Igor; Stupakov, Gennady

2016-11-28

Here, we derived a dispersion relation of a surface wave at a rough metal-air interface. In contrast to previous publications, we assumed that an intrinsic surface impedance due to a finite electric conductivity of the metal can be of the same order as the roughness-induced impedance. We then applied our results to the analysis of a long-standing problem of the discrepancy between the experimental data on the propagation of surface waves in the terahertz range of frequencies and the classical Drude theory.

Mesoporous metallic rhodium nanoparticles

NASA Astrophysics Data System (ADS)

Jiang, Bo; Li, Cuiling; Dag, Ömer; Abe, Hideki; Takei, Toshiaki; Imai, Tsubasa; Hossain, Md. Shahriar A.; Islam, Md. Tofazzal; Wood, Kathleen; Henzie, Joel; Yamauchi, Yusuke

2017-05-01

Mesoporous noble metals are an emerging class of cutting-edge nanostructured catalysts due to their abundant exposed active sites and highly accessible surfaces. Although various noble metal (e.g. Pt, Pd and Au) structures have been synthesized by hard- and soft-templating methods, mesoporous rhodium (Rh) nanoparticles have never been generated via chemical reduction, in part due to the relatively high surface energy of rhodium (Rh) metal. Here we describe a simple, scalable route to generate mesoporous Rh by chemical reduction on polymeric micelle templates [poly(ethylene oxide)-b-poly(methyl methacrylate) (PEO-b-PMMA)]. The mesoporous Rh nanoparticles exhibited a ~2.6 times enhancement for the electrocatalytic oxidation of methanol compared to commercially available Rh catalyst. Surprisingly, the high surface area mesoporous structure of the Rh catalyst was thermally stable up to 400 °C. The combination of high surface area and thermal stability also enables superior catalytic activity for the remediation of nitric oxide (NO) in lean-burn exhaust containing high concentrations of O2.

In-situ Generated Tribomaterial in Metal/Metal Contacts: current understanding and future implications for implants.

PubMed

Espallargas, N; Fischer, A; Muñoz, A Igual; Mischler, S; Wimmer, M A

2017-06-01

Artificial hip joints operate in aqueous biofluids that are highly reactive towards metallic surfaces. The reactivity at the metal interface is enhanced by mechanical interaction due to friction, which can change the near-surface structure of the metal and surface chemistry. There are now several reports in the literature about the in-situ generation of reaction films and tribo-metallurgical transformations on metal-on-metal hip joints. This paper summarizes current knowledge and provides a mechanistic interpretation of the surface chemical and metallurgical phenomena. Basic concepts of corrosion and wear are illustrated and used to interpret available literature on in-vitro and in-vivo studies of metal-on-metal hip joints. Based on this review, three forms of tribomaterial, characterized by different combinations of oxide films and organic layers, can be determined. It is shown that the generation of these tribofilms can be related to specific electrochemical and mechanical phenomena in the metal interface. It is suggested that the generation of this surface reaction layer constitutes a way to minimize (mechanical) wear of MoM hip implants.

In-situ Generated Tribomaterial in Metal/Metal Contacts: current understanding and future implications for implants

PubMed Central

Espallargas, N.; Fischer, A.; Muñoz, A. Igual; Mischler, S.; Wimmer, M.A.

2017-01-01

Artificial hip joints operate in aqueous biofluids that are highly reactive towards metallic surfaces. The reactivity at the metal interface is enhanced by mechanical interaction due to friction, which can change the near-surface structure of the metal and surface chemistry. There are now several reports in the literature about the in-situ generation of reaction films and tribo-metallurgical transformations on metal-on-metal hip joints. This paper summarizes current knowledge and provides a mechanistic interpretation of the surface chemical and metallurgical phenomena. Basic concepts of corrosion and wear are illustrated and used to interpret available literature on in-vitro and in-vivo studies of metal-on-metal hip joints. Based on this review, three forms of tribomaterial, characterized by different combinations of oxide films and organic layers, can be determined. It is shown that the generation of these tribofilms can be related to specific electrochemical and mechanical phenomena in the metal interface. It is suggested that the generation of this surface reaction layer constitutes a way to minimize (mechanical) wear of MoM hip implants. PMID:28808674

Shear strength of metal-sapphire contacts

NASA Technical Reports Server (NTRS)

Pepper, S. V.

1976-01-01

The shear strength of polycrystalline Ag, Cu, Ni, and Fe contacts on clean (0001) sapphire has been studied in ultrahigh vacuum. Both clean metal surfaces and surfaces exposed to O2, Cl2, and C2H4 were used. The results indicate that there are two sources of strength of Al2O3-metal contacts: an intrinsic one that depends on the particular clean metal in contact with Al2O3 and an additional one due to intermediate films. The shear strength of the clean metal contacts correlated directly with the free energy of oxide formation for the lowest metal oxide, in accord with the hypothesis that a chemical bond is formed between metal cations and oxygen anions in the sapphire surface. Contacts formed by metals exposed to chlorine exhibited uniformly low shear strength indicative of van der Waals bonding between chlorinated metal surfaces and sapphire. Contacts formed by metals exposed to oxygen exhibited enhanced shear strength, in accord with the hypothesis that an intermediate oxide layer increases interfacial strength.

Observation of radiative surface plasmons in metal-oxide-metal tunnel junctions

NASA Technical Reports Server (NTRS)

Donohue, J. F.; Yang, E. Y.

1986-01-01

A peak in the UV region of the spectrum of light emitted from metal-oxide-metal (MOM) tunnel junctions has been observed at room temperature. Both the amplitude and wavelength of the peak are sensitive to applied junction bias. The UV peak corresponds to the normal or radiative surface plasmon mode while a visible peak, also present in the present spectra and reported in past MOM literature, is due to the tangential or nonradiative mode. The radiative mode requires no surface roughness or gratings for photon coupling. The results show that it is possible to obtain radiative surface plasmon production followed by a direct decay into photons with MOM tunnel diodes. A MOM diode with a double anode structure is found to emit light associated only with the nonradiative mode. The thickness dependence of the UV peak, along with the experimental results of the double anode MOM diode and the ratio of the UV peak to visible peak, support the contention that the UV light emission is indeed due to the radiative surface plasmon.

Directional emissivity from two-dimensional infrared waveguide arrays

NASA Astrophysics Data System (ADS)

Burckel, D. Bruce; Davids, Paul S.; Finnegan, Patrick S.; Figueiredo, Pedro N.; Ginn, James C.

2015-09-01

Fabrication and optical characterization of surfaces covered with open-ended metallic waveguides are presented along with numerical modeling of these structures. Both modeling and measurement of the structures indicate that the 2-D array of 3D metallic waveguides modify both the direction and spectral content of the emissivity, resulting in directionality normal to the surface due to the optical axis of the waveguides and spectrally narrow emissivity due to the lateral dimensions of the waveguides. Furthermore, the optical behavior of these structures is placed in the broader context of other structured emission/absorption surfaces such as organ pipe modes, surface plasmon modes, and coherent thermal emission from gratings.

Metal Oxide Gas Sensors: Sensitivity and Influencing Factors

PubMed Central

Wang, Chengxiang; Yin, Longwei; Zhang, Luyuan; Xiang, Dong; Gao, Rui

2010-01-01

Conductometric semiconducting metal oxide gas sensors have been widely used and investigated in the detection of gases. Investigations have indicated that the gas sensing process is strongly related to surface reactions, so one of the important parameters of gas sensors, the sensitivity of the metal oxide based materials, will change with the factors influencing the surface reactions, such as chemical components, surface-modification and microstructures of sensing layers, temperature and humidity. In this brief review, attention will be focused on changes of sensitivity of conductometric semiconducting metal oxide gas sensors due to the five factors mentioned above. PMID:22294916

Improvement of Surface Layer Characteristics by Shot Lining

NASA Astrophysics Data System (ADS)

Harada, Yasunori

In the present study, lining of the metal with foils using shot peening was investigated to improve the surface layer characteristics. In the shot peening experiment, the foils set on the metal are pelted with hard particles traveling at a high velocity. The foils are bonded to the metal surface due to plastic deformation induced by the collision of the particles. The foils and the metal are heated to heighten the bondability because of the reduction of flow stress. Lining the metal with the hard powder sandwiched between two aluminum foil sheets was also attempted. In this experiment, a centrifugal shot peening machine wite an electrical heater was employed. The metals are commercially aluminium alloys and magnesium alloys, and the foils are commercially aluminum, titanium and nickel. The effects of shot speed and the heating temperature on the bondability were examined. Wear resistance was also evaluated by grinding. The foils were successfully bonded to the metal surface. It was found that the present method is effective in improving of surface layer characteristics.

Functional Coatings or Films for Hard-Tissue Applications

PubMed Central

Wang, Guocheng; Zreiqat, Hala

2010-01-01

Metallic biomaterials like stainless steel, Co-based alloy, Ti and its alloys are widely used as artificial hip joints, bone plates and dental implants due to their excellent mechanical properties and endurance. However, there are some surface-originated problems associated with the metallic implants: corrosion and wear in biological environments resulting in ions release and formation of wear debris; poor implant fixation resulting from lack of osteoconductivity and osteoinductivity; implant-associated infections due to the bacterial adhesion and colonization at the implantation site. For overcoming these surface-originated problems, a variety of surface modification techniques have been used on metallic implants, including chemical treatments, physical methods and biological methods. This review surveys coatings that serve to provide properties of anti-corrosion and anti-wear, biocompatibility and bioactivity, and antibacterial activity. PMID:28883319

Radiative decay engineering 3. Surface plasmon-coupled directional emission

PubMed Central

Lakowicz, Joseph R.

2009-01-01

A new method of fluorescence detection that promises to increase sensitivity by 20- to 1000-fold is described. This method will also decrease the contribution of sample autofluorescence to the detected signal. The method depends on the coupling of excited fluorophores with the surface plasmon resonance present in thin metal films, typically silver and gold. The phenomenon of surface plasmon-coupled emission (SPCE) occurs for fluorophores 20–250 nm from the metal surface, allowing detection of fluorophores over substantial distances beyond the metal–sample interface. SPCE depends on interactions of the excited fluorophore with the metal surface. This interaction is independent of the mode of excitation; that is, it does not require evanescent wave or surface-plasmon excitation. In a sense, SPCE is the inverse process of the surface plasmon resonance absorption of thin metal films. Importantly, SPCE occurs over a narrow angular distribution, converting normally isotropic emission into easily collected directional emission. Up to 50% of the emission from unoriented samples can be collected, much larger than typical fluorescence collection efficiencies near 1% or less. SPCE is due only to fluorophores near the metal surface and may be regarded as emission from the induced surface plasmons. Autofluorescence from more distal parts of the sample is decreased due to decreased coupling. SPCE is highly polarized and autofluorescence can be further decreased by collecting only the polarized component or only the light propagating with the appropriate angle. Examples showing how simple optical configurations can be used in diagnostics, sensing, or biotechnology applications are presented. Surface plasmon-coupled emission is likely to find widespread applications throughout the biosciences. PMID:14690679

The surface structure of silver-coated gold nanocrystals and its influence on shape control

DOE PAGES

Padmos, J. Daniel; Personick, Michelle L.; Tang, Qing; ...

2015-07-08

Understanding the surface structure of metal nanocrystals with specific facet indices is important due to its impact on controlling nanocrystal shape and functionality. However, this is particularly challenging for halide-adsorbed nanocrystals due to the difficulty in analysing interactions between metals and light halides (for example, chloride). Here we uncover the surface structures of chloride-adsorbed, silver-coated gold nanocrystals with {111}, {110}, {310} and {720} indexed facets by X-ray absorption spectroscopy and density functional theory modelling. The silver–chloride, silver–silver and silver–gold bonding structures are markedly different between the nanocrystal surfaces, and are sensitive to their formation mechanism and facet type. A uniquemore » approach of combining the density functional theory and experimental/simulated X-ray spectroscopy further verifies the surface structure models and identifies the previously indistinguishable valence state of silver atoms on the nanocrystal surfaces. Overall, this work elucidates the thus-far unknown chloride–metal nanocrystal surface structures and sheds light onto the halide-induced growth mechanism of anisotropic nanocrystals.« less

Self-consistent many-electron theory of electron work functions and surface potential characteristics for selected metals

NASA Technical Reports Server (NTRS)

Smith, J. R.

1969-01-01

Electron work functions, surface potentials, and electron number density distributions and electric fields in the surface region of 26 metals were calculated from first principles within the free electron model. Calculation proceeded from an expression of the total energy as a functional of the electron number density, including exchange and correlation energies, as well as a first inhomogeneity term. The self-consistent solution was obtained via a variational procedure. Surface barriers were due principally to many-body effects; dipole barriers were small only for some alkali metals, becoming quite large for the transition metals. Surface energies were inadequately described by this model, which neglects atomistic effects. Reasonable results were obtained for electron work functions and surface potential characteristics, maximum electron densities varying by a factor of over 60.

New biosorbent in removing some metals from industrial wastewater in El Mex Bay, Egypt

NASA Astrophysics Data System (ADS)

Abdallah, Maha Ahmed Mohamed; Mahmoud, Mohamed E.; Osman, Maher M.; Ahmed, Somaia B.

2017-07-01

Biosorption is an extensive technology applied for the removal of heavy metal ions and other pollutants from aqueous solutions. In the present study, the biosorption of cadmium, lead, chromium and mercury ions from polluted surface seawater in El-Max Bay was determined using hybrid active carbon sorbents. These sorbents were treated chemically by acid, base and redox reaction followed by surface loading of baker's yeast biomass for increasing their biosorption capacity and the highest metal uptake values. The surface function and morphology of the hybrid immobilized sorbents were studied by Fourier Transform Infrared analysis and scanning electron microscope imaging. Metal removal values proved that the vital role of baker's yeast as a significant high removable due to functional groups at baker's yeast cell wall surface that have the ability to forming various coordination complexes with metal ions. A noticeable increase in the removal of all studied metals was observed and reached to 100 %.

Regulating the spatial distribution of metal nanoparticles within metal-organic frameworks to enhance catalytic efficiency

DOE PAGES

Yang, Qiu; Liu, Wenxian; Wang, Bingqing; ...

2017-02-14

Composites incorporating metal nanoparticles (MNPs) within metal-organic frameworks (MOFs) have broad applications in many fields. However, the controlled spatial distribution of the MNPs within MOFs remains a challenge for addressing key issues in catalysis, for example, the efficiency of catalysts due to the limitation of molecular diffusion within MOF channels. We report a facile strategy that enables MNPs to be encapsulated into MOFs with controllable spatial localization by using metal oxide both as support to load MNPs and as a sacrificial template to grow MOFs. This strategy is versatile to a variety of MNPs and MOF crystals. By localizing themore » encapsulated MNPs closer to the surface of MOFs, the resultant MNPs@MOF composites not only exhibit effective selectivity derived from MOF cavities, but also enhanced catalytic activity due to the spatial regulation of MNPs as close as possible to the MOF surface.« less

Detection of heavy metal ions in drinking water using a high-resolution differential surface plasmon resonance sensor.

PubMed

Forzani, Erica S; Zhang, Haiqian; Chen, Wilfred; Tao, Nongjian

2005-03-01

We have built a high-resolution differential surface plasmon resonance (SPR) sensor for heavy metal ion detection. The sensor surface is divided into a reference and sensing areas, and the difference in the SPR angles from the two areas is detected with a quadrant cell photodetector as a differential signal. In the presence of metal ions, the differential signal changes due to specific binding of the metal ions onto the sensing area coated with properly selected peptides, which provides an accurate real-time measurement and quantification of the metal ions. Selective detection of Cu2+ and Ni2+ in the ppt-ppb range was achieved by coating the sensing surface with peptides NH2-Gly-Gly-His-COOH and NH2-(His)6-COOH. Cu2+ in drinking water was tested using this sensor.

Flows, strains, and the formation of joints in oblique collision of metal plates

NASA Astrophysics Data System (ADS)

Shtertser, A. A.; Zlobin, B. S.

2015-09-01

The processes of high-velocity oblique collision of metal plates which lead to the formation of their joints (seizure) are considered. It is found that the cleaning of the plate surface necessary for seizure results from a jet flow (particle stream), whose source is at least one of the welded materials or an interlayer of ductile material located in the initial region of collision. It is shown that additional cleaning may occur due to the emergence of rotating microregions in intense gradient flows localized in the joint area; seizure on cleaned surfaces is due to reduction of the surface energy of the system.

Microfluidic platforms for gallium-based liquid metal alloy

NASA Astrophysics Data System (ADS)

Kim, Daeyoung

As an alternative to toxic mercury, non-toxic gallium-based liquid metal alloy has been gaining popularity due to its higher thermal and electrical conductivities, and low toxicity along with liquid property. However, it is difficult to handle as the alloy becomes readily oxidized in atmospheric air environment. This instant oxidation causes the gallium-based liquid metal alloy to wet almost any solid surface. Therefore, it has been primarily limited to applications which rely only on its deformability, not on its mobility. In this research, various approaches to mobilize gallium-based liquid metal alloy were investigated. Multi-scale surface patterned with polydimethylsiloxane (PDMS) micro pillar array showed super-lyophobic property against gallium-based liquid metal alloy by minimizing the contact area between the solid surface and the liquid metal, and it was expanded to a three-dimensional tunnel shaped microfluidic channel. Vertically-aligned carbon nanotube forest leads to another promising super-lyophobic surface due to its hierarchical micro/nano scale combined structures and chemical inertness. When the carbon nanotubes were transferred onto flexible PDMS by imprinting, the super-lyophobic property was still maintained even under the mechanical deformation such as stretching and bending. Alternatively, the gallium-based liquid metal can be manipulated by modifying the surface of liquid metal itself. With chemical reaction with HCl 'vapor', the oxidized surface (mainly Ga2O3/Ga2O) of gallium-based liquid metal was converted to GaCl3/InCl 3 resulting in the recovery of non-wetting characteristics. Paper which is intrinsically porous is attractive as a super-lyophobic surface and it was found that hydrochloric acid (HCl) impregnation enhanced the anti-wetting property by the chemical reaction. As another alternative method, by coating the viscoelastic oxidized surface of liquid metal with ferromagnetic materials (CoNiMnP or Fe), it showed non-wetting property and became moveable by applying a magnetic field. Finally, using its metallic and liquid properties, microfluidic-based applications of gallium-based liquid metal alloy such as inkjet printing and reconfigurable photomask were investigated. A clog-free and oxide-free inkjet printing technique was developed by incorporating HCl-impregnated paper as orifice. Inkjet-printed liquid metal line can be used as a metallic interconnect even with significant deformation of the flexible substrate. Additionally, based on its ultraviolet light blocking property, a reconfigurable photolithography using gallium-based liquid metal alloy was demonstrated in a PDMS-based 7-segments microfluidic channel by showing single digit numbers ('0'˜'9') with attainable minimum feature size of 10 microm.

Hexagonal boron nitride cover on Pt(111): a new route to tune molecule-metal interaction and metal-catalyzed reactions.

PubMed

Zhang, Yanhong; Weng, Xuefei; Li, Huan; Li, Haobo; Wei, Mingming; Xiao, Jianping; Liu, Zhi; Chen, Mingshu; Fu, Qiang; Bao, Xinhe

2015-05-13

In heterogeneous catalysis molecule-metal interaction is often modulated through structural modifications at the surface or under the surface of the metal catalyst. Here, we suggest an alternative way toward this modulation by placing a two-dimensional (2D) cover on the metal surface. As an illustration, CO adsorption on Pt(111) surface has been studied under 2D hexagonal boron nitride (h-BN) overlayer. Dynamic imaging data from surface electron microscopy and in situ surface spectroscopic results under near ambient pressure conditions confirm that CO molecules readily intercalate monolayer h-BN sheets on Pt(111) in CO atmosphere but desorb from the h-BN/Pt(111) interface even around room temperature in ultrahigh vacuum. The interaction of CO with Pt has been strongly weakened due to the confinement effect of the h-BN cover, and consequently, CO oxidation at the h-BN/Pt(111) interface was enhanced thanks to the alleviated CO poisoning effect.

One-process fabrication of metal hierarchical nanostructures with rich nanogaps for highly-sensitive surface-enhanced Raman scattering.

PubMed

Liu, Gui-qiang; Yu, Mei-dong; Liu, Zheng-qi; Liu, Xiao-shan; Huang, Shan; Pan, Ping-ping; Wang, Yan; Liu, Mu-lin; Gu, Gang

2015-05-08

One-process fabrication of highly active and reproducible surface-enhanced Raman scattering (SERS) substrates via ion beam deposition is reported. The fabricated metal-dielectric-metal (MDM) hierarchical nanostructure possesses rich nanogaps and a tunable resonant cavity. Raman scattering signals of analytes are dramatically strengthened due to the strong near-field coupling of localized surface plasmon resonances (LSPRs) and the strong interaction of LSPRs of metal NPs with surface plasmon polaritons (SPPs) on the underlying metal film by crossing over the dielectric spacer. The maximum Raman enhancement for the highest Raman peak at 1650 cm(-1) is 13.5 times greater than that of a single metal nanoparticle (NP) array. Moreover, the SERS activity can be efficiently tailored by varying the size and number of voids between adjacent metal NPs and the thickness of the dielectric spacer. These findings may broaden the scope of SERS applications of MDM hierarchical nanostructures in biomedical and analytical chemistry.

Tribolayer Formation in a Metal-on-Metal (MoM) Hip Joint: An Electrochemical Investigation

PubMed Central

Mathew, MT; Nagelli, C; Pourzal, R; Fischer, A; Laurent, MP; Jacobs, JJ; Wimmer, MA

2013-01-01

The demand for total hip replacement (THR) surgery is increasing in the younger population due to faster rehabilitation and more complete restoration of function. Up to 2009, metal-on-metal (MoM) hip joint bearings were a popular choice due to their design flexibility, post-operative stability and relatively low wear rates. The main wear mechanisms that occur along the bearing surface of MoM joints are tribochemical reactions that deposit a mixture of wear debris, metal ions and organic matrix of decomposed proteins known as a tribolayer. No in-depth electrochemical studies have been reported on the structure and characteristics of this tribolayer or about the parameters involved in its formation. In this study, we conducted an electrochemical investigation of different surfaces (bulk-like: control, nano-crystalline: new implant and tribolayer surface: retrieved implant) made out of two commonly used hip CoCrMo alloys (high-carbon and low-carbon). As per ASTM standard, cyclic polarization tests and electrochemical impedance spectroscopy tests were conducted. The results obtained from electrochemical parameters for different surfaces clearly indicated a reduction in corrosion for the tribolayer surface (Icorr: 0.76 μA/cm2). Further, polarization resistance (Rp:2.39±0.60MΩ/cm2) and capacitance (Cdl:15.20±0.75 μF/cm2) indicated variation in corrosion kinetics for the tribolayer surface, that attributed to its structure and stability in a simulated body environment. PMID:24099949

Terahertz NDE for Metallic Surface Roughness Evaluation

NASA Technical Reports Server (NTRS)

Madaras, Eric I.; Anastasi, Robert F.

2006-01-01

Metallic surface roughness in a nominally smooth surface is a potential indication of material degradation or damage. When the surface is coated or covered with an opaque dielectric material, such as paint or insulation, then inspecting for surface changes becomes almost impossible. Terahertz NDE is a method capable of penetrating the coating and inspecting the metallic surface. The terahertz frequency regime is between 100 GHz and 10 THz and has a free space wavelength of 300 micrometers at 1 THz. Pulsed terahertz radiation, can be generated and detected using optical excitation of biased semiconductors with femtosecond laser pulses. The resulting time domain signal is 320 picoseconds in duration. In this application, samples are inspected with a commercial terahertz NDE system that scans the sample and generates a set of time-domain signals that are a function of the backscatter from the metallic surface. Post processing is then performed in the time and frequency domains to generate C-scan type images that show scattering effects due to surface non-uniformity.

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

Tao, Franklin

Two main categories of heterogeneous catalysts are metal and metal oxide which catalyze 80% chemical reactions at solid-gas and solid-liquid interfaces. Metal oxide catalysts are much more complicated than metal catalysts. The reason is that the cations of the metal atoms could exhibit a few different oxidation states on surface of the same catalyst particle such as Co 3O 4 or change of their oxidation states under different reactive environments. For a metal catalyst, there is only one oxidation state typically. In addition, surface of a metal oxide can be terminated with multiple surface functionalities including O atoms with differentmore » binding configurations and OH group. For metal, only metal atoms are exposed typically. Obviously, the complication of surface chemistry and structure of a metal oxide makes studies of surface of an oxide catalyst very challenging. Due to the complication of surface of a meal oxide, the electronic and geometric structures of surface of a metal oxide and the exposed species have received enormous attention since oxide catalysts catalyze at least 1/3 chemical reactions in chemical and energy industries. Understanding of catalytic reactions on early transition metal oxide-based catalysts is fundamentally intriguing and of great practical interest in energy- and environment-related catalysis. Exploration of surface chemistry of oxide-based catalysts at molecular level during catalysis has remained challenging though it is critical in deeply understanding catalysis on oxide-based catalysts and developing oxide-based catalysts with high activity and selectivity. Thus, the overall objective of this project is to explore surface chemistry and structure of early transition metal oxide-based catalysts through in-situ characterization of surface of catalysts, measurements of catalytic performances, and then build an intrinsic correlation of surface chemistry and structure with their catalytic performances in a few important catalytic reactions, and essentially fundamentally understand catalytic mechanism. Furthermore, this correlation will guide the design of catalysts with high activity and selectivity.« less

Dynamics of the small-scale changes of metal optic surfaces induced by pulsed light

NASA Astrophysics Data System (ADS)

Liukonen, R. A.; Trofimenko, A. M.

1991-10-01

A study is made of small-scale changes in the relief and absorptivity of mirror metal surfaces due to interaction with pulsed infrared irradiation. Several singularities are identified which are associated with the pulsed nature of the interaction and which cannot be explained by the surface temperature change alone. These include small-scale deformations observed even in the case of uniform distribution of the incident radiation intensity; an increase in deformation in excess of the increase attributable to heating only; and a change in the absorptivity of metal mirrors in excess of the theoretically predicted value.

Rapid ultrasensitive single particle surface-enhanced Raman spectroscopy using metallic nanopores.

PubMed

Cecchini, Michael P; Wiener, Aeneas; Turek, Vladimir A; Chon, Hyangh; Lee, Sangyeop; Ivanov, Aleksandar P; McComb, David W; Choo, Jaebum; Albrecht, Tim; Maier, Stefan A; Edel, Joshua B

2013-10-09

Nanopore sensors embedded within thin dielectric membranes have been gaining significant interest due to their single molecule sensitivity and compatibility of detecting a large range of analytes, from DNA and proteins, to small molecules and particles. Building on this concept we utilize a metallic Au solid-state membrane to translocate and rapidly detect single Au nanoparticles (NPs) functionalized with 589 dye molecules using surface-enhanced resonance Raman spectroscopy (SERRS). We show that, due to the plasmonic coupling between the Au metallic nanopore surface and the NP, signal intensities are enhanced when probing analyte molecules bound to the NP surface. Although not single molecule, this nanopore sensing scheme benefits from the ability of SERRS to provide rich vibrational information on the analyte, improving on current nanopore-based electrical and optical detection techniques. We show that the full vibrational spectrum of the analyte can be detected with ultrahigh spectral sensitivity and a rapid temporal resolution of 880 μs.

Structural coloration of metallic surfaces with micro/nano-structures induced by elliptical vibration texturing

NASA Astrophysics Data System (ADS)

Yang, Yang; Pan, Yayue; Guo, Ping

2017-04-01

Creating orderly periodic micro/nano-structures on metallic surfaces, or structural coloration, for control of surface apparent color and optical reflectivity has been an exciting research topic over the years. The direct applications of structural coloration include color marking, display devices, and invisibility cloak. This paper presents an efficient method to colorize metallic surfaces with periodic micro/nano-gratings using elliptical vibration texturing. When the tool vibration is coupled with a constant cutting velocity, controlled periodic ripples can be generated due to the overlapping tool trajectory. These periodic ripples with a wavelength near visible spectrum can act as micro-gratings to introduce iridescent colors. The proposed technique also provides a flexible method for color marking of metallic surfaces with arbitrary patterns and images by precise control of the spacing distance and orientation of induced micro/nano-ripples. Theoretical analysis and experimental results are given to demonstrate structural coloration of metals by a direct mechanical machining technique.

Effect of carbon ion implantation on the tribology of metal-on-metal bearings for artificial joints.

PubMed

Koseki, Hironobu; Tomita, Masato; Yonekura, Akihiko; Higuchi, Takashi; Sunagawa, Sinya; Baba, Koumei; Osaki, Makoto

2017-01-01

Metal-on-metal (MoM) bearings have become popular due to a major advantage over metal-on-polymer bearings for total hip arthroplasty in that the larger femoral head and hydrodynamic lubrication of the former reduce the rate of wear. However, concerns remain regarding adverse reactions to metal debris including metallosis caused by metal wear generated at the taper-head interface and another modular junction. Our group has hypothesized that carbon ion implantation (CII) may improve metal wear properties. The purpose of this study was to investigate the wear properties and friction coefficients of CII surfaces with an aim to ultimately apply these surfaces to MoM bearings in artificial joints. CII was applied to cobalt-chromium-molybdenum (Co-Cr-Mo) alloy substrates by plasma source ion implantation. The substrates were characterized using scanning electron microscopy and a 3D measuring laser microscope. Sliding contact tests were performed with a simple geometry pin-on-plate wear tester at a load of 2.5 N, a calculated contact pressure of 38.5 MPa (max: 57.8 MPa), a reciprocating velocity of 30 mm/s, a stroke length of 60 mm, and a reciprocating cycle count of 172,800 cycles. The surfaces of the CII substrates were generally featureless with a smooth surface topography at the same level as untreated Co-Cr-Mo alloy. Compared to the untreated Co-Cr-Mo alloy, the CII-treated bearings had lower friction coefficients, higher resistance to catastrophic damage, and prevented the adhesion of wear debris. The results of this study suggest that the CII surface stabilizes the wear status due to the low friction coefficient and low infiltration of partner materials, and these properties also prevent the adhesion of wear debris and inhibit excessive wear. Carbon is considered to be biologically inert; therefore, CII is anticipated to be applicable to the bearing surfaces of MoM prostheses.

Effect of carbon ion implantation on the tribology of metal-on-metal bearings for artificial joints

PubMed Central

Koseki, Hironobu; Tomita, Masato; Yonekura, Akihiko; Higuchi, Takashi; Sunagawa, Sinya; Baba, Koumei; Osaki, Makoto

2017-01-01

Metal-on-metal (MoM) bearings have become popular due to a major advantage over metal-on-polymer bearings for total hip arthroplasty in that the larger femoral head and hydrodynamic lubrication of the former reduce the rate of wear. However, concerns remain regarding adverse reactions to metal debris including metallosis caused by metal wear generated at the taper-head interface and another modular junction. Our group has hypothesized that carbon ion implantation (CII) may improve metal wear properties. The purpose of this study was to investigate the wear properties and friction coefficients of CII surfaces with an aim to ultimately apply these surfaces to MoM bearings in artificial joints. CII was applied to cobalt-chromium-molybdenum (Co-Cr-Mo) alloy substrates by plasma source ion implantation. The substrates were characterized using scanning electron microscopy and a 3D measuring laser microscope. Sliding contact tests were performed with a simple geometry pin-on-plate wear tester at a load of 2.5 N, a calculated contact pressure of 38.5 MPa (max: 57.8 MPa), a reciprocating velocity of 30 mm/s, a stroke length of 60 mm, and a reciprocating cycle count of 172,800 cycles. The surfaces of the CII substrates were generally featureless with a smooth surface topography at the same level as untreated Co-Cr-Mo alloy. Compared to the untreated Co-Cr-Mo alloy, the CII-treated bearings had lower friction coefficients, higher resistance to catastrophic damage, and prevented the adhesion of wear debris. The results of this study suggest that the CII surface stabilizes the wear status due to the low friction coefficient and low infiltration of partner materials, and these properties also prevent the adhesion of wear debris and inhibit excessive wear. Carbon is considered to be biologically inert; therefore, CII is anticipated to be applicable to the bearing surfaces of MoM prostheses. PMID:28615939

Influence of surface vacancy defects on the carburisation of Fe 110 surface by carbon monoxide

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

Chakrabarty, Aurab, E-mail: aurab.chakrabarty@qatar.tamu.edu; Bouhali, Othmane; Mousseau, Normand

Adsorption and dissociation of gaseous carbon monoxide (CO) on metal surfaces is one of the most frequently occurring processes of carburisation, known as primary initiator of metal dusting corrosion. Among the various factors that can significantly influence the carburisation process are the intrinsic surface defects such as single surface vacancies occurring at high concentrations due to their low formation energy. Intuitively, adsorption and dissociation barriers of CO are expected to be lowered in the vicinity of a surface vacancy, due to the strong attractive interaction between the vacancy and the C atom. Here the adsorption energies and dissociation pathways ofmore » CO on clean and defective Fe 110 surface are explored by means of density functional theory. Interestingly, we find that the O adatom, resulting from the CO dissociation, is unstable in the electron-deficit neighbourhood of the vacancy due to its large electron affinity, and raises the barrier of the carburisation pathway. Still, a full comparative study between the clean surface and the vacancy-defected surface reveals that the complete process of carburisation, starting from adsorption to subsurface diffusion of C, is more favourable in the vicinity of a vacancy defect.« less

Optical transparency of graphene layers grown on metal surfaces

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

Rut’kov, E. V.; Lavrovskaya, N. P.; Sheshenya, E. S., E-mail: sheshenayket@gmail.ru

It is shown that, in contradiction with the fundamental results obtained for free graphene, graphene films grown on the Rh(111) surface to thicknesses from one to ~(12–15) single layers do not absorb visible electromagnetic radiation emitted from the surface and influence neither the brightness nor true temperature of the sample. At larger thicknesses, such absorption occurs. This effect is observed for the surfaces of other metals, specifically, Pt(111), Re(1010), and Ni(111) and, thus, can be considered as being universal. It is thought that the effect is due to changes in the electronic properties of thin graphene layers because of electronmore » transfer between graphene and the metal substrate.« less

Drag reduction using metallic engineered surfaces with highly ordered hierarchical topographies: nanostructures on micro-riblets

NASA Astrophysics Data System (ADS)

Kim, Taekyung; Shin, Ryung; Jung, Myungki; Lee, Jinhyung; Park, Changsu; Kang, Shinill

2016-03-01

Durable drag-reduction surfaces have recently received much attention, due to energy-saving and power-consumption issues associated with harsh environment applications, such as those experienced by piping infrastructure, ships, aviation, underwater vehicles, and high-speed ground vehicles. In this study, a durable, metallic surface with highly ordered hierarchical structures was used to enhance drag-reduction properties, by combining two passive drag-reduction strategies: an air-layer effect induced by nanostructures and secondary vortex generation by micro-riblet structures. The nanostructures and micro-riblet structures were designed to increase slip length. The top-down fabrication method used to form the metallic hierarchical structures combined laser interference lithography, photolithography, thermal reflow, nanoimprinting, and pulse-reverse-current electrochemical deposition. The surfaces were formed from nickel, which has high hardness and corrosion resistance, making it suitable for use in harsh environments. The drag-reduction properties of various metal surfaces were investigated based on the surface structure: a bare surface, a nanostructured surface, a micro-riblet surface, and a hierarchically structured surface of nanostructures on micro-riblets.

Surface modification by metal ion implantation forming metallic nanoparticles in an insulating matrix

NASA Astrophysics Data System (ADS)

Salvadori, M. C.; Teixeira, F. S.; Sgubin, L. G.; Cattani, M.; Brown, I. G.

2014-08-01

There is special interest in the incorporation of metallic nanoparticles in a surrounding dielectric matrix for obtaining composites with desirable characteristics such as for surface plasmon resonance, which can be used in photonics and sensing, and controlled surface electrical conductivity. We have investigated nanocomposites produced by metal ion implantation into insulating substrates, where the implanted metal self-assembles into nanoparticles. The nanoparticles nucleate near the maximum of the implantation depth profile (projected range), which can be estimated by computer simulation using the TRIDYN code. TRIDYN is a Monte Carlo simulation program based on the TRIM (Transport and Range of Ions in Matter) code that takes into account compositional changes in the substrate due to two factors: previously implanted dopant atoms, and sputtering of the substrate surface. Our study show that the nanoparticles form a bidimentional array buried a few nanometers below the substrate surface. We have studied Au/PMMA (polymethylmethacrylate), Pt/PMMA, Ti/alumina and Au/alumina systems. Transmission electron microscopy of the implanted samples show that metallic nanoparticles form in the insulating matrix. These nanocomposites have been characterized by measuring the resistivity of the composite layer as a function of the implantation dose. The experimental results are compared with a model based on percolation theory, in which electron transport through the composite is explained by conduction through a random resistor network formed by the metallic nanoparticles. Excellent agreement is found between the experimental results and the predictions of the theory. We conclude in that the conductivity process is due only to percolation (when the conducting elements are in geometric contact) and that the contribution from tunneling conduction is negligible.

Hydrothermal ore-forming processes in the light of studies in rock- buffered systems: II. Some general geologic applications

USGS Publications Warehouse

Hemley, J.J.; Hunt, J.P.

1992-01-01

The experimental metal solubilities for rock-buffered hydrothermal systems provide important insights into the acquisition, transport, and deposition of metals in real hydrothermal systems that produced base metal ore deposits. Water-rock reactions that determine pH, together with total chloride and changes in temperature and fluid pressure, play significant roles in controlling the solubility of metals and determining where metals are fixed to form ore deposits. Deposition of metals in hydrothermal systems occurs where changes such as cooling, pH increase due to rock alteration, boiling, or fluid mixing cause the aqueous metal concentration to exceed saturation. Metal zoning results from deposition occurring at successive saturation surfaces. Zoning is not a reflection simply of relative solubility but of the manner of intersection of transport concentration paths with those surfaces. Saturation surfaces will tend to migrate outward and inward in prograde and retrograde time, respectively, controlled by either temperature or chemical variables. -from Authors

PHOTONICS AND NANOTECHNOLOGY Choice of a target with metal coating for laser-induced transfer of ultradispersed materials

NASA Astrophysics Data System (ADS)

Kononenko, Taras V.; Kamalov, M. A.; Popovich, M. Yu; Konov, Vitalii I.; Sentis, M. L.

2010-12-01

The ejection of ultradispersed diamond from a metallised target surface irradiated by nano- and subnanosecond laser pulses is experimentally investigated. Several targets with different transparent bases (quartz, polymethylmethacrylate) and absorbing metal coatings (titanium, aluminium) are investigated. The effect of the metal layer thickness and pulse width on the range of energy densities in which the ejection of diamond nanopowder is due to the transverse strain of metal layer is analysed. The heating of the target rear surface from which transfer occurs, in dependence of the target and laser pulse parameters, is estimated.

Promising Ta-Ti-Zr-Si metallic glass coating without cytotoxic elements for bio-implant applications

NASA Astrophysics Data System (ADS)

Lai, J. J.; Lin, Y. S.; Chang, C. H.; Wei, T. Y.; Huang, J. C.; Liao, Z. X.; Lin, C. H.; Chen, C. H.

2018-01-01

Tantalum (Ta) is considered as one of the most promising metal due to its high corrosion resistance, excellent biocompatibility and cell adhesion/in-growth capabilities. Although there are some researches exploring the biomedical aspects of Ta and Ta based alloys, systematic characterizations of newly developed Ta-based metallic glasses in bio-implant applications is still lacking. This study employs sputtering approach to produced thin-film Ti-based metallic glasses due to the high melting temperature of Ta (3020 °C). Two fully amorphous Ta-based metallic glasses composed of Ta57Ti17Zr15Si11 and Ta75Ti10Zr8Si7 are produced and experimentally characterized in terms of their mechanical properties, bio-corrosion properties, surface hydrophilic characteristics, and in-vitro cell viability and cells attachment tests. Compare to conventional pure Ti and Ta metals, the developed Ta-based metallic glasses exhibit higher hardness and lower modulus which are better match to the mechanical properties of bone. MTS assay results show that Ta-based metallic glasses show comparable cell viability and cell attachment rate compared to that of pure Ti and Ta surface in a 72 h in-vitro test.

Atomic Scale Understanding of Poly-Si/SiO2/c-Si Passivated Contacts: Passivation Degradation Due to Metallization

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

Aguiar, Jeffery A.; Young, David; Lee, Benjamin

2016-11-21

The key attributes for achieving high efficiency crystalline silicon solar cells include class leading developments in the ability to approach the theoretical limits of silicon solar technology (29.4% efficiency). The push for high efficiency devices is further compounded with the clear need for passivation to reduce recombination at the metal contacts. At the same time there is stringent requirement to retain the same material device quality, surface passivation, and performance characteristics following subsequent processing. The development of passivated silicon cell structures that retain active front and rear surface passivation and overall material cell quality is therefore a relevant and activemore » area of development. To address the potential outcomes of metallization on passivated silicon stack, we report on some common microstructural features of degradation due to metallization for a series of silicon device stacks. A fundamental materials understanding of the metallization process on retaining high-efficiency passivated Si devices is therefore gained over these series of results.« less

Mesoporous magnetic secondary nanostructures as versatile adsorbent for efficient scavenging of heavy metals

PubMed Central

Bhattacharya, Kakoli; Parasar, Devaborniny; Mondal, Bholanath; Deb, Pritam

2015-01-01

Porous magnetic secondary nanostructures exhibit high surface area because of the presence of plentiful interparticle spaces or pores. Mesoporous Fe3O4 secondary nanostructures (MFSNs) have been studied here as versatile adsorbent for heavy metal scavenging. The porosity combined with magnetic functionality of the secondary nanostructures has facilitated efficient heavy metal (As, Cu and Cd) remediation from water solution within a short period of contact time. It is because of the larger surface area of MFSNs due to the porous network in addition to primary nanostructures which provides abundant adsorption sites facilitating high adsorption of the heavy metal ions. The brilliance of adsorption property of MFSNs has been realized through comprehensive adsorption studies and detailed kinetics. Due to their larger dimension, MFSNs help in overcoming the Brownian motion which facilitates easy separation of the metal ion sorbed secondary nanostructures and also do not get drained out during filtration, thus providing pure water. PMID:26602613

Ecological risk and pollution history of heavy metals in Nansha mangrove, South China.

PubMed

Wu, Qihang; Tam, Nora F Y; Leung, Jonathan Y S; Zhou, Xizhen; Fu, Jie; Yao, Bo; Huang, Xuexia; Xia, Lihua

2014-06-01

Owing to the Industrial Revolution in the late 1970s, heavy metal pollution has been regarded as a serious threat to mangrove ecosystems in the region of the Pearl River Estuary, potentially affecting human health. The present study attempted to characterize the ecological risk of heavy metals (Cd, Cr, Cu, Mn, Ni, Pb and Zn) in Nansha mangrove, South China, by estimating their concentrations in the surface sediment. In addition, the pollution history of heavy metals was examined by determining the concentrations of heavy metals along the depth gradient. The phytoremediation potential of heavy metals by the dominant plants in Nansha mangrove, namely Sonneratia apetala and Cyperus malaccensis, was also studied. Results found that the surface sediment was severely contaminated with heavy metals, probably due to the discharge of industrial sewage into the Pearl River Estuary. Spatial variation of heavy metals was generally unobvious. The ecological risk of heavy metals was very high, largely due to Cd contamination. All heavy metals, except Mn, decreased with depth, indicating that heavy metal pollution has been deteriorating since 1979. Worse still, the dominant plants in Nansha mangrove had limited capability to remove the heavy metals from sediment. Therefore, we propose that immediate actions, such as regulation of discharge standards of industrial sewage, should be taken by the authorities concerned to mitigate the ecological risk posed by heavy metals. Copyright © 2014 Elsevier Inc. All rights reserved.

Implication of femoral stem on performance of articular surface replacement (ASR) XL total hip arthroplasty.

PubMed

Cip, Johannes; von Strempel, Archibald; Bach, Christian; Luegmair, Matthias; Benesch, Thomas; Martin, Arno

2014-11-01

Taper junctions of large diameter metal-on-metal femoral heads and femoral stems were described as metal ion generator due to accelerated wear and corrosion. However, literature about the Articular Surface Replacement (ASR) total hip arthroplasty (THA) invariably deals with stems manufactured by DePuy Orthopedics (Warsaw, IN, USA). Nothing is known whether different stems with common 12/14 mm tapers affect failure rate or ion release. 99 ASR THA (88 patients) implanted with CoxaFit or ARGE Geradschaft stems (K-Implant, Hannover, Germany) were retrospectively analyzed. After a mean follow-up of 3.5 years revision rate was 24.5%, mostly due to adverse reaction to metal debris (ARMD). CT scan revealed component loosening in 10.3% and pseudotumoral lesions in 12.6%. Elevated ion concentrations (>7 μg/l) were found in 38.6%. Copyright © 2014 Elsevier Inc. All rights reserved.

Titanium Combustion in Turbine Engines

DTIC Science & Technology

1979-07-01

metal fires . Due to the refractory nature of metal oxides, mcst of the heat of reac- tion will reside in the enthalpy of the products. In a surface...more closely approx- imates the conditions prevailing in large-scale accidental metal fires . The objectives of this research have been to better define...conditions on the propagating molten mass of burning metal. Metal fires involve propagating combus- tion, and the propagation of burning-must be

Diminished Metal Accumulation in Riverine Fishes Exposed to Acid Mine Drainage over Five Decades

PubMed Central

Jeffree, Ross A.; Markich, Scott J.; Twining, John R.

2014-01-01

Bony bream (Nematalosa erebi) and black catfish (Neosilurus ater) were sampled from the fresh surface waters of the Finniss River in tropical northern Australia, along a metal pollution gradient draining the Rum Jungle copper/uranium mine, a contaminant source for over five decades. Paradoxically, populations of both fish species exposed to the highest concentrations of mine-related metals (cobalt, copper, lead, manganese, nickel, uranium and zinc) in surface water and sediment had the lowest tissue (bone, liver and muscle) concentrations of these metals. The degree of reduction in tissue concentrations of exposed populations was also specific to each metal and inversely related to its degree of environmental increase above background. Several explanations for diminished metal bioaccumulation in fishes from the contaminated region were evaluated. Geochemical speciation modeling of metal bioavailability in surface water showed no differences between the contaminated region and the control sites. Also, the macro-nutrient (calcium, magnesium and sodium) water concentrations, that may competitively inhibit metal uptake, were not elevated with trace metal contamination. Reduced exposure to contaminants due to avoidance behavior was unlikely due to the absence of refugial water bodies with the requisite metal concentrations lower than the control sites and very reduced connectivity at time of sampling. The most plausible interpretation of these results is that populations of both fish species have modified kinetics within their metal bioaccumulation physiology, via adaptation or tolerance responses, to reduce their body burdens of metals. This hypothesis is consistent with (i) reduced tissue concentrations of calcium, magnesium and sodium (macro-nutrients), in exposed populations of both species, (ii) experimental findings for other fish species from the Finniss River and other contaminated regions, and (iii) the number of generations exposed to likely selection pressure over 50 years. PMID:24663964

Laser processing of metal surfaces for increasing paint adhesion

NASA Astrophysics Data System (ADS)

Hirose, Tomiyasu; Ichihara, Hideki; Sugimoto, Kenji; Sasazawa, Kazuo; Shibasaki, Shouji

2000-01-01

Painted metal exteriors of buildings begin to degrade in about 10 years due to solar heat, UV rays, the sea salt adhesion, the acid rain etc. When degradation and exfoliation of the paint film occurs, rust appears in the metal and replacement or repainting becomes necessary. The adhesion of paints on metal is usually achieved by chemical adhesion or by increasing the surface area by blast processing. In this study, the possibility of improving paint adhesion by forming minute holes on the metal surface by laser irradiation was studied through modeling of the adhesion of the paint film and adaptability to deformation. The viscosity and painting method depend on the size and location of the oles. The presence of the holes makes it possible to form complicated shapes by pressing because the holes absorb some of the strain caused by pressing.

A two dimensional analytical modeling of surface potential in triple metal gate (TMG) fully-depleted Recessed-Source/Drain (Re-S/D) SOI MOSFET

NASA Astrophysics Data System (ADS)

Priya, Anjali; Mishra, Ram Awadh

2016-04-01

In this paper, analytical modeling of surface potential is proposed for new Triple Metal Gate (TMG) fully depleted Recessed-Source/Dain Silicon On Insulator (SOI) Metal Oxide Semiconductor Field Effect Transistor (MOSFET). The metal with the highest work function is arranged near the source region and the lowest one near the drain. Since Recessed-Source/Drain SOI MOSFET has higher drain current as compared to conventional SOI MOSFET due to large source and drain region. The surface potential model developed by 2D Poisson's equation is verified by comparison to the simulation result of 2-dimensional ATLAS simulator. The model is compared with DMG and SMG devices and analysed for different device parameters. The ratio of metal gate length is varied to optimize the result.

Rational design of binder-free noble metal/metal oxide arrays with nanocauliflower structure for wide linear range nonenzymatic glucose detection

PubMed Central

Li, Zhenzhen; Xin, Yanmei; Zhang, Zhonghai; Wu, Hongjun; Wang, Peng

2015-01-01

One-dimensional nanocomposites of metal-oxide and noble metal were expected to present superior performance for nonenzymatic glucose detection due to its good conductivity and high catalytic activity inherited from noble metal and metal oxide respectively. As a proof of concept, we synthesized gold and copper oxide (Au/CuO) composite with unique one-dimensional nanocauliflowers structure. Due to the nature of the synthesis method, no any foreign binder was needed in keeping either Au or CuO in place. To the best of our knowledge, this is the first attempt in combining metal oxide and noble metal in a binder-free style for fabricating nonenzymatic glucose sensor. The Au/CuO nanocauliflowers with large electrochemical active surface and high electrolyte contact area would promise a wide linear range and high sensitive detection of glucose with good stability and reproducibility due to its good electrical conductivity of Au and high electrocatalytic activity of CuO. PMID:26068705

Ion Exchange Strengthening of a Leucite-Reinforced Dental Ceramic

DTIC Science & Technology

1997-07-11

internal surface, due to internal surface flaws (Kelly et, al., 1989; Kelly et al., 1990). Finite - element -stress analysis reveals that the occlusal...associated with the use of metal substructures exist. Numerous all-ceramic systems have been introduced, however strengths equivalent to metal-ceramic...yielded significantly higher flexural strength values than potassium exchange at similar treatment conditions (Student Newman-Keuls analysis , p < 0.05

Study of irradiation damage induced by He2+ ion irradiation in Ni62Ta38 metallic glass and W metal

NASA Astrophysics Data System (ADS)

Zhang, Xiaonan; Mei, Xianxiu; Zhang, Qi; Li, Xiaona; Wang, Yingmin; Wang, Younian

2017-09-01

Metallic glasses are considered to possess good resistant against irradiation due to their inherent structural long-range disorder and a lack of grain boundaries. The He2+ with an energy of 300 keV was used to irradiate Ni62Ta38 binary metallic glass to investigate its resistance against the irradiation, and the irradiated behaviour of the metallic glass was compared with that of W metal. The irradiation fluence range over 2.0 × 1017 ions/cm2-1.6 × 1018 ions/cm2. The TEM results show that nanocrystals of μ-NiTa phase and Ni2Ta phase appeared in Ni62Ta38 metallic glass under the irradiation fluence of 1.6 × 1018 ions/cm2. The SEM results show that the surfaces of Ni62Ta38 metallic glasses maintained flat and smooth, whereas a large area of blisters with peeling formed on the surface of W metal at the irradiation fluence of 1.0 × 1018 ions/cm2. It indicates that the critical irradiation fluence of surface breakage of the Ni62Ta38 metallic glass is higher than that of W metal. After the irradiation, stress was generated in the surface layer of W metal, leading to the increase of the hardness of W metal.

Work function and quantum efficiency study of metal oxide thin films on Ag(100)

NASA Astrophysics Data System (ADS)

Chang, V.; Noakes, T. C. Q.; Harrison, N. M.

2018-04-01

Increasing the quantum efficiency (QE) of metal photocathodes is in the design and development of photocathodes for free-electron laser applications. The growth of metal oxide thin films on certain metal surfaces has previously been shown to reduce the work function (WF). Using a photoemission model B. Camino et al. [Comput. Mater. Sci. 122, 331 (2016), 10.1016/j.commatsci.2016.05.025] based on the three-step model combined with density functional theory calculations we predict that the growth of a finite number of MgO(100) or BaO(100) layers on the Ag(100) surface increases significantly the QE compared with the clean Ag(100) surface for a photon energy of 4.7 eV. Different mechanisms for affecting the QE are identified for the different metal oxide thin films. The addition of MgO(100) increases the QE due to the reduction of the WF and the direct excitation of electrons from the Ag surface to the MgO conduction band. For BaO(100) thin films, an additional mechanism is in operation as the oxide film also photoemits at this energy. We also note that a significant increase in the QE for photons with an energy of a few eV above the WF is achieved due to an increase in the inelastic mean-free path of the electrons.

Electron acceleration by surface plasma waves in double metal surface structure

NASA Astrophysics Data System (ADS)

Liu, C. S.; Kumar, Gagan; Singh, D. B.; Tripathi, V. K.

2007-12-01

Two parallel metal sheets, separated by a vacuum region, support a surface plasma wave whose amplitude is maximum on the two parallel interfaces and minimum in the middle. This mode can be excited by a laser using a glass prism. An electron beam launched into the middle region experiences a longitudinal ponderomotive force due to the surface plasma wave and gets accelerated to velocities of the order of phase velocity of the surface wave. The scheme is viable to achieve beams of tens of keV energy. In the case of a surface plasma wave excited on a single metal-vacuum interface, the field gradient normal to the interface pushes the electrons away from the high field region, limiting the acceleration process. The acceleration energy thus achieved is in agreement with the experimental observations.

Reduced graphene oxide wrapped Ag nanostructures for enhanced SERS activity

NASA Astrophysics Data System (ADS)

Nair, Anju K.; Kala, M. S.; Thomas, Sabu; Kalarikkal, Nandakumar

2018-04-01

Graphene - metal nanoparticle hybrids have received great attention due to their unique electronic properties, large specific surface area, very high conductivity and more charge transfer. Thus, it is extremely advantages to develop a simple and efficient process to disperse metal nanostructures over the surface of graphene sheets. Herein, we report a hydrothermal assisted strategy for developing reduced graphene oxide /Ag nanomorphotypes (cube, wire) for surface enhanced Raman scattering (SERS) applications, considering the advantages of synergistic effect of graphene and plasmonic properties of Ag nanomorphotypes.

Promotional effects of chemisorbed oxygen and hydroxide in the activation of C-H and O-H bonds over transition metal surfaces

NASA Astrophysics Data System (ADS)

Hibbitts, David; Neurock, Matthew

2016-08-01

Electronegative coadsorbates such as atomic oxygen (O*) and hydroxide (OH*) can act as Brønsted bases when bound to Group 11 as well as particular Group 8-10 metal surfaces and aid in the activation of X-H bonds. First-principle density functional theory calculations were carried out to systematically explore the reactivity of the C-H bonds of methane and surface methyl intermediates as well as the O-H bond of methanol directly and with the assistance of coadsorbed O* and OH* intermediates over Group 11 (Cu, Ag, and Au) and Group 8-10 transition metal (Ru, Rh, Pd, Os, Ir, and Pt) surfaces. C-H as well as O-H bond activation over the metal proceeds via a classic oxidative addition type mechanism involving the insertion of the metal center into the C-H or O-H bond. O* and OH* assist C-H and O-H activation over particular Group 11 and Group 8-10 metal surfaces via a σ-bond metathesis type mechanism involving the oxidative addition of the C-H or O-H bond to the metal along with a reductive deprotonation of the acidic C-H and O-H bond over the M-O* or M-OH* site pair. The O*- and OH*-assisted C-H activation paths are energetically preferred over the direct metal catalyzed C-H scission for all Group 11 metals (Cu, Ag, and Au) with barriers that are 0.4-1.5 eV lower than those for the unassisted routes. The barriers for O*- and OH*-assisted C-H activation of CH4 on the Group 8-10 transition metals, however, are higher than those over the bare transition metal surfaces by as much as 1.4 eV. The C-H activation of adsorbed methyl species show very similar trends to those for CH4 despite the differences in structure between the weakly bound methane and the covalently adsorbed methyl intermediates. The activation of the O-H bond of methanol is significantly promoted by O* as well as OH* intermediates over both the Group 11 metals (Cu, Ag, and Au) as well as on all Group 8-10 metals studied (Ru, Rh, Pd, Os, Ir, and Pt). The O*- and OH*-assisted CH3O-H barriers are 0.6 to 2.0 eV lower than unassisted barriers, with the largest differences occurring on Group 11 metals. The higher degree of O*- and OH*-promotion in activating methanol over that in methane and methyl is due to the stronger interaction between the basic O* and OH* sites and the acidic proton in the O-H bond of methanol versus the non-acidic H in the C-H bond of methane. A detailed analysis of the binding energies and the charges for O* and OH* on different metal surfaces indicates that the marked differences in the properties and reactivity of O* and OH* between the Group 11 and Group 8-10 metals is due to the increased negative charge on the O-atoms (in O* as well as OH*) bound to Group 11 metals. The promotional effects of O* and OH* are consistent with a proton-coupled electron transfer and the cooperative role of the metal-O* or metal-OH* pair in carrying out the oxidative addition and reductive deprotonation of the acidic C-H and O-H bonds. Ultimately, the ability of O* or OH* to act as a Brønsted base depends upon its charge, its binding energy on the metal surface (due to shifts in its position during X-H activation), and the acidity of the H-atom being abstracted.

Surface plasmon mediated Raman scattering in metal nanoparticles

NASA Astrophysics Data System (ADS)

Bachelier, G.; Mlayah, A.

2004-05-01

The Raman scattering due to confined acoustic vibrations in metal particles is studied theoretically. Various coupling mechanisms between the surface plasmon polaritons and the confined vibrations are investigated. Their relative contribution to the light scattering is discussed. We found that two mechanisms play an important role: (i) modulation of the interband dielectric susceptibility via deformation potential due to pure radial vibrations and (ii) modulation of the surface polarization charges by quadripolar vibrations. The dependence of the Raman spectra on the nanoparticles size and size distribution and on the excitation energy is studied in connection with the nature of the excited plasmon-polariton states. We found a good agreement between calculated line shapes and relatives intensities of the Raman bands and the experimental spectra reported in the literature.

Wireless Metal Detection and Surface Coverage Sensing for All-Surface Induction Heating

PubMed Central

Kilic, Veli Tayfun; Unal, Emre; Demir, Hilmi Volkan

2016-01-01

All-surface induction heating systems, typically comprising small-area coils, face a major challenge in detecting the presence of a metallic vessel and identifying its partial surface coverage over the coils to determine which of the coils to power up. The difficulty arises due to the fact that the user can heat vessels made of a wide variety of metals (and their alloys). To address this problem, we propose and demonstrate a new wireless detection methodology that allows for detecting the presence of metallic vessels together with uniquely sensing their surface coverages while also identifying their effective material type in all-surface induction heating systems. The proposed method is based on telemetrically measuring simultaneously inductance and resistance of the induction coil coupled with the vessel in the heating system. Here, variations in the inductance and resistance values for an all-surface heating coil loaded by vessels (made of stainless steel and aluminum) at different positions were systematically investigated at different frequencies. Results show that, independent of the metal material type, unique identification of the surface coverage is possible at all freqeuncies. Additionally, using the magnitude and phase information extracted from the coupled coil impedance, unique identification of the vessel effective material is also achievable, this time independent of its surface coverage. PMID:26978367

The evaluation of stack metal emissions from hazardous waste incinerators: assessing human exposure through noninhalation pathways.

PubMed Central

Sedman, R M; Polisini, J M; Esparza, J R

1994-01-01

Potential public health effects associated with exposure to metal emissions from hazardous waste incinerators through noninhalation pathways were evaluated. Instead of relying on modeling the movement of toxicants through various environmental media, an approach based on estimating changes from baseline levels of exposure was employed. Changes in soil and water As, Cd, Hg, Pb, Cr, and Be concentrations that result from incinerator emissions were first determined. Estimates of changes in human exposure due to direct contact with shallow soil or the ingestion of surface water were then ascertained. Projected changes in dietary intakes of metals due to incinerator emissions were estimated based on changes from baseline dietary intakes that are monitored in U.S. Food and Drug Administration total diet studies. Changes from baseline intake were deemed to be proportional to the projected changes in soil or surface water metal concentrations. Human exposure to metals emitted from nine hazardous waste incinerators were then evaluated. Metal emissions from certain facilities resulted in tangible human exposure through noninhalation pathways. However, the analysis indicated that the deposition of metals from ambient air would result in substantially greater human exposure through noninhalation pathways than the emissions from most of the facilities. PMID:7925180

Voltage-dependent cluster expansion for electrified solid-liquid interfaces: Application to the electrochemical deposition of transition metals

NASA Astrophysics Data System (ADS)

Weitzner, Stephen E.; Dabo, Ismaila

2017-11-01

The detailed atomistic modeling of electrochemically deposited metal monolayers is challenging due to the complex structure of the metal-solution interface and the critical effects of surface electrification during electrode polarization. Accurate models of interfacial electrochemical equilibria are further challenged by the need to include entropic effects to obtain accurate surface chemical potentials. We present an embedded quantum-continuum model of the interfacial environment that addresses each of these challenges and study the underpotential deposition of silver on the gold (100) surface. We leverage these results to parametrize a cluster expansion of the electrified interface and show through grand canonical Monte Carlo calculations the crucial need to account for variations in the interfacial dipole when modeling electrodeposited metals under finite-temperature electrochemical conditions.

A Method to Manipulate Surface Tension of a Liquid Metal via Surface Oxidation and Reduction

PubMed Central

Dickey, Michael D.

2016-01-01

Controlling interfacial tension is an effective method for manipulating the shape, position, and flow of fluids at sub-millimeter length scales, where interfacial tension is a dominant force. A variety of methods exist for controlling the interfacial tension of aqueous and organic liquids on this scale; however, these techniques have limited utility for liquid metals due to their large interfacial tension. Liquid metals can form soft, stretchable, and shape-reconfigurable components in electronic and electromagnetic devices. Although it is possible to manipulate these fluids via mechanical methods (e.g., pumping), electrical methods are easier to miniaturize, control, and implement. However, most electrical techniques have their own constraints: electrowetting-on-dielectric requires large (kV) potentials for modest actuation, electrocapillarity can affect relatively small changes in the interfacial tension, and continuous electrowetting is limited to plugs of the liquid metal in capillaries. Here, we present a method for actuating gallium and gallium-based liquid metal alloys via an electrochemical surface reaction. Controlling the electrochemical potential on the surface of the liquid metal in electrolyte rapidly and reversibly changes the interfacial tension by over two orders of magnitude (~500 mN/m to near zero). Furthermore, this method requires only a very modest potential (< 1 V) applied relative to a counter electrode. The resulting change in tension is due primarily to the electrochemical deposition of a surface oxide layer, which acts as a surfactant; removal of the oxide increases the interfacial tension, and vice versa. This technique can be applied in a wide variety of electrolytes and is independent of the substrate on which it rests. PMID:26863045

Microstructure formation on liquid metal surface under pulsed action

NASA Astrophysics Data System (ADS)

Genin, D. E.; Beloplotov, D. V.; Panchenko, A. N.; Tarasenko, V. F.

2018-04-01

Experimental study and theoretical analysis of growth of microstructures (microtowers) on liquid metals by fs laser pulses have been carried out. Theoretical analysis has been performed on the basis of the two-temperature model. Compared to ns laser pulses, in fs irradiation regimes the heat-affected zone is strongly localized resulting in much larger temperatures and temperature gradients. In the experimental irradiation regimes, the surface temperature of liquid metals studied may reach or even exceed a critical level that culminates in phase explosion or direct atomization of a metal surface layer. However, before explosive ablation starts, a stress wave with an amplitude up to several GPa is formed which demolishes oxide covering. Moreover, at high laser fluences laser-induced breakdown is developed in oxide layer covering the metal surface that leads to destruction/ablation of oxide without damaging metal underneath. An overall scenario of microstructure growth with fs laser pulses is similar to that obtained for ns irradiation regimes though the growth threshold is lower due to smaller heat-conduction losses. Also we managed to obtain microstructures formation by the action of spark discharge.

Numerical investigation of narrowband infrared absorber and sensor based on dielectric-metal metasurface.

PubMed

Lu, Xiaoyuan; Zhang, Tongyi; Wan, Rengang; Xu, Yongtao; Zhao, Changhong; Guo, Sheng

2018-04-16

Metasurfaces are investigated intensively for biophotonics applications due to their resonant wavelength flexibly tuned in the near infrared region specially matching biological tissues. Here, we present numerically a metasurface structure combining dielectric resonance with surface plasmon mode of a metal plane, which is a perfect absorber with a narrow linewidth 10 nm wide and quality factor 120 in the near infrared regime. As a sensor, its bulk sensitivity and bulk figure of merit reach respectively 840 nm/RIU and 84/RIU, while its surface sensitivity and surface figure of merit are respectively 1 and 0.1/nm. For different types of adsorbate layers with the same thickness of 8 nm, its surface sensitivity and figure of merit are respectively 32.3 and 3.2/RIU. The enhanced electric field is concentrated on top of dielectric patch ends and in the patch ends simultaneously. Results show that the presented structure has high surface (and bulk) sensing capability in sensing applications due to its narrow linewidth and deep modulation depth. This could pave a new route toward dielectric-metal metasurface in biosensing applications, such as early disease detections and designs of neural stem cell sensing platforms.

Control of the plasmonic near-field in metallic nanohelices.

PubMed

Caridad, José M; Winters, Sinéad; McCloskey, David; Duesberg, Georg S; Donegan, John F; Krstić, Vojislav

2018-08-10

The optical response of metallic nanohelices is mainly governed by a longitudinal localised surface plasmon resonance (LSPR) which arises due to the helical anisotropy of the system. Up to now, experimental studies have predominantly addressed the far-field response, despite the fact that the LSPR being of broad interest for converting incoming light into strongly enhanced (chiral) optical near-fields. Here, we demonstrate the control and spatial reproducibility of the plasmon-induced electromagnetic near-field around metallic nanohelices via surface-enhanced Raman scattering. We discuss how the near-field intensity of these nanostructures can be custom-tailored through both the nanoscaled helical structure and the electronic properties of the constituting metals. Our experiments, which employ graphene as an accurate probing material, are in quantitative agreement with corresponding numerical simulations. The findings demonstrate metallic nanohelices as reference nanostructured surfaces able to provide and fine-tune optical fields for fundamental studies as well as sensing or (chiro-optical) imaging applications.

Corrosion and surface modification on biocompatible metals: A review.

PubMed

Asri, R I M; Harun, W S W; Samykano, M; Lah, N A C; Ghani, S A C; Tarlochan, F; Raza, M R

2017-08-01

Corrosion prevention in biomaterials has become crucial particularly to overcome inflammation and allergic reactions caused by the biomaterials' implants towards the human body. When these metal implants contacted with fluidic environments such as bloodstream and tissue of the body, most of them became mutually highly antagonistic and subsequently promotes corrosion. Biocompatible implants are typically made up of metallic, ceramic, composite and polymers. The present paper specifically focuses on biocompatible metals which favorably used as implants such as 316L stainless steel, cobalt-chromium-molybdenum, pure titanium and titanium-based alloys. This article also takes a close look at the effect of corrosion towards the implant and human body and the mechanism to improve it. Due to this corrosion delinquent, several surface modification techniques have been used to improve the corrosion behavior of biocompatible metals such as deposition of the coating, development of passivation oxide layer and ion beam surface modification. Apart from that, surface texturing methods such as plasma spraying, chemical etching, blasting, electropolishing, and laser treatment which used to improve corrosion behavior are also discussed in detail. Introduction of surface modifications to biocompatible metals is considered as a "best solution" so far to enhanced corrosion resistance performance; besides achieving superior biocompatibility and promoting osseointegration of biocompatible metals and alloys. Copyright © 2017 Elsevier B.V. All rights reserved.

Importance of electronegativity differences and surface structure in molecular dissociation reactions at transition metal surfaces.

PubMed

Crawford, Paul; Hu, P

2006-12-14

The dissociative adsorption of N2 has been studied at both monatomic steps and flat regions on the surfaces of the 4d transition metals from Zr to Pd. Using density functional theory (DFT) calculations, we have determined and analyzed the trends in both straight reactivity and structure sensitivity across the periodic table. With regards to reactivity, we find that the trend in activation energy (Ea) is determined mainly by a charge transfer from the surface metal atoms to the N atoms during transition state formation, namely, the degree of ionicity of the N-surface bond at the transition state. Indeed, we find that the strength of the metal-N bond at the transition state (and therefore the trend in Ea) can be predicted by the difference in Mulliken electronegativity between the metal and N. Structure sensitivity is analyzed in terms of geometric and electronic effects. We find that the lowering of Ea due to steps is more pronounced on the right-hand side of the periodic table. It is found that for the early transition metals the geometric and electronic effects work in opposition when going from terrace to step active site. In the case of the late 4d metals, however, these effects work in combination, producing a more marked reduction in Ea.

Nanostructuring of sapphire using time-modulated nanosecond laser pulses

NASA Astrophysics Data System (ADS)

Lorenz, P.; Zagoranskiy, I.; Ehrhardt, M.; Bayer, L.; Zimmer, K.

2017-02-01

The nanostructuring of dielectric surfaces using laser radiation is still a challenge. The IPSM-LIFE (laser-induced front side etching using in-situ pre-structured metal layer) method allows the easy, large area and fast laser nanostructuring of dielectrics. At IPSM-LIFE a metal covered dielectric is irradiated where the structuring is assisted by a self-organized molten metal layer deformation process. The IPSM-LIFE can be divided into two steps: STEP 1: The irradiation of thin metal layers on dielectric surfaces results in a melting and nanostructuring process of the metal layer and partially of the dielectric surface. STEP 2: A subsequent high laser fluence treatment of the metal nanostructures result in a structuring of the dielectric surface. At this study a sapphire substrate Al2O3(1-102) was covered with a 10 nm thin molybdenum layer and irradiated by an infrared laser with an adjustable time-dependent pulse form with a time resolution of 1 ns (wavelength λ = 1064 nm, pulse duration Δtp = 1 - 600 ns, Gaussian beam profile). The laser treatment allows the fabrication of different surface structures into the sapphire surface due to a pattern transfer process. The resultant structures were investigated by scanning electron microscopy (SEM). The process was simulated and the simulation results were compared with experimental results.

Corrugated metal surface with pillars for terahertz surface plasmon polariton waveguide components

NASA Astrophysics Data System (ADS)

Zhang, Ying; Xu, Yuehong; Tian, Chunxiu; Xu, Quan; Zhang, Xueqian; Li, Yanfeng; Zhang, Xixiang; Han, Jiaguang; Zhang, Weili

2018-01-01

In the terahertz regime, due to perfect conductivity of most metals, it is hard to realize a strong confinement of Surface plasmon polaritons (SPPs) although a propagation loss could be sufficiently low. We experimentally demonstrated a structure with periodic pillars arranged on a thin metal surface that supports bound modes of spoof SPPs at terahertz (THz) frequencies. By using scanning near-field THz microscopy, the electric field distribution above the metal surface within a distance of 130 μm was mapped. The results proved that this structure could guide spoof SPPs propagating along subwavelength waveguides, and at the same time reduce field expansion into free space. Further, for the development of integrated optical circuits, several components including straight waveguide, S-bend, Y-splitter and directional couplers were designed and characterized by the same method. We believe that the waveguide components proposed here will pave a new way for the development of flexible, wideband and compact photonic circuits operating at THz frequencies.

Back-surface gold mirrors for vibrationally resonant sum-frequency (VR-SFG) spectroscopy using 3-mercaptopropyltrimethoxysilane as an adhesion promoter.

PubMed

Quast, Arthur D; Zhang, Feng; Linford, Matthew R; Patterson, James E

2011-06-01

Back-surface mirrors are needed as reference materials for vibrationally resonant sum-frequency generation (VR-SFG) probing of liquid-solid interfaces. Conventional noble metal mirrors are not suitable for back-surface applications due to the presence of a metal adhesion layer (chromium or titanium) between the window substrate and the reflective metal surface. Using vapor deposited 3-mercaptopropyltrimethoxysilane (MPTMS) as a bi-functional adhesion promoter, gold mirrors were fabricated on fused silica substrates. These mirrors exhibit excellent gold adhesion as determined by the Scotch(®) tape test. They also produce minimal spectroscopic interference in the C-H stretching region (2800-3000 cm(-1)), as characterized by VR-SFG. These mirrors are thus robust and can be used as back-surface mirrors for a variety of applications, including reference mirrors for VR-SFG.

On femtosecond laser shock peening of stainless steel AISI 316

NASA Astrophysics Data System (ADS)

Hoppius, Jan S.; Kukreja, Lalit M.; Knyazeva, Marina; Pöhl, Fabian; Walther, Frank; Ostendorf, Andreas; Gurevich, Evgeny L.

2018-03-01

In this paper we report on the competition in metal surface hardening between the femtosecond shock peening on the one hand, and formation of laser-induced periodic surface structures (LIPSS) and surface oxidation on the other hand. Peening of the stainless steel AISI 316 due to shock loading induced by femtosecond laser ablation was successfully demonstrated. However, for some range of processing parameters, surface erosion due to LIPSS and oxidation seems to dominate over the peening effect. Strategies to increase the peening efficiency are discussed.

Optical Properties and Plasmonic Performance of Titanium Nitride

PubMed Central

Patsalas, Panos; Kalfagiannis, Nikolaos; Kassavetis, Spyros

2015-01-01

Titanium nitride (TiN) is one of the most well-established engineering materials nowadays. TiN can overcome most of the drawbacks of palsmonic metals due to its high electron conductivity and mobility, high melting point and due to the compatibility of its growth with Complementary Metal Oxide Semiconductor (CMOS) technology. In this work, we review the dielectric function spectra of TiN and we evaluate the plasmonic performance of TiN by calculating (i) the Surface Plasmon Polariton (SPP) dispersion relations and (ii) the Localized Surface Plasmon Resonance (LSPR) band of TiN nanoparticles, and we demonstrate a significant plasmonic performance of TiN.

Optimization and validation of highly selective microfluidic integrated silicon nanowire chemical sensor

NASA Astrophysics Data System (ADS)

Ehfaed, Nuri. A. K. H.; Bathmanathan, Shillan A. L.; Dhahi, Th S.; Adam, Tijjani; Hashim, Uda; Noriman, N. Z.

2017-09-01

The study proposed characterization and optimization of silicon nanosensor for specific detection of heavy metal. The sensor was fabricated in-house and conventional photolithography coupled with size reduction via dry etching process in an oxidation furnace. Prior to heavy metal heavy metal detection, the capability to aqueous sample was determined utilizing serial DI water at various. The sensor surface was surface modified with Organofunctional alkoxysilanes (3-aminopropyl) triethoxysilane (APTES) to create molecular binding chemistry. This has allowed interaction between heavy metals being measured and the sensor component resulting in increasing the current being measured. Due to its, excellent detection capabilities, this sensor was able to identify different group heavy metal species. The device was further integrated with sub-50 µm for chemical delivery.

Cascaded plasmon-plasmon coupling mediated energy transfer across stratified metal-dielectric nanostructures

PubMed Central

Golmakaniyoon, Sepideh; Hernandez-Martinez, Pedro Ludwig; Demir, Hilmi Volkan; Sun, Xiao Wei

2016-01-01

Surface plasmon (SP) coupling has been successfully applied to nonradiative energy transfer via exciton-plasmon-exciton coupling in conventionally sandwiched donor-metal film-acceptor configurations. However, these structures lack the desired efficiency and suffer poor photoemission due to the high energy loss. Here, we show that the cascaded exciton-plasmon-plasmon-exciton coupling in stratified architecture enables an efficient energy transfer mechanism. The overlaps of the surface plasmon modes at the metal-dielectric and dielectric-metal interfaces allow for strong cross-coupling in comparison with the single metal film configuration. The proposed architecture has been demonstrated through the analytical modeling and numerical simulation of an oscillating dipole near the stratified nanostructure of metal-dielectric-metal-acceptor. Consistent with theoretical and numerical results, experimental measurements confirm at least 50% plasmon resonance energy transfer enhancement in the donor-metal-dielectric-metal-acceptor compared to the donor-metal-acceptor structure. Cascaded plasmon-plasmon coupling enables record high efficiency for exciton transfer through metallic structures. PMID:27698422

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

Yang, Qiu; Liu, Wenxian; Wang, Bingqing

Composites incorporating metal nanoparticles (MNPs) within metal-organic frameworks (MOFs) have broad applications in many fields. However, the controlled spatial distribution of the MNPs within MOFs remains a challenge for addressing key issues in catalysis, for example, the efficiency of catalysts due to the limitation of molecular diffusion within MOF channels. We report a facile strategy that enables MNPs to be encapsulated into MOFs with controllable spatial localization by using metal oxide both as support to load MNPs and as a sacrificial template to grow MOFs. This strategy is versatile to a variety of MNPs and MOF crystals. By localizing themore » encapsulated MNPs closer to the surface of MOFs, the resultant MNPs@MOF composites not only exhibit effective selectivity derived from MOF cavities, but also enhanced catalytic activity due to the spatial regulation of MNPs as close as possible to the MOF surface.« less

Tribological properties of silicon carbide in metal removal process

NASA Technical Reports Server (NTRS)

Miyoshi, K.; Buckley, D. H.

1980-01-01

Material properties are considered as they relate to adhesion, friction, and wear of single crystal silicon carbide in contact with metals and alloys that are likely to be involved in a metal removal process such as grinding. Metal removal from adhesion between sliding surfaces in contact and metal removal as a result of the silicon carbide sliding against a metal, indenting into it, and plowing a series of grooves or furrows are discussed. Fracture and deformation characteristics of the silicon carbide surface are also covered. The adhesion, friction, and metal transfer to silicon carbide is related to the relative chemical activity of the metals. The more active the metal, the higher the adhesion and friction, and the greater the metal transfer to silicon carbide. Atomic size and content of alloying elements play a dominant role in controlling adhesion, friction, and abrasive wear properties of alloys. The friction and abrasive wear (metal removal) decrease linearly as the shear strength of the bulk metal increases. They decrease as the solute to solvent atomic radius ratio increases or decreases linearly from unity, and with an increase of solute content. The surface fracture of silicon carbide is due to cleavages of 0001, 10(-1)0, and/or 11(-2)0 planes.

EPR study of electron bombarded alkali- and alkaline-earth halide crystal surfaces

NASA Technical Reports Server (NTRS)

Fryburg, G. C.; Lad, R. A.

1975-01-01

An EPR study of electron bombarded LiF, NaCl, KCl, CaF2 and BaF2 polycrystalline surfaces has shown that small metal particles are formed on the surfaces of the crystals. Identification was made from CESR signals. The symmetric line-shape of the signals, even at 77 K, indicated that the particles were less than 0.5 micron in diameter. Signals due to F centers were observed in LiF but not in the other halides. Implications to metal deposition are considered.

Multidrug and heavy metal-resistant Raoultella planticola isolated from surface water.

PubMed

Koc, Serkan; Kabatas, Burak; Icgen, Bulent

2013-08-01

A surface water isolate of Raoultella sp. having both multidrug- and multimetal-resistant ability was isolated and identified as Raoultella planticola. R. planticola displayed resistance to 15 drugs like ampicillin, amoxicillin/clavulanic acid, aztreonam, erythromycin, imipenem, oxacillin, pefloxacin, penicillin, piperacillin, piperacillin/tazobactam, rifampin, sulbactam/cefoperazone, ticarsillin, ticarsillin/clavulanic acid, vancomycin, and to 11 heavy metals like aluminum, barium, copper, iron, lead, lithium, manganese, nickel, silver, strontium, and tin. The multidrug and multi-metal-resistant R. planticola may remain present in the environment for a long time. Due to a possible health risk of these pathogenic bacteria, a need exists for an accurate assessment of their acquired resistance to multiple drugs and metals.

Fireside corrosion in kraft recovery boilers

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

Tran, H.N.; Barham, D.; Hupa, M.

1988-01-01

Causes and corrective measures are reviewed for several common types of fireside corrosion in kraft recovery boilers. Corrosion differs significantly with location in the boiler due tio the great differences in metal surface temperature and deposit and flue gas chemistry. Sulphidation corrosion associated with sulphur-bearing gases under reducing conditions is dominant in the lower furnace, while sulphidation/oxidation resulting from gas-deposit-metal reactions is important in the upper boiler. In many cases, although corrosion has been controlled by ensuring the absence of a molten phase at the metal surface, the corrosion mechanism is not fully understood.

Detection of heavy metal ions in contaminated water by surface plasmon resonance based optical fibre sensor using conducting polymer and chitosan.

PubMed

Verma, Roli; Gupta, Banshi D

2015-01-01

Optical fibre surface plasmon resonance (SPR) based sensor for the detection of heavy metal ions in the drinking water is designed. Silver (Ag) metal and indium tin oxide (ITO) are used for the fabrication of the SPR probe which is further modified with the coating of pyrrole and chitosan composite. The sensor works on the wavelength interrogation technique and is capable of detecting trace amounts of Cd(2+), Pb(2+), and Hg(2+) heavy metal ions in contaminated water. Four types of sensing probes are fabricated and characterised for heavy metal ions out of these pyrrole/chitosan/ITO/Ag coated probe is found to be highly sensitive among all other probes. Further, the cadmium ions bind strongly to the sensing surface than other ions and due to this the sensor is highly sensitive for Cd(2+) ions. The sensor's performance is best for the low concentrations of heavy metal ions and its sensitivity decreases with the increasing concentration of heavy metal ions. Copyright © 2014 Elsevier Ltd. All rights reserved.

Thermally generated metals for plasmonic coloring and surface-enhanced Raman sensing

NASA Astrophysics Data System (ADS)

Huang, Zhenping; Chen, Jian; Liu, Guiqiang; Wang, Yan; Liu, Yi; Tang, Li; Liu, Zhengqi

2018-03-01

Spectral coloring glass and its application on the surface-enhanced Raman scattering are demonstrated experimentally via a simple and moderate heat-treating of the top ultrathin gold film to create discrete nanoparticles, which can produce localized surface plasmon resonances and strong plasmonic near-field coupling effects. Ultrathin metal films with a wide range of thicknesses are investigated by different heat-treatment processes. The annealed metal films have been demonstrated with a series of spectral coloring responses. Moreover, the microscopy images of the metal film structures confirm the formation of distinct geometry features in these operation procedures. Densely packed nanoparticles are observed for the ultrathin metal film with the single-digit level of thickness. With increasing the film thickness over 10 nm, metallic clusters and porous morphologies can be obtained. Importantly, the metallic resonators can provide enhanced Raman scattering with the detection limit down to 10 - 7 molL - 1 of Rhodamine 6G molecules due to the excitation of plasmon resonances and strong near-field coupling effects. These features hold great potential for large-scale and low-cost production of colored glass and Raman substrate.

The Effect of Specific Surface Area of Chitin-Metal Silicate Coprocessed Excipient on the Chemical Decomposition of Cefotaxime Sodium.

PubMed

Al-Nimry, Suhair S; Alkhamis, Khouloud A; Alzarieni, Kawthar Z

2017-02-01

Chitin-metal silicates are multifunctional excipients used in tablets. Previously, a correlation between the surface acidity of chitin-calcium and chitin-magnesium silicate and the chemical decomposition of cefotaxime sodium was found but not with chitin-aluminum silicate. This lack of correlation could be due to the catalytic effect of silica alumina or the difference in surface area of the excipients. The objective of this study was to investigate the effect of the specific surface area of the excipient on the chemical decomposition of cefotaxime sodium in the solid state. Chitin was purified and coprocessed with different metal silicates to prepare the excipients. The specific surface area was determined using gas adsorption. The chemical decomposition was studied at constant temperature and relative humidity. Also, the degradation in solution was studied. A correlation was found between the degradation rate constant and the surface area of chitin-aluminum and chitin-calcium silicate but not with chitin-magnesium silicate. This was due to the small average pore diameter of this excipient. Also, the degradation in solution was slower than in solid state. In conclusion, the stability of cefotaxime sodium was dependent on the surface area of the excipient in contact with the drug. Copyright © 2017 American Pharmacists Association®. Published by Elsevier Inc. All rights reserved.

In-situ electrochemical study of interaction of tribology and corrosion in artificial hip prosthesis simulators.

PubMed

Yan, Yu; Dowson, Duncan; Neville, Anne

2013-02-01

The second generation Metal-on-Metal (MoM) hip replacements have been considered as an alternative to commonly used Polyethylene-on-Metal (PoM) joint prostheses due to polyethylene wear debris induced osteolysis. However, the role of corrosion and the biofilm formed under tribological contact are still not fully understood. Enhanced metal ion concentrations have been reported widely from hair, blood and urine samples of patients who received metal hip replacements and in isolated cases when abnormally high levels have caused adverse local tissue reactions. An understanding of the origin of metal ions is really important in order to design alloys for reduced ion release. Reciprocating pin-on-plate wear tester is a standard instrument to assess the interaction of corrosion and wear. However, more realistic hip simulator can provide a better understanding of tribocorrosion process for hip implants. It is very important to instrument the conventional hip simulator to enable electrochemical measurements. In this study, simple reciprocating pin-on-plate wear tests and hip simulator tests were compared. It was found that metal ions originated from two sources: (a) a depassivation of the contacting surfaces due to tribology (rubbing) and (b) corrosion of nano-sized wear particles generated from the contacting surfaces. Copyright © 2012 Elsevier Ltd. All rights reserved.

Plasmon Enhanced Hetero-Junction Solar Cell

NASA Astrophysics Data System (ADS)

Long, Gen; Ching, Levine; Sadoqi, Mostafa; Xu, Huizhong

2015-03-01

Here we report a systematic study of plasmon-enhanced hetero-junction solar cells made of colloidal quantum dots (PbS) and nanowires (ZnO), with/without metal nanoparticles (Au). The structure of solar cell devices was characterized by AFM, SEM and profilometer, etc. The power conversion efficiencies of solar cell devices were characterized by solar simulator (OAI TriSOL, AM1.5G Class AAA). The enhancement in the photocurrent due to introduction of metal nanoparticles was obvious. We believe this is due to the plasmonic effect from the metal nanoparticles. The correlation between surface roughness, film uniformity and device performance was also studied.

Low-dimensional carbon and MXene-based electrochemical capacitor electrodes.

PubMed

Yoon, Yeoheung; Lee, Keunsik; Lee, Hyoyoung

2016-04-29

Due to their unique structure and outstanding intrinsic physical properties such as extraordinarily high electrical conductivity, large surface area, and various chemical functionalities, low-dimension-based materials exhibit great potential for application in electrochemical capacitors (ECs). The electrical properties of electrochemical capacitors are determined by the electrode materials. Because energy charge storage is a surface process, the surface properties of the electrode materials greatly influence the electrochemical performance of the cell. Recently, graphene, a single layer of sp(2)-bonded carbon atoms arrayed into two-dimensional carbon nanomaterial, has attracted wide interest as an electrode material for electrochemical capacitor applications due to its unique properties, including a high electrical conductivity and large surface area. Several low-dimensional materials with large surface areas and high conductivity such as onion-like carbons (OLCs), carbide-derived carbons (CDCs), carbon nanotubes (CNTs), graphene, metal hydroxide, transition metal dichalcogenides (TMDs), and most recently MXene, have been developed for electrochemical capacitors. Therefore, it is useful to understand the current issues of low-dimensional materials and their device applications.

Evaluation of Workpiece Temperature during Drilling of GLARE Fiber Metal Laminates Using Infrared Techniques: Effect of Cutting Parameters, Fiber Orientation and Spray Mist Application.

PubMed

Giasin, Khaled; Ayvar-Soberanis, Sabino

2016-07-28

The rise in cutting temperatures during the machining process can influence the final quality of the machined part. The impact of cutting temperatures is more critical when machining composite-metal stacks and fiber metal laminates due to the stacking nature of those hybrids which subjects the composite to heat from direct contact with metallic part of the stack and the evacuated hot chips. In this paper, the workpiece surface temperature of two grades of fiber metal laminates commercially know as GLARE is investigated. An experimental study was carried out using thermocouples and infrared thermography to determine the emissivity of the upper, lower and side surfaces of GLARE laminates. In addition, infrared thermography was used to determine the maximum temperature of the bottom surface of machined holes during drilling GLARE under dry and minimum quantity lubrication (MQL) cooling conditions under different cutting parameters. The results showed that during the machining process, the workpiece surface temperature increased with the increase in feed rate and fiber orientation influenced the developed temperature in the laminate.

Evaluation of Workpiece Temperature during Drilling of GLARE Fiber Metal Laminates Using Infrared Techniques: Effect of Cutting Parameters, Fiber Orientation and Spray Mist Application

PubMed Central

Giasin, Khaled; Ayvar-Soberanis, Sabino

2016-01-01

The rise in cutting temperatures during the machining process can influence the final quality of the machined part. The impact of cutting temperatures is more critical when machining composite-metal stacks and fiber metal laminates due to the stacking nature of those hybrids which subjects the composite to heat from direct contact with metallic part of the stack and the evacuated hot chips. In this paper, the workpiece surface temperature of two grades of fiber metal laminates commercially know as GLARE is investigated. An experimental study was carried out using thermocouples and infrared thermography to determine the emissivity of the upper, lower and side surfaces of GLARE laminates. In addition, infrared thermography was used to determine the maximum temperature of the bottom surface of machined holes during drilling GLARE under dry and minimum quantity lubrication (MQL) cooling conditions under different cutting parameters. The results showed that during the machining process, the workpiece surface temperature increased with the increase in feed rate and fiber orientation influenced the developed temperature in the laminate. PMID:28773757

Heavy metal contamination and ecological risk assessment in the surface sediments of the coastal area surrounding the industrial complex of Gabes city, Gulf of Gabes, SE Tunisia.

PubMed

El Zrelli, Radhouan; Courjault-Radé, Pierre; Rabaoui, Lotfi; Castet, Sylvie; Michel, Sylvain; Bejaoui, Nejla

2015-12-30

In the present study, the concentrations of 6 trace metals (Hg, Cd, Cu, Pb, Cr and Zn) were assessed in the surface sediments of the central coastal area of Gabes Gulf to determine their contamination status, source, spatial distribution and ecological risks. The ranking of metal contents was found to be Zn>Cd>Cr>Pb>Cu>Hg. Correlation analysis indicated that Cd and Zn derived mainly from the Tunisian Chemical Group phosphogypsum. The other pollutants may originate from other industrial wastes. Metallic contamination was detected in the south of chemical complex, especially in the inter-harbor zone, where the ecological risk of surface sediments is the highest, implying potential negative impacts of industrial pollutants. The spatial distribution of pollutants seems to be due to the effect of harbor installations and coastal currents. The metallic pollution status of surface sediments of Gabes Gulf is obvious, very worrying and requires rapid intervention. Copyright © 2015 Elsevier Ltd. All rights reserved.

Magnetotransport in Dirac metals: Chiral magnetic effect and quantum oscillations

DOE PAGES

Monteiro, Gustavo M.; Abanov, Alexander G.; Kharzeev, Dmitri E.

2015-10-08

Dirac metals are characterized by the linear dispersion of fermionic quasiparticles, with the Dirac point hidden inside a Fermi surface. We study the magnetotransport in these materials using chiral kinetic theory to describe within the same framework both the negative magnetoresistance caused by the chiral magnetic effect and quantum oscillations in the magnetoresistance due to the existence of the Fermi surface. Lastly, we discuss the relevance of obtained results to recent measurements on Cd 3As 2.

Mathematical modelling of convective processes in a weld pool under electric arc surfacing

NASA Astrophysics Data System (ADS)

Sarychev, V. D.; Granovskii, A. Yu; Nevskii, S. A.; Konovalov, S. V.

2017-01-01

The authors develop the mathematical model of convective processes in a molten pool under electric arc surfacing with flux-cored wire. The model is based on the ideas of how convective flows appear due to temperature gradient and action of electromagnetic forces. Influence of alloying elements in the molten metal was modeled as a non-linear dependence of surface tension upon temperature. Surface tension and its temperature coefficient were calculated according to the electron density functional method with consideration to asymmetric electron distribution at the interface “molten metal / shielding gas”. Simultaneous solution of Navier-Stokes and Maxwell equations according to finite elements method with consideration to the moving heat source at the interface showed that there is a multi-vortex structure in the molten metal. This structure gives rise to a downward heat flux which, at the stage of heating, moves from the centre of the pool and stirs it full width. At the cooling stage this flux moves towards the centre of the pool and a single vortex is formed near the symmetry centre. This flux penetration is ∼ 10 mm. Formation of the downward heat flux is determined by sign reversal of the temperature coefficient of surface tension due to the presence of alloying elements.

Recent Progress in Bionic Condensate Microdrop Self-Propelling Surfaces.

PubMed

Gong, Xiaojing; Gao, Xuefeng; Jiang, Lei

2017-12-01

Bionic condensate microdrop self-propelling (CMDSP) surfaces are attracting increased attention as novel, low-adhesivity superhydrophobic surfaces due to their value in fundamental research and technological innovation, e.g., for enhancing heat transfer, energy-effective antifreezing, and electrostatic energy harvesting. Here, the focus is on recent progress in bionic CMDSP surfaces. Metal-based CMDSP surfaces, which are the most promising in their respective fields, are highlighted for use in future applications. The selected topics are divided into four sections: biological prototypes, mechanism and construction rules, fabrication, and applications of metal-based CMDSP surfaces. Finally, the challenges and future development trends in bionic CMDSP surfaces are envisioned, especially the utilization of potential bionic inspiration in the design of more advanced CMDSP surfaces. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

[Research advances in heavy metals pollution ecology of diatom].

PubMed

Ding, Teng-Da; Ni, Wan-Min; Zhang, Jian-Ying

2012-03-01

Diatom, due to its high sensitivity to environmental change, is one of the bio-indicators of aquatic ecosystem health, and some typical diatom species have been applied to indicate the heavy metals pollution of water body. With the focus on the surface water heavy metals pollution, this paper reviewed the research advances in the toxic effect of heavy metals pollution on diatom, biosorption and bioaccumulation of heavy metals by diatom, ecological adaptation mechanisms of diatom to heavy metals pollution, and roles of diatom as bio-indicator and in ecological restoration of heavy metals pollution. The growth tendency of diatom and the morphological change of frustule under heavy metals pollution as well as the differences in heavy metals biosorption and bioaccumulation by diatom, the ecological adaptation mechanisms of diatom on heavy metals surface complexation and ion exchange, and the roles of diatom as bio-indicator and in ecological restoration of heavy metals polluted water body were also discussed. This review could provide scientific evidences for the prevention of aquatic ecosystems heavy metals pollution and related early warning techniques.

Versatile multi-functionalization of protein nanofibrils for biosensor applications

NASA Astrophysics Data System (ADS)

Sasso, L.; Suei, S.; Domigan, L.; Healy, J.; Nock, V.; Williams, M. A. K.; Gerrard, J. A.

2014-01-01

Protein nanofibrils offer advantages over other nanostructures due to the ease in their self-assembly and the versatility of surface chemistry available. Yet, an efficient and general methodology for their post-assembly functionalization remains a significant challenge. We introduce a generic approach, based on biotinylation and thiolation, for the multi-functionalization of protein nanofibrils self-assembled from whey proteins. Biochemical characterization shows the effects of the functionalization onto the nanofibrils' surface, giving insights into the changes in surface chemistry of the nanostructures. We show how these methods can be used to decorate whey protein nanofibrils with several components such as fluorescent quantum dots, enzymes, and metal nanoparticles. A multi-functionalization approach is used, as a proof of principle, for the development of a glucose biosensor platform, where the protein nanofibrils act as nanoscaffolds for glucose oxidase. Biotinylation is used for enzyme attachment and thiolation for nanoscaffold anchoring onto a gold electrode surface. Characterization via cyclic voltammetry shows an increase in glucose-oxidase mediated current response due to thiol-metal interactions with the gold electrode. The presented approach for protein nanofibril multi-functionalization is novel and has the potential of being applied to other protein nanostructures with similar surface chemistry.Protein nanofibrils offer advantages over other nanostructures due to the ease in their self-assembly and the versatility of surface chemistry available. Yet, an efficient and general methodology for their post-assembly functionalization remains a significant challenge. We introduce a generic approach, based on biotinylation and thiolation, for the multi-functionalization of protein nanofibrils self-assembled from whey proteins. Biochemical characterization shows the effects of the functionalization onto the nanofibrils' surface, giving insights into the changes in surface chemistry of the nanostructures. We show how these methods can be used to decorate whey protein nanofibrils with several components such as fluorescent quantum dots, enzymes, and metal nanoparticles. A multi-functionalization approach is used, as a proof of principle, for the development of a glucose biosensor platform, where the protein nanofibrils act as nanoscaffolds for glucose oxidase. Biotinylation is used for enzyme attachment and thiolation for nanoscaffold anchoring onto a gold electrode surface. Characterization via cyclic voltammetry shows an increase in glucose-oxidase mediated current response due to thiol-metal interactions with the gold electrode. The presented approach for protein nanofibril multi-functionalization is novel and has the potential of being applied to other protein nanostructures with similar surface chemistry. Electronic supplementary information (ESI) available: Cyclic voltammetry characterization of biosensor platforms including bare Au electrodes (Fig. S1), biosensor response to various glucose concentrations (Fig. S2), and AFM roughness measurements due to WPNF modifications (Fig. S3). See DOI: 10.1039/c3nr05752f

Multimode Surface Plasmon Excitations on Organic Thin Film/Metallic Diffraction Grating

NASA Astrophysics Data System (ADS)

Baba, Akira; Kanda, Kenji; Ohno, Tsutomu; Ohdaira, Yasuo; Shinbo, Kazunari; Kato, Keizo; Kaneko, Futao

2010-01-01

In this work, we demonstrate multimode surface plasmon (SP) excitations by white light irradiation on metallic diffraction grating/plastic substrates. Recordable compact discs were used as the diffraction grating substrates on which silver films were deposited by vacuum evaporation. Since the grating pitch (1.6 µm) was larger than that of diffraction gratings commonly used for the excitation of SPs, multimode SP excitations due to several diffraction orders were observed simultaneously in the wavelength region from 400 to 800 nm. The obtained SP excitations were then compared with the calculated SP dispersion on the grating. The multimode SP excitations were further studied on spin-coated poly[2-methoxy-5-(2'-ethyl-hexyloxy)-1,4-phenylene vinylene] (MEH-PPV) thin film/silver grating substrates. An increased photoluminescence intensity due to SP excitations was observed on MEH-PPV/silver grating surfaces.

Complexation- and ligand-induced metal release from 316L particles: importance of particle size and crystallographic structure.

PubMed

Hedberg, Yolanda; Hedberg, Jonas; Liu, Yi; Wallinder, Inger Odnevall

2011-12-01

Iron, chromium, nickel, and manganese released from gas-atomized AISI 316L stainless steel powders (sized <45 and <4 μm) were investigated in artificial lysosomal fluid (ALF, pH 4.5) and in solutions of its individual inorganic and organic components to determine its most aggressive component, elucidate synergistic effects, and assess release mechanisms, in dependence of surface changes using atomic absorption spectroscopy, Raman, XPS, and voltammetry. Complexation is the main reason for metal release from 316L particles immersed in ALF. Iron was mainly released, while manganese was preferentially released as a consequence of the reduction of manganese oxide on the surface. These processes resulted in highly complexing media in a partial oxidation of trivalent chromium to hexavalent chromium on the surface. The extent of metal release was partially controlled by surface properties (e.g., availability of elements on the surface and structure of the outermost surface) and partially by the complexation capacity of the different metals with the complexing agents of the different media. In general, compared to the coarse powder (<45 μm), the fine (<4 μm) powder displayed significantly higher released amounts of metals per surface area, increased with increased solution complexation capacity, while less amounts of metals were released into non-complexing solutions. Due to the ferritic structure of lower solubility for nickel of the fine powder, more nickel was released into all solutions compared with the coarser powder.

Insight into induced charges at metal surfaces and biointerfaces using a polarizable Lennard-Jones potential.

PubMed

Geada, Isidro Lorenzo; Ramezani-Dakhel, Hadi; Jamil, Tariq; Sulpizi, Marialore; Heinz, Hendrik

2018-02-19

Metallic nanostructures have become popular for applications in therapeutics, catalysts, imaging, and gene delivery. Molecular dynamics simulations are gaining influence to predict nanostructure assembly and performance; however, instantaneous polarization effects due to induced charges in the free electron gas are not routinely included. Here we present a simple, compatible, and accurate polarizable potential for gold that consists of a Lennard-Jones potential and a harmonically coupled core-shell charge pair for every metal atom. The model reproduces the classical image potential of adsorbed ions as well as surface, bulk, and aqueous interfacial properties in excellent agreement with experiment. Induced charges affect the adsorption of ions onto gold surfaces in the gas phase at a strength similar to chemical bonds while ions and charged peptides in solution are influenced at a strength similar to intermolecular bonds. The proposed model can be applied to complex gold interfaces, electrode processes, and extended to other metals.

Spin polarization of graphene and h -BN on Co(0001) and Ni(111) observed by spin-polarized surface positronium spectroscopy

NASA Astrophysics Data System (ADS)

Miyashita, A.; Maekawa, M.; Wada, K.; Kawasuso, A.; Watanabe, T.; Entani, S.; Sakai, S.

2018-05-01

In spin-polarized surface positronium annihilation measurements, the spin polarizations of graphene and h -BN on Co(0001) were higher than those on Ni(111), while no significant differences were seen between graphene and h -BN on the same metal. The obtained spin polarizations agreed with those expected from first-principles calculations considering the positron wave function and the electron density of states from the first surface layer to the vacuum region. The higher spin polarizations of graphene and h -BN on Co(0001) as compared to Ni(111) simply reflect the spin polarizations of these metals. The comparable spin polarizations of graphene and h -BN on the same metal are attributed to the creation of similar electronic states due to the strong influence of the metals: the Dirac cone of graphene and the band gap of h -BN disappear as a consequence of d -π hybridization.

Effect of Extreme Wettability on Platelet Adhesion on Metallic Implants: From Superhydrophilicity to Superhydrophobicity.

PubMed

Moradi, Sona; Hadjesfandiari, Narges; Toosi, Salma Fallah; Kizhakkedathu, Jayachandran N; Hatzikiriakos, Savvas G

2016-07-13

In order to design antithrombotic implants, the effect of extreme wettability (superhydrophilicity to superhydrophobicity) on the biocompatibility of the metallic substrates (stainless steel and titanium) was investigated. The wettability of the surface was altered by chemical treatments and laser ablation methods. The chemical treatments generated different functionality groups and chemical composition as evident from XPS analysis. The micro/nanopatterning by laser ablation resulted in three different pattern geometry and different surface roughness and consequently wettability. The patterned surface were further modified with chemical treatments to generate a wide range of surface wettability. The influence of chemical functional groups, pattern geometry, and surface wettability on protein adsorption and platelet adhesion was studied. On chemically treated flat surfaces, the type of hydrophilic treatment was shown to be a contributing factor that determines the platelet adhesion, since the hydrophilic oxidized substrates exhibit less platelet adhesion in comparison to the control untreated or acid treated surfaces. Also, the surface morphology, surface roughness, and superhydrophobic character of the surfaces are contributing factors to platelet adhesion on the surface. Our results show that superhydrophobic cauliflower-like patterns are highly resistant to platelet adhesion possibly due to the stability of Cassie-Baxter state for this pattern compared to others. Our results also show that simple surface treatments on metals offer a novel way to improve the hemocompatibility of metallic substrates.

Nonlinear photomagnetism of metals: Theory of nonlinear photoinduced dc current

NASA Astrophysics Data System (ADS)

Afonin, V. V.; Gurevich, V. L.; Laiho, R.

1995-07-01

Photoinduced magnetic flux has recently been observed in normal metals exposed to light. This effect is partly due to the fact that the light reflected from a metal surface transfers to the conduction electrons some of its quasimomentum. This creates a dc surface current which, for an appropriate geometry, brings about the photomagnetic effect. There is another contribution to the current that is due to anisotropy of the probabilities of electron transitions induced by the light, in combination with diffuse reflection of the electrons at the surface. We present here a theory of the dependence of the photoinduced current on the intensity of light Q. We assume that the light intensity is either constant or the time scale of its variation is much larger than the inverse Rabi frequency corresponding to the interband electron transition. At comparatively low intensities the current is proportional to Q. At higher intensities it varies as Q1/2. The physical origin of such behavior is analyzed. Various factors that allow a lowering of the critical intensity for the onset of the nonlinear behavior are discussed.

A stable lithium-rich surface structure for lithium-rich layered cathode materials

PubMed Central

Kim, Sangryun; Cho, Woosuk; Zhang, Xiaobin; Oshima, Yoshifumi; Choi, Jang Wook

2016-01-01

Lithium ion batteries are encountering ever-growing demand for further increases in energy density. Li-rich layered oxides are considered a feasible solution to meet this demand because their specific capacities often surpass 200 mAh g−1 due to the additional lithium occupation in the transition metal layers. However, this lithium arrangement, in turn, triggers cation mixing with the transition metals, causing phase transitions during cycling and loss of reversible capacity. Here we report a Li-rich layered surface bearing a consistent framework with the host, in which nickel is regularly arranged between the transition metal layers. This surface structure mitigates unwanted phase transitions, improving the cycling stability. This surface modification enables a reversible capacity of 218.3 mAh g−1 at 1C (250 mA g−1) with improved cycle retention (94.1% after 100 cycles). The present surface design can be applied to various battery electrodes that suffer from structural degradations propagating from the surface. PMID:27886178

Metal-to-ceramic attachment device

DOEpatents

Pavelka, Edwin A.; Grindstaff, Quirinus G.; Scheppele, Stuart E.

1985-01-01

A metal-to-ceramic fastening device is disclosed for securing a metal member to a ceramic member with respective confronting surfaces thereon clamped together, comprising a threaded bolt adapted to extend through a bolt hole in the metal member and into an aligned opening in the ceramic member, a rod nut threadedly receiving the bolt and adapted to span the opening in the ceramic member, and a pressure limiting member received on the bolt between the nut and the confronting surface of the metal member for limiting the movement of the nut toward the metal member when the bolt is tightened, so as to limit the pressure applied by the nut to the ceramic member to avoid damage thereto. The fastening device also prevents damage to the ceramic member due to thermal stresses. The pressure limiting member may have a shallow dish-shaped depression facing the rod nut to assist in accommodating thermal stresses.

Polymer-based metal nano-coated disposable target for matrix-assisted and matrix-free laser desorption/ionization mass spectrometry.

PubMed

Bugovsky, Stefan; Winkler, Wolfgang; Balika, Werner; Koranda, Manfred; Allmaier, Günter

2016-07-15

The ideal MALDI/LDI mass spectrometry sample target for an axial TOF instrument possesses a variety of properties. Primarily, it should be chemically inert to the sample, i.e. analyte, matrix and solvents, highly planar across the whole target, without any previous chemical contact and provide a uniform surface to facilitate reproducible measurements without artifacts from previous sample or matrix compounds. This can be hard to achieve with a metal target, which has to be extensively cleaned every time after use. Any cleaning step may leave residues behind, may change the surface properties due to the type of cleaning method used or even cause microscopic scratches over time hence altering matrix crystallization behavior. Alternatively, use of disposable targets avoids these problems. As each possesses the same surface they therefore have the potential to replace the conventional full metal targets so commonly employed. Furthermore, low cost single-use targets with high planarity promise an easier compliance with GLP guidelines as they alleviate the problem of low reproducibility due to inconsistent sample/matrix crystallization and changes to the target surface properties. In our tests, polymeric metal nano-coated targets were compared to a stainless steel reference. The polymeric metal nano-coated targets exhibited all the performance characteristics for a MALDI MS sample support, and even surpassed the - in our lab commonly used - reference in some aspects like limit of detection. The target exhibits all necessary features such as electrical conductivity, vacuum, laser and solvent compatibility. Copyright © 2016 Elsevier Inc. All rights reserved.

Plasmon Surface Polariton Dispersion by Direct Optical Observation.

ERIC Educational Resources Information Center

Swalen, J. D.; And Others

1980-01-01

Describes several simple experiments that can be used to observe directly the dispersion curve of plasmon surface polaritons (PSP) on flat metal surfaces. A method is described of observing the increonental change in the wave vector of the PSP due to coatings that differ in thickness by a few nanometers. (Author/CS)

Enhanced Chemisorption of Cu(hfac)2 on Parylene Surface by N2 Plasma Treatment

NASA Astrophysics Data System (ADS)

Pimanpang, S.; Wang, P.-I.; Ye, D.-X.; Juneja, J. S.; Wang, G.-C.; Lu, T.-M.

2006-03-01

The metallization of polymers has been intensively studied due to its wide industrial applications. We report a study of interfacial interaction of metalorganic Cu(hfac)2 with the Parylene surface. Parylene is a low k dielectric polymer prepared by a chemical vapor deposition technique. The as-deposited Parylene surface is shown to be hydrophobic with a measured water droplet contact angle ˜72 . However, after the N2 plasma treatment, the water droplet contact angle decreases to ˜40 due to the formation of oxygen and nitrogen functional groups on the surface, as observed by x-ray photoelectron spectroscopy (XPS). These functional groups improve Cu(hfac)2 chemisorption on the plasma treated Parylene surface. Further studies by XPS show that chemisorption of Cu(hfac)2 is self-limiting up to 20 sec of Cu(hfac)2 precursor exposure time. The enhancement of chemisorption of metalorganic precursors on the polymer surface is an important step for chemical vapor deposition or atomic layer deposition of metal. ^a Supported by Thai govt. fellowship (SP) and SRC (JSJ).

Surface-Potential-Based Metal-Oxide-Silicon-Varactor Model for RF Applications

NASA Astrophysics Data System (ADS)

Miyake, Masataka; Sadachika, Norio; Navarro, Dondee; Mizukane, Yoshio; Matsumoto, Kenji; Ezaki, Tatsuya; Miura-Mattausch, Mitiko; Mattausch, Hans Juergen; Ohguro, Tatsuya; Iizuka, Takahiro; Taguchi, Masahiko; Kumashiro, Shigetaka; Miyamoto, Shunsuke

2007-04-01

We have developed a surface-potential-based metal-oxide-silicon (MOS)-varactor model valid for RF applications up to 200 GHz. The model enables the calculation of the MOS-varactor capacitance seamlessly from the depletion region to the accumulation region and explicitly considers the carrier-response delay causing a non-quasi-static (NQS) effect. It has been observed that capacitance reduction due to this non-quasi-static effect limits the MOS-varactor application to an RF regime.

Creation of wettability contrast patterns on metallic surfaces via pen drawn masks

NASA Astrophysics Data System (ADS)

Choi, Won Tae; Yang, Xiaolong; Breedveld, Victor; Hess, Dennis W.

2017-12-01

Micropatterned surfaces with wettability contrast have attracted considerable attention due to potential applications in 2D microfluidics, bioassays, and water harvesting. A simple method to develop wettability contrast patterns on metallic surfaces by using a commercial marker is described. A marker-drawn ink pattern on a copper surface displays chemical resistance to an aqueous solution of sodium bicarbonate and ammonium persulfate, thereby enabling selective nanowire growth in areas where ink is absent. Subsequent ink removal by an organic solvent followed by fluorocarbon film deposition yields a stable hydrophobic/super-hydrophobic patterned copper surface. Using this approach, hydrophobic dot and line patterns were constructed. The adhesion force of water droplets to the dots was controlled by adjusting pattern size, thus enabling controlled droplet transfer between two surfaces. Anisotropy of water droplet adhesion to line patterns can serve as a basis for directional control of water droplet motion. This general approach has also been employed to generate wettability contrast on aluminum surfaces, thereby demonstrating versatility. Due to its simplicity, low cost, and virtual independence of solid surface material, ink marker pens can be employed to create wettability patterns for a variety of applications, in fields as diverse as biomedicine and energy.

Mechanically durable underwater superoleophobic surfaces based on hydrophilic bulk metals for oil/water separation

NASA Astrophysics Data System (ADS)

Yu, Huadong; Lian, Zhongxu; Xu, Jinkai; Wan, Yanling; Wang, Zuobin; Li, Yiquan; Yu, Zhanjiang; Weng, Zhankun

2018-04-01

Despite the success of previous methods for fabricating underwater superoleophobic surfaces, most of the surfaces based on soft materials are prone to collapse and deformation due to their mechanically fragile nature, and they fail to perform their designed functions after the surface materials are damaged in water. In this work, the nanosecond laser-induced oxide coatings on hydrophilic bulk metals are reported which overcomes the limitation and shows the robust underwater superoleophobicity to a mechanical challenge encountered by surfaces deployed in water environment. The results show that the surface materials have the advantage that the underwater superoleophobicity is still preserved after the surfaces are scratched by knife or sandpaper and even completely destroyed because of the hydrophilic property of damaged materials in water. It is important that the results provide a guide for the design of durable underwater superoleophobic surfaces, and the development of superoleophobic materials in many potential applications such as the oil-repellent and the oil/water separation. Additionally, the nanosecond laser technology is simple, cost-effective and suitable for the large-area and mass fabrication of mechanically durable underwater superoleophobic metal materials.

Analysis of heavy metal sources in storm water from urban areas

NASA Astrophysics Data System (ADS)

Scherer, U.; Fuchs, S.

2009-04-01

The input of heavy metals into surface waters is a serious impairment of the aquatic environment. The emissions of heavy metals via point and diffuse pathways into the German river basins were thus quantified for the period of 1985 through 2005. The total emission into the German river systems decreased for each metal during the observed period. This reduction is mainly caused by the decline of emissions via point sources. The measures taken by industry and implemented within the scope of a stringently water legislation have decisively contributed to an improvement of environmental conditions. Today's emissions of heavy metals into river basins of Germany are dominated by the input via diffuse pathways. One of the most important diffuse input is the storm water discharged from paved urban areas into the surface waters via storm sewers and combined sewer overflows especially for the metals copper, zinc and lead. The objective of this project was to identify the sources of these three heavy metals washed of from paved urban areas. The use of copper, zinc and lead on the outsides of buildings results in emissions to water and soil via rainwater due to weathering and runoff of soluble and insoluble metallic compounds. Copper and zinc are traditionally used materials in the building sector especially for roofs, gutters and facades. Lead, in contrast, plays only a subordinate role due to its more limited outdoor use. The corrosion rates vary widely. Climatic factors (temperature, humidity etc.), above all the presence of corrosive gases (sulphur dioxide, nitrogen oxide, ozone etc.) influence the corrosion processes. Estimates of industrial associations were referred to in order to determine the corrosion relevant metal surfaces. Heavy metal emissions caused by traffic are complex and depend on many parameters which vary by locality, time and substance. In principle, substances can be emitted by vehicles, the road surface and by maintenance. Emissions of copper, lead and zinc are mainly caused by wear and tear of tyres and brake pads. The reference figures of the environmental emissions are usually the kilometres driven per vehicle. The emissions can then be calculated based on the road performance. Furthermore atmospheric deposition on paved urban areas was considered. The heavy metal emission from each individual source and the portion discharged into surface waters via storm sewers and combined sewer overflows was quantified. The emission sum of all sources was validated using emission data of storm sewers based on measured heavy metal concentrations and the discharge volume showing a good agreement.

Surface characterization and cytotoxicity analysis of plasma sprayed coatings on titanium alloys.

PubMed

Rahman, Zia Ur; Shabib, Ishraq; Haider, Waseem

2016-10-01

In the realm of biomaterials, metallic materials are widely used for load bearing joints due to their superior mechanical properties. Despite the necessity for long term metallic implants, there are limitations to their prolonged use. Naturally, oxides of titanium have low solubilities and form passive oxide film spontaneously. However, some inclusion and discontinuity spots in oxide film make implant to adopt the decisive nature. These defects heighten the dissolution of metal ions from the implant surface, which results in diminishing bio-integration of titanium implant. To increase the long-term metallic implant stability, surface modifications of titanium alloys are being carried out. In the present study, biomimetic coatings of plasma sprayed hydroxyapatite and titanium were applied to the surface of commercially pure titanium and Ti6Al4V. Surface morphology and surface chemistry were studied using scanning electron microscopy and X-ray photoelectron spectroscopy, respectively. Cyclic potentiodynamic polarization and electrochemical impedance spectroscopy were carried out in order to study their electrochemical behavior. Moreover, cytotoxicity analysis was conducted for osteoblast cells by performing MTS assay. It is concluded that both hydroxyapatite and titanium coatings enhance corrosion resistance and improve cytocompatibility. Copyright © 2016 Elsevier B.V. All rights reserved.

Superhydrophobic surfaces by electrochemical processes.

PubMed

Darmanin, Thierry; Taffin de Givenchy, Elisabeth; Amigoni, Sonia; Guittard, Frederic

2013-03-13

This review is an exhaustive representation of the electrochemical processes reported in the literature to produce superhydrophobic surfaces. Due to the intensive demand in the elaboration of superhydrophobic materials using low-cost, reproducible and fast methods, the use of strategies based on electrochemical processes have exponentially grown these last five years. These strategies are separated in two parts: the oxidation processes, such as oxidation of metals in solution, the anodization of metals or the electrodeposition of conducting polymers, and the reduction processed such as the electrodeposition of metals or the galvanic deposition. One of the main advantages of the electrochemical processes is the relative easiness to produce various surface morphologies and a precise control of the structures at a micro- or a nanoscale. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Effects of ultrathin oxides in conducting MIS structures on GaAs

NASA Technical Reports Server (NTRS)

Childs, R. B.; Ruths, J. M.; Sullivan, T. E.; Fonash, S. J.

1978-01-01

Schottky barrier-type GaAs baseline devices (semiconductor surface etched and then immediately metalized) and GaAs conducting metal oxide-semiconductor devices are fabricated and characterized. The baseline surfaces (no purposeful oxide) are prepared by a basic or an acidic etch, while the surface for the MIS devices are prepared by oxidizing after the etch step. The metallizations used are thin-film Au, Ag, Pd, and Al. It is shown that the introduction of purposeful oxide into these Schottky barrier-type structures examined on n-type GaAs modifies the barrier formation, and that thin interfacial layers can modify barrier formation through trapping and perhaps chemical reactions. For Au- and Pd-devices, enhanced photovoltaic performance of the MIS configuration is due to increased barrier height.

Expressions to Rayleigh circumferential phase velocity and dispersion relation for a cylindrical surface under mechanical pressure

NASA Astrophysics Data System (ADS)

Sebold, Jean Eduardo; de Lacerda, Luiz Alkimin

2018-04-01

This paper describes a substantiated mathematical theory for Rayleigh waves propagated on some types of metal cylinders. More specifically, it presents not only a new way to express the dispersion relation of Rayleigh waves propagated on the cylindrical surface, but also how it can be used to construct a mathematical equation showing that the applied static mechanical pressure affects the shear modulus of the metal cylinder. All steps, required to conclude the process, consider the equation of motion as a function of radial and circumferential coordinates only, while the axial component can be overlooked without causing any problems. Some numerical experiments are done to illustrate the changes in the Rayleigh circumferential phase velocity in a metal cylindrical section due to static mechanical pressure around its external surface.

Deposition efficiency optimization in cold spraying of metal-ceramic powder mixtures

NASA Astrophysics Data System (ADS)

Klinkov, S. V.; Kosarev, V. F.

2017-10-01

In the present paper, results of optimization of the cold spray deposition process of a metal-ceramic powder mixture involving impacts of ceramic particles onto coating surface are reported. In the optimization study, a two-probability model was used to take into account the surface activation induced by the ceramic component of the mixture. The dependence of mixture deposition efficiency on the concentration and size of ceramic particles was analysed to identify the ranges of both parameters in which the effect due to ceramic particles on the mixture deposition efficiency was positive. The dependences of the optimum size and concentration of ceramic particles, and also the maximum gain in deposition efficiency, on the probability of adhesion of metal particles to non-activated coating surface were obtained.

Characterizing heavy metal build-up on urban road surfaces: implication for stormwater reuse.

PubMed

Liu, An; Liu, Liang; Li, Dunzhu; Guan, Yuntao

2015-05-15

Stormwater reuse is increasingly popular in the worldwide. In terms of urban road stormwater, it commonly contains toxic pollutants such as heavy metals, which could undermine the reuse safety. The research study investigated heavy metal build-up characteristics on urban roads in a typical megacity of South China. The research outcomes show the high variability in heavy metal build-up loads among different urban road sites. The degree of traffic congestion and road surface roughness was found to exert a more significant influence on heavy metal build-up rather than traffic volume. Due to relatively higher heavy metal loads, stormwater from roads with more congested traffic conditions or rougher surfaces might be suitable for low-water-quality required activities while the stormwater from by-pass road sections could be appropriate for relatively high-water-quality required purposes since the stormwater could be relatively less polluted. Based on the research outcomes, a decision-making process for heavy metals based urban road stormwater reuse was proposed. The new finding highlights the importance to undertaking a "fit-for-purpose" road stormwater reuse strategy. Additionally, the research results can also contribute to enhancing stormwater reuse safety. Copyright © 2015 Elsevier B.V. All rights reserved.

Nonlinear Bloch waves in metallic photonic band-gap filaments

NASA Astrophysics Data System (ADS)

Kaso, Artan; John, Sajeev

2007-11-01

We demonstrate the occurrence of nonlinear Bloch waves in metallic photonic crystals (PCs). These periodically structured filaments are characterized by an isolated optical pass band below an effective plasma gap. The pass band occurs in a frequency range where the metallic filament exhibits a negative, frequency-dependent dielectric function and absorption loss. The metallic losses are counterbalanced by gain in two models of inhomogeneously broadened nonlinear oscillators. In the first model, we consider close-packed quantum dots that fill the void regions of a two-dimensional (2D) metallic PC, and whose inhomogeneously broadened emission spectrum spans the original optical pass band of the bare filament. In the second model, we consider thin (10 50 nm) layers of inhomogeneously broadened two-level resonators, with large dipole oscillator strength, that cover the interior surfaces of 2D metallic (silver and tungsten) PCs. These may arise from localized surface plasmon resonances due to small metal particles or an otherwise rough metal surface. For simplicity, we treat electromagnetic modes with electric field perpendicular to the plane of metal periodicity. In both models, a pumping threshold of the resonators is found, above which periodic nonlinear solutions of Maxwell’s equations with purely real frequency within the optical pass band emerge. These nonlinear Bloch waves exhibit a laserlike input pumping to output amplitude characteristic. For strong surface resonances, these nonlinear waves may play a role in light emission from a hot tungsten (suitably microstructured) filament.

Persistent photoconductivity due to trapping of induced charges in Sn/ZnO thin film based UV photodetector

NASA Astrophysics Data System (ADS)

Yadav, Harish Kumar; Sreenivas, K.; Gupta, Vinay

2010-05-01

Photoconductivity relaxation in rf magnetron sputtered ZnO thin films integrated with ultrathin tin metal overlayer is investigated. Charge carriers induced at the ZnO-metal interface by the tin metal overlayer compensates the surface lying trap centers and leads to the enhanced photoresponse. On termination of ultraviolet radiation, recombination of the photoexcited electrons with the valence band holes leaves the excess carriers deeply trapped at the recombination center and holds the dark conductivity level at a higher value. Equilibrium between the recombination centers and valence band, due to trapped charges, eventually stimulates the persistent photoconductivity in the Sn/ZnO photodetectors.

The chemical properties of bimetallic surfaces: Importance of ensemble and electronic effects in the adsorption of sulfur and SO 2

NASA Astrophysics Data System (ADS)

Rodriguez, José A.

The understanding of the interaction of sulfur with bimetallic surfaces is a critical issue for preventing the deactivation of hydrocarbon reforming catalysts and for the design of better hydrodesulfurization catalysts. The alloying or combination of two metals can lead to materials with special chemical properties due to an interplay of “ensemble” and “electronic” effects. In recent years, several new interesting phenomena have been discovered when studying the interaction of sulfur with bimetallic surfaces using the modern techniques of surface science. Very small amounts of sulfur are able to induce dramatic changes in the morphology of bimetallic surfaces that combine noble metals (Cu, Ag, Au) and transition metals. This phenomenon can lead to big modifications in the activity and selectivity of bimetallic catalysts used for hydrocarbon reforming. In many cases, bimetallic bonding produces a significant redistribution of charge around the bonded metals. The electronic perturbations associated with the formation of a heteronuclear metal-metal bond can affect the reactivity of the bonded metals toward sulfur. This can be a very important issue to consider when trying to minimize the negative effects of sulfur poisoning (Sn/Pt versus Ag/Pt and Cu/Pt catalysts) or when trying to improve the performance of desulfurization catalysts (Co/Mo and Ni/Mo systems). Clearly much more work is necessary in this area, but new concepts are emerging that can be useful for designing more efficient bimetallic catalysts.

THE DOMINANCE OF METAL-RICH STREAMS IN STELLAR HALOS: A COMPARISON BETWEEN SUBSTRUCTURE IN M31 AND {lambda}CDM MODELS

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

Gilbert, Karoline M.; Font, Andreea S.; Johnston, Kathryn V.

2009-08-10

Extensive photometric and spectroscopic surveys of the Andromeda galaxy (M31) have discovered tidal debris features throughout M31's stellar halo. We present stellar kinematics and metallicities in fields with identified substructure from our on-going SPLASH survey of M31 red giant branch stars with the DEIMOS spectrograph on the Keck II 10 m telescope. Radial velocity criteria are used to isolate members of the kinematically cold substructures. The substructures are shown to be metal-rich relative to the rest of the dynamically hot stellar population in the fields in which they are found. We calculate the mean metallicity and average surface brightness ofmore » the various kinematical components in each field, and show that, on average, higher surface brightness features tend to be more metal-rich than lower surface brightness features. Simulations of stellar halo formation via accretion in a cosmological context are used to illustrate that the observed trend can be explained as a natural consequence of the observed dwarf galaxy mass-metallicity relation. A significant spread in metallicity at a given surface brightness is seen in the data; we show that this is due to time effects, namely, the variation in the time since accretion of the tidal streams' progenitor onto the host halo. We show that in this theoretical framework a relationship between the alpha-enhancement and surface brightness of tidal streams is expected, which arises from the varying times of accretion of the progenitor satellites onto the host halo. Thus, measurements of the alpha-enrichment, metallicity, and surface brightness of tidal debris can be used to reconstruct the luminosity and time of accretion onto the host halo of the progenitors of tidal streams.« less

An Exploration of Geometric and Electronic Effects in Metal Nanoparticle Catalysts

NASA Astrophysics Data System (ADS)

Childers, David

The goal of this thesis is to investigate the influence geometric and electronic effects on metal nanoparticle catalysis. There are three main methods which alter a catalyst's properties: changing support material, changing nanoparticle size and alloying a second metal. This work will focus on the latter two methods using Pt-group metals and alloys. Platinum and palladium were chosen as the active metals due to a large amount of industry significance and prior literature to draw upon. Neopentane conversion and propane dehydrogenation were the two probe reactions used to evaluate these catalysts mainly due to their relative simplicity and ease of operation on a laboratory scale. The effect of particle size was studied with Pt and Pd monometallic catalysts using neopentane hydrogenolysis/isomerization as the probe reaction. Particle size studies have been done previously using this reaction so there is literature data to compare this study's results. This data will also be used as comparison for the bimetallic studies conducted later so that particle size effects can be accounted for when attempting to determine the effect of alloying a second metal. Bimetallic catalysts have several different possible structures depending on a number of factors from the identity of the two metals to the synthesis procedure. Homogeneous, core-shell and intermetallic alloys are the three structures evaluated in this work. Determining the surface composition of a homogeneous alloy can be difficult especially if both metals adsorb CO. PtPd homogeneous alloys were used to evaluate the ability of EXAFS to give information about surface composition using CO adsorption. These catalysts were also tested using neopentane conversion to evaluate changes in catalytic performance. Core-shell catalysts can also exhibit unique properties although it is not clear whether the identity of the core metal is relevant or if surface changes are most important to changing catalytic behavior. PdAu catalysts were synthesized with varying Pd loadings to determine if the Au-rich core would continue to influence neopentane conversion performance with increasing Pd layers on the surface of the nanoparticle. Finally, intermetallic alloys have produced some very interesting literature results and can drastically alter catalyst surface structure. PdZn showed the potential to improve neopentane isomerization selectivity past that of Pt based on calculated electronic properties. Two PdZn catalysts with different loadings were synthesized to evaluate the electronic and geometric effects using both neopentane conversion and propane dehydrogenation.

The evolution of magnetic hot massive stars: Implementation of the quantitative influence of surface magnetic fields in modern models of stellar evolution

NASA Astrophysics Data System (ADS)

Keszthelyi, Zsolt; Wade, Gregg A.; Petit, Veronique

2017-11-01

Large-scale dipolar surface magnetic fields have been detected in a fraction of OB stars, however only few stellar evolution models of massive stars have considered the impact of these fossil fields. We are performing 1D hydrodynamical model calculations taking into account evolutionary consequences of the magnetospheric-wind interactions in a simplified parametric way. Two effects are considered: i) the global mass-loss rates are reduced due to mass-loss quenching, and ii) the surface angular momentum loss is enhanced due to magnetic braking. As a result of the magnetic mass-loss quenching, the mass of magnetic massive stars remains close to their initial masses. Thus magnetic massive stars - even at Galactic metallicity - have the potential to be progenitors of "heavy" stellar mass black holes. Similarly, at Galactic metallicity, the formation of pair instability supernovae is plausible with a magnetic progenitor.

Effects of size reduction on deformation, microstructure, and surface roughness of micro components for micro metal injection molding

NASA Astrophysics Data System (ADS)

Liu, Lin; Wang, Xin-da; Li, Xiang; Qi, Xiao-tong; Qu, Xuan-hui

2017-09-01

The fabrication of 17-4PH micro spool mandrils by micro metal injection molding was described here. The effects of size reduction on deformation, microstructure and surface roughness were studied by comparing a ϕ500 μm micro post and a ϕ1.7 mm cylinder after debinding and sintering. Experimental results show that slumping of the micro posts occurred due to a dramatic increase in outlet vapor pressure initiated at the thermal degradation onset temperature and the moment of gravity. Asymmetrical stress distribution within the micro component formed during the cooling stage may cause warping. Prior solvent debinding and adjustment in a thermal debinding scheme were useful for preventing the deformation of the micro components. Smaller grain size and higher micro hardness due to impeded grain growth were observed for the micro posts compared with the ϕ1.7 mm cylinder. Surface roughness increased with distance from the gate of the micro spool mandril due to melt front advancement during mold filling and the ensuing pressure distribution. At each position, surface roughness was dictated by injection molding and increased slightly after sintering.

Chemistry-driven structural alterations in short-term retrieved ceramic-on-metal hip implants: Evidence for in vivo incompatibility between ceramic and metal counterparts.

PubMed

Zhu, Wenliang; Pezzotti, Giuseppe; Boffelli, Marco; Chotanaphuti, Thanainit; Khuangsirikul, Saradej; Sugano, Nobuhiko

2017-08-01

Ceramic-on-metal (CoM) hip implants were reported to experience lower wear rates in vitro as compared to metal-on-metal (MoM) bearings, thus hinting metal-ion release at lower levels in vivo. In this article, we show a spectroscopic study of two short-term retrieval cases of zirconia-toughened alumina (ZTA) femoral heads belonging to CoM hip prostheses, which instead showed poor wear performances in vivo. Metal contamination and abnormally high fractions of tetragonal-to-monoclinic (t→m) polymorphic transformation of the zirconia phase could be found on both ZTA heads, which contrasted with the optimistic predictions of in vitro experiments. At the molecular scale, incorporation of metal ions into the ceramic lattices could be recognized as due to frictionally assisted phenomena occurring at the ceramic surface. Driven by abnormal friction, diffusion of metal ions induced lattice shrinkage in the zirconia phases, while residual stress fields became stored at the surface of the femoral head. Diffusional alterations destabilized the chemistry of the ceramic surface and resulted in an abnormal increase in t→m phase transformation in vivo. Frictionally driven metal transfer to the ceramic lattice thus hinders the in vivo performance of CoM prostheses. © 2016 Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater, 105B: 1469-1480, 2017. © 2016 Wiley Periodicals, Inc.

SERS and DFT study of copper surfaces coated with corrosion inhibitor

PubMed Central

Muniz-Miranda, Francesco; Caporali, Stefano

2014-01-01

Summary Azole derivatives are common inhibitors of copper corrosion due to the chemical adsorption occurring on the metal surface that gives rise to a protective film. In particular, 1,2,4-triazole performs comparable to benzotriazole, which is much more widely used, but is by no means an environmentally friendly agent. In this study, we have analyzed the adsorption of 1,2,4-triazole on copper by taking advantage of the surface-enhanced Raman scattering (SERS) effect, which highlights the vibrational features of organic ligand monolayers adhering to rough surfaces of some metals such as gold, silver and copper. To ensure the necessary SERS activation, a roughening procedure was implemented on the copper substrates, resulting in nanoscale surface structures, as evidenced by microscopic investigation. To obtain sufficient information on the molecule–metal interaction and the formation of an anticorrosive thin film, the SERS spectra were interpreted with the aid of theoretical calculations based on the density functional theory (DFT) approach. PMID:25671144

Significant Transient Mobility of Platinum Clusters via a Hot Precursor State on the Alumina Surface.

PubMed

Beniya, Atsushi; Hirata, Hirohito; Watanabe, Yoshihide

2016-11-17

Relaxation dynamics of hot metal clusters on oxide surfaces play a crucial role in a variety of physical and chemical processes. However, their transient mobility has not been investigated as much as other systems such as atoms and molecules on metal surfaces due to experimental difficulties. To study the role of the transient mobility of clusters on the oxide surface, we investigated the initial adsorption process of size-selected Pt clusters on a thin Al 2 O 3 film. Soft-landing the size-selected clusters while suppressing the thermal migration resulted in the transient migration controlling the initial adsorption states as an isolated and aggregated cluster, as revealed using scanning tunneling microscopy. We demonstrate that transient migration significantly contributes to the initial cluster adsorption process; the cross section for aggregation is seven times larger than the expected value from geometrical considerations, indicating that metal clusters are highly mobile during a energy dissipation process on the oxide surface.

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

NASA Astrophysics Data System (ADS)

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

2013-02-01

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

CH3Br adsorption on MgO/Mo ultrathin films: A DFT study

NASA Astrophysics Data System (ADS)

Cipriano, Luis A.; Tosoni, Sergio; Pacchioni, Gianfranco

2018-06-01

The adsorption of methyl bromide on MgO ultrathin films supported on Mo(100) was studied by means of density functional theory calculations, in comparison to the MgO(100) and Mo(100) surfaces. The adsorption energy and geometry were shown to depend on the thickness of the supported oxide film. MgO films as thick as 2ML (or more) display adsorptive properties similar to MgO(100), i.e. the adsorption of CH3Br is mostly due to dispersion and the molecule lies in a tilted geometry almost parallel to the surface. The CH3Br HOMO-LUMO gap is almost unaltered with respect to the gas phase. On metallic Mo(100) surfaces the bonding is completely different with the CH3Br molecule strongly bound and the C-Br bond axis almost vertical with respect to the metal surface. The MgO monolayer supported on Mo exhibits somehow intermediate properties: the tilt angle is larger and the bonding is stronger than on MgO(100), due to the effect of the supporting metal. In this case, a small reduction of the HOMO-LUMO gap of the adsorbed molecule is reported. The results help to rationalize the observed behavior in photodissociation of CH3Br supported on different substrates.

Pb, Cu, and Zn distributions at humic acid-coated metal-oxide surfaces

NASA Astrophysics Data System (ADS)

Wang, Yingge; Michel, F. Marc; Choi, Yongseong; Eng, Peter J.; Levard, Clement; Siebner, Hagar; Gu, Baohua; Bargar, John R.; Brown, Gordon E.

2016-09-01

Mineral surfaces are often coated by natural organic matter (NOM), which has a major influence on metal-ion sorption and sequestration because of the abundance of binding sites in such coatings and the changes they cause in local nanoscale environments. The effects of NOM coatings on mineral surfaces are, however, still poorly understood at the molecular level due to the complexity of these systems. In this study, we have applied long-period X-ray standing wave-fluorescence yield (LP-XSW-FY) spectroscopy to measure the partitioning of naturally present Cu(II) (0.0226%), Zn(II) (0.009%), and Pb(II) (∼0.0004%) between Elliott Soil Humic Acid (ESHA) coatings and three model single-crystal metal-oxide substrates: α-Al2O3 (0 0 0 1), α-Al2O3 (1 -1 0 2), and α-Fe2O3 (0 0 0 1). The competitive sorption effects among these metal ions for binding sites in the ESHA coatings and on the metal-oxide surfaces were investigated as a function of reaction time, calcium content, and solution pH. Pb(II) ions present in the ESHA coatings were found to redistribute to reactive α-Al2O3 (1 -1 0 2) and α-Fe2O3 (0 0 0 1) surfaces after 3 h of reaction (pH = 6.0, [Ca(II)] = 2 mM). Pb(II) partitioning onto these reactive metal-oxide surfaces increased with increasing reaction time (up to 7 d). In addition, the partitioning of Cu(II) and Zn(II) from the ESHA coating to the α-Fe2O3 (0 0 0 1) substrate increased slightly with reaction time (2.4% and 3.7% for Cu(II) and Zn(II), respectively, after 3 h and 6.4% and 7.7% for Cu(II) and Zn(II), respectively, after 72 h of reaction time). However, no changes in the partitioning of Cu(II) and Zn(II) onto the α-Al2O3 (1 -1 0 2) surface were observed with increasing reaction time, suggesting that these ions strongly complex with functional groups in the ESHA coatings. Similar results were obtained for Cu(II) and Zn(II) on the ESHA-coated α-Al2O3 (1 -1 0 2) surfaces in samples without the addition of calcium. However, the amounts of Pb(II) mobilized from the ESHA coatings onto the α-Al2O3 (1 -1 0 2) surfaces increased from 40% (no added Ca) to 58% (with 2 mM Ca) after 72 h of reaction time, possibly due to displacement of Pb(II) by Ca(II) from binding sites in the ESHA coatings. In contrast, Pb(II), Cu(II), and Zn(II) present in the ESHA coatings were found to be unreactive with the α-Al2O3 (0 0 0 1) surface. The observed reactivities of the three ESHA-coated metal-oxide surfaces with respect to metal-ion sorption are consistent with the trend observed for the uncoated metal-oxide surfaces: α-Fe2O3 (0 0 0 1) > α-Al2O3 (1 -1 0 2) > α-Al2O3 (0 0 0 1). In addition, Pb(II) partitioning onto α-Al2O3 (1 -1 0 2) surfaces increased with increasing pH from 4.0 to 9.0 as a result of the increasingly negative surface charge. These results show that intrinsic properties (nature of binding sites, binding affinities, and surface charge) of the ESHA coatings and metal-oxide surfaces, as well as external parameters such as pH and competing ions, are key factors governing the distribution and speciation of metal ions at complex NOM/mineral interfaces.

Regulating Surface Facets of Metallic Aerogel Electrocatalysts by Size-dependent Localized Ostwald Ripening.

PubMed

Wenchao, Duan; Zhang, Peina; Xiahou, Yujiao; Song, Yahui; Bi, Cuixia; Zhan, Jie; Du, Wei; Huang, Lihui; Möhwald, Helmuth; Xia, Haibing

2018-06-21

It is well known that the activity and stability of electrocatalysts are largely dependent on their surface facets. In this work, we have successfully regulated surface facets of three-dimensional (3D) metallic Au m-n aerogels by salt-induced assembly of citrate-stabilized gold nanoparticles (Au NPs) of two different sizes and further size-dependent localized Ostwald ripening at controlled particle-number ratios, where m and n represent the size of Au NPs, respectively. In addition, 3D Au m-n @Pd aerogels were further synthesized on the basis of Au m-n aerogels and also bear controlled surface facets due to the formation of ultrathin Pd layers on Au m-n aerogels. Taking the electrooxidation of small organic molecules (such as methanol and ethanol) by the resulting Au m-n and Au m-n @Pd aerogels as examples, it is found that surface facets of metallic aerogels with excellent performance can be regulated to realize preferential surface facets for methanol oxidation and ethanol oxidation, respectively. Moreover, they also indeed simultaneously bear high activity and excellent stability. Furthermore, their activities and stability are also highly dependent on the area ratio of active facets and inactive facets on their surfaces, respectively, and these ratios are varied via the mismatch of sizes of adjacent nanoparticles. Thus, this work not only demonstrates the realization of the regulation of the surface facets of metallic aerogels by size-dependent localized Ostwald ripening, but also will open up a new way to improve electrocatalytic performance of three-dimensional metallic aerogels by surface regulation.

Metal Surface Modification for Obtaining Nano- and Sub-Nanostructured Protective Layers.

PubMed

Ledovskykh, Volodymyr; Vyshnevska, Yuliya; Brazhnyk, Igor; Levchenko, Sergiy

2017-12-01

Regularities of the phase protective layer formation in multicomponent systems involving inhibitors with different mechanism of protective action have been investigated. It was shown that optimization of the composition of the inhibition mixture allows to obtain higher protective efficiency owing to improved microstructure of the phase layer. It was found that mechanism of the film formation in the presence of NaNO 2 -PHMG is due to deposition of slightly soluble PHMG-Fe complexes on the metal surface. On the basis of the proposed mechanism, the advanced surface engineering methods for obtaining nanoscaled and sub-nanostructured functional coatings may be developed.

Metal Surface Modification for Obtaining Nano- and Sub-Nanostructured Protective Layers

NASA Astrophysics Data System (ADS)

Ledovskykh, Volodymyr; Vyshnevska, Yuliya; Brazhnyk, Igor; Levchenko, Sergiy

2017-03-01

Regularities of the phase protective layer formation in multicomponent systems involving inhibitors with different mechanism of protective action have been investigated. It was shown that optimization of the composition of the inhibition mixture allows to obtain higher protective efficiency owing to improved microstructure of the phase layer. It was found that mechanism of the film formation in the presence of NaNO2-PHMG is due to deposition of slightly soluble PHMG-Fe complexes on the metal surface. On the basis of the proposed mechanism, the advanced surface engineering methods for obtaining nanoscaled and sub-nanostructured functional coatings may be developed.

Binding energies of benzene on coinage metal surfaces: Equal stability on different metals

NASA Astrophysics Data System (ADS)

Maaß, Friedrich; Jiang, Yingda; Liu, Wei; Tkatchenko, Alexandre; Tegeder, Petra

2018-06-01

Interfaces between organic molecules and inorganic solids adapt a prominent role in fundamental science, catalysis, molecular sensors, and molecular electronics. The molecular adsorption geometry, which is dictated by the strength of lateral and vertical interactions, determines the electronic structure of the molecule/substrate system. In this study, we investigate the binding properties of benzene on the noble metal surfaces Au(111), Ag(111), and Cu(111), respectively, using temperature-programmed desorption and first-principles calculations that account for non-locality of both electronic exchange and correlation effects. In the monolayer regime, we observed for all three systems a decrease of the binding energy with increasing coverage due to repulsive adsorbate/adsorbate interactions. Although the electronic properties of the noble metal surfaces are rather different, the binding strength of benzene on these surfaces is equal within the experimental error (accuracy of 0.05 eV), in excellent agreement with our calculations. This points toward the existence of a universal trend for the binding energy of aromatic molecules resulting from a subtle balance between Pauli repulsion and many-body van der Waals attraction.

Assembly, Structure, and Functionality of Metal-Organic Networks and Organic Semiconductor Layers at Surfaces

NASA Astrophysics Data System (ADS)

Tempas, Christopher D.

Self-assembled nanostructures at surfaces show promise for the development of next generation technologies including organic electronic devices and heterogeneous catalysis. In many cases, the functionality of these nanostructures is not well understood. This thesis presents strategies for the structural design of new on-surface metal-organic networks and probes their chemical reactivity. It is shown that creating uniform metal sites greatly increases selectivity when compared to ligand-free metal islands. When O2 reacts with single-site vanadium centers, in redox-active self-assembled coordination networks on the Au(100) surface, it forms one product. When O2 reacts with vanadium metal islands on the same surface, multiple products are formed. Other metal-organic networks described in this thesis include a mixed valence network containing Pt0 and PtII and a network where two Fe centers reside in close proximity. This structure is stable to temperatures >450 °C. These new on-surface assemblies may offer the ability to perform reactions of increasing complexity as future heterogeneous catalysts. The functionalization of organic semiconductor molecules is also shown. When a few molecular layers are grown on the surface, it is seen that the addition of functional groups changes both the film's structure and charge transport properties. This is due to changes in both first layer packing structure and the pi-electron distribution in the functionalized molecules compared to the original molecule. The systems described in this thesis were studied using high-resolution scanning tunneling microscopy, non-contact atomic force microscopy, and X-ray photoelectron spectroscopy. Overall, this work provides strategies for the creation of new, well-defined on-surface nanostructures and adds additional chemical insight into their properties.

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

Hutagalung, H.P.

Shellfish are known for their ability to accumulate trace metals from their environment. The relatively small increase in ambient metal concentration due to pollution will be reflected in measurable increase in mussel metal concentration. The abnormally high concentration of heavy metals in the surface water of Jakarta Bay has been reported. It was reported that the concentration of heavy metals tends to increase, and in surface water around Onrust Island the mercury and cadmium concentration had reached up to 35 ppb and 450 ppb, respectively. The green mussel, Mytilus viridis L., was cultivated around Onrust Island, Jakarta Bay. So far,more » there is no available information on mercury and cadmium contents in marine organisms from the surrounding waters of Onrust Island. The present study reports the result of an observation of the total mercury and cadmium contents in the soft tissue of Mytilus viridis L. collected from Onrust Island waters.« less

Heavy metal concentration in mangrove surface sediments from the north-west coast of South America.

PubMed

Fernández-Cadena, J C; Andrade, S; Silva-Coello, C L; De la Iglesia, R

2014-05-15

Mangrove ecosystems are coastal estuarine systems confined to the tropical and subtropical regions. The Estero Salado mangrove located in Guayaquil, Ecuador, has suffered constant disturbances during the past 20 years, due to industrial wastewater release. However, there are no published data for heavy metals present in its sediments and the relationship with anthropogenic disturbance. In the present study, metal concentrations were evaluated in surface sediment samples of the mangrove, showing that B, Cd, Cu, Pb, Se, V, and Zn levels exceeded those declared in international environmental quality standards. Moreover, several metals (Pb, Sn, Cd, Ag, Mo, Zn and Ni) could be linked to the industrial wastewater present in the studied area. In addition, heavy metal levels detected in this mangrove are higher than previous reports on mangrove sediments worldwide, indicating that this mangrove ecosystem is one of the most disrupted on earth. Copyright © 2014 Elsevier Ltd. All rights reserved.

Perovskite nanoparticle-sensitized Ga 2O 3 nanorod arrays for CO detection at high temperature

DOE PAGES

Lin, Hui -Jan; Baltrus, John P.; Gao, Haiyong; ...

2016-04-04

Here, noble metal nanoparticles are extensively used for sensitizing metal oxide chemical sensors through the catalytic spillover mechanism. However, due to earth-scarcity and high cost of noble metals, finding replacements presents a great economic benefit. Besides, high temperature and harsh environment sensor applications demand material stability under conditions approaching thermal and chemical stability limits of noble metals. In this study, we employed thermally stable perovskite-type La 0.8Sr 0.2FeO 3 (LSFO) nanoparticle surface decoration on Ga 2O 3 nanorod array gas sensors and discovered an order of magnitude enhanced sensitivity to carbon monoxide at 500 °C. The LSFO nanoparticle catalysts wasmore » of comparable performance to that achieved by Pt nanoparticles, with a much lower weight loading than Pt. Detailed electron microscopy and X-ray photoelectron spectroscopy studies suggested the LSFO nanoparticle sensitization effect is attributed to a spillover-like effect associated with the gas-LSFO-Ga 2O 3 triple-interfaces that spread the negatively charged surface oxygen ions from LSFO nanoparticles surfaces over to β-Ga 2O 3 nanorod surfaces with faster surface CO oxidation reactions.« less

Perovskite Nanoparticle-Sensitized Ga2O3 Nanorod Arrays for CO Detection at High Temperature.

PubMed

Lin, Hui-Jan; Baltrus, John P; Gao, Haiyong; Ding, Yong; Nam, Chang-Yong; Ohodnicki, Paul; Gao, Pu-Xian

2016-04-13

Noble metal nanoparticles are extensively used for sensitizing metal oxide chemical sensors through the catalytic spillover mechanism. However, due to earth-scarcity and high cost of noble metals, finding replacements presents a great economic benefit. Besides, high temperature and harsh environment sensor applications demand material stability under conditions approaching thermal and chemical stability limits of noble metals. In this study, we employed thermally stable perovskite-type La(0.8)Sr(0.2)FeO3 (LSFO) nanoparticle surface decoration on Ga2O3 nanorod array gas sensors and discovered an order of magnitude enhanced sensitivity to carbon monoxide at 500 °C. The LSFO nanoparticle catalysts was of comparable performance to that achieved by Pt nanoparticles, with a much lower weight loading than Pt. Detailed electron microscopy and X-ray photoelectron spectroscopy studies suggested the LSFO nanoparticle sensitization effect is attributed to a spillover-like effect associated with the gas-LSFO-Ga2O3 triple-interfaces that spread the negatively charged surface oxygen ions from LSFO nanoparticles surfaces over to β-Ga2O3 nanorod surfaces with faster surface CO oxidation reactions.

TiO2 structures doped with noble metals and/or graphene oxide to improve the photocatalytic degradation of dichloroacetic acid.

PubMed

Ribao, Paula; Rivero, Maria J; Ortiz, Inmaculada

2017-05-01

Noble metals have been used to improve the photocatalytic activity of TiO 2 . Noble metal nanoparticles prevent charge recombination, facilitating electron transport due to the equilibration of the Fermi levels. Furthermore, noble metal nanoparticles show an absorption band in the visible region due to a high localized surface plasmon resonance (LSPR) effect, which contributes to additional electron movements. Moreover, systems based on graphene, titanium dioxide, and noble metals have been used, considering that graphene sheets can carry charges, thereby reducing electron-hole recombination, and can be used as substrates of atomic thickness. In this work, TiO 2 -based nanocomposites were prepared by blending TiO 2 with noble metals (Pt and Ag) and/or graphene oxide (GO). The nanocomposites were mainly characterized via transmission electron microscopy (TEM), X-ray diffraction (XRD), Fourier transformed infrared (FTIR), Raman spectroscopy, and photocurrent analysis. Here, the photocatalytic performance of the composites was analyzed via oxidizing dichloroacetic acid (DCA) model solutions. The influence of the noble metal load on the composite and the ability of the graphene sheets to improve the photocatalytic activity were studied, and the composites doped with different noble metals were compared. The results indicated that the platinum structures show the best photocatalytic degradation, and, although the presence of graphene oxide in the composites is supposed to enhance their photocatalytic performance, graphene oxide does not always improve the photocatalytic process. Graphical abstract It is a schematic diagram. Where NM is Noble Metal and LSPR means Localized Surface Plasmon Resonance.

Plasmon-enhanced photocatalytic activity of Na0.9Mg0.45Ti3.55O8 loaded with noble metals directly observed with scanning Kelvin probe microscopy.

PubMed

Wang, Jing-Zhou; Guo, Ze-Qing; Zhou, Jian-Ping; Lei, Yu-Xi

2018-07-27

The noble metals Au, Ag and Pt were loaded onto Na 0.9 Mg 0.45 Ti 3.55 O 8 (NMTO) using a chemical bath deposition method devised in our recent work for the first time. The composite photocatalysts exhibit more effective photodegradation of methylene blue, due to the Schottky barrier built between NMTO and noble metal. Hot electrons generated during localized surface plasmon processes in metal nanoparticles transfer to the semiconductor, manifesting as a depression of surface potential directly detectable by scanning Kelvin probe microscopy. The key factor responsible for the improved ability of semiconductor-based photocatalysts is charge separation. The most effective weight concentrations of Au, Ag and Pt loaded onto NMTO were found to be 5.00%, 12.6% and 5.55% respectively. NMTO loaded with noble metals shows good photostability and recyclability for the degradation of methylene blue. A possible mechanism for the photodegradation of methylene blue over NMTO loaded with noble metals is proposed. This work highlights the potential application of NMTO-based photocatalysts, and provides an effective method to detect localized surface plasmons.

Sol-gel chemical sensors for surface-enhanced Raman spectroscopy

NASA Astrophysics Data System (ADS)

Lee, Vincent Y.; Farquharson, Stuart; Kwon, Hueong-Chan; Shahriari, Mahmoud R.; Rainey, Petrie M.

1999-02-01

Surface-enhanced Raman spectroscopy (SERS) promises to be one of the most sensitive methods for chemical detection. Unfortunately, the inability of SERS to perform quantitative chemical analysis has slowed its general use in laboratories. This is largely due to the difficulty of manufacturing either active surfaces that yield reproducible enhancements, or surfaces that are capable of reversible chemical adsorption, or both. In an effort to meet this need, we have developed metal-doped sol-gels that provide surface-enhancement of Raman scattering. The porous silica network offers a unique environment for stabilizing SER active metal particles and the high surface area increases the interaction between the analyte and metal particles. This eliminates the need to concentrate the analyte on the surface by evaporating the solvent. The sol-gel is easily coated on a variety of surfaces, such as fiber optics, glass slides, or glass tubing, and can be designed into sample flow systems. Here we present the development of both gold- and silver-doped sol-gels, which have been used to coat the inside walls of glass sample vials for SERS applications. The performance of the metal-doped sol-gels was evaluated using p-aminobenzoic acid, to establish enhancement factors, detection limits, dynamic response range, reversibility, reproducibility, and suitability to commercial spectrometers. Measurements of trace chemicals, such as adenine and cocaine, are also presented.

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

DTIC Science & Technology

2011-04-01

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

The Effect of Cutting Speed in Metallic Glass Grinding

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

Serbest, Erdinc; Bakkal, Mustafa; Karipcin, Ilker

2011-01-17

In this paper, the effects of the cutting speed in metallic glass grinding were investigated in dry conditions. The results showed that grinding forces decrease as grinding energy increase with the increasing cutting speeds. The present investigations on ground surface and grinding chips morphologies -shows that material removal and surface formation of the BMG are mainly due to the ductile chip deformation and ploughing as well as brittle fracture of some particles from the edges of the tracks. The roughness values obtained with the Cubic Boron Nitride wheels are acceptable for the grinding operation.

Plasmon mediated inverse Faraday effect in a graphene-dielectric-metal structure.

PubMed

Bychkov, Igor V; Kuzmin, Dmitry A; Tolkachev, Valentine A; Plaksin, Pavel S; Shavrov, Vladimir G

2018-01-01

This Letter shows the features of inverse Faraday effect (IFE) in a graphene-dielectric-metal (GDM) structure. The constants of propagation and attenuation of the surface plasmon-polariton modes are calculated. The effective magnetic field induced by surface plasmon modes in the dielectric due to the IFE is estimated to reach above 1 tesla. The possibility to control the distribution of the magnetic field by chemical potential of graphene is shown. The concept of strain-driven control of the IFE in the structure has been proposed and investigated.

Evaluation of space environmental effects on metals and optical thin films on EOIM-3

NASA Technical Reports Server (NTRS)

Vaughn, Jason A.; Linton, Roger C.; Finckenor, Miria M.; Kamenetzky, Rachel R.

1995-01-01

Metals and optical thin films exposed to the space environment on the Third Flight of the Evaluation of Oxygen Interactions with Materials (EOIM-3) payload, onboard Space Shuttle mission STS-46 were evaluated. The materials effects described in this paper include the effects of space exposure on various pure metals, optical thin films, and optical thin film metals. The changes induced by exposure to the space environment in the material properties were evaluated using bidirectional reflectance distribution function (BRDF), specular reflectance (250 nm to 2500 nm), ESCA, VUV reflectance (120 nm to 200 nm), ellipsometry, FTIR and optical properties. Using these analysis techniques gold optically thin film metal mirrors with nickel undercoats were observed to darken due to nickel diffusion through the gold to the surface. Also, thin film nickel mirrors formed nickel oxide due to exposure to both the atmosphere and space.

Self-assembly of acetate adsorbates drives atomic rearrangement on the Au(110) surface

DOE PAGES

Hiebel, Fanny; Shong, Bonggeun; Chen, Wei; ...

2016-10-12

Weak inter-adsorbate interactions are shown to play a crucial role in determining surface structure, with major implications for its catalytic reactivity. This is exemplified here in the case of acetate bound to Au(110), where the small extra energy of the van der Waals interactions among the surface-bound groups drives massive restructuring of the underlying Au. Acetate is a key intermediate in electro-oxidation of CO 2 and a poison in partial oxidation reactions. Metal atom migration originates at surface defects and is likely facilitated by weakened Au–Au interactions due to bonding with the acetate. Even though the acetate is a relativelymore » small molecule, weak intermolecular interaction provides the energy required for molecular self-assembly and reorganization of the metal surface.« less

Self-assembly of acetate adsorbates drives atomic rearrangement on the Au(110) surface

PubMed Central

Hiebel, Fanny; Shong, Bonggeun; Chen, Wei; Madix, Robert J.; Kaxiras, Efthimios; Friend, Cynthia M.

2016-01-01

Weak inter-adsorbate interactions are shown to play a crucial role in determining surface structure, with major implications for its catalytic reactivity. This is exemplified here in the case of acetate bound to Au(110), where the small extra energy of the van der Waals interactions among the surface-bound groups drives massive restructuring of the underlying Au. Acetate is a key intermediate in electro-oxidation of CO2 and a poison in partial oxidation reactions. Metal atom migration originates at surface defects and is likely facilitated by weakened Au–Au interactions due to bonding with the acetate. Even though the acetate is a relatively small molecule, weak intermolecular interaction provides the energy required for molecular self-assembly and reorganization of the metal surface. PMID:27731407

Mechanical contact induced transformation from the amorphous to the crystalline state in metallic glass

NASA Technical Reports Server (NTRS)

Miyoshi, K.; Buckley, D. H.

1984-01-01

Friction and wear tests were conducted with 3.2- and 6.4-millimeter-diameter aluminum oxide spheres sliding, in reciprocating motion, on a Fe67Co18B14Si1 metallic foil. Crystallites with a size range of 10 to 150 nanometers were produced on the wear surface of the amorphous alloy. A strong interaction between transition metals and metalloids such as silicon and boron results in strong segregation during repeated sliding, provides preferential transition metal-metalloid clustering in the amorphous alloy, and subsequently produces the diffused honeycomb structure formed by dark grey bands and primary crystals, that is, alpha-Fe in the matrix. Large plastic flow occurs on an amorphous alloy surface with sliding and the flow film of the alloy transfers to the aluminum oxide pin surface. Multiple slip bands due to shear deformation are observed on the side of the wear track. Two distinct types of wear debris were observed as a result of sliding: an alloy wear debris, and/or powdery-whiskery oxide debris.

First principles study of surface stability and segregation of PdRuRh ternary metal alloy system

NASA Astrophysics Data System (ADS)

Aspera, Susan Meñez; Arevalo, Ryan Lacdao; Nakanishi, Hiroshi; Kasai, Hideaki

2018-05-01

The recognized importance on the studies of alloyed materials is due to the high possibility of forming designer materials that caters to different applications. In any reaction and application, the stability and configuration of the alloy combination are important. In this study, we analyzed the surface stability and segregation of ternary metal alloy system PdRuRh through first principles calculation using density functional theory (DFT). We considered the possibility of forming phases as observed in the binary combinations of elements, i.e., completely miscible, and separating phases. With that, the model we analyzed for the ternary metal alloy slabs considers forming complete atomic miscibility, segregation of each component, and segregation of one component with mixing of the two other. Our results show that for the ternary combination of Pd, Rh and Ru, the Pd atoms have high tendency to segregate at the surface, while due to the high tendency of Ru and Rh to mix, core formation of a mixed RuRh is possible. Also, we determined that the trend of stability in the binary alloy system is a good determinant of stability in the ternary alloy system.

Wrinkle-stabilized metal-graphene hybrid fibers with zero temperature coefficient of resistance.

PubMed

Fang, Bo; Xi, Jiabin; Liu, Yingjun; Guo, Fan; Xu, Zhen; Gao, Weiwei; Guo, Daoyou; Li, Peigang; Gao, Chao

2017-08-24

The interfacial adhesion between graphene and metals is poor, as metals tend to generate superlubricity on smooth graphene surface. This problem renders the free assembly of graphene and metals to be a big challenge, and therefore, some desired conducting properties (e.g., stable metal-like conductivities in air, lightweight yet flexible conductors, and ultralow temperature coefficient of resistance, TCR) likely being realized by integrating the merits of graphene and metals remains at a theoretical level. This work proposes a wrinkle-stabilized approach to address the poor adhesion between graphene surface and metals. Cyclic voltammetry (CV) tests and theoretical analysis by Scharifker-Hills models demonstrate that multiscale wrinkles effectively induce nucleation of metal particles, locking in metal nuclei and guiding the continuous growth of metal islands in an instantaneous model on rough graphene surface. The universality and practicability of the wrinkle-stabilized approach is verified by our investigation through the electrodeposition of nine kinds of metals on graphene fibers (GF). The strong interface bonding permits metal-graphene hybrid fibers to show metal-level conductivities (up to 2.2 × 10 7 S m -1 , a record high value for GF in air), reliable weatherability and favorable flexibility. Due to the negative TCR of graphene and positive TCR of metals, the TCR of Cu- and Au-coated GFs reaches zero at a wide temperature range (15 K-300 K). For this layered model, the quantitative analysis by classical theories demonstrates the suitable thickness ratio of graphene layer and metal layer to achieve zero TCR to be 0.2, agreeing well with our experimental results. This wrinkle-stabilized approach and our theoretical analysis of zero-TCR behavior of the graphene-metal system are conducive to the design of high-performance conducting materials based on graphene and metals.

SEMICONDUCTOR TECHNOLOGY: TaN wet etch for application in dual-metal-gate integration technology

NASA Astrophysics Data System (ADS)

Yongliang, Li; Qiuxia, Xu

2009-12-01

Wet-etch etchants and the TaN film method for dual-metal-gate integration are investigated. Both HF/HN O3/H2O and NH4OH/H2O2 solutions can etch TaN effectively, but poor selectivity to the gate dielectric for the HF/HNO3/H2O solution due to HF being included in HF/HNO3/H2O, and the fact that TaN is difficult to etch in the NH4OH/H2O2 solution at the first stage due to the thin TaOxNy layer on the TaN surface, mean that they are difficult to individually apply to dual-metal-gate integration. A two-step wet etching strategy using the HF/HNO3/H2O solution first and the NH4OH/H2O2 solution later can fully remove thin TaN film with a photo-resist mask and has high selectivity to the HfSiON dielectric film underneath. High-k dielectric film surfaces are smooth after wet etching of the TaN metal gate and MOSCAPs show well-behaved C-V and Jg-Vg characteristics, which all prove that the wet etching of TaN has little impact on electrical performance and can be applied to dual-metal-gate integration technology for removing the first TaN metal gate in the PMOS region.

Solid frustrated-Lewis-pair catalysts constructed by regulations on surface defects of porous nanorods of CeO2

PubMed Central

Zhang, Sai; Huang, Zheng-Qing; Ma, Yuanyuan; Gao, Wei; Li, Jing; Cao, Fangxian; Li, Lin; Chang, Chun-Ran; Qu, Yongquan

2017-01-01

Identification on catalytic sites of heterogeneous catalysts at atomic level is important to understand catalytic mechanism. Surface engineering on defects of metal oxides can construct new active sites and regulate catalytic activity and selectivity. Here we outline the strategy by controlling surface defects of nanoceria to create the solid frustrated Lewis pair (FLP) metal oxide for efficient hydrogenation of alkenes and alkynes. Porous nanorods of ceria (PN-CeO2) with a high concentration of surface defects construct new Lewis acidic sites by two adjacent surface Ce3+. The neighbouring surface lattice oxygen as Lewis base and constructed Lewis acid create solid FLP site due to the rigid lattice of ceria, which can easily dissociate H–H bond with low activation energy of 0.17 eV. PMID:28516952

Occurrence and distribution of selected heavy metals in the surface sediments of South Brittany coastal waters: An assessment using pollution indicators

NASA Astrophysics Data System (ADS)

Ong, M. C.; Menier, D.; Noor Azhar, M. S.; Dupont, V.; Révillon, S.

2012-04-01

In order to avoid the pollution of heavy metals in South Brittany water, it is necessary to establish the data and understand the mechanisms influencing the distribution of heavy metals of the area. One of the aims of this work was to assess heavy metals contamination in Gulf of Morbihan and Quiberon Bay. Another aim was to use interpolation surfaces per metals to assess the contamination separately per metal. A total of 196 bottom sediment samples were collected from the coastal waters in order to determine the spatial concentration of Cr, Mn, Co, Cu, Zn, Cd and Pb by Inductively Coupled Plasma Mass Spectrometry (ICPMS) after acid digestion. The average heavy metal concentrations are ranked as follows: Mn>Zn>Cr>Pb>Cu>Cu>Cd. In the gulf, metal enrichments observed compared to the bay environment may due river run-off from three major river (Auray, Le Marle and Novalo rivers) which carried municipal waste and maritime activities along the coastal area within the gulf. Beside those factors, the natural factors such as the sheltered basin morphology itself, fine sediment and low hydrodynamic regime which favour the in situ accumulation of pollutants. The level of pollution levels attributed to heavy metals was evaluated using several pollution indicators in order to determine anthropogenically derived sediment contamination. Comparison to sediment quality guidelines (SQGs), enrichment factors (EFs), index of geoaccumulation (Igeo) and contamination factors (CF) based on reference element and background value to compensate for the influence of the natural variability in sediment mineralogy and to assess whether the concentration observed in surface sediment represent background and contaminated levels and visualize using ArcGIS software. These analyses validated that the bottom sediment only enriched in Pb and the other metals in most sample are not due to artificial contamination. Overall, geochemistry of the samples show the effect of both natural and anthropogenic inputs to the catchment, however, natural processes are more dominant than anthropogenic inputs in concentrating metals in the sediment.

Recent Advances in Superhydrophobic Electrodeposits

PubMed Central

Tam, Jason; Palumbo, Gino; Erb, Uwe

2016-01-01

In this review, we present an extensive summary of research on superhydrophobic electrodeposits reported in the literature over the past decade. As a synthesis technique, electrodeposition is a simple and scalable process to produce non-wetting metal surfaces. There are three main categories of superhydrophobic surfaces made by electrodeposition: (i) electrodeposits that are inherently non-wetting due to hierarchical roughness generated from the process; (ii) electrodeposits with plated surface roughness that are further modified with low surface energy material; (iii) composite electrodeposits with co-deposited inert and hydrophobic particles. A recently developed strategy to improve the durability during the application of superhydrophobic electrodeposits by controlling the microstructure of the metal matrix and the co-deposition of hydrophobic ceramic particles will also be addressed. PMID:28773278

Surface Passivation of CdZnTe Detector by Hydrogen Peroxide Solution Etching

NASA Technical Reports Server (NTRS)

Hayes, M.; Chen, H.; Chattopadhyay, K.; Burger, A.; James, R. B.

1998-01-01

The spectral resolution of room temperature nuclear radiation detectors such as CdZnTe is usually limited by the presence of conducting surface species that increase the surface leakage current. Studies have shown that the leakage current can be reduced by proper surface preparation. In this study, we try to optimize the performance of CdZnTe detector by etching the detector with hydrogen peroxide solution as function of concentration and etching time. The passivation effect that hydrogen peroxide introduces have been investigated by current-voltage (I-V) measurement on both parallel strips and metal-semiconductor-metal configurations. The improvements on the spectral response of Fe-55 and 241Am due to hydrogen peroxide treatment are presented and discussed.

Recent Advances in Superhydrophobic Electrodeposits.

PubMed

Tam, Jason; Palumbo, Gino; Erb, Uwe

2016-03-03

In this review, we present an extensive summary of research on superhydrophobic electrodeposits reported in the literature over the past decade. As a synthesis technique, electrodeposition is a simple and scalable process to produce non-wetting metal surfaces. There are three main categories of superhydrophobic surfaces made by electrodeposition: (i) electrodeposits that are inherently non-wetting due to hierarchical roughness generated from the process; (ii) electrodeposits with plated surface roughness that are further modified with low surface energy material; (iii) composite electrodeposits with co-deposited inert and hydrophobic particles. A recently developed strategy to improve the durability during the application of superhydrophobic electrodeposits by controlling the microstructure of the metal matrix and the co-deposition of hydrophobic ceramic particles will also be addressed.

Adsorption and electronic properties of pentacene on thin dielectric decoupling layers.

PubMed

Koslowski, Sebastian; Rosenblatt, Daniel; Kabakchiev, Alexander; Kuhnke, Klaus; Kern, Klaus; Schlickum, Uta

2017-01-01

With the increasing use of thin dielectric decoupling layers to study the electronic properties of organic molecules on metal surfaces, comparative studies are needed in order to generalize findings and formulate practical rules. In this paper we study the adsorption and electronic properties of pentacene deposited onto h-BN/Rh(111) and compare them with those of pentacene deposited onto KCl on various metal surfaces. When deposited onto KCl, the HOMO and LUMO energies of the pentacene molecules scale with the work functions of the combined KCl/metal surface. The magnitude of the variation between the respective KCl/metal systems indicates the degree of interaction of the frontier orbitals with the underlying metal. The results confirm that the so-called IDIS model developed by Willenbockel et al. applies not only to molecular layers on bare metal surfaces, but also to individual molecules on thin electronically decoupling layers. Depositing pentacene onto h-BN/Rh(111) results in significantly different adsorption characteristics, due to the topographic corrugation of the surface as well as the lateral electric fields it presents. These properties are reflected in the divergence from the aforementioned trend for the orbital energies of pentacene deposited onto h-BN/Rh(111), as well as in the different adsorption geometry. Thus, the highly desirable capacity of h-BN to trap molecules comes at the price of enhanced metal-molecule interaction, which decreases the HOMO-LUMO gap of the molecules. In spite of the enhanced interaction, the molecular orbitals are evident in scanning tunnelling spectroscopy (STS) and their shapes can be resolved by spectroscopic mapping.

Recent advances in nanoscale-metal assisted biochar derived from waste biomass used for heavy metals removal.

PubMed

Ho, Shih-Hsin; Zhu, Shishu; Chang, Jo-Shu

2017-12-01

Pollution of heavy metals (HMs) is a detrimental treat to human health and need to be cleaned up in a proper way. Biochar (BC), a low-cost and "green" adsorbent, has attracted significant attention due to its considerable HMs removal capacity. In particular, nano-metals have recently been used to assist BC in improving its reactivity, surface texture and magnetism. Synthesis methods and metal precursors greatly influence the properties and structures of the nanocomposites, thereby affecting their HMs removal performance. This review presents advances in synthesis methods, formation mechanisms and surface characteristics of BC nanocomposites, along with the discussions on HMs removal mechanisms and the effects of environmental factors on HMs removal efficiency. Performance of using BC nanocomposites to remediate real HMs-containing wastewater and issues associated with its process scale-up are also discussed. This review aims to provide useful information to facilitate the development of HMs removal by nanoscale-metal assisted BC. Copyright © 2017 Elsevier Ltd. All rights reserved.

Heavy metal assessment in surface sediments off Coromandel Coast of India: Implication on marine pollution.

PubMed

N, Anbuselvan; D, Senthil Nathan; M, Sridharan

2018-06-01

The present study investigates the distribution of heavy metals (Fe, Cd, Co, Cr, Cu, Ni, Zn and Pb) in the surface sediments along the Coromandel Coast of Bay of Bengal as an indicator of marine pollution. Pollution indices such as Contamination factor (CF), Enrichment factor (EF) and Geo-accumulation index (I) were performed to assess the spatial distribution and pollution status of the study area. The heavy metal concentration in the study area is closely associated with grain size and organic matter. Both geoaccumulation index and metal contamination factor indicate that the sediments are free from contamination with regards to the metals Cr and Ni, followed by uncontamination to moderate contamination of Co, Cu and Zn. However, sediments are found to be extremely polluted with respect to Cd and Pb. Factor analysis reveals that the accumulation of these heavy metals in the shelf sediments are due to anthropogenic inputs from the adjacent land area. Copyright © 2018 Elsevier Ltd. All rights reserved.

Geochemical assessment of heavy metals pollution in surface sediments of Vellar and Coleroon estuaries, southeast coast of India.

PubMed

Nethaji, S; Kalaivanan, R; Arya Viswam; Jayaprakash, M

2017-02-15

Surface sediments were collected from Vellar and Coleroon estuaries for determine sediment texture, calcium carbonate, organic matter and heavy metals. Pollution indices such as pollution load index (PLI), contamination factor (CF), enrichment factor (EF) and geo-accumulation index (I geo ) were done for this study to know the level of heavy metals pollution in the estuarine ecosystem. Pearson correlation matrix and factor were used to assess the relationship and source of heavy metals in the estuarine sediments. The results of PLI values reveal that the study area was polluted by all the heavy metals. The calculated values of CF and I geo followed the decreasing order Cu>Ni>Pb>Co>Cr>Zn>Mn>Fe and illustrate that Cu, Ni and Pb are contaminated due to anthropogenic sources in both estuaries. Correlation and factor analysis suggest that FeMn oxyhydroxides, organic matter and fine particles are responsible for high concentration of heavy metals. Copyright © 2016 Elsevier Ltd. All rights reserved.

Effects of hydrogen treatment on ohmic contacts to p-type GaN films

NASA Astrophysics Data System (ADS)

Huang, Bohr-Ran; Chou, Chia-Hui; Ke, Wen-Cheng; Chou, Yi-Lun; Tsai, Chia-Lung; Wu, Meng-chyi

2011-06-01

This study investigated the effects of hydrogen (H 2) treatment on metal contacts to Mg-doped p-GaN films by Hall-effect measurement, current-voltage ( I- V) analyzer and X-ray photoemission spectra (XPS). The interfacial oxide layer on the p-GaN surface was found to be the main reason for causing the nonlinear I- V behavior of the untreated p-GaN films. The increased nitrogen vacancy (V N) density due to increased GaN decomposition rate at high-temperature hydrogen treatment is believed to form high density surface states on the surface of p-GaN films. Compared to untreated p-GaN films, the surface Fermi level determined by the Ga 2p core-level peak on 1000 °C H 2-treated p-GaN films lies about ˜2.1 eV closer to the conduction band edge (i.e., the surface inverted to n-type behavior). The reduction in barrier height due to the high surface state density pinned the surface Fermi level close to the conduction band edge, and allowed the electrons to easily flow over the barrier from the metal into the p-GaN films. Thus, a good ohmic contact was achieved on the p-GaN films by the surface inversion method.

Assessment of heavy metal contamination in the sediments of Nansihu Lake Catchment, China.

PubMed

Liu, Enfeng; Shen, Ji; Yang, Liyuan; Zhang, Enlou; Meng, Xianghua; Wang, Jianjun

2010-02-01

At present, anthropogenic contribution of heavy metals far exceeds natural input in some aquatic sediment, but the proportions are difficult to differentiate due to the changes in sediment characters. In this paper, the metal (Al, Fe, K, Mg, Ca, Cr, Cu, Ni, and Zn) concentrations, grain size, and total organic carbon (TOC) content in the surface and core sediments of Nansihu Lake Catchment (the open lake and six inflow rivers) were determined. The chemical speciations of the metals (Al, Fe, Cr, Cu, Ni, and Zn) in the surface sediments were also analyzed. Approaches of factor analysis, normalized enrichment factor (EF) and the new non-residual fractions enrichment factor (K(NRF)) were used to differentiate the sources of the metals in the sediments, from detrital clastic debris or anthropogenic input, and to quantify the anthropogenic contamination. The results indicate that natural processes were more dominant in concentrating the metals in the surface and core sediments of the open lake. High concentration of Ca and deficiency of other metals in the upper layers of the sediment core were attributed to the input of carbonate minerals in the catchment with increasing human activities since 1980s. High TOC content magnified the deficiency of the metals. Nevertheless, the EF and K(NRF) both reveal moderate to significant anthropogenic contamination of Cr, Cu, Ni, and Zn in the surface sediments of Laoyun River and the estuary and Cr in the surface sediments of Baima River. The proportion of non-residual fractions (acid soluble, reducible, and oxidizable fractions) of Cr, Cu, Ni, and Zn in the contaminated sediments increased to 37-99% from the background levels less than 30%.

Biocompatibility and characterization of a Kolsterised® medical grade cobalt-chromium-molybdenum alloy

PubMed Central

Conti, Malcolm Caligari; Karl, Andreas; Wismayer, Pierre Schembri; Buhagiar, Joseph

2014-01-01

High failure rates of cobalt-chromium-molybdenum (Co-Cr-Mo) metal-on-metal hip prosthesis were reported by various authors, probably due to the alloy's limited hardness and tribological properties. This thus caused the popularity of the alloy in metal-on-metal hip replacements to decrease due to its poor wear properties when compared with other systems such as ceramic-on-ceramic. S-phase surface engineering has become an industry standard when citing surface hardening of austenitic stainless steels. This hardening process allows the austenitic stainless steel to retain its corrosion resistance, while at the same time also improving its hardness and wear resistance. By coupling S-phase surface engineering, using the proprietary Kolsterising® treatment from Bodycote Hardiff GmbH, that is currently being used mainly on stainless steel, with Co-Cr-Mo alloys, an improvement in hardness and tribological characteristics is predicted. The objective of this paper is to analyze the biocompatibility of a Kolsterised® Co-Cr-Mo alloy, and to characterize the material surface in order to show the advantages gained by using the Kolsterised® material relative to the original untreated alloy, and other materials. This work has been performed on 3 fronts including; Material characterization, “In-vitro” corrosion testing, and Biological testing conforming to BS EN ISO 10993–18:2009 - Biological evaluation of medical devices. Using these techniques, the Kolsterised® cobalt-chromium-molybdenum alloys were found to have good biocompatibility and an augmented corrosion resistance when compared with the untreated alloy. The Kolsterised® samples also showed a 150% increase in surface hardness over the untreated material thus predicting better wear properties. PMID:24451266

Biocompatibility and characterization of a Kolsterised(®) medical grade cobalt-chromium-molybdenum alloy.

PubMed

Conti, Malcolm Caligari; Karl, Andreas; Wismayer, Pierre Schembri; Buhagiar, Joseph

2014-01-01

High failure rates of cobalt-chromium-molybdenum (Co-Cr-Mo) metal-on-metal hip prosthesis were reported by various authors, probably due to the alloy's limited hardness and tribological properties. This thus caused the popularity of the alloy in metal-on-metal hip replacements to decrease due to its poor wear properties when compared with other systems such as ceramic-on-ceramic. S-phase surface engineering has become an industry standard when citing surface hardening of austenitic stainless steels. This hardening process allows the austenitic stainless steel to retain its corrosion resistance, while at the same time also improving its hardness and wear resistance. By coupling S-phase surface engineering, using the proprietary Kolsterising(®) treatment from Bodycote Hardiff GmbH, that is currently being used mainly on stainless steel, with Co-Cr-Mo alloys, an improvement in hardness and tribological characteristics is predicted. The objective of this paper is to analyze the biocompatibility of a Kolsterised(®) Co-Cr-Mo alloy, and to characterize the material surface in order to show the advantages gained by using the Kolsterised(®) material relative to the original untreated alloy, and other materials. This work has been performed on 3 fronts including; Material characterization, "In-vitro" corrosion testing, and Biological testing conforming to BS EN ISO 10993-18:2009 - Biological evaluation of medical devices. Using these techniques, the Kolsterised(®) cobalt-chromium-molybdenum alloys were found to have good biocompatibility and an augmented corrosion resistance when compared with the untreated alloy. The Kolsterised(®) samples also showed a 150% increase in surface hardness over the untreated material thus predicting better wear properties.

Comparison of Two Surface Contamination Sampling Techniques Conducted for the Characterization of Two Pajarito Site Manhattan Project National Historic Park Properties

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

Lopez, Tammy Ann

Technical Area-18 (TA-18), also known as Pajarito Site, is located on Los Alamos National Laboratory property and has historic buildings that will be included in the Manhattan Project National Historic Park. Characterization studies of metal contamination were needed in two of the four buildings that are on the historic registry in this area, a “battleship” bunker building (TA-18-0002) and the Pond cabin (TA-18-0029). However, these two buildings have been exposed to the elements, are decades old, and have porous and rough surfaces (wood and concrete). Due to these conditions, it was questioned whether standard wipe sampling would be adequate tomore » detect surface dust metal contamination in these buildings. Thus, micro-vacuum and surface wet wipe sampling techniques were performed side-by-side at both buildings and results were compared statistically. A two-tail paired t-test revealed that the micro-vacuum and wet wipe techniques were statistically different for both buildings. Further mathematical analysis revealed that the wet wipe technique picked up more metals from the surface than the microvacuum technique. Wet wipes revealed concentrations of beryllium and lead above internal housekeeping limits; however, using an yttrium normalization method with linear regression analysis between beryllium and yttrium revealed a correlation indicating that the beryllium levels were likely due to background and not operational contamination. PPE and administrative controls were implemented for National Park Service (NPS) and Department of Energy (DOE) tours as a result of this study. Overall, this study indicates that the micro-vacuum technique may not be an efficient technique to sample for metal dust contamination.« less

Universal liquid-phase laser fabrication of various nano-metals encapsulated by ultrathin carbon shells for deep-UV plasmonics.

PubMed

Yu, Miao; Yang, Chao; Li, Xiao-Ming; Lei, Tian-Yu; Sun, Hao-Xuan; Dai, Li-Ping; Gu, Yu; Ning, Xue; Zhou, Ting; Wang, Chao; Zeng, Hai-Bo; Xiong, Jie

2017-06-29

The exploration of localized surface plasmon resonance (LSPR) beyond the usual visible waveband, for example within the ultraviolet (UV) or deep-ultraviolet (D-UV) regions, is of great significance due to its unique applications in secret communications and optics. However, it is still challenging to universally synthesize the corresponding metal nanostructures due to their high activity. Herein, we report a universal, eco-friendly, facile and rapid synthesis of various nano-metals encapsulated by ultrathin carbon shells, significantly with a remarkable deep-UV LSPR characteristic, via a liquid-phase laser fabrication method. Firstly, a new generation of the laser ablation in liquid (LAL) method has been developed with an emphasis on the elaborate selection of solvents to generate ultrathin carbon shells, and hence to stabilize the formed metal nanocrystals. As a result, a series of metal@carbon nanoparticles (NPs), including Cr@C, Ti@C, Fe@C, V@C, Al@C, Sn@C, Mn@C and Pd@C, can be fabricated by this modified LAL method. Interestingly, these NPs exhibit LSPR peaks in the range of 200-330 nm, which are very rare for localized surface plasmon resonance. Consequently, the UV plasmonic effects of these metal@carbon NPs were demonstrated both by the observed enhancement in UV photoluminescence (PL) from the carbon nanoshells and by the improvement of the photo-responsivity of UV GaN photodetectors. This work could provide a universal method for carbon shelled metal NPs and expand plasmonics into the D-UV waveband.

Mechanisms and efficiency of the simultaneous removal of metals and cyanides by using ferrate(VI): crucial roles of nanocrystalline iron(III) oxyhydroxides and metal carbonates.

PubMed

Filip, Jan; Yngard, Ria A; Siskova, Karolina; Marusak, Zdenek; Ettler, Vojtech; Sajdl, Petr; Sharma, Virender K; Zboril, Radek

2011-08-29

The reaction of potassium ferrate(VI), K(2)FeO(4), with weak-acid dissociable cyanides--namely, K(2)[Zn(CN)(4)], K(2)[Cd(CN)(4)], K(2)[Ni(CN)(4)], and K(3)[Cu(CN)(4)]--results in the formation of iron(III) oxyhydroxide nanoparticles that differ in size, crystal structure, and surface area. During cyanide oxidation and the simultaneous reduction of iron(VI), zinc(II), copper(II), and cadmium(II), metallic ions are almost completely removed from solution due to their coprecipitation with the iron(III) oxyhydroxides including 2-line ferrihydrite, 7-line ferrihydrite, and/or goethite. Based on the results of XRD, Mössbauer and IR spectroscopies, as well as TEM, X-ray photoelectron emission spectroscopy, and Brunauer-Emmett-Teller measurements, we suggest three scavenging mechanisms for the removal of metals including their incorporation into the ferrihydrite crystal structure, the formation of a separate phase, and their adsorption onto the precipitate surface. Zn and Cu are preferentially and almost completely incorporated into the crystal structure of the iron(III) oxyhydroxides; the formation of the Cd-bearing, X-ray amorphous phase, together with Cd carbonate is the principal mechanism of Cd removal. Interestingly, Ni remains predominantly in solution due to the key role of nickel(II) carbonate, which exhibits a solubility product constant several orders of magnitude higher than the carbonates of the other metals. Traces of Ni, identified in the iron(III) precipitate, are exclusively adsorbed onto the large surface area of nanoparticles. We discuss the relationship between the crystal structure of iron(III) oxyhydroxides and the mechanism of metal removal, as well as the linear relationship observed between the rate constant and the surface area of precipitates. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Hydrogen generation from water/methanol under visible light using aerogel prepared strontium titanate (SrTiO3) nanomaterials doped with ruthenium and rhodium metals

NASA Astrophysics Data System (ADS)

Kuo, Yenting; Klabunde, Kenneth J.

2012-07-01

Nanostructured strontium titanate visible-light-driven photocatalysts containing rhodium and ruthenium were synthesized by a modified aerogel synthesis using ruthenium chloride and rhodium nitrate as dopant precursors, and titanium isopropoxide and strontium metal as the metal sources. The well-defined crystalline SrTiO3 structure was confirmed by means of x-ray diffraction. After calcination at 500 °C, diffuse reflectance spectroscopy shows an increase in light absorption at 370 nm due to the presence of Rh3 + ; however an increase of the calcination temperature to 600 °C led to a decrease in intensity, probably due to a loss of surface area. An increase in the rhodium doping level also led to an increase in absorption at 370 nm however, the higher amounts of dopant lowered the photocatalytic activity. The modified aerogel synthesis allows greatly enhanced H2 production performance from an aqueous methanol solution under visible light irradiation compared with lower surface area conventional materials. We believe that this enhanced activity is due to the higher surface areas while high quality nanocrystalline materials are still obtained. Furthermore, the surface properties of these nanocrystalline aerogel materials are different, as exhibited by the higher activities in alkaline solutions, while conventional materials (obtained via high temperature solid-state synthesis methods) only exhibit reasonable hydrogen production in acidic solutions. Moreover, an aerogel synthesis approach gives the possibility of thin-film formation and ease of incorporation into practical solar devices.

In Situ Apparatus to Study Gas-Metal Reactions and Wettability at High Temperatures for Hot-Dip Galvanizing Applications

NASA Astrophysics Data System (ADS)

Koltsov, A.; Cornu, M.-J.; Scheid, J.

2018-02-01

The understanding of gas-metal reactions and related surface wettability at high temperatures is often limited due to the lack of in situ surface characterization. Ex situ transfers at low temperature between annealing furnace, wettability device, and analytical tools induce noticeable changes of surface composition distinct from the reality of the phenomena.Therefore, a high temperature wettability device was designed in order to allow in situ sample surface characterization by x-rays photoelectron spectroscopy after gas/metal and liquid metal/solid metal surface reactions. Such airless characterization rules out any contamination and oxidation of surfaces and reveals their real composition after heat treatment and chemical reaction. The device consists of two connected reactors, respectively, dedicated to annealing treatments and wettability measurements. Heat treatments are performed in an infrared lamp furnace in a well-controlled atmosphere conditions designed to reproduce gas-metal reactions occurring during the industrial recrystallization annealing of steels. Wetting experiments are carried out in dispensed drop configuration with the precise control of the deposited droplets kinetic energies. The spreading of drops is followed by a high-speed CCD video camera at 500-2000 frames/s in order to reach information at very low contact time. First trials have started to simulate phenomena occurring during recrystallization annealing and hot-dip galvanizing on polished pure Fe and FeAl8 wt.% samples. The results demonstrate real surface chemistry of steel samples after annealing when they are put in contact with liquid zinc alloy bath during hot-dip galvanizing. The wetting results are compared to literature data and coupled with the characterization of interfacial layers by FEG-Auger. It is fair to conclude that the results show the real interest of such in situ experimental setup for interfacial chemistry studies.

Cobalt deposition in mineralized bone tissue after metal-on-metal hip resurfacing: Quantitative μ-X-ray-fluorescence analysis of implant material incorporation in periprosthetic tissue.

PubMed

Hahn, Michael; Busse, Björn; Procop, Mathias; Zustin, Jozef; Amling, Michael; Katzer, Alexander

2017-10-01

Most resurfacing systems are manufactured from cobalt-chromium alloys with metal-on-metal (MoM) bearing couples. Because the quantity of particulate metal and corrosion products which can be released into the periprosthetic milieu is greater in MoM bearings than in metal-on-polyethylene (MoP) bearings, it is hypothesized that the quantity and distribution of debris released by the MoM components induce a compositional change in the periprosthetic bone. To determine the validity of this claim, nondestructive µ-X-ray fluorescence analysis was carried out on undecalcified histological samples from 13 femoral heads which had undergone surface replacement. These samples were extracted from the patients after gradient time points due to required revision surgery. Samples from nonintervened femoral heads as well as from a MoP resurfaced implant served as controls. Light microscopy and µ-X-ray fluorescence analyses revealed that cobalt debris was found not only in the soft tissue around the prosthesis and the bone marrow, but also in the mineralized bone tissue. Mineralized bone exposed to surface replacements showed significant increases in cobalt concentrations in comparison with control specimens without an implant. A maximum cobalt concentration in mineralized hard tissue of up to 380 ppm was detected as early as 2 years after implantation. Values of this magnitude are not found in implants with a MoP surface bearing until a lifetime of more than 20 years. This study demonstrates that hip resurfacing implants with MoM bearings present a potential long-term health risk due to rapid cobalt ion accumulation in periprosthetic hard tissue. © 2016 Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater, 105B: 1855-1862, 2017. © 2016 Wiley Periodicals, Inc.

Versatile Surface Functionalization of Metal-Organic Frameworks through Direct Metal Coordination with a Phenolic Lipid Enables Diverse Applications

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

Zhu, Wei; Xiang, Guolei; Shang, Jin

Here, a novel strategy for the versatile functionalization of the external surface of metal-organic frameworks (MOFs) has been developed based on the direct coordination of a phenolic-inspired lipid molecule DPGG (1,2-dipalmitoyl-sn-glycero-3-galloyl) with metal nodes/sites surrounding MOF surface. X-ray diffraction and Argon sorption analysis prove that the modified MOF particles retain their structural integrity and porosity after surface modification. Density functional theory calculations reveal that strong chelation strength between the metal sites and the galloyl head group of DPGG is the basic prerequisite for successful coating. Due to the pH-responsive nature of metal-phenol complexation, the modification process is reversible by simplemore » washing in weak acidic water, showing an excellent regeneration ability for water-stable MOFs. Moreover, the colloidal stability of the modified MOFs in the nonpolar solvent allows them to be further organized into 2 dimensional MOF or MOF/polymer monolayers by evaporation-induced interfacial assembly conducted on an air/water interface. Lastly, the easy fusion of a second functional layer onto DPGG-modified MOF cores, enabled a series of MOF-based functional nanoarchitectures, such as MOFs encapsulated within hybrid supported lipid bilayers (so-called protocells), polyhedral core-shell structures, hybrid lipid-modified-plasmonic vesicles and multicomponent supraparticles with target functionalities, to be generated. for a wide range of applications.« less

Probing Selenium-Ion Distributions and Changes in Redox-State at Biofilm/Mineral Interfaces by Coupling Long-period X-ray Standing Wave and XANES Measurements

NASA Astrophysics Data System (ADS)

Templeton, A. S.; Trainor, T. P.; Spormann, A. M.; Brown, G. E.

2002-12-01

Metal sorption and precipitation reactions at biological as well as mineral surfaces are important controls on metal speciation and bioavailability in natural environments. When highly hydrated biofilms form on mineral surfaces, numerous competitive and synergistic effects are predicted to occur. Experimentally, it is challenging to determine where the sorbed metal ions are localized, the relative affinity of the biological vs. mineral surface sites, or to monitor biomineralization reactions or changes in metal speciation that may also occur. A large part of the difficulty is due to the low concentrations of sorbed ions, the small length-scale of the biofilm-mineral interface, and the complex interplay between microbially-catalayzed redox transformations vs. sorption and/or transport processes. Long-period x-ray standing wave (XSW) techniques are well-suited to determining the vertical distribution of metal(oid) species within biofilms overlying mineral surfaces. We will discuss experiments where Se fluorescence yield profiles are used to compare the affinity of Burkholderia cepacia biofilms for binding Se(IV) and Se(VI) species relative to underlying alpha-Al2O3 substrates over three orders of magnitude in [Se]. In addition, we will discuss how coupling the XSW experiments to grazing-incidence, spatially-resolved Se K-edge XANES spectroscopy can be used to differentiate between the oxidation state of the Se complexes localized within the biofilm vs. the mineral surface. This approach is used to monitor changes in the relative distributions of Se(VI), Se(IV) and Se(0) species as a function of time and proximity to the mineral surface. The long-period XSW data show that selenite preferentially binds to the oxide surfaces, particularly at low [Se]. When B. cepacia is metabolically active, B. cepacia rapidly reduces a fraction of the Se(IV) to the red elemental Se form. In contrast, selenate is preferentially partitioned into the B. cepacia biofilms at all [Se] tested due to a lower affinity for binding to the mineral surface. XANES spectra show that rapid reduction of selenate by B. cepacia to Se(IV) and Se(0) species subsequently results in a vertical segregation of Se species at the B. cepacia/alpha-Al2O3 interface. Elemental Se accumulates within the biofilm with the Se(VI), whereas selenite intermediates preferentially sorb to the underlying oxide surface.

Radiative Decay Engineering 6: Fluorescence on One-Dimensional Photonic Crystals

PubMed Central

Badugu, Ramachandram; Nowaczyk, Kazimierz; Descrovi, Emiliano; Lakowicz, Joseph R.

2014-01-01

During the past decade the interactions of fluorophores with metallic particles and surfaces has become an active area of research. These near-field interactions of fluorophores with surface plasmons have resulted in increased brightness and directional emission. However, using metals provide some disadvantages, like quenching at short fluorophore-metal distances, increased rates of energy dissipation due to lossy metals. These unfavorable effects are not expected in dielectrics. In this paper we describe the interactions of fluorophores with one-dimensional (1D) photonic crystals (PCs), which have alternating layers of dielectrics with dimensions that create a photonic bandgap (PBG). Freely propagating light at the PBG wavelength will be reflected. However, similar with metals, we show that fluorophores within near-field distances of the 1DPC interacts with the structure. Our results demonstrated that these fluorophores can interact with both Internal Modes (IM) and Bloch Surface Waves (BSW) of the 1DPC. For fluorophores on the surface of the 1DPC the emission dominantly occurs through the 1DPC and into the substrate. We refer to these two phenomena together as Bragg Grating-Coupled Emission (BGCE). Here we describe our preliminary results on BGCE. 1DPCs are simple to fabricate and can be handled and reused without damage. We believe BGCE provide opportunities for new formats for fluorescence detection and sensing. PMID:23896462

Metal release rate from AISI 316L stainless steel and pure Fe, Cr and Ni into a synthetic biological medium--a comparison.

PubMed

Herting, G; Wallinder, I Odnevall; Leygraf, C

2008-09-01

Metal release rates from stainless steel grade 316L were investigated in artificial lysosomal fluid (ALF), simulating a human inflammatory cell response. The main focus was placed on release rates of main alloying elements using graphite furnace atomic absorption spectroscopy, and changes in surface oxide composition by means of X-ray photoelectron spectroscopy. To emphasise that alloys and pure metals possess totally different intrinsic properties, comparative studies were performed on the pure alloying constituents: iron, nickel and chromium. Significant differences in release rates were observed due to the presence of a passive surface film on stainless steel. Iron and nickel were released at rates more than 300 times lower from the 316L alloy compared with the pure metals whereas the release rate of chromium was similar. Iron was preferentially released compared with nickel and chromium. Immersion in ALF resulted in the gradual enrichment of chromium in the surface film, a small increase of nickel, and the reduction of oxidized iron with decreasing release rates of alloy constituents as a result. As expected, released metals from stainless steel grade 316L were neither in proportion to the bulk alloy composition nor to the surface film composition.

Thin-film metal hydrides.

PubMed

Remhof, Arndt; Borgschulte, Andreas

2008-12-01

The goal of the medieval alchemist, the chemical transformation of common metals into nobel metals, will forever be a dream. However, key characteristics of metals, such as their electronic band structure and, consequently, their electric, magnetic and optical properties, can be tailored by controlled hydrogen doping. Due to their morphology and well-defined geometry with flat, coplanar surfaces/interfaces, novel phenomena may be observed in thin films. Prominent examples are the eye-catching hydrogen switchable mirror effect, the visualization of solid-state diffusion and the formation of complex surface morphologies. Thin films do not suffer as much from embrittlement and/or decrepitation as bulk materials, allowing the study of cyclic absorption and desorption. Therefore, thin-metal hydride films are used as model systems to study metal-insulator transitions, for high throughput combinatorial research or they may be used as indicator layers to study hydrogen diffusion. They can be found in technological applications as hydrogen sensors, in electrochromic and thermochromic devices. In this review, we discuss the effect of hydrogen loading of thin niobium and yttrium films as archetypical examples of a transition metal and a rare earth metal, respectively. Our focus thereby lies on the hydrogen induced changes of the electronic structure and the morphology of the thin films, their optical properties, the visualization and the control of hydrogen diffusion and on the study of surface phenomena and catalysis.

Variations in Heavy Metals Across Urban Streams

NASA Astrophysics Data System (ADS)

Kaushal, S. S.; Belt, K. T.; Stack, W. P.; Pouyat, R. V.; Groffman, P. M.; F, S. E.

2006-05-01

Urbanization has led to increased concentrations of metals such as lead (Pb), zinc (Zn), and copper (Cu) in streams due to industrial sources, domestic activities, vehicle use, and runoff from roadways. These metals can be dangerous to aquatic organisms and humans at high concentrations. We investigated variations in concentrations of heavy metals in streams across Baltimore, Maryland and within the context of convergent increases in salinity and organic carbon (two important variables that are known to affect metal transport in surface waters) due to urbanization. Despite past reductions of lead in gasoline and paints, mean concentrations of lead in some Baltimore streams were still approximately 75 micrograms/L and exceeded the U.S. EPA recommended criteria by 50 times. Mean concentrations of zinc and copper across Baltimore streams were also elevated and ranged between 15 to 140 micrograms/L and 2 to 40 micrograms/L, and mean concentrations of these metals were considerably higher than national means reported by the National Storm Water Quality database (NSWQ), which spans 3,770 storm events across the U.S. There were substantial increases in concentrations of heavy metals in streams during storms with greater than 80 percent, 70 percent, and 20 percent of storm samples exceeding recommended U.S. EPA metals criteria for Cu, Pb, and Zn respectively. Relationships between metal concentrations and stream discharge followed different patterns than nitrate and total phosphorus, other regulated pollutants in the Chesapeake Bay watershed, suggesting differences in sources and transport mechanisms within watersheds. Environmental factors such as increasing salinity from deicer use (with chloride concentrations in streams now ranging up to 5 g/L) may contribute to elevated transport of metals through ion exchange and mobilization of metals in soils and sediments. Environmental factors such as increasing organic carbon in urban streams, with ranges of 2 - 16 times greater in suburban and urban streams than forest watersheds, may also act as a vector for transporting metals due to binding capacity. Results show that metals appear to be present in harmful concentrations in many streams in Baltimore, Maryland, but further work is needed to elucidate shifts in the origin of metal pollution (storage in soils and sediments vs. roadway surfaces), and the effects of widespread changes in environmental factors that can potentially enhance their mobilization to streams.

Metal nanostructures with complex surface morphology: The case of supported lumpy Pd and Pt nanoparticles produced by laser processing of metal films

NASA Astrophysics Data System (ADS)

Ruffino, F.; Maugeri, P.; Cacciato, G.; Zimbone, M.; Grimaldi, M. G.

2016-09-01

In this work we report on the formation of lumpy Pd and Pt nanoparticles on fluorine-doped tin oxide/glass (FTO/glass) substrate by a laser-based approach. In general, complex-surface morphology metal nanoparticles can be used in several technological applications exploiting the peculiarities of their physical properties as modulated by nanoscale morphology. For example plasmonic metal nanoparticles presenting a lumpy morphology (i.e. larger particles coated on the surface by smaller particles) can be used in plasmonic solar cell devices providing broadband scattering enhancement over the smooth nanoparticles leading, so, to the increase of the device efficiency. However, the use of plasmonic lumpy nanoparticles remains largely unexplored due to the lack of simply, versatile, low-cost and high-throughput methods for the controllable production of such nanostructures. Starting from these considerations, we report on the observation that nanoscale-thick Pd and Pt films (17.6 and 27.9 nm, 12.1 and 19.5 nm, respectively) deposited on FTO/glass surface irradiated by nanosecond pulsed laser at fluences E in the 0.5-1.5 J/cm2 range, produce Pd and Pt lumpy nanoparticles on the FTO surface. In addition, using scanning electron microscopy analyses, we report on the observation that starting from each metal film of fixed thickness h, the fraction F of lumpy nanoparticles increases with the laser fluence E and saturates at the higher fluences. For each fixed fluence, F was found higher starting from the Pt films (at each starting film thickness h) with respect to the Pd films. For each fixed metal and fluence, F was found to be higher decreasing the starting thickness of the deposited film. To explain the formation of the lumpy Pd and Pt nanoparticles and the behavior of F as a function of E and h both for Pd and Pt, the thermodynamic behavior of the Pd and Pt films and nanoparticles due to the interaction with the nanosecond laser is discussed. In particular, the photothermal vaporization and Coulomb explosion processes of the Pd and Pt nanoparticles are invoked as possible mechanisms for the lumpy nanoparticles formation.

Description of two-metal biosorption equilibria by Langmuir-type models

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

Chong, K.H.; Volesky, B.

A biosorbent prepared from Ascophyllum nodosum seaweed biomass, FCAN2, was examined for its sorption capacity. Equilibrium batch sorption studies were performed using two-metal systems containing either (Cu+Zn), (Cu+Cd), or (Zn+Cd). In the evaluation of the two-metal sorption system performance, simple isotherm curves had to be replaced by three-dimensional sorption isotherm surfaces. In order to describe the isotherm surfaces mathematically, three Langmuir-type models were evaluated. The apparent one-parameter Langmuir constant (b) was used to quantify FCAN2 ``affinity`` for one metal in the presence of another one. The uptake of Zn decreased drastically when Cu of Cd were present. The uptake ofmore » Cd was much more sensitive to the presence of Cu than to that of Zn. The presence of Cd and Zn alter the ``affinity`` of FCAN2 for Cu the least at high Cu equilibrium concentrations. The mathematical model of the two-metal sorption system enabled quantitative estimation of one-metal (bio)sorption inhibition due to the influence of a second metal.« less

Diffusion Analysis Of Hydrogen-Desorption Measurements

NASA Technical Reports Server (NTRS)

Danford, Merlin D.

1988-01-01

Distribution of hydrogen in metal explains observed desorption rate. Report describes application of diffusion theory to anaylsis of experimental data on uptake and elimination of hydrogen in high-strength alloys of 25 degree C. Study part of program aimed at understanding embrittlement of metals by hydrogen. Two nickel-base alloys, Rene 41 and Waspaloy, and one ferrous alloy, 4340 steel, studied. Desorption of hydrogen explained by distribution of hydrogen in metal. "Fast" hydrogen apparently not due to formation of hydrides on and below surface as proposed.

Cooperative emission of light by an ensemble of dipoles near a metal nanoparticle: the plasmonic Dicke effect.

PubMed

Pustovit, Vitaliy N; Shahbazyan, Tigran V

2009-02-20

We identify a new mechanism for cooperative emission of light by an ensemble of N dipoles near a metal nanostructure supporting a surface plasmon. The cross talk between emitters due to the virtual plasmon exchange leads to the formation of three plasmonic superradiant modes whose radiative decay rates scale with N, while the total radiated energy is thrice that of a single emitter. Our numerical simulations indicate that the plasmonic Dicke effect survives nonradiative losses in the metal.

Simple Preparation of Novel Metal-Containing Mesoporous Starches †

PubMed Central

Ojeda, Manuel; Budarin, Vitaliy; Shuttleworth, Peter S.; Clark, James H.; Pineda, Antonio; Balu, Alina M.; Romero, Antonio A.; Luque, Rafael

2013-01-01

Metal-containing mesoporous starches have been synthesized using a simple and efficient microwave-assisted methodology followed by metal impregnation in the porous gel network. Final materials exhibited surface areas >60 m2 g−1, being essentially mesoporous with pore sizes in the 10–15 nm range with some developed inter-particular mesoporosity. These materials characterized by several techniques including XRD, SEM, TG/DTA and DRIFTs may find promising catalytic applications due to the presence of (hydr)oxides in their composition. PMID:28809249

Improving visibility of rear surface cracks during inductive thermography of metal plates using Autoencoder

NASA Astrophysics Data System (ADS)

Xie, Jing; Xu, Changhang; Chen, Guoming; Huang, Weiping

2018-06-01

Inductive thermography is one kind of infrared thermography (IRT) technique, which is effective in detection of front surface cracks in metal plates. However, rear surface cracks are usually missed due to their weak indications during inductive thermography. Here we propose a novel approach (AET: AE Thermography) to improve the visibility of rear surface cracks during inductive thermography by employing the Autoencoder (AE) algorithm, which is an important block to construct deep learning architectures. We construct an integrated framework for processing the raw inspection data of inductive thermography using the AE algorithm. Through this framework, underlying features of rear surface cracks are efficiently extracted and new clearer images are constructed. Experiments of inductive thermography were conducted on steel specimens to verify the efficacy of the proposed approach. We visually compare the raw thermograms, the empirical orthogonal functions (EOFs) of the prominent component thermography (PCT) technique and the results of AET. We further quantitatively evaluated AET by calculating crack contrast and signal-to-noise ratio (SNR). The results demonstrate that the proposed AET approach can remarkably improve the visibility of rear surface cracks and then improve the capability of inductive thermography in detecting rear surface cracks in metal plates.

Self-propulsion of a metallic superoleophobic micro-boat.

PubMed

Musin, Albina; Grynyov, Roman; Frenkel, Mark; Bormashenko, Edward

2016-10-01

The self-propulsion of a heavy, superoleophobic, metallic micro-boat carrying a droplet of various aqueous alcohol solutions as a fuel tank is reported. The micro-boat is driven by the solutocapillary Marangoni flow. The jump in the surface tension owing to the condensation of alcohols on the water surface was established experimentally. Maximal velocities of the self-propulsion were registered as high as 0.05m/s. The maximal velocity of the center mass of the boat correlates with the maximal change in the surface tension, due to the condensation of alcohols. The mechanism of the self-locomotion is discussed. The phenomenological dynamic model describing the self-propulsion is reported. Copyright © 2016 Elsevier Inc. All rights reserved.

The optical breakdown threshold of air on a polished metal surface for radiation at lambda=10.6 microns

NASA Astrophysics Data System (ADS)

Arkhipov, Iu. V.; Belashkov, I. N.; Datskevich, N. P.; Egorov, V. N.; Iziumov, A. F.

1986-01-01

Threshold conditions for the formation of a plasma due to optical breakdown of air on the polished surfaces of Al, Co, Mi, and W samples have been investigated experimentally. The optical breakdown was initiated by pulsed radiation from two CO2 lasers having pulse powers 0.5 and 1.0 kJ, respectively. The thresholds for the formation of the plasma were determined for two exposure spots of o/14 sq mm and 46 sq cm, respectively. A metallographic study was carried out in order to identify the specific types of defects corresponding to the lowest optical breakdown thresholds. Before-and-after photographs of the metal surfaces are provided.

Numerical modelling of surface plasmonic polaritons

NASA Astrophysics Data System (ADS)

Mansoor, Riyadh; AL-Khursan, Amin Habbeb

2018-06-01

Extending optoelectronics into the nano-regime seems problematic due to the relatively long wavelengths of light. The conversion of light into plasmons is a possible way to overcome this problem. Plasmon's wavelengths are much shorter than that of light which enables the propagation of signals in small size components. In this paper, a 3D simulation of surface plasmon polariton (SPP) excitation is performed. The Finite integration technique was used to solve Maxwell's equations in the dielectric-metal interface. The results show how the surface plasmon polariton was generated at the grating assisted dielectric-metal interface. SPP is a good candidate for signal confinement in small size optoelectronics which allow high density optical integrated circuits in all optical networks.

An Assessment of Molten Metal Detachment Hazards During Electron Beam Welding in Space

NASA Technical Reports Server (NTRS)

Fragomeni, James M.; Nunes, Arthur C., Jr.

1998-01-01

The safety issue has been raised with regards to potential molten metal detachments from the weld pool and cold filler wire during electron beam welding in space. This investigation was undertaken to evaluate if molten metal could detach and come in contact with astronauts and burn through the fabric of the astronauts' Extravehicular Mobility Unit (EMU) during electron beam welding in space. Molten metal detachments from either the weld/cut substrate or weld wire could present harm to a astronaut if the detachment was to burn through the fabric of the EMU. Theoretical models were developed to predict the possibility and size of the molten metal detachment hazards during the electron beam welding exercises at Low Earth Orbit (LEO). The primary molten metal detachment concerns were those cases of molten metal separation from the metal surface due to metal cutting, weld pool splashing, entrainment and release of molten metal due to filler wire snap-out from the weld puddle, and molten metal accumulation and release from the end of the weld wire. Some possible ways of obtaining molten metal drop detachments would include an impulse force, or bump, to the weld sample, cut surface, or filler wire. Theoretical models were developed for these detachment concerns from principles of impact and kinetic energies, surface tension, drop geometry, surface energies, and particle dynamics. The surface tension represents the force opposing the liquid metal drop from detaching whereas the weight of the liquid metal droplet represents a force that is tending to detach the molten metal drop. Theoretical calculations have indicated that only a small amount of energy is required to detach a liquid metal drop; however, much of the energy of an impact is absorbed in the sample or weld plate before it reaches the metal drop on the cut edge or surface. The tendency for detachment is directly proportional to the weld pool radius and metal density and inversely proportional to the surface tension of the liquid metal. For a detachment the initial kinetic energy of the weld pool with respect to the plate has to exceed the energy to form the extra surface required for the detachment of the pool. The difficulty is in transferring the energy from the point of impact through the plate and sample to the cut edge. It is likely that not all of the kinetic energy is available for detaching the pool; some may be sequestered in weld pool oscillations. The coefficient of restitution for the collision will be lower than one if irreversible deformation, for example plastic flow deformation, takes place during the collision. Thus determining the amount of energy from an impact that actually reaches the molten metal droplet is critical. Various molten metal detachment scenarios were tested experimentally in an enclosed vacuum chamber using the Ukrainian Universal Hand Tool, an electron beam welder designed for space welding. The experimental testing was performed in a 4 ft. X 4 ft. vacuum chamber at Marshall Space Flight Center, evacuated to vacuum levels of at least 50 microTorr, and also some welding garment material was utilized to observe the effect of the molten metal detachments on the material. A "carillon" apparatus consisting of four pendulum hammer strikers, each weighing approximately 3.65 lbs, raised to predetermined specific heights was used to apply an impact force to the weld sample/plate during electron beam welding and cutting exercises. The strikers were released by switching on an electric motor to rotate a pin holding wires retaining the strikers at desired heights. The specimens were suspended so as to be free to respond to the blows with a sudden velocity increment. The specimens were mounted on a hinged plate for minimizing effective mass with the option to fasten it down so as to raise its effective mass closer to that anticipated for an actual space welding scenario. Measurements were made of the impact energy and the horizontal fling distances of the detached metal drops. It was not particularly easy to generate the detachments fo

Method and means of reducing erosion of components of plasma devices exposed to helium and hydrogen isotope radiation

DOEpatents

Kaminsky, Manfred S.; Das, Santosh K.; Rossing, Thomas D.

1977-01-25

Surfaces of components of plasma devices exposed to radiation by atoms or ions of helium or isotopes of hydrogen can be protected from damage due to blistering by shielding the surfaces with a structure formed by sintering a powder of aluminum or beryllium and its oxide or by coating the surfaces with such a sintered metal powder.

Dual membrane hollow fiber fuel cell and method of operating same

NASA Technical Reports Server (NTRS)

Ingham, J. D.; Lawson, D. D. (Inventor)

1978-01-01

A gaseous fuel cell is described which includes a pair of electrodes formed by open-ended, ion-exchange hollow fibers, each having a layer of metal catalyst deposited on the inner surface and large surface area current collectors such as braided metal mesh in contact with the metal catalyst layer. A fuel cell results when the electrodes are immersed in electrolytes and electrically connected. As hydrogen and oxygen flow through the bore of the fibers, oxidation and reduction reactions develop an electrical potential. Since the hollow fiber configuration provides large electrode area per unit volume and intimate contact between fuel and oxidizer at the interface, and due to the low internal resistance of the electrolyte, high power densities can be obtained.

Silver Nanocube and Nanobar Growth via Anisotropic Monomer Addition and Particle Attachment Processes

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

Xiao, Dongdong; Wu, Zhigang; Song, Miao

Understanding the growth mechanism of noble metal nanocrystals during solution synthesis is of significant importance for shape and property control. However, much remains unknown about the growth pathways of metal nanoparticles due to lack of direct observation. Using an in-situ transmission electron microscopy technique, we directly observed Ag nanocube and nanobar growth in aqueous solution through both classical monomer-by-monomer addition and non-classical particle attachment processes. During the particle attachment process, Ag nanocubes and nanobars formed via both oriented and non-oriented attachment. Our calculations, along with dynamics of the observed attachment, showed that van der Waals force overcame hydrodynamic and frictionmore » forces and drove the particles toward each other. During classical growth, an anisotropic growth was also revealed, and the resulting unsymmetrical shape constituted an intermediate state for Ag nanocube growth. We hypothesized that the temporary symmetry breaking resulted from different growth rates on {001} surfaces due to a local surface concentration variation caused by the imbalance between the consumption of Ag+ near the surface and the diffusion of Ag+ from bulk to surface.« less

Amplification of intrinsic emittance due to rough metal cathodes: Formulation of a parameterization model

NASA Astrophysics Data System (ADS)

Charles, T. K.; Paganin, D. M.; Dowd, R. T.

2016-08-01

Intrinsic emittance is often the limiting factor for brightness in fourth generation light sources and as such, a good understanding of the factors affecting intrinsic emittance is essential in order to be able to decrease it. Here we present a parameterization model describing the proportional increase in emittance induced by cathode surface roughness. One major benefit behind the parameterization approach presented here is that it takes the complexity of a Monte Carlo model and reduces the results to a straight-forward empirical model. The resulting models describe the proportional increase in transverse momentum introduced by surface roughness, and are applicable to various metal types, photon wavelengths, applied electric fields, and cathode surface terrains. The analysis includes the increase in emittance due to changes in the electric field induced by roughness as well as the increase in transverse momentum resultant from the spatially varying surface normal. We also compare the results of the Parameterization Model to an Analytical Model which employs various approximations to produce a more compact expression with the cost of a reduction in accuracy.

Manipulating the architecture of bimetallic nanostructures and their plasmonic properties

NASA Astrophysics Data System (ADS)

DeSantis, Christopher John

There has been much interest in colloidal noble metal nanoparticles due to their fascinating plasmonic and catalytic properties. These properties make noble metal nanoparticles potentially useful for applications such as targeted drug delivery agents and hydrogen storage devices. Historically, shape-controlled noble metal nanoparticles have been predominantly monometallic. Recent synthetic advances provide access to bimetallic noble metal nanoparticles wherein their inherent multifunctionality and ability to fine tune or expand their surface chemistry and light scattering properties of metal nanoparticles make them popular candidates for many applications. Even so, there are currently few synthetic strategies to rationally design shape-controlled bimetallic nanocrystals; for this reason, few architectures are accessible. For example, the "seed-mediated method" is a popular means of achieving monodisperse shape-controlled bimetallic nanocrystals. In this process, small metal seeds are used as platforms for additional metal addition, allowing for conformal core shell nanostructures. However, this method has only been applied to single metal core/single metal shell structures; therefore, the surface compositions and architectures achievable are limited. This thesis expands upon the seed-mediated method by coupling it with co-reduction. In short, two metal precursors are simultaneously reduced to deposit metal onto pre-formed seeds in hopes that the interplay between two metal species facilitates bimetallic shell nanocrystals. Au/Pd was used as a test system due to favorable reduction potentials of metal precursors and good lattice match between Au and Pd. Alloyed shelled Au Au/Pd nanocrystals were achieved using this "seed-mediated co-reduction" approach. Symmetric eight-branched Au/Pd nanocrystals (octopods) are also prepared using this method. This thesis investigates many synthetic parameters that determine the shape outcome in Au/Pd nanocrystals during seed-mediated co-reduction. Plasmonic, catalytic, and assembly properties are also investigated in relation to nanocrystal shape and architecture. This work provides a foundation for the rational design of architecturally defined bimetallic nanostructures.

Investigation of Dynamic Oxygen Adsorption in Molten Solder Jetting Technology

NASA Technical Reports Server (NTRS)

Megaridis, Constantine M.; Bellizia, Giulio; McNallan, Michael; Wallace, David B.

2003-01-01

Surface tension forces play a critical role in fluid dynamic phenomena that are important in materials processing. The surface tension of liquid metals has been shown to be very susceptible to small amounts of adsorbed oxygen. Consequently, the kinetics of oxygen adsorption can influence the capillary breakup of liquid-metal jets targeted for use in electronics assembly applications, where low-melting-point metals (such as tin-containing solders) are utilized as an attachment material for mounting of electronic components to substrates. By interpreting values of surface tension measured at various surface ages, adsorption and diffusion rates of oxygen on the surface of the melt can be estimated. This research program investigates the adsorption kinetics of oxygen on the surface of an atomizing molten-metal jet. A novel oscillating capillary jet method has been developed for the measurement of dynamic surface tension of liquids, and in particular, metal melts which are susceptible to rapid surface degradation caused by oxygen adsorption. The experimental technique captures the evolution of jet swells and necks continuously along the jet propagation axis and is used in conjunction with an existing linear, axisymmetric, constant-property model to determine the variation of the instability growth rate, and, in turn, surface tension of the liquid as a function of surface age measured from the exit orifice. The conditions investigated so far focus on a time window of 2-4ms from the jet orifice. The surface properties of the eutectic 63%Sn-37%Pb solder alloy have been investigated in terms of their variation due to O2 adsorption from a N2 atmosphere containing controlled amounts of oxygen (from 8 ppm to 1000 ppm). The method performed well for situations where the oxygen adsorption was low in that time window. The value of surface tension for the 63Sn-37Pb solder in pure nitrogen was found to be 0.49 N/m, in good agreement with previously published work. A characteristic time of O(1ms) or less was determined for the molten-metal surface to be saturated by oxygen at 1000 ppm concentration in N2.

Evolution of residual stress, free volume, and hardness in the laser shock peened Ti-based metallic glass

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

Wang, Liang; Wang, Lu; Nie, Zhihua

Laser shock peening (LSP) with different cycles was performed on the Ti-based bulk metallic glasses (BMGs). The sub-surface residual stress of the LSPed specimens was measured by high-energy X-ray diffraction (HEXRD) and the near-surface residual stress was measured by scanning electron microscope/focused ion beam (SEM/FIB) instrument. The sub-surface residual stress in the LSP impact direction (about-170MPa) is much lower than that perpendicular to the impact direction (about -350 MPa), exhibiting anisotropy. The depth of the compressive stress zone increases from 400 mu m to 500 mu m with increasing LSP cycles. The highest near-surface residual stress is about -750 MPa.more » LSP caused the free volume to increase and the maximum increase appeared after the first LSP process. Compared with the hardness (567 +/- 7 HV) of the as-cast BMG, the hardness (590 +/- 9 HV) on the shocked surface shows a hardening effect due to the hardening mechanism of compressive residual stress; and the hardness (420 +/- 9 HV) on the longitudinal section shows a softening effect due to the softening mechanism of free volume.« less

Potential of coconut shell activated carbon (CSAC) in removing contaminants for water quality improvement: A critical review

NASA Astrophysics Data System (ADS)

Akhir, Muhammad Fitri Mohd; Saad, Noor Aida; Zakaria, Nor Azazi

2017-10-01

Commonly, water contaminations occur due to human-induced conditions such as industrial discharge and urban activities. The widely identified contaminants are heavy metal. The toxicity of those heavy metal elements is high and very poisonous to humans' health and environment even at lower dose or concentration of exposure. Chronic poisoning can cause fatal or defect to one's body or environment. Organic contaminants such as oil and microbial are also found due to decomposition of organic matter. The excellent quality adsorption of contaminants is highly related to surface area, pore size, pore volume, and amount plus type of functional group on surface of CSAC. The higher the surface area and pore volume, the higher adsorption that CSAC have towards contaminants. In comparison to meso-pore and macro-pore, micro-pore is better for trapping and adsorbing water contaminants. The purpose of this article is to critically review the potential of CSAC in increasing adsorption to remove contaminants for water quality improvement. A critical review is implemented using search engine like Science Direct. Alkali-modification is shown to have good adsorption in anion elements and organic matter due to improvement of hydrophobic organic compound (HOC) while acid-modification is good in cation elements adsorption. Strong alkali impregnated solution makes CSAC more hydrophobic and positively charge especially after increasing the impregnation dosage. Strong acid of adsorbate affects the quality of adsorption by reducing the surface area, pore volume and it also breaks the Van der Waals forces between adsorbent and adsorbate. However, the formation of oxygen helps the activated carbon surface to become more hydrophilic and negative charge is produced. It helps the effectiveness of metal adsorption. Therefore, by controlling dosage and types of functional groups on surface of CSAC and the pH of adsorbate, it can contribute to high adsorption of organic and inorganic contaminants in the water.

Cobalt, chromium and molybdenum ions kinetics in the human body: data gained from a total hip replacement with massive third body wear of the head and neuropathy by cobalt intoxication.

PubMed

Pazzaglia, U E; Apostoli, P; Congiu, T; Catalani, S; Marchese, M; Zarattini, G

2011-09-01

A patient with a total hip replacement developed optic, acoustic and peripheral neuropathy from metal ions intoxication, due to the wear products released from the prosthesis. Subsequently the kinetics of the metal ions was studied. Massive wear and acute intoxication allowed a study of the metal ions kinetics and of EDTA treatment. Plasma and other organic fluids were saturated by each of the metal ions released from the exposed surface according to the solubility of each ion; a larger fraction of Co ions was bound within red cells, while the plasmatic fraction appeared more movable. In a patient with a prosthesis subjected to wear, the ions released are from the prosthetic and from the debris surface (spread in the body). The latter is a function of the number and size of particles. Revision of the prosthesis from the point of view of the metal ions kinetics corresponded to a reduction of the releasing surface because of debris washed out by irrigation and tissue excision; however, the metal particles spread by lymphatic circulation continued to release ions even though the source of wear had been removed. Early diagnosis of high metal wear can be ascertained with mass spectrometry and after revision high levels of metal ions can only be reduced with repeated chelating treatment. It is preferable not to revise fractured ceramic components with a polyethylene-metal articulation.

Simulation of Nanowires on Metal Vicinal Surfaces: Effect of Growth Parameters and Energetic Barriers

NASA Astrophysics Data System (ADS)

Hamouda, Ajmi B. H.; Blel, Sonia; Einstein, T. L.

2012-02-01

Growing one-dimensional metal structures is an important task in the investigation of the electronic and magnetic properties of new devices. We used kinetic Monte-Carlo (kMC) method to simulate the formation of nanowires of several metallic and non-metallic adatoms on Cu and Pt vicinal surfaces. We found that mono-atomic chains form on step-edges due to energetic barriers (the so-called Ehrlich-shwoebel and exchange barriers) on step-edge. Creation of perfect wires is found to depend on growth parameters and binding energies. We measure the filling ratio of nanowires for different chemical species in a wide range of temperature and flux. Perfect wires were obtained at lower deposition rate for all tested adatoms, however we notice different temperature ranges. Our results were compared with experimental ones [Gambardella et al., Surf. Sci.449, 93-103 (2000), PRB 61, 2254-2262, (2000)]. We review the role of impurities in nanostructuring of surfaces [Hamouda et al., Phys. Rev. B 83, 035423, (2011)] and discuss the effect of their energetic barriers on the obtained quality of nanowires. Our work provides experimentalists with optimum growth parameters for the creation of a uniform distribution of wires on surfaces.

Nonlocal screening in metal surfaces

NASA Technical Reports Server (NTRS)

Krotscheck, E.; Kohn, W.

1986-01-01

Due to the effect of the nonuniform environment on the static screening of the Coulomb potential, the local-density approximation for the particle-hole interaction is found to be inadequate to determine the surface energy of simple metals. Use of the same set of single-particle states, and thus the same one-body density and the same work function, has eliminated the single-electron states in favor of the structure of the short-ranged correlations as the basis of this effect. A posteriori simplifications of the Fermi hypernetted-chain theory may be found to allow the same calculational accuracy with simpler computational tools.

Molecular induced skyhook effect for magnetic interlayer softening

NASA Astrophysics Data System (ADS)

Friedrich, Rico; Caciuc, Vasile; Atodiresei, Nicolae; Blügel, Stefan

2015-11-01

Our first-principles study demonstrates for the first time that by increasing the molecule-surface binding strength, the interlayer magnetic coupling of a ferromagnetic metal can be drastically reduced with respect to that of a clean substrate. Importantly, for a weakly chemisorbed molecule the rehybridization of metal atomic d states within the molecule-induced surface geometry (geometrical effect) plays a crucial role in obtaining interlayer magnetic softening. On the contrary, for a strongly chemisorbed molecule the interlayer magnetic coupling is further reduced due to an interplay between the geometrical effect and the hybridization of atomic d states with molecular ones.

Effects of calcium, magnesium, and sodium on alleviating cadmium toxicity to Hyalella azteca

USGS Publications Warehouse

Jackson, B.P.; Lasier, P.J.; Miller, W.P.; Winger, P.V.

2000-01-01

Toxicity of trace metal ions to aquatic organisms, arising through either anthropogenic inputs or acidification of surface waters, continues to be both a regulatory and environmental problem. It is generally accepted that the free metal ion is the major toxic species (Florence et a1.,1992) and that inorganic or organic complexation renders the metal ion non-bioavailable (Meador, 1991, Galvez and Wood, 1997). However, water chemistry parameters such as alkalinity, hardness, dissolved organic carbon and pH influence metal ion toxicity either directly by lowering free metal ion concentration or indirectly through synergistic or antagonistic effects. Alkalinity and salinity can affect the speciation of metal ions by increasing ion-pair formation, thus decreasing free metal ion concentration. For example, Cu was found to be less toxic to rainbow trout in waters of high alkalinity (Miller and Mackay, 1980), due to formation of CuCO3 ion pair, and corresponding reduction in free Cu2+ concentration. The influence of salinity on the toxicity of cadmium to various organisms has been demonstrated in a number of studies (Bervoets et al., 1995, Hall et al., 1995, Lin and Dunson, 1993, Blust et al., 1992). In all these studies the apparent toxicity of cadmium was lowered as salinity was increased due to increased formation of CdC1+ and CDCl2 aqueous complexes that are non-toxic or of much lower toxicity than the free Cd2+ ion. Changes in pH exert both a biological and chemical effect on metal ion toxicity (Campbell and Stokes, 1985). Low pH favors greater metal ion solubility, and, in the absence of complexing ions, reduced speciation of the metal ion, which tends to increase toxicity compared to higher pH. However, Iow pH also enhances competition between H+ and metal ion for cell surface binding sites, which tends to decrease metal ion toxicity.

Adsorption and electronic properties of pentacene on thin dielectric decoupling layers

PubMed Central

Kabakchiev, Alexander; Kuhnke, Klaus; Kern, Klaus

2017-01-01

With the increasing use of thin dielectric decoupling layers to study the electronic properties of organic molecules on metal surfaces, comparative studies are needed in order to generalize findings and formulate practical rules. In this paper we study the adsorption and electronic properties of pentacene deposited onto h-BN/Rh(111) and compare them with those of pentacene deposited onto KCl on various metal surfaces. When deposited onto KCl, the HOMO and LUMO energies of the pentacene molecules scale with the work functions of the combined KCl/metal surface. The magnitude of the variation between the respective KCl/metal systems indicates the degree of interaction of the frontier orbitals with the underlying metal. The results confirm that the so-called IDIS model developed by Willenbockel et al. applies not only to molecular layers on bare metal surfaces, but also to individual molecules on thin electronically decoupling layers. Depositing pentacene onto h-BN/Rh(111) results in significantly different adsorption characteristics, due to the topographic corrugation of the surface as well as the lateral electric fields it presents. These properties are reflected in the divergence from the aforementioned trend for the orbital energies of pentacene deposited onto h-BN/Rh(111), as well as in the different adsorption geometry. Thus, the highly desirable capacity of h-BN to trap molecules comes at the price of enhanced metal–molecule interaction, which decreases the HOMO–LUMO gap of the molecules. In spite of the enhanced interaction, the molecular orbitals are evident in scanning tunnelling spectroscopy (STS) and their shapes can be resolved by spectroscopic mapping. PMID:28900594

Self-organization of helium precipitates into elongated channels within metal nanolayers

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

Chen, Di; Li, Nan; Yuryev, Dina

Material degradation due to precipitation of implanted helium (He) is a key concern in nuclear energy. Decades of research have mapped out the fate of He precipitates in metals, from nucleation and growth of equiaxed bubbles and voids to formation and bursting of surface blisters. By contrast, we show that He precipitates confined within nanoscale metal layers depart from their classical growth trajectories: They self-organize into elongated channels. These channels form via templated nucleation of He precipitates along layer surfaces followed by their growth and spontaneous coalescence into stable precipitate lines. The total line length and connectivity increases with themore » amount of implanted He, indicating that these channels ultimately interconnect into percolating “vascular” networks. In conclusion, vascularized metal composites promise a transformative solution to He-induced damage by enabling in operando outgassing of He and other impurities while maintaining material integrity.« less

Framework for scalable adsorbate–adsorbate interaction models

DOE PAGES

Hoffmann, Max J.; Medford, Andrew J.; Bligaard, Thomas

2016-06-02

Here, we present a framework for physically motivated models of adsorbate–adsorbate interaction between small molecules on transition and coinage metals based on modifications to the substrate electronic structure due to adsorption. We use this framework to develop one model for transition and one for coinage metal surfaces. The models for transition metals are based on the d-band center position, and the models for coinage metals are based on partial charges. The models require no empirical parameters, only two first-principles calculations per adsorbate as input, and therefore scale linearly with the number of reaction intermediates. By theory to theory comparison withmore » explicit density functional theory calculations over a wide range of adsorbates and surfaces, we show that the root-mean-squared error for differential adsorption energies is less than 0.2 eV for up to 1 ML coverage.« less

Dispersion, Speciation, and Pollution Assessment of Heavy Metals Pb and Zn in Surface Sediment from Disturbed Ecosystem of Jeneberang Waters

NASA Astrophysics Data System (ADS)

Najamuddin; Surahman

2017-10-01

Surface sediments were collected from seventeen stations in Jeneberang waters (riverine, estuarine, and marine). Lead (Pb) and zinc (Zn) concentrations were determined by atomic absorption spectrometry, and the speciation of metals was obtained by a sequential extraction procedure. Dispersion of Pb and Zn were found higher in the riverine and marine samples than the estuarine samples. Following speciation, the metals were found similar composition of fraction in the riverine and estuarine samples but any different in the marine samples. The results indicated that there is a change of dispersion pattern and speciation composition of metals due to the presence of the dam that lies at the boundary between the estuary and the river. The toxicity unit was indicated low toxicity level; pollution level was in weakly to moderately polluted while the aquatic environment risk attributed were no risky to light risk.

Self-organization of helium precipitates into elongated channels within metal nanolayers

DOE PAGES

Chen, Di; Li, Nan; Yuryev, Dina; ...

2017-11-10

Material degradation due to precipitation of implanted helium (He) is a key concern in nuclear energy. Decades of research have mapped out the fate of He precipitates in metals, from nucleation and growth of equiaxed bubbles and voids to formation and bursting of surface blisters. By contrast, we show that He precipitates confined within nanoscale metal layers depart from their classical growth trajectories: They self-organize into elongated channels. These channels form via templated nucleation of He precipitates along layer surfaces followed by their growth and spontaneous coalescence into stable precipitate lines. The total line length and connectivity increases with themore » amount of implanted He, indicating that these channels ultimately interconnect into percolating “vascular” networks. In conclusion, vascularized metal composites promise a transformative solution to He-induced damage by enabling in operando outgassing of He and other impurities while maintaining material integrity.« less

Self-organization of helium precipitates into elongated channels within metal nanolayers

PubMed Central

Chen, Di; Li, Nan; Yuryev, Dina; Baldwin, J. Kevin; Wang, Yongqiang; Demkowicz, Michael J.

2017-01-01

Material degradation due to precipitation of implanted helium (He) is a key concern in nuclear energy. Decades of research have mapped out the fate of He precipitates in metals, from nucleation and growth of equiaxed bubbles and voids to formation and bursting of surface blisters. By contrast, we show that He precipitates confined within nanoscale metal layers depart from their classical growth trajectories: They self-organize into elongated channels. These channels form via templated nucleation of He precipitates along layer surfaces followed by their growth and spontaneous coalescence into stable precipitate lines. The total line length and connectivity increases with the amount of implanted He, indicating that these channels ultimately interconnect into percolating “vascular” networks. Vascularized metal composites promise a transformative solution to He-induced damage by enabling in operando outgassing of He and other impurities while maintaining material integrity. PMID:29152573

Dual-band quantum well infrared photodetector with metallic structure

NASA Astrophysics Data System (ADS)

Wu, Yang; Liu, Hongmei; Li, Pingzhou

2018-02-01

The quantum efficiency of the dual bands quantum well infrared photodetectors(QWIP) has been widely concerned in recent years. A novel structure for the dual-band quantum well infrared detectors which is based on GaAs/AlGaAs designed in this paper is aimed to improve the absorption efficiency. The structure replaces the conventional grating with a metallic grating based on surface plasmon polaritons(SPPS), and we further insert a metal structure in the periodic quantum well layer. The simulation result shows that the use of the different shapes of the metal holes can remarkably improve the optical coupling efficiency due to the surface plasmon effect. By optimizing parameters of the structure, it can work in the dual infrared bands of 3-5um and 8-12um. Moreover, the absorption rate increased by 20% compared with traditional structure of Dual-band QWIP.

Evaluation of ultrasonic cavitation of metallic and non-metallic surfaces

NASA Technical Reports Server (NTRS)

Mehta, Narinder K.

1992-01-01

1,1,2 trichloro-1,2,2 trifluoro ethane (CFC-113) commercially known as Freon-113 is the primary test solvent used for validating the cleaned hardware at the Kennedy Space Center (KSC). Due to the ozone depletion problem, the current United States policy calls for the phase out of Freons by 1995. NASAs chlorofluorocarbon (CFC) replacement group at KSC has opted to use water as a replacement fluid for the validation process since water is non-toxic, inexpensive, and is environmentally friendly. The replacement validation method calls for the ultrasonification of the small parts with water at 52 C for a cycle or two of 10 min duration wash using commercial ultrasonic baths. In this project, experimental data was obtained to assess the applicability of the proposed validation method for any damage of the metallic and non-metallic surfaces resulting from ultrasonic cavitation.

Effect of Impurities on the Josephson Current through Helical Metals: Exploiting a Neutrino Paradigm.

PubMed

Ghaemi, Pouyan; Nair, V P

2016-01-22

In this Letter we study the effect of time-reversal symmetric impurities on the Josephson supercurrent through two-dimensional helical metals such as on a topological insulator surface state. We show that, contrary to the usual superconducting-normal metal-superconducting junctions, the suppression of the supercurrent in the superconducting-helical metal-superconducting junction is mainly due to fluctuations of impurities in the junctions. Our results, which are a condensed matter realization of a part of the Mikheyev-Smirnov-Wolfenstein effect for neutrinos, show that the relationship between normal state conductance and the critical current of Josephson junctions is significantly modified for Josephson junctions on the surface of topological insulators. We also study the temperature dependence of the supercurrent and present a two fluid model which can explain some of the recent experimental results in Josephson junctions on the edge of topological insulators.

Effect of Impurities on the Josephson Current through Helical Metals: Exploiting a Neutrino Paradigm

NASA Astrophysics Data System (ADS)

Ghaemi, Pouyan; Nair, V. P.

2016-01-01

In this Letter we study the effect of time-reversal symmetric impurities on the Josephson supercurrent through two-dimensional helical metals such as on a topological insulator surface state. We show that, contrary to the usual superconducting-normal metal-superconducting junctions, the suppression of the supercurrent in the superconducting-helical metal-superconducting junction is mainly due to fluctuations of impurities in the junctions. Our results, which are a condensed matter realization of a part of the Mikheyev-Smirnov-Wolfenstein effect for neutrinos, show that the relationship between normal state conductance and the critical current of Josephson junctions is significantly modified for Josephson junctions on the surface of topological insulators. We also study the temperature dependence of the supercurrent and present a two fluid model which can explain some of the recent experimental results in Josephson junctions on the edge of topological insulators.

Treatment of electronic waste to recover metal values using thermal plasma coupled with acid leaching--a response surface modeling approach.

PubMed

Rath, Swagat S; Nayak, Pradeep; Mukherjee, P S; Roy Chaudhury, G; Mishra, B K

2012-03-01

The global crisis of the hazardous electronic waste (E-waste) is on the rise due to increasing usage and disposal of electronic devices. A process was developed to treat E-waste in an environmentally benign process. The process consisted of thermal plasma treatment followed by recovery of metal values through mineral acid leaching. In the thermal process, the E-waste was melted to recover the metal values as a metallic mixture. The metallic mixture was subjected to acid leaching in presence of depolarizer. The leached liquor mainly contained copper as the other elements like Al and Fe were mostly in alloy form as per the XRD and phase diagram studies. Response surface model was used to optimize the conditions for leaching. More than 90% leaching efficiency at room temperature was observed for Cu, Ni and Co with HCl as the solvent, whereas Fe and Al showed less than 40% efficiency. Copyright © 2011 Elsevier Ltd. All rights reserved.

Wear Resistance of Steels with Surface Nanocrystalline Structure Generated by Mechanical-Pulse Treatment.

PubMed

Nykyforchyn, Hryhoriy; Kyryliv, Volodymyr; Maksymiv, Olha

2017-12-01

The influence of the surface mechanical-pulse treatment based on high-speed friction with a rapid cooling by the technological environment on the wear resistance of medium- and high-carbon steels was considered. The treatment due to a severe plastic deformation enabled obtaining the nanocrystalline structure with a grain size of 14-40 nm. A high positive effect of this treatment was obtained not only because of metal nanocrystallization but also thanks to other factors, namely, structural-phase transformations, carbon saturation of the surface due to decomposition of the coolant and the friction coefficient decrease. Higher carbon content leads to better strengthening of the surface, and its microhardness can reach 12 GPa.

Carbonaceous thin film coating with Fe-N4 site for enhancement of dioxovanadium ion reduction

NASA Astrophysics Data System (ADS)

Maruyama, Jun; Hasegawa, Takahiro; Iwasaki, Satoshi; Fukuhara, Tomoko; Orikasa, Yuki; Uchimoto, Yoshiharu

2016-08-01

It has been found that carbonaceous materials containing a transition metal coordinated by 4 nitrogens in the square-planar configuration (metal-N4 site) on the surface possessed a catalytic activity for various electrochemical reactions related to energy conversion and storage; i.e., oxygen reduction, hydrogen evolution, and quite recently, the electrode reactions in vanadium redox flow batteries (VRFB). The catalyst for the VRFB positive electrode discharge reaction, i.e., the dioxovanadium ion reduction, was formed by coating the surface of cup-stack carbon nanotubes with a carbonaceous thin film with the Fe-N4 site generated by the sublimation, deposition, and pyrolysis of iron phthalocyanine. In this study, the influence of the physical properties of the catalyst on the electrochemical reactions was investigated to optimize the coating. With an increase in the coating, the specific surface area increased, whereas the pore size decreased. The surface Fe concentration was increased in spite of the Fe aggregation inside the carbon matrix. The catalytic activity enhancement was achieved due to the increase in the specific surface area and the surface Fe concentration, but was lowered due to the decrease in the pore size, which was disadvantageous for the penetration of the electrolyte and the mass transfer.

Prominent metallic surface conduction and the singular magnetic response of topological Dirac fermion in three-dimensional topological insulator Bi1.5Sb0.5Te1.7Se1.3.

PubMed

Dutta, Prithwish; Pariari, Arnab; Mandal, Prabhat

2017-07-07

We report semiconductor to metal-like crossover in the temperature dependence of resistivity (ρ) due to the switching of charge transport from bulk to surface channel in three-dimensional topological insulator Bi 1.5 Sb 0.5 Te 1.7 Se 1.3 . Unlike earlier studies, a much sharper drop in ρ(T) is observed below the crossover temperature due to the dominant surface conduction. Remarkably, the resistivity of the conducting surface channel follows a rarely observable T 2 dependence at low temperature, as predicted theoretically for a two-dimensional Fermi liquid system. The field dependence of magnetization shows a cusp-like paramagnetic peak in the susceptibility (χ) at zero field over the diamagnetic background. The peak is found to be robust against temperature and χ decays linearly with the field from its zero-field value. This unique behavior of the χ is associated with the spin-momentum locked topological surface state in Bi 1.5 Sb 0.5 Te 1.7 Se 1.3 . The reconstruction of the surface state with time is clearly reflected through the reduction of the peak height with the age of the sample.

Investigation of molten pool oscillation during GMAW-P process based on a 3D model

NASA Astrophysics Data System (ADS)

Wang, L. L.; Lu, F. G.; Cui, H. C.; Tang, X. H.

2014-11-01

In order to better reveal the oscillation mechanism of the pulsed gas metal arc welding (GMAW-P) process due to an alternately varied welding current, arc plasma and molten pool oscillation were simulated through a self-consistent three-dimensional model. Based on an experimental analysis of the dynamic variation of the arc plasma and molten pool captured by a high-speed camera, the model was validated by comparison of the measured and predicted results. The calculated results showed that arc pressure was the key factor causing the molten pool to oscillate. The variation in arc size and temperature from peak time to base time resulted in a great difference in the heat input and arc pressure acting on the molten pool. The surface deformation of the molten pool due to the varying degrees of arc pressure induced alternate displacement and backflow in the molten metal. The periodic iteration of deeper and shallower surface deformation, drain and backflow of molten metal caused the molten pool to oscillate at a certain frequency. In this condition, the arc pressure at the peak time is more than six times higher than that at the base time, and the maximum surface depression is 1.4 mm and 0.6 mm, respectively, for peak time and base time.

Spatial confinement effects on spectroscopic and morphological studies of nanosecond laser-ablated Zirconium

NASA Astrophysics Data System (ADS)

Hayat, Asma; Bashir, Shazia; Rafique, Muhammad Shahid; Ahmad, Riaz; Akram, Mahreen; Mahmood, Khaliq; Zaheer, Ali

2017-12-01

Spatial confinement effects on plasma parameters and surface morphology of laser ablated Zr (Zirconium) are studied by introducing a metallic blocker. Nd:YAG laser at various fluencies ranging from 8 J cm-2 to 32 J cm-2 was employed as an irradiation source. All measurements were performed in the presence of Ar under different pressures. Confinement effects offered by metallic blocker are investigated by placing the blocker at different distances of 6 mm, 8 mm and 10 mm from the target surface. It is revealed from LIBS analysis that both plasma parameters i.e. excitation temperature and electron number density increase with increasing laser fluence due to enhancement in energy deposition. It is also observed that spatial confinement offered by metallic blocker is responsible for the enhancement of both electron temperature and electron number density of Zr plasma. This is true for all laser fluences and pressures of Ar. Maximum values of electron temperature and electron number density without blocker are 12,600 K and 14 × 1017 cm-3 respectively whereas, these values are enhanced to 15,000 K and 21 × 1017 cm-3 in the presence of blocker. The physical mechanisms responsible for the enhancement of Zr plasma parameters are plasma compression, confinement and pronounced collisional excitations due to reflection of shock waves. Scanning Electron Microscope (SEM) analysis was performed to explore the surface morphology of laser ablated Zr. It reveals the formation of cones, cavities and ripples. These features become more distinct and well defined in the presence of blocker due to plasma confinement. The optimum combination of blocker distance, fluence and Ar pressure can identify the suitable conditions for defining the role of plasma parameters for surface structuring.

Thermodynamic limit to photonic-plasmonic light-trapping in thin films on metals

NASA Astrophysics Data System (ADS)

Schiff, E. A.

2011-11-01

We calculate the maximum optical absorptance enhancements in thin semiconductor films on metals due to structures that diffuse light and couple it to surface plasmon polaritons. The calculations can be used to estimate plasmonic effects on light-trapping in solar cells. The calculations are based on the statistical distribution of energy in the electromagnetic modes of the structure, which include surface plasmon polariton modes at the metal interface as well as the trapped waveguide modes in the film. The enhancement has the form 4n2+nλ/h (n - film refractive index, λ - optical wavelength, h - film thickness), which is an increase beyond the non-plasmonic "classical" enhancement 4n2. Larger resonant enhancements occur for wavelengths near the surface plasmon frequency; these add up to 2 mA/cm2 to the photocurrent of a solar cell based on a 500 nm film of crystalline silicon. We also calculated the effects of plasmon dissipation in the metal. Dissipation rates typical of silver reverse the resonant enhancement effect for silicon, but a non-resonant enhancement remains.

Human exposure risk to heavy metals through groundwater used for drinking in an intensively irrigated river delta

NASA Astrophysics Data System (ADS)

Vetrimurugan, E.; Brindha, K.; Elango, L.; Ndwandwe, Osman Muzi

2017-10-01

Drinking water containing heavy metals above the maximum permissible limits cause potential risk to human health. The aim of this study was to determine the groundwater suitability for drinking use based on heavy metal concentration and the associated human exposure risk in an intensively irrigated part of the Cauvery river basin, Tamil Nadu, India. Sixteen heavy metals analysed were in the order of dominance of chromium < zinc < copper < cadmium < cobalt < iron < aluminium < nickel < titanium < zirconium < boron < silver < manganese < lead < lithium < silicon in groundwater. Chromium and zinc were within permissible limits of the Bureau of Indian Standards for drinking water quality, and silver, lead and nickel were above limits in all the groundwater samples. In less than 50 % of the groundwater samples, aluminium, boron, cadmium, copper, iron and manganese exceeded their individual permissible limits. Heavy metal pollution index based on 11 heavy metals indicated that groundwater quality of this area is poor-to-unsuitable. Non-carcinogenic risk for humans due to ingestion of groundwater through drinking water pathway was very high for infants, children and adults. Silver, lead, nickel, cadmium and manganese largely contributed to the health hazard. Sources of heavy metals were identified to be geological and from human activities, i.e., application of fertilizers in agricultural fields, seawater intrusion due to intensive pumping for agriculture and wastewater from industries. Groundwater and surface water in this area pose large threat due to high levels of heavy metals, and it is necessary to avoid this water for drinking due to potential risk of health hazard. This study also demonstrated the application of HPI and human exposure hazard index to study the groundwater quality based on heavy metals' concentration.

Potentiodynamic study of Al-Mg alloy with superhydrophobic coating in photobiologically active/not active natural seawater.

PubMed

Benedetti, Alessandro; Cirisano, Francesca; Delucchi, Marina; Faimali, Marco; Ferrari, Michele

2016-01-01

Superhydrophobic coating technology is regarded as an attractive possibility for the protection of materials in a sea environment. DC techniques are a useful tool to characterize metals' behavior in seawater in the presence/absence of coatings and/or corrosion inhibitors. In this work, investigations concerning Al-5%Mg alloy with and without a sprayed superhydrophobic coating were carried out with potentiodynamic scans in photobiologically active and not active seawater (3 weeks of immersion). In not photobiologically active seawater, the presence of the superhydrophobic coating did not prevent pitting corrosion. With time, the coating underwent local exfoliations, but intact areas still preserved superhydrophobicity. In photobiologically active seawater, on samples without the superhydrophobic coating (controls) pitting was inhibited, probably due to the adsorption of organic compounds produced by the photobiological activity. After 3 weeks of immersion, the surface of the coating became hydrophilic due to diatom coverage. As suggested by intermediate observations, the surface below the diatom layer is suspected of having lost its superhydrophobicity due to early stages of biofouling processes (organic molecule adsorption and diatom attachment/gliding). Polarization curves also revealed that the metal below the coating underwent corrosion inhibiting phenomena as observed in controls, likely due to the permeation of organic molecules through the coating. Hence, the initial biofouling stages (days) occurring in photobiologically active seawater can both accelerate the loss of superhydrophobicity of coatings and promote corrosion inhibition on the underlying metal. Finally, time durability of superhydrophobic surfaces in real seawater still remains the main challenge for applications, where the early stages of immersion are demonstrated to be of crucial importance. Copyright © 2015 Elsevier B.V. All rights reserved.

Nanotubular surface modification of metallic implants via electrochemical anodization technique.

PubMed

Wang, Lu-Ning; Jin, Ming; Zheng, Yudong; Guan, Yueping; Lu, Xin; Luo, Jing-Li

2014-01-01

Due to increased awareness and interest in the biomedical implant field as a result of an aging population, research in the field of implantable devices has grown rapidly in the last few decades. Among the biomedical implants, metallic implant materials have been widely used to replace disordered bony tissues in orthopedic and orthodontic surgeries. The clinical success of implants is closely related to their early osseointegration (ie, the direct structural and functional connection between living bone and the surface of a load-bearing artificial implant), which relies heavily on the surface condition of the implant. Electrochemical techniques for modifying biomedical implants are relatively simple, cost-effective, and appropriate for implants with complex shapes. Recently, metal oxide nanotubular arrays via electrochemical anodization have become an attractive technique to build up on metallic implants to enhance the biocompatibility and bioactivity. This article will thoroughly review the relevance of electrochemical anodization techniques for the modification of metallic implant surfaces in nanoscale, and cover the electrochemical anodization techniques used in the development of the types of nanotubular/nanoporous modification achievable via electrochemical approaches, which hold tremendous potential for bio-implant applications. In vitro and in vivo studies using metallic oxide nanotubes are also presented, revealing the potential of nanotubes in biomedical applications. Finally, an outlook of future growth of research in metallic oxide nanotubular arrays is provided. This article will therefore provide researchers with an in-depth understanding of electrochemical anodization modification and provide guidance regarding the design and tuning of new materials to achieve a desired performance and reliable biocompatibility.

Nanotubular surface modification of metallic implants via electrochemical anodization technique

PubMed Central

Wang, Lu-Ning; Jin, Ming; Zheng, Yudong; Guan, Yueping; Lu, Xin; Luo, Jing-Li

2014-01-01

Due to increased awareness and interest in the biomedical implant field as a result of an aging population, research in the field of implantable devices has grown rapidly in the last few decades. Among the biomedical implants, metallic implant materials have been widely used to replace disordered bony tissues in orthopedic and orthodontic surgeries. The clinical success of implants is closely related to their early osseointegration (ie, the direct structural and functional connection between living bone and the surface of a load-bearing artificial implant), which relies heavily on the surface condition of the implant. Electrochemical techniques for modifying biomedical implants are relatively simple, cost-effective, and appropriate for implants with complex shapes. Recently, metal oxide nanotubular arrays via electrochemical anodization have become an attractive technique to build up on metallic implants to enhance the biocompatibility and bioactivity. This article will thoroughly review the relevance of electrochemical anodization techniques for the modification of metallic implant surfaces in nanoscale, and cover the electrochemical anodization techniques used in the development of the types of nanotubular/nanoporous modification achievable via electrochemical approaches, which hold tremendous potential for bio-implant applications. In vitro and in vivo studies using metallic oxide nanotubes are also presented, revealing the potential of nanotubes in biomedical applications. Finally, an outlook of future growth of research in metallic oxide nanotubular arrays is provided. This article will therefore provide researchers with an in-depth understanding of electrochemical anodization modification and provide guidance regarding the design and tuning of new materials to achieve a desired performance and reliable biocompatibility. PMID:25258532

Control of two-dimensional electronic states at anatase Ti O2(001 ) surface by K adsorption

NASA Astrophysics Data System (ADS)

Yukawa, R.; Minohara, M.; Shiga, D.; Kitamura, M.; Mitsuhashi, T.; Kobayashi, M.; Horiba, K.; Kumigashira, H.

2018-04-01

The nature of the intriguing metallic electronic structures appearing at the surface of anatase titanium dioxide (a-Ti O2 ) remains to be elucidated, mainly owing to the difficulty of controlling the depth distribution of the oxygen vacancies generated by photoirradiation. In this study, K atoms were adsorbed onto the (001) surface of a-Ti O2 to dope electrons into the a-Ti O2 and to confine the electrons in the surface region. The success of the electron doping and its controllability were confirmed by performing in situ angle-resolved photoemission spectroscopy as well as core-level measurements. Clear subband structures were observed in the surface metallic states, indicating the creation of quasi-two-dimensional electron liquid (q2DEL) states in a controllable fashion. With increasing electron doping (K adsorption), the q2DEL states exhibited crossover from polaronic liquid states with multiple phonon-loss structures originating from the long-range Fröhlich interaction to "weakly correlated metallic" states. In the q2DEL states in the weakly correlated metallic region, a kink due to short-range electron-phonon coupling was clearly observed at about 80 ±10 meV . The characteristic energy is smaller than that previously observed for the metallic states of a-Ti O2 with three-dimensional nature (˜110 meV ) . These results suggest that the dominant electron-phonon coupling is modulated by anisotropic carrier screening in the q2DEL states.

Improved Bond Strength of Cyanoacrylate Adhesives Through Nanostructured Chromium Adhesion Layers

NASA Astrophysics Data System (ADS)

Gobble, Kyle; Stark, Amelia; Stagon, Stephen P.

2016-09-01

The performance of many consumer products suffers due to weak and inconsistent bonds formed to low surface energy polymer materials, such as polyolefin-based high-density polyethylene (HDPE), with adhesives, such as cyanoacrylate. In this letter, we present an industrially relevant means of increasing bond shear strength and consistency through vacuum metallization of chromium thin films and nanorods, using HDPE as a prototype material and cyanoacrylate as a prototype adhesive. For the as received HDPE surfaces, unmodified bond shear strength is shown to be only 0.20 MPa with a standard deviation of 14 %. When Cr metallization layers are added onto the HDPE at thicknesses of 50 nm or less, nanorod-structured coatings outperform continuous films and have a maximum bond shear strength of 0.96 MPa with a standard deviation of 7 %. When the metallization layer is greater than 50 nm thick, continuous films demonstrate greater performance than nanorod coatings and have a maximum shear strength of 1.03 MPa with a standard deviation of 6 %. Further, when the combination of surface roughening with P400 grit sandpaper and metallization is used, 100-nm-thick nanorod coatings show a tenfold increase in shear strength over the baseline, reaching a maximum of 2.03 MPa with a standard deviation of only 3 %. The substantial increase in shear strength through metallization, and the combination of roughening with metallization, may have wide-reaching implications in consumer products which utilize low surface energy plastics.

Assessing trace metal pollution through high spatial resolution of surface sediments along the Tunis Gulf coast (southwestern Mediterranean).

PubMed

Ennouri, Rym; Zaaboub, Noureddine; Fertouna-Bellakhal, Mouna; Chouba, Lassad; Aleya, Lotfi

2016-03-01

Tunis Gulf (northern Tunisia, Mediterranean Sea) is of great economic importance due to its abundant fish resources. Rising urbanization and industrial development in the surrounding area have resulted in an increase in untreated effluents and domestic waste discharged into the gulf via its tributary streams. Metal (Cd, Pb, Hg, Cu, Zn, Fe, and Mn) and major element (Mg, Ca, Na, and K) concentrations were measured in the grain fine fraction <63 μm by atomic absorption spectrophotometry. Results showed varying spatial distribution patterns for metals, indicating complex origins and controlling factors such as anthropogenic activities. Sediment metal concentrations are ranked as follows: Fe > Mg > Zn > Mn > Pb > Cu > Cd > Hg. Metals tend to be concentrated in proximity to source points, suggesting that the mineral enrichment elements come from sewage of coastal towns and pollution from industrial dumps and located along local rivers, lagoons, and on the gulf shore itself. This study showed that trace metal and major element concentrations in surface sediments along the Tunis Gulf shores were lower than those found in other coastal areas of the Mediterranean Sea.

Bulk and surface half-metallicity: The case of D0{sub 3}-type Mn{sub 3}Ge

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

Liu, Hao; Gao, G. Y., E-mail: guoying-gao@mail.hust.edu.cn; Hu, Lei

2014-01-21

Motivated by the experimental realization of D0{sub 22}-type Mn{sub 3}Ge (001) films [Kurt et al. Appl. Phys. Lett. 101, 132410 (2012)] and the structural stability of D0{sub 3}-type Heusler alloy Mn{sub 3}Ge [Zhang et al. J. Phys.: Condens. Matter 25, 206006 (2013)], we use the first-principles calculations based on the full potential linearized augmented plane-wave method to investigate the electronic and magnetic properties of D0{sub 3}-type Heusler alloy Mn{sub 3}Ge and its (001) surface. We show that bulk D0{sub 3}-Mn{sub 3}Ge is a half-metallic ferromagnet with the minority-spin energy gap of 0.52 eV and the magnetic moment of 1.00 μ{sub B} permore » formula unit. The bulk half-metallicity is preserved at the pure Mn-terminated (001) surface due to the large exchange split, but the MnGe-terminated (001) surface destroys the bulk half-metallicity. We also reveal that the surface stabilities are comparable between the D0{sub 3}-Mn{sub 3}Ge (001) and the experimental D0{sub 22}-Mn{sub 3}Ge (001), which indicates the feasibility to grow the Mn{sub 3}Ge (001) films with D0{sub 3} phase other than D0{sub 22} one. The surface half-metallicity and stability make D0{sub 3}-Mn{sub 3}Ge a promising candidate for spintronic applications.« less

Sorption of Molecular Oxygen by Metal-Ion Exchanger Nanocomposites

NASA Astrophysics Data System (ADS)

Krysanov, V. A.; Plotnikova, N. V.; Kravchenko, T. A.

2018-03-01

Kinetic features are studied of the chemisorption and reduction of molecular oxygen from water by metal-ion exchanger nanocomposites that differ in the nature of the dispersed metal and state of oxidation. In the Pd < Ag < Cu series, the increasing chemical activity of metal nanoparticles raises the degree of oxygen sorption due to its chemisorption and subsequent reduction, while the role of the molecular chemisorption stage increases in the Cu < Ag < Pd series. Metal particles or their oxides are shown to act as adsorption sites on the surface and in the pores of the ion-exchanger matrix; the equilibrium sorption coefficient for oxygen dissolved in water ranges from 20 to 50, depending on the nature and oxidation state of the metal component.

Biomagnetic monitoring of heavy metals contamination in deposited atmospheric dust, a case study from Isfahan, Iran.

PubMed

Norouzi, Samira; Khademi, Hossein; Cano, Angel Faz; Acosta, Jose A

2016-05-15

Tree leaves are considered as one of the best biogenic dust collectors due to their ability to trap and retain particulate matter on their surfaces. In this study, the magnetic susceptibility (MS) and the concentration of selected heavy metals of plane tree (Platanus orientalis L.) leaves and deposited atmospheric dust, sampled by an indirect and a direct method, respectively, were determined to investigate the relationships between leaf magnetic parameters and the concentration of heavy metals in deposited atmospheric dust. The objective was to develop a biomagnetic method as an alternative to the common ones used for determining atmospheric heavy metal contaminations. Plane tree leaves were monthly sampled on the 19th of May to November, 2012 (T1-T7), for seven months from 21 different sites in the city of Isfahan, central Iran. Deposited atmospheric dust samples were also collected using flat glass surfaces from the same sites on the same dates, except for T1. MS (χlf, χhf) values in washed (WL) and unwashed leaves (UL) as well as Cu, Fe, Mn, Ni, Pb, and Zn concentrations in UL and deposited atmospheric dust samples were determined. The results showed that the MS content with a biogenic source was low with almost no significant change during the sampling period, while an increasing trend was observed in the MS content of UL samples due to the deposition of heavy metals and magnetic particles on leaf surfaces throughout the plant growth. The latter type of MS content could be reduced through washing off by rain. Most heavy metals examined, as well as the Tomlinson pollution load index (PLI) in UL, showed statistically significant correlations with MS values. The correlation between heavy metals content in atmospheric dust deposited on glass surfaces and leaf MS values was significant for Cu, Fe, Pb, and Zn. Moreover, the similarity observed between the spatial distribution maps of leaf MS and deposited atmospheric dust PLI provided convincing evidence regarding the suitability of the biomagnetic approach as a relatively rapid and inexpensive method for identifying highly polluted urban areas with selected heavy metals, especially those subjected to anthropogenic and other traffic related sources. Copyright © 2016 Elsevier Ltd. All rights reserved.

Characteristics and formation mechanism for stainless steel fiber with periodic micro-fins

NASA Astrophysics Data System (ADS)

Tang, Tao; Wan, Zhenping; Lu, Longsheng; Tang, Yong

2016-05-01

Metal fibers have been widely used in many industrial applications due to their unique advantages. In certain applications, such as catalyst supports or orthopedic implants, a rough surface or tiny outshoots on the surface of metal fibers to increase surface area are needed. However, it has not been concerned about the surface morphologies of metal fiber in the current research of metal fiber manufacturing. In this paper, a special multi-tooth tool composed of a row of triangular tiny teeth is designed. The entire cutting layer of multi-tooth tool bifurcates into several thin cutting layers due to tiny teeth involved in cutting. As a result, several stainless steel fibers with periodic micro-fins are produced simultaneously. Morphology of periodic micro-fins is found to be diverse and can be classified into three categories: unilateral plane, unilateral tapering and bilateral. There are two forming mechanisms for the micro-fins. One is that periodic burrs remained on the free side of cutting layer of a tiny tooth create micro-fins of stainless steel fiber produced by the next neighboring tiny tooth; the other is that the connections between two fibers stuck together come to be micro-fins if the two fibers are finally detached. Influence of cutting conditions on formation of micro-fins is investigated. Experimental results show that cutting depth has no significant effect on micro-fin formation, high cutting speed is conducive to micro-fin formation, and feed should be between 0.12 mm/r and 0.2 mm/r to reliably obtain stainless steel fiber with micro-fins. This research presents a new pattern of stainless steel fiber characterized by periodic micro-fins formed on the edge of fiber and its manufacturing method.

Systems and Methods for Designing and Fabricating Contact-Free Support Structures for Overhang Geometries of Parts in Powder-Bed Metal Additive Manufacturing

NASA Technical Reports Server (NTRS)

Cooper, Kenneth (Inventor); Chou, Yuag-Shan (Inventor)

2017-01-01

Systems and methods are provided for designing and fabricating contact-free support structures for overhang geometries of parts fabricated using electron beam additive manufacturing. One or more layers of un-melted metallic powder are disposed in an elongate gap between an upper horizontal surface of the support structure and a lower surface of the overhang geometry. The powder conducts heat from the overhang geometry to the support structure. The support structure acts as a heat sink to enhance heat transfer and reduce the temperature and severe thermal gradients due to poor thermal conductivity of metallic powders underneath the overhang. Because the support structure is not connected to the part, the support structure can be removed freely without any post-processing step.

Patterned growth of carbon nanotubes on Si substrates without predeposition of metal catalysts

NASA Astrophysics Data System (ADS)

Chen, Y.; Yu, J.

2005-07-01

Aligned carbon nanotubes (CNTs) can be readily synthesized on quartz or silicon-oxide-coated Si substrates using a chemical vapor deposition method, but it is difficult to grow them on pure Si substrates without predeposition of metal catalysts. We report that aligned CNTs were grown by pyrolysis of iron phthalocyanine at 1000°C on the templates created on Si substrates with simple mechanical scratching. Scanning electron microscopy and x-ray energy spectroscopy analysis revealed that the trenches and patterns created on the surface of Si substrates were preferred nucleation sites for nanotube growth due to a high surface energy, metastable surface structure, and possible capillarity effect. A two-step pyrolysis process maintained Fe as an active catalyst.

Jumping liquid metal droplet in electrolyte triggered by solid metal particles

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

Tang, Jianbo; University of Chinese Academy of Sciences, Beijing 100049; Wang, Junjie

2016-05-30

We report the electron discharge effect due to point contact between liquid metal and solid metal particles in electrolyte. Adding nickel particles induces drastic hydrogen generating and intermittent jumping of a sub-millimeter EGaIn droplet in NaOH solution. Observations from different orientations disclose that such jumping behavior is triggered by pressurized bubbles under the assistance of interfacial interactions. Hydrogen evolution around particles provides clear evidence that such electric instability originates from the varied electric potential and morphology between the two metallic materials. The point-contact-induced charge concentration significantly enhances the near-surface electric field intensity at the particle tips and thus causes electricmore » breakdown of the electrolyte.« less

Impact of Graphene-Metal Interfaces on the Raman and Transport Properties of Graphene Devices

NASA Astrophysics Data System (ADS)

Hsu, Allen; Hofmann, Mario; Fang, Wenjing; Kimg, Ki Kang; Kong, Jing; Palacios, Tomas

2012-02-01

Graphene is an amazing nano-material with many exciting properties and applications. However, due to its low dimensionality, the performance of this material is mainly limited by interfaces and surface properties. One of these interfaces, important for graphene field effect transistors and catalysts supported on graphene membranes, is that between the graphene and a metal layer. In this study, we experimentally examine the impact of various metals on graphene through Raman and Transmission Electron Microscopy. We find that strong graphene-metal interactions have significant impacts on the phonon structure in graphene. Furthermore, we observe changes in our Raman spectra relating to the crystallographic orientation between a metal and graphene.

Investigation of an EMI sensor for detection of large metallic objects in the presence of metallic clutter

NASA Astrophysics Data System (ADS)

Black, Christopher; McMichael, Ian; Riggs, Lloyd

2005-06-01

Electromagnetic induction (EMI) sensors and magnetometers have successfully detected surface laid, buried, and visually obscured metallic objects. Potential military activities could require detection of these objects at some distance from a moving vehicle in the presence of metallic clutter. Results show that existing EMI sensors have limited range capabilities and suffer from false alarms due to clutter. This paper presents results of an investigation of an EMI sensor designed for detecting large metallic objects on a moving platform in a high clutter environment. The sensor was developed by the U.S. Army RDECOM CERDEC NVESD in conjunction with the Johns Hopkins University Applied Physics Laboratory.

Infrared deflectometry for the inspection of diffusely specular surfaces

NASA Astrophysics Data System (ADS)

Höfer, Sebastian; Burke, Jan; Heizmann, Michael

2016-12-01

Deflectometry is a full-field gradient technique that lends itself very well to testing specular surfaces. It uses the geometry of specular reflection to determine the gradient of the surface under inspection. In consequence, a necessary precondition to apply deflectometry is the presence of at least partially specular reflection. Surfaces with larger roughness have increasingly diffuse reflection characteristics, making them inaccessible to usual deflectometry. However, many industrially relevant surfaces exist that change their reflection characteristic during production and processing. An example is metal sheets that are used as car body parts. Whereas the molded but otherwise raw metal sheets show a mostly diffuse reflection without sufficient specular reflection, the final car body panels have a high specular reflectance due to the lacquering. In consequence, it would be advantageous to apply the same inspection approach both for the raw material and for the final product. To solve this challenge, specular reflection from rough surfaces can be achieved using light with a larger wavelength, as the specular reflectivity of a surface depends on the ratio of the surface roughness and the wavelength of the light applied. Wavelengths in the thermal infrared range create enough specular reflection to apply deflectometry on many visually rough metal surfaces. This contribution presents the principles of thermal deflectometry, its special challenges, and illustrates its use with examples from the inspection of industrially produced surfaces.

Vacuum-based surface modification of organic and metallic substrates

NASA Astrophysics Data System (ADS)

Torres, Jessica

Surface physico-chemical properties play an important role in the development and performance of materials in different applications. Consequently, understanding the chemical and physical processes involved during surface modification strategies is of great scientific and technological importance. This dissertation presents results from the surface modification of polymers, organic films and metallic substrates with reactive species, with the intent of simulating important modification processes and elucidating surface property changes of materials under different environments. The reactions of thermally evaporated copper and titanium with halogenated polytetrafluoroethylene (PTFE) and polyvinyl chloride (PVC) are used to contrast the interaction of metals with polymers. Results indicate that reactive metallization is thermodynamically favored when the metal-halogen bond strength is greater than the carbon-halogen bond strength. X-ray post-metallization treatment results in an increase in metal-halide bond formation due to the production of volatile halogen species in the polymer that react with the metallic overlayer. The reactions of atomic oxygen (AO) and atomic chlorine with polyethylene (PE) and self-assembled monolayers (SAMs) films were followed to ascertain the role of radical species during plasma-induced polymer surface modification. The reactions of AO with X-ray modified SAMs are initially the dominated by the incorporation of new oxygen containing functionality at the vacuum/film interface, leading to the production of volatile carbon containing species such as CO2 that erodes the hydrocarbon film. The reaction of atomic chlorine species with hydrocarbon SAMs, reveals that chlorination introduces C-Cl and C-Cl2 functionalities without erosion. A comparison of the reactions of AO and atomic chlorine with PE reveal a maximum incorporation of the corresponding C-O and C-Cl functionalities at the polymer surface. A novel method to prepare phosphorous-containing polymer surfaces through ion implantation of trimethyl phosphine onto PE is presented. Air exposure of the resulting P-implanted PE leads to the surface selective oxidation of phosphorous moieties. P-containing hydrocarbon films are used to model the surface chemical changes of P-containing polymers exposed to AO. Results indicate that oxidized phosphorous species protect the film from AO-induced erosion. The low temperature (<150 K) oxidation of nitrided iron surfaces exposed to oxygen reveal the formation of iron oxynitride (FexNyO z, nitrosonium ions (NO+) as well as nitrite/nitrito and nitrate type species. The production of nitrite/nitrito and nitrate species is taken as evidence for the existence of oxygen insertion chemistry into the iron nitride lattice under these low temperature oxidation conditions. Upon annealing the oxidized iron nitride surface, nitrogen desorbs exclusively as nitric oxide (NO).

Biocorrosion of mild steel and copper used in cooling tower water and its control.

PubMed

Li, Xiao Lei; Narenkumar, Jayaraman; Rajasekar, Aruliah; Ting, Yen-Peng

2018-03-01

The present study describes the biocorrosion of mild steel (MS1010) and pure copper (Cu) in cooling water environments (both field and lab study). Electrochemical and surface analyses of both metals were carried out to confirm the corrosion susceptibility in the presence of bacteria and inhibitor. Surface analysis of the MS and Cu coupons revealed that biofilm was developed with increasing exposure time in the field study. In the lab study, accumulation of extracellular polymeric substance over the metal surface was noticed and led to the severe pitting type of corrosion on both metal surfaces. Besides, the anti-corrosive study was carried out using the combinations of commercial corrosion inhibitor (S7653-10 ppm) with biocide (F5100-5 ppm), and the results reveal that the corrosion rate of MS and Cu was highly reduced to 0.0281 and 0.0021 mm/year (inhibitor system) than 0.1589 and 0.0177 mm/year (control system). Inhibition efficiency for both metals in the presence of inhibitor with biocide was found as 82 and 88% for MS and Cu, respectively. The present study concluded that MS was very susceptible to biocorrosion, compared to copper metal in cooling water environment. Further, the combination of the both inhibitor and biocide was effectively inhibiting the biocorrosion which was due to its antibacterial and anti-corrosive properties.

The Development and Study of Surface Bound Ruthenium Organometallic Complexes

NASA Astrophysics Data System (ADS)

Abbott, Geoffrey Reuben

The focus of this project has been on the use of mono-diimine ruthenium organometallic complexes, of the general structure [H(Ru)(CO)(L)2(L') 2][PF6] (L=PPh3, DPPENE and L'=Bpy, DcBpy, MBpyC, Phen, AminoPhen) bound to surfaces as luminescent probes. Both biological and inorganic/organic hybrid surfaces have been studied. The complexes were characterized both bound and unbound using standard analytical techniques such as NMR, IR and X-ray crystallography, as well as through several photophysical methods as well. Initially the study focused on how the photophyscial properties of the complexes were affected by incorporation into biological membranes. It was found that by conjugating the probes to a more rigid cholesterol moiety that luminescence was conserved, compared to conjugation with a far more flexible lipid moiety, where luminescence was either lost or reduced. Both the cholesterol and lipid conjugates were able to insert into a lipid membrane, and in the more rigid environment some of the lipid conjugates regained some of their luminescence, but often blue shifted and reduced, depending on the conjugation site. Silica Polyamine Composites (SPCs) were a hybrid material developed in the Rosenberg Lab as useful metal separation materials, that could be easily modified, and had several benefits over current commercially available polymers, or inorganic materials. These SPCs also provided an opportunity for the development of a heterogeneous platform for luminescent complexes as either catalysts or sensors. Upon binding of the luminescent Ru complexes to the surface no loss, or major change in luminescence was seen, however, when bound to the rigid surface a significant increase in excited state lifetime was measured. It is likely that through binding and interacting with the surface that the complexes lost non-radiative decay pathways, resulting in the increase in lifetime, however, these interactions do not seem to affect the energy level of the MLCT band in a large way. With a better understanding of the effects of surface binding on the complexes, the study turned to possible applications, as either sensors or catalysts. Recently the bound complexes have been found to be very useful as toxic metal sensors, as the free amines left on the surface could bind toxic metal ions in close proximity leading to either a quenching or enhancement of the luminescence of the complexes, depending on the metal ion. This process was determined to be a static process, requiring the toxic metal to remain bound to the surface in order to affect the luminescence of the Ru complex. The quenching is thought to be due to a metal-centered electron-transfer reaction, in which the excited-state electron is transferred from the Ru to the toxic metal, but relaxes back to the Ru center. The enhancement of luminescence is due to the external heavy-atom effect, in which heavier atoms mixes MLCT singlet state with the triplet state through spin-orbit coupling.

Fluid mechanics of additive manufacturing of metal objects by accretion of droplets - a survey

NASA Astrophysics Data System (ADS)

Tesař, Václav

2016-03-01

Paper presents a survey of principles of additive manufacturing of metal objects by accretion of molten metal droplets, focusing on fluid-mechanical problems that deserve being investigated. The main problem is slowness of manufacturing due to necessarily small size of added droplets. Increase of droplet repetition rate calls for basic research of the phenomena that take place inside and around the droplets: ballistics of their flight, internal flowfield with heat and mass transfer, oscillation of surfaces, and the ways to elimination of satellite droplets.

Backscatter from metal surfaces in diagnostic radiology

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

Kodera, Y.; Schmidt, R.A.; Chan, H.P.

Backscatter from four commonly used metals (aluminum, lead, copper, and iron) was measured under diagnostic imaging conditions, using screen-film systems as detectors. The results indicate that for an 80-kV filtered beam and Par Speed/XRP system, backscatter increases as aluminum (Al) thickness increases until it reaches a plateau of approximately 12% at 50 mm Al. The amount of backscatter depends strongly on the screen used, possibly due to their attenuation and energy response. Backscatter from aluminum was significantly greater than that from the other metals tested.

Surface enhanced Raman scattering substrates prepared by thermal evaporation on liquid surfaces.

PubMed

Ye, Ziran; Sun, Guofang; Sui, Chenghua; Yan, Bo; Gao, Fan; Cai, Pinggen; Lv, Bin; Li, Yun; Chen, Naibo; Xu, Fengyun; Wang, Ke; Ye, Gaoxiang; Yang, Shikuan

2018-06-25

We present an effective surface-enhancement Raman scattering(SERS) substrate enabled by depositing metallic film on a liquid surface at room temperature. Thermal evaporation is used to deposit Au atoms on silicone oil surface and then form quasi-continuous films. Due to the isotropic characteristics of the liquid surface, this film consists of substantial nanoparticles with uniform diameter, which is different from films fabricated on solid substrates and can be served as an applicable substrate for SERS detection. With the assistance of this substrate, SERS signals of Rhodamine 6G(R6G) were significantly enhanced, the dependence between SERS spectra and film thickness was investigated. Analytical simulation results confirm the experimental observations and the superiorities of our proposed method for preparation of SERS substrate. This work provides a potential application of metallic film deposition on free-sustained surface and holds promise as an efficient sensor in rapid trace detection of small molecule analytes. © 2018 IOP Publishing Ltd.

Red mud (RM)-Induced enhancement of iron plaque formation reduces arsenic and metal accumulation in two wetland plant species.

PubMed

Yang, J X; Guo, Q J; Yang, J; Zhou, X Y; Ren, H Y; Zhang, H Z; Xu, R X; Wang, X D; Peters, M; Zhu, G X; Wei, R F; Tian, L Y; Han, X K

2016-01-01

Human activities have resulted in arsenic (As) and heavy metals accumulation in paddy soils in China. Phytoremediation has been suggested as an effective and low-cost method to clean up contaminated soils. A combined soil-sand pot experiment was conducted to investigate the influence of red mud (RM) supply on iron plaque formation and As and heavy metal accumulation in two wetland plant species (Cyperus alternifolius Rottb., Echinodorus amazonicus Rataj), using As and heavy metals polluted paddy soil combined with three rates of RM application (0, 2%, 5%). The results showed that RM supply significantly decreased As and heavy metals accumulation in shoots of the two plants due to the decrease of As and heavy metal availability and the enhancement of the formation of iron plaque on the root surface and in the rhizosphere. Both wetland plants supplied with RM tended to have more Fe plaque, higher As and heavy metals on roots and in their rhizospheres, and were more tolerant of As and heavy metal toxicity. The results suggest that RM-induced enhancement of the formation of iron plaque on the root surface and in the rhizosphere of wetland plants may be significant for remediation of soils contaminated with As and heavy metals.

Informal e-waste recycling: environmental risk assessment of heavy metal contamination in Mandoli industrial area, Delhi, India.

PubMed

Pradhan, Jatindra Kumar; Kumar, Sudhir

2014-01-01

Nowadays, e-waste is a major source of environmental problems and opportunities due to presence of hazardous elements and precious metals. This study was aimed to evaluate the pollution risk of heavy metal contamination by informal recycling of e-waste. Environmental risk assessment was determined using multivariate statistical analysis, index of geoaccumulation, enrichment factor, contamination factor, degree of contamination and pollution load index by analysing heavy metals in surface soils, plants and groundwater samples collected from and around informal recycling workshops in Mandoli industrial area, Delhi, India. Concentrations of heavy metals like As (17.08 mg/kg), Cd (1.29 mg/kg), Cu (115.50 mg/kg), Pb (2,645.31 mg/kg), Se (12.67 mg/kg) and Zn (776.84 mg/kg) were higher in surface soils of e-waste recycling areas compared to those in reference site. Level exceeded the values suggested by the US Environmental Protection Agency (EPA). High accumulations of heavy metals were also observed in the native plant samples (Cynodon dactylon) of e-waste recycling areas. The groundwater samples collected form recycling area had high heavy metal concentrations as compared to permissible limit of Indian Standards and maximum allowable limit of WHO guidelines for drinking water. Multivariate analysis and risk assessment studies based on total metal content explains the clear-cut differences among sampling sites and a strong evidence of heavy metal pollution because of informal recycling of e-waste. This study put forward that prolonged informal recycling of e-waste may accumulate high concentration of heavy metals in surface soils, plants and groundwater, which will be a matter of concern for both environmental and occupational hazards. This warrants an immediate need of remedial measures to reduce the heavy metal contamination of e-waste recycling sites.

Impinging jet separators for liquid metal magnetohydrodynamic power cycles

NASA Technical Reports Server (NTRS)

Bogdanoff, D. W.

1973-01-01

In many liquid metal MHD power, cycles, it is necessary to separate the phases of a high-speed liquid-gas flow. The usual method is to impinge the jet at a glancing angle against a solid surface. These surface separators achieve good separation of the two phases at a cost of a large velocity loss due to friction at the separator surface. This report deals with attempts to greatly reduce the friction loss by impinging two jets against each other. In the crude impinging jet separators tested to date, friction losses were greatly reduced, but the separation of the two phases was found to be much poorer than that achievable with surface separators. Analyses are presented which show many lines of attack (mainly changes in separator geometry) which should yield much better separation for impinging jet separators).

Adsorption of heavy metals by road deposited solids.

PubMed

Gunawardana, Chandima; Goonetilleke, Ashantha; Egodawatta, Prasanna

2013-01-01

The research study discussed in the paper investigated the adsorption/desorption behaviour of heavy metals commonly deposited on urban road surfaces, namely, Zn, Cu, Cr and Pb, for different particle size ranges of solids. The study outcomes, based on field studies and batch experiments, confirmed that road deposited solids particles contain a significantly high amount of vacant charge sites with the potential to adsorb additional heavy metals. Kinetic studies and adsorption experiments indicated that Cr is the most preferred metal element to associate with solids due to the relatively high electronegativity and high charge density of trivalent cation (Cr(3+)). However, the relatively low availability of Cr in the urban road environment could influence this behaviour. Comparing total adsorbed metals present in solids particles, it was found that Zn has the highest capacity for adsorption to solids. Desorption experiments confirmed that a low concentration of Cu, Cr and Pb in solids was present in water-soluble and exchangeable form, whilst a significant fraction of adsorbed Zn has a high likelihood of being released back into solution. Among heavy metals, Zn is considered to be the most commonly available metal among road surface pollutants.

Molecular dynamics modeling of periodic nanostructuring of metals with a short UV laser pulse under spatial confinement by a water layer

NASA Astrophysics Data System (ADS)

Ivanov, D. S.; Blumenstein, A.; Ihlemann, J.; Simon, P.; Garcia, M. E.; Rethfeld, B.

2017-12-01

The possibility of material surfaces restructuring on the nanoscale due to ultrashort laser pulses has recently found a number of practical applications. It was found experimentally that under spatial confinement due to a liquid layer atop the surface, one can achieve even finer and cleaner structures as compared to that in air or in vacuum. The mechanism of the materials restructuring under the liquid confinement, however, is not clear and its experimental study is limited by the extreme conditions realized during the intense and localized laser energy deposition that takes place on nanometer spatial and picosecond time-scales. In this theoretical work, we suggest a molecular dynamics-based approach that is capable of simulating the processes of periodic nanostructuring with ultrashort UV laser pulse on metals. The theoretical results of the simulations are directly compared with the experimental data on the same spatial and temporal scales.

The Impact of Diffuse Ionized Gas on Emission-line Ratios and Gas Metallicity Measurements

NASA Astrophysics Data System (ADS)

Zhang, Kai; Yan, Renbin; MaNGA Team

2016-01-01

Diffuse Ionized Gas (DIG) is prevalent in star-forming galaxies. Using a sample of galaxies observed by MaNGA, we demonstrate how DIG in star-forming galaxies impact the measurements of emission line ratios, hence the gas-phase metallicity measurements and the interpretation of diagnostic diagrams. We demonstrate that emission line surface brightness (SB) is a reasonably good proxy to separate HII regions from regions dominated by diffuse ionized gas. For spatially-adjacent regions or regions at the same radius, many line ratios change systematically with emission line surface brightness, reflecting a gradual increase of dominance by DIG towards low SB. DIG could significantly bias the measurement of gas metallicity and metallicity gradient. Because DIG tend to have a higher temperature than HII regions, at fixed metallicity DIG displays lower [NII]/[OII] ratios. DIG also show lower [OIII]/[OII] ratios than HII regions, due to extended partially-ionized regions that enhance all low-ionization lines ([NII], [SII], [OII], [OI]). The contamination by DIG is responsible for a substantial portion of the scatter in metallicity measurements. At different surface brightness, line ratios and line ratio gradients can differ systematically. As DIG fraction could change with radius, it can affect the metallicity gradient measurements in systematic ways. The three commonly used strong-line metallicity indicators, R23, [NII]/[OII], O3N2, are all affected in different ways. To make robust metallicity gradient measurements, one has to properly isolate HII regions and correct for DIG contamination. In line ratio diagnostic diagrams, contamination by DIG moves HII regions towards composite or LINER-like regions.

Comments on stellar boundary cooling and the reality of supermetallicity

NASA Technical Reports Server (NTRS)

Deming, D.

1980-01-01

The paper discusses the 'super-metal-rich' (SMR) stars and reexamines Peterson's analysis of the SMR prototype mu Leo (1978) with regard to a postulated error in continuum error. Model atmospheres are used to compute theoretical equivalent widths and to explore the sensitivity of these widths to metallicity, temperature, surface gravity, and microturbulence. It is shown that Peterson's results are sensitive to continuum placement, and that her data does not indicate that the temperature gradient is steeper in mu Leo than in normal giants. It is concluded that the SMR stars are very metal rich and are also somewhat boundary cooled, possibly due to high metallicity.

Backscatter from metal surfaces in diagnostic radiology.

PubMed

Kodera, Y; Schmidt, R A; Chan, H P; Doi, K

1984-01-01

Backscatter from four commonly used metals (aluminum, lead, copper, and iron) was measured under diagnostic imaging conditions, using screen-film systems as detectors. The results indicate that for an 80-kV filtered beam and Par Speed/XRP system, backscatter increases as aluminum (Al) thickness increases until it reaches a plateau of approximately 12% at 50 mm Al. The amount of backscatter from any of these four metals increases as the tube voltage is raised from 60 to 115 kV. Measured backscatter depends strongly on the screens used, possibly due to their attenuation and energy response. Backscatter from aluminum was significantly greater than that from the other metals tested.

Metal-on-metal surface replacement: a triumph of hope over reason: opposes.

PubMed

Su, Edwin P; Su, Sherwin L

2011-09-09

Hip resurfacing has been performed for over a decade but still raises controversy as an alternative to traditional total hip arthroplasty (THA). Concerns exist about the potential complications of hip resurfacing, including femoral neck fracture and osteonecrosis of the femoral head. Recently, attention has been given to the metal-on-metal bearing of hip resurfacing with regard to production of metal ions, possible tissue necrosis, and rare instances of metal hypersensitivity. Given the success of the gold-standard THA, it is understandable why some surgeons believe metal-on-metal surface replacement to be "a triumph of hope over reason." However, this article opposes that viewpoint, demonstrating that data exist to justify the practice of preserving bone in younger patients. Hip resurfacing can maintain femoral bone without the expense of removing additional acetabular bone by using modern implants with incremental sizing. Furthermore, many of the problems cited with the bearing couple (such as excess metal production) have been due to poor implant designs, which have now been removed from the market. Finally, we now realize that the metal-on-metal articulation is more sensitive to malposition; thus, good surgical technique and experience can solve many of the problems that have been cited in the past. National registry results confirm that in a select population, hip resurfacing performs comparably to THA, while fulfilling the goal of bone preservation. Copyright 2011, SLACK Incorporated.

Disinfection of Escherichia coli Gram negative bacteria using surface modified TiO2: optimization of Ag metallization and depiction of charge transfer mechanism.

PubMed

Gomathi Devi, LakshmipathiNaik; Nagaraj, Basavalingaiah

2014-01-01

The antibacterial activity of silver deposited TiO2 (Ag-TiO2 ) against Gram negative Escherichia coli bacteria was investigated by varying the Ag metal content from 0.10 to 0.50% on the surface of TiO2 . Ag depositions by the photoreduction method were found to be stable. Surface silver metallization was confirmed by EDAX and XPS studies. Photoluminescence studies show that the charge carrier recombination is less for 0.1% Ag-TiO2 and this catalyst shows superior bactericidal activity under solar light irradiation compared to Sol gel TiO2 (SG-TiO2 ) due to the surface plasmon effect. The energy levels of deposited Ag are dependent on the Ag content and it varies from -4.64 eV to -1.30 eV with respect to the vacuum energy level based on atomic silver to bulk silver deposits. The ability of electron transfer from Ag deposit to O2 depends on the position of the energy levels. The 0.25% and 0.50% Ag depositions showed detrimental effect on bactericidal activity due to the mismatch of energy levels. The effect of the EROS (External generation of the Reactive Oxygen Species by 0.1% Ag-TiO2 ) and IROS (Interior generation of Reactive Oxygen Species within the bacteria) on the bactericidal inactivation is discussed in detail. © 2014 The American Society of Photobiology.

Mixing of multiple metal vapours into an arc plasma in gas tungsten arc welding of stainless steel

NASA Astrophysics Data System (ADS)

Park, Hunkwan; Trautmann, Marcus; Tanaka, Keigo; Tanaka, Manabu; Murphy, Anthony B.

2017-11-01

A computational model of the mixing of multiple metal vapours, formed by vaporization of the surface of an alloy workpiece, into the thermal arc plasma in gas tungsten arc welding (GTAW) is presented. The model incorporates the combined diffusion coefficient method extended to allow treatment of three gases, and is applied to treat the transport of both chromium and iron vapour in the helium arc plasma. In contrast to previous models of GTAW, which predict that metal vapours are swept away to the edge of the arc by the plasma flow, it is found that the metal vapours penetrate strongly into the arc plasma, reaching the cathode region. The predicted results are consistent with published measurements of the intensity of atomic line radiation from the metal vapours. The concentration of chromium vapour is predicted to be higher than that of iron vapour due to its larger vaporization rate. An accumulation of chromium vapour is predicted to occur on the cathode at about 1.5 mm from the cathode tip, in agreement with published measurements. The arc temperature is predicted to be strongly reduced due to the strong radiative emission from the metal vapours. The driving forces causing the diffusion of metal vapours into the helium arc are examined, and it is found that diffusion due to the applied electric field (cataphoresis) is dominant. This is explained in terms of large ionization energies and the small mass of helium compared to those of the metal vapours.

Nanostructured GaAs solar cells via metal-assisted chemical etching of emitter layers.

PubMed

Song, Yunwon; Choi, Keorock; Jun, Dong-Hwan; Oh, Jungwoo

2017-10-02

GaAs solar cells with nanostructured emitter layers were fabricated via metal-assisted chemical etching. Au nanoparticles produced via thermal treatment of Au thin films were used as etch catalysts to texture an emitter surface with nanohole structures. Epi-wafers with emitter layers 0.5, 1.0, and 1.5 um in thickness were directly textured and a window layer removal process was performed before metal catalyst deposition. A nanohole-textured emitter layer provides effective light trapping capabilities, reducing the surface reflection of a textured solar cell by 11.0%. However, because the nanostructures have high surface area to volume ratios and large numbers of defects, various photovoltaic properties were diminished by high recombination losses. Thus, we have studied the application of nanohole structures to GaAs emitter solar cells and investigated the cells' antireflection and photovoltaic properties as a function of the nanohole structure and emitter thickness. Due to decreased surface reflection and improved shunt resistance, the solar cell efficiency increased from 4.25% for non-textured solar cells to 7.15% for solar cells textured for 5 min.

Field enhancement in plasmonic nanostructures

NASA Astrophysics Data System (ADS)

Piltan, Shiva; Sievenpiper, Dan

2018-05-01

Efficient generation of charge carriers from a metallic surface is a critical challenge in a wide variety of applications including vacuum microelectronics and photo-electrochemical devices. Replacing semiconductors with vacuum/gas as the medium of electron transport offers superior speed, power, and robustness to radiation and temperature. We propose a metallic resonant surface combining optical and electrical excitations of electrons and significantly reducing powers required using plasmon-induced enhancement of confined electric field. The properties of the device are modeled using the exact solution of the time-dependent Schrödinger equation at the barrier. Measurement results exhibit strong agreement with an analytical solution, and allow us to extract the field enhancement factor at the surface. Significant photocurrents are observed using combination of {{W}} {{{c}}{{m}}}-2 optical power and 10 V DC excitation on the surface. The model suggests optical field enhancement of 3 orders of magnitude at the metal interface due to plasmonic resonance. This simple planar structure provides valuable evidence on the electron emission mechanisms involved and it can be used for implementation of semiconductor compatible vacuum devices.

Modifying the catalytic and adsorption properties of metals and oxides

NASA Astrophysics Data System (ADS)

Yagodovskii, V. D.

2015-11-01

A new approach to interpreting the effect of promoters (inhibitors) of nonmetals and metals added to a host metal (catalyst) is considered. Theoretical calculations are based on a model of an actual two-dimensional electron gas and adsorbate particles. An equation is derived for the isotherm of induced adsorption on metals and semiconductors with respect to small fillings of θ ~ 0.1-0.15. The applicability of this equation is verified experimentally for metals (Ag, Pd, Cu, Fe, and Ni), graphitized ash, and semiconductor oxides Ta2O5, ZnO, and Ni. The applicability of the theoretical model of promotion is verified by the hydrogenation reaction of CO on ultradispersed nickel powder. The use of plasmachemical surface treatments of metals and oxides, accompanied by an increase in activity and variation in selectivity, are investigated based on the dehydrocyclization reactions of n-hexane and the dehydrogenation and dehydration of alcohols. It is established that such treatments for metals (Pt, Cu, Ni, and Co) raise their activity due to the growth of the number of active centers upon an increase in the activation energy. Applying XPES and XRD methods to metallic catalysts, it is shown that the rise in activity is associated with a change in their surface states (variation in the structural characteristics of metal particles and localization of certain forms of carbon in catalytically active centers). It is shown that plasmachemical treatments also alter their surface composition, surface activity, and raise their activity when used with complex phosphate oxides of the NASICON type. It is shown by the example of conversion of butanol-2 that abrupt variations in selectivity (prevalence of dehydration over dehydrogenation and vice versa) occur, depending on the type of plasma. It is concluded that plasmachemical treatments of metals and ZnO and NiO alter the isosteric heats and entropies of adsorption of isopropanol.

Correlation between the Knight shift of chemisorbed CO and the Fermi level local density of states at clean platinum catalyst surfaces

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

Tong, Y.Y.; Rice, C.; Godbout, N.

1999-04-07

Due to its fundamental importance in heterogeneous catalysis, as well as in electrocatalysis, the chemisorption and reaction of CO on transition metal surfaces has been an important focus of modern surface science. Here, the NMR spectroscopy of {sup 13}CO adsorbed onto transition metal surfaces has been shown to be a very powerful probe of molecular structure and dynamics of CO itself, as well as a probe of the electronic properties of the transition metal surfaces onto which it is adsorbed. The authors have investigated the {sup 195}Pt and {sup 13}C nuclear magnetic resonance (NMR) spectroscopy of clean-surface platinum catalysts andmore » of CO chemisorbed onto Pt catalysts surfaces. They use Knight shift, relaxation, and J-coupling data to deduce information about the Fermi level local density of states (E{sub f}-LDOS) at catalyst surfaces. There is a linear correlation between the Knight shifts of chemisorbed CO and the clean surface E{sub f}-LDOS of platinum onto which the CO is bound, as determined by {sup 13}C and {sup 195}Pt NMR. The correlation amounts to {approximately} 12 ppm/Ry{sup {minus}1} {center_dot} atom{sup {minus}1}, the same as that which can be deduced for CO on palladium, as well as from the electrode potential dependence of {sup 13}C Knight shifts and infrared vibrational frequencies, {nu}{sub CO}, and the relationship between {nu}{sub CO} and the E{sub f}-LDOS at clean platinum surfaces. The ability to now directly relate meal and adsorbate electronic properties opens up new avenues for investigating metal-ligand interactions in heterogeneous catalysis and electrocatalysis.« less

Surface polyPEGylation of Eu3+ doped luminescent hydroxyapatite nanorods through the combination of ligand exchange and metal free surface initiated atom transfer radical polymerization

NASA Astrophysics Data System (ADS)

Zeng, Guangjian; Liu, Meiying; Heng, Chunning; Huang, Qiang; Mao, Liucheng; Huang, Hongye; Hui, Junfeng; Deng, Fengjie; Zhang, Xiaoyong; Wei, Yen

2017-03-01

The Eu3+ doped luminescent hydroxyapatite (HAp) nanorods with uniform size and morphology can be synthesized by hydrothermal route. However, these HAp nanorods are coated by hydrophobic oleylamine, which makes them difficult to be dispersed in aqueous solution and impede their biomedical applications. In this work, Eu3+ doped luminescent polymers functionalized HAp nanorods were prepared through the combination of ligand exchange reaction and metal free surface initiated atom transfer radical polymerization (ATRP) method. In this procedure, the amino group functionalized HAp nanorods were first prepared by ligand exchange reaction using adenosine monophosphate (AMP) as ligand. Then the Br-containing initiators (HAp-Br) were introduced onto the surface of HAp-AMP nanorods through the amidation reaction. Finally, polymers functionalized HAp nanorods were prepared by metal free ATRP method using poly(ethylene glycol) methacrylate (PEGMA) as monomer and 10-phenylphenothiazine (PTH) as organic photocatalyst. The properties of these obtained HAp nanocomposites (HAP-polyPEGMA nanorods) were characterized by means of transmission electron microscopy, Fourier transformed infrared spectroscopy, X-ray photoelectron spectroscopy and thermogravimetric analysis in detail. The cell imaging of these HAP-polyPEGMA nanorods was examined using laser scanning confocal microscope to evaluate their biomedical applications. We demonstrated for the first time that hydrophobic luminescent HAp nanorods can be functionalized with polyPEGMA through the combination of ligand exchange reaction and metal free surface initiated ATRP. As compared with the traditional ATRP, the metal free ATRP can overcome the toxic and fluorescence quenching effects of metal catalysts such as copper ions. More importantly, the strategy described in this work should also be utilized for fabrications of many other luminescent polymer nanocomposites due to its good monomer adoptability.

Machining of Molybdenum by EDM-EP and EDC Processes

NASA Astrophysics Data System (ADS)

Wu, K. L.; Chen, H. J.; Lee, H. M.; Lo, J. S.

2017-12-01

Molybdenum metal (Mo) can be machined with conventional tools and equipment, however, its refractory propertytends to chip when being machined. In this study, the nonconventional processes of electrical discharge machining (EDM) and electro-polishing (EP) have been conducted to investigate the machining of Mo metal and fabrication of Mo grid. Satisfactory surface quality was obtained using appropriate EDM parameters of Ip ≦ 3A and Ton < 80μs at a constant pulse interval of 100μs. The finished Mometal has accomplished by selecting appropriate EP parameters such as electrolyte flow rate of 0.42m/s under EP voltage of 50V and flush time of 20 sec to remove the recast layer and craters on the surface of Mo metal. The surface roughness of machined Mo metal can be improved from Ra of 0.93μm (Rmax = 8.51μm) to 0.23μm (Rmax = 1.48μm). Machined Mo metal surface, when used as grid component in electron gun, needs to be modified by coating materials with high work function, such as silicon carbide (SiC). The main purpose of this study is to explore the electrical discharge coating (EDC) process for coating the SiC layer on EDMed Mo metal. Experimental results proved that the appropriate parameters of Ip = 5A and Ton = 50μs at Toff = 10μs can obtain the deposit with about 60μm thickness. The major phase of deposit on machined Mo surface was SiC ceramic, while the minor phases included MoSi2 and/or SiO2 with the presence of free Si due to improper discharging parameters and the use of silicone oil as the dielectric fluid.

Precise measurement of surface plasmon forces at a metal-dielectric interface using a calibrated evanescent wave

NASA Astrophysics Data System (ADS)

Liu, Lulu; Woolf, Alex

2015-03-01

By observing the motion of an optically trapped microscopic colloid, sub-piconewton static and dynamical forces have been measured using a technique called photonic force microscopy. This technique, though potentially powerful, has in the past struggled to make precise measurements in the vicinity of a reflective or metallic interface, due to distortions of the optical field. We introduce a new in-situ, contact-free calibration method for particle tracking using an evanescent wave, and demonstrate its expanded capability by the precise measurement of forces of interaction between a single colloid and the optical field generated by a propagating surface plasmon polariton on gold.

Electrical Detection of Charge-Current-Induced Spin Polarization Due to Spin-Momentum Locking in Bi2Se3

DTIC Science & Technology

2014-01-01

Robinson2, Y. Liu3, L. Li3 and B. T. Jonker1* Topological insulators exhibit metallic surface states populated by massless Dirac fermions with spin...classic dichotomy of metals and semi- conductors1–4. Whereas the bulk states form a bandgap, the surface states form a Dirac cone similar to graphene (Fig...magnetoelectric coupling12. Examples of TI materials include Bi1–xSbx (ref. 4), Bi2Se3, Bi2Te3 and Sb2Te3 (refs 13–15). One of the most striking properties is spin

Biosorption of precious metals.

PubMed

Mack, C; Wilhelmi, B; Duncan, J R; Burgess, J E

2007-01-01

Biosorption has emerged as a low-cost and often low-tech option for removal or recovery of base metals from aqueous wastes. The conditions under which precious metals such as gold, platinum and palladium are sorbed by biomass are often very different to those under which base metals are sorbed. This, coupled with the increasingly high demand for precious metals, drives the increase in research into efficient recovery of precious metal ions from all waste material, especially refining wastewaters. Common biosorbents for precious metal ions include various derivatives of chitosan, as well as other compounds with relatively high surface amine functional group content. This is generally due to the ability of the positively charged amine groups to attract anionic precious metal ions at low pH. Recent research regarding the biosorption of some precious metals is reviewed here, with emphasis on the effects of the biosorption environment and the biosorption mechanisms identified.

Antimicrobial Activity of Nitric Oxide-Releasing Ti-6Al-4V Metal Oxide

PubMed Central

Reger, Nina A.; Meng, Wilson S.; Gawalt, Ellen S.

2017-01-01

Titanium and titanium alloy materials are commonly used in joint replacements, due to the high strength of the materials. Pathogenic microorganisms can easily adhere to the surface of the metal implant, leading to an increased potential for implant failure. The surface of a titanium-aluminum-vanadium (Ti-6Al-4V) metal oxide implant material was functionalized to deliver an small antibacterial molecule, nitric oxide. S-nitroso-penicillamine, a S-nitrosothiol nitric oxide donor, was covalently immobilized on the metal oxide surface using self-assembled monolayers. Infrared spectroscopy was used to confirm the attachment of the S-nitrosothiol donor to the Ti-Al-4V surface. Attachment of S-nitroso-penicillamine resulted in a nitric oxide (NO) release of 89.6 ± 4.8 nmol/cm2 under physiological conditions. This low concentration of nitric oxide reduced Escherichia coli and Staphylococcus epidermidis growth by 41.5 ± 1.2% and 25.3 ± 0.6%, respectively. Combining the S-nitrosothiol releasing Ti-6Al-4V with tetracycline, a commonly-prescribed antibiotic, increased the effectiveness of the antibiotic by 35.4 ± 1.3%, which allows for lower doses of antibiotics to be used. A synergistic effect of ampicillin with S-nitroso-penicillamine-modified Ti-6Al-4V against S. epidermidis was not observed. The functionalized Ti-6Al-4V surface was not cytotoxic to mouse fibroblasts. PMID:28635681

Ultrafine and Smooth Full Metal Nanostructures for Plasmonics

NASA Astrophysics Data System (ADS)

Zhu, Xinli; Zhang, Jaseng; Xu, Jun; Liao, Zhimin; Wu, Xiaosong; Yu, Dapeng

2013-03-01

Surface plasmon polaritons (SPPs), which are coupled excitations of electrons bound to a metal-dielectric interface, show great potential for application in future nanoscale photonic systems due to the strong field confinement at the nanoscale, intensive local field enhancement, and interplay between strongly localized and propagating SPPs. The fabrication of sufficiently smooth metal surface with nanoscale feature size is crucial for SPPs to have practical applications. A template stripping (ST) method combined with PMMA as a template was successfully developed to create extraordinarily smooth metal nanostructures with a desirable feature size and morphology for plasmonics and metamaterials. The advantages of this method, including the high resolution, precipitous top-to bottom profile with a high aspect ratio, and three-dimensional characteristics, make it very suitable for the fabrication of plasmonic structures. By using this ST method, boxing ring-shaped nanocavities have been fabricated and the confined modes of surface plasmon polaritons in these nanocavities have been investigated and imaged by using cathodoluminescence spectroscopy. The mode of the out-of-plane field components of surface plasmon polaritons dominates the experimental mode patterns, indicating that the electron beam locally excites the out-of-plane field component of surface plasmon polaritons, and quality factors can be directly acquired. Numerous applications, such as plasmonic filter, nanolaser, and efficient light-emitting devices, can be expected to arise from these developments.

Metal-Organic Framework-Derived Materials for Sodium Energy Storage.

PubMed

Zou, Guoqiang; Hou, Hongshuai; Ge, Peng; Huang, Zhaodong; Zhao, Ganggang; Yin, Dulin; Ji, Xiaobo

2018-01-01

Recently, sodium-ion batteries (SIBs) are extensively explored and are regarded as one of the most promising alternatives to lithium-ion batteries for electrochemical energy conversion and storage, owing to the abundant raw material resources, low cost, and similar electrochemical behavior of elemental sodium compared to lithium. Metal-organic frameworks (MOFs) have attracted enormous attention due to their high surface areas, tunable structures, and diverse applications in drug delivery, gas storage, and catalysis. Recently, there has been an escalating interest in exploiting MOF-derived materials as anodes for sodium energy storage due to their fast mass transport resulting from their highly porous structures and relatively simple preparation methods originating from in situ thermal treatment processes. In this Review, the recent progress of the sodium-ion storage performances of MOF-derived materials, including MOF-derived porous carbons, metal oxides, metal oxide/carbon nanocomposites, and other materials (e.g., metal phosphides, metal sulfides, and metal selenides), as SIB anodes is systematically and completely presented and discussed. Moreover, the current challenges and perspectives of MOF-derived materials in electrochemical energy storage are discussed. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Oscillatory vapour shielding of liquid metal walls in nuclear fusion devices.

PubMed

van Eden, G G; Kvon, V; van de Sanden, M C M; Morgan, T W

2017-08-04

Providing an efficacious plasma facing surface between the extreme plasma heat exhaust and the structural materials of nuclear fusion devices is a major challenge on the road to electricity production by fusion power plants. The performance of solid plasma facing surfaces may become critically reduced over time due to progressing damage accumulation. Liquid metals, however, are now gaining interest in solving the challenge of extreme heat flux hitting the reactor walls. A key advantage of liquid metals is the use of vapour shielding to reduce the plasma exhaust. Here we demonstrate that this phenomenon is oscillatory by nature. The dynamics of a Sn vapour cloud are investigated by exposing liquid Sn targets to H and He plasmas at heat fluxes greater than 5 MW m -2 . The observations indicate the presence of a dynamic equilibrium between the plasma and liquid target ruled by recombinatory processes in the plasma, leading to an approximately stable surface temperature.Vapour shielding is one of the interesting mechanisms for reducing the heat load to plasma facing components in fusion reactors. Here the authors report on the observation of a dynamic equilibrium between the plasma and the divertor liquid Sn surface leading to an overall stable surface temperature.

Deuterium supersaturation in low-energy plasma-loaded tungsten surfaces

NASA Astrophysics Data System (ADS)

Gao, L.; Jacob, W.; von Toussaint, U.; Manhard, A.; Balden, M.; Schmid, K.; Schwarz-Selinger, T.

2017-01-01

Fundamental understanding of hydrogen-metal interactions is challenging due to a lack of knowledge on defect production and/or evolution upon hydrogen ingression, especially for metals undergoing hydrogen irradiation with ion energy below the displacement thresholds reported in literature. Here, applying a novel low-energy argon-sputter depth profiling method with significantly improved depth resolution for tungsten (W) surfaces exposed to deuterium (D) plasma at 300 K, we show the existence of a 10 nm thick D-supersaturated surface layer (DSSL) with an unexpectedly high D concentration of ~10 at.% after irradiation with ion energy of 215 eV. Electron back-scatter diffraction reveals that the W lattice within this DSSL is highly distorted, thus strongly blurring the Kikuchi pattern. We explain this strong damage by the synergistic interaction of energetic D ions and solute D atoms with the W lattice. Solute D atoms prevent the recombination of vacancies with interstitial W atoms, which are produced by collisions of energetic D ions with W lattice atoms (Frenkel pairs). This proposed damaging mechanism could also be active on other hydrogen-irradiated metal surfaces. The present work provides deep insight into hydrogen-induced lattice distortion at plasma-metal interfaces and sheds light on its modelling work.

Laser-induced Self-organizing Microstructures on Steel for Joining with Polymers

NASA Astrophysics Data System (ADS)

van der Straeten, Kira; Burkhardt, Irmela; Olowinsky, Alexander; Gillner, Arnold

The combination of different materials such as thermoplastic composites and metals is an important way to improve lightweight construction. As direct connections between these materials fail due to their physical and chemical properties, other joining techniques are required. A new joining approach besides fastening and adhesive joining is a laser-based two-step process. Within the first step the metal surface is modified by laser-microstructuring. In order to enlarge the boundary surface and create undercuts, random self-organizing microstructures are generated on stainless steel substrates. In a second process step both joining partners, metal and composite, are clamped together, the steel surface is heated up with laser radiation and through heat conduction the thermoplastic matrix is melted and flows into the structures. After cooling-down a firm joint between both materials is created. The presented work shows the influence of different laser parameters on the generation of the microstructures. The joint strength is investigated through tensile shear strength tests.

Controlling the electronic and geometric structures of 2D insertions to realize high performance metal/insertion-MoS2 sandwich interfaces.

PubMed

Su, Jie; Feng, Liping; Zeng, Wei; Liu, Zhengtang

2017-06-08

Metal/insertion-MoS 2 sandwich interfaces are designed to reduce the Schottky barriers at metal-MoS 2 interfaces. The effects of geometric and electronic structures of two-dimensional (2D) insertion materials on the contact properties of metal/insertion-MoS 2 interfaces are comparatively studied by first-principles calculations. Regardless of the geometric and electronic structures of 2D insertion materials, Fermi level pinning effects and charge scattering at the metal/insertion-MoS 2 interface are weakened due to weak interactions between the insertion and MoS 2 layers, no gap states and negligible structural deformations for MoS 2 layers. The Schottky barriers at metal/insertion-MoS 2 interfaces are induced by three interface dipoles and four potential steps that are determined by the charge transfers and structural deformations of 2D insertion materials. The lower the electron affinities of 2D insertion materials, the more are the electrons lost from the Sc surface, resulting in lower n-type Schottky barriers at Sc/insertion-MoS 2 interfaces. The larger the ionization potentials and the thinner the thicknesses of 2D insertion materials, the fewer are the electrons that accumulate at the Pt surface, leading to lower p-type Schottky barriers at Pt/insertion-MoS 2 interfaces. All Sc/insertion-MoS 2 interfaces exhibited ohmic characters. The Pt/BN-MoS 2 interface exhibits the lowest p-type Schottky barrier of 0.52 eV due to the largest ionization potential (∼6.88 eV) and the thinnest thickness (single atomic layer thickness) of BN. These results in this work are beneficial to understand and design high performance metal/insertion-MoS 2 interfaces through 2D insertion materials.

Quantum impurity models for magnetic adsorbates on superconductor surfaces

NASA Astrophysics Data System (ADS)

Žitko, Rok

2018-05-01

Magnetic atoms adsorbed on surfaces have a quenched orbital moment while their ground-state spin multiplet is partially split as a consequence of the spin-orbit coupling which, even if intrinsically weak, has a large effect due to the abrupt change of the potential at the surface. Such metal adsorbates should be modelled using quantum impurity models that include the relevant internal degrees of freedom and the interaction terms, in particular the magnetic anisotropy and the Kondo exchange coupling. When adsorbed on superconducting surfaces, these impurities have complex spectra of sub-gap excitations due to magnetic anisotropy splitting and Kondo screening. Both anisotropy splitting and Zeeman splitting due to the external magnetic field are significantly renormalized by the coupling to the substrate electrons. In this work I discuss the quantum-to-classical crossover and the applicability of classical static-local-spin picture for discussing magnetic nanostructures on superconductors.

Simple fabrication of antireflective silicon subwavelength structure with self-cleaning properties.

PubMed

Kim, Bo-Soon; Ju, Won-Ki; Lee, Min-Woo; Lee, Cheon; Lee, Seung-Gol; Beom-Hoan, O

2013-05-01

A subwavelength structure (SWS) was formed via a simple chemical wet etching using a gold (Au) catalyst. Single nano-sized Au particles were fabricated by metallic self-aggregation. The deposition and thermal annealing of the thin metallic film were carried out. Thermal annealing of a thin metallic film enables the creation of metal nano particles by isolating them from each other by means of the self-aggregation of the metal. After annealing, the samples were soaked in an aqueous etching solution of hydrofluoric acid and hydrogen peroxide. When silicon (Si) was etched for 2 minutes using the Au nano particles, the reflectance was decreased almost 0% over the entire wavelength range from 300 to 1300 nm due to its deep and steeply double tapered structure. When given varying incident angle degrees from 30 degrees to 60 degrees, the reflectance was also maintained at less than 3%. Following this, the etched silicon was treated with a plasma-polymerized fluorocarbon (PPFC) film of about 5 nm using an ICP reactor for surface modification. The result of this surface treatment, the contact angle increased significantly from 27.5 degrees to 139.3 degrees. The surface modification was successful and maintained almost 0% reflectance because of the thin film deposition.

Assessment of mean-field microkinetic models for CO methanation on stepped metal surfaces using accelerated kinetic Monte Carlo

NASA Astrophysics Data System (ADS)

Andersen, Mie; Plaisance, Craig P.; Reuter, Karsten

2017-10-01

First-principles screening studies aimed at predicting the catalytic activity of transition metal (TM) catalysts have traditionally been based on mean-field (MF) microkinetic models, which neglect the effect of spatial correlations in the adsorbate layer. Here we critically assess the accuracy of such models for the specific case of CO methanation over stepped metals by comparing to spatially resolved kinetic Monte Carlo (kMC) simulations. We find that the typical low diffusion barriers offered by metal surfaces can be significantly increased at step sites, which results in persisting correlations in the adsorbate layer. As a consequence, MF models may overestimate the catalytic activity of TM catalysts by several orders of magnitude. The potential higher accuracy of kMC models comes at a higher computational cost, which can be especially challenging for surface reactions on metals due to a large disparity in the time scales of different processes. In order to overcome this issue, we implement and test a recently developed algorithm for achieving temporal acceleration of kMC simulations. While the algorithm overall performs quite well, we identify some challenging cases which may lead to a breakdown of acceleration algorithms and discuss possible directions for future algorithm development.

Band gap modulation of graphene by metal substrate: A first principles study

NASA Astrophysics Data System (ADS)

Sahoo, Mihir Ranjan; Sahu, Sivabrata; Kushwaha, Anoop Kumar; Nayak, S. K.

2018-04-01

Due to high in-plane charge carrier mobility with high electron velocity and long spin diffusion length, graphene guarantees as a completely unique material for devices with various applications. Unaffected 2pz orbitals of carbon atoms in graphene can be highly influenced by substrates and leads to tuning in electronic properties. We report here a density functional calculation of graphene monolayer based on metallic substrate like nickel surfaces. Band-gap of graphene near K points opens due to interactions between 2pz and d-orbitals of nickel atoms and the gap modulation can be done with the increasing number of layers of substrates.

Inhalation toxicity of 316L stainless steel powder in relation to bioaccessibility.

PubMed

Stockmann-Juvala, H; Hedberg, Y; Dhinsa, N K; Griffiths, D R; Brooks, P N; Zitting, A; Wallinder, I Odnevall; Santonen, T

2013-11-01

The Globally Harmonized System for Classification and Labelling of Chemicals (GHS) considers metallic alloys, such as nickel (Ni)-containing stainless steel (SS), as mixtures of substances, without considering that alloys behave differently compared to their constituent metals. This study presents an approach using metal release, explained by surface compositional data, for the prediction of inhalation toxicity of SS AISI 316L. The release of Ni into synthetic biological fluids is >1000-fold lower from the SS powder than from Ni metal, due to the chromium(III)-rich surface oxide of SS. Thus, it was hypothesized that the inhalation toxicity of SS is significantly lower than what could be predicted based on Ni metal content. A 28-day inhalation study with rats exposed to SS 316L powder (<4 µm, mass median aerodynamic diameter 2.5-3.0 µm) at concentrations up to 1.0 mg/L showed accumulation of metal particles in the lung lobes, but no signs of inflammation, although Ni metal caused lung toxicity in a similar published study at significantly lower concentrations. It was concluded that the bioaccessible (released) fraction, rather than the elemental nominal composition, predicts the toxicity of SS powder. The study provides a basis for an approach for future validation, standardization and risk assessment of metal alloys.

Growth of polymer-metal nanocomposites by pulsed laser deposition

NASA Astrophysics Data System (ADS)

Röder, Johanna; Faupel, Jörg; Krebs, Hans-Ulrich

2008-12-01

Complex polymer-metal nanocomposites have a wide range of applications, e.g. as flexible displays and packaging materials. Pulsed laser deposition was applied to form nanostructured materials consisting of metal clusters (Ag, Au, Pd and Cu) embedded in a polymer (polycarbonate, PC) matrix. The size and amount of the metal clusters are controlled by the number of laser pulses hitting the respective targets. For Cu and Pd, smaller clusters and higher cluster densities are obtained as in the cases of Ag and Au due to a stronger reactivity with the polymers and thus a lower diffusivity. Implantation effects, differences in metal diffusivity and reactivity on the polymer surfaces, and the coalescence properties are discussed with respect to the observed microstructures on PC and compared to the metal growth on poly (methyl methacrylate), PMMA.

Study of polymorphism using patterned self-assembled monolayers approach on metal substrates

NASA Astrophysics Data System (ADS)

Quiñones, Rosalynn; Brown, Ryanne T.; Searls, Noah; Richards-Waugh, Lauren

2018-01-01

Polymorphism is a molecule's ability to possess altered physical crystalline structures and has become an active interest in pharmaceuticals due to its ability to influence a drug's physical and chemical properties. Crystal stability and solubility are crucial in determining a drug's pharmacokinetics and pharmacodynamics. Changes in these properties due to polymorphisms have contributed to recalls and modifications in industrial production. For this study, the effects of surface interactions with pharmaceuticals were examined through surface modification methodology using organic phosphonic and sulfonic acid self-assembled monolayers (SAMs) developed on a nickel or zinc oxide metal substrate. Drugs analyzed included carbamazepine, cimetidine, tolfenamic acid, and flufenamic acid. All drugs were thermodynamically applied to the reformed surface to aid in recrystallization. It was hypothesized and confirmed that intermolecular bonds, especially hydrogen bonds between the SAMs and pharmaceutical drugs, were the force that assisted in polymorph development. The study was successful in revealing multiple forms for each drug, including their commercial form and at least one additional form using micro FT-IR, Raman spectroscopy, and PXRD. Visual comparisons of crystal polymorphisms were performed with IR microscopy.

Casimir forces from conductive silicon carbide surfaces

NASA Astrophysics Data System (ADS)

Sedighi, M.; Svetovoy, V. B.; Broer, W. H.; Palasantzas, G.

2014-05-01

Samples of conductive silicon carbide (SiC), which is a promising material due to its excellent properties for devices operating in severe environments, were characterized with the atomic force microscope for roughness, and the optical properties were measured with ellipsometry in a wide range of frequencies. The samples show significant far-infrared absorption due to concentration of charge carriers and a sharp surface phonon-polariton peak. The Casimir interaction of SiC with different materials is calculated and discussed. As a result of the infrared structure and beyond to low frequencies, the Casimir force for SiC-SiC and SiC-Au approaches very slowly the limit of ideal metals, while it saturates significantly below this limit if interaction with insulators takes place (SiC-SiO2). At short separations (<10 nm) analysis of the van der Waals force yielded Hamaker constants for SiC-SiC interactions lower but comparable to those of metals, which is of significance to adhesion and surface assembly processes. Finally, bifurcation analysis of microelectromechanical system actuation indicated that SiC can enhance the regime of stable equilibria against stiction.

Heavy metal accumulation during the last 30 years in the Karnaphuli River estuary, Chittagong, Bangladesh.

PubMed

Wang, Ai-Jun; Kawser, Ahmed; Xu, Yong-Hang; Ye, Xiang; Rani, Seema; Chen, Ke-Liang

2016-01-01

Heavy metal contamination of aquatic environment has attracted global attention owing to its abundance, persistence, and environmental toxicity, especially in developing countries like Bangladesh. Five heavy metals, namely chromium (Cr), copper (Cu), nickel (Ni), lead (Pb) and zinc (Zn) were investigated in surface and core sediments of the Karnaphuli River (KR) estuary in Chittagong, Bangladesh, in order to reveal the heavy metal contamination history in estuarine sediments and its response to catastrophic events and human activities. The surface sediment was predominantly composed of silt and sand, and the surface sediment was contaminated with Cr and Pb. Based on the 210 Pb chronology, the sedimentation rate in the inter-tidal zone of KR estuary was 1.02 cm/a before 2007, and 1.14 cm/a after 2008. The core sediment collected from 8 to 20 cm below the surface mainly originated from terrestrial materials induced by catastrophic events such as cyclone, heavy rainfall and landslides in 2007 and 2008. The values of contamination factor ( CF ) showed that the sediment became moderately contaminated with Cr and Pb in the last 30 years. The variation and accumulation of heavy metals in core sediment before 2000 was mainly related to natural variations in sediment sources; however, in subsequent years, the anthropogenic inputs of heavy metals have increased due to rapid physical growth of urban and industrial areas in the Chittagong city. In general, the accumulation pattern of heavy metals after normalization to Aluminum in sediments of KR estuary indicated an accelerated rate of urbanization and industrialization in the last 30 years, and also suggested the influence of natural catastrophic event on estuarine environment.

Effect of Siloxane Ring Strain and Cation Charge Density on the Formation of Coordinately Unsaturated Metal Sites on Silica: Insights from Density Functional Theory (DFT) Studies

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

Das, Ujjal; Zhang, Guanghui; Hu, Bo

2015-10-28

Amorphous silica (SiO 2) is commonly used as a support in heterogeneous catalysis. However, due to the structural disorder and temperature induced change of surface morphology, the structures of silica supported metal catalysts are difficult to determine. Most studies are primarily focused on understanding the interactions of different types of surface hydroxyl groups with metal ions. In comparison, the effect of siloxane ring size on the structure of silica supported metal catalysts and how it affects catalytic activity is poorly understood. Here, we have used density functional theory calculations to understand the effect of siloxane ring strain on structure andmore » activity of different monomeric Lewis acid metal sites on silica. In particular, we have found that large siloxane rings favor strong dative bonding interaction between metal ion and surface hydroxyls, leading to the formation of high-coordinate metal sites. In comparison, metal-silanol interaction is weak in small siloxane rings, resulting in low-coordinate metal sites. The physical origin of this size dependence is associated with siloxane ring strain, and, a correlation between metal-silanol interaction energy and ring strain energy has been observed. In addition to ring strain, the strength of the metal-silanol interaction also depends on the positive charge density of the cations. In fact, a correlation also exists between metal-silanol interaction energy and charge density of several first-row transition and post-transition metals. The theoretical results are compared with the EXAFS data of monomeric Zn(II) and Ga(III) ions grafted on silica. In conclusion, the molecular level insights of how metal ion coordination on silica depends on siloxane ring strain and cation charge density will be useful in the synthesis of new catalysts.« less

Thin metal nanostructures: synthesis, properties and applications

PubMed Central

Fan, Zhanxi; Huang, Xiao; Tan, Chaoliang

2015-01-01

Two-dimensional nanomaterials, especially graphene and single- or few-layer transition metal dichalcogenide nanosheets, have attracted great research interest in recent years due to their distinctive physical, chemical and electronic properties as well as their great potentials for a broad range of applications. Recently, great efforts have also been devoted to the controlled synthesis of thin nanostructures of metals, one of the most studied traditional materials, for various applications. In this minireview, we review the recent progress in the synthesis and applications of thin metal nanostructures with a focus on metal nanoplates and nanosheets. First of all, various methods for the synthesis of metal nanoplates and nanosheets are summarized. After a brief introduction of their properties, some applications of metal nanoplates and nanosheets, such as catalysis, surface enhanced Raman scattering (SERS), sensing and near-infrared photothermal therapy are described. PMID:28553459

Post-Hartree-Fock studies of the He/Mg(0001) interaction: Anti-corrugation, screening, and pairwise additivity

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

Lara-Castells, María Pilar de, E-mail: Pilar.deLara.Castells@csic.es; Fernández-Perea, Ricardo; Madzharova, Fani

2016-06-28

The adsorption of noble gases on metallic surfaces represents a paradigmatic case of van-der-Waals (vdW) interaction due to the role of screening effects on the corrugation of the interaction potential [J. L. F. Da Silva et al., Phys. Rev. Lett. 90, 066104 (2003)]. The extremely small adsorption energy of He atoms on the Mg(0001) surface (below 3 meV) and the delocalized nature and mobility of the surface electrons make the He/Mg(0001) system particularly challenging, even for state-of-the-art vdW-corrected density functional-based (vdW-DFT) approaches [M. P. de Lara-Castells et al., J. Chem. Phys. 143, 194701 (2015)]. In this work, we meet thismore » challenge by applying two different procedures. First, the dispersion-corrected second-order Möller-Plesset perturbation theory (MP2C) approach is adopted, using bare metal clusters of increasing size. Second, the method of increments [H. Stoll, J. Chem. Phys. 97, 8449 (1992)] is applied at coupled cluster singles and doubles and perturbative triples level, using embedded cluster models of the metal surface. Both approaches provide clear evidences of the anti-corrugation of the interaction potential: the He atom prefers on-top sites, instead of the expected hollow sites. This is interpreted as a signature of the screening of the He atom by the metal for the on-top configuration. The strong screening in the metal is clearly reflected in the relative contribution of successively deeper surface layers to the main dispersion contribution. Aimed to assist future dynamical simulations, a pairwise potential model for the He/surface interaction as a sum of effective He–Mg pair potentials is also presented, as an improvement of the approximation using isolated He–Mg pairs.« less

Post-Hartree-Fock studies of the He/Mg(0001) interaction: Anti-corrugation, screening, and pairwise additivity

NASA Astrophysics Data System (ADS)

de Lara-Castells, María Pilar; Fernández-Perea, Ricardo; Madzharova, Fani; Voloshina, Elena

2016-06-01

The adsorption of noble gases on metallic surfaces represents a paradigmatic case of van-der-Waals (vdW) interaction due to the role of screening effects on the corrugation of the interaction potential [J. L. F. Da Silva et al., Phys. Rev. Lett. 90, 066104 (2003)]. The extremely small adsorption energy of He atoms on the Mg(0001) surface (below 3 meV) and the delocalized nature and mobility of the surface electrons make the He/Mg(0001) system particularly challenging, even for state-of-the-art vdW-corrected density functional-based (vdW-DFT) approaches [M. P. de Lara-Castells et al., J. Chem. Phys. 143, 194701 (2015)]. In this work, we meet this challenge by applying two different procedures. First, the dispersion-corrected second-order Möller-Plesset perturbation theory (MP2C) approach is adopted, using bare metal clusters of increasing size. Second, the method of increments [H. Stoll, J. Chem. Phys. 97, 8449 (1992)] is applied at coupled cluster singles and doubles and perturbative triples level, using embedded cluster models of the metal surface. Both approaches provide clear evidences of the anti-corrugation of the interaction potential: the He atom prefers on-top sites, instead of the expected hollow sites. This is interpreted as a signature of the screening of the He atom by the metal for the on-top configuration. The strong screening in the metal is clearly reflected in the relative contribution of successively deeper surface layers to the main dispersion contribution. Aimed to assist future dynamical simulations, a pairwise potential model for the He/surface interaction as a sum of effective He-Mg pair potentials is also presented, as an improvement of the approximation using isolated He-Mg pairs.

Non-adiabatic effects in elementary reaction processes at metal surfaces

NASA Astrophysics Data System (ADS)

Alducin, M.; Díez Muiño, R.; Juaristi, J. I.

2017-12-01

Great success has been achieved in the modeling of gas-surface elementary processes by the use of the Born-Oppenheimer approximation. However, in metal surfaces low energy electronic excitations are generated even by thermal and hyperthermal molecules due to the absence of band gaps in the electronic structure. This shows the importance of performing dynamical simulations that incorporate non-adiabatic effects to analyze in which way they affect most common gas-surface reactions. Here we review recent theoretical developments in this problem and their application to the study of the effect of electronic excitations in the adsorption and relaxation of atoms and molecules in metal surfaces, in scattering processes, and also in recombinative processes between impinging atoms and adsorbates at the surface. All these studies serve us to establish what properties of the gas-surface interaction favor the excitation of low-energy electron-hole pairs. A general observation is that the nature of these excitations usually requires long lasting interactions at the surface in order to observe deviations from the adiabatic behaviour. We also provide the basis of the local density friction approximation (LDFA) that have been used in all these studies, and show how it has been employed to perform ab initio molecular dynamics with electronic friction (AIMDEF). As a final remark, we will shortly review on recent applications of the LDFA to successfully simulate desorption processes induced by intense femtosecond laser pulses.

Theoretical Investigation of the Structural Stabilities of Ceria Surfaces and Supported Metal Nanocluster in Vapor and Aqueous Phases

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

Ren, Zhibo; Liu, Ning; Chen, Biaohua

Understanding the structural stability and dynamics at the interface between the solid metal oxide and aqueous phase is significant in a variety of industrial applications including heterogeneous catalysis and environmental remediation. In the present work, the stabilities of three low-index ceria (CeO2) surfaces, i.e., (111), (110) and (100) in vapor and aqueous phases were studied using ab initio molecular dynamics simulations and density functional theory (DFT) calculations. Gibbs surface free energies as a function of temperature, water partial pressure, and water coverages were calculated using DFT based atomistic thermodynamic approach. On the basis of surface free energies, the morphology andmore » exposed surface structures of the CeO2 nanoparticle were predicted using Wulff construction principle. It is found that the partially hydroxylated (111) and (100) are two major surface structures of CeO2 nanoparticles in vapor phase at ambient temperature (300 K). As the temperature increases, the fully dehydrated (111) surface gradually becomes the most dominant surface structure. While in aqueous phase, the exposed surface of the CeO2 nanoparticle is dominated by the hydroxylated (110) structure at 393 K. Finally, the morphology and stability of a cuboctahedron Pt13 nanocluster supported on CeO2 surfaces in both gas and aqueous phases were investigated. In gas phase, the supported Pt13 nanocluster has the tendency to wetting the CeO2 surface due to the strong metal-support interaction. The calculated interaction energies suggest the CeO2(110) surface provides the best stability for the Pt13 nanocluster. The CeO2 supported Pt13 nanoclusters are oxidized. Compared to the gas phase, the morphology of the CeO2 supported Pt13 nanocluster is less distorted due to the solvation effect provided by surrounding water molecules in aqueous phase. More electrons are transferred from the Pt13 nanocluster to the CeO2 support, implying the supported Pt13 nanocluster is further oxidized in aqueous phase.« less

Liquid Metal Embrittlement in Resistance Spot Welding and Hot Tensile Tests of Surface-refined TWIP Steels

NASA Astrophysics Data System (ADS)

Barthelmie, J.; Schram, A.; Wesling, V.

2016-03-01

Automotive industry strives to reduce vehicle weight and therefore fuel consumption and carbon dioxide emissions. Especially in the auto body, material light weight construction is practiced, but the occupant safety must be ensured. These requirements demand high-strength steels with good forming and crash characteristics. Such an approach is the use of high- manganese-content TWIP steels, which achieve strengths of around 1,000 MPa and fracture strains of more than 60%. Welding surface-refined TWIP steels reduces their elongation at break and produces cracks due to the contact with liquid metal and the subsequent liquid metal embrittlement (LME). The results of resistance spot welds of mixed joints of high-manganese- content steel in combination with micro-alloyed ferritic steel and hot tensile tests are presented. The influence of different welding parameters on the sensitivity to liquid metal embrittlement is investigated by means of spot welding. In a high temperature tensile testing machine, the influence of different parameters is determined regardless of the welding process. Defined strains just below or above the yield point, and at 25% of elongation at break, show the correlation between the applied strain and liquid metal crack initiation. Due to the possibility to carry out tensile tests on a wide range of temperatures, dependencies of different temperatures of the zinc coating to the steel can be identified. Furthermore, the attack time of the zinc on the base material is investigated by defined heating periods.

Nanostructuring of Palladium with Low-Temperature Helium Plasma

PubMed Central

Fiflis, P.; Christenson, M.P.; Connolly, N.; Ruzic, D.N.

2015-01-01

Impingement of high fluxes of helium ions upon metals at elevated temperatures has given rise to the growth of nanostructured layers on the surface of several metals, such as tungsten and molybdenum. These nanostructured layers grow from the bulk material and have greatly increased surface area over that of a not nanostructured surface. They are also superior to deposited nanostructures due to a lack of worries over adhesion and differences in material properties. Several palladium samples of varying thickness were biased and exposed to a helium helicon plasma. The nanostructures were characterized as a function of the thickness of the palladium layer and of temperature. Bubbles of ~100 nm in diameter appear to be integral to the nanostructuring process. Nanostructured palladium is also shown to have better catalytic activity than not nanostructured palladium. PMID:28347109

Nanostructuring of Palladium with Low-Temperature Helium Plasma.

PubMed

Fiflis, P; Christenson, M P; Connolly, N; Ruzic, D N

2015-11-25

Impingement of high fluxes of helium ions upon metals at elevated temperatures has given rise to the growth of nanostructured layers on the surface of several metals, such as tungsten and molybdenum. These nanostructured layers grow from the bulk material and have greatly increased surface area over that of a not nanostructured surface. They are also superior to deposited nanostructures due to a lack of worries over adhesion and differences in material properties. Several palladium samples of varying thickness were biased and exposed to a helium helicon plasma. The nanostructures were characterized as a function of the thickness of the palladium layer and of temperature. Bubbles of ~100 nm in diameter appear to be integral to the nanostructuring process. Nanostructured palladium is also shown to have better catalytic activity than not nanostructured palladium.

In situ reduction of antibacterial silver ions to metallic silver nanoparticles on bioactive glasses functionalized with polyphenols

NASA Astrophysics Data System (ADS)

Ferraris, S.; Miola, M.; Cochis, A.; Azzimonti, B.; Rimondini, L.; Prenesti, E.; Vernè, E.

2017-02-01

The realization of surfaces with antibacterial properties due to silver nanoparticles loaded through a green approach is a promising research challenge of the biomaterial field. In this research work, two bioactive glasses have been doubly surface functionalized with polyphenols (gallic acid or natural polyphenols extracted from red grape skins and green tea leaves) and silver nanoparticles deposited by in situ reduction from a silver nitrate aqueous solution. The presence of biomolecules - showing reducing ability to directly obtain in situ metallic silver - and silver nanoparticles was investigated by means of UV-vis spectroscopy, X-Ray Photoelectron Spectroscopy (XPS) and Field Emission Scanning Electron Microscopy (FESEM). The antibacterial activity of the modified surfaces was tested against a multidrug resistant Staphylococcus aureus bacterial strain.

Interaction of slow highly charged ions with a metal surface covered with a thin dielectric film. The role of the neutralization energy in the nanostructures formation

NASA Astrophysics Data System (ADS)

Majkić, M. D.; Nedeljković, N. N.; Dojčilović, R. J.

2017-09-01

We consider the slow highly charged ions impinging upon a metal surface covered with a thin dielectric film, and formation of the surface nanostructures (craters) from the standpoint of the required energy. For the moderate ionic velocities, the size of the surface features depends on the deposited kinetic energy of the projectile and the ionic neutralization energy. The neutralization energy is calculated by employing the recently developed quasi-resonant two-state vector model for the intermediate Rydberg state population and the micro-staircase model for the cascade neutralization. The electron interactions with the ionic core, polarized dielectric and charge induced on the metal surface are modelled by the appropriate asymptotic expressions and the method for calculation of the effective ionic charges in the dielectric is proposed. The results are presented for the interaction of \\text{X}{{\\text{e}}Z+} ions (velocity v=0.25 a.u.; 25) with the metal surface (Co) covered with a thin dielectric film, for model values of dielectric constant inside the interaction region. In the absence of dielectric film, the neutralization energy is lower than the potential (ionization) energy due to the incomplete neutralization. The presence of dielectric film additionally decreases the neutralization energy. We calculate the projectile neutralization energy in the perturbed dielectric (perturbation is caused by the ionic motion and the surface structure formation). We correlate the neutralization energy added to the deposited kinetic energy with the experimentally obtained energy necessary for the formation of the nano-crater of a given depth.

Practical significance and calculation of surface tension of glass, enamels and glazes

NASA Technical Reports Server (NTRS)

Dietzel, A.

1987-01-01

Surface tension is important in the formation of streaks in the whole procedure of enameling and glazing., in the action of TiO2 as opacifier, in the addition of borax to enamels, or metals to glasses, and in the corrosion of refractories by molten charges. By the use of known methods for measuring surface tension additive constants are found which give correct results within 1% with no discrepancy due to B2O3.

Direct laser interference patterning of metallic sleeves for roll-to-roll hot embossing

NASA Astrophysics Data System (ADS)

Lang, Valentin; Rank, Andreas; Lasagni, Andrés. F.

2017-03-01

Surfaces equipped with periodic patterns with feature sizes in the micrometer, submicrometer and nanometer range present outstanding surface properties. Many of these surfaces can be found on different plants and animals. However, there are few methods capable to produce such patterns in a one-step process on relevant technological materials. Direct laser interference patterning (DLIP) provides both high resolution as well as high throughput. Recently, fabrication rates up to 1 m2·min-1 could be achieved. However, resolution was limited to a few micrometers due to typical thermal effects that arise when nanosecond pulsed laser systems are used. Therefore, this study introduces an alternative to ns-DLIP for the fabrication of multi-scaled micrometer and submicrometer structures on nickel surfaces using picosecond pulses (10 ps at a wavelength of 1064 nm). Due to the nature of the interaction process of the metallic surfaces with the ultrashort laser pulses, it was not only possible to directly transfer the shape of the interference pattern intensity distribution to the material (with spatial periods ranging from 1.5 μm to 5.7 μm), but also to selectively obtain laser induce periodic surface structures with feature sizes in the submicrometer and nanometer range. Finally, the structured nickel sleeves are utilized in a roll-to-roll hot embossing unit for structuring of polymer foils. Processing speeds up to 25 m·min-1 are reported.

Bioaccessibility, bioavailability and toxicity of commercially relevant iron- and chromium-based particles: in vitro studies with an inhalation perspective.

PubMed

Hedberg, Yolanda; Gustafsson, Johanna; Karlsson, Hanna L; Möller, Lennart; Odnevall Wallinder, Inger

2010-09-03

Production of ferrochromium alloys (FeCr), master alloys for stainless steel manufacture, involves casting and crushing processes where particles inevitably become airborne and potentially inhaled. The aim of this study was to assess potential health hazards induced by inhalation of different well-characterized iron- and chromium-based particles, i.e. ferrochromium (FeCr), ferrosiliconchromium (FeSiCr), stainless steel (316L), iron (Fe), chromium (Cr), and chromium(III)oxide (Cr2O3), in different size fractions using in vitro methods. This was done by assessing the extent and speciation of released metals in synthetic biological medium and by analyzing particle reactivity and toxicity towards cultured human lung cells (A549). The amount of released metals normalized to the particle surface area increased with decreasing particle size for all alloy particles, whereas the opposite situation was valid for particles of the pure metals. These effects were evident in artificial lysosomal fluid (ALF) of pH 4.5 containing complexing agents, but not in neutral or weakly alkaline biological media. Chromium, iron and nickel were released to very low extent from all alloy particles, and from particles of Cr due to the presence of a Cr(III)-rich protective surface oxide. Released elements were neither proportional to the bulk nor to the surface composition after the investigated 168 hours of exposure. Due to a surface oxide with less protective properties, significantly more iron was released from pure iron particles compared with the alloys. Cr was predominantly released as Cr(III) from all particles investigated and was strongly complexed by organic species of ALF. Cr2O3 particles showed hemolytic activity, but none of the alloy particles did. Fine-sized particles of stainless steel caused however DNA damage, measured with the comet assay after 4 h exposure. None of the particles revealed any significant cytotoxicity in terms of cell death after 24 h exposure. It is evident that particle and alloy characteristics such as particle size and surface composition are important aspects to consider when assessing particle toxicity and metal release from alloy particles compared to pure metal particles. Generated results clearly elucidate that neither the low released concentrations of metals primarily as a result of protective and poorly soluble surface oxides, nor non-bioavailable chromium complexes, nor the particles themselves of occupational relevance induced significant acute toxic response, with exception of DNA damage from stainless steel.

Bioaccessibility, bioavailability and toxicity of commercially relevant iron- and chromium-based particles: in vitro studies with an inhalation perspective

PubMed Central

2010-01-01

Background Production of ferrochromium alloys (FeCr), master alloys for stainless steel manufacture, involves casting and crushing processes where particles inevitably become airborne and potentially inhaled. The aim of this study was to assess potential health hazards induced by inhalation of different well-characterized iron- and chromium-based particles, i.e. ferrochromium (FeCr), ferrosiliconchromium (FeSiCr), stainless steel (316L), iron (Fe), chromium (Cr), and chromium(III)oxide (Cr2O3), in different size fractions using in vitro methods. This was done by assessing the extent and speciation of released metals in synthetic biological medium and by analyzing particle reactivity and toxicity towards cultured human lung cells (A549). Results The amount of released metals normalized to the particle surface area increased with decreasing particle size for all alloy particles, whereas the opposite situation was valid for particles of the pure metals. These effects were evident in artificial lysosomal fluid (ALF) of pH 4.5 containing complexing agents, but not in neutral or weakly alkaline biological media. Chromium, iron and nickel were released to very low extent from all alloy particles, and from particles of Cr due to the presence of a Cr(III)-rich protective surface oxide. Released elements were neither proportional to the bulk nor to the surface composition after the investigated 168 hours of exposure. Due to a surface oxide with less protective properties, significantly more iron was released from pure iron particles compared with the alloys. Cr was predominantly released as Cr(III) from all particles investigated and was strongly complexed by organic species of ALF. Cr2O3 particles showed hemolytic activity, but none of the alloy particles did. Fine-sized particles of stainless steel caused however DNA damage, measured with the comet assay after 4 h exposure. None of the particles revealed any significant cytotoxicity in terms of cell death after 24 h exposure. Conclusion It is evident that particle and alloy characteristics such as particle size and surface composition are important aspects to consider when assessing particle toxicity and metal release from alloy particles compared to pure metal particles. Generated results clearly elucidate that neither the low released concentrations of metals primarily as a result of protective and poorly soluble surface oxides, nor non-bioavailable chromium complexes, nor the particles themselves of occupational relevance induced significant acute toxic response, with exception of DNA damage from stainless steel. PMID:20815895

Titanium Dioxide as a Catalyst Support in Heterogeneous Catalysis

PubMed Central

Bagheri, Samira; Muhd Julkapli, Nurhidayatullaili; Bee Abd Hamid, Sharifah

2014-01-01

The lack of stability is a challenge for most heterogeneous catalysts. During operations, the agglomeration of particles may block the active sites of the catalyst, which is believed to contribute to its instability. Recently, titanium oxide (TiO2) was introduced as an alternative support material for heterogeneous catalyst due to the effect of its high surface area stabilizing the catalysts in its mesoporous structure. TiO2 supported metal catalysts have attracted interest due to TiO2 nanoparticles high activity for various reduction and oxidation reactions at low pressures and temperatures. Furthermore, TiO2 was found to be a good metal oxide catalyst support due to the strong metal support interaction, chemical stability, and acid-base property. The aforementioned properties make heterogeneous TiO2 supported catalysts show a high potential in photocatalyst-related applications, electrodes for wet solar cells, synthesis of fine chemicals, and others. This review focuses on TiO2 as a support material for heterogeneous catalysts and its potential applications. PMID:25383380

Density functional theory study of phase stability and defect thermodynamics in iron-oxyhydroxide mineral materials

NASA Astrophysics Data System (ADS)

Pinney, Nathan Douglas

Due to their high surface area and reactivity toward a variety of heavy metal and oxyanion species of environmental concern, Fe-(oxyhydr)oxide materials play an important role in the geochemical fate of natural and anthropogenic contaminants in soils, aquifers and surface water environments worldwide. In this research, ab initio simulations describe the bulk structure, magnetic properties, and relative phase stability of major Fe-(oxyhydr)oxide materials, including hematite, goethite, lepidocrocite, and ferrihydrite.These bulk models are employed in further studies of point defect and alloy/dopant thermodynamics in these materials, allowing construction of a phase stability model that better replicates the structure and composition of real materials. Li + adsorption at the predominant goethite (101) surface is simulated using ab initio methods, offering energetic and structural insight into the binding mechanisms of metal cations over a range of surface protonation conditions.

Surface roughness analysis after laser assisted machining of hard to cut materials

NASA Astrophysics Data System (ADS)

Przestacki, D.; Jankowiak, M.

2014-03-01

Metal matrix composites and Si3N4 ceramics are very attractive materials for various industry applications due to extremely high hardness and abrasive wear resistance. However because of these features they are problematic for the conventional turning process. The machining on a classic lathe still requires special polycrystalline diamond (PCD) or cubic boron nitride (CBN) cutting inserts which are very expensive. In the paper an experimental surface roughness analysis of laser assisted machining (LAM) for two tapes of hard-to-cut materials was presented. In LAM, the surface of work piece is heated directly by a laser beam in order to facilitate, the decohesion of material. Surface analysis concentrates on the influence of laser assisted machining on the surface quality of the silicon nitride ceramic Si3N4 and metal matrix composite (MMC). The effect of the laser assisted machining was compared to the conventional machining. The machining parameters influence on surface roughness parameters was also investigated. The 3D surface topographies were measured using optical surface profiler. The analysis of power spectrum density (PSD) roughness profile were analyzed.

Specific anion effects on copper surface through electrochemical treatment: Enhanced photoelectrochemical CO2 reduction activity of derived nanostructures induced by chaotropic anions

NASA Astrophysics Data System (ADS)

Navaee, Aso; Salimi, Abdollah

2018-05-01

Copper derivatives are the most prominent CO2 reduction electrocatalyst. Herein, the metallic copper has been electrochemically treated with some of common ionic salts such as N3bar, HPO2bar, S2bar, Fbar, Clbar, Brbar and Ibar based on the dissolution of a metallic working electrode in an aqueous solution to derive the surface roughness incorporated with nanostructures. Diverse surface morphology can be obtained when the ionic radii of anions are changed. Surface study reveals various roughness shapes based on the size and polarity of the anions, where the ions with higher ionic radii have higher impact on the Cu surface. In comparison, polyatomic oxyanion such as HPO2bar even with large ionic radii do not have enough strength to create the surface roughness than that of oxygen-free anions with large ionic radii. The photoelectrochemical behavior of the modified surfaces toward CO2 reduction is studied at a wide potential window in bicarbonate aqueous solution. Based on our investigations, treated surfaces by Ibar, Clbar and S2bargive a more surface roughness, while Ibar and N3bar offer higher catalytic activity toward CO2 reduction due to possible complexing ability of these anions with Cu cations, followed by formation of the co-catalyst semiconductor and facilitate electron transfer. This methodology can be applied to investigate the effect of ions on transition metals along with obtaining different surface morphologies tailored to different applications.

On the widths of Stokes lines in Raman scattering from molecules adsorbed at metal surfaces and in molecular conduction junctions

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

Gao, Yi, E-mail: yig057@ucsd.edu; Galperin, Michael, E-mail: migalperin@ucsd.edu; Nitzan, Abraham, E-mail: nitzan@post.tau.ac.il

Within a generic model we analyze the Stokes linewidth in surface enhanced Raman scattering (SERS) from molecules embedded as bridges in molecular junctions. We identify four main contributions to the off-resonant Stokes signal and show that under zero voltage bias (a situation pertaining also to standard SERS experiments) and at low bias junctions only one of these contributions is pronounced. The linewidth of this component is determined by the molecular vibrational relaxation rate, which is dominated by interactions with the essentially bosonic thermal environment when the relevant molecular electronic energy is far from the metal(s) Fermi energy(ies). It increases whenmore » the molecular electronic level is close to the metal Fermi level so that an additional vibrational relaxation channel due to electron-hole (eh) exciton in the molecule opens. Other contributions to the Raman signal, of considerably broader linewidths, can become important at larger junction bias.« less

Ultra-broadband and efficient surface plasmon polariton launching through metallic nanoslits of subwavelength period.

PubMed

Li, Guangyuan; Zhang, Jiasen

2014-08-01

Ultra-broadband, efficient and unidirectional surface plasmon polariton (SPP) launching is of great concern in plasmonic devices and circuits. To address this challenge, a novel method adopting deep-subwavelength slits of subwavelength period (λSPP/4 ~ λSPP/3) in a thick metal film and under backside illumination is proposed. A new band pattern featuring broadband and wide angular characteristics, which is due to the coupling of the zeroth-order SPP resonance at the superstrate-metal interface and the first-order SPP resonance at the metal-substrate interface, is observed for the first time in the dispersion diagram. Unidirectional SPP launching efficiency of ~50%, ultra-broad bandwidth of up to 780 nm, covering the entire optical fiber communication bands, and relatively wide angular range of 7° are achieved. This remarkable efficient, ultra-broadband and wide angular performance is demonstrated by carefully designed experiments in the near infrared regime, showing good agreement with numerical results.

Platinum redispersion on metal oxides in low temperature fuel cells.

PubMed

Tripković, Vladimir; Cerri, Isotta; Nagami, Tetsuo; Bligaard, Thomas; Rossmeisl, Jan

2013-03-07

We have analyzed the aptitude of several metal oxide supports (TiO(2), SnO(2), NbO(2), ZrO(2), SiO(2), Ta(2)O(5) and Nb(2)O(5)) to redisperse platinum under electrochemical conditions pertinent to the Proton Exchange Membrane Fuel Cell (PEMFC) cathode. The redispersion on oxide supports in air has been studied in detail; however, due to different operating conditions it is not straightforward to link the chemical and the electrochemical environment. The largest differences reflect in (1) the oxidation state of the surface (the oxygen species coverage), (2) temperature and (3) the possibility of platinum dissolution at high potentials and the interference of redispersion with normal working potential of the PEMFC cathode. We have calculated the PtO(x) (x = 0, 1, 2) adsorption energies on different metal oxides' surface terminations as well as inside the metal oxides' bulk, and we have concluded that NbO(2) might be a good support for platinum redispersion at PEMFC cathodes.

Electron transport characteristics of silicon nanowires by metal-assisted chemical etching

NASA Astrophysics Data System (ADS)

Qi, Yangyang; Wang, Zhen; Zhang, Mingliang; Wang, Xiaodong; Ji, An; Yang, Fuhua

2014-03-01

The electron transport characteristics of silicon nanowires (SiNWs) fabricated by metal-assisted chemical etching with different doping concentrations were studied. By increasing the doping concentration of the starting Si wafer, the resulting SiNWs were prone to have a rough surface, which had important effects on the contact and the electron transport. A metal-semiconductor-metal model and a thermionic field emission theory were used to analyse the current-voltage (I-V) characteristics. Asymmetric, rectifying and symmetric I-V curves were obtained. The diversity of the I-V curves originated from the different barrier heights at the two sides of the SiNWs. For heavily doped SiNWs, the critical voltage was one order of magnitude larger than that of the lightly doped, and the resistance obtained by differentiating the I-V curves at large bias was also higher. These were attributed to the lower electron tunnelling possibility and higher contact barrier, due to the rough surface and the reduced doping concentration during the etching process.

Chemical Ni-C Bonding in Ni-Carbon Nanotube Composite by a Microwave Welding Method and Its Induced High-Frequency Radar Frequency Electromagnetic Wave Absorption.

PubMed

Sha, Linna; Gao, Peng; Wu, Tingting; Chen, Yujin

2017-11-22

In this work, a microwave welding method has been used for the construction of chemical Ni-C bonding at the interface between carbon nanotubes (CNTs) and metal Ni to provide a different surface electron distribution, which determined the electromagnetic (EM) wave absorption properties based on a surface plasmon resonance mechanism. Through a serial of detailed examinations, such as X-ray diffraction, scanning electron microscopy, transmission electron microscopy, high-resolution transmission electron microscopy, X-ray photoelectron spectroscopy, and Raman spectrum, the as-expected chemical Ni-C bonding between CNTs and metal Ni has been confirmed. And the Brunauer-Emmett-Teller and surface zeta potential measurements uncovered the great evolution of structure and electronic density compared with CNTs, metal Ni, and Ni-CNT composite without Ni-C bonding. Correspondingly, except the EM absorption due to CNTs and metal Ni in the composite, another wide and strong EM absorption band ranging from 10 to 18 GHz was found, which was induced by the Ni-C bonded interface. With a thinner thickness and more exposed Ni-C interfaces, the Ni-CNT composite displayed less reflection loss.

A mini-review on rare earth metal-doped TiO2 for photocatalytic remediation of wastewater.

PubMed

Saqib, Najm Us; Adnan, Rohana; Shah, Irfan

2016-08-01

Titanium dioxide (TiO2) has been considered a useful material for the treatment of wastewater due to its non-toxic character, chemical stability and excellent electrical and optical properties which contribute in its wide range of applications, particularly in environmental remediation technology. However, the wide band gap of TiO2 photocatalyst (anatase phase, 3.20 eV) limits its photocatalytic activity to the ultraviolet region of light. Besides that, the electron-hole pair recombination has been found to reduce the efficiency of the photocatalyst. To overcome these problems, tailoring of TiO2 surface with rare earth metals to improve its surface, optical and photocatalytic properties has been investigated by many researchers. The surface modifications with rare earth metals proved to enhance the efficiency of TiO2 photocatalyts by way of reducing the band gap by shifting the working wavelength to the visible region and inhibiting the anatase-to-rutile phase transformations. This review paper summarises the attempts on modification of TiO2 using rare earth metals describing their effect on the photocatalytic activities of the modified TiO2 photocatalyst.

Hydrogen collisions with transition metal surfaces: Universal electronically nonadiabatic adsorption

NASA Astrophysics Data System (ADS)

Dorenkamp, Yvonne; Jiang, Hongyan; Köckert, Hansjochen; Hertl, Nils; Kammler, Marvin; Janke, Svenja M.; Kandratsenka, Alexander; Wodtke, Alec M.; Bünermann, Oliver

2018-01-01

Inelastic scattering of H and D atoms from the (111) surfaces of six fcc transition metals (Au, Pt, Ag, Pd, Cu, and Ni) was investigated, and in each case, excitation of electron-hole pairs dominates the inelasticity. The results are very similar for all six metals. Differences in the average kinetic energy losses between metals can mainly be attributed to different efficiencies in the coupling to phonons due to the different masses of the metal atoms. The experimental observations can be reproduced by molecular dynamics simulations based on full-dimensional potential energy surfaces and including electronic excitations by using electronic friction in the local density friction approximation. The determining factors for the energy loss are the electron density at the surface, which is similar for all six metals, and the mass ratio between the impinging atoms and the surface atoms. Details of the electronic structure of the metal do not play a significant role. The experimentally validated simulations are used to explore sticking over a wide range of incidence conditions. We find that the sticking probability increases for H and D collisions near normal incidence—consistent with a previously reported penetration-resurfacing mechanism. The sticking probability for H or D on any of these metals may be represented as a simple function of the incidence energy, Ein, metal atom mass, M, and incidence angle, 𝜗i n. S =(S0+a ṡEi n+b ṡM ) *(1 -h (𝜗i n-c ) (1 -cos(𝜗 i n-c ) d ṡh (Ei n-e ) (Ei n-e ) ) ) , where h is the Heaviside step function and for H, S0 = 1.081, a = -0.125 eV-1, b =-8.40 ṡ1 0-4 u-1, c = 28.88°, d = 1.166 eV-1, and e = 0.442 eV; whereas for D, S0 = 1.120, a = -0.124 eV-1, b =-1.20 ṡ1 0-3 u-1, c = 28.62°, d = 1.196 eV-1, and e = 0.474 eV.

Excitation of surface plasmons in Al-coated SNOM tips

NASA Astrophysics Data System (ADS)

Palm, Viktor; Rähn, Mihkel; Jäme, Joonas; Hizhnyakov, Vladimir

2012-10-01

The mesoscopic effect of spectral modulation occurring due to the interference of two photonic fiber modes filtered out by a metal-coated SNOM tip is used to observe the surface plasmon polariton (SPP) excitation in SNOM tips. In a spectrum of the broadband light transmitted by a SNOM tip a region of highly regular spectral modulation can be found, indicating the spectral interval in which only two photonic modes (apparently HE11 and TM01) are transmitted with significant and comparable amplitudes. The modulation period yields the value of optical path difference (OPD) for this pair of modes. Due to the multimode fiber's inherent modal dispersion, this OPD value depends linearly on the fiber tail length l. An additional contribution to OPD can be generated in a metal-coated SNOM tip due to a mode-dependent photon-plasmon coupling strength resulting in generation of SPPs with different propagation velocities. For an Al-coated 200 nm SNOM tip spectra of transmitted light have been registered for ten different l values. An extrapolation of the linear OPD (l) dependence to l=0 yields a significant residual OPD value, indicating according to our theoretical considerations a mode-selective SPP excitation in the metal-coated tip. The modal dispersion is shown to switch its sign in the SNOM tip. First results of analogous experiments with an Al-coated 150 nm SNOM tip confirm our conclusions.

The growth of the metallic ZrNx thin films on P-GaN substrate by pulsed laser deposition

NASA Astrophysics Data System (ADS)

Gu, Chengyan; Sui, Zhanpeng; Li, Yuxiong; Chu, Haoyu; Ding, Sunan; Zhao, Yanfei; Jiang, Chunping

2018-03-01

Although metal nitride thin films have attractive prospects in plasmonic applications due to its stable properties in harsh environments containing high temperatures, shock, and contaminants, the effect of deposition parameters on the properties of the metallic ZrN grown on III-N semiconductors by pulse laser deposition still lacks of detailed exploration. Here we have successfully prepared metallic ZrNx films on p-GaN substrate by pulsed laser deposition in N2 ambient of various pressures at a fixed substrate temperature (475 °C). It is found that the films exhibit quite smooth surfaces and (111) preferred orientation. The X-ray photoelectron spectroscopy measurements indicate that carbon contamination can be completely removed and oxygen contamination is significantly reduced on the film surfaces after cleaning using Ar+ sputtering. The N/Zr ratio increases from 0.64 to 0.75 when the N2 pressure increases from 0.5 Pa to 3 Pa. The optical reflectivity spectra measured by the UV-vis-NIR spectrophotometer show that the ZrNx is a typical and good metallic-like material and its metallic properties can be tuned with changing the film compositions.

Heavy Metal Contents of Soils, Durum and Bread Wheats in Harran Plain, Southeast Turkey

NASA Astrophysics Data System (ADS)

Büyükkılıç Yanardaǧ, Asuman

2013-04-01

Soils are vital for regulating the biological effects and mobility of metals in nature. Iron and zinc are some of the essential nutrients for plants and animals, while other metals are potentially toxic such as lead and cadmium. Toxic heavy metals (HMs) can be taken up easily by organisms. HMs inputs to soil via the application of metal-contained fertilizers often exceed outputs in crops and drainage waters, thus toxic HMs content in many agricultural soils tends to be gradually increasing. Thus adverse human health effects due to soil-plant and plant-human transfer of HMs have been enhanced. HMs may cause harmful effects on human health due to the ingestion of food grain grown in soils. The objectives of this study were (1) to understand the chemistry of metals in soils for managing their agricultural and ecological impacts, (2) to identify metal uptakes of different genotypes of wheat. Concentrations of HMs (Cd, Zn, Ni, Mn, Cu, Mo, Pb) in wheat were investigated in different agricultural areas in Southeast, Turkey. The results showed that concentrations of HMs were in following order: Mn>Ni>Zn>Cu>Pb>Mo>Cd in surface and next to surface soil and Mn>Zn>Cu>Pb> Ni>Mo>Cd in wheat, respectively. HMs concentrations of several soil samples exceeded the permissible limits of Europe standard except for Ni and Mn. In addition, concentration of Cd, Zn, Cu, and Pb were higher in bread wheat than in durum wheat; however, concentration of Mn, Ni and Mo were higher in durum wheat than in bread wheat. Unusual amount of heavy metals found in some fertilizers used in the Southeast region of Turkey, it becomes an important subject to determine the amount of metals added to the soil every year. Heavy metals uptake by plants still remains to be an interest for researchers. As the heavy metals contents of plants were below the threshold levels, we conclude that the quality of wheat is high and it should receive attention in national and international markets. Keywords: Heavy Metals (HMs), Soil, Durum and Bread Wheat, Fertilizers.

Methane combustion reactivity during the metal→metallic oxide transformation of Pd-Pt catalysts: Effect of oxygen pressure

NASA Astrophysics Data System (ADS)

Qi, Wenjie; Ran, Jingyu; Zhang, Zhien; Niu, Juntian; Zhang, Peng; Fu, Lijuan; Hu, Bo; Li, Qilai

2018-03-01

Density functional theory combined with kinetic models were used to probe different kinetics consequences by which methane activation on different oxygen chemical potential surfaces as oxygen pressure increased. The metallic oxide → metal transformation temperature of Pd-Pt catalysts increased with the increase of the Pd content or/and O2 pressure. The methane conversion rate on Pt catalyst increased and then decreased to a constant value when increasing the O2 pressure, and Pd catalyst showed a poor activity performance in the case of low O2 pressure. Moreover, its activity increased as the oxygen chemical potential for O2 pressure increased in the range of 2.5-10 KPa. For metal clusters, the Csbnd H bond and Odbnd O bond activation steps occurred predominantly on *-* site pairs. The methane conversion rate was determined by O2 pressure because the adsorbed O atoms were rapidly consumed by other adsorbed species in this kinetic regime. As the O2 pressure increased, the metallic active sites for methane activation were decreased and there was no longer lack of adsorbed O atoms, resulting in the decrease of the methane conversion rate. Furthermore, when the metallic surfaces were completely covered by adsorbed oxygen atoms at higher oxygen chemical potentials, Pt catalyst showed a poor activity due to a high Csbnd H bond activation barrier on O*sbnd O*. In the case of high O2 pressure, Pd atoms preferred to segregate to the active surface of Pd-Pt catalysts, leading to the formation of PdO surfaces. The increase of Pd segregation promoted a subsequent increase in active sites and methane conversion rate. The PdO was much more active than metallic and O* saturated surfaces for methane activation, inferred from the theory and experimental study. Pd-rich bimetallic catalyst (75% molar Pd) showed a dual high methane combustion activity on O2-poor and O2-rich conditions.

New SERS Substrates For Polycyclic Aromatic Hydrocarbon (PAH) Detection: Towards Quantitative SERS Sensors For Environmental Analysis

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

Peron, O.; Laboratoire de Nanotechnologie et d'instrumentation Optique, Institut Charles Delaunay, FRE 2848, Universite de technologie de Troyes, 12 rue Marie Curie, 10010 Troyes; Rinnert, E.

2010-08-06

In the investigation of chemical pollutions, such as PAHs (Polycyclic Aromatic Hydrocarbons) at low concentration in aqueous medium, surface-enhanced Raman scattering (SERS) stands for an alternative to the inherent low cross-section of normal Raman scattering. Indeed, SERS is a very sensitive spectroscopic technique due to the excitation of the surface plasmon modes of the nanostructured metallic film.

Pb, Cu, and Zn distributions at humic acid-coated metal-oxide surfaces

DOE PAGES

Wang, Yingge; Michel, F. Marc; Choi, Yongseong; ...

2016-05-09

Here, mineral surfaces are often coated by natural organic matter (NOM), which has a major influence on metal-ion sorption and sequestration because of the abundance of binding sites in such coatings and the changes they cause in local nanoscale environments. The effects of NOM coatings on mineral surfaces are, however, still poorly understood at the molecular level due to the complexity of these systems. In this study, we have applied long-period X-ray standing wave-fluorescence yield (LP-XSW-FY) spectroscopy to measure the partitioning of naturally present Cu(II) (0.0226%), Zn(II) (0.009%), and Pb(II) ( 0.0004%) between Elliott Soil Humic Acid (ESHA) coatings andmore » three model single-crystal metal-oxide substrates: α-Al 2O 3 (0 0 0 1), α-Al 2O 3 (1 1 0 2), and α-Fe 2O 3 (0 0 0 1). The competitive sorption effects among these metal ions for binding sites in the ESHA coatings and on the metal-oxide surfaces were investigated as a function of reaction time, calcium content, and solution pH. Pb(II) ions present in the ESHA coatings were found to redistribute to reactive α-Al 2O 3 (1 1 0 2) and α-Fe 2O 3 (0 0 0 1) surfaces after 3 h of reaction (pH = 6.0, [Ca(II)] = 2 mM). Pb(II) partitioning onto these reactive metal-oxide surfaces increased with increasing reaction time (up to 7 d). In addition, the partitioning of Cu(II) and Zn(II) from the ESHA coating to the α-Fe 2O 3 (0 0 0 1) substrate increased slightly with reaction time (2.4% and 3.7% for Cu(II) and Zn(II), respectively, after 3 h and 6.4% and 7.7% for Cu(II) and Zn(II), respectively, after 72 h of reaction time).« less

Method for laser welding a fin and a tube

DOEpatents

Fuerschbach, Phillip W.; Mahoney, A. Roderick; Milewski, John O

2001-01-01

A method of laser welding a planar metal surface to a cylindrical metal surface is provided, first placing a planar metal surface into approximate contact with a cylindrical metal surface to form a juncture area to be welded, the planar metal surface and cylindrical metal surface thereby forming an acute angle of contact. A laser beam, produced, for example, by a Nd:YAG pulsed laser, is focused through the acute angle of contact at the juncture area to be welded, with the laser beam heating the juncture area to a welding temperature to cause welding to occur between the planar metal surface and the cylindrical metal surface. Both the planar metal surface and cylindrical metal surface are made from a reflective metal, including copper, copper alloys, stainless steel alloys, aluminum, and aluminum alloys.

Carbon composites with metal nanoparticles for Alcohol fuel cells

NASA Astrophysics Data System (ADS)

Ventrapragada, Lakshman; Siddhardha, R. S.; Podilla, Ramakrishna; Muthukumar, V. S.; Creager, Stephen; Rao, A. M.; Ramamurthy, Sai Sathish

2015-03-01

Graphene due to its high surface area and superior conductivity has attracted wide attention from both industrial and scientific communities. We chose graphene as a substrate for metal nanoparticle deposition for fuel cell applications. There are many chemical routes for fabrication of metal-graphene composites, but they have an inherent disadvantage of low performance due to the usage of surfactants, that adsorb on their surface. Here we present a design for one pot synthesis of gold nanoparticles and simultaneous deposition on graphene with laser ablation of gold strip and functionalized graphene. In this process there are two natural advantages, the nanoparticles are synthesized without any surfactants, therefore they are pristine and subsequent impregnation on graphene is linker free. These materials are well characterized with electron microscopy to find their morphology and spectroscopic techniques like Raman, UV-Vis. for functionality. This gold nanoparticle decorated graphene composite has been tested for its electrocatalytic oxidation of alcohols for alkaline fuel cell applications. An electrode made of this composite showed good stability for more than 200 cycles of operation and reported a low onset potential of 100 mV more negative, an important factor for direct ethanol fuel cells.

Self-organization of palladium nanoislands on GaN and AlxGa1-xN/GaN heterostructures

NASA Astrophysics Data System (ADS)

Stafiniak, Andrzej; Szymański, Tomasz; Paszkiewicz, Regina

2017-12-01

We report on systematic study on the dewetting process of thin Pd layer and self-organized Pd nano-islands on SiO2, GaN and AlxGa1-xN/GaN heterostructures with various Al content. The influence of factors such as the thickness of metal layer, type of top layer of AlGaN/GaN heterostructures, temperature and time of annealing process on the dimensions, shapes and density of Pd islands was analyzed. Comparing the behavior of self-organization of Pd islands on Al0.25Ga0.75N/GaN and SiO2 we can conclude that solid-state dewetting process on SiO2 occures much faster than on Al0.25Ga0.75N. For substrates with SiO2 this process requires less energy and can arise for thicker layer. On the Al0.25Ga0.75N surface the islands take more crystalline shape which is probably due to surface reconstruction of Pd-Ga alloy thin layer on interface. For thin metal layer the coalescence of islands into larger islands similar to Ostwald ripening mechanism was observed. Greater surface roughness of AlxGa1-xN/GaN heterostructures with higher Al content causes an increase of surface density of islands and the reduction of their sizes which improves the roundness. In case of GaN and AlxGa1-xN layers with Al content lower than 20%, the surface degradation caused by annealing process was observed. Probably, this is due to the decomposition of layers with gallium droplet formation on catalytic metal islands.

Spectral dependence of fluorescence near plasmon resonant metal nanoparticles

NASA Astrophysics Data System (ADS)

Chen, Yeechi

The optical properties of fluorophores are significantly modified when placed within the near field (0--100 nm) of plasmon resonant metal nanostructures, due to the competition between increased decay rates and "hotspots" of concentrated electric fields. The decay rates and effective electric field intensities are highly dependent on the relative position of dye and metal and the overlap between plasmon resonance and dye absorption and emission. Understanding these dependencies can greatly improve the performance of biosensing and nanophotonic devices. In this dissertation, the fluorescence intensity of organic dyes and CdSe quantum dots near single metal nanoparticles is studied as a function of the local surface plasmon resonance (LSPR) of the nanoparticle. Single metal nanoparticles have narrow, well-defined, intense local surface plasmon resonances that are tunable across the visible spectrum by changes in size and shape. First, we show that organic dyes can be self-assembled on single silver nanoprisms into known configurations by the hybridization of thiolated DNA oligomers. We correlate the fluorescence intensity of the dyes to the LSPR of the individual nanoprism to which they are attached. For each of three different organic dyes, we observe a strong correlation between the fluorescence intensity of the dye and the degree of spectral overlap with the plasmon resonance of the nanoparticle. On average, we observe the brightest fluorescence from dyes attached to metal nanoparticles that have a LSPR scattering peak 40--120 meV higher in energy than the emission peak of the fluorophore. Second, the plasmon-enhanced fluorescence from CdSe/CdS/CdZnS/ZnS core/shell quantum dots is studied near a variety of silver and gold nanoparticles. With single-particle scattering spectroscopy, the localized surface plasmon resonance spectra of single metal nanoparticles is correlated with the photoluminescence excitation (PLE) spectra of the nearby quantum dots. The PLE spectra closely track the scattering spectra of the metal nanoparticles. By taking advantage of the ability to excite quantum dots across a wide range of wavelengths while detecting a single emission wavelength, we measure an excitation enhancement factor for single metal nanoparticles. The data also provide a calculation of a lower-bound of experimentally attainable enhancement factors solely due to increased near-field excitation. This factor was found to range from ˜3 to 10 for Au spheres, Ag cubes and Ag nanoprisms.

Backscatter from metal surfaces in diagnostic radiology

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

Kodera, Y.; Schmidt, R.A.; Chan, H.P.

Backscatter from four commonly used metals (aluminum, lead, copper, and iron) was measured under diagnostic imaging conditions, using screen-film systems as detectors. The results indicate that for an 80-kV filtered beam and Par Speed/XRP system, backscatter increases as aluminum (Al) thickness increases until it reaches a plateau of approximately 12% at 50 mm Al. The amount of backscatter from any of these four metals increases as the tube voltage is raised from 60 to 115 kV. Measured backscatter depends strongly on the screens used, possibly due to their attenuation and energy response. Backscatter from aluminum was significantly greater than thatmore » from the other metals tested.« less

Surface characterization of anodized zirconium for biomedical applications

NASA Astrophysics Data System (ADS)

Sanchez, A. Gomez; Schreiner, W.; Duffó, G.; Ceré, S.

2011-05-01

Mechanical properties and corrosion resistance of zirconium make this material suitable for biomedical implants. Its good in vivo performance is mainly due to the presence of a protective oxide layer that minimizes corrosion rate, diminishes the amount of metallic ions released to the biological media and facilitates the osseointegration process. Since the implant surface is the region in contact with living tissues, the characteristics of the surface film are of great interest. Surface modification is a route to enhance both biocompatibility and corrosion resistance of permanent implant materials. Anodizing is presented as an interesting process to modify metal surfaces with good reproducibility and independence of the geometry. In this work the surface of zirconium before and after anodizing in 1 mol/L phosphoric acid solution at a fixed potential between 3 and 30 V, was characterized by means of several surface techniques. It was found that during anodization the surface oxide grows with an inhomogeneous coverage on zirconium surface, modifying the topography. The incorporation of P from the electrolyte to the surface oxide during the anodizing process changes the surface chemistry. After 30 days of immersion in Simulated Body Fluid (SBF) solution, Ca-P rich compounds were present on anodized zirconium.

Ion implantation enhanced metal-Si-metal photodetectors

NASA Astrophysics Data System (ADS)

Sharma, A. K.; Scott, K. A. M.; Brueck, S. R. J.; Zolper, J. C.; Myers, D. R.

1994-05-01

The quantum efficiency and frequency response of simple Ni-Si-Ni metal-semiconductor-metal (MSM) photodetectors at long wavelengths are significantly enhanced with a simple, ion-implantation step to create a highly absorbing region approx. 1 micron below the Si surface. The internal quantum efficiency is improved by a factor of approx. 3 at 860 nm (to 64%) and a full factor of ten at 1.06 microns (to 23%) as compared with otherwise identical unimplanted devices. Dark currents are only slightly affected by the implantation process and are as low as 630 pA for a 4.5-micron gap device at 10-V bias. Dramatic improvement in the impulse response is observed, 100 ps vs. 600 ps, also at 10-V bias and 4.5-micron gap, due to the elimination of carrier diffusion tails in the implanted devices. Due to its planar structure, this device is fully VLSI compatible. Potential applications include optical interconnections for local area networks and multi-chip modules.

Intercalated layered clay composites and their applications

NASA Astrophysics Data System (ADS)

Phukan, Anjali

Supported inorganic reagents are rapidly emerging as new and environmentally acceptable reagents and catalysts. The smectite group of layered clay minerals, such as, Montmorillonite, provides promising character for adsorption, catalytic activity, supports etc. for their large surface area, swelling behavior and ion exchange properties. Aromatic compounds intercalated in layered clays are useful in optical molecular devices. Clay is a unique material for adsorption of heavy metals and various toxic substances. Clay surfaces are known to be catalytically active due to their surface acidity. Acid activated clays possess much improved surface areas and acidities and have higher pore volumes so that can absorb large molecules in the pores. The exchangeable cations in clay minerals play a key role in controlling surface acidity and catalytic activity. Recently, optically active metal-complex-Montmorillonite composites are reported to be active in antiracemization purposes. In view of the above, a research work, relating to the preparation of different modified clay composites and their catalytic applications were carried out. The different aspects and results of the present work have been reported in four major chapters. Chapter I: This is an introductory chapter, which contains a review of the literature regarding clay-based materials. Clay minerals are phyllosilicates with layer structure. Montmorillonite, a member of smectite group of clay, is 2:1 phyllosilicate, where a layer is composed of an octahedral sheet sandwiched by two tetrahedral sheets. Such clay shows cation exchange capacity (CEC) and is expressed in milli-equivalents per 100 gm of dry clay. Clays can be modified by interaction with metal ion, metal complexes, metal cluster and organic cations for various applications. Clays are also modified by treating with acid followed by impregnation with metal salts or ions. Montmorillonite can intercalate suitable metal complexes in excess of CEC to form double or pseudo-trilayer composites. Metal ion and metal ion metal salts intercalated on Montmorillonite are efficient catalysts for Friedel-Crafts (FC) reactions, such as benzylation of benzene, synthesis of Raspberry ketone [4-(4'-hydroxyphenyl)butan-2-one] etc. Montmorillonite clay can be used as a good support for controlled release of pesticides and medicinal drugs, adsorbent for cationic dyes, toxic substances and heavy metals effective adsorbent for radioactive and toxic industrial wastes,...

Characterization of charge and kinetic energy distribution of ions emitted during nanosecond pulsed laser ablation of several metals

NASA Astrophysics Data System (ADS)

Dogar, A. H.; Ullah, S.; Qayyum, H.; Rehman, Z. U.; Qayyum, A.

2017-09-01

The ion flux from various metals (Al, Ti, Cu, Sn and W) ablated with 20 ns Nd:YAG laser radiation at a wavelength of 1064 nm was investigated by an ion collector operating in time-of-flight (TOF) configuration. The laser irradiance at the target was varied in the range of 1.7  ×  108-5.73  ×  108 W cm-2. Ion yield from various metals showed a linearly increasing trend with increasing laser irradiance, whereas ion yield was found to decrease with an increasing atomic mass of the target. Our results clearly indicate that ion yield is not a function of the volatility of the metal. TOF ion spectra showed at least two groups of low intensity peaks due to fast ions. The first group of ion peaks, which was present in the spectra of all five metals, was due to surface contamination. The additional fast ion structures in the spectra of Sn and W can be related to the ion acceleration due to the prompt electron emission from these high-Z metals. The ion velocity follows the anticipated inverse square root dependence on the ion mass. For the range of laser irradiance investigated here, the most probable energy of the Cu ions increases from about 100-600 eV. The fast increase in ion energy above ~3  ×  108 W cm-2 is related to the increase of the Columb part of the ion energy due to the production of multiply charged ions.

Modeling quantum yield, emittance, and surface roughness effects from metallic photocathodes

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

Dimitrov, D. A.; Bell, G. I.; Smedley, J.

Here, detailed measurements of momentum distributions of emitted electrons have allowed the investigation of the thermal limit of the transverse emittance from metal photocathodes. Furthermore, recent developments in material design and growth have resulted in photocathodes that can deliver high quantum efficiency and are sufficiently robust to use in high electric field gradient photoinjectors and free electron lasers. The growth process usually produces photoemissive material layers with rough surface profiles that lead to transverse accelerating fields and possible work function variations, resulting in emittance growth. To better understand the effects of temperature, density of states, and surface roughness on themore » properties of emitted electrons, we have developed realistic three-dimensional models for photocathode materials with grated surface structures. They include general modeling of electron excitation due to photon absorption, charge transport, and emission from flat and rough metallic surfaces. The models also include image charge and field enhancement effects. We report results from simulations with flat and rough surfaces to investigate how electron scattering, controlled roughness, work function variation, and field enhancement affect emission properties. Comparison of simulation results with measurements of the quantum yield and transverse emittance from flat Sb emission surfaces shows the importance of including efficient modeling of photon absorption, temperature effects, and the material density of states to achieve agreement with the experimental data.« less

Modeling quantum yield, emittance, and surface roughness effects from metallic photocathodes

DOE PAGES

Dimitrov, D. A.; Bell, G. I.; Smedley, J.; ...

2017-10-26

Here, detailed measurements of momentum distributions of emitted electrons have allowed the investigation of the thermal limit of the transverse emittance from metal photocathodes. Furthermore, recent developments in material design and growth have resulted in photocathodes that can deliver high quantum efficiency and are sufficiently robust to use in high electric field gradient photoinjectors and free electron lasers. The growth process usually produces photoemissive material layers with rough surface profiles that lead to transverse accelerating fields and possible work function variations, resulting in emittance growth. To better understand the effects of temperature, density of states, and surface roughness on themore » properties of emitted electrons, we have developed realistic three-dimensional models for photocathode materials with grated surface structures. They include general modeling of electron excitation due to photon absorption, charge transport, and emission from flat and rough metallic surfaces. The models also include image charge and field enhancement effects. We report results from simulations with flat and rough surfaces to investigate how electron scattering, controlled roughness, work function variation, and field enhancement affect emission properties. Comparison of simulation results with measurements of the quantum yield and transverse emittance from flat Sb emission surfaces shows the importance of including efficient modeling of photon absorption, temperature effects, and the material density of states to achieve agreement with the experimental data.« less

ARTICLES: Thermohydrodynamic models of the interaction of pulse-periodic radiation with matter

NASA Astrophysics Data System (ADS)

Arutyunyan, R. V.; Baranov, V. Yu; Bol'shov, Leonid A.; Malyuta, D. D.; Mezhevov, V. S.; Pis'mennyĭ, V. D.

1987-02-01

Experimental and theoretical investigations were made of the processes of drilling and deep melting of metals by pulsed and pulse-periodic laser radiation. Direct photography of the surface revealed molten metal splashing due to interaction with single CO2 laser pulses. A proposed thermohydrodynamic model was used to account for the experimental results and to calculate the optimal parameters of pulse-periodic radiation needed for deep melting. The melt splashing processes were simulated numerically.

Control of GaAs Microwave Schottky Diode Electrical Characteristics by Contact Geometry: The Gap Diode.

DTIC Science & Technology

1982-05-01

semiconductor Schottky-barrier contacts are used in many semiconductor devices, including switches, rectifiers, varactors , IMPATTs, mixer and detector...ionic materials such as most of the II-VI compound semiconductors (e.g. ZnS and ZnO) and the transition-metal oxides , the barrier height is strongly...the alloying process described above is nonuniformity, due to the incomplete removal of residual surface oxides prior to the evaporation of the metal

Defect Control of the WC Hardmetal by Mixing Recycled WC Nano Powder and Tungsten Powder

NASA Astrophysics Data System (ADS)

Hur, Man Gyu; Shin, Mi Kyung; Kim, Deug Joong; Yoon, Dae Ho

2018-03-01

Tungsten metal powder was added to recycled WC nano powder to control the macro and micro defects of WC hardmetal. The macro and micro defects caused by the excess carbon in the recycled WC powder were markedly removed after the addition of tungsten metal powder ranging from 2 to 6 wt%. The density and hardness of the WC hardmetals also increased due to the removal of defects after adding the tungsten metal powder. The density and hardness of WC hardmetals with the addition of W metal powder ranged from 8 to 12 wt% increased linearly as the W metal powder content increased due to the formation of a new (Co- and W-rich WC) composition. The surface morphology of the WC hardmetals was observed via field emission scanning electron microscopy, and a quantitative elemental analysis was conducted via X-ray fluorescence spectrometry and energy dispersive X-ray analysis. The density and hardness of the WC hardmetals were respectively measured using an analytical balance and a Vikers hardness tester. The effect on the defects in the recycled WC hardmetals through the addition of the tungsten metal powder was discussed in detail.

Design and fabrication of Ni nanowires having periodically hollow nanostructures

NASA Astrophysics Data System (ADS)

Sada, Takao; Fujigaya, Tsuyohiko; Nakashima, Naotoshi

2014-09-01

We propose a concept for the design and fabrication of metal nanowires having periodically hollow nanostructures inside the pores of an anodic aluminum oxide (AAO) membrane using a sacrificial metal. In this study, nickel (Ni) and silver (Ag) were used as the base metal and the sacrificial metal, respectively. Alternating an applied potential between -0.4 and -1.0 V provided alternatively deposited Ni and Ag segments in a Ni-Ag `barcode' nanowire with a diameter of 18 or 35 nm. After etching away the Ag segments, we fabricated Ni nanowires with nanopores of 12 +/- 5.3 nm. Such nanostructure formation is explained by the formation of a Ni shell layer over the surface of the Ag segments due to the strong affinity of Ni2+ for the interior surfaces of AAO. The Ni shell layer allows the Ni segments to remain even after dissolution of the Ag segments. Because the electroplating conditions can be easily controlled, we could carefully adjust the size and pitch of the periodically hollow nanospaces. We also describe a method for the fabrication of Ni nanorods by forming an Ag shell instead of a Ni shell on the Ni-Ag barcode nanowire, in which the interior of the AAO surfaces was modified with a compound bearing a thiol group prior to electroplating.We propose a concept for the design and fabrication of metal nanowires having periodically hollow nanostructures inside the pores of an anodic aluminum oxide (AAO) membrane using a sacrificial metal. In this study, nickel (Ni) and silver (Ag) were used as the base metal and the sacrificial metal, respectively. Alternating an applied potential between -0.4 and -1.0 V provided alternatively deposited Ni and Ag segments in a Ni-Ag `barcode' nanowire with a diameter of 18 or 35 nm. After etching away the Ag segments, we fabricated Ni nanowires with nanopores of 12 +/- 5.3 nm. Such nanostructure formation is explained by the formation of a Ni shell layer over the surface of the Ag segments due to the strong affinity of Ni2+ for the interior surfaces of AAO. The Ni shell layer allows the Ni segments to remain even after dissolution of the Ag segments. Because the electroplating conditions can be easily controlled, we could carefully adjust the size and pitch of the periodically hollow nanospaces. We also describe a method for the fabrication of Ni nanorods by forming an Ag shell instead of a Ni shell on the Ni-Ag barcode nanowire, in which the interior of the AAO surfaces was modified with a compound bearing a thiol group prior to electroplating. Electronic supplementary information (ESI) available: Information on the current profile during pulsed-electroplating, the histogram for the Ni and nanopores, and STEM images of obtained nanowires. See DOI: 10.1039/c4nr02625j

Surface modifications induced by pulsed-laser texturing—Influence of laser impact on the surface properties

NASA Astrophysics Data System (ADS)

Costil, S.; Lamraoui, A.; Langlade, C.; Heintz, O.; Oltra, R.

2014-01-01

Laser cleaning technology provides a safe, environmentally friendly and very cost effective way to improve cleaning and surface preparation of metallic materials. Compared with efficient cleaning processes, it can avoid the disadvantages of ductile materials prepared by conventional technologies (cracks induced by sand-blasting for example) and treat only some selected areas (due to the optical fibers). By this way, laser technology could have several advantages and expand the range of thermal spraying. Moreover, new generations of lasers (fiber laser, disc laser) allow the development of new methods. Besides a significant bulk reduction, no maintenance, low operating cost, laser fibers can introduce alternative treatments. Combining a short-pulse laser with a scanner allows new applications in terms of surface preparation. By multiplying impacts using scanning laser, it is possible to shape the substrate surface to improve the coating adhesion as well as the mechanical behaviour. In addition, during the interactions of the laser beam with metallic surfaces, several modifications can be induced and particularly thermal effects. Indeed, under ambient conditions, a limited oxidation of the clean surface can occur. This phenomenon has been investigated in detail for silicon but few works have been reported concerning metallic materials. This paper aims at studying the surface modifications induced on aluminium alloy substrates after laser texturing. After morphological observations (SEM), a deeper surface analysis will be performed using XPS (X-ray photoelectron spectroscopy) measures and microhardness testing.

Studies of the kinetics and mechanisms of perfluoroether reactions on iron and oxidized iron surfaces

NASA Technical Reports Server (NTRS)

Napier, Mary E.; Stair, Peter C.

1992-01-01

Polymeric perfluoroalkylethers are being considered for use as lubricants in high temperature applications, but have been observed to catalytically decompose in the presence of metals. X-ray photoelectron spectroscopy (XPS) and temperature programmed desorption (TPD) were used to explore the decomposition of three model fluorinated ethers on clean polycrystalline iron surfaces and iron surfaces chemically modified with oxygen. Low temperature adsorption of the model fluorinated ethers on the clean, oxygen modified and oxidized iron surfaces was molecular. Thermally activated defluorination of the three model compounds was observed on the clean iron surface at remarkably low temperatures, 155 K and below, with formation of iron fluoride. Preferential C-F bond scission occurred at the terminal fluoromethoxy, CF3O, of perfluoro-1-methoxy-2-ethoxy ethane and perfluoro-1-methoxy-2-ethoxy propane and at CF3/CF2O of perfluoro-1,3-diethoxy propane. The reactivity of the clean iron toward perfluoroalkylether decomposition when compared to other metals is due to the strength of the iron fluoride bond and the strong electron donating ability of the metallic iron. Chemisorption of an oxygen overlayer lowered the reactivity of the iron surface to the adsorption and decomposition of the three model fluorinated ethers by blocking active sites on the metal surface. Incomplete coverage of the iron surface with chemisorbed oxygen results in a reaction which resembles the defluorination reaction observed on the clean iron surface. Perfluoro-1-methoxy-2-ethoxy ethane reacts on the oxidized iron surface at 138 K, through a Lewis acid assisted cleavage of the carbon oxygen bond, with preferential attack at the terminal fluoromethoxy, CF3O. The oxidized iron surface did not passivate, but became more reactive with time. Perfluoro-1-methoxy-2-ethoxy propane and perfluoro-1,3-diethoxy propane desorbed prior to the observation of decomposition on the oxidized iron surface.

Fabrication methods and applications of microstructured gallium based liquid metal alloys

NASA Astrophysics Data System (ADS)

Khondoker, M. A. H.; Sameoto, D.

2016-09-01

This review contains a comparative study of reported fabrication techniques of gallium based liquid metal alloys embedded in elastomers such as polydimethylsiloxane or other rubbers as well as the primary challenges associated with their use. The eutectic gallium-indium binary alloy (EGaIn) and gallium-indium-tin ternary alloy (galinstan) are the most common non-toxic liquid metals in use today. Due to their deformability, non-toxicity and superior electrical conductivity, these alloys have become very popular among researchers for flexible and reconfigurable electronics applications. All the available manufacturing techniques have been grouped into four major classes. Among them, casting by needle injection is the most widely used technique as it is capable of producing features as small as 150 nm width by high-pressure infiltration. One particular fabrication challenge with gallium based liquid metals is that an oxide skin is rapidly formed on the entire exposed surface. This oxide skin increases wettability on many surfaces, which is excellent for keeping patterned metal in position, but is a drawback in applications like reconfigurable circuits, where the position of liquid metal needs to be altered and controlled accurately. The major challenges involved in many applications of liquid metal alloys have also been discussed thoroughly in this article.

Calcium phosphate-titanium composites for articulating surfaces of load-bearing implants.

PubMed

Bandyopadhyay, Amit; Dittrick, Stanley; Gualtieri, Thomas; Wu, Jeffrey; Bose, Susmita

2016-04-01

Calcium phosphate (CaP)-titanium (Ti) composites were processed using a commercial laser engineered net shaping (LENS™) machine to increase wear resistance of articulating surfaces of load-bearing implants. Such composites could be used to cover the surface of titanium implants and potentially increase the lifetime of a joint replacement. It was hypothesized that adding calcium phosphate to commercially pure titanium (CP-Ti) and Ti6Al4V alloy via laser processing would decrease the material loss when subjected to wear. This added protection would be due to the in situ formation of a CaP tribofilm. Different amounts of CaP were mixed by weight with pure Ti and Ti6Al4V powders. The mixed powders were then made into cylindrical samples using a commercial LENS™-750 system. Microstructures were observed and it was found the CaP had integrated into the titanium metal matrix. Compression test revealed that CaP significantly increased the 0.2% offset yield strength as well as the ultimate compressive strength of CP-Ti. It was found that the addition of CaP to pure titanium reduced the material loss and increased wear resistance. This was due to the formation of CaP tribofilm on the articulating surface. The in situ formed tribofilm also lowered the coefficient of friction and acted as a solid lubricant between the two interacting metal surfaces. Overall, CaP addition to Ti and its alloy Ti6Al4V show an effective way to minimize wear induced damage due to the formation of in situ tribofilm at the articulating surface, a strategy that can be utilized in various biomedical devices. Copyright © 2015 Elsevier Ltd. All rights reserved.

Terahertz transmission properties of an individual slit in a thin metallic plate.

PubMed

Lee, J W; Park, T H; Nordlander, Peter; Mittleman, Daniel M

2009-07-20

We report on the terahertz transmission properties through a single slit in a thin metallic film. The properties are studied by comparing the transmissions of TE- and TM-polarized electromagnetic waves over a broad spectral range from the geometrical regime to the subwavelength limit. In the geometrical regime, the remarkable terahertz transmission due to guided modes is observed even without the contribution of surface waves. Whereas in the subwavelength limit, the surface charge oscillations associated with the TM-polarized guided mode give rise to strong transmission enhancement. The nature of the mechanisms for the terahertz transmission is elucidated using theoretical simulations of the near-field distributions and electromagnetic energy flow.

Surface functionalization of metal organic frameworks for mixed matrix membranes

DOEpatents

Albenze, Erik; Lartey, Michael; Li, Tao; Luebke, David R.; Nulwala, Hunaid B.; Rosi, Nathaniel L.; Venna, Surendar R.

2017-03-21

Mixed Matrix Membrane (MMM) are composite membranes for gas separation and comprising a quantity of inorganic filler particles, in particular metal organic framework (MOF), dispersed throughout a polymer matrix comprising one or more polymers. This disclosure is directed to MOF functionalized through addition of a pendant functional group to the MOF, in order to improve interaction with a surrounding polymer matrix in a MMM. The improved interaction aids in avoiding defects in the MMM due to incompatible interfaces between the polymer matrix and the MOF particle, in turn increasing the mechanical and gas separation properties of the MMM. The disclosure is also directed to a MMM incorporating the surface functionalized MOF.

Plasmonic Films Can Easily Be Better: Rules and Recipes

PubMed Central

2015-01-01

High-quality materials are critical for advances in plasmonics, especially as researchers now investigate quantum effects at the limit of single surface plasmons or exploit ultraviolet- or CMOS-compatible metals such as aluminum or copper. Unfortunately, due to inexperience with deposition methods, many plasmonics researchers deposit metals under the wrong conditions, severely limiting performance unnecessarily. This is then compounded as others follow their published procedures. In this perspective, we describe simple rules collected from the surface-science literature that allow high-quality plasmonic films of aluminum, copper, gold, and silver to be easily deposited with commonly available equipment (a thermal evaporator). Recipes are also provided so that films with optimal optical properties can be routinely obtained. PMID:25950012

Reduction of metallosis in hip implant using thin film coating

NASA Astrophysics Data System (ADS)

Rajeshshyam, R.; Chockalingam, K.; Gayathri, V.; Prakash, T.

2018-04-01

Hip implant finds its emerging attraction due to it continuous demand over the years. The hip implants (femoral head) and acetabulum cup) mainly fabricated by metals such as stainless steel, cobalt chrome and titanium alloys, other than that ceramics and polyethylene have been used. The metal-on-metal hip implant was found to be best implant material for most of the surgeons due to its high surface finish, low wear rate and low chance of dislocation from its position after implanting. Where in metal based hip implant shows less wear rate of 0.01mm3/year. Metal-on-metal implant finds its advantage over other materials both in its mechanical and physical stability against human load. In M-O-M Cobalt- chromium alloys induce metal allergy. The metal allergy (particulate debris) that is generated by wear, fretting, fragmentation and which is unavoidable when a prosthesis is implanted, can induce an inflammatory reaction in some circumstances. The objectives of this research to evaluate thin film coating with Nano particle additives to reduce the wear leads to regarding metal ion release. Experimental results reveals that thin film Sol-Gel coating with 4wt. % of specimen reduced the cobalt and chromium ion release and reduces the wear rate. Wear rate reduced by 98% for 4wt. % graphene in 20N and 95% for 4wt. % graphene in 10N.

Metal segregation in hierarchically structured cathode materials for high-energy lithium batteries

DOE PAGES

Lin, Feng; Xin, Huolin L.; Nordlund, Dennis; ...

2016-01-11

Controlling surface and interfacial properties of battery materials is key to improving performance in rechargeable Li-ion devices. Surface reconstruction from a layered to a rock salt structure in metal oxide cathode materials is commonly observed and results in poor high-voltage cycling performance, impeding attempts to improve energy density. Hierarchically structured LiNi 0.4Mn 0.4Co 0.2O 2 (NMC-442) spherical powders, made by spray pyrolysis, exhibit local elemental distribution gradients that deviate from the global NMC-442 composition; specifically, they are Ni-rich and Mn-poor at particle surfaces. These materials demonstrate improved Coulombic efficiencies, discharge capacities, and high-voltage capacity retention in lithium half-cell configurations. Themore » subject powders show superior resistance against surface reconstruction due to the tailored surface chemistry, compared to conventional NMC-442 materials. This paves the way towards the development of a new generation of robust and stable high-energy NMC cathodes for Li-ion batteries.« less

Digital holographic profilometry of the inner surface of a pipe using a current-induced wavelength change of a laser diode.

PubMed

Yokota, Masayuki; Adachi, Toru

2011-07-20

Phase-shifting digital holography is applied to the measurement of the surface profile of the inner surface of a pipe for the detection of a hole in its wall. For surface contouring of the inner wall, a two-wavelength method involving an injection-current-induced wavelength change of a laser diode is used. To illuminate and obtain information on the inner surface, a cone-shaped mirror is set inside the pipe and moved along in a longitudinal direction. The distribution of a calculated optical path length in an experimental alignment is used to compensate for the distortion due to the misalignment of the mirror in the pipe. Using the proposed method, two pieces of metal sheet pasted on the inner wall of the pipe and a hole in the wall are detected. This shows that the three-dimensional profile of a metal plate on the inner wall of a pipe can be measured using simple image processing. © 2011 Optical Society of America

Microwelding of various metallic materials under ultravacuum (A0138-10)

NASA Technical Reports Server (NTRS)

Assie, J. P.

1984-01-01

In the space vacuum environment, the spacecraft mechanisms are liable to sustain damaging effects from microwelds due to molecular diffusion of the spacecraft constituent metals. Such microwelds result in a continuing increase in the friction factors and are even liable to jam the mechanisms altogether. The object of this experiment is to check the metal surfaces representative of the mechanism constituent metals (treated or untreated, lubricated or unlubricated) for microwelds afater an extended stay in the space environment. The experimental approach is to passively expose inert metal specimens to the space vacuum and to conduct end-of-mission verification of the significance of microwelds between various pairs of metal washers. The experiment will be located in one of the FRECOPA boxes in a 12-in. -deep peripheral tray that contains nine other experiments from France.

3D Architectured Graphene/Metal Oxide Hybrids for Gas Sensors: A Review

PubMed Central

Xia, Yi; Li, Ran; Chen, Ruosong; Wang, Jing; Xiang, Lan

2018-01-01

Graphene/metal oxide-based materials have been demonstrated as promising candidates for gas sensing applications due to the enhanced sensing performance and synergetic effects of the two components. Plenty of metal oxides such as SnO2, ZnO, WO3, etc. have been hybridized with graphene to improve the gas sensing properties. However, graphene/metal oxide nanohybrid- based gas sensors still have several limitations in practical application such as the insufficient sensitivity and response rate, and long recovery time in some cases. To achieve higher sensing performances of graphene/metal oxides nanocomposites, many recent efforts have been devoted to the controllable synthesis of 3D graphene/metal oxides architectures owing to their large surface area and well-organized structure for the enhanced gas adsorption/diffusion on sensing films. This review summarizes recent advances in the synthesis, assembly, and applications of 3D architectured graphene/metal oxide hybrids for gas sensing. PMID:29735951

Assessment of acid leachable trace metals in sediment cores from River Uppanar, Cuddalore, Southeast coast of India.

PubMed

Ayyamperumal, T; Jonathan, M P; Srinivasalu, S; Armstrong-Altrin, J S; Ram-Mohan, V

2006-09-01

An acid leachable technique is employed in core samples (C1, C2 and C3) to develop a baseline data on the sediment quality for trace metals of River Uppanar, Cuddalore, southeast coast of India. Acid leachable metals (Fe, Mn, Cr, Cu, Ni, Co, Pb, Zn and Cd) indicate peak values at the sulphidic phase and enrichment of metals in the surface layers are due to the anthropogenic activities. Association of trace metals with Fe, Mn indicates their adsorption onto Fe-Mn oxyhydroxides and their correlation with S indicate that they are precipitated as metal sulphides. Factor analysis identified three possible types of geochemical associations and the supremacy of trace metals along with Fe, Mn, S and mud supports their geochemical associations. Factor analysis also signifies that anthropogenic activities have affected both the estuarine and fresh water regions of River Uppanar.

Li Metal Anodes and Rechargeable Lithium Metal Batteries. Springer Series in Materials Science

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

Zhang, Jiguang; Xu, Wu; Henderson, Wesley A.

Lithium (Li) metal is an ideal anode material for rechargeable batteries. With the urgent need for the “next generation” rechargeable batteries, such as Li-S, Li-air batteries as well as rechargeable Li metal batteries using Li intercalation compounds as the cathode, the use of Li metal anode has attracted significant interests in recent years. Unfortunately, rechargeable batteries based on Li metal anode have not yet been commercialized mainly due to two barriers: one is the growth of Li dendrites and associated safety hazard, and another is the low Coulombic efficiency (CE) of Li cycling and associated early battery failure due tomore » Li powdering and increasing cell impedance. To have a high CE, minimum side reactions between freshly/native deposited Li and electrolyte has to be minimized. These reactions are proportional to the chemical and electrochemical activity of native Li when they are in direct contact with surrounding electrolyte. They are also proportional to the surface area of deposited Li. This means that high CE of Li deposition/stripping always related to a low surface area Li deposition and suppressed Li dendrite growth. Therefore, the enhancement of CE is a more fundamental factors controlling long term, stable cycling of Li metal anode. In this book, we will first review the general models of the dendrite growth mechanism. The effect of SEI layer on the modeling of Li dendrite growth will also be discussed. Then we will discuss various instruments/tools that are critical for the investigation of Li dendrite growth. In the Chapter 3, various factors which affect CE of Li cycling and dendrite growth will be discussed together with an emphasize on enhancement of CE. Chapter 4 of the book will discuss the specific application of Li metal anode in several key rechargeable Li metal batteries, including Li-air batteries, Li-S batteries and Li metal batteries using intercalation compounds as cathode. At last, the perspective on the future development and application of Li metal batteries will be discussed in the Chapter 5.« less

Heavy metals in Iberian soils: Removal by current adsorbents/amendments and prospective for aerogels.

PubMed

Vareda, João P; Valente, Artur J M; Durães, Luisa

2016-11-01

Heavy metals are dangerous pollutants that in spite of occurring naturally are released in major amounts to the environment due to anthropogenic activities. After being released in the environment, the heavy metals end up in the soils where they accumulate as they do not degrade, adversely affecting the biota. Because of the dynamic equilibria between soil constituents, the heavy metals may be present in different phases such as the solid phase (immobilized contaminants) or dissolved in soil solution. The latter form is the most dangerous because the ions are mobile, can leach and be absorbed by living organisms. Different methods for the decontamination of polluted soils have been proposed and they make use of two different approaches: mobilizing the heavy metals, which allows their removal from soil, or immobilization that maintains the metal concentrations in soils but keeps them in an inert form due to mechanisms like precipitation, complexation or adsorption. Mobilization of the heavy metals is known to cause leaching and increase plant uptake, so this treatment can cause greater problems. Aerogels are incredible nanostructured, lightweight materials with high surface area and tailorable surface chemistry. Their application in environmental cleaning has been increasing in recent years and very promising results have been obtained. The functionalization of the aerogels can give them the ability to interact with heavy metals, retaining the latter via strong adsorptive interactions. Thus, this review surveys the existing literature for remediation of soils using an immobilization approach, i.e. with soil amendments that increase the soil sorption/retention capacity for heavy metals. The considered framework was a set of heavy metals with relevance in polluted Iberian soils, namely Cd, Cr, Cu, Ni, Pb and Zn. Moreover, other adsorbents, especially aerogels, have been used for the removal of these contaminants from aqueous media; because groundwater and soil solution have dynamic equilibria with the soil solid phase, these works allowed to draw conclusions and perspectives for the use of aerogels not only as adsorbents in aqueous media but also as amendments for the remediation of heavy metal polluted soils. Copyright © 2016 Elsevier B.V. All rights reserved.

Temporal variability in trace metal solubility in a paddy soil not reflected in uptake by rice (Oryza sativa L.).

PubMed

Pan, Yunyu; Koopmans, Gerwin F; Bonten, Luc T C; Song, Jing; Luo, Yongming; Temminghoff, Erwin J M; Comans, Rob N J

2016-12-01

Alternating flooding and drainage conditions have a strong influence on redox chemistry and the solubility of trace metals in paddy soils. However, current knowledge of how the effects of water management on trace metal solubility are linked to trace metal uptake by rice plants over time is still limited. Here, a field-contaminated paddy soil was subjected to two flooding and drainage cycles in a pot experiment with two rice plant cultivars, exhibiting either high or low Cd accumulation characteristics. Flooding led to a strong vertical gradient in the redox potential (Eh). The pH and Mn, Fe, and dissolved organic carbon concentrations increased with decreasing Eh and vice versa. During flooding, trace metal solubility decreased markedly, probably due to sulfide mineral precipitation. Despite its low solubility, the Cd content in rice grains exceeded the food quality standards for both cultivars. Trace metal contents in different rice plant tissues (roots, stem, and leaves) increased at a constant rate during the first flooding and drainage cycle but decreased after reaching a maximum during the second cycle. As such, the high temporal variability in trace metal solubility was not reflected in trace metal uptake by rice plants over time. This might be due to the presence of aerobic conditions and a consequent higher trace metal solubility near the root surface, even during flooding. Trace metal solubility in the rhizosphere should be considered when linking water management to trace metal uptake by rice over time.

Reactive Molecular Dynamics Investigations of Alkoxysilane Sol-Gel and Surface Coating Processes

NASA Astrophysics Data System (ADS)

Deetz, Joshua David

The ability to generate nanostructured materials with tailored morphology or chemistry is of great technological interest. One proven method of generating metal-oxide materials, and chemically modifying metal-oxide surfaces is through the reactions of molecular building blocks known as alkoxysilanes. Alkoxysilanes are a class of chemicals which contain one or more organic alkoxy groups bonded to silicon atoms. Alkoxysilane (Si-O-R) chemical groups can undergo reactions to form bridges (Si-O-M) with metal oxides. Due to their ability to "attach" to metal-oxides through condensation reactions, alkoxysilanes have a number of interesting applications, such as: the generation of synthetic siloxane materials through the sol-gel process, and the formation of functionalized surface coatings on metal-oxide surfaces. Despite widespread study of sol-gel and surface coatings processes, it is difficult to predict the morphology of the final products due to the large number of process variables involved, such as precursor molecule structure, solvent effects, solution composition, temperature, and pH. To determine the influence of these variables on the products of sol-gel and coatings processes reactive molecular dynamics simulations are used. A reactive force field was used (ReaxFF) to allow the chemical bonds in simulation to dynamically form and break. The force field parameters were optimized using a parallel optimization scheme with a combination of experimental information, and density functional theory calculations. Polycondensation of alkoxysilanes in mixtures of alcohol and water were studied. Steric effects were observed to influence the rates of hydrolysis and condensation in solutions containing different precursor monomers. By restricting the access of nucleophiles to the central silicon atom, the nucleation rate of siloxanes can be controlled. The influence of solution precursor, water, and methanol composition on reaction rates was explored. It was determined that the rate of alkoxysilane hydrolysis is strongly dependent on the concentration of water. The dynamics of siloxane cluster formation are revealed, which provides insight for experimentalists. The silanization of hydroxylated silica surfaces by alkoxysilanes was modeled in pseudo-infinite liquid solution. Butyl-, octyl-, or dodecylsilanes were exposed to hydroxylated silica surfaces in order to observe the influence of silyl headgroup size on the morphology and formation kinetics of silane films on silica substrates. The radius of gyration and order parameter of the hydrocarbon silyl groups were found to increase with grafting density. This was the first simulation study of the dynamic grafting of alkoxysilanes to a substrate.

Enantioselective recognition at mesoporous chiral metal surfaces.

PubMed

Wattanakit, Chularat; Côme, Yémima Bon Saint; Lapeyre, Veronique; Bopp, Philippe A; Heim, Matthias; Yadnum, Sudarat; Nokbin, Somkiat; Warakulwit, Chompunuch; Limtrakul, Jumras; Kuhn, Alexander

2014-01-01

Chirality is widespread in natural systems, and artificial reproduction of chiral recognition is a major scientific challenge, especially owing to various potential applications ranging from catalysis to sensing and separation science. In this context, molecular imprinting is a well-known approach for generating materials with enantioselective properties, and it has been successfully employed using polymers. However, it is particularly difficult to synthesize chiral metal matrices by this method. Here we report the fabrication of a chirally imprinted mesoporous metal, obtained by the electrochemical reduction of platinum salts in the presence of a liquid crystal phase and chiral template molecules. The porous platinum retains a chiral character after removal of the template molecules. A matrix obtained in this way exhibits a large active surface area due to its mesoporosity, and also shows a significant discrimination between two enantiomers, when they are probed using such materials as electrodes.

Integration of Heat Treatment with Shot Peening of 17-4 Stainless Steel Fabricated by Direct Metal Laser Sintering

NASA Astrophysics Data System (ADS)

AlMangour, Bandar; Yang, Jenn-Ming

2017-11-01

Direct metal laser sintering (DMLS) is a promising powder-based additive manufacturing process for fabrication of near-net-shape parts. However, the typically poor fatigue performance of DMLS parts must be addressed for use in demanding industrial applications. Post-treatment can be applied to enhance the performance of such components. Earlier attempts at inducing grain refinement through severe plastic deformation of part surfaces using shot peening improved the physical and mechanical properties of metals without chemical alteration. However, heat treatment can modify the surface-hardening effects attained by shot peening. Hence, we examined the feasibility of applying shot peening combined with heat treatment to improve the performance of DMLS-fabricated 17-4 stainless steel parts through microstructural evolution studies and hardness measurements. Compared to a specimen treated only by shot peening, the sample exposed to additional heat treatment showed increased hardness due to aging of the dominant phase.

Development of an Innovative Laser-Assisted Coating Process for Extending Lifetime of Metal Casting Dies. Final Report

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

Madhav Rao Gonvindaraju

1999-10-18

Die casting dies used in the metal casting industry fail due to thermal fatigue cracking accompanied by the presence of residual tensile stresses, corrosion, erosion and wear of die surfaces. This phase 1 SBIR Final Report summarize Karta Technologies research involving the development of an innovative laser coating technology for metal casting dies. The process involves depositing complex protective coatings of nanocrystalline powders of TiC followed by a laser shot peening. The results indicate a significant improvement in corrosion and erosion resistance in molten aluminum for H13 die casting die steels. The laser-coated samples also showed improved surface finish, amore » homogeneous and uniform coating mircrostructure. The technology developed in this research can have a significant impact on the casting industry by saving the material costs involved in replacing dies, reducing downtime and improving the quality.« less

Plasma polymer-functionalized silica particles for heavy metals removal.

PubMed

Akhavan, Behnam; Jarvis, Karyn; Majewski, Peter

2015-02-25

Highly negatively charged particles were fabricated via an innovative plasma-assisted approach for the removal of heavy metal ions. Thiophene plasma polymerization was used to deposit sulfur-rich films onto silica particles followed by the introduction of oxidized sulfur functionalities, such as sulfonate and sulfonic acid, via water-plasma treatments. Surface chemistry analyses were conducted by X-ray photoelectron spectroscopy and time-of-flight secondary ion mass spectroscopy. Electrokinetic measurements quantified the zeta potentials and isoelectric points (IEPs) of modified particles and indicated significant decreases of zeta potentials and IEPs upon plasma modification of particles. Plasma polymerized thiophene-coated particles treated with water plasma for 10 min exhibited an IEP of less than 3.5. The effectiveness of developed surfaces in the adsorption of heavy metal ions was demonstrated through copper (Cu) and zinc (Zn) removal experiments. The removal of metal ions was examined through changing initial pH of solution, removal time, and mass of particles. Increasing the water plasma treatment time to 20 min significantly increased the metal removal efficiency (MRE) of modified particles, whereas further increasing the plasma treatment time reduced the MRE due to the influence of an ablation mechanism. The developed particulate surfaces were capable of removing more than 96.7% of both Cu and Zn ions in 1 h. The combination of plasma polymerization and oxidative plasma treatment is an effective method for the fabrication of new adsorbents for the removal of heavy metals.

Role of surfaces and interfaces in controlling the mechanical properties of metallic alloys.

PubMed

Lee, Won-Jong; Chia, Wen-Jui; Wang, Jinliu; Chen, Yanfeng; Vaynman, Semyon; Fine, Morris E; Chung, Yip-Wah

2010-11-02

This article explores the subtle effects of surfaces and interfaces on the mechanical properties of bulk metallic alloys using three examples: environmental effects on fatigue life, hydrogen embrittlement effects on the ductility of intermetallics, and the role of coherent precipitates in the toughness of steels. It is demonstrated that the marked degradation of the fatigue life of metals is due to the strong chemisorption of adsorbates on exposed slip steps that are formed during fatigue deformation. These adsorbates reduce the reversibility of slip, thus accelerating fatigue damage in a chemically active gas environment. For certain intermetallic alloys such as Ni(3)Al and Ni(3)Fe, the ductility depends on the ambient gas composition and the atomic ordering in these alloys, both of which govern the complex surface chemical reactions taking place in the vicinity of crack tips. Finally, it is shown that local stresses at a coherent precipitate-matrix interface can activate dislocation motion at low temperatures, thus improving the fracture toughness of bulk alloys such as steels at cryogenic temperatures. These examples illustrate the complex interplay between surface chemistry and mechanics, often yielding unexpected results.

Partitioning of metals in a degraded acid sulfate soil landscape: influence of tidal re-inundation.

PubMed

Claff, Salirian R; Sullivan, Leigh A; Burton, Edward D; Bush, Richard T; Johnston, Scott G

2011-11-01

The oxidation and acidification of sulfidic soil materials results in the re-partitioning of metals, generally to more mobile forms. In this study, we examine the partitioning of Fe, Cr, Cu, Mn, Ni and Zn in the acidified surface soil (0-0.1 m) and the unoxidised sub-soil materials (1.3-1.5 m) of an acid sulfate soil landscape. Metal partitioning at this acidic site was then compared to an adjacent site that was previously acidified, but has since been remediated by tidal re-inundation. Differences in metal partitioning were determined using an optimised six-step sequential extraction procedure which targets the "labile", "acid-soluble", "organic", "crystalline oxide", "pyritic" and "residual" fractions. The surficial soil materials of the acidic site had experienced considerable losses of Cr, Cu, Mn and Ni compared to the underlying parent material due to oxidation and acidification, yet only minor losses of Fe and Zn. In general, the metals most depleted from the acidified surface soil materials exhibited the greatest sequestration in the surface soil materials of the tidally remediated site. An exception to this was iron, which accumulated to highly elevated concentrations in the surficial soil materials of the tidally remediated site. The "acid-soluble", "organic" and "pyritic" fractions displayed the greatest increase in metals following tidal remediation. This study demonstrates that prolonged tidal re-inundation of severely acidified acid sulfate soil landscapes leads to the immobilisation of trace metals through the surficial accumulation of iron oxides, organic material and pyrite. Copyright © 2011 Elsevier Ltd. All rights reserved.

Photoluminescent Au-Ge composite nanodots formation on SiO2 surface by ion induced dewetting

NASA Astrophysics Data System (ADS)

Datta, D. P.; Siva, V.; Singh, A.; Kanjilal, D.; Sahoo, P. K.

2017-09-01

Medium energy ion irradiation on a bilayer of Au and Ge on SiO2 is observed to result in gradual morphological evolution from an interconnected network to a nanodot array on the insulator surface. Structural and compositional analyses reveal composite nature of the nanodots, comprising of both Au and Ge. The growing nanostructures are found to be photoluminescent at room temperature where the emission intensity and wavelengths vary with morphology. The growth of such nanostructures can be understood in terms of dewetting of the metal layer under ion irradiation due to ion-induced melting along the ion tracks. The visible PL emission is found to be related with evolution of the Au-Ge nanodots. The study indicates a route towards single step synthesis of metal-semiconductor nanodots on insulator surface.

Investigation of Selective Laser Melting Surface Alloyed Aluminium Metal Matrix Dispersive Reinforced Layers

NASA Astrophysics Data System (ADS)

Kamburov, V. V.; Dimitrova, R. B.; Kandeva, M. K.; Sofronov, Y. P.

2018-01-01

The aim of the paper is to investigate the improvement of mechanical properties and in particular wear resistance of laser surface alloyed dispersive reinforced thin layers produced by selective laser melting (SLM) technology. The wear resistance investigation of aluminium matrix composite layers in the conditions of dry friction surface with abrasive particles and nanoindentation tests were carried out. The process parameters (as scan speed) and their impact on the wear resistant layers have been evaluated. The alloyed layers containing metalized SiC particles were studied by Optical and Scanning Electron Microscopy (SEM) and Energy Dispersive X-ray microanalysis (EDX). The obtained experimental results of the laser alloyed thin layers show significant development of their wear resistance and nanohardness due to the incorporated reinforced phase of electroless nickel coated SiC particles.

Adsorption of Atoms of 3 d Metals on the Surfaces of Aluminum and Magnesium Oxide Films

NASA Astrophysics Data System (ADS)

Ramonova, A. G.; Kibizov, D. D.; Kozyrev, E. N.; Zaalishvili, V. B.; Grigorkina, G. S.; Fukutani, K.; Magkoev, T. T.

2018-01-01

The adsorption and formation of submonolayer structures of Ti, Cr, Fe, Ni, Cu on the surfaces of aluminum and magnesium oxide films formed on Mo(110) under ultrahigh vacuum conditions are studied via X-ray, ultraviolet photo-, and Auger electron spectroscopy (XPS, UVES, AES); spectroscopy of energy losses of high-resolution electrons (SELHRE); spectroscopy of the backscattering of low-energy ions (SBSLEI); infrared absorption spectroscopy (IAS); and the diffraction of slow electrons (DSE). Individual atoms and small clusters of all the investigated metals deposited on oxides acquire a positive charge, due presumably to interaction with surface defects. As the concentration of adatoms increases when the adsorption centers caused by defects are filled, charge transfer from adatoms to substrates is reduced. This is accompanied by further depolarization caused by the lateral interaction of adatoms.

Using expansive grasses for monitoring heavy metal pollution in the vicinity of roads.

PubMed

Vachová, Pavla; Vach, Marek; Najnarová, Eva

2017-10-01

We propose a method for monitoring heavy metal deposition in the vicinity of roads using the leaf surfaces of two expansive grass species which are greatly abundant. A principle of the proposed procedure is to minimize the number of operations in collecting and preparing samples for analysis. The monitored elements are extracted from the leaf surfaces using dilute nitric acid directly in the sample-collection bottle. The ensuing steps, then, are only to filter the extraction solution and the elemental analysis itself. The verification results indicate that the selected grasses Calamagrostis epigejos and Arrhenatherum elatius are well suited to the proposed procedure. Selected heavy metals (Zn, Cu, Pb, Ni, Cr, and Cd) in concentrations appropriate for direct determination using methods of elemental analysis can be extracted from the surface of leaves of these species collected in the vicinity of roads with medium traffic loads. Comparing the two species showed that each had a different relationship between the amounts of deposited heavy metals and distance from the road. This disparity can be explained by specific morphological properties of the two species' leaf surfaces. Due to the abundant occurrence of the two species and the method's general simplicity and ready availability, we regard the proposed approach to constitute a broadly usable and repeatable one for producing reproducible results. Copyright © 2017 Elsevier Ltd. All rights reserved.

Technological effect of vibroprocessing by flows of organic granular media

NASA Astrophysics Data System (ADS)

Lebedev, V. A.; Shishkina, A. P.; Davydova, I. V.; Morozova, A. V.

2018-03-01

The analysis of approaches to modeling of vibrational processing by granulated media is carried out. The vibroprocessing model which provides effective finishing of the surfaces of the parts due to the stone fruit organic media granules is developed. The model is based on the granule flow energy impact on the surface being treated. As the main characteristic of the organic media processing, a specific volumetric metal scrap is used, the physical meaning of which is the increase rate in the thickness of the material removed from the surface at a given velocity and pressure of the medium. It is shown that the metal scrap depends on the medium flow velocity, the height of the loading column of the granular medium, and the conditions for the formation of a medium stationary circulation motion. Based on the analysis of the results of experimental studies of the influence of amplitude-frequency characteristics on the removal of metal in the process of vibroprocessing with abrasive granules, the dependence of the specific volume metal removal is proposed for organic media processing, taking into account the threshold amplitude and frequency of oscillations of the working chamber, at which the effect of surface treatment is observed. The established set of relationships describing the effective conditions for vibroprocessing with stone organic media was obtained using experimental data, which allows us to assume that the model obtained is valid.

Heat Transfer Performances of Pool Boiling on Metal-Graphite Composite Surfaces

NASA Technical Reports Server (NTRS)

Zhang, Nengli; Chao, David F.; Yang, Wen-Jei

2000-01-01

Nucleate boiling, especially near the critical heat flux (CHF), can provide excellent economy along with high efficiency of heat transfer. However, the performance of nucleate boiling may deteriorate in a reduced gravity environment and the nucleate boiling usually has a potentially dangerous characteristic in CHF regime. That is, any slight overload can result in burnout of the boiling surface because the heat transfer will suddenly move into the film-boiling regime. Therefore, enhancement of nucleate boiling heat transfer becomes more important in reduced gravity environments. Enhancing nucleate boiling and critical heat flux can be reached using micro-configured metal-graphite composites as the boiling surface. Thermocapillary force induced by temperature difference between the graphite-fiber tips and the metal matrix, which is independent of gravity, will play an important role in bubble detachment. Thus boiling heat transfer performance does not deteriorate in a reduced-gravity environment. Based on the existing experimental data, and a two-tier theoretical model, correlation formulas are derived for nucleate boiling on the copper-graphite and aluminum-graphite composite surfaces, in both the isolated and coalesced bubble regimes. Experimental studies were performed on nucleate pool boiling of pentane on cooper-graphite (Cu-Gr) and aluminum-graphite (Al-Gr) composite surfaces with various fiber volume concentrations for heat fluxes up to 35 W per square centimeter. It is revealed that a significant enhancement in boiling heat transfer performance on the composite surfaces is achieved, due to the presence of micro-graphite fibers embedded in the matrix. The onset of nucleate boiling (the isolated bubble regime) occurs at wall superheat of about 10 C for the Cu-Gr surface and 15 C for the Al-Gr surface, much lower than their respective pure metal surfaces. Transition from an isolated bubble regime to a coalesced bubble regime in boiling occurs at a superheat of about 14 C on Cu-Gr surface and 19 C on Al-Gr surface.

Two dimensional layered materials: First-principle investigation

NASA Astrophysics Data System (ADS)

Tang, Youjian

Two-dimensional layered materials have emerged as a fascinating research area due to their unique physical and chemical properties, which differ from those of their bulk counterparts. Some of these unique properties are due to carriers and transport being confined to 2 dimensions, some are due to lattice symmetry, and some arise from their large surface area, gateability, stackability, high mobility, spin transport, or optical accessibility. How to modify the electronic and magnetic properties of two-dimensional layered materials for desirable long-term applications or fundamental physics is the main focus of this thesis. We explored the methods of adsorption, intercalation, and doping as ways to modify two-dimensional layered materials, using density functional theory as the main computational methodology. Chapter 1 gives a brief review of density functional theory. Due to the difficulty of solving the many-particle Schrodinger equation, density functional theory was developed to find the ground-state properties of many-electron systems through an examination of their charge density, rather than their wavefunction. This method has great application throughout the chemical and material sciences, such as modeling nano-scale systems, analyzing electronic, mechanical, thermal, optical and magnetic properties, and predicting reaction mechanisms. Graphene and transition metal dichalcogenides are arguably the two most important two-dimensional layered materials in terms of the scope and interest of their physical properties. Thus they are the main focus of this thesis. In chapter 2, the structure and electronic properties of graphene and transition metal dichalcogenides are described. Alkali adsorption onto the surface of bulk graphite and metal intecalation into transition metal dichalcogenides -- two methods of modifying properties through the introduction of metallic atoms into layered systems -- are described in chapter 2. Chapter 3 presents a new method of tuning the electronic properties of 2D materials: resonant physisorption. An example is given for adsorption of polycyclic aromatic hydrocarbon molecules onto graphene. The energy levels of these molecules were fine tuned to make them resonate with the graphene Fermi level, thus enhancing the strength of their effect on the graphene electronic structure. Chapter 4 develops the idea of coupling two distinct surface adsorption systems across a suspended atomically thin membrane. We examine a system of dual-sided adsorption of potassium onto a graphene membrane. The sequence of adsorption patterns predicted undergoes a striking devil's staircase of intermediate coverage fractions as the difference in adsorbate chemical potential between the two sides of the membrane varies. Chapter 5 is devoted to magnetic and band structure engineering of transition metal dichalcogenides through introduction of magnetic atoms into the lattice. Semiconducting transition metal dichalcogenide systems such as MoS2 and WS2 have band gaps suitable for electronic and optoelectronic applications, but are not magnetic. By intercalating and doping in a carefully designed stoichiometric ratio that precisely controls the occupation and relative placement of the dopant and host levels, we can convert a semiconducting transition metal dichalcogenide system into a half-metal or -- more surprisingly -- a half-semiconductor, where the conduction band is fully spin polarized and the energy scale for magnetism is the band gap.

Role of bond adaptability in the passivation of colloidal quantum dot solids.

PubMed

Thon, Susanna M; Ip, Alexander H; Voznyy, Oleksandr; Levina, Larissa; Kemp, Kyle W; Carey, Graham H; Masala, Silvia; Sargent, Edward H

2013-09-24

Colloidal quantum dot (CQD) solids are attractive materials for photovoltaic devices due to their low-cost solution-phase processing, high absorption cross sections, and their band gap tunability via the quantum size effect. Recent advances in CQD solar cell performance have relied on new surface passivation strategies. Specifically, cadmium cation passivation of surface chalcogen sites in PbS CQDs has been shown to contribute to lowered trap state densities and improved photovoltaic performance. Here we deploy a generalized solution-phase passivation strategy as a means to improving CQD surface management. We connect the effects of the choice of metal cation on solution-phase surface passivation, film-phase trap density of states, minority carrier mobility, and photovoltaic power conversion efficiency. We show that trap passivation and midgap density of states determine photovoltaic device performance and are strongly influenced by the choice of metal cation. Supported by density functional theory simulations, we propose a model for the role of cations, a picture wherein metals offering the shallowest electron affinities and the greatest adaptability in surface bonding configurations eliminate both deep and shallow traps effectively even in submonolayer amounts. This work illustrates the importance of materials choice in designing a flexible passivation strategy for optimum CQD device performance.

Optical fiber sensors for damage analysis in aerospace materials

NASA Technical Reports Server (NTRS)

Schindler, Paul; May, Russell; Claus, Richard

1995-01-01

Under this grant, fiber optic sensors were investigated for use in the nondestructive evaluation of aging aircraft. Specifically, optical fiber sensors for detection and location of impacts on a surface, and for detection of corrosion in metals were developed. The use of neural networks was investigated for determining impact location by processing the output of a network of fiberoptic strain sensors distributed on a surface. This approach employs triangulation to determine location by comparing the arrival times at several sensors, of the acoustic signal generated by the impact. For this study, a neural network simulator running on a personal computer was used to train a network using a back-propagation algorithm. Fiber optic extrinsic Fabry-Perot interferometer (EFPI) strain sensors are attached to or embedded in the surface, so that stress waves emanating from an impact can be detected. The ability of the network to determine impact location by time-or-arrival of acoustic signals was assessed by comparing network outputs with actual experimental results using impacts on a panel instrumented with optical fiber sensors. Using the neural network to process the sensor outputs, the impact location can be inferred to centimeter range accuracy directly from the arrival time data. In addition, the network can be trained to determine impact location, regardless of material anisotropy. Results demonstrate that a back-propagation network identifies impact location for an anisotropic graphite/bismaleimide plate with the same accuracy as that for an isotropic aluminum plate. Two different approaches were investigated for the development of fiber optic sensors for corrosion detection in metals, both utilizing optical fiber sensors with metal coatings. In the first approach, an extrinsic Fabry-Perot interferometric fiber optic strain sensor was placed under tensile stress, and while in the resulting strained position, a thick coating of metal was applied. Due to an increase in the quantity of material, the sensor does not return to its original position upon removal of the applied stress, and some residual strain is maintained within the sensor element. As the metal thickness decreases due to corrosion, this strain is released, providing the sensing mechanism for corrosion detection. In the second approach, photosensitive optical fibers with long period Bragg gratings in the core were coated with metal. The Bragg gratings serve to couple core modes at discrete wavelengths to cladding modes. Since cladding modes interact with the metal coating surrounding the fiber cladding, the specific wavelengths coupled from core to cladding depend on the refractive index of the metal coating. Therefore, as the metal corrodes, the resulting change in index of the coating may be measured by measuring the change in wavelength of the coupled mode. Results demonstrate that both approaches can be successfully used to track the loss in metal coating on the optical fiber sensors due to corrosion.

Mechanistic study on antibacterial action of zinc oxide nanoparticles synthesized using green route.

PubMed

Happy Agarwal; Soumya Menon; Venkat Kumar, S; Rajeshkumar, S

2018-04-25

A large array of diseases caused by bacterial pathogens and origination of multidrug resistance in their gene provokes the need of developing new vectors or novel drug molecules for effective drug delivery and thus, better treatment of disease. The nanoparticle has emerged as a novel drug molecule in last decade and has been used in various industrial fields like cosmetics, healthcare, agricultural, pharmaceuticals due to their high optical, electronic, medicinal properties. Use of nanoparticles as an antibacterial agent remain in current studies with metal nanoparticles like silver, gold, copper, iron and metal oxide nanoparticles like zinc oxide, copper oxide, titanium oxide and iron oxide nanoparticles. The high anti-bacterial activity of nanoparticles is due to their large surface area to volume ratio which allows binding of a large number of ligands on nanoparticle surface and hence, its complexation with receptors present on the bacterial surface. Green synthesis of Zinc Oxide Nanoparticle (ZnO NP) and its anti-bacterial application has been particularly discussed in the review literature. The present study highlights differential nanoparticle attachment to gram + and gram - bacterial surface and different mechanism adopted by nanoparticle for bacterial control. Pharmacokinetics and applications of ZnO NP are also discussed briefly. Copyright © 2018 Elsevier B.V. All rights reserved.

Growth morphology and properties of metals on graphene

DOE PAGES

Liu, Xiaojie; Han, Yong; Evans, James W.; ...

2015-12-01

Graphene, a single atomic layer of graphite, has been the focus of recent intensive studies due to its novel electronic and structural properties. With this study, metals grown on graphene also have been of interest because of their potential use as metal contacts in graphene devices, for spintronics applications, and for catalysis. All of these applications require good understanding and control of the metal growth morphology, which in part reflects the strength of the metal–graphene bond. The interaction between graphene and metal is sufficiently strong to modify the electronic structure of graphene is also of great importance. We will discussmore » recent experimental and computational studies related to deposition of metals on graphene supported on various substrates (SiC, SiO 2, and hexagonal close-packed metal surfaces). Of specific interest are the metal–graphene interactions (adsorption energies and diffusion barriers of metal adatoms), and the crystal structures and thermal stability of the metal nanoclusters.« less

Spatial distribution of heavy metals in surficial sediments from Guanabara Bay: Rio de Janeiro, Brazil

NASA Astrophysics Data System (ADS)

Neto, José Antônio Baptista; Gingele, Franz Xaver; Leipe, Thomas; Brehme, Isa

2006-04-01

Ninety-two surface sediment samples were collected in Guanabara Bay, one of the most prominent urban bays in SE Brazil, to investigate the spatial distribution of anthropogenic pollutants. The concentrations of heavy metals, organic carbon and particle size were examined in all samples. Large spatial variations of heavy metals and particle size were observed. The highest concentrations of heavy metals were found in the muddy sediments from the north western region of the bay near the main outlets of the most polluted rivers, municipal waste drainage systems and one of the major oil refineries. Another anomalous concentration of metals was found adjacent to Rio de Janeiro Harbour. The heavy metal concentrations decrease to the northeast, due to intact rivers and the mangrove systems in this area, and to the south where the sand fraction and open-marine processes dominate. The geochemical normalization of metal data to Li or Al has also demonstrated that the anthropogenic input of heavy metals have altered the natural sediment heavy metal distribution.

Metal-enhanced fluorescence platforms based on plasmonic ordered copper arrays: wavelength dependence of quenching and enhancement effects.

PubMed

Sugawa, Kosuke; Tamura, Takahiro; Tahara, Hironobu; Yamaguchi, Daisuke; Akiyama, Tsuyoshi; Otsuki, Joe; Kusaka, Yasuyuki; Fukuda, Nobuko; Ushijima, Hirobumi

2013-11-26

Ordered arrays of copper nanostructures were fabricated and modified with porphyrin molecules in order to evaluate fluorescence enhancement due to the localized surface plasmon resonance. The nanostructures were prepared by thermally depositing copper on the upper hemispheres of two-dimensional silica colloidal crystals. The wavelength at which the surface plasmon resonance of the nanostructures was generated was tuned to a longer wavelength than the interband transition region of copper (>590 nm) by controlling the diameter of the underlying silica particles. Immobilization of porphyrin monolayers onto the nanostructures was achieved via self-assembly of 16-mercaptohexadecanoic acid, which also suppressed the oxidation of the copper surface. The maximum fluorescence enhancement of porphyrin by a factor of 89.2 was achieved as compared with that on a planar Cu plate (CuP) due to the generation of the surface plasmon resonance. Furthermore, it was found that while the fluorescence from the porphyrin was quenched within the interband transition region, it was efficiently enhanced at longer wavelengths. It was demonstrated that the enhancement induced by the proximity of the fluorophore to the nanostructures was enough to overcome the highly efficient quenching effects of the metal. From these results, it is speculated that the surface plasmon resonance of copper has tremendous potential for practical use as high functional plasmonic sensor and devices.

Effects of drying-wetting and freezing-thawing cycle on leachability of metallic elements in mine soils

NASA Astrophysics Data System (ADS)

Bang, H.; Kim, J.; Hyun, S.

2016-12-01

Mine leachate derived from contaminated mine sites with metallic elements can pose serious risks on human society and environment. Only labile fraction of metallic elements in mine soils is subject to leaching and movement by rainfall. Lability of metallic element in soil is a function of bond strengths between metal and soil surfaces, which is influenced by environmental condition (e.g., rainfall intensity, duration, temperature, etc.) The purpose of this study was to elucidate the effects of various climate conditions on the leaching patterns and lability of metallic elements in mine soils. To do this, two mine soils were sampled from two abandoned mine sites located in Korea. Leaching test were conducted using batch decant-refill method. Various climatic conditions were employed in leaching test such as (1) oven drying (40oC) - wetting cycles, (2) air drying (20oC) - wetting cycle, and (3) freezing (-40oC) - thawing cycles. Duration of drying and freezing were varied from 4 days to 2 weeks. Concentration of metallic elements, pH, Eh and concentration of dissolved iron and sulfate in leachate from each leaching process was measured. To identify the changes of labile fraction in mine soils after each of drying or freezing period, sequential extraction procedure (five fraction) was used to compare labile fraction (i.e., F1 + F2) of metallic elements. The concentration of metallic elements in mine leachate was increased after drying and freezing procedure. The amounts of released metallic element from mine soils was changed depending on their drying or freezing period. In addition, labile fraction of metallic elements in soil was also changed after drying and freezing. The changes in labile fraction after drying and freezing might be due to the increased soil surface area by pore water volume expansion. Further study is therefore needed to evaluate the impact of altered physical properties of soils such as hydration of soil surface area and shrinking by drying and freezing cycles.

Model of thermal fatigue of a copper surface under the action of high-power microwaves

NASA Astrophysics Data System (ADS)

Kuzikov, S. V.; Plotkin, M. E.

2007-10-01

The accelerating structures of modern supercolliders, as well as the components of high-power microwave electron devices operated in strong cyclic electromagnetic fields should have long lifetimes. Along with the electric breakdown, the surfaces of these microwave components deteriorate and their lifetimes decrease due to thermal strains and subsequent mechanical loads on the surface metal layer. The elementary theory of thermal fatigue was developed in the 1970s. In particular, a model of metal as a continuous medium was considered. Within the framework of this model, thermal fatigue is caused by the strains arising between the hot surface layer and the cold internal layer of the metal. However, this theory does not describe all the currently available experimental data. In particular, the notion of “safe temperature” of the heating, i.e., temperature at which the surface is not destroyed during an arbitrarily long series of pulses, which was proposed in the theoretical model, is in poor agreement with the experiment performed in the Stanford Linear Accelerator Center (SLAC, USA). In this work, the thermal-fatigue theory is developed on the basis of consideration of the copper polycrystalline structure. The necessity to take it into account was demonstrated by the results of the SLAC experiment, in which a change in the mutual orientation of copper grains and the formation of cracks at their boundaries was recorded for the first time. The developed theory makes it possible to use the experimental data to refine the coefficients in the obtained formulas for the lifetime of the metal surface and to predict the number of microwave pulses before its destruction as a function of the radiation power, the surface-temperature increase at the pulse peak, and the pulse duration.

Electro-Reduction of Nitrogen on Molybdenum Nitride: Structure, Energetics, and Vibrational Spectra from DFT

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

Matanovic, Ivana; Garzon, Fernando; Henson, Neil J.

2014-02-21

We used density functional theory to study the electrochemical conversion of nitrogen to ammonia on the (001), (100/010), (101), and (111) surfaces of g-Mo2N. Based on the calculated free energy profiles for the reduction of nitrogen by the associative and dissociative mechanisms, reactivity was found to decrease in the order (111) > (101) > (100/010) E (001). Namely, the cell potentials needed to drive the reduction to ammonia increase in the following order: *0.7 V on (111), *1.2 V on (101), and *1.4 V on (100/010) and (001) surfaces. The (111) surface was found to be the most reactive formore » nitrogen due to (i) its ability to adsorb the N2 in the side-on position which activates N–N bonding and (ii) its high affinity for N-adatoms which also prevents accumulation of H-adatoms on the catalytic surface at low cell potentials. We have also calculated vibrational frequencies of different NxHy species adsorbed on various g-Mo2N surfaces. The frequencies are found to depend strongly on the type of the binding sites available on the crystal facets. A comparison of the calculated frequencies with the frequencies of the corresponding species in transition metal complexes and other metal surfaces shows that the frequencies of several signature modes fall in a similar region and might be used to assign the spectra of hydrogen and nitrogen containing surface species on different metal surfaces.« less

On the stability of the electronic system in transition metal dichalcogenides.

PubMed

Faraggi, M N; Zubizarreta, X; Arnau, A; Silkin, V M

2016-05-11

Based on first-principles calculations, we prove that the origin of charge-density wave formation in metallic layered transition metal dichalcogenides (TMDC) is not due to an electronic effect, like the Fermi surface (FS) nesting, as it had been proposed. In particular, we consider NbSe2, NbS2, TaSe2, and TaS2 as representative examples of 2H-TMDC polytypes. Our main result consists that explicit inclusion of the matrix elements in first-principles calculations of the electron susceptibility [Formula: see text] removes, due to strong momentum dependence of the matrix elements, almost all the information about the FS topologies in the resulting [Formula: see text]. This finding strongly supports an interpretation in which the momentum dependence of the electron-phonon interaction is the only reason why the phenomenon of charge-density waves appears in this class of materials.

Studies on adsorption capacity of clay-Sargassum sp biosorbent for Cr (VI) removal in wastewater from electroplating industry

NASA Astrophysics Data System (ADS)

Aprianti, Tine; Aprilyanti, Selvia; Apriani, Rachmawati; Sisnayati

2017-11-01

Various raw biosorbents have been studied for pollutant treatment of heavy metals contained in wastewater. In this study, clay and brown seaweed, Sargassum sp, are used for hexavalent chromium [Cr (VI)] biosorption. The adsorption capacity is adequately improved by combining clay and Sargassum sp as the adsorbent agent. Ion exchange of metal ions has shown strong coordination cross-linkage due to organic functional hydroxyl groups (OH-) contained in brown seaweed that provide sites to capture and bind the metal ions. Clay is known as an inexpensive adsorbent due to its wide availability besides its large specific surface area. Combining clay and Sargassum sp as biosorbent resulting better adsorption, the adsorption capacity reaches most favorable results of 99.39% at Sargassum: clay ratio of 40:60 on contact time 10 h. This study has proven that composit biosorbent used has succeeded in reducing hexavalent chromium pollutant in wastewater.

Revision of Articular Surface Replacement (ASR) Total Hip Arthroplasty: Correlation of Perioperative Data and Early Post-Revision Outcome Results.

PubMed

Cip, Johannes; Bach, Christian; Widemschek, Mark; Luegmair, Matthias; Martin, Arno

2015-09-01

The articular surface replacement (ASR) total hip arthroplasty (THA) showed accelerated failure rates due to adverse-reaction to metal debris (ARMD). Literature correlating preoperative with intraoperative revision findings respectively post-revision outcome results are rare. 30 of 99 available ASR THA were revised due to ARMD. Mean post-revision follow-up term was 2.3 years. In part, preoperative data did not correlate with intraoperative revision findings. ARMD was even found in asymptomatic patients with non-elevated ion levels. Postoperative pain and metal ions decreased significantly (P ≤ 0.016). Cobalt decreased faster than chrome. Patients with intraoperative pseudotumors, osteolysis or bilateral THA did not have higher pre- or postoperative ion values (P ≥ 0.053). Females showed higher postoperative chrome levels (P=0.031). One major post-revision complication (femoral nerve palsy) and one re-revision (late onset infection) occurred. Copyright © 2015 Elsevier Inc. All rights reserved.

Method of coating metal surfaces to form protective metal coating thereon

DOEpatents

Krikorian, Oscar H.; Curtis, Paul G.

1992-01-01

A process is disclosed for forming a protective metal coating on a metal surface using a flux consisting of an alkali metal fluoride, an alkaline earth metal fluoride, an alkali metal fluoaluminate, an alkali metal fluosilicate, and mixtures thereof. The flux, in particulate form, is mixed with particles of a metal coating material which may comprise aluminum, chromium, mixtures thereof, and alloys containing at least 50 wt. % aluminum and the particulate mixture is applied to the metal surface in a single step, followed by heating the coated metal surface to a temperature sufficient to cause the metal coating material to react with the metal surface to form a protective reaction product in the form of a metal coating bonded to the metal surface. The metal surface which reacts with the metal coating material to form the protective coating may comprise Fe, Co, Ni, Ti, V, Cr, Mn, Zr, Nb, Mo, Tc, Hf, Ta, W, Re and alloys thereof.

Method of coating metal surfaces to form protective metal coating thereon

DOEpatents

Krikorian, O.H.; Curtis, P.G.

1992-03-31

A process is disclosed for forming a protective metal coating on a metal surface using a flux consisting of an alkali metal fluoride, an alkaline earth metal fluoride, an alkali metal fluoaluminate, an alkali metal fluosilicate, and mixtures thereof. The flux, in particulate form, is mixed with particles of a metal coating material which may comprise aluminum, chromium, mixtures thereof, and alloys containing at least 50 wt. % aluminum and the particulate mixture is applied to the metal surface in a single step, followed by heating the coated metal surface to a temperature sufficient to cause the metal coating material to react with the metal surface to form a protective reaction product in the form of a metal coating bonded to the metal surface. The metal surface which reacts with the metal coating material to form the protective coating may comprise Fe, Co, Ni, Ti, V, Cr, Mn, Zr, Nb, Mo, Tc, Hf, Ta, W, Re and alloys thereof. 1 figure.

Rubber pad forming - Efficient approach for the manufacturing of complex structured sheet metal blanks for food industry

NASA Astrophysics Data System (ADS)

Spoelstra, Paul; Djakow, Eugen; Homberg, Werner

2017-10-01

The production of complex organic shapes in sheet metals is gaining more importance in the food industry due to increasing functional and hygienic demands. Hence it is necessary to produce parts with complex geometries promoting cleanability and general sanitation leading to improvement of food safety. In this context, and especially when stainless steel has to be formed into highly complex geometries while maintaining desired surface properties, it is inevitable that alternative manufacturing processes will need to be used which meet these requirements. Rubber pad forming offers high potential when it comes to shaping complex parts with excellent surface quality, with virtually no tool marks and scratches. Especially in cases where only small series are to be produced, rubber pad forming processes offers both technological and economic advantages. Due to the flexible punch, variation in metal thickness can be used with the same forming tool. The investments to set-up Rubber pad forming is low in comparison to conventional sheet metal forming processes. The process facilitates production of shallow sheet metal parts with complex contours and bends. Different bending sequences in a multiple tool set-up can also be conducted. The planned contribution thus describes a brief overview of the rubber pad technology. It shows the prototype rubber pad forming machine which can be used to perform complex part geometries made from stainless steel (1.4301). Based on an analysis of the already existing systems and new machines for rubber pad forming processes, together with their process properties, influencing variables and areas of application, some relevant parts for the food industry are presented.

Free Carrier Induced Spectral Shift for GaAs Filled Metallic Hole Arrays

DTIC Science & Technology

2012-03-13

Bahae , G. I . Stegeman, K. Al-hemyari, J. S. Aitchison, and C. N. Ironside, “Limitation due to three-photon absorption on the useful spectral range...Free carrier induced spectral shift for GaAs filled metallic hole arrays Jingyu Zhang 1,2,* , Bin Xiang 3 , Mansoor Sheik- Bahae 4 , and S. R. J...OCIS codes: (310.6628) Subwavelength structures;(190.4350) Nonlinear optics at surfaces References and links 1. J. M. Luther, P. K. I . Jain, T. Ewers

Melt layer erosion of metallic armour targets during off-normal events in tokamaks

NASA Astrophysics Data System (ADS)

Bazylev, B.; Wuerz, H.

2002-12-01

Melt layer erosion by melt motion is the dominating erosion mechanism for metallic armours under high heat loads. A 1-D fluid dynamics simulation model for calculation of melt motion was developed and validated against experimental results for tungsten from the e-beam facility JEBIS and beryllium from the e-beam facility JUDITH. The driving force in each case is the gradient of the surface tension. Due to the high velocity which develops in the Be melt considerable droplet splashing occurs.

Surface plasmons in new waveguide structures containing ultra-thin metal and silicon layers

NASA Astrophysics Data System (ADS)

Shabat, M. M.; Ubeid, M. F.; Abu Rahma, M. A.

2018-05-01

Reflected and transmitted powers due to the interaction of electromagnetic waves with a structure containing thin metal and silicon layer are investigated in more detail. The formulations for the transverse electric wave case are provided. Transfer matrix method is used to find the reflection and the transmission coefficients at each interface. Numerical results are presented to show the effect of the structure parameters, the incidence angle and the wavelength on the reflected, transmitted and loss powers.

Superplasticity. Revision

DTIC Science & Technology

1989-09-01

angle to the applied tension and failure rapidly follows, as the volume of metal now deforming is small. Local necking Contributes virtually nothing...into components. It is thought that the 9 phase may be responsible for grain refinement, but it may be due to minute traces of oxide on the original...order to minimize oxidation and related detrimental surface degradation due to the reactivity of titanium. The use of such protective gases is not

Development of 1-m primary mirror for a spaceborne camera

NASA Astrophysics Data System (ADS)

Kihm, Hagyong; Yang, Ho-Soon; Rhee, Hyug-Gyo; Lee, Yun-Woo

2015-09-01

We present the development of a 1-m lightweight mirror system for a spaceborne electro-optical camera. The mirror design was optimized to satisfy the performance requirements under launch loads and space environment. The mirror made of Zerodur® has pockets at the back surface and three square bosses at the rim. Metallic bipod flexures support the mirror at the bosses and adjust the mirror's surface distortion due to gravity. We also show an analytical formulation of the bipod flexure, where compliance and stiffness matrices of the bipod flexure are derived to estimate theoretical performance and to make initial design guidelines. Optomechanical performances such as surface distortions due to gravity is explained. Environmental verification of the mirror is achieved by vibration tests.

Surface Mechanoengineering of a Zr-based Bulk Metallic Glass via Ar-Nanobubble Doping to Probe Cell Sensitivity to Rigid Materials

DOE PAGES

Huang, Lu; Tian, Mengkun; Wu, Dong; ...

2017-11-24

In this paper, a new materials platform, utilizing the amorphous microstructure of bulk metallic glasses (BMGs) and the versatility of ion implantation, was developed for the fundamental investigation of cell responses to substrate-rigidity variations in the gigapascal modulus range, which was previously unattainable with polymeric materials. The surface rigidity of a Zr-Al- Ni-Cu-Y BMG was modulated with low-energy Ar-ion implantation owing to the impartment of Ar nanobubbles into the amorphous matrix. Surface softening was achieved due to the formation of nanobubble-doped transitional zones in the Zrbased BMG substrate. Bone-forming cell studies on this newly designed platform demonstrated that mechanical cues,more » accompanied with the potential effects of other surface properties (i.e. roughness, morphology, and chemistry), contributed to modulating cell behaviors. Cell adhesion and actin filaments were found to be less established on less stiff surfaces, especially on the surface with an elastic modulus of 51 GPa. Cell growth appeared to be affected by surface mechanical properties. A lower stiffness was generally related to a higher growth rate. Findings in this study broadened our fundamental understanding concerning the mechanosensing of bone cells on stiff substrates. It also suggests that surface mechano-engineering of metallic materials could be a potential strategy to promote osseointegration of such materials for bone-implant applications. Further investigations are proposed to fine tune the ion implantation variables in order to further distinguish the surface-mechanical effect on bone-forming cell activities from the contributions of other surface properties.« less

Laser Driven Compression Equations of State and Hugoniot Pressure Measurements in Thick Solid Metallic Targets at ˜0.17-13 TW/cm2

NASA Astrophysics Data System (ADS)

Remo, John L.

2010-10-01

An electro-optic laser probe was developed to obtain parameters for high energy density equations of state (EoS), Hugoniot pressures (PH), and strain rates for high energy density laser irradiation intensity, I, experiments at ˜170 GW/cm2 (λ = 1064 nm) to ˜13 TW/cm2 (λ = 527 nm) on Al, Cu, Ti, Fe, Ni metal targets in a vacuum. At I ˜7 TW/cm2 front surface plasma pressures and temperatures reached 100's GPa and over two million K. Rear surface PH ranged from 7-120 GPa at average shock wave transit velocities 4.2-8.5 km/s, depending on target thickness and I. A surface plasma compression ˜100's GPa generated an impulsive radial expanding shock wave causing compression, rarefactions, and surface elastic and plastic deformations depending on I. A laser/fiber optic system measured rear surface shock wave emergence and particle velocity with ˜3 GHz resolution by monitoring light deflection from diamond polished rear surfaces of malleable metallic targets, analogous to an atomic force microscope. Target thickness, ˜0.5-2.9 mm, prevented front surface laser irradiation penetration, due to low radiation skin depth, from altering rear surface reflectivity (refractive index). At ˜10 TW electromagnetic plasma pulse noise generated from the target chamber overwhelmed detector signals. Pulse frequency analysis using Moebius loop antennae probed transient noise characteristics. Average shock (compression) and particle (rear surface displacement) velocity measurements determined rear surface PH and GPa) EoS that are compared with gas guns.

Surface Mechanoengineering of a Zr-based Bulk Metallic Glass via Ar-Nanobubble Doping to Probe Cell Sensitivity to Rigid Materials

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

Huang, Lu; Tian, Mengkun; Wu, Dong

In this paper, a new materials platform, utilizing the amorphous microstructure of bulk metallic glasses (BMGs) and the versatility of ion implantation, was developed for the fundamental investigation of cell responses to substrate-rigidity variations in the gigapascal modulus range, which was previously unattainable with polymeric materials. The surface rigidity of a Zr-Al- Ni-Cu-Y BMG was modulated with low-energy Ar-ion implantation owing to the impartment of Ar nanobubbles into the amorphous matrix. Surface softening was achieved due to the formation of nanobubble-doped transitional zones in the Zrbased BMG substrate. Bone-forming cell studies on this newly designed platform demonstrated that mechanical cues,more » accompanied with the potential effects of other surface properties (i.e. roughness, morphology, and chemistry), contributed to modulating cell behaviors. Cell adhesion and actin filaments were found to be less established on less stiff surfaces, especially on the surface with an elastic modulus of 51 GPa. Cell growth appeared to be affected by surface mechanical properties. A lower stiffness was generally related to a higher growth rate. Findings in this study broadened our fundamental understanding concerning the mechanosensing of bone cells on stiff substrates. It also suggests that surface mechano-engineering of metallic materials could be a potential strategy to promote osseointegration of such materials for bone-implant applications. Further investigations are proposed to fine tune the ion implantation variables in order to further distinguish the surface-mechanical effect on bone-forming cell activities from the contributions of other surface properties.« less

Substrate dependent structure of adsorbed aryl isocyanides studied by sum frequency generation (SFG) spectroscopy.

PubMed

Ito, Mikio; Noguchi, Hidenori; Ikeda, Katsuyoshi; Uosaki, Kohei

2010-04-07

Effects of metal substrate on the bonding nature of isocyanide group of two aryl isocyanides, 1,4-phenylene diisocyanide (PDI) and 4-methylphenyl isocyanide (MPI), and tilt angle of MPI were examined by measuring sum frequency generation (SFG) spectra of the self-assembled monolayers (SAMs) of these molecules on Au, Pt, Ag, and Pd surfaces. The SFG peaks due to "metal bonded" and "free"-NC groups were resolved by comparing the SFG spectra of PDI with IR spectra obtained by DFT calculations and previous results of vibrational spectroscopy. Based on the peak positions of the "metal bonded"-NC, it is clarified that while PDI and MPI were adsorbed at top sites on Au, Ag, and Pt surfaces, they adsorbed at bridge sites on the Pd surface. The tilt angles of MPI were determined from the intensity ratio between the SFG peaks of C-H symmetric and asymmetric stretching vibrational modes of the CH(3) group. The tilt angles of the MPI SAMs were in the order of Pt < Pd < Ag < Au, reflecting the bonding nature between the -NC group and the substrate atoms.

One pot electrochemical synthesis of polymer/CNT/metal nanoparticles for fuel cell applications

NASA Astrophysics Data System (ADS)

Ventrapragada, Lakshman; Zhu, Jingyi; Karakaya, Mehmet; Podila, Ramakrishna; Rao, Apparao; Clemson Nanomaterials center Team

Carbon nanotubes (CNTs) have become a key player in the design of materials for energy applications. They gained their popularity in industrial and scientific research due to their unique properties like excellent conductivity, high surface area, etc. Here we used chemical vapor deposition (CVD) to synthesize two types of CNTs namely, helically coiled CNTs and vertically aligned CNTs. These CNTs were subsequently used to make composites with conducting polymers and metal nanoparticles. One pot electrochemical synthesis was designed to electropolymerize aniline, pyrrole etc. on the surface of the electrode with simultaneous deposition of platinum and gold metal nanoparticles, and CNTs in the polymer matrix. The as synthesized composite materials were characterized with scanning electron microscope for surface morphology and spectroscopic techniques like Raman, UV-Vis for functionality. These were used to study electrocatalytic oxidation of methanol and ethanol for alkaline fuel cell applications. Electrodes fabricated from these composites not only showed good kinetics but also exhibited excellent stability. Uniqueness of this composite lies in its simple two step synthesis and it doesn't involve any surfactants unlike conventional chemical synthesis routes.

Ellipsometric Measurement of Bacterial Films at Metal-Electrolyte Interfaces

PubMed Central

Busalmen, J. P.; de Sánchez, S. R.; Schiffrin, D. J.

1998-01-01

Ellipsometric measurements were used to monitor the formation of a bacterial cell film on polarized metal surfaces (Al-brass and Ti). Under cathodic polarization bacterial attachment was measured from changes in the ellipsometric angles. These were fitted to an effective medium model for a nonabsorbing bacterial film with an effective refractive index (nf) of 1.38 and a thickness (df) of 160 ± 10 nm. From the optical measurements a surface coverage of 17% was estimated, in agreement with direct microscopic observations. The influence of bacteria on the formation of oxide films was monitored by ellipsometry following the film growth in situ. A strong inhibition of metal oxide film formation was observed, which was assigned to the decrease in oxygen concentration due to the presence of bacteria. It is shown that the irreversible adhesion of bacteria to the surface can be monitored ellipsometrically. Electrophoretic mobility is proposed as one of the factors determining bacterial attachment. The high sensitivity of ellipsometry and its usefulness for the determination of growth of interfacial bacterial films is demonstrated. PMID:9758786

Kinetics of pulse photothermal surface deformation as a method of studying the phase interface movement in a first-order phase transition

NASA Astrophysics Data System (ADS)

Vintzentz, S. V.; Kiselev, V. F.; Levshin, N. L.; Sandomirskii, V. B.

1991-01-01

The photothermal surface deformation (PTSD) method is used for characterization of the first-order phase transition (PT) for the first time. The advantages of the method are demonstrated experimentally for the well known metal-to-semiconductor PT in VO 2. It is found that near the PT temperature the PTSD pulse in a VO 2 film has a sign opposite to that of the thermoelastic response. The conclusion is drawn that this phenomenon is determined primarily by the contribution of the decrease in the specific volume (Δ V/ V) of the substance involved in the semiconductor-to-metal PT. The sign of Δ V/ V for a submicron polycrystalline VO 2 film is determined. Besides, analysis shows that in the PTSD kinetics measured as a whole we can "separate" a law for the metal-semicon- ductor interface movement (i.e. the interface moves towards the interior of the film when the latter is heated and back towards the surface when it is cooling down). The relative density change due to the PT is estimated based on this law.

Split Fermi Surfaces of the Spin-Orbit-Coupled Metal Cd2Re2O7 Probed by de Haas-van Alphen Effect

NASA Astrophysics Data System (ADS)

Matsubayashi, Yasuhito; Sugii, Kaori; Hirose, Hishiro T.; Hirai, Daigorou; Sugiura, Shiori; Terashima, Taichi; Uji, Shinya; Hiroi, Zenji

2018-05-01

The superconducting pyrochlore oxide Cd2Re2O7 shows a structural transition with inversion symmetry breaking (ISB) at Ts1 = 200 K. A recent theory [L. Fu, Phys. Rev. Lett. 115, 026401 (2015)] suggests that the origin is an electronic instability that leads to a multipolar order in the spin-orbit-coupled metal. To observe the Fermi surface of the low-temperature phase of Cd2Re2O7, we perform de Haas-van Alphen effect measurements by means of magnetic torque. In reference to a calculated band structure, the spin-split Fermi surfaces with large cyclotron masses of 5-9m0 are revealed. The splitting is suggested to be due to an antisymmetric spin-orbit coupling induced by ISB, the strength of which is estimated to be approximately 67 K, which is rather smaller than those of typical non-centrosymmetric metals.

Combination of Functional Nanoengineering and Nanosecond Laser Texturing for Design of Superhydrophobic Aluminum Alloy with Exceptional Mechanical and Chemical Properties.

PubMed

Boinovich, Ludmila B; Modin, Evgeny B; Sayfutdinova, Adeliya R; Emelyanenko, Kirill A; Vasiliev, Alexander L; Emelyanenko, Alexandre M

2017-10-24

Industrial application of metallic materials is hindered by several shortcomings, such as proneness to corrosion, erosion under abrasive loads, damage due to poor cold resistance, or weak resistance to thermal shock stresses, etc. In this study, using the aluminum-magnesium alloy as an example of widely spread metallic materials, we show that a combination of functional nanoengineering and nanosecond laser texturing with the appropriate treatment regimes can be successfully used to transform a metal into a superhydrophobic material with exceptional mechanical and chemical properties. It is demonstrated that laser chemical processing of the surface may be simultaneously used to impart multimodal roughness and to modify the composition and physicochemical properties of a thick surface layer of the substrate itself. Such integration of topographical and physicochemical modification leads to specific surface nanostructures such as nanocavities filled with hydrophobic agent and hard oxynitride nanoinclusions. The combination of superhydrophobic state, nano- and micro features of the hierarchical surface, and the appropriate composition of the surface textured layer allowed us to provide the surface with the outstanding level of resistance of superhydrophobic coatings to external chemical and mechanical impacts. In particular, experimental data presented in this study indicate high resistance of the fabricated coatings to pitting corrosion, superheated water vapor, sand abrasive wear, and rapid temperature cycling from liquid nitrogen to room temperatures, without notable degradation of superhydrophobic performance.

Magnetite impregnation effects on the sorbent properties of activated carbons and biochars.

PubMed

Han, Zhantao; Sani, Badruddeen; Mrozik, Wojciech; Obst, Martin; Beckingham, Barbara; Karapanagioti, Hrissi K; Werner, David

2015-03-01

This paper discusses the sorbent properties of magnetic activated carbons and biochars produced by wet impregnation with iron oxides. The sorbents had magnetic susceptibilities consistent with theoretical predictions for carbon-magnetite composites. The high BET surface areas of the activated carbons were preserved in the synthesis, and enhanced for one low surface area biochar by dissolving carbonates. Magnetization decreased the point of zero charge. Organic compound sorption correlated strongly with BET surface areas for the pristine and magnetized materials, while metal cation sorption did not show such a correlation. Strong sorption of the hydrophobic organic contaminant phenanthrene to the activated carbon or biochar surfaces was maintained following magnetite impregnation, while phenol sorption was diminished, probably due to enhanced carbon oxidation. Copper, zinc and lead sorption to the activated carbons and biochars was unchanged or slightly enhanced by the magnetization, and iron oxides also contributed to the composite metal sorption capacity. While a magnetic biochar with 219 ± 3.7 m(2)/g surface area nearly reached the very strong organic pollutant binding capacity of the two magnetic activated carbons, a magnetic biochar with 68 ± 2.8 m(2)/g surface area was the best metal sorbent. Magnetic biochars thus hold promise as more sustainable alternatives to coal-derived magnetic activated carbons. Copyright © 2014 Elsevier Ltd. All rights reserved.

Ultra-sensitive molecular detection using surface-enhanced Raman scattering on periodic metal-dielectric nanostructures

NASA Astrophysics Data System (ADS)

Nien, Chun; Li, Yi-Hsuan; Su, Vin-Cent; Kuan, Chieh-Hsiung

2017-02-01

Surface-enhanced Raman scattering (SERS) is a powerful technique for trace chemical analysis and single molecule detection in the application of biochemical monitoring and food safety due to its ability to enhance the Raman scattering of molecules near the metallic surface or nanostructures. Here, we present a comprehensive study of the SERS enhancement by the periodically nanostructured surface, where the thin film of silver is deposited onto the surface, except the sidewall of posts, of 1-D lamellar gratings with varying pitch to forming metal-dielectric composite nanostructures. By enhancing the localized and surface-propagating mode in the vicinity of the concaves, the SERS signal can be improved by amplifying the intensity of electric field and increasing the optical path length of the incident light. Experimental investigations show that the enhancement factor can be manipulated by varying the polarization of incident light and the pitch size of gratings. To demonstrate the SERS effects of the proposed structures, thin layers of benzoic acid, which is commonly used as a food preservative, are deposited on the SERS substrates by spin-coating a solution of benzoic acid and dried at room temperature. A Confocal Raman microscope with a 532 nm laser source is used to illuminate light and measure the Raman spectrum of benzoic acid. We demonstrate the Raman signal of benzoic acid can be enhanced on the order of 102 on the SERS substrates.

Photovoltaic enhancement due to surface-plasmon assisted visible-light absorption at the inartificial surface of lead zirconate-titanate film

NASA Astrophysics Data System (ADS)

Zheng, Fengang; Zhang, Peng; Wang, Xiaofeng; Huang, Wen; Zhang, Jinxing; Shen, Mingrong; Dong, Wen; Fang, Liang; Bai, Yongbin; Shen, Xiaoqing; Sun, Hua; Hao, Jianhua

2014-02-01

PZT film of 300 nm thickness was deposited on tin indium oxide (ITO) coated quartz by a sol-gel method. Four metal electrodes, such as Pt, Au, Cu and Ag, were used as top electrodes deposited on the same PZT film by sputtering at room temperature. In ITO-PZT-Ag and ITO-PZT-Au structures, the visible light (400-700 nm) can be absorbed partially by a PZT film, and the maximum efficiency of photoelectric conversion of the ITO-PZT-Ag structure was enhanced to 0.42% (100 mW cm-2, AM 1.5G), which is about 15 times higher than that of the ITO-PZT-Pt structure. Numerical simulations show that the natural random roughness of polycrystalline-PZT-metal interface can offer a possibility of coupling between the incident photons and SPs at the metal surface. The coincidence between the calculated SP properties and the measured EQE spectra reveals the SP origin of the photovoltaic enhancement in these ITO-PZT-metal structures, and the improved photocurrent output is caused by the enhanced optical absorption in the PZT region near the metal surface, rather than by the direct charge-transfer process between two materials.PZT film of 300 nm thickness was deposited on tin indium oxide (ITO) coated quartz by a sol-gel method. Four metal electrodes, such as Pt, Au, Cu and Ag, were used as top electrodes deposited on the same PZT film by sputtering at room temperature. In ITO-PZT-Ag and ITO-PZT-Au structures, the visible light (400-700 nm) can be absorbed partially by a PZT film, and the maximum efficiency of photoelectric conversion of the ITO-PZT-Ag structure was enhanced to 0.42% (100 mW cm-2, AM 1.5G), which is about 15 times higher than that of the ITO-PZT-Pt structure. Numerical simulations show that the natural random roughness of polycrystalline-PZT-metal interface can offer a possibility of coupling between the incident photons and SPs at the metal surface. The coincidence between the calculated SP properties and the measured EQE spectra reveals the SP origin of the photovoltaic enhancement in these ITO-PZT-metal structures, and the improved photocurrent output is caused by the enhanced optical absorption in the PZT region near the metal surface, rather than by the direct charge-transfer process between two materials. Electronic supplementary information (ESI) available. See DOI: 10.1039/c3nr05757g

Failure Investigation & Design Optimization of a Photo-Multiplier Tube Assembly Under Thermal Loading

NASA Technical Reports Server (NTRS)

Dahya, Kevin

2004-01-01

Analysis of GLAST ACD Photo-Multiplier Tube (PMT) assembly under thermal loading demonstrates that the glass tube experiences high stresses due to Coefficient of Thermal Expansion mismatch, as well as increased stress due to high stiffness and incompressibility of potting compound. Further investigation shows adverse loading effects due to the magnetic shield, a thin piece of steel wrapped around the PMT. This steel, Mu Metal, contained an overlap region that directly attributed to crack propagation in the outside surface of the tube. Sensitivities to different configurations were studied to reduce the stress and provide a more uniform loading throughout the PMT to ensure mission success. Studies indicate substituting a softer and more compressible potting compound and moving the Mu metal from the glass tube to the outside wall of the aluminum housing yields lower stress.

High-Performance, Large Format Surfaces for Surface-Enhanced Raman Spectroscopy: Increasing the Accessibility of an Analytical Platform

NASA Astrophysics Data System (ADS)

Kanipe, Katherine Nicole

Although surface-enhanced Raman spectroscopy (SERS) is a spectroscopic technique with unusually high sensitivity and molecular specificity, few practical analytical applications have been implemented that take advantage of its power. Based on what is understood about SERS from the experimental and theoretical research of the past forty years, we developed a few well-defined design principles on the basis of which a reliable and reproducibly manufacturable SERS-active substrate could be fabricated that is highly enhancing, highly uniform, stable, and based on a broad range of metals so that various chemical processes could be probed. Finally, we restricted ourselves to using only readily scalable fabrication techniques. The resulting SERS-active device was a metal over silica, two-dimensional nano-grating that was shown to produce enhancements of ˜107 when compared to a smooth surface of the same metal. This SERS substrate also shows unprecedented signal uniformity over square centimeters, and is fabricated using commonly-available foundry-based approaches exclusively. Initially, we explored the properties of a gold-coated substrates in which a first-order grating resonance due to long-range symmetry is augmented by a local resonance due to the individual core-shell grating elements. The SERS properties of such grating systems were systematically studied as a function of various structural parameters such as the grating pitch, the inter-element gap and the thickness of the metal layer. The most enhancing substrates were found to have a grating parameter with a radiative, rather than evanescent, first-order resonance; a sufficiently small gap between nearest neighbor grating elements to produce near-field interactions; and a gold layer whose thickness was larger than the electronic mean-free-path of the conduction electrons, so as to ensure a high conductivity for the metal layer to sustain strong surface plasmons. We applied these same architectural principles to metals other than gold, and concluded that every workable metal (and virtually any material with sufficiently high electrical conductivity) when appropriately nanostructured, has the potential to be an efficient SERS substrate. The use of materials for SERS beyond silver and gold, has significant advantages, most importantly, allowing SERS to be used to study the surface chemistry and catalysis taking place on metals with more interesting chemistries than those of Au and Ag. Additionally, SERS substrates can be fabricated from high natural abundance, low cost materials. This was illustrated by producing SERS substrates using copper, aluminum, and nickel in addition to silver and gold which were used as benchmarks. All five metals were found to yield high SERS intensities. The variation of the SERS enhancement among them is ascribed mainly to local field effects, with the (larger) grating-based enhancement making an approximately equivalent contribution to the SERS enhancement of the five metals. This conclusion is supported by local electric field simulations. The utility of these new grating-based SERS substrates was demonstrated by implementing them in chemical analysis in both aqueous and gas phases for which, for example, we were able to readily detect opioids such as fentanyl and morphine at concentrations as low as less than one part per billion. Additionally, we have made good progress toward integration of this substrate architecture into a microfluidic channel for a higher degree of sample workup and control.

Friction and wear of single-crystal manganese-zinc ferrite

NASA Technical Reports Server (NTRS)

Miyoshi, K.; Buckley, D. H.

1979-01-01

Sliding friction experiments were conducted with single crystal manganese-zinc ferrite in contact with itself and with transition metals. Results indicate mating highest atomic density directions (110) on matched crystallographic planes exhibit the lowest coefficient of friction, indicating that direction is important in the friction behavior of ferrite. Matched parallel high atomic density planes and crystallographic directions at the interface exhibit low coefficients of friction. The coefficients of friction for ferrite in contact with various metals are related to the relative chemical activity of these metals. The more active the metal, the higher the coefficient of friction. Cracking and the formation of hexagon- and rectangular-shaped platelet wear debris due to cleavages of (110) planes are observed on the ferrite surfaces as a result of sliding.

Interaction of Heavy Metal Ions with Carbon and Iron Based Particles

PubMed Central

Fialova, Dana; Kremplova, Monika; Melichar, Lukas; Kopel, Pavel; Hynek, David; Adam, Vojtech; Kizek, Rene

2014-01-01

Due to the rapid development of industry and associated production of toxic waste, especially heavy metals, there is a great interest in creating and upgrading new sorption materials to remove these pollutants from the environment. This study aims to determine the effectiveness of different carbon forms (graphene, expanded carbon, multi-wall nanotubes) and paramagnetic particles (Fe2O3) for adsorption of cadmium(II), lead(II), and copper(II) on its surface, with different interaction time from 1 min to 24 h. The main attention is paid to the detection of these metals using differential pulse voltammetry. Based on the obtained results, graphene and Fe2O3 are found to be good candidates for removal of heavy metals from the environment. PMID:28788566

Electrically driven plasmon-exciton coupled random lasing in ZnO metal-semiconductor-metal devices

NASA Astrophysics Data System (ADS)

Suja, Mohammad; Debnath, Bishwajit; Bashar, Sunayna B.; Su, Longxing; Lake, Roger; Liu, Jianlin

2018-05-01

Electrically driven plasmon-exciton coupled random lasing is demonstrated by incorporating Ag nanoparticles on Cu-doped ZnO metal-semiconductor-metal (MSM) devices. Both photoluminescence and electroluminescence studies show that emission efficiencies have been enhanced significantly due to coupling between ZnO excitons and Ag surface plasmons. With the incorporation of Ag nanoparticles on ZnO MSM structures, internal quantum efficiency up to 6 times is demonstrated. Threshold current for lasing is decreased by as much as 30% while the output power is increased up to 350% at an injection current of 40 mA. A numerical simulation study reveals that hole carriers are generated in the ZnO MSM devices from impact ionization processes for subsequent plasmon-exciton coupled lasing.

Carbon-containing compounds on fusion-related surfaces: Thermal and ion-induced formation and erosion

NASA Astrophysics Data System (ADS)

Linsmeier, Christian

2004-12-01

The deposition of carbon on metals is the unavoidable consequence of the application of different wall materials in present and future fusion experiments like ITER. Presently used and prospected materials besides carbon (CFC materials in high heat load areas) are tungsten and beryllium. The simultaneous application of different materials leads to the formation of surface compounds due to the erosion, transport and re-deposition of material during plasma operations. The formation and erosion processes are governed by widely varying surface temperatures and kinetic energies as well as the spectrum of impinging particles from the plasma. The knowledge of the dependence on these parameters is crucial for the understanding and prediction of the compound formation on wall materials. The formation of surface layers is of great importance, since they not only determine erosion rates, but also influence the ability of the first wall for hydrogen isotope inventory accumulation and release. Surface compound formation, diffusion and erosion phenomena are studied under well-controlled ultra-high vacuum conditions using in-situ X-ray photoelectron spectroscopy (XPS) and ion beam analysis techniques available at a 3 MV tandem accelerator. XPS provides chemical information and allows distinguishing elemental and carbidic phases with high surface sensitivity. Accelerator-based spectroscopies provide quantitative compositional analysis and sensitivity for deuterium in the surface layers. Using these techniques, the formation of carbidic layers on metals is studied from room temperature up to 1700 K. The formation of an interfacial carbide of several monolayers thickness is not only observed for metals with exothermic carbide formation enthalpies, but also in the cases of Ni and Fe which form endothermic carbides. Additional carbon deposited at 300 K remains elemental. Depending on the substrate, carbon diffusion into the bulk starts at elevated temperatures together with additional carbide formation. Depending on the bond nature in the carbide (metallic in the transition metal carbides, ionic e.g. in Be2C), the surface carbide layer is dissolved upon further increased temperatures or remains stable. Carbide formation can also be initiated by ion bombardment, both of chemically inert noble gas ions or C+ or CO+ ions. In the latter case, a deposition-erosion equilibrium develops which leads to a ternary surface layer of constant thickness. A chemical erosion channel is also discussed for the enhanced erosion of thin carbon films on metals by deuterium ions.

On Thermocapillary Mechanism of Spatial Separation of Metal Melts

NASA Astrophysics Data System (ADS)

Demin, V. A.; Mizev, A. I.; Petukhov, M. I.

2018-02-01

Theoretical research has been devoted to the study of binary metal melts behavior in a thin capillary. Earlier it has been found experimentally that unusually significant and quick redistribution of melts components takes place along capillary after the cooling. Numerical simulation of concentration-induced convection has been carried out to explain these experimental data. Two-component melt of both liquid metals filling vertical thin capillary with non-uniform temperature distribution on the boundaries is considered. It is assumed that the condition of absolute non-wetting is valid on the sidewalls. Because of this effect there is a free surface on vertical boundaries, where thermocapillary force is appeared due to the external longitudinal temperature gradient. It makes to move liquid elements at a big distance, compared with axial size of capillary. Effects of adsorption-desorption on the surface, thermal and concentration-capillary forces, convective motion in a volume and diffusion generate the large-scale circulation. This process includes the admixture carrying-out on the surface in the more hot higher part of the channel, its following transfer down along the boundary due to the thermocapillary force and its return in the volume over the desorption in the lower part of capillary. Intensity of motion and processes of adsorption-desorption on the free boundary have the decisive influence upon the formation of concentration fields and speed of components redistribution. Thus, one of the possible mechanisms of longitudinal division on components of liquid binary mixtures in thin channels has been demonstrated.

Technology of high-speed combined machining with brush electrode

NASA Astrophysics Data System (ADS)

Kirillov, O. N.; Smolentsev, V. P.; Yukhnevich, S. S.

2018-03-01

The new method was proposed for high-precision dimensional machining with a brush electrode when the true position of bundles of metal wire is adjusted by means of creating controlled centrifugal forces appeared due to the increased frequency of rotation of a tool. There are the ultimate values of circumferential velocity at which the bundles are pressed against a machined area of a workpiece in a stable manner despite the profile of the machined surface and variable stock of the workpiece. The special aspects of design of processing procedures for finishing standard parts, including components of products with low rigidity, are disclosed. The methodology of calculation and selection of processing modes which allow one to produce high-precision details and to provide corresponding surface roughness required to perform finishing operations (including the preparation of a surface for metal deposition) is presented. The production experience concerned with the use of high-speed combined machining with an unshaped tool electrode in knowledge-intensive branches of the machine-building industry for different types of production is analyzed. It is shown that the implementation of high-speed dimensional machining with an unshaped brush electrode allows one to expand the field of use of the considered process due to the application of a multipurpose tool in the form of a metal brush, as well as to obtain stable results of finishing and to provide the opportunities for long-term operation of the equipment without its changeover and readjustment.

Process for separating metallic from semiconducting single-walled carbon nanotubes

NASA Technical Reports Server (NTRS)

Sun, Ya-Ping (Inventor)

2008-01-01

A method for separating semiconducting single-walled carbon nanotubes from metallic single-walled carbon nanotubes is disclosed. The method utilizes separation agents that preferentially associate with semiconducting nanotubes due to the electrical nature of the nanotubes. The separation agents are those that have a planar orientation, .pi.-electrons available for association with the surface of the nanotubes, and also include a soluble portion of the molecule. Following preferential association of the separation agent with the semiconducting nanotubes, the agent/nanotubes complex is soluble and can be solubilized with the solution enriched in semiconducting nanotubes while the residual solid is enriched in metallic nanotubes.

Nature of the transition between a ferromagnetic metal and a spin-glass insulator in pyrochlore molybdates.

PubMed

Hanasaki, N; Watanabe, K; Ohtsuka, T; Kézsmárki, I; Iguchi, S; Miyasaka, S; Tokura, Y

2007-08-24

The metal-insulator transition has been investigated for pyrochlore molybdates R(2)Mo(2)O(7) with nonmagnetic rare-earth ions R. The dynamical scaling analysis of ac susceptibility reveals that the geometrical frustration causes the atomic spin-glass state. The reentrant spin-glass phase exists below the ferromagnetic transition. The electronic specific heat is enhanced as compared to the band calculation result, perhaps due to the orbital fluctuation in the half-metallic ferromagnetic state. The large specific heat is rather reduced upon the transition, likely because the short-range antiferromagnetic fluctuation shrinks the Fermi surface.

Metallic Biomaterials: Current Challenges and Opportunities

PubMed Central

Prasad, Karthika; Bazaka, Olha; Chua, Ming; Rochford, Madison; Fedrick, Liam; Spoor, Jordan; Symes, Richard; Tieppo, Marcus; Collins, Cameron; Cao, Alex; Ostrikov, Kostya (Ken); Bazaka, Kateryna

2017-01-01

Metallic biomaterials are engineered systems designed to provide internal support to biological tissues and they are being used largely in joint replacements, dental implants, orthopaedic fixations and stents. Higher biomaterial usage is associated with an increased incidence of implant-related complications due to poor implant integration, inflammation, mechanical instability, necrosis and infections, and associated prolonged patient care, pain and loss of function. In this review, we will briefly explore major representatives of metallic biomaterials along with the key existing and emerging strategies for surface and bulk modification used to improve biointegration, mechanical strength and flexibility of biometals, and discuss their compatibility with the concept of 3D printing. PMID:28773240

Achieving an ultra-narrow multiband light absorption meta-surface via coupling with an optical cavity.

PubMed

Liu, Zhengqi; Liu, Guiqiang; Liu, Xiaoshan; Huang, Shan; Wang, Yan; Pan, Pingping; Liu, Mulin

2015-06-12

Resonant plasmonic and metamaterial absorbers are of particular interest for applications in a wide variety of nanotechnologies including thermophotovoltaics, photothermal therapy, hot-electron collection and biosensing. However, it is rather challenging to realize ultra-narrow absorbers using plasmonic materials due to large optical losses in metals that inevitably decrease the quality of optical resonators. Here, we theoretically report methods to achieve an ultra-narrow light absorption meta-surface by using photonic modes of the optical cavities, which strongly couple with the plasmon resonances of the metallic nanostructures. Multispectral light absorption with absorption amplitude exceeding 99% and a bandwidth approaching 10 nm is achieved at the optical frequencies. Moreover, by introducing a thick dielectric coupling cavity, the number of absorption bands can be strongly increased and the bandwidth can even be narrowed to less than 5 nm due to the resonant spectrum splitting enabled by strong coupling between the plasmon resonances and the optical cavity modes. Designing such optical cavity-coupled meta-surface structures is a promising route for achieving ultra-narrow multiband absorbers, which can be used in absorption filters, narrow-band multispectral thermal emitters and thermophotovoltaics.

Development of nanoparticle applications in cell imaging, bioassay and reactive oxygen species detection based on surface-enhanced raman spectroscopy

NASA Astrophysics Data System (ADS)

Huang, Yiming

Surface-enhanced Raman scattering (SERS) has been developed over forty years with a wide variety of applications. Signals enhanced from single molecule absorbed on the surface of metallic nanoparticles can be up to 14-order-of-magnitude. This is due to the resonance between the optical field and surface plasmon of the metal substrate. Nanoshells have been chosen as substrates since they do not need to pre-aggregate due to their tunable optical property. We developed Raman imaging system by incorporating functionalized nanoshells, cells and SERS. Nanoshells have been coated with different self-assembled monolayers containing poly(ethylene glycol) (PEG) molecules. Probes have been designed by coating nanoshells with Raman active PEG molecules and delivered into macrophage cells. The imaging technique requires less preparation and provides the information of nanoshells in semi-quantitative way in vitro. We developed half-sandwich bioassay by detecting low volume of antigens on nitrocellulose membrane, detected by SERS. Antibodies were grafted to the surface of nanoshells and were conjugated to the antigens on the nitrocellulose membrane for detection. Raman active PEGs were conjugated onto the metal substrate for recognition and quantification. The benefits of this assay are that it is faster, easier to execute and requires less volume of antigen to conjugate onto the substrate. We also developed reactive oxygen species (ROS) sensors by incubating PEGs and either 4-nitrobenzenethiol (4-NBT) or 4-mercaptophenol (4-MP) on the surface of nanoshells. By analyzing the changes of SERS spectrum, the production of hydroxyl radicals produced in the Fenton reaction can be tracked in low concentrations. The sensors were designed to track ROS production within cells when they are under oxidative stress. The methods developed in this thesis are versatile, and can be broadly applied to the study of different subtracts, such as gold colloid.

A multifunctional metal-organic framework based tumor targeting drug delivery system for cancer therapy

NASA Astrophysics Data System (ADS)

Wang, Xiao-Gang; Dong, Zhi-Yue; Cheng, Hong; Wan, Shuang-Shuang; Chen, Wei-Hai; Zou, Mei-Zhen; Huo, Jia-Wei; Deng, He-Xiang; Zhang, Xian-Zheng

2015-09-01

Drug delivery systems (DDSs) with biocompatibility and precise drug delivery are eagerly needed to overcome the paradox in chemotherapy that high drug doses are required to compensate for the poor biodistribution of drugs with frequent dose-related side effects. In this work, we reported a metal-organic framework (MOF) based tumor targeting DDS developed by a one-pot, and organic solvent-free ``green'' post-synthetic surface modification procedure, starting from the nanoscale MOF MIL-101. Owing to the multifunctional surface coating, premature drug release from this DDS was prevented. Due to the pH responsive benzoic imine bond and the redox responsive disulfide bond at the modified surface, this DDS exhibited tumor acid environment enhanced cellular uptake and intracellular reducing environment triggered drug release. In vitro and in vivo results showed that DOX loaded into this DDS exhibited effective cancer cell inhibition with much reduced side effects.Drug delivery systems (DDSs) with biocompatibility and precise drug delivery are eagerly needed to overcome the paradox in chemotherapy that high drug doses are required to compensate for the poor biodistribution of drugs with frequent dose-related side effects. In this work, we reported a metal-organic framework (MOF) based tumor targeting DDS developed by a one-pot, and organic solvent-free ``green'' post-synthetic surface modification procedure, starting from the nanoscale MOF MIL-101. Owing to the multifunctional surface coating, premature drug release from this DDS was prevented. Due to the pH responsive benzoic imine bond and the redox responsive disulfide bond at the modified surface, this DDS exhibited tumor acid environment enhanced cellular uptake and intracellular reducing environment triggered drug release. In vitro and in vivo results showed that DOX loaded into this DDS exhibited effective cancer cell inhibition with much reduced side effects. Electronic supplementary information (ESI) available: Synthesis procedure, 1HNMR, ESI-MS and additional data. See DOI: 10.1039/c5nr04045k

Spatial Patterns of Airborne Exposures of Tungsten and Cobalt in Fallon, Nevada, From Lichens and Surface Sediments

NASA Astrophysics Data System (ADS)

Sheppard, P. R.; Speakman, R. J.; Ridenour, G.; Glascock, M. D.; Farris, C.; Witten, M. L.

2005-12-01

This paper describes spatial patterns of airborne exposures of heavy metals in Fallon, Nevada, where a cluster of childhood leukemia has been on-going since 1997. Lichen chemistry, the measurement and interpretation of element concentrations in lichens, and surface sediment chemistry were used. Lichens were collected from within as well as from well outside of Fallon. Surface sediments were collected in a gridded spatial pattern, also within and outside of Fallon. Both the lichen and the surface sediment samples were measured chemically for a large suite of metals and other elements. Lichens indicate that Fallon itself has a high dual airborne exposure of tungsten and cobalt relative to sites well away from the town. Surface sediments samples also show high peaks of tungsten and cobalt within Fallon with nothing more than background contents away from the town. The tungsten and cobalt peaks coincide spatially with one another, with the highest values located right at a "hard-metal" facility that processes these metals. This present research confirms earlier research on total suspended particulates showing that Fallon is distinct in Nevada for its high dual exposure of airborne tungsten and cobalt and that the source of these two metals can be pinpointed to the hard-metal industry that exists just north of Highway 50 and west of Highway 95. While it is still not possible to conclude that high airborne exposure of tungsten and/or cobalt causes childhood leukemia, it can now be concluded beyond reasonable doubt that Fallon is unique environmentally due to its high airborne concentrations of tungsten and cobalt. Given that Fallon's cluster of childhood leukemia is the "most convincing cluster ever reported," it stands to reason that additional biomedical research should directly test the leukogenecity of combined airborne exposures of tungsten and cobalt.

Magic C60 islands forming due to moiré interference between islands and substrate

NASA Astrophysics Data System (ADS)

Olyanich, D. A.; Mararov, V. V.; Utas, T. V.; Utas, O. A.; Gruznev, D. V.; Zotov, A. V.; Saranin, A. A.

2015-05-01

Recently proposed mechanism for self-organized formation of magic islands [Nat.Comm. 4(2013)1679] has received a new experimental confirmation. According to this mechanism, self-assembly is mediated by the moiré interference between an island and underlying substrate lattice. It was first detected at C60 island growth on In-adsorbed Si(111)√{ 3} ×√{ 3}-Au surface. Changing In adsorbate for Tl results in lowering the corrugations of the surface potential relief due to a greater surface metallization. This allows formation of the C60 arrays with novel moiré pattern. As a result, a new set of magic C60 islands is formed on Tl-adsorbed Au/Si(111) surface differing from that observed on In-adsorbed surface. For example, the 19-C60 magic island which has a non-compact boomerang shape on In-adsorbed Au/Si(111) surfaces adopts a shape of a regular hexagon on Tl-adsorbed surface.

Directional Emission from Metal-Dielectric-Metal Structures: Effect of Mixed Metal Layers, Dye Location and Dielectric Thickness.

PubMed

Choudhury, Sharmistha Dutta; Badugu, Ramachandram; Ray, Krishanu; Lakowicz, Joseph R

2015-02-12

Metal-dielectric-metal (MDM) structures provide directional emission close to the surface normal, which offers opportunities for new design formats in fluorescence based applications. The directional emission arises due to near-field coupling of fluorophores with the optical modes present in the MDM substrate. Reflectivity simulations and dispersion diagrams provide a basic understanding of the mode profiles and the factors that affect the coupling efficiency and the spatial distribution of the coupled emission. This work reveals that the composition of the metal layers, the location of the dye in the MDM substrate and the dielectric thickness are important parameters that can be chosen to tune the color of the emission wavelength, the angle of observation, the angular divergence of the emission and the polarization of the emitted light. These features are valuable for displays and optical signage.

Directional Emission from Metal-Dielectric-Metal Structures: Effect of Mixed Metal Layers, Dye Location and Dielectric Thickness

PubMed Central

Choudhury, Sharmistha Dutta; Badugu, Ramachandram; Ray, Krishanu; Lakowicz, Joseph R.

2015-01-01

Metal-dielectric-metal (MDM) structures provide directional emission close to the surface normal, which offers opportunities for new design formats in fluorescence based applications. The directional emission arises due to near-field coupling of fluorophores with the optical modes present in the MDM substrate. Reflectivity simulations and dispersion diagrams provide a basic understanding of the mode profiles and the factors that affect the coupling efficiency and the spatial distribution of the coupled emission. This work reveals that the composition of the metal layers, the location of the dye in the MDM substrate and the dielectric thickness are important parameters that can be chosen to tune the color of the emission wavelength, the angle of observation, the angular divergence of the emission and the polarization of the emitted light. These features are valuable for displays and optical signage. PMID:25844110

Impact of humic/fulvic acid on the removal of heavy metals from aqueous solutions using nanomaterials: a review.

PubMed

Tang, Wang-Wang; Zeng, Guang-Ming; Gong, Ji-Lai; Liang, Jie; Xu, Piao; Zhang, Chang; Huang, Bin-Bin

2014-01-15

Nowadays nanomaterials have been widely used to remove heavy metals from water/wastewater due to their large surface area and high reactivity. Humic acid (HA) and fulvic acid (FA) exist ubiquitously in aquatic environments and have a variety of functional groups which allow them to complex with metal ions and interact with nanomaterials. These interactions can not only alter the environmental behavior of nanomaterials, but also influence the removal and transportation of heavy metals by nanomaterials. Thus, the interactions and the underlying mechanisms involved warrant specific investigations. This review outlined the effects of HA/FA on the removal of heavy metals from aqueous solutions by various nanomaterials, mainly including carbon-based nanomaterials, iron-based nanomaterials and photocatalytic nanomaterials. Moreover, mechanisms involved in the interactions were discussed and potential environmental implications of HA/FA to nanomaterials and heavy metals were evaluated. © 2013.

Understanding photocatalytic metallization of preadsorbed ionic gold on titania, ceria, and zirconia.

PubMed

Kydd, Richard; Scott, Jason; Teoh, Wey Yang; Chiang, Ken; Amal, Rose

2010-02-02

A nonaqueous photodeposition procedure for forming Au nanoparticles on semiconducting supports (TiO(2), CeO(2), and ZrO(2)) was investigated. Intrinsic excitation of the support was sufficient to induce Au(0) nucleation, without the need for an organic hole-scavenging species. Photoreduction rates were higher over TiO(2) and ZrO(2) than over CeO(2), likely due to a lower rate of photogenerated electron recombination. Illumination resulted in metallization of the adsorbed Au species and formation of crystalline Au nanoparticles dispersed across the oxide surfaces. On the basis of transmission electron microscopy (TEM) evidence of a strong Au particle-metal oxide interaction, it is proposed that Au deposit formation proceeds via the nucleation of highly dispersed clusters which can diffuse and amalgamate at room temperature to form larger surface-defect-immobilized clusters, with the final particle size being significantly smaller than that achieved by conventional aqueous photodeposition. From this work, it is possible to draw several new fundamental insights, with regards to both the nonaqueous photodeposition process and the general mechanism by which dispersed metallic Au nanoparticles are formed from ionic precursors adsorbed upon metal oxide supports.

Microstructural Features Controlling the Variability in Low-Cycle Fatigue Properties of Alloy Inconel 718DA at Intermediate Temperature

NASA Astrophysics Data System (ADS)

Texier, Damien; Gómez, Ana Casanova; Pierret, Stéphane; Franchet, Jean-Michel; Pollock, Tresa M.; Villechaise, Patrick; Cormier, Jonathan

2016-03-01

The low-cycle fatigue behavior of two direct-aged versions of the nickel-based superalloy Inconel 718 (IN718DA) was examined in the low-strain amplitude regime at intermediate temperature. High variability in fatigue life was observed, and abnormally short lifetimes were systematically observed to be due to crack initiation at (sub)-surface non-metallic inclusions. However, crack initiation within (sub)-surface non-metallic inclusions did not necessarily lead to short fatigue life. The macro- to micro-mechanical mechanisms of deformation and damage have been examined by means of detailed microstructural characterization, tensile and fatigue mechanical tests, and in situ tensile testing. The initial stages of crack micro-propagation from cracked non-metallic particles into the surrounding metallic matrix occupies a large fraction of the fatigue life and requires extensive local plastic straining in the matrix adjacent to the cracked inclusions. Differences in microstructure that influence local plastic straining, i.e., the δ-phase content and the grain size, coupled with the presence of non-metallic inclusions at the high end of the size distribution contribute strongly to the fatigue life variability.

Effect of the Crevice Former on the Corrosion Behavior of 316L Stainless Steel in Chloride-Containing Synthetic Tap Water

NASA Astrophysics Data System (ADS)

Kim, Seon-Hong; Lee, Ji-Hoon; Kim, Jung-Gu; Kim, Woo-Cheol

2018-05-01

To restrain the failure of the plate heat exchanger (PHE) in customer boiler working fluid, the effect of crevice former type on the corrosion behavior of the 316L stainless steel plate was investigated using electrochemical methods and surface analyses in chloride-containing synthetic tap water (60 °C). The localized corrosion under metal-metal crevice condition was initiated more easily than that under the metal-gasket crevice condition due to the restricted mass transport at the gasket crevice mouth. However, the anodic current under the metal-metal crevice condition was lower than that under metal-gasket crevice condition at a higher anodic potential, indicating that that the metal dissolution under EPDM crevice would be higher than that under metal crevice under the accelerated corrosion condition. Because narrow crevice gap that was formed under gasket accelerated the anodic dissolution at the crevice mouth, the perforation tendency under metal-gasket crevice condition is much higher than that under metal-metal crevice condition. As a result, the crevice geometry, especially the crevice gap, mainly affected the corrosion behavior of PHE material.

Effect of the Crevice Former on the Corrosion Behavior of 316L Stainless Steel in Chloride-Containing Synthetic Tap Water

NASA Astrophysics Data System (ADS)

Kim, Seon-Hong; Lee, Ji-Hoon; Kim, Jung-Gu; Kim, Woo-Cheol

2018-03-01

To restrain the failure of the plate heat exchanger (PHE) in customer boiler working fluid, the effect of crevice former type on the corrosion behavior of the 316L stainless steel plate was investigated using electrochemical methods and surface analyses in chloride-containing synthetic tap water (60 °C). The localized corrosion under metal-metal crevice condition was initiated more easily than that under the metal-gasket crevice condition due to the restricted mass transport at the gasket crevice mouth. However, the anodic current under the metal-metal crevice condition was lower than that under metal-gasket crevice condition at a higher anodic potential, indicating that that the metal dissolution under EPDM crevice would be higher than that under metal crevice under the accelerated corrosion condition. Because narrow crevice gap that was formed under gasket accelerated the anodic dissolution at the crevice mouth, the perforation tendency under metal-gasket crevice condition is much higher than that under metal-metal crevice condition. As a result, the crevice geometry, especially the crevice gap, mainly affected the corrosion behavior of PHE material.

Preservation of NOM-metal complexes in a modern hyperalkaline stalagmite: Implications for speleothem trace element geochemistry

NASA Astrophysics Data System (ADS)

Hartland, Adam; Fairchild, Ian J.; Müller, Wolfgang; Dominguez-Villar, David

2014-03-01

We report the first quantitative study of the capture of colloidal natural organic matter (NOM) and NOM-complexed trace metals (V, Co, Cu, Ni) in speleothems. This study combines published NOM-metal dripwater speciation measurements with high-resolution laser ablation ICPMS (LA-ICPMS) and sub-annual stable isotope ratio (δ18O and δ13C), fluorescence and total organic carbon (TOC) analyses of a fast-growing hyperalkaline stalagmite (pH ˜11) from Poole’s Cavern, Derbyshire UK, which formed between 1997 and 2008 AD. We suggest that the findings reported here elucidate trace element variations arising from colloidal transport and calcite precipitation rate changes observed in multiple, natural speleothems deposited at ca. pH 7-8. We find that NOM-metal(aq) complexes on the boundary between colloidal and dissolved (˜1 nm diameter) show an annual cyclicity which is inversely correlated with the alkaline earth metals and is explained by calcite precipitation rate changes (as recorded by kinetically-fractionated stable isotopes). This relates to the strength of the NOM-metal complexation reaction, resulting in very strongly bound metals (Co in this system) essentially recording NOM co-precipitation (ternary complexation). More specifically, empirical partition coefficient (Kd) values between surface-reactive metals (V, Co, Cu, Ni) [expressed as ratio of trace element to Ca ratios in calcite and in solution] arise from variations in the ‘free’ fraction of total metal in aqueous solution (fm). Hence, differences in the preservation of each metal in calcite can be explained quantitatively by their complexation behaviour with aqueous NOM. Differences between inorganic Kd values and field measurements for metal partitioning into calcite occur where [free metal] ≪ [total metal] due to complexation reactions between metals and organic ligands (and potentially inorganic colloids). It follows that where fm ≈ 0, apparent inorganic Kd app values are also ≈0, but the true partition coefficient (Kd actual) is significantly higher. Importantly, the Kd of NOM-metal complexes [organic carbon-metal ratio) approaches 1 for the most stable aqueous complexes, as is shown here for Co, but has values of 24-150 for V, Ni and Cu. This implies that ternary surface complexation (metal-ligand co-adsorption) can occur (as for NOM-Co), but is the exception rather than the rule. We also demonstrate the potential for trace metals to record information on NOM composition as expressed through changing NOM-metal complexation patterns in dripwaters. Therefore, a suite of trace metals in stalagmites show variations clearly attributable to changes in organic ligand concentration and composition, and which potentially reflect the state of overlying surface ecosystems. The heterogeneous speciation and size distribution of aqueous NOM and metals (Lead and Wilkinson, 2006; Aiken et al., 2011). The variability in NOM-metal transport in caves that arises from the interaction between infiltration, flow routing, and the hydrodynamic properties of the fine colloids and particulates (Hartland et al., 2012). Variable dissociation kinetics through time as a function of (a) (Hartland et al., 2011). The surface charge of calcite and the availability of CaCO3 lattice sites as well as increased incidence of crystallographic defects with implications for incorporation of a range of trace species (Fairchild and Treble, 2009; Fairchild and Hartland, 2010). Thus, incorporation in speleothem calcite with consistent surface site properties will be determined by: The size and composition (i.e. hydrophilicity/hydrophobicity) of the NOM ligand, affecting adsorption and stability at the calcite surface. The lability (i.e. exchangeability) of the complexed metal and its binding affinity for the calcite surface. The concentration of aqueous complexes. Given the complexities, a partitioning approach to the problem is appropriate as a first approximation rather than a precise description. This study seeks to make the first quantitative connection between the organic and inorganic compositions of speleothems and thus determine the potential for speleothems to encode fluctuations in colloid-facilitated trace metal transport in karst aquifers. Recent findings of direct relevance to the present studyThe conjugate dripwater (PE1) to the stalagmite studied here (PC-08-1) was characterised in June 2009 using an array of complementary techniques, in which the size, speciation and lability of NOM-metal complexes was characterised (Hartland et al., 2011), where lability is defined as the capacity for complexes to dissociate in the context of the on-going interfacial process at the stalagmite surface. In PE1 dripwater, the most stable aqueous complexes were formed between Co and the finest, low molecular weight component of the NOM spectrum (Hartland et al., 2011). Speciation experiments demonstrated that Co was essentially non-exchangeable (free metal (fm) = <0.05), being retained in aqueous complexes, whilst Cu, Ni and V were all predominantly bound by NOM (fm = 0.2-0.3).In contrast, Sr and Ba were freely exchangeable between the solution and solid phase (Hartland et al., 2011) and Mg was absent, presumably due to the poor solubility of Mg(OH)2 at hyperalkaline pH (Ksp = 1.5 × 10-11): Mg2+(aq)+2OH-(aq)↔Mg( On the other hand, the transition metals were not lost as insoluble hydroxides (Hartland et al., 2012), despite having lower solubility than Mg (e.g. Cu(OH)2Ksp = 2.2 × 10-20); and this is consistent with the dominant role of NOM in solubilising and transporting the transition metals in this system (Hartland et al., 2011).The transport of metals by complexes with NOM in PE1 dripwater through the hydrological year was studied by Hartland et al. (2012). This study had two findings of direct relevance to the study of trace metal variations in the conjugate PC-08-1 stalagmite: Complexes between metals and the smallest, low-molecular weight fraction of NOM showed an attenuated delivery in dripwaters consistent with the non-conservative behaviour of analogous tracers in fractured-rock studies due to diffusion into micro-fractures. This mode of transport was termed ‘low-flux’ and was the dominant mode of transport for Co and V. Complexes between metals and coarse colloids (>100 nm) and particulates (>1000 nm) showed a rapid responsiveness to infiltration events. This was termed the ‘high-flux’ mode of NOM-metal transport and was interpreted as being dominantly fracture-fed. This mode of transport was dominated by Cu, Zn and Ni. The ‘high-flux’ vs ‘low-flux’ interplay of trace metal transport is summarised in Fig. 1.The PC-08-1 stalagmite studied here was deposited following the removal of stalagmite PC-97-1 studied by Baker et al. (1999b) and which grew under the PE1 drip point between 1927 and 1997. Both the PC-97-1 stalagmite and its regrowth (PC-08-1) are characterised by annual lamina couplets consisting of a porous pale layer and a dense fluorescent layer. Fluorescence in the PC-97-1 stalagmite displayed a marked sinusoidal pattern with 10% of laminae exhibiting a double band structure (Baker et al., 1999b).

Mode suppression in metal filled photonic crystal vertical cavity lasers

NASA Astrophysics Data System (ADS)

Griffin, Benjamin G.; Arbabi, Amir; Goddard, Lynford L.

2012-03-01

Simulation results for an etched air hole photonic crystal (PhC) vertical cavity surface emitting laser (VCSEL) structure with various thicknesses of metal deposited inside the holes are presented. The higher-order modes of the structure are more spread out than the fundamental mode, and penetrate into the metal-filled holes. Due to the lossy nature of the metal, these higher-order modes experience a greater loss than the fundamental mode, resulting in an enhanced side mode suppression ratio (SMSR). A figure of merit for determining which metals would have the greatest impact on the SMSR is derived and validated using a transmission matrix method calculation. A full three-dimensional simulation of the PhC VCSEL structure is performed using the plane wave admittance method, and SMSRs are calculated for increasing metal thicknesses. Of the metals simulated, chromium provided the greatest SMSR enhancement with more than a 4 dB improvement with 500 nm of metal for an operating current of 12 times threshold.

Evaluating nanoscale ultra-thin metal films by means of lateral photovoltaic effect in metal-semiconductor structure.

PubMed

Zheng, Diyuan; Yu, Chongqi; Zhang, Qian; Wang, Hui

2017-12-15

Nanoscale metal-semiconductor (MS) structure materials occupy an important position in semiconductor and microelectronic field due to their abundant physical phenomena and effects. The thickness of metal films is a critical factor in determining characteristics of MS devices. How to detect or evaluate the metal thickness is always a key issue for realizing high performance MS devices. In this work, we propose a direct surface detection by use of the lateral photovoltaic effect (LPE) in MS structure, which can not only measure nanoscale thickness, but also detect the fluctuation of metal films. This method is based on the fact that the output of lateral photovoltaic voltage (LPV) is closely linked with the metal thickness at the laser spot. We believe this laser-based contact-free detection is a useful supplement to the traditional methods, such as AFM, SEM, TEM or step profiler. This is because these traditional methods are always incapable of directly detecting ultra-thin metal films in MS structure materials.

Evaluating nanoscale ultra-thin metal films by means of lateral photovoltaic effect in metal-semiconductor structure

NASA Astrophysics Data System (ADS)

Zheng, Diyuan; Yu, Chongqi; Zhang, Qian; Wang, Hui

2017-12-01

Nanoscale metal-semiconductor (MS) structure materials occupy an important position in semiconductor and microelectronic field due to their abundant physical phenomena and effects. The thickness of metal films is a critical factor in determining characteristics of MS devices. How to detect or evaluate the metal thickness is always a key issue for realizing high performance MS devices. In this work, we propose a direct surface detection by use of the lateral photovoltaic effect (LPE) in MS structure, which can not only measure nanoscale thickness, but also detect the fluctuation of metal films. This method is based on the fact that the output of lateral photovoltaic voltage (LPV) is closely linked with the metal thickness at the laser spot. We believe this laser-based contact-free detection is a useful supplement to the traditional methods, such as AFM, SEM, TEM or step profiler. This is because these traditional methods are always incapable of directly detecting ultra-thin metal films in MS structure materials.

The Tribology of Explanted Hip Resurfacings Following Early Fracture of the Femur.

PubMed

Lord, James K; Langton, David J; Nargol, Antoni V F; Meek, R M Dominic; Joyce, Thomas J

2015-10-15

A recognized issue related to metal-on-metal hip resurfacings is early fracture of the femur. Most theories regarding the cause of fracture relate to clinical factors but an engineering analysis of failed hip resurfacings has not previously been reported. The objective of this work was to determine the wear volumes and surface roughness values of a cohort of retrieved hip resurfacings which were removed due to early femoral fracture, infection and avascular necrosis (AVN). Nine resurfacing femoral heads were obtained following early fracture of the femur, a further five were retrieved due to infection and AVN. All fourteen were measured for volumetric wear using a co-ordinate measuring machine. Wear rates were then calculated and regions of the articulating surface were divided into "worn" and "unworn". Roughness values in these regions were measured using a non-contacting profilometer. The mean time to fracture was 3.7 months compared with 44.4 months for retrieval due to infection and AVN. Average wear rates in the early fracture heads were 64 times greater than those in the infection and AVN retrievals. Given the high wear rates of the early fracture components, such wear may be linked to an increased risk of femoral neck fracture.

Space environmental effects on spacecraft: LEO materials selection guide, part 1

NASA Astrophysics Data System (ADS)

Silverman, Edward M.

1995-08-01

This document provides performance properties on major spacecraft materials and subsystems that have been exposed to the low-Earth orbit (LEO) space environment. Spacecraft materials include metals, polymers, composites, white and black paints, thermal-control blankets, adhesives, and lubricants. Spacecraft subsystems include optical components, solar cells, and electronics. Information has been compiled from LEO short-term spaceflight experiments (e.g., space shuttle) and from retrieved satellites of longer mission durations (e.g., Long Duration Exposure Facility). Major space environment effects include atomic oxygen (AO), ultraviolet radiation, micrometeoroids and debris, contamination, and particle radiation. The main objective of this document is to provide a decision tool to designers for designing spacecraft and structures. This document identifies the space environments that will affect the performance of materials and components, e.g., thermal-optical property changes of paints due to UV exposures, AO-induced surface erosion of composites, dimensional changes due to thermal cycling, vacuum-induced moisture outgassing, and surface optical changes due to AO/UV exposures. Where appropriate, relationships between the space environment and the attendant material/system effects are identified. Part 1 covers spacecraft design considerations for the space environment; advanced composites; polymers; adhesives; metals; ceramics; protective coatings; and lubricants, greases, and seals.

Space environmental effects on spacecraft: LEO materials selection guide, part 1

NASA Technical Reports Server (NTRS)

Silverman, Edward M.

1995-01-01

This document provides performance properties on major spacecraft materials and subsystems that have been exposed to the low-Earth orbit (LEO) space environment. Spacecraft materials include metals, polymers, composites, white and black paints, thermal-control blankets, adhesives, and lubricants. Spacecraft subsystems include optical components, solar cells, and electronics. Information has been compiled from LEO short-term spaceflight experiments (e.g., space shuttle) and from retrieved satellites of longer mission durations (e.g., Long Duration Exposure Facility). Major space environment effects include atomic oxygen (AO), ultraviolet radiation, micrometeoroids and debris, contamination, and particle radiation. The main objective of this document is to provide a decision tool to designers for designing spacecraft and structures. This document identifies the space environments that will affect the performance of materials and components, e.g., thermal-optical property changes of paints due to UV exposures, AO-induced surface erosion of composites, dimensional changes due to thermal cycling, vacuum-induced moisture outgassing, and surface optical changes due to AO/UV exposures. Where appropriate, relationships between the space environment and the attendant material/system effects are identified. Part 1 covers spacecraft design considerations for the space environment; advanced composites; polymers; adhesives; metals; ceramics; protective coatings; and lubricants, greases, and seals.

Investigations on the micro-scale surface interactions at the tool and workpiece interface in micro-manufacturing of bipolar plates for proton exchange membrane fuel cells

NASA Astrophysics Data System (ADS)

Peker, Mevlut Fatih

Micro-forming studies have been more attractive in recent years because of miniaturization trend. One of the promising metal forming processes, micro-stamping, provides durability, strength, surface finish, and low cost for metal products. Hence, it is considered a prominent method for fabricating bipolar plates (BPP) with micro-channel arrays on large metallic surfaces to be used in Proton Exchange Membrane Fuel Cells (PEMFC). Major concerns in micro-stamping of high volume BPPs are surface interactions between micro-stamping dies and blank metal plates, and tribological changes. These concerns play a critical role in determining the surface quality, channel formation, and dimensional precision of bipolar plates. The surface quality of BPP is highly dependent on the micro-stamping die surface, and process conditions due to large ratios of surface area to volume (size effect) that cause an increased level of friction and wear issues at the contact interface. Due to the high volume and fast production rates, BPP surface characteristics such as surface roughness, hardness, and stiffness may change because of repeated interactions between tool (micro-forming die) and workpiece (sheet blank of interest). Since the surface characteristics of BPPs have a strong effect on corrosion and contact resistance of bipolar plates, and consequently overall fuel cell performance, evolution of surface characteristics at the tool and workpiece should be monitored, controlled, and kept in acceptable ranges throughout the long production cycles to maintain the surface quality. Compared to macro-forming operations, tribological changes in micro-forming process are bigger challenges due to their dominance and criticality. Therefore, tribological size effect should be considered for better understanding of tribological changes in micro-scale. The integrity of process simulation to the experiments, on the other hand, is essential. This study describes an approach that aims to investigate the surface topography changes during long-run micro-stamping of BPPs, and establish relationships between surface roughness--corrosion resistance and surface roughness-contact resistance characteristics of BPPs. Formability levels of formed BPPs and repeatability characteristics of the process were investigated. In addition, blank thickness changes, von-Mises stress, plastic strain levels and distributions of micro-stamping process were determined via finite element analysis (FEA). Test results revealed that the surface roughness change for the stamping dies and BPPs was unsteady (no trend) due to the continuous change of surface topography (i.e. asperity deformation). Sub-micron range local plastic deformations on stamping dies led to surface topography changes on BPP in long-run manufacturing case. As surface defects trigger corrosion, the correlation between surface roughness and corrosion resistance of BPPs was found to be direct. Increasing number of surface irregularities (asperities) lowered contact surface area that resulted in increased contact resistance. ZrN coated BPPs, on the other hand, did not change surface roughness, however; it improved the protection of BPPs against corrosion significantly. In addition, ZrN coating increased the conductivity of BPPs and reduced the contact resistance between BPP and gas diffusion layer (GDL), at certain extent. As dimensional stability and repeatability was confirmed in forming of both uncoated and coated BPPs during the long run manufacturing, different formability levels were achieved for coated and uncoated samples. Lower channel height values were obtained for coated plates because of the different surface hardness of uncoated and coated plates. In tribological size effect part of study, micro stamping experiments using three different dies with distinct channel height values at different stamping force levels were performed. It was concluded that decrease in forming die dimensions led to increase in coefficient of friction as previously reported by other researchers as one of the consequences of tribological size effect. On the other hand, coefficient of friction values were not affected by the force levels used in the experiments and simulations, whereas plastic strain, equivalent stress, and formability levels were increased with increasing stamping force, as expected. In essence, this study proposed a methodology to investigate the long-run manufacturing effects on dimensional stability and surface characteristics of micro-stamped sheets. It also correlates these parameters to fuel cell performance measures such as interfacial contact and corrosion resistance.

Design and fabrication of Ni nanowires having periodically hollow nanostructures.

PubMed

Sada, Takao; Fujigaya, Tsuyohiko; Nakashima, Naotoshi

2014-10-07

We propose a concept for the design and fabrication of metal nanowires having periodically hollow nanostructures inside the pores of an anodic aluminum oxide (AAO) membrane using a sacrificial metal. In this study, nickel (Ni) and silver (Ag) were used as the base metal and the sacrificial metal, respectively. Alternating an applied potential between -0.4 and -1.0 V provided alternatively deposited Ni and Ag segments in a Ni-Ag 'barcode' nanowire with a diameter of 18 or 35 nm. After etching away the Ag segments, we fabricated Ni nanowires with nanopores of 12 ± 5.3 nm. Such nanostructure formation is explained by the formation of a Ni shell layer over the surface of the Ag segments due to the strong affinity of Ni(2+) for the interior surfaces of AAO. The Ni shell layer allows the Ni segments to remain even after dissolution of the Ag segments. Because the electroplating conditions can be easily controlled, we could carefully adjust the size and pitch of the periodically hollow nanospaces. We also describe a method for the fabrication of Ni nanorods by forming an Ag shell instead of a Ni shell on the Ni-Ag barcode nanowire, in which the interior of the AAO surfaces was modified with a compound bearing a thiol group prior to electroplating.

Salt flux synthesis of single and bimetallic carbide nanowires

NASA Astrophysics Data System (ADS)

Leonard, Brian M.; Waetzig, Gregory R.; Clouser, Dale A.; Schmuecker, Samantha M.; Harris, Daniel P.; Stacy, John M.; Duffee, Kyle D.; Wan, Cheng

2016-07-01

Metal carbide compounds have a broad range of interesting properties and are some of the hardest and highest melting point compounds known. However, their high melting points force very high reaction temperatures and thus limit the formation of high surface area nanomaterials. To avoid the extreme synthesis temperatures commonly associated with these materials, a new salt flux technique has been employed to reduce reaction temperatures and form these materials in the nanometer regime. Additionally, the use of multiwall carbon nanotubes as a reactant further reduces the diffusion distance and provides a template for the final carbide materials. The metal carbide compounds produced through this low temperature salt flux technique maintain the nanowire morphology of the carbon nanotubes but increase in size to ˜15-20 nm diameter due to the incorporation of metal in the carbon lattice. These nano-carbides not only have nanowire like shape but also have much higher surface areas than traditionally prepared metal carbides. Finally, bimetallic carbides with composition control can be produced with this method by simply using two metal precursors in the reaction. This method provides the ability to produce nano sized metal carbide materials with size, morphology, and composition control and will allow for these compounds to be synthesized and studied in a whole new size and temperature regime.

Evaporation as the transport mechanism of metals in arid regions.

PubMed

Lima, Ana T; Safar, Zeinab; Loch, J P Gustav

2014-09-01

Soils of arid regions are exposed to drought and drastic temperature oscillations throughout the year. Transport mechanisms in these soils are therefore very different from the ones in temperate regions, where rain dictates the fate of most elements in soils. Due to the low rainfall and high evaporation rates in arid regions, groundwater quality is not threatened and all soil contamination issues tend to be overlooked. But if soil contamination happens, where do contaminants go? This study tests the hypothesis of upward metal movement in soils when evaporation is the main transport mechanism. Laboratory evaporation tests were carried out with heavy metal spiked Saudi soil, using circulation of air as the driving force (Fig. 1). Main results show that loamy soil retains heavy metals quite well while evaporation drives heavy metals to the surface of a sandy soil. Evaporation transports heavy metals upward in sandy soils of arid regions, making them accumulate at the soil surface. Sand being the dominating type of soil in arid regions, soils can then be a potential source of contaminated aerosols and atmospheric pollution - a transboundary problem. Some other repercussions for this problem are foreseen, such as the public ingestion or inhalation of dust. Copyright © 2014 Elsevier Ltd. All rights reserved.

Build-up of toxic metals on the impervious surfaces of a commercial seaport.

PubMed

Ziyath, Abdul M; Egodawatta, Prasanna; Goonetilleke, Ashantha

2016-05-01

In the context of increasing threats to the sensitive marine ecosystem by toxic metals, this study investigated the metal build-up on impervious surfaces specific to commercial seaports. The knowledge generated from this study will contribute to managing toxic metal pollution of the marine ecosystem. The study found that inter-modal operations and main access roadway had the highest loads followed by container storage and vehicle marshalling sites, while the quay line and short term storage areas had the lowest. Additionally, it was found that Cr, Al, Pb, Cu and Zn were predominantly attached to solids, while significant amount of Cu, Pb and Zn were found as nutrient complexes. As such, treatment options based on solids retention can be effective for some metal species, while ineffective for other species. Furthermore, Cu and Zn are more likely to become bioavailable in seawater due to their strong association with nutrients. Mathematical models to replicate the metal build-up process were also developed using experimental design approach and partial least squares regression. The models for Cr and Pb were found to be reliable, while those for Al, Zn and Cu were relatively less reliable, but could be employed for preliminary investigations. Copyright © 2016 Elsevier Inc. All rights reserved.

Porewater dynamics of silver, lead and copper in coastal sediments and implications for benthic metal fluxes

USGS Publications Warehouse

Kalnejais, Linda H.; Martin, W. R.; Bothner, Michael H.

2015-01-01

To determine the conditions that lead to a diffusive release of dissolved metals from coastal sediments, porewater profiles of Ag, Cu, and Pb have been collected over seven years at two contrasting coastal sites in Massachusetts, USA. The Hingham Bay (HB) site is a contaminated location in Boston Harbor, while the Massachusetts Bay (MB) site is 11 km offshore and less impacted. At both sites, the biogeochemical cycles include scavenging by Fe-oxyhydroxides and release of dissolved metals when Fe-oxyhydroxides are reduced. Important differences in the metal cycles at the two sites, however, result from different redox conditions. Porewater sulfide and seasonal variation in redox zone depth is observed at HB, but not at MB. In summer, as the conditions become more reducing at HB, trace metals are precipitated as sulfides and are no longer associated with Fe-oxyhydroxides. Sulfide precipitation close to the sediment–water interface limits the trace metal flux in summer and autumn at HB, while in winter, oxidation of the sulfide phases drives high benthic fluxes of Cu and Ag, as oxic conditions return. The annual diffusive flux of Cu at HB is found to be significant and contributes to the higher than expected water column Cu concentrations observed in Boston Harbor. At MB, due to the lower sulfide concentrations, the association of trace metals with Fe-oxyhydroxides occurs throughout the year, leading to more stable fluxes. A surface enrichment of solid phase trace metals was found at MB and is attributed to the persistent scavenging by Fe-oxyhydroxides. This process is important, particularly at sites that are less reducing, because it maintains elevated metal concentrations at the surface despite the effects of bioturbation and sediment accumulation, and because it may increase the persistence of metal contamination in surface sediments.

Resolving colocalization of bacteria and metal(loid)s on plant root surfaces by combining fluorescence in situ hybridization (FISH) with multiple-energy micro-focused X-ray fluorescence (ME μXRF).

PubMed

Honeker, Linnea K; Root, Robert A; Chorover, Jon; Maier, Raina M

2016-12-01

Metal(loid)-contamination of the environment due to anthropogenic activities is a global problem. Understanding the fate of contaminants requires elucidation of biotic and abiotic factors that influence metal(loid) speciation from molecular to field scales. Improved methods are needed to assess micro-scale processes, such as those occurring at biogeochemical interfaces between plant tissues, microbial cells, and metal(loid)s. Here we present an advanced method that combines fluorescence in situ hybridization (FISH) with synchrotron-based multiple-energy micro-focused X-ray fluorescence microprobe imaging (ME μXRF) to examine colocalization of bacteria and metal(loid)s on root surfaces of plants used to phytostabilize metalliferous mine tailings. Bacteria were visualized on a small root section using SytoBC nucleic acid stain and FISH probes targeting the domain Bacteria and a specific group (Alphaproteobacteria, Gammaproteobacteria, or Actinobacteria). The same root region was then analyzed for elemental distribution and metal(loid) speciation of As and Fe using ME μXRF. The FISH and ME μXRF images were aligned using ImageJ software to correlate microbiological and geochemical results. Results from quantitative analysis of colocalization show a significantly higher fraction of As colocalized with Fe-oxide plaques on the root surfaces (fraction of overlap 0.49±0.19) than to bacteria (0.072±0.052) (p<0.05). Of the bacteria that colocalized with metal(loid)s, Actinobacteria, known for their metal tolerance, had a higher correlation with both As and Fe than Alphaproteobacteria or Gammaproteobacteria. This method demonstrates how coupling these micro-techniques can expand our understanding of micro-scale interactions between roots, metal(loid)s and microbes, information that should lead to improved mechanistic models of metal(loid) speciation and fate. Copyright © 2016 Elsevier B.V. All rights reserved.

Li 2S Film Formation on Lithium Anode Surface of Li–S batteries

DOE PAGES

Liu, Zhixiao; Bertolini, Samuel; Balbuena, Perla B.; ...

2016-02-02

The precipitation of lithium sulfide (Li 2S) on the Li metal anode surface adversely impacts the performance of lithium–sulfur (Li–S) batteries. In this work, a first-principles approach including density functional theory (DFT) and ab initio molecular dynamics (AIMD) simulations is employed to theoretically elucidate the Li 2S/Li metal surface interactions and the nucleation and growth of a Li 2S film on the anode surface due to long-chain polysulfide decomposition during battery operation. DFT analyses of the energetic properties and electronic structures demonstrate that a single molecule adsorption on Li surface releases energy forming chemical bonds between the S atoms andmore » Li atoms from the anode surface. Reaction pathways of the Li 2S film formation on Li metal surfaces are investigated based on DFT calculations. It is found that a distorted Li 2S (111) plane forms on a Li(110) surface and a perfect Li 2S (111) plane forms on a Li(111) surface. The total energy of the system decreases along the reaction pathway; hence Li 2S film formation on the Li anode surface is thermodynamically favorable. Finally, the calculated difference charge density of the Li 2S film/Li surface suggests that the precipitated film would interact with the Li anode via strong chemical bonds. AIMD simulations reveal the role of the anode surface structure and the origin of the Li 2S formation via decomposition of Li 2S 8 polysulfide species formed at the cathode side and dissolved in the electrolyte medium in which they travel to the anode side during battery cycling.« less

Li 2S Film Formation on Lithium Anode Surface of Li–S batteries

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

Liu, Zhixiao; Bertolini, Samuel; Balbuena, Perla B.

The precipitation of lithium sulfide (Li 2S) on the Li metal anode surface adversely impacts the performance of lithium–sulfur (Li–S) batteries. In this work, a first-principles approach including density functional theory (DFT) and ab initio molecular dynamics (AIMD) simulations is employed to theoretically elucidate the Li 2S/Li metal surface interactions and the nucleation and growth of a Li 2S film on the anode surface due to long-chain polysulfide decomposition during battery operation. DFT analyses of the energetic properties and electronic structures demonstrate that a single molecule adsorption on Li surface releases energy forming chemical bonds between the S atoms andmore » Li atoms from the anode surface. Reaction pathways of the Li 2S film formation on Li metal surfaces are investigated based on DFT calculations. It is found that a distorted Li 2S (111) plane forms on a Li(110) surface and a perfect Li 2S (111) plane forms on a Li(111) surface. The total energy of the system decreases along the reaction pathway; hence Li 2S film formation on the Li anode surface is thermodynamically favorable. Finally, the calculated difference charge density of the Li 2S film/Li surface suggests that the precipitated film would interact with the Li anode via strong chemical bonds. AIMD simulations reveal the role of the anode surface structure and the origin of the Li 2S formation via decomposition of Li 2S 8 polysulfide species formed at the cathode side and dissolved in the electrolyte medium in which they travel to the anode side during battery cycling.« less

Li2S Film Formation on Lithium Anode Surface of Li-S batteries.

PubMed

Liu, Zhixiao; Bertolini, Samuel; Balbuena, Perla B; Mukherjee, Partha P

2016-02-01

The precipitation of lithium sulfide (Li2S) on the Li metal anode surface adversely impacts the performance of lithium-sulfur (Li-S) batteries. In this study, a first-principles approach including density functional theory (DFT) and ab initio molecular dynamics (AIMD) simulations is employed to theoretically elucidate the Li2S/Li metal surface interactions and the nucleation and growth of a Li2S film on the anode surface due to long-chain polysulfide decomposition during battery operation. DFT analyses of the energetic properties and electronic structures demonstrate that a single molecule adsorption on Li surface releases energy forming chemical bonds between the S atoms and Li atoms from the anode surface. Reaction pathways of the Li2S film formation on Li metal surfaces are investigated based on DFT calculations. It is found that a distorted Li2S (111) plane forms on a Li(110) surface and a perfect Li2S (111) plane forms on a Li(111) surface. The total energy of the system decreases along the reaction pathway; hence Li2S film formation on the Li anode surface is thermodynamically favorable. The calculated difference charge density of the Li2S film/Li surface suggests that the precipitated film would interact with the Li anode via strong chemical bonds. AIMD simulations reveal the role of the anode surface structure and the origin of the Li2S formation via decomposition of Li2S8 polysulfide species formed at the cathode side and dissolved in the electrolyte medium in which they travel to the anode side during battery cycling.

METHOD OF FORMING A PROTECTIVE COATING ON FERROUS METAL SURFACES

DOEpatents

Schweitzer, D.G.; Weeks, J.R.; Kammerer, O.F.; Gurinsky, D.H.

1960-02-23

A method is described of protecting ferrous metal surfaces from corrosive attack by liquid metals, such as liquid bismuth or lead-bismuth alloys. The nitrogen content of the ferrous metal surface is first reduced by reacting the metal surface with a metal which forms a stable nitride. Thereafter, the surface is contacted with liquid metal containing at least 2 ppm zirconium at a temperature in the range of 550 to 1100 deg C to form an adherent zirconium carbide layer on the ferrous surface.

Method for preparing hydride configurations and reactive metal surfaces

DOEpatents

Silver, G.L.

1984-05-18

A method for preparing reactive metal surfaces, particularly uranium surfaces is disclosed, whereby the metal is immediately reactive to hydrogen gas at room temperature and low pressure. The metal surfaces are first pretreated by exposure to an acid which forms an adherent hydride-bearing composition on the metal surface. Subsequent heating of the pretreated metal at a temperature sufficient to decompose the hydride coating in vacuum or inert gas renders the metal surface instantaneously reactive to hydrogen gas at room temperature and low pressure.

Effects on optical systems from interactions with oxygen atoms in low earth orbits

NASA Technical Reports Server (NTRS)

Peters, P. N.; Swann, J. T.; Gregory, J. C.

1986-01-01

Modifications of material surface properties due to interactions with ambient atomic oxygen have been observed on surfaces facing the orbital direction in low earth orbits. Some effects are very damaging to surface optical properties while some are more subtle and even beneficial. Most combustible materials are heavily etched, and some coatings, such as silver and osmium, are seriously degraded or removed as volatile oxides. The growth of oxide films on metals and semiconductors considered stable in dry air was measured. Material removal, surface roughness, reflectance, and optical densities are reported. Effects of temperature, contamination, and overcoatings are noted.

Effects on optical systems from interactions with oxygen atoms in low earth orbits

NASA Astrophysics Data System (ADS)

Peters, P. N.; Swann, J. T.; Gregory, J. C.

1986-04-01

Modifications of material surface properties due to interactions with ambient atomic oxygen have been observed on surfaces facing the orbital direction in low earth orbits. Some effects are very damaging to surface optical properties while some are more subtle and even beneficial. Most combustible materials are heavily etched, and some coatings, such as silver and osmium, are seriously degraded or removed as volatile oxides. The growth of oxide films on metals and semiconductors considered stable in dry air was measured. Material removal, surface roughness, reflectance, and optical densities are reported. Effects of temperature, contamination, and overcoatings are noted.

Plasmonic gold nanoparticles modified titania nanotubes for antibacterial application

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

Li, Jinhua; Zhou, Huaijuan; Qian, Shi

Close-packed TiO{sub 2} nanotube arrays are prepared on metallic Ti surface by electrochemical anodization. Subsequently, by magnetron sputtering, Au nanoparticles are coated onto the top sidewall and tube inwall. The Au@TiO{sub 2} systems can effectively kill Staphylococcus aureus and Escherichia coli in darkness due to the existence of Au nanoparticles. On the basis of classical optical theories, the antibacterial mechanism is proposed from the perspective of localized surface plasmon resonance. Respiratory electrons of bacterial membrane transfer to Au nanoparticles and then to TiO{sub 2}, which makes bacteria steadily lose electrons until death. This work provides insights for the better understandingmore » and designing of noble metal nanoparticles-based plasmonic heterostructures for antibacterial application.« less

Cavitation in Amorphous Solids

NASA Astrophysics Data System (ADS)

Guan, Pengfei; Lu, Shuo; Spector, Michael J. B.; Valavala, Pavan K.; Falk, Michael L.

2013-05-01

Molecular dynamics simulations of cavitation in a Zr50Cu50 metallic glass exhibit a waiting time dependent cavitation rate. On short time scales nucleation rates and critical cavity sizes are commensurate with a classical theory of nucleation that accounts for both the plastic dissipation during cavitation and the cavity size dependence of the surface energy. All but one parameter, the Tolman length, can be extracted directly from independent calculations or estimated from physical principles. On longer time scales strain aging in the form of shear relaxations results in a systematic decrease of cavitation rate. The high cavitation rates that arise due to the suppression of the surface energy in small cavities provide a possible explanation for the quasibrittle fracture observed in metallic glasses.

Efficient magnetic recycling of covalently attached enzymes on carbon-coated metallic nanomagnets.

PubMed

Zlateski, Vladimir; Fuhrer, Roland; Koehler, Fabian M; Wharry, Scott; Zeltner, Martin; Stark, Wendelin J; Moody, Thomas S; Grass, Robert N

2014-04-16

In the pursuit of robust and reusable biocatalysts for industrial synthetic chemistry, nanobiotechnology is currently taking a significant part. Recently, enzymes have been immobilized on different nanoscaffold supports. Carbon coated metallic nanoparticles were found to be a practically useful support for enzyme immobilization due to their large surface area, high magnetic saturation, and manipulatable surface chemistry. In this study carbon coated cobalt nanoparticles were chemically functionalized (diazonium chemistry), activated for bioconjugation (N,N-disuccinimidyl carbonate), and subsequently used in enzyme immobilization. Three enzymes, β-glucosidase, α-chymotrypsin, and lipase B were successfully covalently immobilized on the magnetic nonsupport. The enzyme-particle conjugates formed retained their activity and stability after immobilization and were efficiently recycled from milliliter to liter scales in short recycle times.

Steam reforming of n-hexane on pellet and monolithic catalyst beds. A comparative study on improvements due to heat transfer

NASA Technical Reports Server (NTRS)

1981-01-01

Monolithic catalysts with higher available active surface areas and better thermal conductivity than conventional pellets beds, making possible the steam reforming of fuels heavier than naphtha, were examined. Performance comparisons were made between conventional pellet beds and honeycomb monolith catalysts using n-hexane as the fuel. Metal-supported monoliths were examined. These offer higher structural stability and higher thermal conductivity than ceramic supports. Data from two metal monoliths of different nickel catalyst loadings were compared to pellets under the same operating conditions. Improved heat transfer and better conversion efficiencies were obtained with the monolith having higher catalyst loading. Surface-gas interaction was observed throughout the length of the monoliths.

Water repellent properties of dispersed metals containing low-dimensional forms of ammonium compounds on the surface

NASA Astrophysics Data System (ADS)

Syrkov, A. G.; Kabirov, V. R.; Silivanov, M. O.

2017-07-01

For the first time the change of the water repellent properties of dispersed copper, modified using quaternary ammonium compounds on 24 h time scale in saturated water vapours was studied. Exponential time dependences of the water repellent properties of dispersed copper with adsopted QAC were derived and characterized. It was established that the samples modified in mixed and consistent modes by both modifiers reach the saturation state faster than others, due to the small number of hydrophilic centers on the surface of metals. The last conclusion was confirmed by the distribution spectra of centers of adsorption, which were obtained by the adsorption of acid-base indicators for more dispersed samples based on aluminum powder.

Scaling laws and edge effects for polymer surface discharges

NASA Technical Reports Server (NTRS)

Balmain, K. G.

1979-01-01

Specimens of Mylar sheet were exposed to a 20 kV electron beam. The resulting surface discharge arcs were photographed and the discharge current into a metal backing plate measured as a function of time. The area of the Mylar sheet was defined by a round aperture in a close-fitting metal mask, and the current pulse characteristics were plotted against area on log-log paper. The plots appear as straight lines (due to power-law behavior) with slopes of 0.50 for the peak current, 1.00 for the charge released, 1.49 for the energy and 0.55 for the pulse duration. Evidence is presented for the occurrence of banded charge distributions near grounded edges, on both Teflon and Mylar.

Initial Plasma Testing of the Ion Proportional Surface Emission Cathode

DTIC Science & Technology

2008-07-15

REPRINT 3. DATES COVERED (From - To) 4. TITLE AND SUBTITLE Initial Plasma Testing of the Ion Proportional Surface Emission Cathode 5a. CONTRACT NUMBER...substrate and an adjacent metal cathode element. The substrate potential is held positive of the cathode with gate elements. In plasma , the gate is...eliminated due to ambient ion flux which maintains the substrate potential near plasma ground. Prototype devices have been tested using a laboratory plasma

Adsorption of guaiacol on Fe (110) and Pd (111) from first principles

NASA Astrophysics Data System (ADS)

Hensley, Alyssa J. R.; Wang, Yong; McEwen, Jean-Sabin

2016-06-01

The catalytic properties of surfaces are highly dependent upon the effect said surfaces have on the geometric and electronic structure of adsorbed reactants, products, and intermediates. It is therefore crucial to have a surface-level understanding of the adsorption of the key species in a reaction in order to design active and selective catalysts. Here, we study the adsorption of guaiacol on Fe (110) and Pd (111) using dispersion-corrected density functional theory calculations as both of these metals are of interest as hydrodeoxygenation catalysts for the conversion of bio-oils to useable biofuels. Both vertical (via the oxygen functional groups) and horizontal (via the aromatic ring) adsorption configurations were examined and the resulting adsorption and molecular distortion energies showed that the vertical sites were only physisorbed while the horizontal sites were chemisorbed on both metal surfaces. A comparison of guaiacol's horizontal adsorption on Fe (110) and Pd (111) showed that guaiacol had a stronger adsorption on Pd (111) while the Fe (110) surface distorted the Csbnd O bonds to a greater degree. Electronic analyses on the horizontal systems showed that the greater adsorption strength for guaiacol on Pd (111) was likely due to the greater charge transfer between the aromatic ring and the surface Pd atoms. Additionally, the greater distortion of the Csbnd O bonds in adsorbed guaiacol on Fe (110) is likely due to the greater degree of interaction between the oxygen and surface Fe atoms. Overall, our results show that the Fe (110) surface has a greater degree of interaction with the functional groups and the Pd (111) surface has a greater degree of interaction with the aromatic ring.

Electronic transport in bismuth selenide in the topological insulator regime

NASA Astrophysics Data System (ADS)

Kim, Dohun

The 3D topological insulators (TIs) have an insulating bulk but spin-momentum coupled metallic surface states stemming from band inversion due to strong spin-orbit interaction, whose existence is guaranteed by the topology of the band structure of the insulator. While the STI surface state has been studied spectroscopically by e.g. photoemission and scanned probes, transport experiments have failed to demonstrate clear signature of the STI due to high level of bulk conduction. In this thesis, I present experimental results on the transport properties of TI material Bi2Se3 in the absence of bulk conduction (TI regime), achieved by applying novel p-type doping methods. Field effect transistors consisting of thin (thickness: 5-17 nm) Bi2Se3 are fabricated by mechanical exfoliation of single crystals, and a combination of conventional dielectric (300 nm thick SiO2) and electrochemical or chemical gating methods are used to move the Fermi energy through the surface Dirac point inside bulk band gap, revealing the ambipolar gapless nature of transport in the Bi2Se3 surface states. The minimum conductivity of the topological surface state is understood within the self-consistent theory of Dirac electrons in the presence of charged impurities. The intrinsic finite-temperature resistivity of the topological surface state due to electron-acoustic phonon scattering is measured to be 60 times larger than that of graphene largely due to the smaller Fermi and sound velocities in Bi2Se 3, which will have implications for topological electronic devices operating at room temperature. Along with semi-classical Boltzmann transport, I also discuss 2D weak anti-localization (WAL) behavior of the topological surface states. By investigating gate-tuned WAL behavior in thin (5-17 nm) TI films, I show that WAL in the TI regime is extraordinarily sensitive to the hybridization induced quantum mechanical tunneling between top and bottom topological surfaces, and interplay of phase coherence time and inter-surface tunneling time results in a crossover from two decoupled (top and bottom) symplectic 2D metal surfaces to a coherently coupled single channel. Furthermore, a complete suppression of WAL is observed in the 5 nm thick Bi2Se 3 film which was found to occur when the hybridization gap becomes comparable to the disorder strength.

Samarium Hexaboride: The First True 3D Topological Insulator?

NASA Astrophysics Data System (ADS)

Wolgast, Steven G.

The recent theoretical prediction of a topologically protected surface state in the mixed-valent insulator SmB6 has motivated a series of charge transport studies, which are presented here. It is first studied using a specialized configuration designed to distinguish bulk-dominated conduction from surface-dominated conduction. As the material is cooled below 4 K, it exhibits a crossover from thermally activated bulk transport to metallic surface conduction with a fully insulating bulk. The robustness and magnitude of the surface conductivity, as is manifest in the literature of SmB6, is strong evidence for the topological insulator (TI) metallic surface states predicted for this material. This resolves a decades-old puzzle surrounding the low-temperature behavior of SmB6. Next, the magnetotransport properties of the surface are investigated using a Corbino disk geometry, which can directly measure the conductivity of individual surfaces. Both (011) and (001) crystal surfaces show a strong negative magnetoresistance at all magnetic field angles, due primarily to changes in the carrier density. The low mobility value accounts for the failure so far to observe Shubnikov-de Haas oscillations below 95 T. Small variations in the mobility and temperature dependence suggest a suppression of Kondo scattering from native oxide-layer magnetic moments. At low fields, a dynamical field-sweep-rate-dependent hysteretic behavior is observed. It persists at the slowest sweep rates, and cannot be explained by quantum interference corrections; it is likely due to extrinsic effects such as the magnetocaloric effect or glassy ordering of the native oxide moments. Pulsed magnetic field measurements up to 60 T at temperatures throughout the crossover regime clearly distinguish the surface magnetoresistance from the bulk magnetoresistance. The bulk magnetoresistance is due to a reduction in the bulk gap with increasing magnetic field. Finally, small subsurface cracks formed in SmB6 via systematic scratching or sanding results in a counter-intuitive increase in the electrical conduction due to the unique surface-conducting property of TIs, strengthening the building case for SmB 6's topological nature. This material is attractive as a TI because its bulk is fully insulating at a readily achieved 2 K, but it presents a large number of scientific mysteries and experimental challenges for future research.

Roughness evolution of metallic implant surfaces under contact loading and nanometer-scale chemical etching.

PubMed

Ryu, J J; Letchuman, S; Shrotriya, P

2012-10-01

Surface damage of metallic implant surface at taper lock and clamped interfaces may take place through synergistic interactions between repeated contact loading and corrosion. In the present research, we investigated the influence of surface roughness and contact loading on the mechanical and chemical damage phenomena. Cobalt-chromium (CoCrMo) specimens with two different roughness configurations created by milling and grinding process were subjected to normal and inclined contact loading. During repeated contact loading, amplitude of surface roughness reached a steady value after decreasing during the first few cycles. During the second phase, the alternating experiment of rough surface contact and micro-etching was conducted to characterize surface evolution behavior. As a result, surface roughness amplitude continuously evolved-decreasing during contact loading due to plastic deformation of contacting asperities and increasing on exposure to corrosive environment by the preferential corrosion attack on stressed area. Two different instabilities could be identified in the surface roughness evolution during etching of contact loaded surfaces: increase in the amplitude of dominant wavenumber and increase in amplitude of a small group of roughness modes. A damage mechanism that incorporates contact-induced residual stress development and stress-assisted dissolution is proposed to elucidate the measured instabilities in surface roughness evolution. Copyright © 2012 Elsevier Ltd. All rights reserved.

Broadband absorption enhancement in amorphous Si solar cells using metal gratings and surface texturing

NASA Astrophysics Data System (ADS)

Magdi, Sara; Swillam, Mohamed A.

2017-02-01

The efficiencies of thin film amorphous silicon (a-Si) solar cells are restricted by the small thickness required for efficient carrier collection. This thickness limitations result in poor light absorption. In this work, broadband absorption enhancement is theoretically achieved in a-Si solar cells by using nanostructured back electrode along with surface texturing. The back electrode is formed of Au nanogratings and the surface texturing consists of Si nanocones. The results were then compared to random texturing surfaces. Three dimensional finite difference time domain (FDTD) simulations are used to design and optimize the structure. The Au nanogratings achieved absorption enhancement in the long wavelengths due to sunlight coupling to surface plasmon polaritons (SPP) modes. High absorption enhancement was achieved at short wavelengths due to the decreased reflection and enhanced scattering inside the a-Si absorbing layer. Optimizations have been performed to obtain the optimal geometrical parameters for both the nanogratings and the periodic texturing. In addition, an enhancement factor (i.e. absorbed power in nanostructured device/absorbed power in reference device) was calculated to evaluate the enhancement obtained due to the incorporation of each nanostructure.

Numerical analysis of thermal drilling technique on titanium sheet metal

NASA Astrophysics Data System (ADS)

Kumar, R.; Hynes, N. Rajesh Jesudoss

2018-05-01

Thermal drilling is a technique used in drilling of sheet metal for various applications. It involves rotating conical tool with high speed in order to drill the sheet metal and formed a hole with bush below the surface of sheet metal. This article investigates the finite element analysis of thermal drilling on Ti6Al4Valloy sheet metal. This analysis was carried out by means of DEFORM-3D simulation software to simulate the performance characteristics of thermal drilling technique. Due to the contribution of high temperature deformation in this technique, the output performances which are difficult to measure by the experimental approach, can be successfully achieved by finite element method. Therefore, the modeling and simulation of thermal drilling is an essential tool to predict the strain rate, stress distribution and temperature of the workpiece.

Corrosion on the acetabular liner taper from retrieved modular metal-on-metal total hip replacements.

PubMed

Gascoyne, Trevor C; Dyrkacz, Richard M; Turgeon, Thomas R; Burnell, Colin D; Wyss, Urs P; Brandt, Jan-M

2014-10-01

Eight retrieved metal-on-metal total hip replacements displayed corrosion damage along the cobalt-chromium alloy liner taper junction with the Ti alloy acetabular shell. Scanning electron microscopy indicated the primary mechanism of corrosion to be grain boundary and associated crevice corrosion, which was likely accelerated through mechanical micromotion and galvanic corrosion resulting from dissimilar alloys. Coordinate measurements revealed up to 4.3mm(3) of the cobalt-chromium alloy taper surface was removed due to corrosion, which is comparable to previous reports of corrosion damage on head-neck tapers. The acetabular liner-shell taper appears to be an additional source of metal corrosion products in modular total hip replacements. Patients with these prostheses should be closely monitored for signs of adverse reaction towards corrosion by-products. Copyright © 2014 Elsevier Inc. All rights reserved.

Second- and third-harmonic generation in metal-based structures

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

Scalora, M.; Akozbek, N.; Bloemer, M. J.

We present a theoretical approach to the study of second- and third-harmonic generation from metallic structures and nanocavities filled with a nonlinear material in the ultrashort pulse regime. We model the metal as a two-component medium, using the hydrodynamic model to describe free electrons and Lorentz oscillators to account for core electron contributions to both the linear dielectric constant and harmonic generation. The active nonlinear medium that may fill a metallic nanocavity, or be positioned between metallic layers in a stack, is also modeled using Lorentz oscillators and surface phenomena due to symmetry breaking are taken into account. We studymore » the effects of incident TE- and TM-polarized fields and show that a simple reexamination of the basic equations reveals additional, exploitable dynamical features of nonlinear frequency conversion in plasmonic nanostructures.« less

Spinterface between tris(8-hydroxyquinoline)metal(III) molecules and magnetic surfaces: a first-principles study

NASA Astrophysics Data System (ADS)

Jiang, W.; Wang, Jingying; Dougherty, Daniel; Liu, Feng; Feng Liu Team; Daniel Dougherty Team

Using first-principles calculations, we have systematically investigated the hybridization between tris(8-hydroxyquinoline)metal(III) (Mq3, M = Fe, Cr, Al) molecules and magnetic substrates (Co and Cr). Mq3 with different central metal elements but the same organic framework has dramatically different interaction with different magnetic substrates, which affect the interface state significantly. AFM coupling was observed between magnetic Mq3 molecules and ferromagnetic (Co) as well as antiferromagnetic (Cr) substrate, manifested with a superexchange and direct exchange interaction, respectively. Such strong magnetic interfacial coupling may open a gap around the Fermi level and significantly change interface transport properties. Nonmagnetic Alq3 molecule was found to enhance the interface spin polarization due to hybridization between the lowest unoccupied molecular orbitals (LUMO) of Alq3 and metallic surface state. These findings will help better understand spinterface and shed new light on future application of Mq3 molecules in spintronics devices. This work was support by NSF-MRSEC (DMR-1121252) and DOE-BES (DE-FG02-04ER46148).

Fabrication of monolayer MoS2/rGO hybrids with excellent tribological performances through a surfactant-assisted hydrothermal route

NASA Astrophysics Data System (ADS)

Chen, Jinsuo; Xia, Yunfei; Yang, Jin; Chen, Beibei

2018-06-01

The extremely low friction between incommensurate two-dimensional (2D) atomic layers has recently attracted a great interest. Here, we demonstrated a promising surfactant-assisted strategy for the synthesis of MoS2/reduced graphene oxide (MoS2/rGO) hybrid materials with monolayer MoS2 and rGO, which exhibited excellent tribological metrics with a friction coefficient of ˜ 0.09 and a wear rate of ˜ 2.08 × 10-5 mm3/Nm in the ethanol dispersion. The incommensurate 2D atomic layer interface formed due to intrinsic lattice mismatch between MoS2 and graphene was thought to be responsible for the excellent lubricating performances. In addition to the benefits of unique hybrid structure, MoS2/rGO hybrids could also adsorb on metal surfaces and screen the metal-metal interaction to passivate the metal surfaces with a consequent reduction of corrosion wear during sliding. This work could pave a new pathway to design novel materials for pursuing excellent tribological properties by hybridizing different 2D atomic-layered materials.

Effect of process variables on the sulfate reduction process in bioreactors treating metal-containing wastewaters: factorial design and response surface analyses.

PubMed

Villa-Gomez, D K; Pakshirajan, K; Maestro, R; Mushi, S; Lens, P N L

2015-07-01

The individual and combined effect of the pH, chemical oxygen demand (COD) and SO4 (2-) concentration, metal to sulfide (M/S(2-)) ratio and hydraulic retention time (HRT) on the biological sulfate reduction (SR) process was evaluated in an inverse fluidized bed reactor by factorial design analysis (FDA) and response surface analysis (RSA). The regression-based model of the FDA described the experimental results well and revealed that the most significant variable affecting the process was the pH. The combined effect of the pH and HRT was barely observable, while the pH and COD concentration positive effect (up to 7 and 3 gCOD/L, respectively) enhanced the SR process. Contrary, the individual COD concentration effect only enhanced the COD removal efficiency, suggesting changes in the microbial pathway. The RSA showed that the M/S(2-) ratio determined whether the inhibition mechanism to the SR process was due to the presence of free metals or precipitated metal sulfides.

Self-consistent field calculations of conductance through conjugated molecules at finite bias

NASA Astrophysics Data System (ADS)

Paulsson, Magnus; Stafström, Sven

2001-03-01

Conductance through conjugated molecules have previously been calculated for a large number of systems using the Landauer formula but only a few calculations have included charging effects. In this study we present calculations in the mean field approximation of the conductance of metal-molecule-metal systems using two different kinds of molecules for a large number of configurations and applied biases. The molecules are described in the Pariser-Parr Pople model. Current-voltage (I-V) characteristics and charge distribution of the molecule connected by one dimensional leads to reservoirs is solved within the Hartree-Fock approximation. Charging of the molecule occurs when the chemical potential of the reservoirs approach the resonant tunneling levels. The ensuing potential difference, due to the charging, shifts the tunneling peaks which affects the I-V curves considerably. Asymmetrical interaction with the metal leads, e.g. molecule on a metal surface contacted with an STM-tip, also give asymmetrical I-V curves where the potential of the molecule is shown to more closely follow the potential of the surface. Negative differential conductance is discussed in systems consisting of two weakly coupled molecules.

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

PubMed

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

2010-01-15

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

Biochar as possible long-term soil amendment for phytostabilisation of TE-contaminated soils.

PubMed

Bopp, Charlotte; Christl, Iso; Schulin, Rainer; Evangelou, Michael W H

2016-09-01

Soils contaminated by trace elements (TEs) pose a high risk to their surrounding areas as TEs can spread by wind and water erosion or leaching. A possible option to reduce TE transfer from these sites is phytostabilisation. It is a long-term and cost-effective rehabilitation strategy which aims at immobilising TEs within the soil by vegetation cover and amendment application. One possible amendment is biochar. It is charred organic matter which has been shown to immobilise metals due to its high surface area and alkaline pH. Doubts have been expressed about the longevity of this immobilising effect as it could dissipate once the carbonates in the biochar have dissolved. Therefore, in a pot experiment, we determined plant metal uptake by ryegrass (Lolium perenne) from three TE-contaminated soils treated with two biochars, which differed only in their pH (acidic, 2.80; alkaline, 9.33) and carbonate (0.17 and 7.3 %) content. Root biomass was increased by the application of the alkaline biochar due to the decrease in TE toxicity. Zinc and Cu bioavailability and plant uptake were equally reduced by both biochars, showing that surface area plays an important role in metal immobilisation. Biochar could serve as a long-term amendment for TE immobilisation even after its alkalinity effect has dissipated.

Kinetic study of Chromium VI adsorption onto palm kernel shell activated carbon

NASA Astrophysics Data System (ADS)

Mohammad, Masita; Sadeghi Louyeh, Shiva; Yaakob, Zahira

2018-04-01

Heavy metal contamination of industrial effluent is one of the significant environmental problems due to their toxicity and its accumulation throughout the food chain. Adsorption is one of the promising methods for removal of heavy metals from aqua solution because of its simple technique, efficient, reliable and low-cost due to the utilization of residue from the agricultural industry. In this study, activated carbon from palm kernel shells has been produced through chemical activation process using zinc chloride as an activating agent and carbonized at 800 °C. Palm kernel shell activated carbon, PAC was assessed for its efficiency to remove Chromium (VI) ions from aqueous solutions through a batch adsorption process. The kinetic mechanisms have been analysed using Lagergren first-order kinetics model, second-order kinetics model and intra-particle diffusion model. The characterizations such as BET surface area, surface morphology, SEM-EDX have been done. The result shows that the activation process by ZnCl2 was successfully improved the porosity and modified the functional group of palm kernel shell. The result shows that the maximum adsorption capacity of Cr is 11.40mg/g at 30ppm initial metal ion concentration and 0.1g/50mL of adsorbent concentration. The adsorption process followed the pseudo second orders kinetic model.

Effect of abalone farming on sediment geochemistry in the Shallow Sea near Wando, South Korea

NASA Astrophysics Data System (ADS)

Kang, Jeongwon; Lee, Yeon Gyu; Jeong, Da Un; Lee, Jung Sick; Choi, Yang Ho; Shin, Yun Kyung

2015-12-01

Wando County has grown up to 93% of the total abalone produced in South Korea since the late 1990s; however, this production has been decreasing in recent years. The objectives of this study were to understand the potential contamination risks of abalone farming and to examine the influence of intensive abalone farming on sediment quality by analyzing grain-size composition, organic matter (total organic carbon (TOC), total nitrogen (TN), total sulfur (TS)) and heavy metal content, pH, and 210Pb geochronology. The results of organic matter analysis from surface and core sediment (length: 64 cm) showed that the area around the abalone farm had oxic marine-to-brackish conditions, but that the area directly below an abalone cage (location 7) had reductive conditions, with a C/S ratio of ~2. The average TN levels in the surface and core sediments were 0.25% and 0.29%, respectively, and this was predominantly due to the use of seaweed for feed. The low sediment pH (surface, 7.23; core, 7.04), indicates that acidification of the bottom sediment has gradually increased since the initiation of abalone farming and is likely due to the continuous accumulation of uneaten feed and feces. Heavy metal pollution was not apparent based on the examination of EF and Igeo, although the excess metal flux of Ni, Pb, Cu, Co, As, and Cd increased toward surface of the sediment core. These sediment changes may be caused by the rapid accumulation (sedimentation rate: 1.45 cm/year) of sludge discharged from the abalone farm and may be controlled by tidal currents, physiography, water depth, and tidal ranges.

Platinum recycling going green via induced surface potential alteration enabling fast and efficient dissolution

PubMed Central

Hodnik, Nejc; Baldizzone, Claudio; Polymeros, George; Geiger, Simon; Grote, Jan-Philipp; Cherevko, Serhiy; Mingers, Andrea; Zeradjanin, Aleksandar; Mayrhofer, Karl J. J.

2016-01-01

The recycling of precious metals, for example, platinum, is an essential aspect of sustainability for the modern industry and energy sectors. However, due to its resistance to corrosion, platinum-leaching techniques rely on high reagent consumption and hazardous processes, for example, boiling aqua regia; a mixture of concentrated nitric and hydrochloric acid. Here we demonstrate that complete dissolution of metallic platinum can be achieved by induced surface potential alteration, an ‘electrode-less' process utilizing alternatively oxidative and reductive gases. This concept for platinum recycling exploits the so-called transient dissolution mechanism, triggered by a repetitive change in platinum surface oxidation state, without using any external electric current or electrodes. The effective performance in non-toxic low-concentrated acid and at room temperature is a strong benefit of this approach, potentially rendering recycling of industrial catalysts, including but not limited to platinum-based systems, more sustainable. PMID:27767178

Non-plasmonic nanoantennas for surface enhanced spectroscopies with ultra-low heat conversion

PubMed Central

Caldarola, Martín; Albella, Pablo; Cortés, Emiliano; Rahmani, Mohsen; Roschuk, Tyler; Grinblat, Gustavo; Oulton, Rupert F.; Bragas, Andrea V.; Maier, Stefan A.

2015-01-01

Nanoplasmonics has recently revolutionized our ability to control light on the nanoscale. Using metallic nanostructures with tailored shapes, it is possible to efficiently focus light into nanoscale field ‘hot spots'. High field enhancement factors have been achieved in such optical nanoantennas, enabling transformative science in the areas of single molecule interactions, highly enhanced nonlinearities and nanoscale waveguiding. Unfortunately, these large enhancements come at the price of high optical losses due to absorption in the metal, severely limiting real-world applications. Via the realization of a novel nanophotonic platform based on dielectric nanostructures to form efficient nanoantennas with ultra-low light-into-heat conversion, here we demonstrate an approach that overcomes these limitations. We show that dimer-like silicon-based single nanoantennas produce both high surface enhanced fluorescence and surface enhanced Raman scattering, while at the same time generating a negligible temperature increase in their hot spots and surrounding environments. PMID:26238815

Improved battery performance using Pd nanoparticles synthesized on the surface of LiFePO4/C by ultrasound irradiation

NASA Astrophysics Data System (ADS)

Saliman, Muhammad Ali; Okawa, Hirokazu; Takai, Misaki; Ono, Yuki; Kato, Takahiro; Sugawara, Katsuyasu; Sato, Mineo

2016-07-01

LiFePO4 has been attracting interest as a cathode material for Li-ion batteries due to its high energy density, low cost, and eco-friendliness. The electrochemical performance of LiFePO4 is limited because it exhibits low Li-ion diffusivity and low electronic conductivity. Numerous solutions have been considered, such as carbon coating, which is widely known to improve the electronic conductivity of LiFePO4. The deposition of metal nanoparticles (NPs) on the surface of carbon-coated LiFePO4 further enhances the electronic conductivity. In this study, we deposited Pd NPs onto the surface of LiFePO4/C and investigated the resulting electrochemical performance. Sonochemical synthesis was used to prepare the metal NPs; the procedure did not require any surfactants and the reaction was rapid.

Laser dispersing of ceramic powders into Al-alloys

NASA Astrophysics Data System (ADS)

Jendrzejewski, Rafał; Van Acker, Karel; Vanhoyweghen, Dirk

2007-02-01

The general objective of the work was formation of highly wear resistant metal matrix composite (MMC) surface layers on aluminium based Al 6061 alloy by means of laser dispersing. The surface of the substrate is locally melted by the high power diode laser beam and simultaneously powder particles are injected into molten material. The optimal process parameter window for the laser dispersing of SiC in Al 6061 has been found. The measured values of the wear rates of the sample with dispersed SiC particles are about seven times lower than that of the reference Al-substrates. Results show that laser dispersing is highly promising technology to improve the surface, mainly wear properties of light metals. However the possibilities of industrial application are still limited due to considerable laser beam power and preheating temperature applied as well low productivity because of low scanning speed, and therefore further investigations are required.

All-metal meta-surfaces for narrowband light absorption and high performance sensing

NASA Astrophysics Data System (ADS)

Liu, Zhengqi; Liu, Guiqiang; Fu, Guolan; Liu, Xiaoshan; Huang, Zhenping; Gu, Gang

2016-11-01

We report an experimental scheme for high performance sensing by an all-metal meta-surface (AMMS) platform. A dual-band resonant absorption spectrum with a bandwidth down to a single-digit nanometer level and an absorbance up to 89% is achieved due to the surface lattice resonances supported by the resonators array and their hybridization coupling with the particle plasmon resonances. The sensing application in the analysis of the sodium chloride solution has been demonstrated, where remarkable changes from a spectral ‘dark state’ to ‘bright state’ and vice versa are observed. Sensing performance factors of the figure of merit exceeding 50 and the spectral intensity change related FoM* up to 1075 are simultaneously achieved. The corresponding detection limit is as low as 8.849  ×  10-6 RIU. These features make such an AMMS-based sensor a promising route for efficient bio-chemical sensing, etc.

Mechanical work makes important contributions to surface chemistry at steps.

PubMed

Francis, M F; Curtin, W A

2015-02-13

The effect of mechanical strain on the binding energy of adsorbates to late transition metals is believed to be entirely controlled by electronic factors, with tensile stress inducing stronger binding. Here we show, via computation, that mechanical strain of late transition metals can modify binding at stepped surfaces opposite to well-established trends on flat surfaces. The mechanism driving the trend is mechanical, arising from the relaxation of stored mechanical energy. The mechanical energy change can be larger than, and of opposite sign than, the energy changes due to electronic effects and leads to a violation of trends predicted by the widely accepted electronic 'd-band' model. This trend has a direct impact on catalytic activity, which is demonstrated here for methanation, where biaxial tension is predicted to shift the activity of nickel significantly, reaching the peak of the volcano plot and comparable to cobalt and ruthenium.

Critical examination of quantum oscillations in SmB6

NASA Astrophysics Data System (ADS)

Riseborough, Peter S.; Fisk, Z.

2017-11-01

We critically review the results of magnetic torque measurements on SmB6 that show quantum oscillations. Similar studies have been given two different interpretations. One interpretation is based on the existence of metallic surface states, while the second interpretation is in terms of a three-dimensional Fermi surface involving neutral fermionic excitations. We suggest that the low-field oscillations that are seen by both groups for B fields as small as 6 T might be due to metallic surface states. The high-field three-dimensional oscillations are only seen by one group for fields B >18 T. The phenomenon of magnetic breakthrough occurs at high fields and involves the formation of Landau orbits that produces a directional-dependent suppression of Bragg scattering. We argue that the measurements performed under higher-field conditions are fully consistent with expectations based on a three-dimensional semiconducting state with magnetic breakthrough.

Non-plasmonic nanoantennas for surface enhanced spectroscopies with ultra-low heat conversion.

PubMed

Caldarola, Martín; Albella, Pablo; Cortés, Emiliano; Rahmani, Mohsen; Roschuk, Tyler; Grinblat, Gustavo; Oulton, Rupert F; Bragas, Andrea V; Maier, Stefan A

2015-08-04

Nanoplasmonics has recently revolutionized our ability to control light on the nanoscale. Using metallic nanostructures with tailored shapes, it is possible to efficiently focus light into nanoscale field 'hot spots'. High field enhancement factors have been achieved in such optical nanoantennas, enabling transformative science in the areas of single molecule interactions, highly enhanced nonlinearities and nanoscale waveguiding. Unfortunately, these large enhancements come at the price of high optical losses due to absorption in the metal, severely limiting real-world applications. Via the realization of a novel nanophotonic platform based on dielectric nanostructures to form efficient nanoantennas with ultra-low light-into-heat conversion, here we demonstrate an approach that overcomes these limitations. We show that dimer-like silicon-based single nanoantennas produce both high surface enhanced fluorescence and surface enhanced Raman scattering, while at the same time generating a negligible temperature increase in their hot spots and surrounding environments.

Spatial variation of permittivity of an electrolyte solution in contact with a charged metal surface: a mini review

PubMed Central

Gongadze, E.; van Rienen, U.; Kralj-Iglič, V.; Iglič, A.

2012-01-01

Contact between a charged metal surface and an electrolyte implies a particular ion distribution near the charged surface, i.e. the electrical double layer. In this mini review, different mean-field models of relative (effective) permittivity are described within a simple lattice model, where the orientational ordering of water dipoles in the saturation regime is taken into account. The Langevin-Poisson-Boltzmann (LPB) model of spatial variation of the relative permittivity for point-like ions is described and compared to a more general Langevin-Bikerman (LB) model of spatial variation of permittivity for finite-sized ions. The Bikerman model and the Poisson-Boltzmann model are derived as limiting cases. It is shown that near the charged surface, the relative permittivity decreases due to depletion of water molecules (volume-excluded effect) and orientational ordering of water dipoles (saturation effect). At the end, the LPB and LB models are generalised by also taking into account the cavity field. PMID:22263808

The influence of surface area, porous structure, and surface state on the supercapacitor performance of titanium oxynitride: implications for a nanostructuring strategy.

PubMed

Lee, Eun Joo; Lee, Lanlee; Abbas, Muhammad Awais; Bang, Jin Ho

2017-08-09

A recent surge of interest in metal (oxy)nitride materials for energy storage devices has given rise to the rapid development of various nanostructuring strategies for these materials. In supercapacitor applications, early transition metal (oxy)nitrides have been extensively explored, among which titanium oxynitride stands out due to its great potential for charge storage. Despite recent advances in supercapacitors based on titanium oxynitride, many underlying factors governing their capacitive performance remain elusive. In this work, nanostructured titanium oxynitride is prepared by firing an organic-inorganic hybrid precursor under a hot ammonia atmosphere, and the influence of its physical characteristics on the supercapacitor performance is investigated. New insights into the effects of surface area, porous structure, and surface state of titanium oxynitride on the supercapacitor performance are revealed through which a comprehensive understanding about the capacitive behavior of titanium oxynitride is provided. In addition, the implications of these insights for a nanostructuring strategy striving for higher capacitance and improved stability are discussed.

Non-Equilibrium Plasma Processing for the Preparation of Antibacterial Surfaces

PubMed Central

Sardella, Eloisa; Palumbo, Fabio; Camporeale, Giuseppe; Favia, Pietro

2016-01-01

Non-equilibrium plasmas offer several strategies for developing antibacterial surfaces that are able to repel and/or to kill bacteria. Due to the variety of devices, implants, and materials in general, as well as of bacteria and applications, plasma assisted antibacterial strategies need to be tailored to each specific surface. Nano-composite coatings containing inorganic (metals and metal oxides) or organic (drugs and biomolecules) compounds can be deposited in one step, and used as drug delivery systems. On the other hand, functional coatings can be plasma-deposited and used to bind antibacterial molecules, for synthesizing surfaces with long lasting antibacterial activity. In addition, non-fouling coatings can be produced to inhibit the adhesion of bacteria and reduce the formation of biofilm. This paper reviews plasma-based strategies aimed to reduce bacterial attachment and proliferation on biomedical materials and devices, but also onto materials used in other fields. Most of the activities described have been developed in the lab of the authors. PMID:28773637

Super-reduced polyoxometalates: excellent molecular cluster battery components and semipermeable molecular capacitors.

PubMed

Nishimoto, Yoshio; Yokogawa, Daisuke; Yoshikawa, Hirofumi; Awaga, Kunio; Irle, Stephan

2014-06-25

Theoretical investigations are presented on the molecular and electronic structure changes that occur as α-Keggin-type polyoxometalate (POM(3-)) clusters [PM12O40](3-) (M = Mo, W) are converted toward their super-reduced POM(27-) state during the discharging process in lithium-based molecular cluster batteries. Density functional theory was employed in geometry optimization, and first-principles molecular dynamics simulations were used to explore local minima on the potential energy surface of neutral POM clusters adorned with randomly placed Li atoms as electron donors around the cluster surface. On the basis of structural, electron density, and molecular orbital studies, we present evidence that the super-reduction is accompanied by metal-metal bond formation, beginning from the 12th to 14th excess electron transferred to the cluster. Afterward, the number of metal-metal bonds increases nearly linearly with the number of additionally transferred excess electrons. In α-Keggin-type POMs, metal triangles are a prominently emerging structural feature. The origin of the metal triangle formation during super-reduction stems from the formation of characteristic three-center two-electron bonds in triangular metal atom sites, created under preservation of the POM skeleton via "squeezing out" of oxygen atoms bridging two metal atoms when the underlying metal atoms form covalent bonds. The driving force for this unusual geometrical and electronic structure change is a local Jahn-Teller distortion at individual transition-metal octahedral sites, where the triply degenerate t2 d orbitals become partially filled during reduction and gain energy by distortion of the octahedron in such a way that metal-metal bonds are formed. The bonding orbitals show strong contributions from mixing with metal-oxygen antibonding orbitals, thereby "shuffling away" excess electrons from the cluster center to the outside of the cage. The high density of negatively charged yet largely separated oxygen atoms on the surface of the super-reduced POM(27-) polyanion allows the huge Coulombic repulsion due to the presence of the excess electrons to be counterbalanced by the presence of Li countercations, which partially penetrate into the outer oxygen shell. This "semiporous molecular capacitor" structure is likely the reason for the effective electron uptake in POMs.

Hydrogen adsorption in HKUST-1: a combined inelastic neutron scattering and first-principles study.

PubMed

Brown, Craig M; Liu, Yun; Yildirim, Taner; Peterson, Vanessa K; Kepert, Cameron J

2009-05-20

Hydrogen adsorption in high surface area nanoporous coordination polymers has attracted a great deal of interest in recent years due to the potential applications in energy storage. Here we present combined inelastic neutron scattering measurements and detailed first-principles calculations aimed at unraveling the nature of hydrogen adsorption in HKUST-1 (Cu3(1,3,5-benzenetricarboxylate)2), a metal-organic framework (MOF) with unsaturated metal centers. We reveal that, in this system, the major contribution to the overall binding comes from the classical Coulomb interaction which is not screened due to the open metal site; this explains the relatively high binding energies and short H2-metal distances observed in MOFs with exposed metal sites as compared to traditional ones. Despite the short distances, there is no indication of an elongation of the H-H bond for the bound H2 molecule at the metal site. We find that both the phonon and rotational energy levels of the hydrogen molecule are closely similar, making the interpretation of the inelastic neutron scattering data difficult. Finally, we show that the orientation of H2 has a surprisingly large effect on the binding potential, reducing the classical binding energy by almost 30%. The implication of these results for the development of MOF materials for better hydrogen storage is discussed.

Hydrogen adsorption in HKUST-1: a combined inelastic neutron scattering and first-principles study

NASA Astrophysics Data System (ADS)

Brown, Craig M.; Liu, Yun; Yildirim, Taner; Peterson, Vanessa K.; Kepert, Cameron J.

2009-05-01

Hydrogen adsorption in high surface area nanoporous coordination polymers has attracted a great deal of interest in recent years due to the potential applications in energy storage. Here we present combined inelastic neutron scattering measurements and detailed first-principles calculations aimed at unraveling the nature of hydrogen adsorption in HKUST-1 (Cu3(1,3,5-benzenetricarboxylate)2), a metal-organic framework (MOF) with unsaturated metal centers. We reveal that, in this system, the major contribution to the overall binding comes from the classical Coulomb interaction which is not screened due to the open metal site; this explains the relatively high binding energies and short H2-metal distances observed in MOFs with exposed metal sites as compared to traditional ones. Despite the short distances, there is no indication of an elongation of the H-H bond for the bound H2 molecule at the metal site. We find that both the phonon and rotational energy levels of the hydrogen molecule are closely similar, making the interpretation of the inelastic neutron scattering data difficult. Finally, we show that the orientation of H2 has a surprisingly large effect on the binding potential, reducing the classical binding energy by almost 30%. The implication of these results for the development of MOF materials for better hydrogen storage is discussed.

Effect of greenhouse vegetable farming duration on Zinc accumulation in Northeast China

NASA Astrophysics Data System (ADS)

Wang, Jun; Yu, Peiying; Cui, Shuang; Chen, Xin; Shi, Yi

2018-02-01

Greenhouse vegetable production (GVP) has rapidly expanded, and reqiures more attention due to its heavy metal contamination. In this study, different cultivation greenhouses of 1, 2, 3, 5 and 13 years were selected to investigate the effects of GVP duration on Zn accumulation. The results revealed high Zn (total Zn and available Zn) accumulation in GVP surface layers (0-20 cm), and Zn contents in 0-20 cm soil layers were positively correlated with GVP duration (P<0.01). Zn accumulation was mainly attributed to manure fertilizer application due to higher concentrations of Zn in manures. For greenhouse sustainability, reduction of manure application and reasonable use of passivation materials may alleviate metal phytoavailability and the health risk.

Label-free histamine detection with nanofluidic diodes through metal ion displacement mechanism.

PubMed

Ali, Mubarak; Ramirez, Patricio; Duznovic, Ivana; Nasir, Saima; Mafe, Salvador; Ensinger, Wolfgang

2017-02-01

We design and characterize a nanofluidic device for the label-free specific detection of histamine neurotransmitter based on a metal ion displacement mechanism. The sensor consists of an asymmetric polymer nanopore fabricated via ion track-etching technique. The nanopore sensor surface having metal-nitrilotriacetic (NTA-Ni 2+ ) chelates is obtained by covalent coupling of native carboxylic acid groups with N α ,N α -bis(carboxymethyl)-l-lysine (BCML), followed by exposure to Ni 2+ ion solution. The BCML immobilization and subsequent Ni 2+ ion complexation with NTA moieties change the surface charge concentration, which has a significant impact on the current-voltage (I-V) curve after chemical modification of the nanopore. The sensing mechanism is based on the displacement of the metal ion from the NTA-Ni 2+ chelates. When the modified pore is exposed to histamine solution, the Ni 2+ ion in NTA-Ni 2+ chelate recognizes histamine through a metal ion coordination displacement process and formation of stable Ni-histamine complexes, leading to the regeneration of metal-free NTA groups on the pore surface, as shown in the current-voltage characteristics. Nanomolar concentrations of the histamine in the working electrolyte can be detected. On the contrary, other neurotransmitters such as glycine, serotonin, gamma-aminobutyric acid, and dopamine do not provoke significant changes in the nanopore electronic signal due to their inability to displace the metal ion and form a stable complex with Ni 2+ ion. The nanofluidic sensor exhibits high sensitivity, specificity and reusability towards histamine detection and can then be used to monitor the concentration of biological important neurotransmitters. Copyright © 2016 Elsevier B.V. All rights reserved.

Optical properties of MgF2 nano-composite films dispersed with noble metal nanoparticles synthesized by sol-gel method

NASA Astrophysics Data System (ADS)

Wakaki, Moriaki; Soujima, Nobuaki; Shibuya, Takehisa

2015-03-01

Porous MgF2 films synthesized by a sol-gel method exhibit the lowest refractive index among the dielectric optical materials and are the most useful materials for the anti-reflection coatings. On the other hand, surface plasmon resonance (SPR) absorptions of noble metal nanoparticles in various solid matrices have been extensively studied. New functional materials like a SERS (Surface Enhanced Raman Spectroscopy) tips are expected by synthesizing composite materials between porous MgF2 films featured by the network of MgF2 nanoparticles and noble metal nanoparticles introduced within the network. In this study, fundamental physical properties including morphology and optical properties are characterized for these materials to make clear the potential of the composite system. Composite materials of MgF2 films dispersed with noble metal (Ag, Au) nanoparticles were prepared using the sol-gel technique with various annealing temperatures and densities of noble metal nanoparticles. The structural morphology was analyzed by an X-ray diffractometer (XRD) and a scanning electron microscope (SEM). The size and shape distributions of the metal nanoparticles were observed using a transmission electron microscope (TEM). The optical properties of fabricated composite films were characterized by UV-Vis-NIR and FT-IR spectrophotometers. The absorption spectra due to the surface plasmon resonance (SPR) of the metal nanoparticles were analyzed using the dielectric function considering the effective medium approximation, typically Maxwell-Garnett model. The Raman scattering spectra were also studied to check the enhancement effect of specimen dropped on the MgF2: Ag nano-composite films deposited on Si substrate. Enhancement of the Raman intensity of pyridine solution specimen was observed.

Spatial variability of heavy metals in estuarine, mangrove and coastal ecosystems along Parangipettai, Southeast coast of India.

PubMed

Sundaramanickam, Arumugam; Shanmugam, Nadanasabesan; Cholan, Shanmugam; Kumaresan, Saravanan; Madeswaran, Perumal; Balasubramanian, Thangavel

2016-11-01

An elaborate survey on the contamination of heavy metals was carried out in surface sediments of different ecosystems such as Vellar-Coleroon estuarine, Pichavaram mangrove and coastal region of Parangipettai, Southeast coast of India. The study was intended since, the coal based thermal power plant and oil refinery plant are proposed to set up along this coast and aquaculture industries and dredging activities are developing. The parameters such as soil texture, pH, total organic carbon (TOC) and heavy metal (Fe, Mn, Cu, Cd, Zn and Ni) concentrations were analyzed for the surface sediments during pre and postmonsoon seasons. Among the metals analyzed, Fe and Mn were found to have dominant as the levels were recorded as 11,804 μg g - 1 and 845.2 μg g - 1 respectively. A significant correlation was observed between total organic carbon (TOC) and heavy metals. In the mangrove ecosystem, the levels of heavy metals found to be maximum indicating that the rich organic matter acts as an efficient binding agent for metals. The overall finding of the present study indicated that the sediments from the entire Vellar-Coleroon estuarine and Pichavaram mangrove ecosystems were found moderately polluted with cadmium metal. The result of cluster analysis indicated disparity in accumulation of heavy metals in sediments of different ecosystems due to the variations in organic matter. The heavy metals were transported from land to coastal through flood during monsoon season reflecting the variations in their levels in different ecosystems at postmonsoon season. Copyright © 2016 Elsevier Ltd. All rights reserved.

X-Ray Scattering Studies of the Liquid-Vapor Interface of Gallium.

NASA Astrophysics Data System (ADS)

Kawamoto, Eric Hitoshi

A UHV system was developed for performing X-ray scattering studies and in situ analyses of liquid metal surfaces. A nearly ideal choice for this study, gallium has a melting point just above room temperature; is amenable to handling in both air and vacuum; its surface oxides can be removed while its cleanliness is maintained and monitored. Using argon glow-discharge sputtering techniques to remove intervening surface oxides, thin wetting layers of gallium were prepared atop nonreactive substrates, to be used as samples suited for liquid surface scattering experiments. Preliminary measurements of X-ray reflectivity from the liquid-vapor interface of gallium were performed with the X-ray UHV chamber configured for use in conjunction with liquid surface spectrometers at two synchrotron beamlines. A novel technique for carrying out and interpreting scattering measurements from curved liquid surfaces was demonstrated. The energy tunability and intense focused white beam flux from a wiggler source was shown to place within reach the large values of wavevector transfer at which specular reflectivity data yield small length scale information about surface structure. Various theoretical treatments and simulations predict quasi-lamellar ordering of atoms near the free surface of metallic liquids due to energetics particular to metals (electron delocalization, the dependence of system energy on ion and electron densities, surface tension and electrostatic energy). However, the experimental data reported to date is insufficient to distinguish between a monotonic, sigmoidal electron density profile found at the free surfaces of dielectric liquids, and the damped oscillatory layer-like profiles anticipated for metallic liquids. Out to a wavevector transfer of Q = 0.55 A ^{-1}, the reflectivity data measured from a curved Ga surface is not inconsistent with what is expected for a liquid-vapor electron density profile of Gaussian width sigma = 1.3 +/- 0.2 A. Subsequent measurements roughly tripled the range of Q, but an oxidized surface led to poor data and hindered interpretation. The analysis presented is speculative at best, but within the context of the thermally excited capillary wave model of simple liquid surfaces, there seems to be no serious deviation from the simple Gaussian interfacial profile with the aforementioned roughness.

Characterization of soil heavy metal contamination and potential health risk in metropolitan region of northern China.

PubMed

Qiao, Min; Cai, Chao; Huang, Yizong; Liu, Yunxia; Lin, Aijun; Zheng, Yuanming

2011-01-01

Soil in metropolitan region suffers great contamination risk due to the rapid urbanization especially in developing countries. Beijing and Tianjin, together with their surrounding regions, form a mega-metropolitan region in northern China. To assess the soil environmental quality, a total of 458 surface soil samples were collected from this area. Concentrations of Cr, Cu, Pb, Zn, As, Cd, and Hg were analyzed and compared to the Chinese environmental quality standards for soil. Multivariate analysis was carried out to identify the possible sources and Geographic Information Systems techniques were applied to visualize the spatial data. It was found that the primary inputs of As were due to pedogenic sources, whereas Hg was mainly of anthropogenic source. Other elements including Cr, Cu, Pb, Zn, and Cd were from both lithogenic and anthropogenic origins. Health risk assessment based on the maximum heavy metal concentration indicated that As derived from sewage irrigation area can result in carcinogenic lifetime risk due to ingestion and/or dermal contact of soil. The potential non-carcinogenic risk for children is significant for Pb and the cumulative effect of multiple metals is of concern for children in the vicinity of mining site. The results increased our knowledge for understanding natural and anthropogenic sources as well as health risk for metals in metropolitan soil.

Metal/Ion Interactions Induced p–i–n Junction in Methylammonium Lead Triiodide Perovskite Single Crystals

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

Wu, Ting; Mukherjee, Rupam; Ovchinnikova, Olga S.

Hybrid perovskites, as emerging multifunctional semiconductors, have demonstrated dual electronic/ionic conduction properties. Here, we report a metal/ion interaction induced p-i-n junction across slightly n-type doped MAPbI 3 single crystals with Au/MAPbI 3/Ag configuration based on interface dependent Seebeck effect, Hall effect and time-of-flight secondary ion mass spectrometry analysis. The organic cations (MA +) interact with Au atoms, forming positively charged coordination complexes at Au/MAPbI 3 interface, whereas iodine anions (I –) can react with Ag contacts, leading to interfacial ionic polarization. Such metal/ion interactions establish a p-doped region near the Au/MAPbI 3 interface due to the formation of MA +more » vacancies, and an n-doped region near the Ag/MAPbI 3 interface due to formation of I – vacancies, consequently forming a p-i-n junction across the crystal in Au/MAPbI 3/Ag configuration. Therefore, the metal/ion interaction plays a role in determining the surface electronic structure and semiconducting properties of hybrid perovskites.« less

Metal/Ion Interactions Induced p–i–n Junction in Methylammonium Lead Triiodide Perovskite Single Crystals

DOE PAGES

Wu, Ting; Mukherjee, Rupam; Ovchinnikova, Olga S.; ...

2017-11-17

Hybrid perovskites, as emerging multifunctional semiconductors, have demonstrated dual electronic/ionic conduction properties. Here, we report a metal/ion interaction induced p-i-n junction across slightly n-type doped MAPbI 3 single crystals with Au/MAPbI 3/Ag configuration based on interface dependent Seebeck effect, Hall effect and time-of-flight secondary ion mass spectrometry analysis. The organic cations (MA +) interact with Au atoms, forming positively charged coordination complexes at Au/MAPbI 3 interface, whereas iodine anions (I –) can react with Ag contacts, leading to interfacial ionic polarization. Such metal/ion interactions establish a p-doped region near the Au/MAPbI 3 interface due to the formation of MA +more » vacancies, and an n-doped region near the Ag/MAPbI 3 interface due to formation of I – vacancies, consequently forming a p-i-n junction across the crystal in Au/MAPbI 3/Ag configuration. Therefore, the metal/ion interaction plays a role in determining the surface electronic structure and semiconducting properties of hybrid perovskites.« less

Adsorption of xenon on vicinal copper and platinum surfaces

NASA Astrophysics Data System (ADS)

Baker, Layton

The adsorption of xenon was studied on Cu(111), Cu(221), Cu(643) and on Pt(111), Pt(221), and Pt(531) using low energy electron diffraction (LEED), temperature programmed desorption (TPD) of xenon, and ultraviolet photoemission of adsorbed xenon (PAX). These experiments were performed to study the atomic and electronic structure of stepped and step-kinked, chiral metal surfaces. Xenon TPD and PAX were performed on each surface in an attempt to titrate terrace, step edge, and kink adsorption sites by adsorption energetics (TPD) and local work function differences (PAX). Due to the complex behavior of xenon on the vicinal copper and platinum metal surfaces, adsorption sites on these surfaces could not be adequately titrated by xenon TPD. On Cu(221) and Cu(643), xenon desorption from step adsorption sites was not apparent leading to the conclusion that the energy difference between terrace and step adsorption is minuscule. On Pt(221) and Pt(531), xenon TPD indicated that xenon prefers to bond at step edges and that the xenon-xenon interaction at step edges in repulsive but no further indication of step-kink adsorption was observed. The Pt(221) and Pt(531) TPD spectra indicated that the xenon overlayer undergoes strong compression near monolayer coverage on these surfaces due to repulsion between step-edge adsorbed xenon and other encroaching xenon atoms. The PAX experiments on the copper and platinum surfaces demonstrated that the step adsorption sites have lower local work functions than terrace adsorption sites and that higher step density leads to a larger separation in the local work function of terrace and step adsorption sites. The PAX spectra also indicated that, for all surfaces studied at 50--70 K, step adsorption is favored at low coverage but the step sites are not saturated until monolayer coverage is reached; this observation is due to the large entropy difference between terrace and step adsorption states and to repulsive interactions between xenon atoms adsorbed at step edges (on the platinum surfaces). The results herein provide several novel observations regarding the adsorptive behavior of xenon on vicinal copper and platinum surfaces.

Use of reagents to convert chrysotile and amosite asbestos used as insulation or protection for metal surfaces

DOEpatents

Sugama, Toshifumi; Petrakis, Leon

2000-12-12

A composition for converting asbestos-containing material, covering metal pipes or other metal surfaces, to non-regulated, environmentally benign-materials, and inhibiting the corrosion of the metal pipes or other metal surfaces. The composition comprises a combination of at least two multiple-functional group reagents, in which each reagent includes a Fluro acid component and a corrosion inhibiting compoment. A method for converting asbestos-containing material, covering metal pipes or other metal surfaces, to non-regulated, environmentally benign-materials, and inhibiting the corrosion of the metal pipes or other metal surfaces is also provided.

Adhesion and failure analysis of metal-polymer interface in flexible printed circuits boards

NASA Astrophysics Data System (ADS)

Park, Sanghee; Kim, Ye Chan; Choi, Kisuk; Chae, Heeyop; Suhr, Jonghwan; Nam, Jae-Do

2017-12-01

As device miniaturization in microelectronics is currently requested in the development of high performance device, which usually include highly-integrated metal-polyimide multilayer structures. A redistribution layer (RDL) process is currently emerging as one of the most advance fabrication techniques for on-chip interconnect and packaging. One of the major issues in this process is the poor adhesion of the metal-polyimide interfaces particularly in flexible circuit boards due to the flexibility and bendability of devices. In this study, low pressure O2 plasma treatment was investigated to improve the adhesion of metal-polyimide interfaces, using inductively coupled plasma (ICP) treatment. We identified that the adhesion of metal-polyimide interfaces was greatly improved by the surface roughness control providing 46.1 MPa of shear force in the ball shear test after O2 plasma treatment, compared 14.2 MPa without O2 plasma treatment. It was seemingly due to the fact that the adhesion in metal-polyimide interfaces was improved by a chemical conversion of C=O to C-O bonds and by a ring opening reaction of imide groups, which was confirmed with FT-IR analysis. In the finite element numerical analysis of metal-polyimide interfaces, the O2 plasma treated interface showed that the in-plane stress distribution and the vertical directional deformation agreed well with real failure modes in flexible circuits manufacturing.

Atomistic simulation of laser-pulse surface modification: Predictions of models with various length and time scales

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

Starikov, Sergey V., E-mail: starikov@ihed.ras.ru; Pisarev, Vasily V.; Joint Institute for High Temperatures, Russian Academy of Sciences, Moscow 125412

2015-04-07

In this work, the femtosecond laser pulse modification of surface is studied for aluminium (Al) and gold (Au) by use of two-temperature atomistic simulation. The results are obtained for various atomistic models with different scales: from pseudo-one-dimensional to full-scale three-dimensional simulation. The surface modification after laser irradiation can be caused by ablation and melting. For low energy laser pulses, the nanoscale ripples may be induced on a surface by melting without laser ablation. In this case, nanoscale changes of the surface are due to a splash of molten metal under temperature gradient. Laser ablation occurs at a higher pulse energymore » when a crater is formed on the surface. There are essential differences between Al ablation and Au ablation. In the first step of shock-wave induced ablation, swelling and void formation occur for both metals. However, the simulation of ablation in gold shows an additional athermal type of ablation that is associated with electron pressure relaxation. This type of ablation takes place at the surface layer, at a depth of several nanometers, and does not induce swelling.« less

Surface plasmon dispersion in a mid-infrared Ge/Si quantum dot photodetector coupled with a perforated gold metasurface

NASA Astrophysics Data System (ADS)

Yakimov, A. I.; Kirienko, V. V.; Armbrister, V. A.; Bloshkin, A. A.; Dvurechenskii, A. V.

2018-04-01

The photodetection improvement previously observed in mid-infrared (IR) quantum dot photodetectors (QDIPs) coupled with periodic metal metasurfaces is usually attributed to the surface light trapping and confinement due to generation of surface plasmon waves (SPWs). In the present work, a Ge/Si QDIP integrated with a metal plasmonic structure is fabricated to experimentally measure the photoresponse enhancement and verify that this enhancement is caused by the excitation of the mid-IR surface plasmons. A 50 nm-thick gold film perforated with a 1.2 μm-period two-dimensional square array of subwavelength holes is employed as a plasmonic coupler to convert the incident electromagnetic IR radiation into SPWs. Measurements of the polarization and angular dependencies of the photoresponse allow us to determine the dispersion of plasmon modes. We find that experimental dispersion relations agree well with that derived from a computer simulation for fundamental plasmon resonance, which indicates that the photodetection improvement in the mid-IR spectral region is actually caused by the excitations of surface plasmon Bloch waves.

Self-Limiting Oxides on WSe2 as Controlled Surface Acceptors and Low-Resistance Hole Contacts.

PubMed

Yamamoto, Mahito; Nakaharai, Shu; Ueno, Keiji; Tsukagoshi, Kazuhito

2016-04-13

Transition metal oxides show much promise as effective p-type contacts and dopants in electronics based on transition metal dichalcogenides. Here we report that atomically thin films of under-stoichiometric tungsten oxides (WOx with x < 3) grown on tungsten diselenide (WSe2) can be used as both controlled charge transfer dopants and low-barrier contacts for p-type WSe2 transistors. Exposure of atomically thin WSe2 transistors to ozone (O3) at 100 °C results in self-limiting oxidation of the WSe2 surfaces to conducting WOx films. WOx-covered WSe2 is highly hole-doped due to surface electron transfer from the underlying WSe2 to the high electron affinity WOx. The dopant concentration can be reduced by suppressing the electron affinity of WOx by air exposure, but exposure to O3 at room temperature leads to the recovery of the electron affinity. Hence, surface transfer doping with WOx is virtually controllable. Transistors based on WSe2 covered with WOx show only p-type conductions with orders of magnitude better on-current, on/off current ratio, and carrier mobility than without WOx, suggesting that the surface WOx serves as a p-type contact with a low hole Schottky barrier. Our findings point to a simple and effective strategy for creating p-type devices based on two-dimensional transition metal dichalcogenides with controlled dopant concentrations.

Electroluminescence analysis for spatial characterization of parasitic optical losses in silicon heterojunction solar cells

NASA Astrophysics Data System (ADS)

Ahmed, Nuha; Zhang, Lei; Sriramagiri, Gowri; Das, Ujjwal; Hegedus, Steven

2018-04-01

Electroluminescence (EL) coupled with reflection measurements are used to spatially quantify optical losses in silicon heterojunction solar cells due to plasmonic absorption in the metal back contacts. The effect of indium tin oxide back reflector in decreasing this plasmonic absorption is found to increase the reflection from the back nickel (Ni)-aluminum (Al) and Al metals by ˜12% and ˜41%, respectively, in both bifacial and front junction silicon solar cells. Losses due to back reflection are calculated by comparison between the EL emission signals in high and low back reflection samples and are shown to be in agreement with standard reflection measurements. We conclude that the optical properties of the back contact can significantly influence the EL intensity which complicates the interpretation of EL as being primarily due to recombination especially when comparing two different devices with spatially varying back surface structures.

A complementary set of electrochemical and X-ray synchrotron techniques to determine the passivation mechanism of iron treated in a new corrosion inhibitor solution specifically developed for the preservation of metallic artefacts

NASA Astrophysics Data System (ADS)

Mirambet, F.; Reguer, S.; Rocca, E.; Hollner, S.; Testemale, D.

2010-05-01

Metallic artefacts of the cultural heritage are often stored in uncontrolled environmental conditions. They are very sensitive to atmospheric corrosion caused by a succession of wet and dry periods due to variations of relative humidity and temperature. To avoid the complete degradation of the metallic artefacts, new preventive strategies must be developed. In this context, we have studied new compounds based on sodium carboxylates solutions CH3(CH2) n-2COO-, Na+ hereafter called NaC n . They allow the formation of a passive layer at the metallic surface composed of a metal-carboxylate complex. To understand the action of those inhibitors in the passivation process of iron we have performed electrochemical measurements and surface characterisation. Moreover, to monitor in real time the growth of the coating, in situ X-ray absorption spectroscopy (XAS) experiments at iron K-edge were carried out in an electrochemical cell. These analyses have shown that in the case of NaC10 solution, the protection of iron surface is correlated to the precipitation of a well-organised layer of FeC10. These experiments confirmed that this compound is a fully oxidised trinuclear Fe(III) complex containing decanoate anions as ligands. Such information concerning the passive layer is a key factor to evaluate its stability and finally the long-term efficiency of the protection treatment.

Wick for metal vapor laser

DOEpatents

Duncan, David B.

1992-01-01

An improved wick for a metal vapor laser is made of a refractory metal cylinder, preferably molybdenum or tungsten for a copper laser, which provides the wicking surface. Alternately, the inside surface of the ceramic laser tube can be metalized to form the wicking surface. Capillary action is enhanced by using wire screen, porous foam metal, or grooved surfaces. Graphite or carbon, in the form of chunks, strips, fibers or particles, is placed on the inside surface of the wick to reduce water, reduce metal oxides and form metal carbides.

Two-dimensional transient temperature distribution within a metal undergoing multiple phase changes caused by laser irradiation at the surface

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

Minardi, A.; Bishop, P.J.

1988-11-01

Metal-laser interactions have become increasingly important due to advances in laser-machining processes, laser weaponry, and rocket propulsion using laser beams. An interesting physical phenomenon that is not well understood is the interaction of the metal plasma above a surface with a laser beam. Although most models neglect the natural convection, other papers, such as by Sparrow et al., have considered this effect and found it to be of importance at low energy fluxes. This study assumes that the laser beam has a spatial variation, and thus a two-dimensional model for the temperature distribution within the substrate is required. Further, itmore » was assumed at first that the thermophysical properties are constant, but modifications were made to allow for different thermal conductivities of the liquid and solid phases. The model was developed to describe the physical processes until the vapor just forms, so that movement of the vapor away from the surface will not be considered. Natural convection will be neglected in the liquid pool, and radiation losses from the surface wil be neglected since these are very small in comparison to the energy absorbed from the high intensity laser beam.« less

Hierarchically structured nanowires on and nanosticks in ZnO microtubes

PubMed Central

Rivaldo-Gómez, C. M.; Cabrera-Pasca, G. A.; Zúñiga, A.; Carbonari, A. W.; Souza, J. A.

2015-01-01

We report both coaxial core-shell structured microwires and ZnO microtubes with growth of nanosticks in the inner and nanowires on the outer surface as a novel hierarchical micro/nanoarchitecture. First, a core-shell structure is obtained—the core is formed by metallic Zn and the semiconducting shell is comprised by a thin oxide layer covered with a high density of nanowires. Such Zn/ZnO core-shell array showed magnetoresistance effect. It is suggested that magnetic moments in the nanostructured shell superimposes to the external magnetic field enhancing the MR effect. Second, microtubes decorated with nanowires on the external surface are obtained. In an intermediate stage, a hierarchical morphology comprised of discrete nanosticks in the inner surface of the microtube has been found. Hyperfine interaction measurements disclosed the presence of confined metallic Zn regions at the interface between linked ZnO grains forming a chain and a ZnO thicker layer. Surprisingly, the metallic clusters form highly textured thin flat regions oriented parallel to the surface of the microtube as revealed by the electrical field gradient direction. The driving force to grow the internal nanosticks has been ascribed to stress-induced migration of Zn ions due to compressive stress caused by the presence of these confined regions. PMID:26456527

Ultrathin metal-semiconductor-metal resonator for angle invariant visible band transmission filters

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

Lee, Kyu-Tae; Seo, Sungyong; Yong Lee, Jae

We present transmission visible wavelength filters based on strong interference behaviors in an ultrathin semiconductor material between two metal layers. The proposed devices were fabricated on 2 cm × 2 cm glass substrate, and the transmission characteristics show good agreement with the design. Due to a significantly reduced light propagation phase change associated with the ultrathin semiconductor layer and the compensation in phase shift of light reflecting from the metal surface, the filters show an angle insensitive performance up to ±70°, thus, addressing one of the key challenges facing the previously reported photonic and plasmonic color filters. This principle, described in this paper, canmore » have potential for diverse applications ranging from color display devices to the image sensors.« less

A novel metal flow imaging using electrical capacitance tomography

NASA Astrophysics Data System (ADS)

Wondrak, Thomas; Soleimani, Manuchehr

2017-06-01

The measurement of gas-liquid metal two phase flow is a challenging task due to the opaqueness and the high temperatures. For instance, during continuous casting of steel the distribution of argon gas and liquid steel in the submerged entry nozzle is of high interest, since it influences the quality of the produced steel. In this paper we present the results of a feasibility study for applying the electrical capacitance tomography (ECT) to detect the outer surface of a liquid metal stream. The results of this study are the basis for the development of a new contactless sensor which should be able to detect the outer shape of a liquid metal jet using ECT and the bubbles inside the jet at the same time with mutual inductance tomography.

Modifications of aluminum film caused by micro-plasmoids and plasma spots in the effluent of an argon non-equilibrium plasma jet

NASA Astrophysics Data System (ADS)

Engelhardt, Max; Ries, Stefan; Hermanns, Patrick; Bibinov, Nikita; Awakowicz, Peter

2017-09-01

A smooth layer of hard aluminium film is deposited onto a glass substrate with a multi-frequency CCP discharge and then treated in the effluent of a non-equilibrium atmospheric pressure plasma jet (N-APPJ) operated with Ar flow. A thin filament is formed in the argon N-APPJ through contraction of a diffuse feather-like discharge. The aluminium surface treated in the effluents of the N-APPJ is significantly modified. Erosion tracks of different forms and micro-balls composed of aluminium are observed on the treated surface. Based on CCD images of active plasma discharge channels, SEM images of the treated surface and current-voltage characteristics, these surface modifications are interpreted as traces of plasma spots and plasmoids. Plasma spots are focused plasma channels, which are characterized by an intense emission in CCD images at the contact point of a plasma channel with the treated metal surface and by deep short tracks on the aluminium surface, observed in SEM images. Plasmoids are plasma objects without contact to any power supply which can produce long, thin and shallow traces, as can be observed on the treated surface using electron microscopy. Based on observed traces and numerous transformations of plasma spots to plasmoids and vice versa, it is supposed that both types of plasma objects are formed by an extremely high axial magnetic field and differ from each other due to the existence or absence of contact to a power supply and the consequential transport of electric current. The reason for the magnetic field at the axis of these plasma objects is possibly a circular current of electron pairs in vortices, which are formed in plasma by the interaction of ionization waves with the substrate surface. The extremely high magnetic field of plasma spots and plasmoids leads to a local destruction of the metal film and top layer of the glass substrate and to an attraction of paramagnetic materials, namely aluminium and oxygen. The magnetic attraction of aluminium is a reason for the extraction of some pieces of metal and the formation of erosion tracks and holes in the metal film. In the absence of metal atomization, the extracted aluminium forms spherical micro-particles, which are distributed over the surface of the treated metal film by the gas flow. A thin (100 nm) gold (diamagnetic) layer on top of the aluminium film surface reduces the erosion rate of plasma spots and plasmoids drastically (more than three orders of magnitude).