Ligand-modified metal clusters for gas separation and purification

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

Okrut, Alexander; Ouyang, Xiaoying; Runnebaum, Ron

2017-02-21

Provided is an organic ligand-bound metal surface that selects one gaseous species over another. The species can be closely sized molecular species having less than 1 Angstrom difference in kinetic diameter. In one embodiment, the species comprise carbon monoxide and ethylene. Such organic ligand-bound metal surfaces can be successfully used in gas phase separations or purifications, sensing, and in catalysis.

Surface functionalization of metal-organic polyhedron for homogeneous cyclopropanation catalysis.

PubMed

Lu, Weigang; Yuan, Daqiang; Yakovenko, Andrey; Zhou, Hong-Cai

2011-05-07

A super-paddlewheel (comprised of two paddlewheels) metal-organic polyhedron (MOP) containing surface hydroxyl groups was synthesized and characterized. Condensation reactions with linear alkyl anhydrides lead to new MOPs with enhanced solubility. As a result, the surface-modified MOP 4 was demonstrated as a homogeneous Lewis-acid catalyst. © The Royal Society of Chemistry 2011

Antibacterial properties of modified biodegradable PHB non-woven fabric.

PubMed

Slepička, P; Malá, Z; Rimpelová, S; Švorčík, V

2016-08-01

The antibacterial properties of poly(hydroxybutyrate) (PHB) non-woven fabric were explored in this study. The PHB was activated by plasma modification and subsequently processed with either immersion into a solution of nanoparticles or direct metallization. The wettability and surface chemistry of the PHB surface was determined. The thickness of the sputtered nanolayer on PHB fabric was characterized. It was found that plasma modification led to a formation of strongly hydrophilic surface, while the subsequent metallization by silver or gold resulted in a significantly increased water contact angle. Further, it was found that antibacterial activity may be controlled by the type of a metal and deposition method used. The immersion of plasma modified fabric into Ag nanoparticle solution led to enhanced antibacterial efficiency of PHB against Escherichia coli (E. coli). Direct silver sputtering on PHB fabric was proved to be a simple method for construction of a surface with strong antibacterial potency against both Escherichia coli (E. coli) and Staphylococcus epidermidis (S. epidermidis). We demonstrated the antibacterial activity of PHB fabric modified by plasma activation and consecutive selection of a treatment method for an effective antibacterial surface construction. Copyright © 2016 Elsevier B.V. All rights reserved.

A comparison of multi-metal deposition processes utilising gold nanoparticles and an evaluation of their application to 'low yield' surfaces for finger mark development.

PubMed

Fairley, C; Bleay, S M; Sears, V G; NicDaeid, N

2012-04-10

This paper reports a comparison of the effectiveness and practicality of using different multi-metal deposition processes for finger mark development. The work investigates whether modifications can be made to improve the performance of the existing process published by Schnetz. Secondly, we compare the ability of different multi-metal deposition processes to develop finger marks on a range of surfaces with that of other currently used development processes. All published multi-metal deposition processes utilise an initial stage of colloidal gold deposition followed by enhancement of the marks with using a physical developer. All possible combinations of colloidal gold and physical developer stages were tested. The method proposed by Schnetz was shown to be the most effective process, however a modification which reduced the pH of the enhancement solution was revealed to provide the best combination of effectiveness and practicality. In trials comparing the modified formulation with vacuum metal deposition, superglue and powder suspensions on surfaces which typically give low finger mark yields (cling film, plasticised vinyl, leather and masking tape), the modified method produced significantly better results over existing processes for cling film and plasticised vinyl. The modified formulation was found to be ineffective on both masking tape and leather. It is recommended that further tests be carried out on the modified multi-metal deposition formulation to establish whether it could be introduced for operational work on cling film material in particular. Copyright © 2011 Elsevier Ireland Ltd. All rights reserved.

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.

Modified Electrodes Used for Electrochemical Detection of Metal Ions in Environmental Analysis

PubMed Central

March, Gregory; Nguyen, Tuan Dung; Piro, Benoit

2015-01-01

Heavy metal pollution is one of the most serious environmental problems, and regulations are becoming stricter. Many efforts have been made to develop sensors for monitoring heavy metals in the environment. This review aims at presenting the different label-free strategies used to develop electrochemical sensors for the detection of heavy metals such as lead, cadmium, mercury, arsenic etc. The first part of this review will be dedicated to stripping voltammetry techniques, on unmodified electrodes (mercury, bismuth or noble metals in the bulk form), or electrodes modified at their surface by nanoparticles, nanostructures (CNT, graphene) or other innovative materials such as boron-doped diamond. The second part will be dedicated to chemically modified electrodes especially those with conducting polymers. The last part of this review will focus on bio-modified electrodes. Special attention will be paid to strategies using biomolecules (DNA, peptide or proteins), enzymes or whole cells. PMID:25938789

Surface-coupling of Cerenkov radiation from a modified metallic metamaterial slab via Brillouin-band folding.

PubMed

Bera, Anirban; Barik, Ranjan Kumar; Sattorov, Matlabjon; Kwon, Ohjoon; Min, Sun-Hong; Baek, In-Keun; Kim, Seontae; So, Jin-Kyu; Park, Gun-Sik

2014-02-10

Metallic metamaterials with positive dielectric responses are promising as an alternative to dielectrics for the generation of Cerenkov radiation [J.-K. So et al., Appl. Phys. Lett. 97(15), 151107 (2010)]. We propose here by theoretical analysis a mechanism to couple out Cerenkov radiation from the slab surfaces in the transverse direction. The proposed method based on Brillouin-zone folding is to periodically modify the thickness of the metamaterial slab in the axial direction. Moreover, the intensity of the surface-coupled radiation by this mechanism shows an order-of-magnitude enhancement compared to that of ordinary Smith-Purcell radiation.

Reactions of water and C1 molecules on carbide and metal-modified carbide surfaces

DOE PAGES

Wan, Weiming; Tackett, Brian M.; Chen, Jingguang G.

2017-02-23

The formation of carbides can significantly modify the physical and chemical properties of the parent metals. In the current review, we summarize the general trends in the reactions of water and C1 molecules over transition metal carbide (TMC) and metal-modified TMC surfaces and thin films. Although the primary focus of the current review is on the theoretical and experimental studies of reactions of C1 molecules (CO, CO 2, CH 3OH, etc.), the reactions of water will also be reviewed because water plays an important role in many of the C1 transformation reactions. This review is organized by discussing separately thermalmore » reactions and electrochemical reactions, which provides insights into the application of TMCs in heterogeneous catalysis and electrocatalysis, respectively. In thermal reactions, we discuss the thermal decomposition of water and methanol, as well as the reactions of CO and CO 2 over TMC surfaces. In electrochemical reactions, we summarize recent studies in the hydrogen evolution reaction, electrooxidation of methanol and CO, and electroreduction of CO 2. Lastly, future research opportunities and challenges associated with using TMCs as catalysts and electrocatalysts are also discussed.« less

Method for producing hydrophobic aerogels

DOEpatents

Hrubesh, Lawrence W.; Poco, John F.; Coronado, Paul R.

1999-01-01

A method for treating a dried monolithic aerogel containing non-dispersed particles, with an organometallic surface modifying agent to produce hydrophobic aerogels. The dried, porous hydrophobic aerogels contain a protective layer of alkyl groups, such as methyl groups, on the modified surfaces of the pores of the aerogel. The alkyl groups at the aerogel surface typically contain at least one carbon-metal bond per group.

Modified clay sorbents for wastewater treatment and immobilization of heavy metals in soils

NASA Astrophysics Data System (ADS)

Burlakovs, Juris; Klavins, Maris; Vincevica-Gaile, Zane; Stapkevica, Mara

2014-05-01

Soil and groundwater pollution with heavy metals is the result of both, anthropogenic and natural processes in the environment. Anthropogenic influence in great extent appears from industry, mining, treatment of metal ores and waste incineration. Contamination of soil and water can be induced by diffuse sources such as applications of agrochemicals and fertilizers in agriculture, air pollution from industry and transport, and by point sources, e.g., wastewater streams, runoff from dump sites and factories. Treatment processes used for metal removal from polluted soil and water include methodologies based on chemical precipitation, ion exchange, carbon adsorption, membrane filtration, adsorption and co-precipitation. Optimal removal of heavy metal ions from aqueous medium can be achieved by adsorption process which is considered as one of the most effective methods due to its cost-effectiveness and high efficiency. Immobilization of metals in contaminated soil also can be done with different adsorbents as the in situ technology. Use of natural and modified clay can be developed as one of the solutions in immobilization of lead, zinc, copper and other elements in polluted sites. Within the present study clay samples of different geological genesis were modified with sodium and calcium chlorides, iron oxyhydroxides and ammonium dihydrogen phosphate in variable proportions of Ca/P equimolar ratio to test and compare immobilization efficiency of metals by sorption and batch leaching tests. Sorption capacity for raw clay samples was considered as relatively lower referring to the modified species of the same clay type. In addition, clay samples were tested for powder X-ray difractometry, cation exchange, surface area properties, elemental composition, as well as scanning electron microscopy pictures of clay sample surface structures were obtained. Modified clay sorbents were tested for sorption of lead as monocontaminant and for complex contamination of heavy metals. The highest sorption capacity was observed for clay modified with hydroxyapatite and calcium salts. Sorption capacity increased with a rise of temperature; the best pH value for sorption was 5. Immobilization of metals in soil, as well as industrial wastewater treatment can be accomplished by using sorbents on modified clay basis.

Understanding the Role of M/Pt(111) (M = Fe, Co, Ni, Cu) Bimetallic Surfaces for Selective Hydrodeoxygenation of Furfural

DOE PAGES

Jiang, Zhifeng; Wan, Weiming; Lin, Zhexi; ...

2017-07-24

Selectively cleaving the C=O bond of the aldehyde group in furfural is critical for converting this biomass-derived platform chemical to an important biofuel molecule, 2-methylfuran. This work combined density functional theory (DFT) calculations and temperature-programmed desorption (TPD) and high-resolution electron energy loss spectroscopy (HREELS) measurements to investigate the hydrodeoxygenation (HDO) activity of furfural on bimetallic surfaces prepared by modifying Pt(111) with 3d transition metals (Cu, Ni, Fe, and Co). The stronger binding energy of furfural and higher tilted degree of the furan ring on the Co-terminated bimetallic surface resulted in a higher activity for furfural HDO to produce 2-methylfuran inmore » comparison to that on either Pt(111) or Pt-terminated PtCoPt(111). The 3d-terminated bimetallic surfaces with strongly oxophilic 3d metals (Co and Fe) showed higher 2-methylfuran yield in comparison to those surfaces modified with weakly oxophilic 3d metals (Cu and Ni). The effect of oxygen on the HDO selectivity was also investigated on oxygen-modified bimetallic surfaces, revealing that the presence of surface oxygen resulted in a decrease in 2-methylfuran yield. Furthermore, the combined theoretical and experimental results presented here should provide useful guidance for designing Pt-based bimetallic HDO catalysts.« less

Understanding the Role of M/Pt(111) (M = Fe, Co, Ni, Cu) Bimetallic Surfaces for Selective Hydrodeoxygenation of Furfural

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

Jiang, Zhifeng; Wan, Weiming; Lin, Zhexi

Selectively cleaving the C=O bond of the aldehyde group in furfural is critical for converting this biomass-derived platform chemical to an important biofuel molecule, 2-methylfuran. This work combined density functional theory (DFT) calculations and temperature-programmed desorption (TPD) and high-resolution electron energy loss spectroscopy (HREELS) measurements to investigate the hydrodeoxygenation (HDO) activity of furfural on bimetallic surfaces prepared by modifying Pt(111) with 3d transition metals (Cu, Ni, Fe, and Co). The stronger binding energy of furfural and higher tilted degree of the furan ring on the Co-terminated bimetallic surface resulted in a higher activity for furfural HDO to produce 2-methylfuran inmore » comparison to that on either Pt(111) or Pt-terminated PtCoPt(111). The 3d-terminated bimetallic surfaces with strongly oxophilic 3d metals (Co and Fe) showed higher 2-methylfuran yield in comparison to those surfaces modified with weakly oxophilic 3d metals (Cu and Ni). The effect of oxygen on the HDO selectivity was also investigated on oxygen-modified bimetallic surfaces, revealing that the presence of surface oxygen resulted in a decrease in 2-methylfuran yield. Furthermore, the combined theoretical and experimental results presented here should provide useful guidance for designing Pt-based bimetallic HDO catalysts.« less

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

Addleman, Raymond S; Atkinson, David A; Bays, John T

An enhanced swipe sampler and method of making are described. The swipe sampler is made of a fabric containing selected glass, metal oxide, and/or oxide-coated glass or metal fibers. Fibers are modified with silane ligands that are directly attached to the surface of the fibers to functionalize the sampling surface of the fabric. The swipe sampler collects various target analytes including explosives and other threat agents on the surface of the sampler.

Dithiocarbamate Self-Assembled Monolayers as Efficient Surface Modifiers for Low Work Function Noble Metals

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

Meyer, Dominik; Schäfer, Tobias; Schulz, Philip

2016-09-06

Tuning the work function of the electrode is one of the crucial steps to improve charge extraction in organic electronic devices. Here, we show that N,N-dialkyl dithiocarbamates (DTC) can be effectively employed to produce low work function noble metal electrodes. Work functions between 3.1 and 3.5 eV are observed for all metals investigated (Cu, Ag, and Au). Ultraviolet photoemission spectroscopy (UPS) reveals a maximum decrease in work function by 2.1 eV as compared to the bare metal surface. Electronic structure calculations elucidate how the complex interplay between intrinsic dipoles and dipoles induced by bond formation generates such large work functionmore » shifts. Subsequently, we quantify the improvement in contact resistance of organic thin film transistor devices with DTC coated source and drain electrodes. These findings demonstrate that DTC molecules can be employed as universal surface modifiers to produce stable electrodes for electron injection in high performance hybrid organic optoelectronics.« less

Creep, creep-rupture tests of Al-surface-alloyed T91 steel in liquid lead bismuth at 500 and 550 °C

NASA Astrophysics Data System (ADS)

Weisenburger, A.; Jianu, A.; An, W.; Fetzer, R.; Del Giacco, Mattia; Heinzel, A.; Müller, G.; Markov, V. G.; Kasthanov, A. D.

2012-12-01

Surface layers made of FeCrAl alloys on T91 steel have shown their capability as corrosion protection barriers in lead bismuth. Pulsed electron beam treatment improves the density and more over the adherence of such layers. After the treatment of previously deposited coatings a surface graded material is achieved with a metallic bonded interface. Creep-rupture tests of T91 in lead-alloy at 550 °C reveal significant reduced creep strength of non-modified T91 test specimens. Oxide scales protecting the steels from attacks of the liquid metal will crack at a certain strain leading to a direct contact between the steel and the liquid metal. The negative influence of the lead-alloy on the creep behavior of non-modified T91 is stress dependent, but below a threshold stress value of 120 MPa at 550 °C this influence becomes almost negligible. At 500 °C and stress values of 200 MPa and 220 MPa the creep rates are comparable between them and significantly lower than creep rates at 180 MPa of original T91 in air at 550 °C. No signs of LBE influence are detected. The surface modified specimens tested at high stress levels instead had creep-rupture times similar to T91 (original state) tested in air. The thin oxide layers formed on the surface modified steel samples are less susceptible to crack formation and therefore to lead-alloy enhanced creep.

A feasible strategy to balance the crystallinity and specific surface area of metal oxide nanocrystals

NASA Astrophysics Data System (ADS)

Zhang, Q. P.; Xu, X. N.; Liu, Y. T.; Xu, M.; Deng, S. H.; Chen, Y.; Yuan, H.; Yu, F.; Huang, Y.; Zhao, K.; Xu, S.; Xiong, G.

2017-04-01

Practical, efficient synthesis of metal oxide nanocrystals with good crystallinity and high specific surface area by a modified polymer-network gel method is demonstrated, taking ZnO nanocrystals as an example. A novel stepwise heat treatment yields significant improvement in crystal quality. Such nanophase materials can effectively degrade common organic dyes under solar radiation and can perform very well in photo-assisted detection of NO2 gas. Other typical metal oxide nanocrystals with good crystallinity and high specific surface area were also synthesized successfully under similar conditions. This work provides a general strategy for the synthesis of metal oxide nanocrystals, balancing the crystallinity and specific surface area.

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.

Heavy-metal detectors based on modified ferrite nanoparticles

PubMed Central

Klekotka, Urszula; Wińska, Ewelina; Zambrzycka-Szelewa, Elżbieta; Satuła, Dariusz

2018-01-01

In this work, we analyze artificial heavy-metal solutions with ferrite nanoparticles. Measurements of adsorption effectiveness of different kinds of particles, pure magnetite or magnetite doped with calcium, cobalt, manganese, or nickel ions, were carried out. A dependence of the adsorption efficiency on the composition of the inorganic core has been observed. Ferrites surfaces were modified by phthalic anhydride (PA), succinic anhydride (SA), acetic anhydride (AA), 3-phosphonopropionic acid (3-PPA), or 16-phosphohexadecanoic acid (16-PHDA) to compare the adsorption capability of the heavy metals Cd, Cu and Pb. The obtained nanoparticles were structurally characterized by transmission electron microscopy (TEM), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR) and Mössbauer spectroscopy. The amounts of Cd, Cu and Pb were measured out by atomic absorption spectroscopy (AAS) and energy dispersive X-ray (EDX) as comparative techniques. The performed study shows that SA linker appears to be the most effective in the adsorption of heavy metals. Moreover, regarding the influence of the composition of the inorganic core on the detection ability, the most effective ferrite Mn0.5Fe2.5O4 was selected for discussion. The highest heavy-metal adsorption capability and universality was observed for SA as a surface modifier. PMID:29600137

Heavy-metal detectors based on modified ferrite nanoparticles.

PubMed

Klekotka, Urszula; Wińska, Ewelina; Zambrzycka-Szelewa, Elżbieta; Satuła, Dariusz; Kalska-Szostko, Beata

2018-01-01

In this work, we analyze artificial heavy-metal solutions with ferrite nanoparticles. Measurements of adsorption effectiveness of different kinds of particles, pure magnetite or magnetite doped with calcium, cobalt, manganese, or nickel ions, were carried out. A dependence of the adsorption efficiency on the composition of the inorganic core has been observed. Ferrites surfaces were modified by phthalic anhydride (PA), succinic anhydride (SA), acetic anhydride (AA), 3-phosphonopropionic acid (3-PPA), or 16-phosphohexadecanoic acid (16-PHDA) to compare the adsorption capability of the heavy metals Cd, Cu and Pb. The obtained nanoparticles were structurally characterized by transmission electron microscopy (TEM), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR) and Mössbauer spectroscopy. The amounts of Cd, Cu and Pb were measured out by atomic absorption spectroscopy (AAS) and energy dispersive X-ray (EDX) as comparative techniques. The performed study shows that SA linker appears to be the most effective in the adsorption of heavy metals. Moreover, regarding the influence of the composition of the inorganic core on the detection ability, the most effective ferrite Mn 0.5 Fe 2.5 O 4 was selected for discussion. The highest heavy-metal adsorption capability and universality was observed for SA as a surface modifier.

A Modified Electrostatic Adsorption Apparatus for Latent Fingerprint Development on Unfired Cartridge Cases.

PubMed

Xu, Jingyang; Zhang, Ziyuan; Zheng, Xiaochun; Bond, John W

2017-05-01

Visualization of latent fingerprints on metallic surfaces by the method of applying electrostatic charging and adsorption is considered as a promising chemical-free method, which has the merit of nondestruction, and is considered to be effective for some difficult situations such as aged fingerprint deposits or those exposed to environmental extremes. In fact, a portable electrostatic generator can be easily accessible in a local forensic technology laboratory, which is already widely used in the visualization of footwear impressions. In this study, a modified version of this electrostatic apparatus is proposed for latent fingerprint development and has shown great potential in visualizing fingerprints on metallic surfaces such as cartridge cases. Results indicate that this experimental arrangement can successfully develop aged latent fingerprints on metal surfaces, and we demonstrate its effectiveness compared with existing conventional fingerprint recovery methods. © 2016 American Academy of Forensic Sciences.

Guided evolution of bulk metallic glass nanostructures: A platform for designing three-dimensional electrocatalytic surfaces

DOE PAGES

Doubek, Gustavo; Sekol, Ryan C.; Li, Jinyang; ...

2015-12-22

Precise control over catalyst surface composition and structure is necessary to improve the function of electrochemical systems. To that end, bulk metallic glass (BMG) alloys with atomically dispersed elements provide a highly processable, nanoscale platform for electrocatalysis and surface modification. Here we report on nanostructures of Pt-based BMGs that are modified with various subtractive and additive processes to improve their electrochemical performance.

Computer-aided study of key factors determining high mechanical properties of nanostructured surface layers in metal-ceramic composites

NASA Astrophysics Data System (ADS)

Konovalenko, Igor S.; Shilko, Evgeny V.; Ovcharenko, Vladimir E.; Psakhie, Sergey G.

2017-12-01

The paper presents the movable cellular automaton method. It is based on numerical models of surface layers of the metal-ceramic composite NiCr-TiC modified under electron beam irradiation in inert gas plasmas. The models take into account different geometric, concentration and mechanical parameters of ceramic and metallic components. The authors study the contributions of key structural factors in mechanical properties of surface layers and determine the ranges of their variations by providing the optimum balance of strength, strain hardening and fracture toughness.

The adsorption and dissociation of O2 on Pd and Pt modified TaC (1 0 0) surface: A first principles study

NASA Astrophysics Data System (ADS)

Meng, Yanan; Zhang, Xilin; Mao, Jianjun; Xu, Xiaopei; Yang, Zongxian

2018-05-01

The adsorption and dissociation of O2 on the palladium and platinum modified TaC (1 0 0) surfaces were investigated based on the density functional theory calculations. It is found that the adsorption sites of O2 are the Ta-Ta bridge sites on both the partially covered TaC (1 0 0) surfaces by Pd and Pt, M4/TaC (1 0 0) (M = Pd and Pt), while the 4-fold metal hollow sites and the metal-metal bridge sites are preferred on the fully covered TaC (1 0 0) surfaces by Pd and Pt monolayer, MML/TaC (1 0 0), respectively. The deposition of Pd or Pt can enhance the oxidation resistance of TaC (1 0 0). Meanwhile, the TaC (1 0 0) decorated by monolayer Pd still exhibited outstanding catalytic activity for O2 dissociation. Our study might be useful to designing efficient catalysts for the oxygen reduction reaction.

Organically Modified Silicas on Metal Nanowires

PubMed Central

2010-01-01

Organically modified silica coatings were prepared on metal nanowires using a variety of silicon alkoxides with different functional groups (i.e., carboxyl groups, polyethylene oxide, cyano, dihydroimidazole, and hexyl linkers). Organically modified silicas were deposited onto the surface of 6-μm-long, ∼300-nm-wide, cylindrical metal nanowires in suspension by the hydrolysis and polycondensation of silicon alkoxides. Syntheses were performed at several ratios of tetraethoxysilane to an organically modified silicon alkoxide to incorporate desired functional groups into thin organosilica shells on the nanowires. These coatings were characterized using transmission electron microscopy, X-ray photoelectron spectroscopy, and infrared spectroscopy. All of the organically modified silicas prepared here were sufficiently porous to allow the removal of the metal nanowire cores by acid etching to form organically modified silica nanotubes. Additional functionality provided to the modified silicas as compared to unmodified silica prepared using only tetraethoxysilane precursors was demonstrated by chromate adsorption on imidazole-containing silicas and resistance to protein adsorption on polyethyleneoxide-containing silicas. Organically modified silica coatings on nanowires and other nano- and microparticles have potential application in fields such as biosensing or nanoscale therapeutics due to the enhanced properties of the silica coatings, for example, the prevention of biofouling. PMID:20715881

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,...

Polyrhodanine modified anodic aluminum oxide membrane for heavy metal ions removal.

PubMed

Song, Jooyoung; Oh, Hyuntaek; Kong, Hyeyoung; Jang, Jyongsik

2011-03-15

Polyrhodanine was immobilized onto the inner surface of anodic aluminum oxide (AAO) membrane via vapor deposition polymerization method. The polyrhodanine modified membrane was applied to remove heavy metal ions from aqueous solution because polyrhodanine could be coordinated with specific metal ions. Several parameters such as initial metal concentration, contact time and metal species were evaluated systematically for uptake efficiencies of the fabricated membrane under continuous flow condition. Adsorption isotherms of Hg(II) ion on the AAO-polyrhodanine membrane were analyzed with Langmuir and Freundlich isotherm models. The adsorption rate of Hg(II) ion on the membrane was obeyed by a pseudo-second order equation, indicating the chemical adsorption. The maximum removal capacity of Hg(II) ion onto the fabricated membrane was measured to be 4.2 mmol/g polymer. The AAO-polyrhodanine membrane had also remarkable uptake performance toward Ag(I) and Pb(II) ions. Furthermore, the polyrhodanine modified membrane could be recycled after recovery process. These results demonstrated that the polyrhodanine modified AAO membrane provided potential applications for removing the hazardous heavy metal ions from wastewater. Copyright © 2011 Elsevier B.V. All rights reserved.

Growth of metal phthalocyanine on deactivated semiconducting surfaces steered by selective orbital coupling

DOE PAGES

Wagner, Sean R.; Feng, Jiagui; Yoon, Mina; ...

2015-08-25

Using scanning tunneling microscopy and density functional theory, we show that the molecular ordering and orientation of metal phthalocyanine molecules on the deactivated Si surface display a strong dependency on the central transition-metal ion, driven by the degree of orbital hybridization at the heterointerface via selective p – d orbital coupling. As a result, this Letter identifies a selective mechanism for modifying the molecule-substrate interaction which impacts the growth behavior of transition-metal-incorporated organic molecules on a technologically relevant substrate for silicon-based devices.

Modification of the acid/base properties of γ-Al2O3 by oxide additives: An ethanol TPD investigation

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

Kwak, Ja Hun; Lee, Jaekyoung; Szanyi, Janos

2016-02-26

The electronic properties of oxide-modified γ Al2O3 surfaces were investigated by using ethanol TPD. Ethanol TPD showed remarkable sensitivity toward the surface structures and electronic properties of the aluminas modified by various transition metal oxides. Maximum desorption rates for the primary product of ethanol adsorption, ethylene, were observed at 225 °C on non-modified γ-Al2O3. Desorption temperature of ethanol over a γ Al2O3 samples with different amounts of BaO linearly increased with increasing loading. On the contrary, ethanol desorption temperature on Pt modified γ-Al2O3 after calcined at 500 oC linearly decreased with increasing Pt loading. These results clearly suggested that themore » acid/base properties of the γ-Al2O3 surface can be strongly affected by ad-atoms. For confirming these arguments, we performed ethanol TPD experiments on various oxide modified γ-Al2O3 and normalized the maximum desorption temperatures based on the same number of oxide dopants. These normalized ethanol desorption temperatures linearly correlate with the electronegativity of the metal atom in the oxide. This linear relationship clearly demonstrates that the acidic properties of alumina surfaces can be systematically changed by ad-atoms.« less

Effects of GlidArc plasma treatment on metallic surface

NASA Astrophysics Data System (ADS)

Astanei, D.; Ursache, M.; Hnatiuc, E.; Stoica, I.; Hnatiuc, B.; Felea, C.

2016-12-01

This paper presents the GlidArc plasma effects on some metallic surfaces often used in dentistry: zirconium, titanium and nickel - chromium alloy plates. For the experiments performed, a GlidArc reactor with two planar electrodes has been used. During the tests, the gas flow has been kept constant while the treatment time and the distance between the plasma and the sample were modified. The surfaces were analyzed using atomic force microscopy (AFM) in order to determine the surface morphological modifications induced by the plasma treatment.

A Genetically Modified Tobacco Mosaic Virus that can Produce Gold Nanoparticles from a Metal Salt Precursor

PubMed Central

Love, Andrew J.; Makarov, Valentine V.; Sinitsyna, Olga V.; Shaw, Jane; Yaminsky, Igor V.; Kalinina, Natalia O.; Taliansky, Michael E.

2015-01-01

We genetically modified tobacco mosaic virus (TMV) to surface display a characterized peptide with potent metal ion binding and reducing capacity (MBP TMV), and demonstrate that unlike wild type TMV, this construct can lead to the formation of discrete 10–40 nm gold nanoparticles when mixed with 3 mM potassium tetrachloroaurate. Using a variety of analytical physicochemical approaches it was found that these nanoparticles were crystalline in nature and stable. Given that the MBP TMV can produce metal nanomaterials in the absence of chemical reductants, it may have utility in the green production of metal nanomaterials. PMID:26617624

General and Direct Method for Preparing Oligonucleotide-Functionalized Metal-Organic Framework Nanoparticles.

PubMed

Wang, Shunzhi; McGuirk, C Michael; Ross, Michael B; Wang, Shuya; Chen, Pengcheng; Xing, Hang; Liu, Yuan; Mirkin, Chad A

2017-07-26

Metal-organic frameworks (MOFs) are a class of modular, crystalline, and porous materials that hold promise for storage and transport of chemical cargoes. Though MOFs have been studied in bulk forms, ways of deliberately manipulating the external surface functionality of MOF nanoparticles are less developed. A generalizable approach to modify their surfaces would allow one to impart chemical functionality onto the particle surface that is independent of the bulk MOF structure. Moreover, the use of a chemically programmable ligand, such as DNA, would allow for the manipulation of interparticle interactions. Herein, we report a coordination chemistry-based strategy for the surface functionalization of the external metal nodes of MOF nanoparticles with terminal phosphate-modified oligonucleotides. The external surfaces of nine distinct archetypical MOF particles containing four different metal species (Zr, Cr, Fe, and Al) were successfully functionalized with oligonucleotides, illustrating the generality of this strategy. By taking advantage of the programmable and specific interactions of DNA, 11 distinct MOF particle-inorganic particle core-satellite clusters were synthesized. In these hybrid nanoclusters, the relative stoichiometry, size, shape, and composition of the building blocks can all be independently controlled. This work provides access to a new set of nucleic acid-nanoparticle conjugates, which may be useful as programmable material building blocks and as probes for measuring and manipulating intracellular processes.

Separation of macromolecular proteins and rejection of toxic heavy metal ions by PEI/cSMM blend UF membranes.

PubMed

Kanagaraj, P; Nagendran, A; Rana, D; Matsuura, T; Neelakandan, S

2015-01-01

The charged surface modifying macromolecule (cSMM) was blended into the casting solution of poly(ether imide) (PEI) to prepare surface modified ultrafiltration membranes by phase inversion technique. The separation of proteins including bovine serum albumin, egg albumin, pepsin and trypsin was investigated by the fabricated membranes. On increasing cSMM content, solute rejection decreases whereas membrane flux increases. The pore size and surface porosity of the 5 wt% cSMM blend PEI membranes increases to 41.4 Å and 14.8%, respectively. Similarly, the molecular weight cut-off of the membranes ranged from 20 to 45 kDa, depending on the various compositions of the prepared membranes. The toxic heavy metal ions Cu(II), Cr(III), Zn(II) and Pb(II) from aqueous solutions were subjected to rejection by the prepared blended membrane with various concentration of polyethyleneimine (PETIM) as water soluble polymeric ligand. It was found that the rejection behavior of metal ion depends on the PETIM concentration and the stability complexation of metal ion with ligand. Copyright © 2014 Elsevier B.V. All rights reserved.

Hydrophobic Materials Based on Salts of Di(2-ethylhexyl)phosphoric Acid

NASA Astrophysics Data System (ADS)

Kizim, N. F.; Golubina, E. N.

2018-03-01

Interfacial formations of material based on metals di(2-ethylhexyl)phosphates of various metals exhibit hydrophobic properties. The contact angle of the surface, modified by the interfacial formations materials, could reach up to 140° depending on the nature of the solvent, the metal salt, the number of applications.

Thin-film chemical sensors based on electron tunneling

NASA Technical Reports Server (NTRS)

Khanna, S. K.; Lambe, J.; Leduc, H. G.; Thakoor, A. P.

1985-01-01

The physical mechanisms underlying a novel chemical sensor based on electron tunneling in metal-insulator-metal (MIM) tunnel junctions were studied. Chemical sensors based on electron tunneling were shown to be sensitive to a variety of substances that include iodine, mercury, bismuth, ethylenedibromide, and ethylenedichloride. A sensitivity of 13 parts per billion of iodine dissolved in hexane was demonstrated. The physical mechanisms involved in the chemical sensitivity of these devices were determined to be the chemical alteration of the surface electronic structure of the top metal electrode in the MIM structure. In addition, electroreflectance spectroscopy (ERS) was studied as a complementary surface-sensitive technique. ERS was shown to be sensitive to both iodine and mercury. Electrolyte electroreflectance and solid-state MIM electroreflectance revealed qualitatively the same chemical response. A modified thin-film structure was also studied in which a chemically active layer was introduced at the top Metal-Insulator interface of the MIM devices. Cobalt phthalocyanine was used for the chemically active layer in this study. Devices modified in this way were shown to be sensitive to iodine and nitrogen dioxide. The chemical sensitivity of the modified structure was due to conductance changes in the active layer.

Glow discharge plasma pretreatment enhances osteoclast differentiation and survival on titanium plates.

PubMed

Kawai, Hiroyuki; Shibata, Yo; Miyazaki, Takashi

2004-05-01

Despite the fact that several reports have demonstrated osteoclast activity on various bioactive ceramics, osteoclast functions on surface-modified titanium have not come under focus. This study aimed to examine whether the increasing surface energy of glow discharge plasma (GDP) involved in protein adhesion containing the RGD (Arg-Gly-Asp) sequence affects osteoclast responses on titanium plates. We examined osteoclast differentiation and survival rates on titanium plates with and without GDP. The amounts of osteoclasts on titanium plates were not increased by GDP after 1 week. However, osteoclast differentiation was greatly activated by GDP pretreatment, as tartrate-resistant acid phosphatase synthesis significantly increased on the titanium plates with GDP. Additionally, since the presence of osteoclasts was detected only on the titanium plates with GDP, even after 4h cultivation in a coculture test, the osteoclasts survival rate was increased by GDP pretreatment. As osteoclast responses were affected even on surface modified metallic materials, we concluded that novel approaches are needed not only for osteoclastic resorption on ceramic materials but also for osteoclast responses on surface-modified metallic materials.

DNA Detection by Flow Cytometry using PNA-Modified Metal-Organic Framework Particles.

PubMed

Mejia-Ariza, Raquel; Rosselli, Jessica; Breukers, Christian; Manicardi, Alex; Terstappen, Leon W M M; Corradini, Roberto; Huskens, Jurriaan

2017-03-23

A DNA-sensing platform is developed by exploiting the easy surface functionalization of metal-organic framework (MOF) particles and their highly parallelized fluorescence detection by flow cytometry. Two strategies were employed to functionalize the surface of MIL-88A, using either covalent or non-covalent interactions, resulting in alkyne-modified and biotin-modified MIL-88A, respectively. Covalent surface coupling of an azide-dye and the alkyne-MIL-88A was achieved by means of a click reaction. Non-covalent streptavidin-biotin interactions were employed to link biotin-PNA to biotin-MIL-88A particles mediated by streptavidin. Characterization by confocal imaging and flow cytometry demonstrated that DNA can be bound selectively to the MOF surface. Flow cytometry provided quantitative data of the interaction with DNA. Making use of the large numbers of particles that can be simultaneously processed by flow cytometry, this MOF platform was able to discriminate between fully complementary, single-base mismatched, and randomized DNA targets. © 2017 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

Modified dipole-dipole interaction and dissipation in an atomic ensemble near surfaces

NASA Astrophysics Data System (ADS)

Jones, Ryan; Needham, Jemma A.; Lesanovsky, Igor; Intravaia, Francesco; Olmos, Beatriz

2018-05-01

We study how the radiative properties of a dense ensemble of atoms can be modified when they are placed near or between metallic or dielectric surfaces. If the average separation between the atoms is comparable or smaller than the wavelength of the scattered photons, the coupling to the radiation field induces long-range coherent interactions based on the interatomic exchange of virtual photons. Moreover, the incoherent scattering of photons back to the electromagnetic field is known to be a many-body process, characterized by the appearance of superradiant and subradiant emission modes. By changing the radiation field properties, in this case by considering a layered medium where the atoms are near metallic or dielectric surfaces, these scattering properties can be dramatically modified. We perform a detailed study of these effects, with focus on experimentally relevant parameter regimes. We finish with a specific application in the context of quantum information storage, where the presence of a nearby surface is shown to increase the storage time of an atomic excitation that is transported across a one-dimensional chain.

Surface modification of TiO2 with metal oxide nanoclusters: a route to composite photocatalytic materials.

PubMed

Nolan, Michael

2011-08-14

Density functional theory simulations show that modifying rutile TiO(2) with metal oxide nanoclusters produces composite materials with potential visible light photocatalytic activity. This journal is © The Royal Society of Chemistry 2011

Vibrations that live long and prosper

NASA Astrophysics Data System (ADS)

Utz, Arthur L.

2018-06-01

Molecular vibrations can be highly effective promoters of gas-phase chemistry. Now, measurements show that excited vibrational states can survive on metal surfaces far longer than expected — reshaping our understanding of how vibrational excitation might also promote or modify heterogeneously catalysed chemistry on metals.

Diffusion and surface alloying of gradient nanostructured metals

PubMed Central

Lu, Ke

2017-01-01

Gradient nanostructures (GNSs) have been optimized in recent years for desired performance. The diffusion behavior in GNS metals is crucial for understanding the diffusion mechanism and relative characteristics of different interfaces that provide fundamental understanding for advancing the traditional surface alloying processes. In this paper, atomic diffusion, reactive diffusion, and surface alloying processes are reviewed for various metals with a preformed GNS surface layer. We emphasize the promoted atomic diffusion and reactive diffusion in the GNS surface layer that are related to a higher interfacial energy state with respect to those in relaxed coarse-grained samples. Accordingly, different surface alloying processes, such as nitriding and chromizing, have been modified significantly, and some diffusion-related properties have been enhanced. Finally, the perspectives on current research in this field are discussed. PMID:28382244

Photocatalysis of Modified Transition Metal Oxide Surfaces

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

Batzill, Matthias

The goal of this project has been to establish a cause-effect relationship for photocatalytic activity variations of different structures of the same material; and furthermore gain fundamental understanding on modification of photocatalysts by compositional or surface modifications. The reasoning is that gaining atomic scale understanding of how surface and bulk modifications alter the photo reactivity will lead to design principles for next generation photocatalysts. As a prototypical photocatalyst the research focused on TiO 2 synthesized in well-defined single crystalline form to enable fundamental characterizations.We have obtained results in the following areas: (a) Preparation of epitaxial anatase TiO 2 samples bymore » pulsed laser deposition. (b) Comparison of hydrogen diffusion on different crystallographic surface. (c) Determining the stability of the TiO 2(011)-2x1 reconstruction upon interactions with adsorbates. (d) Characterization of adsorption and (thermal and photo) reaction of molecules with nitro-endgroups, (e) Exploring the possibility of modifying planar model photocatalyst surfaces with graphene to enable fundamental studies on reported enhanced photocatalytic activities of graphene modified transition metal oxides, (f) gained fundamental understanding on the role of crystallographic polymorphs of the same material for their photocatalytic activities.« less

Nanostructure-Directed Chemical Sensing: The IHSAB Principle and the Effect of Nitrogen and Sulfur Functionalization on Metal Oxide Decorated Interface Response

PubMed Central

Laminack, William I.; Gole, James L.

2013-01-01

The response matrix, as metal oxide nanostructure decorated n-type semiconductor interfaces are modified in situ through direct amination and through treatment with organic sulfides and thiols, is demonstrated. Nanostructured TiO2, SnOx, NiO and CuxO (x = 1,2), in order of decreasing Lewis acidity, are deposited to a porous silicon interface to direct a dominant electron transduction process for reversible chemical sensing in the absence of significant chemical bond formation. The metal oxide sensing sites can be modified to decrease their Lewis acidity in a process appearing to substitute nitrogen or sulfur, providing a weak interaction to form the oxynitrides and oxysulfides. Treatment with triethylamine and diethyl sulfide decreases the Lewis acidity of the metal oxide sites. Treatment with acidic ethane thiol modifies the sensor response in an opposite sense, suggesting that there are thiol (SH) groups present on the surface that provide a Brønsted acidity to the surface. The in situ modification of the metal oxides deposited to the interface changes the reversible interaction with the analytes, NH3 and NO. The observed change for either the more basic oxynitrides or oxysulfides or the apparent Brønsted acid sites produced from the interaction of the thiols do not represent a simple increase in surface basicity or acidity, but appear to involve a change in molecular electronic structure, which is well explained using the recently developed inverse hard and soft acids and bases (IHSAB) model. PMID:28348345

Geometrically induced surface polaritons in planar nanostructured metallic cavities

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

Davids, P. S.; Intravia, F; Dalvit, Diego A.

2014-01-14

We examine the modal structure and dispersion of periodically nanostructured planar metallic cavities within the scattering matrix formulation. By nanostructuring a metallic grating in a planar cavity, artificial surface excitations or spoof plasmon modes are induced with dispersion determined by the periodicity and geometric characteristics of the grating. These spoof surface plasmon modes are shown to give rise to new cavity polaritonic modes at short mirror separations that modify the density of modes in nanostructured cavities. The increased modal density of states form cavity polarirons have a large impact on the fluctuation induced electromagnetic forces and enhanced hear transfer atmore » short separations.« less

Friction modifier using adherent metallic multilayered or mixed element layer conversion coatings

NASA Technical Reports Server (NTRS)

Schramm, Harry F. (Inventor); Defalco, Frank G. (Inventor); Starks, Sr., Lloyd L. (Inventor)

2012-01-01

A process for creating conversion coatings and spin, drawing, and extrusion finishes for surfaces, wherein the conversion coatings and spin, drawing, and extrusion finishes contain potassium, phosphorus, nitrogen, silicon, and one or more non-alkaline metals. The process comprises forming a first aqueous solution of silicate, potassium hydroxide, and ammonium hydroxide; forming a second aqueous solution of water, phosphoric acid, ammonium hydroxide, an alkali metal hydroxide, and one or more non-alkaline metals, and then combining the first solution with the second solution to form a final solution. This final solution forms an anti-friction multi-layer conversion coating or a spin, drawing, and extrusion finish on a surface when applied to the surface, either directly or as an additive in lubricating fluids.

Friction Modifier Using Adherent Metallic Multilayered or Mixed Element Layer Conversion Coatings

NASA Technical Reports Server (NTRS)

Schramm, Harry F. (Inventor); Defalco, Francis G. (Inventor); Starks, Lloyd L., Sr. (Inventor)

2013-01-01

A process for creating conversion coatings and spin, drawing, and extrusion finishes for surfaces, wherein the conversion coatings and spin, drawing, and extrusion finishes contain potassium, phosphorus, nitrogen, and one or more non-alkaline metals and/or one or more metalloids. The process comprises forming an aqueous solution of water, phosphoric acid or sulfuric acid, ammonium hydroxide, an alkali metal hydroxide, and one or more non-alkaline metals and/or one or more metalloids. The aqueous solution forms an anti-friction multilayer conversion and/or mixed element coating or a spin, drawing, and extrusion finish on a surface when applied to the surface, either directly without the use of applied external electromotive force, or as an additive in lubricating fluids.

Controlling electron transfer processes on insulating surfaces with the non-contact atomic force microscope.

PubMed

Trevethan, Thomas; Shluger, Alexander

2009-07-01

We present the results of theoretical modelling that predicts how a process of transfer of single electrons between two defects on an insulating surface can be induced using a scanning force microscope tip. A model but realistic system is employed which consists of a neutral oxygen vacancy and a noble metal (Pt or Pd) adatom on the MgO(001) surface. We show that the ionization potential of the vacancy and the electron affinity of the metal adatom can be significantly modified by the electric field produced by an ionic tip apex at close approach to the surface. The relative energies of the two states are also a function of the separation of the two defects. Therefore the transfer of an electron from the vacancy to the metal adatom can be induced either by the field effect of the tip or by manipulating the position of the metal adatom on the surface.

Surface Modification Enhanced Reflection Intensity of Quartz Crystal Microbalance Sensors upon Molecular Adsorption.

PubMed

Kojima, Taisuke

2018-01-01

Molecular adsorption on a sensing surface involves molecule-substrate and molecule-molecule interactions. Combining optical systems and a quartz crystal microbalance (QCM) on the same sensing surface allows the quantification of such interactions and reveals the physicochemical properties of the adsorbed molecules. However, low sensitivity of the current reflection-based techniques compared to the QCM technique hinders the quantitative analysis of the adsorption events. Here, a layer-by-layer surface modification of a QCM sensor is studied to increase the optical sensitivity. The intermediate layers of organic-inorganic molecules and metal-metal oxide were explored on a gold (Au) surface of a QCM sensor. First, polyhedral oligomeric silsesquioxane-derivatives that served as the organic-inorganic intermediate layer were synthesized and modified on the Au-QCM surface. Meanwhile, titanium oxide, fabricated by anodic oxidation of titanium, was used as a metal-metal oxide intermediate layer on a titanium-coated QCM surface. The developed technique enabled interrogation of the molecular adsorption owing to the enhanced optical sensitivity.

Controlling Surface Chemistry of Gallium Liquid Metal Alloys to Enhance their Fluidic Properties

NASA Astrophysics Data System (ADS)

Ilyas, Nahid; Cumby, Brad; Cook, Alexander; Durstock, Michael; Tabor, Christopher; Materials; Manufacturing Directorate Team

Gallium liquid metal alloys (GaLMAs) are one of the key components of emerging technologies in reconfigurable electronics, such as tunable radio frequency antennas and electronic switches. Reversible flow of GaLMA in microchannels of these types of devices is hindered by the instantaneous formation of its oxide skin in ambient environment. The oxide film sticks to most surfaces leaving unwanted metallic residues that can cause undesired electronic properties. In this report, residue-free reversible flow of a binary alloy of gallium (eutectic gallium indium) is demonstrated via two types of surface modifications where the oxide film is either protected by an organic thin film or chemically removed. An interface modification layer (alkyl phosphonic acids) was introduced into the microfluidic system to modify the liquid metal surface and protect its oxide layer. Alternatively, an ion exchange membrane was utilized as a 'sponge-like' channel material to store and slowly release small amounts of HCl to react with the surface oxide of the liquid metal. Characterization of these interfaces at molecular level by surface spectroscopy and microscopy provided with mechanistic details for the interfacial interactions between the liquid metal surface and the channel materials.

Surface modification of a biodegradable magnesium alloy with phosphorylcholine (PC) and sulfobetaine (SB) functional macromolecules for reduced thrombogenicity and acute corrosion resistance.

PubMed

Ye, Sang-Ho; Jang, Yong-Seok; Yun, Yeo-Heung; Shankarraman, Venkat; Woolley, Joshua R; Hong, Yi; Gamble, Lara J; Ishihara, Kazuhiko; Wagner, William R

2013-07-02

Siloxane functionalized phosphorylcholine (PC) or sulfobetaine (SB) macromolecules (PCSSi or SBSSi) were synthesized to act as surface modifying agents for degradable metallic surfaces to improve acute blood compatibility and slow initial corrosion rates. The macromolecules were synthesized using a thiol-ene radical photopolymerization technique and then utilized to modify magnesium (Mg) alloy (AZ31) surfaces via an anhydrous phase deposition of the silane functional groups. X-ray photoelectron spectroscopy surface analysis results indicated successful surface modification based on increased nitrogen and phosphorus or sulfur composition on the modified surfaces relative to unmodified AZ31. In vitro acute thrombogenicity assessment after ovine blood contact with the PCSSi and SBSSi modified surfaces showed a significant decrease in platelet deposition and bulk phase platelet activation compared with the control alloy surfaces. Potentiodynamic polarization and electrochemical impedance spectroscopy data obtained from electrochemical corrosion testing demonstrated increased corrosion resistance for PCSSi- and SBSSi-modified AZ31 versus unmodified surfaces. The developed coating technique using PCSSi or SBSSi showed promise in acutely reducing both the corrosion and thrombotic processes, which would be attractive for application to blood contacting devices, such as vascular stents, made from degradable Mg alloys.

Microwave-assisted synthesis of gold, silver, platinum and palladium nanostructures and their use in electrocatalytic applications.

PubMed

Safavi, Afsaneh; Tohidi, Maryam

2014-09-01

Microwave-assisted ionic liquid method was used for synthesis of various noble metals, such as gold, silver, platinum and palladium nanomaterials. This route does not employ any template agent, surface capping agents or reducing agents. The process is fast, simple and of high yield. Different metal precursors in various ionic liquids media (1-butyl-3-methylimidazolium tetrafluoroborate, octyl pyridinium hexaflurophosphate and 1-octyl-3-methylimidazolium hexaflurophosphate) were applied to produce metal nanomaterials. Silver, platinium and palladium nanoparticles exhibit spherical morphology while nanosheets with high aspect ratio were obtained for gold. These metal nanostructures were incorporated into a carbon ionic liquid electrode to investigate their electrocatalytic properties. It was found that synthesis in different ionic liquids result in different activity. Excellent electrocatalytic effects toward adenine, hydrazine, formaldehyde and ethanol were observed for the modified electrodes with different nanoparticles synthesized in 1-butyl-3-methylimidazolium tetrafluoroborate. The high conductivity, large surface-to-volume ratio and active sites of nanosized metal particles are responsible for their electrocatalytic activity. In contrast, the carbon ionic liquid electrode modified with synthesized metal nanoparticles in octyl pyridinium hexaflurophosphate and 1-octyl-3-methylimidazolium hexaflurophosphate showed negligible activity for detection of these probes.

Electrocatalytic activity of spots of electrodeposited noble-metal catalysts on carbon nanotubes modified glassy carbon.

PubMed

Chen, Xingxing; Eckhard, Kathrin; Zhou, Min; Bron, Michael; Schuhmann, Wolfgang

2009-09-15

A strategy for the screening of the electrocatalytic activity of electrocatalysts for possible application in fuel cells and other devices is presented. In this approach, metal nanoclusters (Pt, Au, Ru, and Rh and their codeposits) were prepared using a capillary-based droplet-cell by pulsed electrodeposition in a diffusion-restricted viscous solution. A glassy carbon surface was modified with carbon nanotubes (CNTs) by electrophoretic accumulation and was used as substrate for metal nanoparticle deposition. The formed catalyst spots on the CNT-modified glassy carbon surface were investigated toward their catalytic activity for oxygen reduction as a test reaction employing the redox competition mode of scanning electrochemical microscopy (RC-SECM). Qualitative information on the electrocatalytic activity of the catalysts was obtained by varying the potential applied to the substrate; semiquantitative evaluation was based on the determination of the electrochemically deposited catalyst loading by means of the charge transferred during the metal nanoparticle deposition. Qualitatively, Au showed the highest electrocatalytic activity toward the oxygen reduction reaction (ORR) in phosphate buffer among all investigated single metal catalysts which was attributed to the much higher loading of Au achieved during electrodeposition. Coelectrodeposited Au-Pt catalysts showed a more positive onset potential (-150 mV in RC-SECM experiments) of the ORR in phosphate buffer at pH 6.7. After normalizing the SECM image by the charge during the metal nanocluster deposition which represents the mass loading of the catalyst, Ru showed a higher electrocatalytic activity toward the ORR than Au.

Adsorption of Cu2+ to biomass ash and its modified product.

PubMed

Xu, Lei; Cui, Hongbiao; Zheng, Xuebo; Liang, Jiani; Xing, Xiangyu; Yao, Lunguang; Chen, Zhaojin; Zhou, Jing

2017-04-01

Ash produced by biomass power plants has great potential for the removal of heavy metal ions from aqueous solution. The pollution of toxic heavy metals to water is a worldwide environmental problem. Discharges containing copper, in particular, are strictly controlled because the excessive copper can cause serious harm to the environment and human health. This work aims to investigate the adsorption characteristics of copper ions in aqueous solution by biomass ash and the modified products, and to evaluate their potential application in water pollution control. The biomass ash was modified with a mesoporous siliceous material and functionalized with 3-aminopropyltriethoxysilane. The surface properties of the biomass ash and the new matrix were studied to evaluate their adsorption property for Cu 2+ ions at different pHs, initial metal concentrations and the thermodynamic and kinetic were studied. The chemical and morphological properties of this modified material are analyzed; the specific surface area of the modified biomass ash was nine times that of the initial ash. Both of the two materials showed a strong affinity for Cu 2+ , and the Langmuir model could best represent the adsorption characteristics of Cu 2+ on the two kinds of materials. The adsorption capacity of copper on the material increased with the increase of pH and pH 6 was the optimum pH. Thermodynamic analysis results showed that the adsorption of Cu 2+ was spontaneous and endothermic in nature. The adsorptions of Cu 2+ onto the modified biomass ash followed pseudo-second-order kinetics.

Control of surface adatom kinetics for the growth of high-indium content InGaN throughout the miscibility gap

NASA Astrophysics Data System (ADS)

Moseley, Michael; Lowder, Jonathan; Billingsley, Daniel; Doolittle, W. Alan

2010-11-01

The surface kinetics of InGaN alloys grown via metal-modulated epitaxy (MME) are explored in combination with transient reflection high-energy electron diffraction intensities. A method for monitoring and controlling indium segregation in situ is demonstrated. It is found that indium segregation is more accurately associated with the quantity of excess adsorbed metal, rather than the metal-rich growth regime in general. A modified form of MME is developed in which the excess metal dose is managed via shuttered growth, and high-quality InGaN films throughout the miscibility gap are grown.

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.

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

Lu, Weigang; Yuan, Daqiang; Yakovenko, Andrey

A super-paddlewheel (comprised of two paddlewheels) metal-organic polyhedron (MOP) containing surface hydroxyl groups was synthesized and characterized. Condensation reactions with linear alkyl anhydrides lead to new MOPs with enhanced solubility. As a result, the surface-modified MOP 4 was demonstrated as a homogeneous Lewis-acid catalyst.

Investigation of fatigue strength of tool steels in sheet-bulk metal forming

NASA Astrophysics Data System (ADS)

Pilz, F.; Gröbel, D.; Merklein, M.

2018-05-01

To encounter trends regarding an efficient production of complex functional components in forming technology, the process class of sheet-bulk metal forming (SBMF) can be applied. SBMF is characterized by the application of bulk forming operations on sheet metal, often in combination with sheet forming operations [1]. The combination of these conventional process classes leads to locally varying load conditions. The resulting load conditions cause high tool loads, which lead to a reduced tool life, and an uncontrolled material flow. Several studies have shown that locally modified tool surfaces, so-called tailored surfaces, have the potential to control the material flow and thus to increase the die filling of functional elements [2]. A combination of these modified tool surfaces and high tool loads in SBMF is furthermore critical for the tool life and leads to fatigue. Tool fatigue is hardly predictable and due to a lack of data [3], a challenge in tool design. Thus, it is necessary to provide such data for tool steels used in SBMF. The aim of this study is the investigation of the influence of tailored surfaces on the fatigue strength of the powder metallurgical tool steel ASP2023 (1.3344, AISI M3:2), which is typically used in cold forging applications, with a hardness 60 HRC ± 1 HRC. To conduct this investigation, the rotating bending test is chosen. As tailored surfaces, a DLC-coating and a surface manufactured by a high-feed-milling process are chosen. As reference a polished surface which is typical for cold forging tools is used. Before the rotating bending test, the surface integrity is characterized by measuring topography and residual stresses. After testing, the determined values of the surface integrity are correlated with the reached fracture load cycle to derive functional relations. Based on the gained results the investigated tailored surfaces are evaluated regarding their feasibility to modify tool surfaces within SBMF.

Tracking metal ions with polypyrrole thin films adhesively bonded to diazonium-modified flexible ITO electrodes.

PubMed

Lo, Momath; Diaw, Abdou K D; Gningue-Sall, Diariatou; Aaron, Jean-Jacques; Oturan, Mehmet A; Chehimi, Mohamed M

2018-05-09

Adhesively bonded polypyrrole thin films doped with benzene sulfonic acid (BSA) were electrodeposited on aminobenzenediazonium-modified flexible ITO electrodes and further employed for the detection of Pb 2+ , Cu 2+ , and Cd 2+ metal ions in aqueous medium. The aminophenyl (AP) adhesive layer was grafted to ITO by electroreduction of the in situ generated parent diazonium compound. Polypyrrole (PPy) thin films exhibited remarkable adhesion to aminophenyl (ITO-AP). The strongly adherent polypyrrole films exhibited excellent electroactivity in the doped state with BSA which itself served to chelate the metal ions in aqueous medium. The surface of the resulting, modified flexible electrode was characterized by XPS, SEM, and electrochemical methods. The ITO-AP-PPy electrodes were then used for the simultaneous detection of Cu 2+ , Cd 2+ , and Pb 2+ by differential pulse voltammetry (DPV). The detection limits were 11.1, 8.95, and 0.99 nM for Cu 2+ , Cd 2+ , and Pb 2+ , respectively. In addition, the modified electrodes displayed a good reproducibility, making them suitable for the determination of heavy metals in real wastewater samples.

Microwave capillary torch as a means for modifying the electrophysical characteristics of metal surfaces

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

Artem’ev, K. V.; Davydov, A. M.; Ivanov, V. A.

2016-07-15

An experiment layout based on a pulsed capillary microwave torch and making it possible to excite an explosive emission microplasma on a metal surface in open air is implemented for the first time. It is shown that a microrelief in the form of micron-size microcraters forms on the initially smooth surface under the action of microsparks. As a result, the maximum secondary electron emission yield σ{sub max} decreases from ∼2 for the untreated surface to ∼0.4 for the rough treated surface and remains low for a long time when exposed to atmospheric air.

Noble metal free photocatalytic H 2 generation on black TiO 2: On the influence of crystal facets vs. crystal damage

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

Liu, Ning; Steinrück, Hans-Georg; Osvet, Andres

In this study, we investigate noble metal free photocatalytic water splitting on natural anatase single crystal facets and on wafer slices of the [001] plane before and after these surfaces have been modified by high pressure hydrogenation and hydrogen ion-implantation. Here, we find that on the natural, intact low index planes, photocatalytic H 2 evolution (in the absence of a noble metal co-catalyst) can only be achieved when the hydrogenation treatment is accompanied by the introduction of crystal damage, such as simple scratching and miscut in the crystal, or by implantation damage. X-ray reflectivity, Raman, and optical reflection measurements showmore » that plain hydrogenation leads to a ≈ 1 nm thick black titania surface layer without activity, while a colorless, density modified, and ≈7 nm thick layer with broken crystal symmetry is present on the ion implanted surface. These results demonstrate that (i) the H-treatment of an intact anatase surface needs to be combined with defect formation for catalytic activation and (ii) activation does not necessarily coincide with the presence of black color.« less

Noble metal free photocatalytic H 2 generation on black TiO 2: On the influence of crystal facets vs. crystal damage

DOE PAGES

Liu, Ning; Steinrück, Hans-Georg; Osvet, Andres; ...

2017-02-13

In this study, we investigate noble metal free photocatalytic water splitting on natural anatase single crystal facets and on wafer slices of the [001] plane before and after these surfaces have been modified by high pressure hydrogenation and hydrogen ion-implantation. Here, we find that on the natural, intact low index planes, photocatalytic H 2 evolution (in the absence of a noble metal co-catalyst) can only be achieved when the hydrogenation treatment is accompanied by the introduction of crystal damage, such as simple scratching and miscut in the crystal, or by implantation damage. X-ray reflectivity, Raman, and optical reflection measurements showmore » that plain hydrogenation leads to a ≈ 1 nm thick black titania surface layer without activity, while a colorless, density modified, and ≈7 nm thick layer with broken crystal symmetry is present on the ion implanted surface. These results demonstrate that (i) the H-treatment of an intact anatase surface needs to be combined with defect formation for catalytic activation and (ii) activation does not necessarily coincide with the presence of black color.« less

Engineering the internal surfaces of three-dimensional nanoporous catalysts by surfactant-modified dealloying.

PubMed

Wang, Zhili; Liu, Pan; Han, Jiuhui; Cheng, Chun; Ning, Shoucong; Hirata, Akihiko; Fujita, Takeshi; Chen, Mingwei

2017-10-20

Tuning surface structures by bottom-up synthesis has been demonstrated as an effective strategy to improve the catalytic performances of nanoparticle catalysts. Nevertheless, the surface modification of three-dimensional nanoporous metals, fabricated by a top-down dealloying approach, has not been achieved despite great efforts devoted to improving the catalytic performance of three-dimensional nanoporous catalysts. Here we report a surfactant-modified dealloying method to tailor the surface structure of nanoporous gold for amplified electrocatalysis toward methanol oxidation and oxygen reduction reactions. With the assistance of surfactants, {111} or {100} faceted internal surfaces of nanoporous gold can be realized in a controllable manner by optimizing dealloying conditions. The surface modified nanoporous gold exhibits significantly enhanced electrocatalytic activities in comparison with conventional nanoporous gold. This study paves the way to develop high-performance three-dimensional nanoporous catalysts with a tunable surface structure by top-down dealloying for efficient chemical and electrochemical reactions.

Nanocomposite protective coatings for battery anodes

DOEpatents

Lemmon, John P; Xiao, Jie; Liu, Jun

2014-01-21

Modified surfaces on metal anodes for batteries can help resist formation of malfunction-inducing surface defects. The modification can include application of a protective nanocomposite coating that can inhibit formation of surface defects. such as dendrites, on the anode during charge/discharge cycles. For example, for anodes having a metal (M'), the protective coating can be characterized by products of chemical or electrochemical dissociation of a nanocomposite containing a polymer and an exfoliated compound (M.sub.a'M.sub.b''X.sub.c). The metal, M', comprises Li, Na, or Zn. The exfoliated compound comprises M' among lamella of M.sub.b''X.sub.c, wherein M'' is Fe, Mo, Ta, W, or V, and X is S, O, or Se.

SnO2 promoted by alkali metal oxides for soot combustion: The effects of surface oxygen mobility and abundance on the activity

NASA Astrophysics Data System (ADS)

Rao, Cheng; Shen, Jiating; Wang, Fumin; Peng, Honggen; Xu, Xianglan; Zhan, Hangping; Fang, Xiuzhong; Liu, Jianjun; Liu, Wenming; Wang, Xiang

2018-03-01

In this study, SnO2-based catalysts promoted by different alkali metal oxides with a Sn/M (M = Li, Na, K, Cs) molar ratio of 9/1 have been prepared for soot combustion. In comparison with the un-modified SnO2 support, the activity of the modified catalysts has been evidently enhanced, following the sequence of CsSn1-9 > KSn1-9 > NaSn1-9 > LiSn1-9 > SnO2. As testified by Raman, H2-TPR, soot-TPR-MS, XPS and O2-TPD results, the incorporation of various alkali metal oxides can induce the formation of more abundant and mobile oxygen species on the surface of the catalysts. Moreover, quantified results have proved that the amount of the surface active oxygen species is nearly proportional to the activity of the catalysts. CsSn1-9, the catalyst promoted by cesium oxide, owns the largest amount of surface mobile oxygen species, thus having the highest activity among all the studied catalysts. It is concluded that the amount of surface active and mobile oxygen species is the major factor determining the activity of the catalysts for soot combustion.

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.

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.

Modification of hydroxyapatite with ion-selective complexants: 1-hydroxyethane-1,1-diphosphonic acid

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

Daniels, Yasmine; Lyczko, Nathalie; Nzihou, Ange

Hydroxyapatite (HAP) was modified with 1-hydroxyethane-1,1-diphosphonic acid (HEDP), and its effect on divalent metal ion binding was determined. HAP was synthesized from calcium hydroxide and phosphoric acid. After calcination, it was modified with HEDP, and the influence of time and temperature on the modification was investigated. HEDP incorporation increased as its initial solution concentration increased from 0.01 to 0.50 M. Unmodified and modified HAP were characterized using Fourier transform infrared spectroscopy, X-ray diffraction, scanning electron microscopy, energy dispersive X-ray spectroscopy, and specific surface area analysis. Ca/P ratios, acid capacities, and phosphorus elemental analyses gave the effect of modification on compositionmore » and surface characteristics. A high reaction temperature produced new phosphonate bands at 993, 1082, and 1144 cm –1 that indicated the presence of HEDP. HAP modification at a high temperature–long reaction time had the highest HEDP loading and gave the sharpest XRD peaks. The emergence of new HAP–HEDP strands was observed in SEM images for treated samples while EDS showed high phosphorus contents in these strands. Modified HAP had a high acid capacity from the additional P–OH groups in HEDP. The P(O)OH groups maintain their ability to bind metal ions within the HAP matrix: contacting the modified HAP with 10–4 N nitrate solutions of five transition metal ions gives an affinity sequence of Pb(II) > Cd(II) > Zn(II) > Ni(II) > Cu(II). Here, this result is comparable to that of commercially available di(2-ethylhexyl)phosphoric acid, a common solvent extractant, and the trend is consistent with the Misono softness parameter of metal ion polarizabilities.« less

Modification of hydroxyapatite with ion-selective complexants: 1-hydroxyethane-1,1-diphosphonic acid

DOE PAGES

Daniels, Yasmine; Lyczko, Nathalie; Nzihou, Ange; ...

2014-12-29

Hydroxyapatite (HAP) was modified with 1-hydroxyethane-1,1-diphosphonic acid (HEDP), and its effect on divalent metal ion binding was determined. HAP was synthesized from calcium hydroxide and phosphoric acid. After calcination, it was modified with HEDP, and the influence of time and temperature on the modification was investigated. HEDP incorporation increased as its initial solution concentration increased from 0.01 to 0.50 M. Unmodified and modified HAP were characterized using Fourier transform infrared spectroscopy, X-ray diffraction, scanning electron microscopy, energy dispersive X-ray spectroscopy, and specific surface area analysis. Ca/P ratios, acid capacities, and phosphorus elemental analyses gave the effect of modification on compositionmore » and surface characteristics. A high reaction temperature produced new phosphonate bands at 993, 1082, and 1144 cm –1 that indicated the presence of HEDP. HAP modification at a high temperature–long reaction time had the highest HEDP loading and gave the sharpest XRD peaks. The emergence of new HAP–HEDP strands was observed in SEM images for treated samples while EDS showed high phosphorus contents in these strands. Modified HAP had a high acid capacity from the additional P–OH groups in HEDP. The P(O)OH groups maintain their ability to bind metal ions within the HAP matrix: contacting the modified HAP with 10–4 N nitrate solutions of five transition metal ions gives an affinity sequence of Pb(II) > Cd(II) > Zn(II) > Ni(II) > Cu(II). Here, this result is comparable to that of commercially available di(2-ethylhexyl)phosphoric acid, a common solvent extractant, and the trend is consistent with the Misono softness parameter of metal ion polarizabilities.« less

Surface modification of a biodegradable magnesium alloy with phosphorylcholine (PC) and sulfobetaine (SB) functional macromolecules for reduced thrombogenicity and acute corrosion resistance

PubMed Central

Ye, Sang-Ho; Jang, Yong-Seok; Yun, Yeo-Heung; Shankarraman, Venkat; Woolley, Joshua R.; Hong, Yi; Gamble, Lara J.; Ishihara, Kazuhiko; Wagner, William R.

2013-01-01

Siloxane functionalized phosphorylcholine (PC) or sulfobetaine (SB) macromolecules (PCSSi or SBSSi) were synthesized to act as surface modifying agents for degradable metallic surfaces to improve acute blood compatibility and slow initial corrosion rates. The macromolecules were synthesized using a thiol-ene radical photopolymerization technique and then utilized to modify magnesium (Mg) alloy (AZ31) surfaces via an anhydrous phase deposition of the silane functional groups. X-ray photoelectron spectroscopy surface analysis results indicated successful surface modification based on increased nitrogen and phosphorus or sulfur composition on the modified surfaces relative to unmodified AZ31. In vitro acute thrombogenicity assessment after ovine blood contact with the PCSSi and SBSSi modified surfaces showed a significant decrease in platelet deposition and bulk phase platelet activation compared with the control alloy surfaces. Potentiodynamic polarization and electrochemical impedance spectroscopy data obtained from electrochemical corrosion testing demonstrated increased corrosion resistance for PCSSi and SBSSi modified AZ31 versus unmodified surfaces. The developed coating technique using PCSSi or SBSSi showed promise in acutely reducing both the corrosion and thrombotic processes, which would be attractive for application to blood contacting devices, such as vascular stents, made from degradable Mg alloys. PMID:23705967

Strongly reduced Ehrlich-Schwoebel barriers at the Cu (111) stepped surface with In and Pb surfactants

NASA Astrophysics Data System (ADS)

Hao, Jialei; Zhang, Lixin

2018-01-01

A surfactant can modify the properties of the surface and induce different mode of epitaxy growth. The atomistic mechanism is not fully understood yet. In this first-principles study, taking Cu homoepitaxy along (111) direction as an example, we show that the distribution of the surfactant atoms on the surface is the key. For In and Pb, they prefer to locate at the step edges and remain isolated. Once the growth is started, the distribution can be further modified by Cu adatoms. The uniquely decorated step edges have much lowered Ehrlich-Schwoebel (ES) barriers than that of the clean edges, thus the two dimensional growth on Cu (111) surface is promoted significantly. On the other hand, for Rh, Ir, and Au, these atoms are not favored at the step edges. The ES barriers can't be affected and these metals are not surfactants. The result is very helpful for searching of the optimal surfactants in metal homoepitaxy.

21 CFR 888.3150 - Elbow joint metal/polymer constrained cemented prosthesis.

Code of Federal Regulations, 2010 CFR

2010-04-01

... use with bone cement (§ 888.3027). (b) Classification. Class II. The special controls for this device...) “Guidance Document for Testing Orthopedic Implants with Modified Metallic Surfaces Apposing Bone or Bone... Biomaterials (Nonporous) for Surgical Implant with Respect to Effect of Material on Muscle and Bone,” (v) F...

21 CFR 888.3150 - Elbow joint metal/polymer constrained cemented prosthesis.

Code of Federal Regulations, 2012 CFR

2012-04-01

... use with bone cement (§ 888.3027). (b) Classification. Class II. The special controls for this device...) “Guidance Document for Testing Orthopedic Implants with Modified Metallic Surfaces Apposing Bone or Bone... Biomaterials (Nonporous) for Surgical Implant with Respect to Effect of Material on Muscle and Bone,” (v) F...

21 CFR 888.3150 - Elbow joint metal/polymer constrained cemented prosthesis.

Code of Federal Regulations, 2014 CFR

2014-04-01

... use with bone cement (§ 888.3027). (b) Classification. Class II. The special controls for this device...) “Guidance Document for Testing Orthopedic Implants with Modified Metallic Surfaces Apposing Bone or Bone... Biomaterials (Nonporous) for Surgical Implant with Respect to Effect of Material on Muscle and Bone,” (v) F...

21 CFR 888.3150 - Elbow joint metal/polymer constrained cemented prosthesis.

Code of Federal Regulations, 2013 CFR

2013-04-01

... use with bone cement (§ 888.3027). (b) Classification. Class II. The special controls for this device...) “Guidance Document for Testing Orthopedic Implants with Modified Metallic Surfaces Apposing Bone or Bone... Biomaterials (Nonporous) for Surgical Implant with Respect to Effect of Material on Muscle and Bone,” (v) F...

21 CFR 888.3150 - Elbow joint metal/polymer constrained cemented prosthesis.

Code of Federal Regulations, 2011 CFR

2011-04-01

... use with bone cement (§ 888.3027). (b) Classification. Class II. The special controls for this device...) “Guidance Document for Testing Orthopedic Implants with Modified Metallic Surfaces Apposing Bone or Bone... Biomaterials (Nonporous) for Surgical Implant with Respect to Effect of Material on Muscle and Bone,” (v) F...

SYNTHESIS AND CHARACTERIZATION OF LIX-84 NON-COVALENTLY BOUND SILICA SORBENTS FOR METAL-ION RECOVERY

EPA Science Inventory

Mesoporous silica particles were modified with LIX-84: (2-hydroxy-5-nonylacetophenome oxime). The LIX-84: was attached to the surface of silica via non-covelent forces. The effects of silica particle size, temperature, and pH on metal ion adsorption properties were studied and co...

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.

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.

Role of sublayers in mechanical response of pulsed electron beam irradiated surface layers to contact load

NASA Astrophysics Data System (ADS)

Konovalenko, Igor S.

2017-12-01

Here we develop the movable cellular automaton method based a numerical model of surface layers in a NiCr-TiC metal ceramic composite modified by pulsed electron beam irradiation in inert gas plasmas. The model explicitly takes into account the presence of several sublayers differing in structure and mechanical properties. The contribution of each sublayer to the mechanical response of the modified surface to contact loading is studied. It is shown that the maximum strength and fracture toughness are achieved in surface layers containing thin and stiff external sublayers and a more ductile thick internal sublayer.

Polyethylenimine-modified fungal biomass as a high-capacity biosorbent for Cr(VI) anions: sorption capacity and uptake mechanisms.

PubMed

Deng, Shubo; Ting, Yen Peng

2005-11-01

Heavy metal pollution in the aqueous environment is a problem of global concern. Biosorption has been considered as a promising technology for the removal of low levels of toxic metals from industrial effluents and natural waters. A modified fungal biomass of Penicillium chrysogenum with positive surface charges was prepared by grafting polyethylenimine (PEI) onto the biomass surface in a two-step reaction. The presence of PEI on the biomass surface was verified by FTIR and X-ray photoelectron spectroscopy (XPS) analyses. Due to the high density of amine groups in the long chains of PEI molecules on the surface, the modified biomass was found to possess positive zeta potential at pH below 10.4 as well as high sorption capacity for anionic Cr(VI). Using the Langmuir adsorption isotherm, the maximum sorption capacity for Cr(VI) at a pH range of 4.3-5.5 was 5.37 mmol/g of biomass dry weight, the highest sorption capacity for Cr(VI) compared to other sorbents reported in the literature. Scanning electronic microscopy (SEM) provided evidence of chromium aggregates formed on the biomass surface. XPS results verified the presence of Cr(III) on the biomass surface in the pH range 2.5-10.5, suggesting that some Cr(VI) anions were reduced to Cr(III) during the sorption. The sorption kinetics indicated that redox reaction occurred on the biomass surface, and whether the converted Cr(III) ions were released to solution or adsorbed on the biomass depended on the solution pH. Sorption mechanisms including electrostatic interaction, chelation, and precipitation were found to be involved in the complex sorption of chromium on the PEI-modified biomass.

Fabrication and condensation characteristics of metallic superhydrophobic surface with hierarchical micro-nano structures

NASA Astrophysics Data System (ADS)

Chu, Fuqiang; Wu, Xiaomin

2016-05-01

Metallic superhydrophobic surfaces have various applications in aerospace, refrigeration and other engineering fields due to their excellent water repellent characteristics. This study considers a simple but widely applicable fabrication method using a two simultaneous chemical reactions method to prepare the acid-salt mixed solutions to process the metal surfaces with surface deposition and surface etching to construct hierarchical micro-nano structures on the surface and then modify the surface with low surface-energy materials. Al-based and Cu-based superhydrophobic surfaces were fabricated using this method. The Al-based superhydrophobic surface had a water contact angle of 164° with hierarchical micro-nano structures similar to the lotus leaves. The Cu-based surface had a water contact angle of 157° with moss-like hierarchical micro-nano structures. Droplet condensation experiments were also performed on these two superhydrophobic surfaces to investigate their condensation characteristics. The results show that the Al-based superhydrophobic surface has lower droplet density, higher droplet jumping probability, slower droplet growth rate and lower surface coverage due to the more structured hierarchical structures.

Temperature effects on the atomic structure and kinetics in single crystal electrochemistry

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

Gründer, Yvonne; Markovic, Nenad M.; Thompson, Paul

2015-01-01

The influence of temperature on the atomic structure at the electrochemical interface has been studied using in-situ surface x-ray scattering (SXS) during the formation of metal monolayers on a Au(111) electrode. For the surface reconstruction of Au(111), higher temperatures increase the mobility of surface atoms in the unreconstructed phase which then determines the surface ordering during the formation of the reconstruction. For the underpotential deposition (UPD) systems, the surface diffusion of the depositing metal adatoms is significantly reduced at low temperatures which results in the frustration of ordered structures in the case of Cu UPD, occurring on a Br-modified surface,more » and in the formation of a disordered Ag monolayer during Ag UPD. The results indicate that temperature changes affect the mass transport and diffusion of metal adatoms on the electrode surface. This demonstrates the importance of including temperature as a variable in studying surface structure and reactions at the electrochemical interface.« less

Atomic scale characterization and surface chemistry of metal modified titanate nanotubes and nanowires

NASA Astrophysics Data System (ADS)

Kukovecz, Ákos; Kordás, Krisztián; Kiss, János; Kónya, Zoltán

2016-10-01

Titanates are salts of polytitanic acid that can be synthesized as nanostructures in a great variety concerning crystallinity, morphology, size, metal content and surface chemistry. Titanate nanotubes (open-ended hollow cylinders measuring up to 200 nm in length and 15 nm in outer diameter) and nanowires (solid, elongated rectangular blocks with length up to 1500 nm and 30-60 nm diameter) are the most widespread representatives of the titanate nanomaterial family. This review covers the properties and applications of these two materials from the surface science point of view. Dielectric, vibrational, electron and X-ray spectroscopic results are comprehensively discussed first, then surface modification methods including covalent functionalization, ion exchange and metal loading are covered. The versatile surface chemistry of one-dimensional titanates renders them excellent candidates for heterogeneous catalytic, photocatalytic, photovoltaic and energy storage applications, therefore, these fields are also reviewed.

Surface treatment of magnetic recording heads

DOEpatents

Komvopoulos, Kyriakos; Brown, Ian G.; Wei, Bo; Anders, Simone; Anders, Andre; Bhatia, C. Singh

1998-01-01

Surface modification of magnetic recording heads using plasma immersion ion implantation and deposition is disclosed. This method may be carried out using a vacuum arc deposition system with a metallic or carbon cathode. By operating a plasma gun in a long-pulse mode and biasing the substrate holder with short pulses of a high negative voltage, direct ion implantation, recoil implantation, and surface deposition are combined to modify the near-surface regions of the head or substrate in processing times which may be less than 5 min. The modified regions are atomically mixed into the substrate. This surface modification improves the surface smoothness and hardness and enhances the tribological characteristics under conditions of contact-start-stop and continuous sliding. These results are obtained while maintaining original tolerances.

Surface treatment of magnetic recording heads

DOEpatents

Komvopoulos, Kyriakos; Brown, Ian G.; Wei, Bo; Anders, Simone; Anders, Andre; Bhatia, Singh C.

1995-01-01

Surface modification of magnetic recording heads using plasma immersion ion implantation and deposition is disclosed. This method may be carried out using a vacuum arc deposition system with a metallic or carbon cathode. By operating a plasma gun in a long-pulse mode and biasing the substrate holder with short pulses of a high negative voltage, direct ion implantation, recoil implantation, and surface deposition are combined to modify the near-surface regions of the head or substrate in processing times which may be less than 5 min. The modified regions are atomically mixed into the substrate. This surface modification improves the surface smoothness and hardness and enhances the tribological characteristics under conditions of contact-start-stop and continuous sliding. These results are obtained while maintaining original tolerances.

Surface treatment of magnetic recording heads

DOEpatents

Komvopoulos, K.; Brown, I.G.; Wei, B.; Anders, S.; Anders, A.; Bhatia, C.S.

1998-11-17

Surface modification of magnetic recording heads using plasma immersion ion implantation and deposition is disclosed. This method may be carried out using a vacuum arc deposition system with a metallic or carbon cathode. By operating a plasma gun in a long-pulse mode and biasing the substrate holder with short pulses of a high negative voltage, direct ion implantation, recoil implantation, and surface deposition are combined to modify the near-surface regions of the head or substrate in processing times which may be less than 5 min. The modified regions are atomically mixed into the substrate. This surface modification improves the surface smoothness and hardness and enhances the tribological characteristics under conditions of contact-start-stop and continuous sliding. These results are obtained while maintaining original tolerances. 22 figs.

Chemically modified electrodes by nucleophilic substitution of chlorosilylated platinum oxide surfaces

NASA Astrophysics Data System (ADS)

Chen, Chun-Hsien; Hutchison, James H.; Postlethwaite, Timothy A.; Richardson, John N.; Murray, R. W.

1994-07-01

Chlorosilylated platinum oxide electrode surfaces can be generated by reaction of SiCl4 vapor with an electrochemically prepared monolayer of platinum oxide. A variety of nucleophilic agents (such as alcohols, amines, thiols, and Grignard reagents) can be used to displace chloride and thereby functionalize the metal surface. Electroactive surfaces prepared with ferrocene methanol as the nucleophile show that derivatization by small molecules can achieve coverages on the order of a full monolayer. Surfaces modified with long-chain alkyl groups efficiently block electrode reactions of redox probes dissolved in the contacting solution, but other electrochemical (double layer capacitance and surface coverage) and contact angle measurements suggest that these molecule films are not highly ordered, self-assembled monolayers.

Surface treatment of magnetic recording heads

DOEpatents

Komvopoulos, K.; Brown, I.G.; Wei, B.; Anders, S.; Anders, A.; Bhatia, S.C.

1995-12-19

Surface modification of magnetic recording heads using plasma immersion ion implantation and deposition is disclosed. This method may be carried out using a vacuum arc deposition system with a metallic or carbon cathode. By operating a plasma gun in a long-pulse mode and biasing the substrate holder with short pulses of a high negative voltage, direct ion implantation, recoil implantation, and surface deposition are combined to modify the near-surface regions of the head or substrate in processing times which may be less than 5 min. The modified regions are atomically mixed into the substrate. This surface modification improves the surface smoothness and hardness and enhances the tribological characteristics under conditions of contact-start-stop and continuous sliding. These results are obtained while maintaining original tolerances. 15 figs.

Effect of plastic-covered ultrasonic scalers on titanium implant surfaces.

PubMed

Mann, M; Parmar, D; Walmsley, A D; Lea, S C

2012-01-01

Maintaining oral health around titanium implants is essential. The formation of a biofilm on the titanium surface will influence the continuing success of the implant. These concerns have led to modified ultrasonic scaler instruments that look to reduce implant damage while maximising the cleaning effect. This study aimed to assess the effect of instrumentation, with traditional and modified ultrasonic scalers, on titanium implant surfaces and to correlate this with the oscillations of the instruments. Two ultrasonic insert designs (metallic TFI-10 and a plastic-tipped implant insert) were selected. Each scaler probe was scanned using a scanning laser vibrometer, under loaded and unloaded conditions, to determine their oscillation characteristics. Loads were applied against a titanium implant (100g and 200 g) for 10 s. The resulting implant surfaces were then scanned using laser profilometry and scanning electron microscopy (SEM). Insert probes oscillated with an elliptical motion with the maximum amplitude at the probe tip. Laser profilometry detected defects in the titanium surface only for the metallic scaler insert. Defect widths at 200 g high power were significantly larger than all other load/power conditions (P<0.02). Using SEM, it was observed that modifications to the implant surface had occurred following instrumentation with the plastic-tipped insert. Debris was also visible around the defects. Metal scalers produce defects in titanium implant surfaces and load and power are important factors in the damage caused. Plastic-coated scaler probes cause minimal damage to implant surfaces and have a polishing action but can leave plastic deposits behind on the implant surface. © 2011 John Wiley & Sons A/S.

Antimicrobial activity of transition metal acid MoO(3) prevents microbial growth on material surfaces.

PubMed

Zollfrank, Cordt; Gutbrod, Kai; Wechsler, Peter; Guggenbichler, Josef Peter

2012-01-01

Serious infectious complications of patients in healthcare settings are often transmitted by materials and devices colonised by microorganisms (nosocomial infections). Current strategies to generate material surfaces with an antimicrobial activity suffer from the consumption of the antimicrobial agent and emerging multidrug-resistant pathogens amongst others. Consequently, materials surfaces exhibiting a permanent antimicrobial activity without the risk of generating resistant microorganisms are desirable. This publication reports on the extraordinary efficient antimicrobial properties of transition metal acids such as molybdic acid (H(2)MoO(4)), which is based on molybdenum trioxide (MoO(3)). The modification of various materials (e.g. polymers, metals) with MoO(3) particles or sol-gel derived coatings showed that the modified materials surfaces were practically free of microorganisms six hours after contamination with infectious agents. The antimicrobial activity is based on the formation of an acidic surface deteriorating cell growth and proliferation. The application of transition metal acids as antimicrobial surface agents is an innovative approach to prevent the dissemination of microorganisms in healthcare units and public environments. Copyright © 2011 Elsevier B.V. All rights reserved.

Nanoscale Fluorescent Metal-Organic Framework@Microporous Organic Polymer Composites for Enhanced Intracellular Uptake and Bioimaging.

PubMed

Wang, Lei; Wang, Weiqi; Zheng, Xiaohua; Li, Zhensheng; Xie, Zhigang

2017-01-26

Polymer-modified metal-organic frameworks combine the advantages of both soft polymers and crystalline metal-organic frameworks (MOFs). It is a big challenge to develop simple methods for surface modification of MOFs. In this work, MOF@microporous organic polymer (MOP) hybrid nanoparticles (UNP) have been synthesized by epitaxial growth of luminescent boron-dipyrromethene (BODIPYs)-imine MOPs on the surface of UiO-MOF seeds, which exhibit low cytotoxicity, smaller size distribution, well-retained pore integrity, and available functional sites. After folic acid grafting, the enhanced intracellular uptake and bioimaging was validated. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

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.

Platinated DNA oligonucleotides: new probes forming ultrastable conjugates with graphene oxide

NASA Astrophysics Data System (ADS)

Wang, Feng; Liu, Juewen

2014-05-01

Metal containing polymers have expanded the property of polymers by involving covalently associated metal complexes. DNA is a special block copolymer. While metal ions are known to influence DNA, little is explored on its polymer property when strong metal complexes are associated. In this work, we study cisplatin modified DNA as a new polymer and probe. Out of the complexes formed between cisplatin-A15, HAuCl4-A15, Hg2+-T15 and Ag+-C15, only the cisplatin adduct is stable under the denaturing gel electrophoresis condition. Each Pt-nucleobase bond gives a positive charge and thus makes DNA a zwitterionic polymer. This allows ultrafast adsorption of DNA by graphene oxide (GO) and the adsorbed complex is highly stable. Non-specific DNA, protein, surfactants and thiolated compounds cannot displace platinated DNA from GO, while non-modified DNA is easily displaced in most cases. The stable GO/DNA conjugate is further tested for surface hybridization. This is the first demonstration of using metallated DNA as a polymeric material for interfacing with nanoscale materials.Metal containing polymers have expanded the property of polymers by involving covalently associated metal complexes. DNA is a special block copolymer. While metal ions are known to influence DNA, little is explored on its polymer property when strong metal complexes are associated. In this work, we study cisplatin modified DNA as a new polymer and probe. Out of the complexes formed between cisplatin-A15, HAuCl4-A15, Hg2+-T15 and Ag+-C15, only the cisplatin adduct is stable under the denaturing gel electrophoresis condition. Each Pt-nucleobase bond gives a positive charge and thus makes DNA a zwitterionic polymer. This allows ultrafast adsorption of DNA by graphene oxide (GO) and the adsorbed complex is highly stable. Non-specific DNA, protein, surfactants and thiolated compounds cannot displace platinated DNA from GO, while non-modified DNA is easily displaced in most cases. The stable GO/DNA conjugate is further tested for surface hybridization. This is the first demonstration of using metallated DNA as a polymeric material for interfacing with nanoscale materials. Electronic supplementary information (ESI) available: Methods, additional gels, kinetics, mass spectrum. See DOI: 10.1039/c4nr00867g

Induced superhydrophobic and antimicrobial character of zinc metal modified ceramic wall tile surfaces

NASA Astrophysics Data System (ADS)

Özcan, Selçuk; Açıkbaş, Gökhan; Çalış Açıkbaş, Nurcan

2018-04-01

Hydrophobic surfaces are also known to have antimicrobial effect by restricting the adherence of microorganisms. However, ceramic products are produced by high temperature processes resulting in a hydrophilic surface. In this study, an industrial ceramic wall tile glaze composition was modified by the inclusion of metallic zinc powder in the glaze suspension applied on the pre-sintered wall tile bodies by spraying. The glazed tiles were gloss fired at industrially applicable peak temperatures ranging from 980 °C to 1100 °C. The fired tile surfaces were coated with a commercial fluoropolymer avoiding water absorption. The surfaces were characterized with SEM, EDS, XRD techniques, roughness, sessile water drop contact angle, surface energy measurements, and standard antimicrobial tests. The surface hydrophobicity and the antimicrobial activity results were compared with that of unmodified, uncoated gloss fired wall tiles. A superhydrophobic contact angle of 150° was achieved at 1000 °C peak temperature due to the formation of micro-structured nanocrystalline zinc oxide granules providing a specific surface topography. At higher peak temperatures the hydrophobicity was lost as the specific granular surface topography deteriorated with the conversion of zinc oxide granules to the ubiquitous willemite crystals embedded in the glassy matrix. The antimicrobial efficacy also correlated with the hydrophobic character.

Effect of substrate surface treatment on electrochemically assisted photocatalytic activity of N-S co-doped TiO2 films

NASA Astrophysics Data System (ADS)

Parada-Gamboa, N. J.; Pedraza-Avella, J. A.; Meléndez, A. M.

2017-01-01

To investigate whether different metal surface treatments, performed on meshes of stainless steel 304 and titanium, affect the photocatalytic activity (PCA) of supported modified anodic TiO2 films, metallic substrates were coated with titanium isopropoxide sol-gel precursor modified with thiourea. Substrates were pretreated by some of the following techniques: a) sandblasting, b) pickling, c) hydroxylation and d) passivation. The as-prepared electrode materials were characterized by X-ray photoelectron spectroscopy (XPS), field emission scanning electron microscopy (FESEM), and voltammetry in the dark and under light UVA irradiation. PCA of modified N-S-TiO2 electrodes was evaluated by electrochemically assisted photocatalytic degradation of methyl orange. The results of XPS revealed that N and S were incorporated into the lattice of TiO2. FESEM showed that surface roughness and thickness of films varies depending on surface treatment. Voltammetric and XPS characterization of N-S co-doped TiO2 films supported on stainless steel revealed that their surface contains alpha-Fe2O3/FeOOH. Accordingly, iron contamination of the films coming from stainless steel was detrimental to the degradation of methyl orange. Prior to sol-gel coating process, sandblasting followed by nitric acid passivation for stainless steel or hydrofluoric acid pickling process in the case of titanium improved the PCA of N-S co-doped TiO2 films.

Determination of morphological characteristics of metallic nanoparticles based on modified Maxwell-Garnett fitting of optical responses

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

Battie, Y., E-mail: yann.battie@univ-lorraine.fr; Resano-Garcia, A.; En Naciri, A.

2015-10-05

A modified effective medium theory (MEMT) is introduced to determine morphological characteristics and the volume fraction of colloidal metallic nanoparticles. By analyzing the optical absorption spectra of gold nanoparticles (NPs), this model is used to determine the distribution of prolate and oblate NPs and to demonstrate the presence of spherical NPs. In addition to interband transition, the model takes into account the longitudinal and transversal surface plasmon resonances. The results predicted by the MEMT theory were found to be in very good agreement with the shape distributions obtained by transmission electron microscopy. We found that fitting optical absorption spectra usingmore » MEMT provides a robust tool for measuring the shape and concentration of metallic NPs.« less

Effectiveness of Devices to Monitor Biofouling and Metals Deposition on Plumbing Materials Exposed to a Full-Scale Drinking Water Distribution System

PubMed Central

Garbin, Scott; Wylie, Jason; Krishna, K. C. Bal

2017-01-01

A Modified Robbins Device (MRD) was installed in a full-scale water distribution system to investigate biofouling and metal depositions on concrete, high-density polyethylene (HDPE) and stainless steel surfaces. Bulk water monitoring and a KIWA monitor (with glass media) were used to offline monitor biofilm development on pipe wall surfaces. Results indicated that adenosine triphosphate (ATP) and metal concentrations on coupons increased with time. However, bacterial diversities decreased. There was a positive correlation between increase of ATP and metal deposition on pipe surfaces of stainless steel and HDPE and no correlation was observed on concrete and glass surfaces. The shared bacterial diversity between bulk water and MRD was less than 20% and the diversity shared between the MRD and KIWA monitor was only 10%. The bacterial diversity on biofilm of plumbing material of MRD however, did not show a significant difference suggesting a lack of influence from plumbing material during early stage of biofilm development. PMID:28060947

Light emitting diode with high aspect ratio submicron roughness for light extraction and methods of forming

DOEpatents

Li, Ting [Ventura, CA

2011-04-26

The surface morphology of an LED light emitting surface is changed by applying a reactive ion etch (RIE) process to the light emitting surface. High aspect ratio, submicron roughness is formed on the light emitting surface by transferring a thin film metal hard-mask having submicron patterns to the surface prior to applying a reactive ion etch process. The submicron patterns in the metal hard-mask can be formed using a low cost, commercially available nano-patterned template which is transferred to the surface with the mask. After subsequently binding the mask to the surface, the template is removed and the RIE process is applied for time duration sufficient to change the morphology of the surface. The modified surface contains non-symmetric, submicron structures having high aspect ratio which increase the efficiency of the device.

New advanced surface modification technique: titanium oxide ceramic surface implants: long-term clinical results

NASA Astrophysics Data System (ADS)

Szabo, Gyorgy; Kovacs, Lajos; Barabas, Jozsef; Nemeth, Zsolt; Maironna, Carlo

2001-11-01

The purpose of this paper is to discuss the background to advanced surface modification technologies and to present a new technique, involving the formation of a titanium oxide ceramic coating, with relatively long-term results of its clinical utilization. Three general techniques are used to modify surfaces: the addition or removal of material and the change of material already present. Surface properties can also be changed without the addition or removal of material, through the laser or electron beam thermal treatment. The new technique outlined in this paper relates to the production of a corrosion-resistant 2000-2500 A thick, ceramic oxide layer with a coherent crystalline structure on the surface of titanium implants. The layer is grown electrochemically from the bulk of the metal and is modified by heat treatment. Such oxide ceramic-coated implants have a number of advantageous properties relative to implants covered with various other coatings: a higher external hardness, a greater force of adherence between the titanium and the oxide ceramic coating, a virtually perfect insulation between the organism and the metal (no possibility of metal allergy), etc. The coated implants were subjected to various physical, chemical, electronmicroscopic, etc. tests for a qualitative characterization. Finally, these implants (plates, screws for maxillofacial osteosynthesis and dental root implants) were applied in surgical practice for a period of 10 years. Tests and the experience acquired demonstrated the good properties of the titanium oxide ceramic-coated implants.

Behavior of Ti-5Al-2.5Sn ELI titanium alloy sheet parent and weld metal in the presence of cracks at 20 K

NASA Technical Reports Server (NTRS)

Sullivan, T. L.

1971-01-01

Through- and surface-cracked specimens of two thicknesses were tested in uniaxial tension. Surface-cracked specimens were generally found to be stronger than through-cracked specimens with the same crack length. Apparent surface-crack fracture toughness calculated using the Anderson modified Irwin equation remained relatively constant for cracks as deep as 90 percent of the sheet thickness. Subcritical growth of surface cracks was investigated. Comparison of chamber and open air welds showed chamber welds to be slightly tougher. Both methods produced welds with toughness that compared favorably with that of the parent metal. Weld efficiencies were above 94 percent.

Hybrid biosorbents for removal of pollutants and remediation

NASA Astrophysics Data System (ADS)

Burlakovs, Juris; Klavins, Maris; Robalds, Artis; Ansone, Linda

2014-05-01

For remediation of soils and purification of polluted waters, wastewaters, biosorbents might be considered as prospective groups of materials. Amongst them peat have a special role due to low cost, biodegradability, high number of functional groups, well developed surface area and combination of hydrophilic/hydrophobic structural elements. Peat as sorbent have good application potential for removal of trace metals, and we have demonstrated peat sorption capacities, sorption kinetics, thermodynamics in respect to metals with different valencies - Tl(I), Cu(II), Cr(III). However, peat sorption capacity in respect to nonmetallic (anionic species) elements is low. Also peat mechanical properties do not support application in large scale column processes thereby, to expand peat application sphere, the approach of biomass based hybrid sorbents has been elaborated. The concept "hybrid sorbent" in understanding of biosorbent means natural, biomass based modified material, covered with another sorbent material, thus combining properties of both such as sorbent functionalities, surface properties etc. As the "covering layer" both inorganic substances, mineral phases (iron oxohydroxides, oxyappatite) and organic polymers (using graft polymerization) were used. The obtained sorbents were characterised by their spectral properties, surface area and elemental composition. The obtained hybrid sorbents were tested for sorption of compounds in anionic speciation forms, for example of arsenic, antimony, tellurium and phosphorous compounds in comparison with weakly basic anionites. The highest sorption capacity was observed when peat sorbents modified with iron compounds were used. Sorption of different arsenic speciation forms onto iron-modified peat sorbents was investigated as a function of pH and temperature. It was established that sorption capacity increases with a rise in temperature as the calculation of sorption process thermodynamic parameters indicates the spontaneity of sorption process and its endothermic nature. The recycling options of obtained compounds after their saturation with metal or non-metallic species are suggested.

Friction surfacing and linear friction welding

NASA Astrophysics Data System (ADS)

Nicholas, E. D.

The paper describes the development of the friction-surfacing and linear-friction welding technologies, with particular attention given to the equipment evolution and the application of the processes and advanced materials (such as intermetallics, metal-matrix composites (MMCs), ODS alloys, and powder metallurgy alloys) for the aerospace industry. The use of friction surfacing to modify the surface material with MMCs, to repair defects by plugging, and manufacture/reprocess materials is described.

Understanding Organic Film Behavior on Alloy and Metal Oxides

PubMed Central

Raman, Aparna; Quiñones, Rosalynn; Barriger, Lisa; Eastman, Rachel; Parsi, Arash

2010-01-01

Native oxide surfaces of stainless steel 316L and Nitinol alloys and their constituent metal oxides namely, nickel, chromium, molybdenum, manganese, iron and titanium were modified with long chain organic acids to better understand organic film formation. The adhesion and stability of films of octadecylphosphonic acid, octadecylhydroxamic acid, octadecylcarboxylic acid and octadecylsulfonic acid on these substrates was examined in this study. The films formed on these surfaces were analyzed by diffuse reflectance infrared Fourier transform spectroscopy, contact angle goniometry, atomic force microscopy and matrix assisted laser desorption ionization mass spectrometry. The effect of the acidity of the organic moiety and substrate composition on the film characteristics and stability is discussed. Interestingly, on the alloy surfaces, the presence of less reactive metal sites does not inhibit film formation. PMID:20039608

Condensation Dynamics on Mimicked Metal Matrix Hydrophobic Nanoparticle-Composites

NASA Astrophysics Data System (ADS)

Damle, Viraj; Sun, Xiaoda; Rykaczewski, Konrad

2014-11-01

Use of hydrophobic surfaces promotes condensation in the dropwise mode, which is significantly more efficient than the common filmwise mode. However, limited longevity of hydrophobic surface modifiers has prevented their wide spread use in industry. Recently, metal matrix composites (MMCs) having microscale hydrophobic heterogeneities dispersed in hydrophilic metal matrix have been proposed as durable and self-healing alternative to hydrophobic surface coatings interacting with deposited water droplets. While dispersion of hydrophobic microparticles in MMC is likely to lead to surface flooding during condensation, the effect of dispersion of hydrophobic nanoparticles (HNPs) with size comparable to water nuclei critical radii and spacing is not obvious. To this end, we fabricated highly ordered arrays of Teflon nanospheres on silicon substrates that mimic the top surface of the MMCs with dispersed HNPs. We used light and electron microscopy to observe breath figures resulting from condensation on these surfaces at varied degrees of subcooling. Here, we discuss the relation between the droplet size distribution, Teflon nanosphere diameter and spacing, and condensation mode. KR acknowledges startup funding from ASU.

Removal of phosphorus using chemically modified lignocellulosic materials

Treesearch

James S. Han; N. Hur; B. Choi; Soo-Hong Min

2003-01-01

Heavy metals from an acid mine drainage (AMD) site were precipitated on the surface of juniper fiber. The modified fiber was tested in lab-scaled batch and column tests and in the field. Elemental analysis showed that soluble iron species deposited on the fiber act as an inorganic adsorbent for anions. Sorption capacity, determined by fitting results to a Langmuir...

Tribology of Ceramics

DTIC Science & Technology

1988-01-01

Surface crystallography must be studied as modified by friction. Toughening and embrittling phase transformations have been discovered and modify the...2) dispersed ceramic whiskers, (3) long fiber rein- forcement, (4) precipitation , and (5) ductile metal phase . Each of these results in a...structure. Metastable structures of certain ceramics (Kingery et al., 1976) such as ZrO 2 allow a martensitic transformation under stress, which confers

Removal of phosphorus using AMD-treated lignocellulosic material

Treesearch

James S. Han; Soo-Hong Min; Yeong-Kwan Kim

2005-01-01

Excess nutrients, including phosphorus, can cause eutrophication in surface water and reservoirs. We tested the phosphate removal capacity of juniper fiber through isotherm, kinetic, column, and field tests. Heavy metals from an acid mine drainage (AMD) site were precipitated on the surface ofjuniper fiber. The modified fiber was tested in laboratory- caled batch and...

Removal of metal ions and humic acids through polyetherimide membrane with grafted bentonite clay.

PubMed

Hebbar, Raghavendra S; Isloor, Arun M; Prabhu, Balakrishna; Inamuddin; Asiri, Abdullah M; Ismail, A F

2018-03-16

Functional surfaces and polymers with branched structures have a major impact on physicochemical properties and performance of membrane materials. With the aim of greener approach for enhancement of permeation, fouling resistance and detrimental heavy metal ion rejection capacity of polyetherimide membrane, novel grafting of poly (4-styrenesulfonate) brushes on low cost, natural bentonite was carried out via distillation-precipitation polymerisation method and employed as a performance modifier. It has been demonstrated that, modified bentonite clay exhibited significant improvement in the hydrophilicity, porosity, and water uptake capacity with 3 wt. % of additive dosage. SEM and AFM analysis showed the increase in macrovoides and surface roughness with increased additive concentration. Moreover, the inclusion of modified bentonite displayed an increase in permeation rate and high anti-irreversible fouling properties with reversible fouling ratio of 75.6%. The humic acid rejection study revealed that, PEM-3 membrane having rejection efficiency up to 87.6% and foulants can be easily removed by simple hydraulic cleaning. Further, nanocomposite membranes can be significantly employed for the removal of hazardous heavy metal ions with a rejection rate of 80% and its tentative mechanism was discussed. Conspicuously, bentonite clay-bearing poly (4-styrenesulfonate) brushes are having a synergistic effect on physicochemical properties of nanocomposite membrane to enhance the performance in real field applications.

Electrochemical growth of CoNi and Pt-CoNi soft magnetic composites on an alkanethiol monolayer-modified ITO substrate.

PubMed

Escalera-López, D; Gómez, E; Vallés, E

2015-07-07

CoNi and Pt-CoNi magnetic layers on indium-tin oxide (ITO) substrates modified by an alkanethiol self-assembled monolayer (SAM) have been electrochemically obtained as an initial stage to prepare semiconducting layer-SAM-magnetic layer hybrid structures. The best conditions to obtain the maximum compactness of adsorbed layers of dodecanethiol (C12-SH) on ITO substrate have been studied using contact angle, AFM, XPS and electrochemical tests. The electrochemical characterization (electrochemical probe or voltammetric response in blank solutions) is fundamental to ensure the maximum blocking of the substrate. Although the electrodeposition process on the SAM-modified ITO substrate is very slow if the blocking of the surface is significant, non-cracked metallic layers of CoNi, with or without a previously electrodeposited seed-layer of platinum, have been obtained by optimizing the deposition potentials. Initial nucleation is expected to take place at the pinhole defects of the C12-SH SAM, followed by a mushroom-like growth regime through the SAM interface that allows the formation of a continuous metallic layer electrically connected to the ITO surface. Due to the potential of the methodology, the preparation of patterned metallic deposits on ITO substrate using SAMs with different coverage as templates is feasible.

Ag Nanoparticles-Modified 3D Graphene Foam for Binder-Free Electrodes of Electrochemical Sensors.

PubMed

Han, Tao; Jin, Jianli; Wang, Congxu; Sun, Youyi; Zhang, Yinghe; Liu, Yaqing

2017-02-16

Ag nanoparticles-modified 3D graphene foam was synthesized through a one-step in-situ approach and then directly applied as the electrode of an electrochemical sensor. The composite foam electrode exhibited electrocatalytic activity towards Hg(II) oxidation with high limit of detection and sensitivity of 0.11 μM and 8.0 μA/μM, respectively. Moreover, the composite foam electrode for the sensor exhibited high cycling stability, long-term durability and reproducibility. These results were attributed to the unique porous structure of the composite foam electrode, which enabled the surface of Ag nanoparticles modified reduced graphene oxide (Ag NPs modified rGO) foam to become highly accessible to the metal ion and provided more void volume for the reaction with metal ion. This work not only proved that the composite foam has great potential application in heavy metal ions sensors, but also provided a facile method of gram scale synthesis 3D electrode materials based on rGO foam and other electrical active materials for various applications.

Ag Nanoparticles-Modified 3D Graphene Foam for Binder-Free Electrodes of Electrochemical Sensors

PubMed Central

Han, Tao; Jin, Jianli; Wang, Congxu; Sun, Youyi; Zhang, Yinghe; Liu, Yaqing

2017-01-01

Ag nanoparticles-modified 3D graphene foam was synthesized through a one-step in-situ approach and then directly applied as the electrode of an electrochemical sensor. The composite foam electrode exhibited electrocatalytic activity towards Hg(II) oxidation with high limit of detection and sensitivity of 0.11 µM and 8.0 µA/µM, respectively. Moreover, the composite foam electrode for the sensor exhibited high cycling stability, long-term durability and reproducibility. These results were attributed to the unique porous structure of the composite foam electrode, which enabled the surface of Ag nanoparticles modified reduced graphene oxide (Ag NPs modified rGO) foam to become highly accessible to the metal ion and provided more void volume for the reaction with metal ion. This work not only proved that the composite foam has great potential application in heavy metal ions sensors, but also provided a facile method of gram scale synthesis 3D electrode materials based on rGO foam and other electrical active materials for various applications. PMID:28336878

On the structural and electronic properties of Ir-silicide nanowires on Si(001) surface

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

Fatima,; Hossain, Sehtab; Mohottige, Rasika

Iridium (Ir) modified Silicon (Si) (001) surface is studied with Scanning Tunneling Microscopy/Spectroscopy (STM/STS) and Density Functional Theory (DFT). A model for Ir-silicide nanowires based on STM images and ab-initio calculations is proposed. According to our model, the Ir adatom is on the top of the substrate dimer row and directly binds to the dimer atoms. I-V curves measured at 77 K shows that the nanowires are metallic. DFT calculations confirm strong metallic nature of the nanowires.

Passivation of uranium towards air corrosion by N 2+ and C + ion implantation

NASA Astrophysics Data System (ADS)

Arkush, R.; Mintz, M. H.; Shamir, N.

2000-10-01

The passivation of uranium surfaces against air corrosion, by ion implantation processes was studied, using surface analysis methods. Implanting 45 keV N +2 and C + ions produces thin modified surface layers with gradual gradients of the corresponding compounds (i.e., nitrides and carbides, respectively), which avoid the formation of discontinuous interfaces typical to coatings. Such gradual interfaces impart excellent mechanical stability and adhesion to the modified layers, in spite of the large misfit between the metal substrate and the implantation on induced compounds. It turns out that these layers provide an almost absolute protection against air corrosion. A rapid initial stage of oxidation of the modified surface layers takes place, forming very thin protective oxidation zones (1-4 nm thick), which practically stop further air oxidation for years. The mechanism of the initial oxidation stage of the modified layers seems to vary with the type of surface (i.e., either nitrides or carbides). However, in any case the protection ability of the formed oxidation products is excellent, probably due to the close match between these compounds and the underlying nitrides or carbides.

Electrostatic interactions between ions near Thomas-Fermi substrates and the surface energy of ionic crystal at imperfect metals

PubMed Central

Kaiser, V.; Comtet, J.; Niguès, A.; Siria, A.; Coasne, B.; Bocquet, L.

2017-01-01

The electrostatic interaction between two charged particles is strongly modified in the vicinity of a metal. This situation is usually accounted for by the celebrated image charges approach, which was further extended to account for the electronic screening properties of the metal at the level of the Thomas-Fermi description. In this paper we build upon the approach by [Kornyshev et al. Zh. Eksp. Teor. Fiz., 78(3):1008–1019, 1980] and successive works to calculate the 1-body and 2-body electrostatic energy of ions near a metal in terms of the Thomas-Fermi screening length. We propose workable approximations suitable for molecular simulations of ionic systems close to metallic walls. Furthermore, we use this framework to calculate analytically the electrostatic contribution to the surface energy of a one dimensional crystal at a metallic wall and its dependence on the Thomas-Fermi screening length. These calculations provide a simple interpretation for the surface energy in terms of image charges, which allow for an estimate of interfacial properties in more complex situations of a disordered ionic liquid close to a metal surface. A counterintuitive outcome is that electronic screening, as characterized by a molecular Thomas-Fermi length ℓTF, profoundly affects the wetting of ionic systems close to a metal, in line with the recent experimental observation of capillary freezing of ionic liquids in metallic confinement. PMID:28436506

Nanoscale surface modifications of medically relevant metals: state-of-the art and perspectives.

PubMed

Variola, Fabio; Brunski, John B; Orsini, Giovanna; Tambasco de Oliveira, Paulo; Wazen, Rima; Nanci, Antonio

2011-02-01

Evidence that nanoscale surface properties stimulate and guide various molecular and biological processes at the implant/tissue interface is fostering a new trend in designing implantable metals. Cutting-edge expertise and techniques drawn from widely separated fields, such as nanotechnology, materials engineering and biology, have been advantageously exploited to nanoengineer surfaces in ways that control and direct these processes in predictable manners. In this review, we present and discuss the state-of-the-art of nanotechnology-based approaches currently adopted to modify the surface of metals used for orthopedic and dental applications, and also briefly consider their use in the cardiovascular field. The effects of nanoengineered surfaces on various in vitro molecular and cellular events are firstly discussed. This review also provides an overview of in vivo and clinical studies with nanostructured metallic implants, and addresses the potential influence of nanotopography on biomechanical events at interfaces. Ultimately, the objective of this work is to give the readership a comprehensive picture of the current advances, future developments and challenges in the application of the infinitesimally small to biomedical surface science. We believe that an integrated understanding of the in vitro and particularly of the in vivo behavior is mandatory for the proper exploitation of nanostructured implantable metals and, indeed, of all biomaterials.

Nanoscale surface modifications of medically-relevant metals: state-of-the art and perspectives

PubMed Central

Variola, Fabio; Brunski, John; Orsini, Giovanna; de Oliveira, Paulo Tambasco; Wazen, Rima; Nanci, Antonio

2011-01-01

Evidence that nanoscale surface properties stimulate and guide various molecular and biological processes at the implant/tissue interface is fostering a new trend in designing implantable metals. Cutting-edge expertise and techniques drawn from widely separated fields, such as nanotechnology, materials engineering and biology, have been advantageously exploited to nanoengineer surfaces in ways that control and direct these processes in predictable manners. In this review, we present and discuss the state-of-the-art of nanotechnology-based approaches currently used to modify the surface of metals used for orthopedic and dental applications, and also briefly consider their use in the cardiovascular field. The effects of nanoengineered surfaces on various in vitro molecular and cellular events are firstly discussed. Importantly, this review also provides an overview of in vivo and clinical studies with nanostructured metallic implants, and addresses the potential influence of nanotopography on biomechanical events at interfaces. Ultimately the objective of this work is to give the readership a comprehensive picture of the current advances, future developments and challenges in the application of the infinitesimally small to biomedical surface science. We believe that an integrated understanding of the in vitro and particularly of the in vivo behavior is mandatory for the proper exploitation of nanostructured implantable metals and, as a matter of fact, all biomaterials. PMID:20976359

Metal-free g-C{sub 3}N{sub 4} photocatalyst by sulfuric acid activation for selective aerobic oxidation of benzyl alcohol under visible light

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

Zhang, Ligang; University of Chinese Academy of Sciences, Beijing 100049; Liu, Di

2014-11-15

Highlights: • A novel visible-light-driven acid-modified g-C{sub 3}N{sub 4} was prepared. • The texture, electronic and surface property were tuned by acid modification. • Acid-modified g-C{sub 3}N{sub 4} shows much higher activity for photocatalytic activity. • Acid sites on the surface of g-C{sub 3}N{sub 4} favor efficient charge separation. - Abstract: In this work, modification of graphitic carbon nitride photocatalyst with acid was accomplished with a facile method through reflux in different acidic substances. The g-C{sub 3}N{sub 4}-based material was found to be a metal-free photocatalyst useful for the selective oxidation of benzyl alcohol with dioxygen as the oxidant undermore » visible light irradiation. Acid modification had a significant influence on the photocatalytic performance of g-C{sub 3}N{sub 4}. Among all acid tested, sulfuric acid-modified g-C{sub 3}N{sub 4} showed the highest catalytic activity and gave benzaldehyde in 23% yield for 4 h under visible light irradiation, which was about 2.5 times higher than that of g-C{sub 3}N{sub 4}. The acid modification effectively improved surface area, reduced structural size, enlarged band gap, enhanced surface chemical state, and facilitated photoinduced charge separation, contributing to the enhanced photocatalytic activity. It is hoped that our work can open promising prospects for the utilization of metal free g-C{sub 3}N{sub 4}-based semiconductor as visible-light photocatalyst for selective organic transformation.« less

Light emitting diode with high aspect ratio submicron roughness for light extraction and methods of forming

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

Li, Ting

The surface morphology of an LED light emitting surface is changed by applying a reactive ion etch (RIE) process to the light emitting surface. High aspect ratio, submicron roughness is formed on the light emitting surface by transferring a thin film metal hard-mask having submicron patterns to the surface prior to applying a reactive ion etch process. The submicron patterns in the metal hard-mask can be formed using a low cost, commercially available nano-patterned template which is transferred to the surface with the mask. After subsequently binding the mask to the surface, the template is removed and the RIE processmore » is applied for time duration sufficient to change the morphology of the surface. The modified surface contains non-symmetric, submicron structures having high aspect ratio which increase the efficiency of the device.« less

In vivo surface roughness evolution of a stressed metallic implant

NASA Astrophysics Data System (ADS)

Tan, Henry

2016-10-01

Implant-associated infection, a serious medical issue, is caused by the adhesion of bacteria to the surface of biomaterials; for this process the surface roughness is an important property. Surface nanotopography of medical implant devices can control the extent of bacterial attachment by modifying the surface morphology; to this end a model is introduced to facilitate the analysis of a nanoscale smooth surface subject to mechanical loading and in vivo corrosion. At nanometre scale rough surface promotes friction, hence reduces the mobility of the bacteria; this sessile environment expedites the biofilm growth. This manuscript derives the controlling equation for surface roughness evolution for metallic implant subject to in-plane stresses, and predicts the in vivo roughness changes within 6 h of continued mechanical loading at different stress level. This paper provides analytic tool and theoretical information for surface nanotopography of medical implant devices.

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.

Autothermal reforming of propane over Mg-Al hydrotalcite-like catalysts.

PubMed

Lim, You-Soon; Park, Nam-Cook; Shin, Jae-Soon; Kim, Jong-Ho; Moon, Dong-Ju; Kim, Young-Chul

2008-10-01

The performance of hydrotalcite-like catalysts in propane autothermal reforming for hydrogen production was studied in fixed-bed flow reactor. Hydrotalcite-like catalysts were synthesized by coprecipitation and modified co-precipitation by the impregnation method and those were promoted by the addition of noble metals. Reaction test results indicated that hydrotalcite-like catalysts of modified method were showed higher H2-yield than co-precipitation method because surface Ni particles of catalysts by modified method were more abundant. When added noble metals, the activity was enhanced because the size of nickel particles was decreased and degree of dispersion was increased. Also the carbon deposit is low after the reaction. When solvent of solution was changed, activity was increased. It is because degree of dispersion was increased.

Metal-organic framework thin films on a surface of optical fibre long period grating for chemical sensing

NASA Astrophysics Data System (ADS)

Hromadka, J.; Tokay, B.; James, S.; Korposh, S.

2017-04-01

An optical fibre long period grating (LPG) modified with a thin film of HKUST-1, a material from metal organic framework (MOF) family, was employed for the detection of carbon dioxide. The sensing mechanism is based on the measurement of the change of the refractive index (RI) of the coating that is induced by the penetration of CO2 molecules into the HKUST-1 pores. The responses of the resonance bands in the transmission spectrum of an LPG modified with 40 layers of HKUST-1 upon exposure to carbon dioxide in mixture with nitrogen were investigated.

Optimisation of Copper Oxide Impregnation on Carbonised Oil Palm Empty Fruit Bunch for Nitric Oxide Removal using Response Surface Methodology

NASA Astrophysics Data System (ADS)

Ahmad, Norhidayah; Yong, Sing Hung; Ibrahim, Naimah; Ali, Umi Fazara Md; Ridwan, Fahmi Muhammad; Ahmad, Razi

2018-03-01

Oil palm empty fruit bunch (EFB) was successfully modified with phosphoric acid hydration followed by impregnation with copper oxide (CuO) to synthesize CuO modified catalytic carbon (CuO/EFBC) for low-temperature removal of nitric oxide (NO) from gas streams. CuO impregnation was optimised through response surface methodology (RSM) using Box-Behnken Design (BBD) in terms of metal loading (5-20%), sintering temperature (200-800˚C) and sintering time (2-6 hours). The model response for the variables was NO adsorption capacity, which was obtained from an up-flow column adsorption experiment with 100 mL/min flow of 500 ppm NO/He at different operating conditions. The optimum operating variables suggested by the model were 20% metal loading, 200˚C sintering temperature and 6 hours sintering time. A good agreement (R2 = 0.9625) was achieved between the experimental data and model prediction. ANOVA analysis indicated that the model terms (metal loading and sintering temperature) are significant (Prob.>F less than 0.05).

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

Wan, Weiming; Tackett, Brian M.; Chen, Jingguang G.

The formation of carbides can significantly modify the physical and chemical properties of the parent metals. In the current review, we summarize the general trends in the reactions of water and C1 molecules over transition metal carbide (TMC) and metal-modified TMC surfaces and thin films. Although the primary focus of the current review is on the theoretical and experimental studies of reactions of C1 molecules (CO, CO 2, CH 3OH, etc.), the reactions of water will also be reviewed because water plays an important role in many of the C1 transformation reactions. This review is organized by discussing separately thermalmore » reactions and electrochemical reactions, which provides insights into the application of TMCs in heterogeneous catalysis and electrocatalysis, respectively. In thermal reactions, we discuss the thermal decomposition of water and methanol, as well as the reactions of CO and CO 2 over TMC surfaces. In electrochemical reactions, we summarize recent studies in the hydrogen evolution reaction, electrooxidation of methanol and CO, and electroreduction of CO 2. Lastly, future research opportunities and challenges associated with using TMCs as catalysts and electrocatalysts are also discussed.« less

Imidazolium salt-modified porous hypercrosslinked polymers for synergistic CO2 capture and conversion.

PubMed

Wang, Jinquan; Sng, Waihong; Yi, Guangshun; Zhang, Yugen

2015-08-04

A new type of imidazolium salt-modified porous hypercrosslinked polymer (BET surface area up to 926 m(2) g(-1)) was reported. These porous materials exhibited good CO2 capture capacities (14.5 wt%) and catalytic activities for the conversion of CO2 into various cyclic carbonates under metal-free conditions. The synergistic effect of CO2 capture and conversion was observed.

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

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.

Electronic coupling in iron oxide-modified TiO2 leads to a reduced band gap and charge separation for visible light active photocatalysis.

PubMed

Nolan, Michael

2011-10-28

In recent experiments Tada et al. have shown that TiO(2) surfaces modified with iron oxide display visible light photocatalytic activity. This paper presents first principles simulations of iron oxide clusters adsorbed at the rutile TiO(2) (110) surface to elucidate the origin of the visible light photocatalytic activity of iron oxide modified TiO(2). Small iron oxide clusters adsorb at rutile (110) surface and their presence shifts the valence band so that the band gap of the composite is narrowed towards the visible, thus confirming the origin of the visible light activity of this composite material. The presence of iron oxide at the TiO(2) surface leads to charge separation, which is the origin of enhanced photocatalytic efficiency, consistent with experimental photoluminesence and photocurrent data. Surface modification of a metal oxide is thus an interesting route in the development of visible light photocatalytic materials. This journal is © the Owner Societies 2011

Modified silica-based heterogeneous catalysts for etherification of glycerol

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

Gholami, Zahra, E-mail: zahra.gholami@petronas.com.my; Abdullah, Ahmad Zuhairi, E-mail: chzuhairi@usm.my; Gholami, Fatemeh, E-mail: fgholami59@gmail.com

2015-07-22

The advent of mesoporous silicas such as MCM-41 has provided new opportunities for research into supported metal catalysis. The loading of metals into framework structures and particularly into the pores of porous molecular sieves, has long been of interest because of their potential catalytic activity. Stable heterogeneous mesoporous basic catalysts were synthesized by wet impregnation of MCM-41 with calcium nitrate and lanthanum nitrate. The surface and structural properties of the prepared catalysts were characterized using BET surface analysis, SEM and TEM. MCM-41 and modified MCM-41 were used in the solventless etherification of glycerol to produce diglycerol as the desired product.more » The reaction was performed at 250 °C for 8 h, and catalyst activity was evaluated. Catalytic etherification over the 20%Ca{sub 1.6}La{sub 0.6}/MCM-41 catalyst resulted in the highest glycerol conversion of 91% and diglycerol yield of 43%.« less

Anomalous transport phenomena in Weyl metal beyond the Drude model for Landau's Fermi liquids.

PubMed

Kim, Ki-Seok; Kim, Heon-Jung; Sasaki, M; Wang, J-F; Li, L

2014-12-01

Landau's Fermi-liquid theory is the standard model for metals, characterized by the existence of electron quasiparticles near a Fermi surface as long as Landau's interaction parameters lie below critical values for instabilities. Recently this fundamental paradigm has been challenged by the physics of strong spin-orbit coupling, although the concept of electron quasiparticles remains valid near the Fermi surface, where Landau's Fermi-liquid theory fails to describe the electromagnetic properties of this novel metallic state, referred to as Weyl metal. A novel ingredient is that such a Fermi surface encloses a Weyl point with definite chirality, referred to as a chiral Fermi surface, which can arise from breaking of either time reversal or inversion symmetry in systems with strong spin-orbit coupling, responsible for both the Berry curvature and the chiral anomaly. As a result, electromagnetic properties of the Weyl metallic state are described not by conventional Maxwell equations but by axion electrodynamics, where Maxwell equations are modified with a topological-in-origin spatially modulated [Formula: see text] term. This novel metallic state was realized recently in Bi[Formula: see text]Sb x around [Formula: see text] under magnetic fields, where the Dirac spectrum appears around the critical point between the normal semiconducting ([Formula: see text]) and topological semiconducting phases ([Formula: see text]) and the time reversal symmetry breaking perturbation causes the Dirac point to split into a pair of Weyl points along the direction of the applied magnetic field for a very strong spin-orbit coupled system. In this review article, we discuss how the topological structure of both the Berry curvature and the chiral anomaly (axion electrodynamics) gives rise to anomalous transport phenomena in [Formula: see text]Sb x around [Formula: see text] under magnetic fields, thus modifying the Drude model of Landau's Fermi liquids.

Effects of anisotropic surface texture on the performance of ionic polymer-metal composite (IPMC)

NASA Astrophysics Data System (ADS)

He, Qingsong; Yu, Min; Ding, Haitao; Guo, Dongjie; Dai, Zhendong

2010-04-01

Ionic polymer metal composite (IPMC), an electrically activated polymer (EAP), has attracted great attention for the excellent properties such as large deformation, light weight, low noise, flexibility and low driving voltages, which makes the material a possible application as artificial muscle if the output force can be increased. To improve the property, we manufactured the Nafion membrane by casting from liquid solution, modified the surface by sandblasting or polishing, and obtained the isotropic and anisotropic surface texture respectively. The microstructure of the Nafion surface and metal electrode, effects of surface texture on the output force and displacement of IPMC were studied. Results show that the output force of IPMC with the anisotropic surface texture is 2~4 times higher than that with the isotropic surface texture without enormous sacrifice of the displacement. The output force may reach to 6.63gf (Sinusoidal 3.5V and 0.1Hz, length 20mm, width 5mm and thickness 0.66mm), which suggest an effective way to improve the mechanical properties of IPMC.

Changes of electrical conductivity of the metal surface layer by the laser alloying with foreign elements

NASA Astrophysics Data System (ADS)

Kostrubiec, Franciszek; Pawlak, Ryszard; Raczynski, Tomasz; Walczak, Maria

1994-09-01

Laser treatment of the surface of materials is of major importance for many fields technology. One of the latest and most significant methods of this treatment is laser alloying consisting of introducing foreign atoms into the metal surface layer during the reaction of laser radiation with the surface. This opens up vast possibilities for the modification of properties of such a layer (obtaining layers of increased microhardness, increased resistance to electroerosion in an electric arc, etc.). Conductivity of the material is a very important parameter in case of conductive materials used for electrical contacts. The paper presents the results of studies on change in electrical conductivity of the surface layer of metals alloyed with a laser. A comparative analysis of conductivity of base metal surface layers prior to and following laser treatment has been performed. Depending on the base metal and the alloying element, optical treatment parameters allowing a required change in the surface layer conductivity have been selected. A very important property of the contact material is its resistance to plastic strain. It affects the real value of contact surface coming into contact and, along with the material conductivity, determines contact resistance and the amount of heat generated in place of contact. These quantities are directly related to the initiation and the course of an arc discharge, hence they also affect resistance to electroerosion. The parameter that reflects plastic properties with loads concentrated on a small surface, as is the case with a reciprocal contact force of two real surfaces with their irregularities being in contact, is microhardness. In the paper, the results of investigations into microhardness of modified surface layers compared with base metal microhardness have been presented.

[GIS Spatial Distribution and Ecological Risk Assessment of Heavy Metals in Surface Sediments of Shallow Lakes in Jiangsu Province].

PubMed

Li, Ying-jie; Zhang, Lie-yu; Wu, Yi-wen; Li, Cao-le; Yang, Tian-xue; Tang, Jun

2016-04-15

To understand pollution of heavy metals in surface sediments of shallow lakes, surface sediments samples of 11 lakes in Jiangsu province were collected to determine the content of six heavy metals including As, Cr, Cu, Pb, Zn and Ni. GIS was used to analyze the spatial distribution of heavy metals, and geological accumulation index (Igeo), modified contamination index (mCd) pollution load index (PLI) and potential ecological risk index (RI) were used to evaluate heavy metal contamination in the sediments. The results showed that: in the lakes' surface sediments, the average content of As, Cu, Zn, Cr, Pb, Ni in multiples of soil background of Jiangsu province were 1.74-3.85, 0.65-2.66, 0.48-3.56, 0.43-1.52, 0.02-1.49 and 0.12-1.42. According to the evaluation results of Igeo and RI, As, which had high degree of enrichment and great potential ecological risk, was the main pollutant, followed by Cu, and pollution of the rest of heavy metals was relatively light. Combining the results of several evaluation methods, in surface sediments of Sanjiu Lake, Gaoyou Lake and Shaobo Lake, these heavy metals had the most serious pollution, the maximum pollution loading and moderate potential ecological risk; in surface sediments of Gehu Lake, Baima Lake and Hongze Lake, some regions were polluted by certain metals, the overall trend of pollution was aggravating, the pollution loading was large, and the potential ecological risk reached moderate; in the other 5 lakes, the risk of sediments polluted by heavy metals, as well as the pollution loading, was small, and the overall was not polluted.

Proliferation and osteogenic differentiation of rat BMSCs on a novel Ti/SiC metal matrix nanocomposite modified by friction stir processing

NASA Astrophysics Data System (ADS)

Zhu, Chenyuan; Lv, Yuting; Qian, Chao; Qian, Haixin; Jiao, Ting; Wang, Liqiang; Zhang, Fuqiang

2016-12-01

The aims of this study were to fabricate a novel titanium/silicon carbide (Ti/SiC) metal matrix nanocomposite (MMNC) by friction stir processing (FSP) and to investigate its microstructure and mechanical properties. In addition, the adhesion, proliferation and osteogenic differentiation of rat bone marrow stromal cells (BMSCs) on the nanocomposite surface were investigated. The MMNC microstructure was observed by both scanning and transmission electron microscopy. Mechanical properties were characterized by nanoindentation and Vickers hardness testing. Integrin β1 immunofluorescence, cell adhesion, and MTT assays were used to evaluate the effects of the nanocomposite on cell adhesion and proliferation. Osteogenic and angiogenic differentiation were evaluated by alkaline phosphatase (ALP) staining, ALP activity, PCR and osteocalcin immunofluorescence. The observed microstructures and mechanical properties clearly indicated that FSP is a very effective technique for modifying Ti/SiC MMNC to contain uniformly distributed nanoparticles. In the interiors of recrystallized grains, characteristics including twins, fine recrystallized grains, and dislocations formed concurrently. Adhesion, proliferation, and osteogenic and angiogenic differentiation of rat BMSCs were all enhanced on the novel Ti/SiC MMNC surface. In conclusion, nanocomposites modified using FSP technology not only have superior mechanical properties under stress-bearing conditions but also provide improved surface and physicochemical properties for cell attachment and osseointegration.

Balancing the Hydrogen Evolution Reaction, Surface Energetics, and Stability of Metallic MoS2 Nanosheets via Covalent Functionalization.

PubMed

Benson, Eric E; Zhang, Hanyu; Schuman, Samuel A; Nanayakkara, Sanjini U; Bronstein, Noah D; Ferrere, Suzanne; Blackburn, Jeffrey L; Miller, Elisa M

2018-01-10

We modify the fundamental electronic properties of metallic (1T phase) nanosheets of molybdenum disulfide (MoS 2 ) through covalent chemical functionalization, and thereby directly influence the kinetics of the hydrogen evolution reaction (HER), surface energetics, and stability. Chemically exfoliated, metallic MoS 2 nanosheets are functionalized with organic phenyl rings containing electron donating or withdrawing groups. We find that MoS 2 functionalized with the most electron donating functional group (p-(CH 3 CH 2 ) 2 NPh-MoS 2 ) is the most efficient catalyst for HER in this series, with initial activity that is slightly worse compared to the pristine metallic phase of MoS 2 . The p-(CH 3 CH 2 ) 2 NPh-MoS 2 is more stable than unfunctionalized metallic MoS 2 and outperforms unfunctionalized metallic MoS 2 for continuous H 2 evolution within 10 min under the same conditions. With regards to the entire studied series, the overpotential and Tafel slope for catalytic HER are both directly correlated with the electron donating strength of the functional group. The results are consistent with a mechanism involving ground-state electron donation or withdrawal to/from the MoS 2 nanosheets, which modifies the electron transfer kinetics and catalytic activity of the MoS 2 nanosheet. The functional groups preserve the metallic nature of the MoS 2 nanosheets, inhibiting conversion to the thermodynamically stable semiconducting state (2H) when mildly annealed in a nitrogen atmosphere. We propose that the electron density and, therefore, reactivity of the MoS 2 nanosheets are controlled by the attached functional groups. Functionalizing nanosheets of MoS 2 and other transition metal dichalcogenides provides a synthetic chemical route for controlling the electronic properties and stability within the traditionally thermally unstable metallic state.

Design and functionalization of photocatalytic systems within mesoporous silica.

PubMed

Qian, Xufang; Fuku, Kojirou; Kuwahara, Yasutaka; Kamegawa, Takashi; Mori, Kohsuke; Yamashita, Hiromi

2014-06-01

In the past decades, various photocatalysts such as TiO2, transition-metal-oxide moieties within cavities and frameworks, or metal complexes have attracted considerable attention in light-excited catalytic processes. Owing to high surface areas, transparency to UV and visible light as well as easily modified surfaces, mesoporous silica-based materials have been widely used as excellent hosts for designing efficient photocatalytic systems under the background of environmental remediation and solar-energy utilization. This Minireview mainly focuses on the surface-chemistry engineering of TiO2/mesoporous silica photocatalytic systems and fabrication of binary oxides and nanocatalysts in mesoporous single-site-photocatalyst frameworks. Recently, metallic nanostructures with localized surface plasmon resonance (LSPR) have been widely studied in catalytic applications harvesting light irradiation. Accordingly, silver and gold nanostructures confined in mesoporous silica and their corresponding catalytic activity enhanced by the LSPR effect will be introduced. In addition, the integration of metal complexes within mesoporous silica materials for the construction of functional inorganic-organic supramolecular photocatalysts will be briefly described. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Development of an iron chelating polyethylene film for active packaging applications.

PubMed

Tian, Fang; Decker, Eric A; Goddard, Julie M

2012-02-29

Metal-promoted oxidation reactions are a major cause of food quality deterioration. Active packaging offers novel approaches to controlling such oxidation for the purpose of extending shelf life. Herein, we report modification of the surface of polyethylene (PE) films to possess metal chelating activity. Metal chelating carboxylic acids were introduced to the film surface using cross-linking agents [polyethylenimine (PEI) or ethylenediamine (ED)] to increase the number of available carboxylic acids. ATR-FTIR, contact angle, dye assay, and iron chelating assay were used to characterize changes in surface chemistry after each functionalization step. The chelator poly(acrylic acid) (PAA) was attached to the surface at a density of 9.12 ± 0.71 nmol carboxyl groups/cm², and exhibited an iron chelating activity. The results indicate that PAA-modified PE films might have a higher affinity to Fe³⁺ than Fe²⁺ with the optimum binding pH at 5.0. Such inexpensive active packaging materials are promising in food industry for the preservation of liquid and semiliquid food products and have application in heavy metal chelation therapy for biomedical materials as well.

Electrostatic interactions between ions near Thomas-Fermi substrates and the surface energy of ionic crystals at imperfect metals.

PubMed

Kaiser, V; Comtet, J; Niguès, A; Siria, A; Coasne, B; Bocquet, L

2017-07-01

The electrostatic interaction between two charged particles is strongly modified in the vicinity of a metal. This situation is usually accounted for by the celebrated image charges approach, which was further extended to account for the electronic screening properties of the metal at the level of the Thomas-Fermi description. In this paper we build upon a previous approach [M. A. Vorotyntsev and A. A. Kornyshev, Zh. Eksp. Teor. Fiz., 1980, 78(3), 1008-1019] and successive works to calculate the 1-body and 2-body electrostatic energy of ions near a metal in terms of the Thomas-Fermi screening length. We propose workable approximations suitable for molecular simulations of ionic systems close to metallic walls. Furthermore, we use this framework to calculate analytically the electrostatic contribution to the surface energy of a one dimensional crystal at a metallic wall and its dependence on the Thomas-Fermi screening length. These calculations provide a simple interpretation for the surface energy in terms of image charges, which allows for an estimation of the interfacial properties in more complex situations of a disordered ionic liquid close to a metal surface. The counter-intuitive outcome is that electronic screening, as characterized by a molecular Thomas-Fermi length l TF , profoundly affects the wetting of ionic systems close to a metal, in line with the recent experimental observation of capillary freezing of ionic liquids in metallic confinement.

Replaceable filters and cones for flared-tubing connectors

NASA Technical Reports Server (NTRS)

Grant, L. E.; Howland, B. T.

1970-01-01

Connector is modified by machining the cone from one end before the fitting is bored to accommodate a metallic-filament type of slip-in filter. Thus, when surface of the cone is damaged, only the cone needs replacement.

Hybrid Nanoparticles as Oil Lubricant Additives for Friction and Wear Reduction

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

Zhao, Bin; Dai, Sheng; Qu, Jun

A new class of organic-inorganic/metallic hybrid nanoparticles (NPs), including oil-soluble polymer brush-grafted metal oxide NPs and organic-modified metallic NPs, was developed and used as oil lubricant additives for friction and wear reduction to improve engine energy efficiency. The tribological properties of these hybrid NPs in polyalphaolefin (PAO) base oil were investigated by high contact stress ball-on-flat reciprocating sliding tribological tests at 100 oC. Using surface-initiated “living”/controlled radical polymerization from initiator- or chain transfer agent-functionalized metal oxide (silica and titania) NPs, we synthesized a series of hairy NPs and systematically studied the effects of molecular weight and chemical composition of graftedmore » polymer brushes on oil dispersibility, stability, and lubrication properties of hairy NPs in PAO. In addition, several types of organic-modified metallic NPs, including silver and palladium NPs, were synthesized by using thiol compounds and ionic liquids (ILs) as ligands. Significant reductions in friction (up to 40%) and wear volume (up to 90%) were achieved by using PAO mixed with hairy NPs or organic-modified metal NPs compared to PAO base oil. Moreover, a positive effect on lubricating performance was observed when oil-soluble hairy silica NPs and an IL were used simultaneously as additives for PAO for friction reduction. The lubrication mechanisms of these hybrid NPs were elucidated by both experimental and simulation studies.« less

Surface Plasmon Resonance Evaluation of Colloidal Metal Aerogel Filters

NASA Technical Reports Server (NTRS)

Smith, David D.; Sibille, Laurent; Cronise, Raymond J.; Noever, David A.

1997-01-01

We have fabricated aerogels containing gold, silver, and platinum nanoparticles for gas catalysis applications. By applying the concept of an average or effective dielectric constant to the heterogeneous interlayer surrounding each particle, we extend the technique of immersion spectroscopy to porous or heterogeneous media. Specifically, we apply the predominant effective medium theories for the determination of the average fractional composition of each component in this inhomogeneous layer. Hence, the surface area of metal available for catalytic gas reaction is determined. The technique is satisfactory for statistically random metal particle distributions but needs further modification for aggregated or surfactant modified systems. Additionally, the kinetics suggest that collective particle interactions in coagulated clusters are perturbed during silica gelation resulting in a change in the aggregate geometry.

Surface phonons and elastic surface waves

NASA Astrophysics Data System (ADS)

Büscher, H.; Klein-Heßling, W.; Ludwig, W.

Theoretical investigations on the dynamics of the (001), (110) and (111) surfaces of some cubic metals (Ag, Cu, Ni) will be reviewed. Both, lattice dynamical and continuum theoretical results are obtained via a Green's function formalism. The main attitude of this paper is the comparison of our results with experiments and with results obtained via slab-calculations. The calculation of elastic surface waves has been performed using a modified surface-green-function-matching method. We have used two different approaches of calculation the bulk Green's function (a) using the spectral representation and (b) a method, what works on residues. The investigations are carried out using shortrange phenomenological potentials. The atomic force constants in the first surface layers are modified to describe surface phonon anomalies, observed by experiments. In the case of Ag (100) and Ag(110) we conclude that the detection of odd symmetry shear modes by Erskine et al. [1 a, b] was not very accurate.

Creating metamaterial building blocks with directed photochemical metallization of silver onto DNA origami templates.

PubMed

Hossen, Md Mir; Bendickson, Lee; Palo, Pierre E; Yao, Zhiqi; Nilsen-Hamilton, Marit; Hillier, Andrew C

2018-08-31

DNA origami can be used to create a variety of complex and geometrically unique nanostructures that can be further modified to produce building blocks for applications such as in optical metamaterials. We describe a method for creating metal-coated nanostructures using DNA origami templates and a photochemical metallization technique. Triangular DNA origami forms were fabricated and coated with a thin metal layer by photochemical silver reduction while in solution or supported on a surface. The DNA origami template serves as a localized photosensitizer to facilitate reduction of silver ions directly from solution onto the DNA surface. The metallizing process is shown to result in a conformal metal coating, which grows in height to a self-limiting value with increasing photoreduction steps. Although this coating process results in a slight decrease in the triangle dimensions, the overall template shape is retained. Notably, this coating method exhibits characteristics of self-limiting and defect-filling growth, which results in a metal nanostructure that maps the shape of the original DNA template with a continuous and uniform metal layer and stops growing once all available DNA sites are exhausted.

New Developments for Radiation Enhancements from Metal Surfaces by Using Nanoscale Materials in the Membrane

NASA Astrophysics Data System (ADS)

Yamada, Koji; Matsuda, Masami

2017-12-01

The enhancements of thermal radiations from the surfaces of devices are very important for electric machines to prevent from heating up and/or efficiency degradations. In this investigation, new applications of micro-scale membrane of Si, SiO2 etc. on the metal surfaces have been studied to cool down the temperature without breaking insulations of the devices by selecting materials. The modified black-body radiations were sensitively detected by thermisters with sub-second responses. The optimum membrane thicknesses were successfully determined by subtractions a of radiation intensities between those at membranes with and without membrane, respectively. We obtained the best cooling condition in SiO2 membrane with 20μmt for an Al-plate of 10cmx10cmx1mmt. Further, we observed the detaching/attaching processes of massive molecule clusters from the metal surface as a sudden change in temperature changes just like the noises in the detectors. A characteristic pattern of temperature change was observed in diatomite membranes during the cooling process in a temperature range between 200-50°C. These radiation phenomena as a function of temperature might be available as a molecular analysis on the metal surface.

Plasma Processing of Metallic and Semiconductor Thin Films in the Fisk Plasma Source

NASA Technical Reports Server (NTRS)

Lampkin, Gregory; Thomas, Edward, Jr.; Watson, Michael; Wallace, Kent; Chen, Henry; Burger, Arnold

1998-01-01

The use of plasmas to process materials has become widespread throughout the semiconductor industry. Plasmas are used to modify the morphology and chemistry of surfaces. We report on initial plasma processing experiments using the Fisk Plasma Source. Metallic and semiconductor thin films deposited on a silicon substrate have been exposed to argon plasmas. Results of microscopy and chemical analyses of processed materials are presented.

Stabilization of heavy metals in soil using two organo-bentonites.

PubMed

Yu, Kai; Xu, Jian; Jiang, Xiaohong; Liu, Cun; McCall, Wesley; Lu, Jinlong

2017-10-01

Stabilization of Cu, Zn, Cd, Hg, Cr and As in soil using tetramethylammonium (TMA) and dodecyltrimethylammonium (DTMA) modified bentonites (T-Bents and D-Bents) as amendments was investigated. Toxicity characteristic leaching procedure (TCLP) was used to quantify the metal mobility after soil treatment. The structural parameters of modified bentonites, including the BET surface area, basal spacing and zeta potential were obtained as a function of the TMA and DTMA loading at 40, 80, 120, 160 and 200% of the bentonite's cation exchange capacity, respectively. The results indicated that the characteristics of the organo-bentonites fundamentally varied depending on the species and concentration of modifiers loaded on bentonite. T-Bents and D-Bents manifested distinct immobilization effectiveness towards various metals. In association with the organo-bentonite characteristics, the main interactive mechanisms for Cu, Zn and Cd proceeded via cation exchange, Hg proceeded via physical adsorption and partitioning, Cr and As proceeded via specific adsorption and electrostatic attraction, respectively. This study provided operational and mechanistic basis for optimizing the organic clay synthesis and selecting as the appropriate amendment for remediation of heavy metal contaminated soils. Copyright © 2017 Elsevier Ltd. All rights reserved.

Design of Solid-Gas Interfaces for Enhanced Thermal Transfer

DTIC Science & Technology

2015-09-28

modifications. Specifically, for metal surfaces modified with organic self - assembled monolayers (SAMs), both TAC and MAC are close to its theoretical...we designed solid surfaces functionalized with organic self - assembled monolayers (SAMs) and demonstrated associated significant improvement of the...at solid-gas interfaces by self - assembled monolayers ” Applied Physics Letters 102, 061907 (2013). 2. Zhi Liang, William Evans, and Pawel Keblinski

Laser-induced Hertzian fractures in silica initiated by metal micro-particles on the exit surface

DOE PAGES

Feigenbaum, Eyal; Raman, Rajesh N.; Cross, David; ...

2016-05-16

Laser-induced Hertzian fractures on the exit surface of silica glass are found to result from metal surface-bound micro particles. Two types of metal micro-spheres are studied (stainless-steel and Al) using ultraviolet laser light. The fracture initiation probability curve as a function of fluence is obtained, resulting in an initiation threshold fluence of 11.1 ± 4.7 J/cm 2 and 16.5 ± 4.5 J/cm 2 for the SS and Al particles, accordingly. The modified damage density curve is calculated based on the fracture probability. Here, the calculated momentum coupling coefficient linking incident laser fluence to the resulting plasma pressure is found tomore » be similar for both particles: 32.6 ± 15.4 KN/J and 28.1 ± 10.4 KN/J for the SS and Al cases accordingly.« less

Coating and dispersion of ceramic nanoparticles by UV-ozone etching assisted surface-initiated living radical polymerization.

PubMed

Arita, Toshihiko

2010-10-01

Commercially available unmodified ceramic nanoparticles (NPs) in dry powder state were surface-modified and dispersed in almost single-crystal size. The surface-initiated living radical polymerization after just UV-ozone soft etching enables one to graft polymers onto the surface of ceramic NPs and disperse them in solvents. Furthermore, a number of NPs were dispersed with single-crystal sizes. The technique developed here could be applied to almost all ceramic NPs including metal nitrides.

Controlled mechnical modification of manganite surface with nanoscale resolution

DOE PAGES

Kelly, Simon J.; Kim, Yunseok; Eliseev, Eugene; ...

2014-11-07

We investigated the surfaces of magnetoresistive manganites, La1-xCaxMnO3 and La2-2xSr1+2xMn2O7, using a combination of ultrahigh vacuum conductive, electrostatic and magnetic force microscopy methods. Scanning as-grown film with a metal tip, even with zero applied bias, was found to modify the surface electronic properties such that in subsequent scans, the conductivity is reduced below the noise level of conductive probe microscopy. Scanned areas also reveal a reduced contact potential difference relative to the pristine surface by ~0.3 eV. We propose that contact-pressure of the tip modifies the electrochemical potential of oxygen vacancies via the Vegard effect, causing vacancy motion and concomitantmore » changes of the electronic properties.« less

Nanopatterning the electronic properties of gold surfaces with self-organized superlattices of metallic nanostructures.

PubMed

Didiot, Clement; Pons, Stephane; Kierren, Bertrand; Fagot-Revurat, Yannick; Malterre, Daniel

2007-10-01

The self-organized growth of nanostructures on surfaces could offer many advantages in the development of new catalysts, electronic devices and magnetic data-storage media. The local density of electronic states on the surface at the relevant energy scale strongly influences chemical reactivity, as does the shape of the nanoparticles. The electronic properties of surfaces also influence the growth and decay of nanostructures such as dimers, chains and superlattices of atoms or noble metal islands. Controlling these properties on length scales shorter than the diffusion lengths of the electrons and spins (some tens of nanometres for metals) is a major goal in electronics and spintronics. However, to date, there have been few studies of the electronic properties of self-organized nanostructures. Here we report the self-organized growth of macroscopic superlattices of Ag or Cu nanostructures on Au vicinal surfaces, and demonstrate that the electronic properties of these systems depend on the balance between the confinement and the perturbation of the surface states caused by the steps and the nanostructures' superlattice. We also show that the local density of states can be modified in a controlled way by adjusting simple parameters such as the type of metal deposited and the degree of coverage.

Analytic modified embedded atom potentials for HCP metals

NASA Astrophysics Data System (ADS)

Hu, Wangyu; Zhang, Bangwei; Huang, Baiyun; Gao, Fei; Bacon, David J.

2001-02-01

Analytic modified embedded atom method (AMEAM) type many-body potentials have been constructed for ten hcp metals: Be, Co, Hf, Mg, Re, Ru, Sc, Ti, Y and Zr. The potentials are parametrized using analytic functions and fitted to the cohesive energy, unrelaxed vacancy formation energy, five independent second-order elastic constants and two equilibrium conditions. Hence, each of the constructed potentials represents a stable hexagonal close-packed lattice with a particular non-ideal c/a ratio. In order to treat the metals with negative Cauchy pressure, a modified term has been added to the total energy. For all the metals considered, the hcp lattice is shown to be energetically most stable when compared with the fcc and bcc structure and the hcp lattice with ideal c/a. The activation energy for vacancy diffusion in these metals has been calculated. They agree well with experimental data available and those calculated by other authors for both monovacancy and divacancy mechanisms and the most possible diffusion paths are predicted. Stacking fault and surface energy have also been calculated and their values are lower than typical experimental data. Finally, the self-interstitial atom (SIA) formation energy and volume have been evaluated for eight possible sites. This calculation suggests that the basal split or crowdion is the most stable configuration for metals with a rather large deviation from the ideal c/a value and the non-basal dumbbell (C or S) is the most stable configuration for metals with c/a near ideal. The relationship between SIA formation energy and melting temperature roughly obeys a linear relation for most metals except Ru and Re.

Peat hybrid sorbents for treatment of wastewaters and remediation of polluted environment

NASA Astrophysics Data System (ADS)

Klavins, Maris; Burlakovs, Juris; Robalds, Artis; Ansone-Bertina, Linda

2015-04-01

For remediation of soils and purification of polluted waters, wastewaters, sorbents might be considered as an prospective group of materials and amongst them peat have a special role due to low cost, biodegradability, high number of functional groups, well developed surface area and combination of hydrophilic/hydrophobic structural elements. Peat as sorbent have good application potential for removal of trace metals, and we have demonstrated peat sorption capacities, sorption kinetics, thermodynamics in respect to metals with different valencies - Tl(I), Cu(II), Cr(III). However peat sorption capacity in respect to nonmetallic (anionic species) elements is low. Also peat mechanical properties do not support application in large scale column processes. To expand peat application possibilities the approach of biomass based hybrid sorbents has been elaborated. The concept "hybrid sorbent" in our understanding means natural, biomass based sorbent modified, covered with another sorbent material, thus combining two types of sorbent properties, sorbent functionalities, surface properties etc. As the "covering layer" both inorganic substances, mineral phases (iron oxohydroxides, oxyapatite) both organic polymers (using graft polymerization) were used. The obtained sorbents were characterised by their spectral properties, surface area, elemental composition. The obtained hybrid sorbents were tested for sorption of compounds in anionic speciation forms, for example of arsenic, antimony, tellurium and phosphorous compounds in comparison with weakly basic anionites. The highest sorption capacity was observed when peat sorbents modified with iron compounds were used. Sorption of different arsenic speciation forms onto iron-modified peat sorbents was investigated as a function of pH and temperature. It was established that sorption capacity increases with a rise in temperature, and the calculation of sorption process thermodynamic parameters indicates the spontaneity of sorption process and its endothermic nature. The recycling options of obtained compounds after their saturation with metal or non-metallic species are suggested. Acknowledgement: Support from a project 2014/0009/1DP/1.1.1.2.0/13/APIA/VIAA/044

Lead and cadmium sorption mechanisms on magnetically modified biochars.

PubMed

Trakal, Lukáš; Veselská, Veronika; Šafařík, Ivo; Vítková, Martina; Číhalová, Sylva; Komárek, Michael

2016-03-01

This paper discusses Cd(II) and Pb(II) sorption efficiency of biochars modified by impregnation with magnetic particles. All selected biochar characteristics were significantly affected after the modification. More specifically, the cation exchange capacity increased after the modification, except for grape stalk biochar. However, the changes in the pH value, PZC, and BET surface after modification process were less pronounced. The metal loading rate was also significantly improved, especially for Cd(II) sorption on/in nut shield and plum stone biochars (10- and 16-times increase, respectively). The results indicated that cation exchange (as a metal sorption mechanism) was strengthened after Fe oxide impregnation, which limited the desorbed amount of tested metals. In contrast, the magnetization of grape stalk biochar reduced Pb(II) sorption in comparison with that of pristine biochar. Magnetic modification is, therefore, more efficient for biochars with well-developed structure and for more mobile metals, such as Cd(II). Copyright © 2015 Elsevier Ltd. All rights reserved.

Metal-organic framework tethering PNIPAM for ON-OFF controlled release in solution.

PubMed

Nagata, Shunjiro; Kokado, Kenta; Sada, Kazuki

2015-05-21

A smart metal-organic framework (MOF) exhibiting controlled release was achieved by modification with a thermoresponsive polymer (PNIPAM) via a surface-selective post-synthetic modification technique. Simple temperature variation readily switches "open" (lower temperature) and "closed" (higher temperature) states of the polymer-modified MOF through conformational change of PNIPAM grafted onto the MOF, resulting in controlled release of the included guest molecules such as resorufin, caffeine, and procainamide.

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.

Theoretical model of gravitational perturbation of current collector axisymmetric flow field

NASA Astrophysics Data System (ADS)

Walker, John S.; Brown, Samuel H.; Sondergaard, Neal A.

1989-03-01

Some designs of liquid metal collectors in homopolar motors and generators are essentially rotating liquid metal fluids in cylindrical channels with free surfaces and will, at critical rotational speeds, become unstable. The role of gravity in modifying this ejection instability is investigated. Some gravitational effects can be theoretically treated by perturbation techniques on the axisymmetric base flow of the liquid metal. This leads to a modification of previously calculated critical current collector ejection values neglecting gravity effects. The derivation of the mathematical model which determines the perturbation of the liquid metal base flow due to gravitational effects is documented. Since gravity is a small force compared with the centrifugal effects, the base flow solutions can be expanded in inverse powers of the Froude number and modified liquid flow profiles can be determined as a function of the azimuthal angle. This model will be used in later work to theoretically study the effects of gravity on the ejection point of the current collector. A rederivation of the hydrodynamic instability threshold of a liquid metal current collector is presented.

Evaluation of anti-freeze viscosity modifier for potential external tank applications

NASA Technical Reports Server (NTRS)

Lynn, R. O. L.

1981-01-01

Viscosity modifiers and gelling agents were evaluated in combination with ethylene glycol and dimethyl sulfoxide water eutectics. Pectin and agarose are found to gel these eutectics effectively in low concentration, but the anti-freeze protection afforded by these compositions is found to be marginal in simulations of the intended applications. Oxygen vent shutters and vertical metallic surfaces were simulated, with water supplied as a spray, dropwise, and by condensation from the air.

Enhancing the mechanical and biological performance of a metallic biomaterial for orthopedic applications through changes in the surface oxide layer by nanocrystalline surface modification.

PubMed

Bahl, Sumit; Shreyas, P; Trishul, M A; Suwas, Satyam; Chatterjee, Kaushik

2015-05-07

Nanostructured metals are a promising class of biomaterials for application in orthopedics to improve the mechanical performance and biological response for increasing the life of biomedical implants. Surface mechanical attrition treatment (SMAT) is an efficient way of engineering nanocrystalline surfaces on metal substrates. In this work, 316L stainless steel (SS), a widely used orthopedic biomaterial, was subjected to SMAT to generate a nanocrystalline surface. Surface nanocrystallization modified the nature of the oxide layer present on the surface. It increased the corrosion-fatigue strength in saline by 50%. This increase in strength is attributed to a thicker oxide layer, residual compressive stresses, high strength of the surface layer, and lower propensity for intergranular corrosion in the nanocrystalline layer. Nanocrystallization also enhanced osteoblast attachment and proliferation. Intriguingly, wettability and surface roughness, the key parameters widely acknowledged for controlling the cellular response remained unchanged after nanocrystallization. The observed cellular behavior is explained in terms of the changes in electronic properties of the semiconducting passive oxide film present on the surface of 316L SS. Nanocrystallization increased the charge carrier density of the n-type oxide film likely preventing denaturation of the adsorbed cell-adhesive proteins such as fibronectin. In addition, a net positive charge developed on the otherwise neutral oxide layer, which is known to facilitate cellular adhesion. The role of changes in the electronic properties of the oxide films on metal substrates is thus highlighted in this work. This study demonstrates the advantages of nanocrystalline surface modification by SMAT for processing metallic biomaterials used in orthopedic implants.

Direct quantitative identification of the “surface trans-effect”

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

Deimel, Peter S.; Bababrik, Reda M.; Wang, Bin

The strong parallels between coordination chemistry and adsorption on metal surfaces, with molecules and ligands forming local bonds to individual atoms within a metal surface, have been established over many years of study. The recently proposed “surface trans-effect” (STE) appears to be a further manifestation of this analogous behaviour, but so far the true nature of the modified molecule–metal surface bonding has been unclear. The STE could play an important role in determining the reactivities of surface-supported metal–organic complexes, influencing the design of systems for future applications. However, the current understanding of this effect is incomplete and lacks reliable structuralmore » parameters with which to benchmark theoretical calculations. Using X-ray standing waves, we demonstrate that ligation of ammonia and water to iron phthalocyanine (FePc) on Ag(111) increases the adsorption height of the central Fe atom; dispersion corrected density functional theory calculations accurately model this structural effect. The calculated charge redistribution in the FePc/H 2O electronic structure induced by adsorption shows an accumulation of charge along the σ-bonding direction between the surface, the Fe atom and the water molecule, similar to the redistribution caused by ammonia. Finally, this apparent σ-donor nature of the observed STE on Ag(111) is shown to involve bonding to the delocalised metal surface electrons rather than local bonding to one or more surface atoms, thus indicating that this is a true surface trans-effect.« less

Direct quantitative identification of the “surface trans-effect”

DOE PAGES

Deimel, Peter S.; Bababrik, Reda M.; Wang, Bin; ...

2016-06-09

The strong parallels between coordination chemistry and adsorption on metal surfaces, with molecules and ligands forming local bonds to individual atoms within a metal surface, have been established over many years of study. The recently proposed “surface trans-effect” (STE) appears to be a further manifestation of this analogous behaviour, but so far the true nature of the modified molecule–metal surface bonding has been unclear. The STE could play an important role in determining the reactivities of surface-supported metal–organic complexes, influencing the design of systems for future applications. However, the current understanding of this effect is incomplete and lacks reliable structuralmore » parameters with which to benchmark theoretical calculations. Using X-ray standing waves, we demonstrate that ligation of ammonia and water to iron phthalocyanine (FePc) on Ag(111) increases the adsorption height of the central Fe atom; dispersion corrected density functional theory calculations accurately model this structural effect. The calculated charge redistribution in the FePc/H 2O electronic structure induced by adsorption shows an accumulation of charge along the σ-bonding direction between the surface, the Fe atom and the water molecule, similar to the redistribution caused by ammonia. Finally, this apparent σ-donor nature of the observed STE on Ag(111) is shown to involve bonding to the delocalised metal surface electrons rather than local bonding to one or more surface atoms, thus indicating that this is a true surface trans-effect.« less

Enhancement of solar hydrogen evolution from water by surface modification with CdS and TiO2 on porous CuInS2 photocathodes prepared by an electrodeposition-sulfurization method.

PubMed

Zhao, Jiao; Minegishi, Tsutomu; Zhang, Li; Zhong, Miao; Gunawan; Nakabayashi, Mamiko; Ma, Guijun; Hisatomi, Takashi; Katayama, Masao; Ikeda, Shigeru; Shibata, Naoya; Yamada, Taro; Domen, Kazunari

2014-10-27

Porous films of p-type CuInS2, prepared by sulfurization of electrodeposited metals, are surface-modified with thin layers of CdS and TiO2. This specific porous electrode evolved H2 from photoelectrochemical water reduction under simulated sunlight. Modification with thin n-type CdS and TiO2 layers significantly increased the cathodic photocurrent and onset potential through the formation of a p-n junction on the surface. The modified photocathodes showed a relatively high efficiency and stable H2 production under the present reaction conditions. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Demonstration Of A Nanomaterial-Modified Primer For Use In Corrosion-Inhibiting Coating Systems

DTIC Science & Technology

2011-11-01

abrasive blasting or other means. This report documents the materials and methodologies used for testing and application of the new coating systems on the...method with improved corrosion resistant coatings will provide the DoD with a means to cost effectively rehabilitate the outer metal surfaces of...contained with environmental controls in place. ........................................ 9 Figure 6. Abrasive blast-cleaned tank surface

Biomimetic PDMS-hydroxyurethane terminated with catecholic moieties for chemical grafting on transition metal oxide-based surfaces

NASA Astrophysics Data System (ADS)

de Aguiar, Kelen R.; Rischka, Klaus; Gätjen, Linda; Noeske, Paul-Ludwig Michael; Cavalcanti, Welchy Leite; Rodrigues-Filho, Ubirajara P.

2018-01-01

The aim of this work was to synthesize a non-isocyanate poly(dimethylsiloxane) hydroxyurethane with biomimetic terminal catechol moieties, as a candidate for inorganic and metallic surface modification. Such surface modifier is capable to strongly attach onto metallic and inorganic substrates forming layers and, in addition, providing water-repellent surfaces. The non-isocyanate route is based on carbon dioxide cycloaddition into bis-epoxide, resulting in a precursor bis(cyclic carbonate)-polydimethylsiloxane (CCPDMS), thus fully replacing isocyanate in the manufacture process. A biomimetic approach was chosen with the molecular composition being inspired by terminal peptides present in adhesive proteins of mussels, like Mefp (Mytilus edulis foot protein), which bear catechol moieties and are strong adhesives even under natural and saline water. The catechol terminal groups were grafted by aminolysis reaction into a polydimethylsiloxane backbone. The product, PDMSUr-Dopamine, presented high affinity towards inhomogeneous alloy surfaces terminated by native oxide layers as demonstrated by quartz crystal microbalance (QCM-D), as well as stability against desorption by rinsing with ethanol. As revealed by QCM-D, X-ray photoelectron spectroscopy (XPS) and computational studies, the thickness and composition of the resulting nanolayers indicated an attachment of PDMSUr-Dopamine molecules to the substrate through both terminal catechol groups, with the adsorbate exposing the hydrophobic PDMS backbone. This hypothesis was investigated by classical molecular dynamic simulation (MD) of pure PDMSUr-Dopamine molecules on SiO2 surfaces. The computationally obtained PDMSUr-Dopamine assembly is in agreement with the conclusions from the experiments regarding the conformation of PDMSUr-Dopamine towards the surface. The tendency of the terminal catechol groups to approach the surface is in agreement with proposed model for the attachment PDMSUr-Dopamine. Remarkably, the versatile PDMSUr-Dopamine modifier facilitates such functionalization for various substrates such as titanium alloy, steel and ceramic surfaces.

Biomaterial strategies for engineering implants for enhanced osseointegration and bone repair

PubMed Central

Agarwal, Rachit; García, Andrés J.

2015-01-01

Bone tissue has a remarkable ability to regenerate and heal itself. However, large bone defects and complex fractures still present a significant challenge to the medical community. Current treatments center on metal implants for structural and mechanical support and auto- or allo-grafts to substitute long bone defects. Metal implants are associated with several complications such as implant loosening and infections. Bone grafts suffer from donor site morbidity, reduced bioactivity, and risk of pathogen transmission. Surgical implants can be modified to provide vital biological cues, growth factors and cells in order to improve osseointegration and repair of bone defects. Here we review strategies and technologies to engineer metal surfaces to promote osseointegration with the host tissue. We also discuss strategies for modifying implants for cell adhesion and bone growth via integrin signaling and growth factor and cytokine delivery for bone defect repair. PMID:25861724

Proliferation and osteogenic differentiation of rat BMSCs on a novel Ti/SiC metal matrix nanocomposite modified by friction stir processing

PubMed Central

Zhu, Chenyuan; Lv, Yuting; Qian, Chao; Qian, Haixin; Jiao, Ting; Wang, Liqiang; Zhang, Fuqiang

2016-01-01

The aims of this study were to fabricate a novel titanium/silicon carbide (Ti/SiC) metal matrix nanocomposite (MMNC) by friction stir processing (FSP) and to investigate its microstructure and mechanical properties. In addition, the adhesion, proliferation and osteogenic differentiation of rat bone marrow stromal cells (BMSCs) on the nanocomposite surface were investigated. The MMNC microstructure was observed by both scanning and transmission electron microscopy. Mechanical properties were characterized by nanoindentation and Vickers hardness testing. Integrin β1 immunofluorescence, cell adhesion, and MTT assays were used to evaluate the effects of the nanocomposite on cell adhesion and proliferation. Osteogenic and angiogenic differentiation were evaluated by alkaline phosphatase (ALP) staining, ALP activity, PCR and osteocalcin immunofluorescence. The observed microstructures and mechanical properties clearly indicated that FSP is a very effective technique for modifying Ti/SiC MMNC to contain uniformly distributed nanoparticles. In the interiors of recrystallized grains, characteristics including twins, fine recrystallized grains, and dislocations formed concurrently. Adhesion, proliferation, and osteogenic and angiogenic differentiation of rat BMSCs were all enhanced on the novel Ti/SiC MMNC surface. In conclusion, nanocomposites modified using FSP technology not only have superior mechanical properties under stress-bearing conditions but also provide improved surface and physicochemical properties for cell attachment and osseointegration. PMID:27958394

Increasing the Energy Efficiency of Aluminum-Reduction Cells Using Modified Cathodes

NASA Astrophysics Data System (ADS)

Jianping, Peng; Yang, Song; Yuezhong, Di; Yaowu, Wang; Naixiang, Feng

2017-10-01

A cathode with an inclined surface (5°) and increased bar collector height (230 mm high) was incorporated into two 300-kA industrial aluminum-reduction cells. The voltage of the cells with the modified cathode was reduced by approximately 200 mV when compared with that of a conventional cell with a flat cathode. Through the use of simulations, the reduction in the cell voltage was attributed to the cathode modification (40 mV) and a reduced electrolyte level of 0.5 cm (160 mV). As a result of reduced anode cathode distance (ACD), the ledge toe was extended to the anode shadow by 12 cm. This caused a large inverted horizontal current and a velocity increase. The ledge profile returned to the desired position when the cells were insulated more effectively, and the metal velocity and metal crest in the modified cells were reduced accordingly.

Mesoporous Aluminosilicate Catalysts for the Selective Isomerization of n-Hexane: The Roles of Surface Acidity and Platinum Metal.

PubMed

Musselwhite, Nathan; Na, Kyungsu; Sabyrov, Kairat; Alayoglu, Selim; Somorjai, Gabor A

2015-08-19

Several types of mesoporous aluminosilicates were synthesized and evaluated in the catalytic isomerization of n-hexane, both with and without Pt nanoparticles loaded into the mesopores. The materials investigated included mesoporous MFI and BEA type zeolites, MCF-17 mesoporous silica, and an aluminum modified MCF-17. The acidity of the materials was investigated through pyridine adsorption and Fourier Transform-Infrared Spectroscopy (FT-IR). It was found that the strong Brönsted acid sites in the micropores of the zeolite catalysts facilitated the cracking of hexane. However, the medium strength acid sites on the Al modified MCF-17 mesoporous silica greatly enhanced the isomerization reaction. Through the loading of different amounts of Pt into the mesopores of the Al modified MCF-17, the relationship between the metal nanoparticles and acidic sites on the support was revealed.

Surface-modified biochar in a bioretention system for Escherichia coli removal from stormwater.

PubMed

Lau, Abbe Y T; Tsang, Daniel C W; Graham, Nigel J D; Ok, Yong Sik; Yang, Xin; Li, Xiang-Dong

2017-02-01

Bioretention systems have been recommended as one of the best management practices for low impact development for water recycling/reuse systems. Although improvement of the stormwater quality has been reported regarding pollutants eliminations such as suspended solids and heavy metals, a substantial removal of indicator bacteria is required for possible non-potable reuse. This study investigated the efficiency of wood biochar with H 2 SO 4 -, H 3 PO 4 -, KOH-, and amino-modifications for E. coli removal from synthetic stormwater under intermittent flow. The H 2 SO 4 -modified biochar showed a specific surface area of 234.7 m 2  g -1 (approximately double the area of original biochar), whereas a substantial reduction in surface area was found with amino-modified biochar. The E. coli removal (initial concentration of 0.3-3.2 × 10 6  CFU mL -1 ) by modified biochars as filter media was very promising with, for example, over 98% removal efficiency in the first 20 pore volumes of stormwater infiltration and over 92% removal by the end of the second infiltration cycle. Only a small portion of E. coli attached on the modified biochars (<0.3%, except KOH- and amino-modified biochars) was remobilized during the drainage phase of intermittent flow. The high removal capacity and stability against drainage were attributed to the high surface area, porous structure, and surface characteristics (e.g. hydrophobicity and O-containing functional groups) of the biochars. Thus, the H 2 SO 4 -modified biochar appeared to give the best treatment performance. Copyright © 2016 Elsevier Ltd. All rights reserved.

SPECTROSCOPIC INVESTIGATION OF (NH4)2S TREATED GaSeTe FOR RADIATION DETECTOR APPLICATIONS

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

Nelson, A; Laurence, T; Conway, A

2009-08-04

The surface of the layered III-VI chalcogenide semiconductor GaSeTe was treated with (NH{sub 4}){sub 2}S at 60 C to modify the surface chemistry and determine the effect on transport properties. Room temperature photoluminescence (PL) measurements were used to assess the effect of the (NH{sub 4}){sub 2}S treatment on surface defect states. Evaluation of the subsequent surface chemistry was performed with high-resolution core-level photoemission measurements. Metal overlayers were deposited on the (NH{sub 4}){sub 2}S treated surfaces and the I-V characteristics were measured. The measurements were correlated to understand the effect of (NH{sub 4}){sub 2}S modification of the interfacial electronic structure withmore » the goal of optimizing the metal/GaSeTe interface for radiation detector devices.« less

Adsorption and redox reactions of heavy metals on synthesized Mn oxide minerals.

PubMed

Feng, Xiong Han; Zhai, Li Mei; Tan, Wen Feng; Liu, Fan; He, Ji Zheng

2007-05-01

Several Mn oxide minerals commonly occurring in soils were synthesized by modified or optimized methods. The morphologies, structures, compositions and surface properties of the synthesized Mn oxide minerals were characterized. Adsorption and redox reactions of heavy metals on these minerals in relation to the mineral structures and surface properties were also investigated. The synthesized birnessite, todorokite, cryptomelane, and hausmannite were single-phased minerals and had the typical morphologies from analyses of XRD and TEM/ED. The PZCs of the synthesized birnessite, todorokite and cryptomelane were 1.75, 3.50 and 2.10, respectively. The magnitude order of their surface variable negative charge was: birnessite> or =cryptomelane>todorokite. The hausmannite had a much higher PZC than others with the least surface variable negative charge. Birnessite exhibited the largest adsorption capacity on heavy metals Pb(2+), Cu(2+), Co(2+), Cd(2+) and Zn(2+), while hausmannite the smallest one. Birnessite, cryptomelane and todorokite showed the greatest adsorption capacity on Pb(2+) among the tested heavy metals. Hydration tendency (pK(1)) of the heavy metals and the surface variable charge of the Mn minerals had significant impacts on the adsorption. The ability in Cr(III) oxidation and concomitant release of Mn(2+) varied greatly depending on the structure, composition, surface properties and crystallinity of the minerals. The maximum amounts of Cr(III) oxidized by the Mn oxide minerals in order were (mmol/kg): birnessite (1330.0)>cryptomelane (422.6)>todorokite (59.7)>hausmannite (36.6).

Surface-mode-assisted amplification of radiative heat transfer between nanoparticles

NASA Astrophysics Data System (ADS)

Messina, Riccardo; Biehs, Svend-Age; Ben-Abdallah, Philippe

2018-04-01

We show that the radiative heat flux between two nanoparticles can be significantly amplified when they are placed in proximity of a planar substrate supporting a surface resonance. The amplification factor goes beyond two orders of magnitude in the case of dielectric nanoparticles, whereas it is lower in the case of metallic nanoparticles. We analyze how this effect depends on the frequency and on the particle-surface distance by clearly identifying the signature of the surface mode producing the amplification. Finally, we show how the presence of a graphene sheet on top of the substrate can modify the effect by making an amplification of two orders of magnitude possible also in the case of metallic nanoparticles. This long-range amplification effect should play an important role in the thermal relaxation dynamics of nanoparticle networks.

Chemically Modified Metal Oxide Nanostructure for Photoelectrochemical Water Splitting

NASA Astrophysics Data System (ADS)

Wang, Gongming

Hydrogen gas is chemical fuel with high energy density, and represents a clean, renewable and carbon-free burning fuel, which has the potential to solve the more and more urgent energy crisis in today's society. Inspired by natural photosynthesis, artificial photosynthesis to generate hydrogen energy has attracted a lot of attentions in the field of chemistry, physics and material. Photoelectrochemical water splitting based on semiconductors represents a green and low cost method to generate hydrogen fuel. However, the current overall efficiency of solar to hydrogen is quite low, due to some intrinsic limitations such as bandgap, diffusion distance, carrier lifetime and photostability of semiconductors. Although nanostructured semiconductors can improve their photoelectrochemical water splitting performance to some extent, by increasing electrolyte accessible area and shortening minority carrier diffusion distance, nanostructure engineering cannot change their intrinsic electronic properties. Recent development in chemically modified nanostructures such as surface catalyst decoration, element doping, plasmonic modification and interfacial hetero-junction design have led to significant advancement in the photoelectrochemical water splitting, by improving surface reaction kinetics and charge separation, transportation and collection efficiency. In this thesis, I will give a detailed discussion on the chemically modified metal oxide nanostructures for photoelectrocemical hydrogen generation, with a focus on the element doping, hydrogen treatment and catalyst modification. I have demonstrated nitrogen doping on ZnO and Ti doping on hematite can improve their photoelectrochemical performance. In addition, we found hydrogen treatment is a general and effective method to improve the photocatalytic performance, by increasing their carrier desities. Hydrogen treatment has been demonstrated on TiO2, WO3 and BiVO4. In the end, we also used electrochemical catalyt to modify these metal oxide photoelectrode for waste water treatment and chemical fuel generation.

Laser-induced selective metallization of polypropylene doped with multiwall carbon nanotubes

NASA Astrophysics Data System (ADS)

Ratautas, Karolis; Gedvilas, Mindaugas; Stankevičiene, Ina; Jagminienė, Aldona; Norkus, Eugenijus; Pira, Nello Li; Sinopoli, Stefano; Račiukaitis, Gediminas

2017-08-01

Moulded interconnect devices (MID) offer the material, weight and cost saving by integration electronic circuits directly into polymeric components used in automotive and other consumer products. Lasers are used to write circuits directly by modifying the surface of polymers followed by an electroless metal plating. A new composite material - the polypropylene doped with multiwall carbon nanotubes was developed for the laser-induced selective metallization. Mechanism of surface activation by laser irradiation was investigated in details utilising pico- and nanoseconds lasers. Deposition of copper was performed in the autocatalytic electroless plating bath. The laser-activated polymer surfaces have been studied using the Raman spectroscopy and scanning electron microscope (SEM). Microscopic images revealed that surface becomes active only after its melting by a laser. Alterations in the Raman spectra of the D and G bands indicated the clustering of carbon additives in the composite material. Optimal laser parameters for the surface activation were found by measuring a sheet resistance of the finally metal-plated samples. A spatially selective copper plating was achieved with the smallest conductor line width of 22 μm at the laser scanning speed of 3 m/s and the pulse repetition rate of 100 kHz. Finally, the technique was validated by making functional electronic circuits by this MID approach.

Heavy metals adsorption by novel EDTA-modified chitosan-silica hybrid materials.

PubMed

Repo, Eveliina; Warchoł, Jolanta K; Bhatnagar, Amit; Sillanpää, Mika

2011-06-01

Novel adsorbents were synthesized by functionalizing chitosan-silica hybrid materials with (ethylenediaminetetraacetic acid) EDTA ligands. The synthesized adsorbents were found to combine the advantages of both silica gel (high surface area, porosity, rigid structure) and chitosan (surface functionality). The Adsorption potential of hybrid materials was investigated using Co(II), Ni(II), Cd(II), and Pb(II) as target metals by varying experimental conditions such as pH, contact time, and initial metal concentration. The kinetic results revealed that the pore diffusion process played a key role in adsorption kinetics, which might be attributed to the porous structure of synthesized adsorbents. The obtained maximum adsorption capacities of the hybrid materials for the metal ions ranged from 0.25 to 0.63 mmol/g under the studied experimental conditions. The adsorbent with the highest chitosan content showed the best adsorption efficiency. Bi-Langmuir and Sips isotherm model fitting to experimental data suggested the surface heterogeneity of the prepared adsorbents. In multimetal solutions, the hybrid adsorbents showed the highest affinity toward Pb(II). Copyright © 2011 Elsevier Inc. All rights reserved.

Surface Modification and Nanojunction Fabrication with Molecular Metal Wires

DTIC Science & Technology

2012-12-21

single - crystal X-ray diffraction studies of 2 and 3. Both the single - crystal structural data of 2 and 3 and the spectroscopic/voltammetric data...structure, magnetic properties, and single -molecule conductance of two new trinuclear metal string complexes, [Ni3(dzp)4(NCS)2] (2) and [ Co3 (dzp)4(NCS...modifying the crystallization conditions. The [s- Co3 (dpa)4(Cl)2] contains a symmetrical tricobalt framework with identical Co–Co bond lengths (2.34 Å

Layered Metal Nanoparticle Structures on Electrodes for Sensing, Switchable Controlled Uptake/Release, and Photo-electrochemical Applications.

PubMed

Tel-Vered, Ran; Kahn, Jason S; Willner, Itamar

2016-01-06

Layered metal nanoparticle (NP) assemblies provide highly porous and conductive composites of unique electrical and optical (plasmonic) properties. Two methods to construct layered metal NP matrices are described, and these include the layer-by-layer deposition of NPs, or the electropolymerization of monolayer-functionalized NPs, specifically thioaniline-modified metal NPs. The layered NP composites are used as sensing matrices through the use of electrochemistry or surface plasmon resonance (SPR) as transduction signals. The crosslinking of the metal NP composites with molecular receptors, or the imprinting of molecular recognition sites into the electropolymerized NP matrices lead to selective and chiroselective sensing interfaces. Furthermore, the electrosynthesis of redox-active, imprinted, bis-aniline bridged Au NP composites yields electrochemically triggered "sponges" for the switchable uptake and release of electron-acceptor substrates, and results in conductive surfaces of electrochemically controlled wettability. Also, photosensitizer-relay-crosslinked Au NP composites, or electrochemically polymerized layered semiconductor quantum dot/metal NP matrices on electrodes, are demonstrated as functional nanostructures for photoelectrochemical applications. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Transition metal modified and partially calcined inorganic-organic pillared clays for the adsorption of salicylic acid, clofibric acid, carbamazepine, and caffeine from water.

PubMed

Cabrera-Lafaurie, Wilman A; Román, Félix R; Hernández-Maldonado, Arturo J

2012-11-15

Pharmaceutical and Personal Care Products (PPCPs) are considered emerging contaminants, and their efficient removal from water is going to be a challenging endeavor. Microporous adsorbent materials, including pillared clays, could offer a potential solution if tailored properly. Although pillared clays have been employed previously for the removal of organics, the effective removal of PPCPs will only be possible if their surface and textural properties are manipulated from the bottom-up. This work presents the use of modified inorganic-organic pillared clays (IOCs) for the adsorption of salicylic acid, clofibric acid, carbamazepine, and caffeine. The IOCs have been modified with Co(2+), Cu(2+), or Ni(2+) to induce complexation-like adsorbate-adsorbent interactions at ambient conditions, in an attempt to provide an efficient and yet reversible driving force in the sub-ppm concentration range. Furthermore, the IOCs were partially calcined to increase effective surface area by an order of magnitude while preserving some hydrophobicity. In general, the Ni(2+) IOCs exhibited the greatest interaction with salicylic and clofibric acids, respectively, while the Co(2+) adsorbents excelled at adsorbing caffeine at low concentrations. All of the metal-modified IOCs showed comparable adsorption capacities for the case of carbamazepine, probably due to the lack of availability of particular functional groups in this adsorbate. Copyright © 2012 Elsevier Inc. All rights reserved.

Metals and metalloids treatment in contaminated neutral effluents using modified materials.

PubMed

Calugaru, Iuliana Laura; Neculita, Carmen Mihaela; Genty, Thomas; Zagury, Gérald J

2018-04-15

Circumneutral surface water and groundwater can contain hazardous concentrations of metals and metalloids that can threaten organisms in surrounding ecosystems. Extensive research has been conducted over the past two decades to prevent, limit, and treat water pollution. Among the currently available treatment options is the use of natural and residual materials, which is generally regarded as effective and inexpensive. The modification of such materials enhances the removal capacity of metals and metalloids, as well as the physical and chemical stability of the materials and resulting sludge (after treatment). This paper reviews several modified materials that have produced and evaluated in the past twenty years to treat various contaminants in water under specific conditions. Important factors on performance improvement following the modifications are emphasized. Sorption capacity and kinetics, and element removal mechanisms are also discussed. Element recovery, material regeneration, water reuse, evaluation of treatment efficiency for real effluents are also considered, as well as the applicability of these materials in both active and passive treatment systems. Modified natural and residual materials are a promising option for the treatment of metals and metalloids in circumneutral contaminated waters. However, further research is necessary to evaluate their field-scale performance and to properly assess treatment costs. Copyright © 2018 Elsevier Ltd. All rights reserved.

Synthesis of adsorbent from Tamarix hispida and modified by lanthanum metal for fluoride ions removal from wastewater: Adsorbent characteristics and real wastewater treatment data.

PubMed

Habibi, Nasim; Rouhi, Parham; Ramavandi, Bahman

2017-08-01

This data article describes a facile method for production of an adsorbent from Tamarix hispida wasted wood and modified by lanthanum metal for fluoride ions removal from wastewater. The main characteristics of the adsorbent consist of BET surface area, functional groups, and elemental analysis is presented. The data for attenuating the pollutants from a real wastewater treatment which was provided from a glass factory is also represented. More than 90% of fluoride content of the real wastewater was treated by the adsorbent. Generally, these data would be informative for extend research aim to industrial wastewater treatment and those who work in the wastewater treatment plants.

Electrophoretic formation of semiconductor layers with adjustable band gap

NASA Astrophysics Data System (ADS)

Shindrov, Alexander; Yuvchenko, Sergey; Vikulova, Maria; Tretyachenko, Elena; Zimnyakov, Dmitry; Gorokhovsky, Alexander

2017-11-01

The ceramic layers of the potassium polytitanates modified by transition metal salts were electrophoretically deposited onto the surface of glassy substrate coated with indium-tin oxide. The deposition allows obtaining a dense ceramic layer formed by composite agglomerates consisting of nanoscale particles with average size of 130-190 nm. The optical absorption spectra of the coatings modified in the mixtures of aqueous solutions of different transition metal salts were investigated. It was recognized that a bandgap value of these composites can be adjusted in a range from 1.4 to 2.3 eV depending the chemical composition of layered double hydroxide obtained during modification. This might be very promising for optoelectronic applications of such coatings due to an explicit control of optical properties.

Mechanisms of metal sorption by biochars: Biochar characteristics and modifications.

PubMed

Li, Hongbo; Dong, Xiaoling; da Silva, Evandro B; de Oliveira, Letuzia M; Chen, Yanshan; Ma, Lena Q

2017-07-01

Biochar produced by thermal decomposition of biomass under oxygen-limited conditions has received increasing attention as a cost-effective sorbent to treat metal-contaminated waters. However, there is a lack of information on the roles of different sorption mechanisms for different metals and recent development of biochar modification to enhance metal sorption capacity, which is critical for biochar field application. This review summarizes the characteristics of biochar (e.g., surface area, porosity, pH, surface charge, functional groups, and mineral components) and main mechanisms governing sorption of As, Cr, Cd, Pb, and Hg by biochar. Biochar properties vary considerably with feedstock material and pyrolysis temperature, with high temperature producing biochars with higher surface area, porosity, pH, and mineral contents, but less functional groups. Different mechanisms dominate sorption of As (complexation and electrostatic interactions), Cr (electrostatic interactions, reduction, and complexation), Cd and Pb (complexation, cation exchange, and precipitation), and Hg (complexation and reduction). Besides sorption mechanisms, recent advance in modifying biochar by loading with minerals, reductants, organic functional groups, and nanoparticles, and activation with alkali solution to enhance metal sorption capacity is discussed. Future research needs for field application of biochar include competitive sorption mechanisms of co-existing metals, biochar reuse, and cost reduction of biochar production. Published by Elsevier Ltd.

Modulation of Crystal Surface and Lattice by Doping: Achieving Ultrafast Metal-Ion Insertion in Anatase TiO2.

PubMed

Wang, Hsin-Yi; Chen, Han-Yi; Hsu, Ying-Ya; Stimming, Ulrich; Chen, Hao Ming; Liu, Bin

2016-10-26

We report that an ultrafast kinetics of reversible metal-ion insertion can be realized in anatase titanium dioxide (TiO 2 ). Niobium ions (Nb 5+ ) were carefully chosen to dope and drive anatase TiO 2 into very thin nanosheets standing perpendicularly onto transparent conductive electrode (TCE) and simultaneously construct TiO 2 with an ion-conducting surface together with expanded ion diffusion channels, which enabled ultrafast metal ions to diffuse across the electrolyte/solid interface and into the bulk of TiO 2 . To demonstrate the superior metal-ion insertion rate, the electrochromic features induced by ion intercalation were examined, which exhibited the best color switching speed of 4.82 s for coloration and 0.91 s for bleaching among all reported nanosized TiO 2 devices. When performed as the anode for the secondary battery, the modified TiO 2 was capable to deliver a highly reversible capacity of 61.2 mAh/g at an ultrahigh specific current rate of 60 C (10.2 A/g). This fast metal-ion insertion behavior was systematically investigated by the well-controlled electrochemical approaches, which quantitatively revealed both the enhanced surface kinetics and bulk ion diffusion rate. Our study could provide a facile methodology to modulate the ion diffusion kinetics for metal oxides.

Self-assembled monolayers of alendronate on Ti6Al4V alloy surfaces enhance osteogenesis in mesenchymal stem cells

NASA Astrophysics Data System (ADS)

Rojo, Luis; Gharibi, Borzo; McLister, Robert; Meenan, Brian J.; Deb, Sanjukta

2016-07-01

Phosphonates have emerged as an alternative for functionalization of titanium surfaces by the formation of homogeneous self-assembled monolayers (SAMs) via Ti-O-P linkages. This study presents results from an investigation of the modification of Ti6Al4V alloy by chemisorption of osseoinductive alendronate using a simple, effective and clean methodology. The modified surfaces showed a tailored topography and surface chemistry as determined by SEM microscopy and RAMAN spectroscopy. X-ray photoelectron spectroscopy revealed that an effective mode of bonding is created between the metal oxide surface and the phosphate residue of alendronate, leading to formation of homogenous drug distribution along the surface. In-vitro studies showed that alendronate SAMs induce differentiation of hMSC to a bone cell phenotype and promote bone formation on modified surfaces. Here we show that this novel method for the preparation of functional coatings on titanium-based medical devices provides osseoinductive bioactive molecules to promote enhanced integration at the site of implantation.

Self-assembled monolayers of alendronate on Ti6Al4V alloy surfaces enhance osteogenesis in mesenchymal stem cells

PubMed Central

Rojo, Luis; Gharibi, Borzo; McLister, Robert; Meenan, Brian J.; Deb, Sanjukta

2016-01-01

Phosphonates have emerged as an alternative for functionalization of titanium surfaces by the formation of homogeneous self-assembled monolayers (SAMs) via Ti-O-P linkages. This study presents results from an investigation of the modification of Ti6Al4V alloy by chemisorption of osseoinductive alendronate using a simple, effective and clean methodology. The modified surfaces showed a tailored topography and surface chemistry as determined by SEM microscopy and RAMAN spectroscopy. X-ray photoelectron spectroscopy revealed that an effective mode of bonding is created between the metal oxide surface and the phosphate residue of alendronate, leading to formation of homogenous drug distribution along the surface. In-vitro studies showed that alendronate SAMs induce differentiation of hMSC to a bone cell phenotype and promote bone formation on modified surfaces. Here we show that this novel method for the preparation of functional coatings on titanium-based medical devices provides osseoinductive bioactive molecules to promote enhanced integration at the site of implantation. PMID:27468811

Preparation of granular activated carbons from composite of powder activated carbon and modified β-zeolite and application to heavy metals removal.

PubMed

Seyedein Ghannad, S M R; Lotfollahi, M N

2018-03-01

Heavy metals are continuously contaminating the surface and subsurface water. The adsorption process is an attractive alternative for removing the heavy metals because of its low cost, simple operation, high efficiency, and flexible design. In this study, influences of β-zeolite and Cu-modified β-zeolite on preparation of granular activated carbons (GACs) from a composite of powder activated carbon (PAC), methylcellulose as organic binder, bentonite as inorganic binder, and water were investigated. A number of granular samples were prepared by controlling the weight percentage of binder materials, PAC and zeolites as a reinforcing adsorbent. Fourier transform infrared spectroscopy (FT-IR) and X-ray diffraction techniques were employed to characterize zeolite, modified zeolite and produced GAC. The produced GACs were used as the adsorbent for removal of Zn +2 , Cd 2+ and Pb 2+ ions from aqueous solutions. The results indicated that the adsorption of metals ions depended on the pH (5.5) and contact time (30 min). Maximum adsorption of 97.6% for Pb 2+ , 95.9% for Cd 2+ and 91.1% for Zn +2 occurred with a new kind of GAC made of Cu-modified β-zeolite. The Zn +2 , Cd 2+ and Pb 2+ ions sorption kinetics data were well described by a pseudo-second order model for all sorbents. The Langmuir and Freundlich isotherm models were applied to analyze the experimental equilibrium data.

Engineering of Nanoscale Antifouling and Hydrophobic Surfaces on Naval Structural Steel HY-80 by Anodizing

DTIC Science & Technology

2015-06-01

examination of the morphologies of the nanoporous structures and the evaluation of the anodization parameters such as anodization potential, time... sponges , anemones, tunicates, and hydroids, whilst hard fouling comprises invertebrates such as barnacles, mussels, and tubeworms. The specific...of metals by making them more stable and highly resistant, but also to modify the surface by giving it a desired morphology . Ferrous alloys such as

A multifunctional polymeric nanofilm with robust chemical performances for special wettability.

PubMed

Wang, Yabin; Lin, Feng; Dong, Yaping; Liu, Zhong; Li, Wu; Huang, Yudong

2016-03-07

A multifunctional polymeric nanofilm of a triazinedithiolsilane compound, which can protect metallic substrates and activate the corresponding surface simultaneously, is introduced onto a copper mesh surface via facile solution-immersion approaches. The resultant interface exhibits hydrophilic features due to the existence of silanol groups (SiOH) outward and has the potential to act as a superhydrophilic and underwater superoleophobic material. As the polymeric nanofilm atop the copper mesh is modified with long-chain octadecyltrichlorosilane (OTS), the functionalized surface becomes superhydrophobic and superoleophilic. The OTS-modified polymeric nanofilm shows outstanding chemical durability and stability that are seldom concurrently satisfied for a material with special wettability, owing to its inherent architecture. These textures generate high separation efficiency, durable separation capability and excellent thermal stability. The protective ability, originating from the textures of the underlying cross-linked disulfide units (-SS-) and siloxane networks (SiOSi) on the top of the nanofilm, prolongs the chemical durability. The activating capability stemming from the residual SiOH groups improves the chemical stability as a result of the chemical bonds developed by these sites. The significant point of this investigation lies in enlightening us on the fabrication of multifunctional polymeric nanofilms on different metal surfaces using various triazinedithiolsilane compounds, and on the construction of interfaces with controllable wettable performances in demanding research or industrial applications.

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.

Phonon dispersion on Ag (100) surface: A modified analytic embedded atom method study

NASA Astrophysics Data System (ADS)

Xiao-Jun, Zhang; Chang-Le, Chen

2016-01-01

Within the harmonic approximation, the analytic expression of the dynamical matrix is derived based on the modified analytic embedded atom method (MAEAM) and the dynamics theory of surface lattice. The surface phonon dispersions along three major symmetry directions , and X¯M¯ are calculated for the clean Ag (100) surface by using our derived formulas. We then discuss the polarization and localization of surface modes at points X¯ and M¯ by plotting the squared polarization vectors as a function of the layer index. The phonon frequencies of the surface modes calculated by MAEAM are compared with the available experimental and other theoretical data. It is found that the present results are generally in agreement with the referenced experimental or theoretical results, with a maximum deviation of 10.4%. The agreement shows that the modified analytic embedded atom method is a reasonable many-body potential model to quickly describe the surface lattice vibration. It also lays a significant foundation for studying the surface lattice vibration in other metals. Project supported by the National Natural Science Foundation of China (Grant Nos. 61471301 and 61078057), the Scientific Research Program Funded by Shaanxi Provincial Education Department, China (Grant No. 14JK1301), and the Specialized Research Fund for the Doctoral Program of Higher Education, China (Grant No. 20126102110045).

Balancing the Hydrogen Evolution Reaction, Surface Energetics, and Stability of Metallic MoS 2 Nanosheets via Covalent Functionalization

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

Benson, Eric E.; Zhang, Hanyu; Schuman, Samuel A.

We modify the fundamental electronic properties of metallic (1T phase) nanosheets of molybdenum disulfide (MoS 2) through covalent chemical functionalization, and thereby directly influence the kinetics of the hydrogen evolution reaction (HER), surface energetics, and stability. Chemically exfoliated, metallic MoS 2 nanosheets are functionalized with organic phenyl rings containing electron donating or withdrawing groups. We find that MoS 2 functionalized with the most electron donating functional group (p-(CH 3CH 2) 2NPh-MoS 2) is the most efficient catalyst for HER in this series, with initial activity that is slightly worse compared to the pristine metallic phase of MoS 2. The p-(CHmore » 3CH 2) 2NPh-MoS 2 is more stable than unfunctionalized metallic MoS 2 and outperforms unfunctionalized metallic MoS 2 for continuous H 2 evolution within 10 min under the same conditions. With regards to the entire studied series, the overpotential and Tafel slope for catalytic HER are both directly correlated with the electron donating strength of the functional group. The results are consistent with a mechanism involving ground-state electron donation or withdrawal to/from the MoS 2 nanosheets, which modifies the electron transfer kinetics and catalytic activity of the MoS 2 nanosheet. The functional groups preserve the metallic nature of the MoS 2 nanosheets, inhibiting conversion to the thermodynamically stable semiconducting state (2H) when mildly annealed in a nitrogen atmosphere. We propose that the electron density and, therefore, reactivity of the MoS 2 nanosheets are controlled by the attached functional groups. Functionalizing nanosheets of MoS 2 and other transition metal dichalcogenides provides a synthetic chemical route for controlling the electronic properties and stability within the traditionally thermally unstable metallic state.« less

Balancing the Hydrogen Evolution Reaction, Surface Energetics, and Stability of Metallic MoS 2 Nanosheets via Covalent Functionalization

DOE PAGES

Benson, Eric E.; Zhang, Hanyu; Schuman, Samuel A.; ...

2017-12-27

We modify the fundamental electronic properties of metallic (1T phase) nanosheets of molybdenum disulfide (MoS 2) through covalent chemical functionalization, and thereby directly influence the kinetics of the hydrogen evolution reaction (HER), surface energetics, and stability. Chemically exfoliated, metallic MoS 2 nanosheets are functionalized with organic phenyl rings containing electron donating or withdrawing groups. We find that MoS 2 functionalized with the most electron donating functional group (p-(CH 3CH 2) 2NPh-MoS 2) is the most efficient catalyst for HER in this series, with initial activity that is slightly worse compared to the pristine metallic phase of MoS 2. The p-(CHmore » 3CH 2) 2NPh-MoS 2 is more stable than unfunctionalized metallic MoS 2 and outperforms unfunctionalized metallic MoS 2 for continuous H 2 evolution within 10 min under the same conditions. With regards to the entire studied series, the overpotential and Tafel slope for catalytic HER are both directly correlated with the electron donating strength of the functional group. The results are consistent with a mechanism involving ground-state electron donation or withdrawal to/from the MoS 2 nanosheets, which modifies the electron transfer kinetics and catalytic activity of the MoS 2 nanosheet. The functional groups preserve the metallic nature of the MoS 2 nanosheets, inhibiting conversion to the thermodynamically stable semiconducting state (2H) when mildly annealed in a nitrogen atmosphere. We propose that the electron density and, therefore, reactivity of the MoS 2 nanosheets are controlled by the attached functional groups. Functionalizing nanosheets of MoS 2 and other transition metal dichalcogenides provides a synthetic chemical route for controlling the electronic properties and stability within the traditionally thermally unstable metallic state.« less

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.

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.

Large area compatible broadband superabsorber surfaces in the VIS-NIR spectrum utilizing metal-insulator-metal stack and plasmonic nanoparticles.

PubMed

Dereshgi, Sina Abedini; Okyay, Ali Kemal

2016-08-08

Plasmonically enhanced absorbing structures have been emerging as strong candidates for photovoltaic (PV) devices. We investigate metal-insulator-metal (MIM) structures that are suitable for tuning spectral absorption properties by modifying layer thicknesses. We have utilized gold and silver nanoparticles to form the top metal (M) region, obtained by dewetting process compatible with large area processes. For the middle (I) and bottom (M) layers, different dielectric materials and metals are investigated. Optimum MIM designs are discussed. We experimentally demonstrate less than 10 percent reflection for most of the visible (VIS) and near infrared (NIR) spectrum. In such stacks, computational analysis shows that the bottom metal is responsible for large portion of absorption with a peak of 80 percent at 1000 nm wavelength for chromium case.

A new powder production route for transparent spinel windows: powder synthesis and window properties

NASA Astrophysics Data System (ADS)

Cook, Ronald; Kochis, Michael; Reimanis, Ivar; Kleebe, Hans-Joachim

2005-05-01

Spinel powders for the production of transparent polycrystalline ceramic windows have been produced using a number of traditional ceramic and sol-gel methods. We have demonstrated that magnesium aluminate spinel powders produced from the reaction of organo-magnesium compounds with surface modified boehmite precursors can be used to produce high quality transparent spinel parts. The new powder production method allows fine control over the starting particle size, size distribution, purity and stoichiometry. The new process involves formation of a boehmite sol-gel from the hydrolysis of aluminum alkoxides followed by surface modification of the boehmite nanoparticles using carboxylic acids. The resulting surface modified boehmite nanoparticles can then be metal exchanged at room temperature with magnesium acetylacetonate to make a precursor powder that is readily transformed into pure phase spinel.

General and Direct Method for Preparing Oligonucleotide-Functionalized Metal–Organic Framework Nanoparticles

PubMed Central

2017-01-01

Metal–organic frameworks (MOFs) are a class of modular, crystalline, and porous materials that hold promise for storage and transport of chemical cargoes. Though MOFs have been studied in bulk forms, ways of deliberately manipulating the external surface functionality of MOF nanoparticles are less developed. A generalizable approach to modify their surfaces would allow one to impart chemical functionality onto the particle surface that is independent of the bulk MOF structure. Moreover, the use of a chemically programmable ligand, such as DNA, would allow for the manipulation of interparticle interactions. Herein, we report a coordination chemistry-based strategy for the surface functionalization of the external metal nodes of MOF nanoparticles with terminal phosphate-modified oligonucleotides. The external surfaces of nine distinct archetypical MOF particles containing four different metal species (Zr, Cr, Fe, and Al) were successfully functionalized with oligonucleotides, illustrating the generality of this strategy. By taking advantage of the programmable and specific interactions of DNA, 11 distinct MOF particle–inorganic particle core–satellite clusters were synthesized. In these hybrid nanoclusters, the relative stoichiometry, size, shape, and composition of the building blocks can all be independently controlled. This work provides access to a new set of nucleic acid–nanoparticle conjugates, which may be useful as programmable material building blocks and as probes for measuring and manipulating intracellular processes. PMID:28718644

In situ FTIR spectroscopic assessment of methylbutynol catalytic conversion products in relation to the surface acid-base properties of systematically modified aluminas

NASA Astrophysics Data System (ADS)

Mekhemer, Gamal A. H.; Zaki, Mohamed I.

2016-10-01

The present investigation was designed to assess the credibility of methylbutynol (MBOH) as an infrared (IR) reactive probe molecule for surface acid-base properties of metal oxides. Accordingly, pure alumina was systematically modified with varied amounts (0.5-10 wt.%) of K+ or SO42 - additives. Then, the influence of nature and amount of the additive on the following alumina properties were examined: (i) bulk composition and structure by X-ray powder diffractometry and ex-situ IR spectroscopy, (ii) surface area and net charge by N2 sorptiometry and pH-metry, respectively, and (iii) nature and strength of exposed surface acid sites by in-situ IR spectroscopy of adsorbed pyridine at ambient and higher temperatures. Results obtained were correlated with IR-identified product distribution of MBOH catalytic decomposition/conversion at 200 °C. It is thereby concluded that MBOH is superior to conventional IR inactive probe molecules in gauging sensitively the prevailing acid or base character, availability of base sites, relative population of Bronsted to Lewis acid sites, and strength and reactivity of the sites exposed on metal oxide surfaces. Hence, all that is needed to get this information is to handle IR spectra taken from the gas phase, a task that is experimentally much more accessible than taking spectra from adsorbed species of irreactive probe molecules.

Surface Preparation and Deposited Gate Oxides for Gallium Nitride Based Metal Oxide Semiconductor Devices

PubMed Central

Long, Rathnait D.; McIntyre, Paul C.

2012-01-01

The literature on polar Gallium Nitride (GaN) surfaces, surface treatments and gate dielectrics relevant to metal oxide semiconductor devices is reviewed. The significance of the GaN growth technique and growth parameters on the properties of GaN epilayers, the ability to modify GaN surface properties using in situ and ex situ processes and progress on the understanding and performance of GaN metal oxide semiconductor (MOS) devices are presented and discussed. Although a reasonably consistent picture is emerging from focused studies on issues covered in each of these topics, future research can achieve a better understanding of the critical oxide-semiconductor interface by probing the connections between these topics. The challenges in analyzing defect concentrations and energies in GaN MOS gate stacks are discussed. Promising gate dielectric deposition techniques such as atomic layer deposition, which is already accepted by the semiconductor industry for silicon CMOS device fabrication, coupled with more advanced physical and electrical characterization methods will likely accelerate the pace of learning required to develop future GaN-based MOS technology.

Microarray of neuroblastoma cells on the selectively functionalized nanocrystalline diamond thin film surface

NASA Astrophysics Data System (ADS)

Park, Young-Sang; Son, Hyeong-Guk; Kim, Dae-Hoon; Oh, Hong-Gi; Lee, Da-Som; Kim, Min-Hye; Lim, Ki-Moo; Song, Kwang-Soup

2016-01-01

Nanocrystalline diamond (NCD) film surfaces were modified with fluorine or oxygen by plasma treatment in an O2 or C3F8 gas environment in order to induce wettability. The oxygenated-NCD (O-NCD) film surface was hydrophilic and the fluorinated-NCD (F-NCD) surface was hydrophobic. The efficiency of early cell adhesion, which is dependent on the wettability of the cell culture plate and necessary for the growth and proliferation of cells, was 89.62 ± 3.92% on the O-NCD film and 7.78 ± 0.77% on the F-NCD film surface after 3 h of cell culture. The wettability of the NCD film surface was artificially modified using a metal mask and plasma treatment to fabricate a micro-pattern. Four types of micro-patterns were fabricated (line, circle, mesh, and word) on the NCD film surface. We precisely arrayed the neuroblastoma cells on the micro-patterned NCD film surfaces by controlling the surface wettability and cell seeding density. The neuroblastoma cells adhered and proliferated along the O-NCD film surface.

Trapping gases in metal-organic frameworks with a selective surface molecular barrier layer

DOE PAGES

Tan, Kui; Zuluaga, Sebastian; Fuentes, Erika; ...

2016-12-13

The main challenge for gas storage and separation in nanoporous materials is that many molecules of interest adsorb too weakly to be effectively retained. Instead of synthetically modifying the internal surface structure of the entire bulk—as is typically done to enhance adsorption—here we show that post exposure of a prototypical porous metal-organic framework to ethylenediamine can effectively retain a variety of weakly adsorbing molecules (for example, CO, CO 2, SO 2, C 2H 4, NO) inside the materials by forming a monolayer-thick cap at the external surface of microcrystals. Furthermore, this capping mechanism, based on hydrogen bonding as explained bymore » ab initio modelling, opens the door for potential selectivity. For example, water molecules are shown to disrupt the hydrogen-bonded amine network and diffuse through the cap without hindrance and fully displace/release the retained small molecules out of the metal-organic framework at room temperature. Lastly, these findings may provide alternative strategies for gas storage, delivery and separation.« less

Structure and Dynamics of Zr6O8 Metal-Organic Framework Node Surfaces Probed with Ethanol Dehydration as a Catalytic Test Reaction.

PubMed

Yang, Dong; Ortuño, Manuel A; Bernales, Varinia; Cramer, Christopher J; Gagliardi, Laura; Gates, Bruce C

2018-03-14

Some metal-organic frameworks (MOFs) incorporate nodes that are metal oxide clusters such as Zr 6 O 8 . Vacancies on the node surfaces, accidental or by design, act as catalytic sites. Here, we report elucidation of the chemistry of Zr 6 O 8 nodes in the MOFs UiO-66 and UiO-67 having used infrared and nuclear magnetic resonance spectroscopies to determine the ligands on the node surfaces originating from the solvents and modifiers used in the syntheses and having elucidated the catalytic properties of the nodes for ethanol dehydration, which takes place selectively to make diethyl ether but not ethylene at 473-523 K. Density functional theory calculations show that the key to the selective catalysis is the breaking of node-linker bonds (or the accidental adjacency of open/defect sites) that allows catalytically fruitful bonding of the reactant ethanol to neighboring sites on the nodes, facilitating the bimolecular ether formation through an S N 2 mechanism.

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.

Semiconductor assisted metal deposition for nanolithography applications

DOEpatents

Rajh, Tijana; Meshkov, Natalia; Nedelijkovic, Jovan M.; Skubal, Laura R.; Tiede, David M.; Thurnauer, Marion

2001-01-01

An article of manufacture and method of forming nanoparticle sized material components. A semiconductor oxide substrate includes nanoparticles of semiconductor oxide. A modifier is deposited onto the nanoparticles, and a source of metal ions are deposited in association with the semiconductor and the modifier, the modifier enabling electronic hole scavenging and chelation of the metal ions. The metal ions and modifier are illuminated to cause reduction of the metal ions to metal onto the semiconductor nanoparticles.

Semiconductor assisted metal deposition for nanolithography applications

DOEpatents

Rajh, Tijana; Meshkov, Natalia; Nedelijkovic, Jovan M.; Skubal, Laura R.; Tiede, David M.; Thurnauer, Marion

2002-01-01

An article of manufacture and method of forming nanoparticle sized material components. A semiconductor oxide substrate includes nanoparticles of semiconductor oxide. A modifier is deposited onto the nanoparticles, and a source of metal ions are deposited in association with the semiconductor and the modifier, the modifier enabling electronic hole scavenging and chelation of the metal ions. The metal ions and modifier are illuminated to cause reduction of the metal ions to metal onto the semiconductor nanoparticles.

Inkjet-printed microelectrodes on PDMS as biosensors for functionalized microfluidic systems.

PubMed

Wu, Jianwei; Wang, Ridong; Yu, Haixia; Li, Guijun; Xu, Kexin; Tien, Norman C; Roberts, Robert C; Li, Dachao

2015-02-07

Microfluidic systems based on polydimethylsiloxane (PDMS) have gained popularity in recent years. However, microelectrode patterning on PDMS to form biosensors in microchannels remains a worldwide technical issue due to the hydrophobicity of PDMS and its weak adhesion to metals. In this study, an additive technique using inkjet-printed silver nanoparticles to form microelectrodes on PDMS is presented. (3-Mercaptopropyl)trimethoxysilane (MPTMS) was used to modify the surface of PDMS to improve its surface wettability and its adhesion to silver. The modified surface of PDMS is rendered relatively hydrophilic, which is beneficial for the silver droplets to disperse and thus effectively avoids the coalescence of adjacent droplets. Additionally, a multilevel matrix deposition (MMD) method is used to further avoid the coalescence and yield a homogeneous pattern on the MPTMS-modified PDMS. A surface wettability comparison and an adhesion test were conducted. The resulting silver pattern exhibited good uniformity, conductivity and excellent adhesion to PDMS. A three-electrode electrochemical biosensor was fabricated successfully using this method and sealed in a PDMS microchannel, forming a lab-on-a-chip glucose biosensing system.

Method for fabricating prescribed flaws in the interior of metals

DOEpatents

Hsu, David K.; Thompson, Donald O.

1989-03-07

The method for fabricating a metal body having a flaw of predetermined size and shape located therein comprises placing half of the metal powder required to make the metal body in the die of a press and pressing it to create a flat upper surface thereon. A piece of copper foil is cut to the size and shape of the desired interior crack and placed on the upper surface of the powder and centered in position. The remaining powder is then placed in the die to cover the copper foil. The powder is first cold pressed and removed from the press. The powder metal piece is then sintered in a furnace at a temperature above the melting point of the copper and below the melting point of the metal. It is then removed from the furnace, cooled to room temperature, and placed back in the die and pressed further. This procedure results in an interior flaw or crack. Modified forms of the method involve using a press-sinter-press-sinter cycle with the first sinter being below the melting point of the copper and the second sinter being above the melting point of the copper and below the melting point of the metal.

Progress in the preparation and application of modified biochar for improved contaminant removal from water and wastewater.

PubMed

Ahmed, Mohammad Boshir; Zhou, John L; Ngo, Huu H; Guo, Wenshan; Chen, Mengfang

2016-08-01

Modified biochar (BC) is reviewed in its preparation, functionality, applications and regeneration. The nature of precursor materials, preparatory conditions and modification methods are key factors influencing BC properties. Steam activation is unsuitable for improving BC surface functionality compared with chemical modifications. Alkali-treated BC possesses the highest surface functionality. Both alkali modified BC and nanomaterial impregnated BC composites are highly favorable for enhancing the adsorption of different contaminants from wastewater. Acidic treatment provides more oxygenated functional groups on BC surfaces. The Langmuir isotherm model provides the best fit for sorption equilibria of heavy metals and anionic contaminants, while the Freundlich isotherm model is the best fit for emerging contaminants. The pseudo 2(nd) order is the most appropriate model of sorption kinetics for all contaminants. Future research should focus on industry-scale applications and hybrid systems for contaminant removal due to scarcity of data. Copyright © 2016 Elsevier Ltd. All rights reserved.

Method of removing arsenic and other anionic contaminants from contaminated water using enhanced coagulation

DOEpatents

Teter, David M.; Brady, Patrick V.; Krumhansl, James L.; Khandaker, Nadim R.

2006-11-21

An improved water decontamination process comprising contacting water containing anionic contaminants with an enhanced coagulant to form an enhanced floc, which more efficiently binds anionic species (e.g., arsenate, arsenite, chromate, fluoride, selenate, and borate, and combinations thereof) predominantly through the formation of surface complexes. The enhanced coagulant comprises a trivalent metal cation coagulant (e.g., ferric chloride or aluminum sulfate) mixed with a divalent metal cation modifier (e.g., copper sulfate or zinc sulfate).

Application of polymer-coated metal-insulator-semiconductor sensors for the detection of dissolved hydrogen

NASA Astrophysics Data System (ADS)

Li, Dongmei; Medlin, J. W.; Bastasz, R.

2006-06-01

The detection of dissolved hydrogen in liquids is crucial to many industrial applications, such as fault detection for oil-filled electrical equipment. To enhance the performance of metal-insulator-semiconductor (MIS) sensors for dissolved hydrogen detection, a palladium MIS sensor has been modified by depositing a polyimide (PI) layer above the palladium surface. Response measurements of the PI-coated sensors in mineral oil indicate that hydrogen is sensitively detected, while the effect of interfering gases on sensor response is minimized.

Composite Pulse Tube

NASA Technical Reports Server (NTRS)

Martin, Jerry L.; Cloyd, Jason H.

2007-01-01

A modification of the design of the pulse tube in a pulse-tube cryocooler reduces axial thermal conductance while preserving radial thermal conductance. It is desirable to minimize axial thermal conductance in the pulse-tube wall to minimize leakage of heat between the warm and cold ends of the pulse tube. At the same time, it is desirable to maximize radial thermal conductance at the cold end of the pulse tube to ensure adequate thermal contact between (1) a heat exchanger in the form of a stack of copper screens inside the pulse tube at the cold end and (2) the remainder of the cold tip, which is the object to which the heat load is applied and from which heat must be removed. The modified design yields a low-heat-leak pulse tube that can be easily integrated with a cold tip. A typical pulse tube of prior design is either a thin-walled metal tube or a metal tube with a nonmetallic lining. It is desirable that the outer surface of a pulse tube be cylindrical (in contradistinction to tapered) to simplify the design of a regenerator that is also part of the cryocooler. Under some conditions, it is desirable to taper the inner surface of the pulse tube to reduce acoustic streaming. The combination of a cylindrical outer surface and a tapered inner surface can lead to unacceptably large axial conduction if the pulse tube is made entirely of metal. Making the pulse-tube wall of a nonmetallic, lowthermal- conductivity material would not solve the problem because the wall would not afford the needed thermal contact for the stack of screens in the cold end. The modified design calls for fabricating the pulse tube in two parts: a longer, nonmetallic part that is tapered on the inside and cylindrical on the outside and a shorter, metallic part that is cylindrical on both the inside and the outside. The nonmetallic part can be made from G-10 fiberglass-reinforced epoxy or other low-thermal-conductivity, cryogenically compatible material. The metallic part must have high thermal conductivity in the cryogenic temperature range and would typically be made of pure copper to satisfy this requirement. The metallic part is bonded to the nonmetallic part with epoxy. Copper screens are inserted in the metallic part to form the cold-end heat exchanger, then the assembled pulse tube is inserted in the cold tip.

Size-Dependent Surface Energy Density of Spherical Face-Centered-Cubic Metallic Nanoparticles.

PubMed

Wei, Yaochi; Chen, Shaohua

2015-12-01

The surface energy density of nano-sized elements exhibits a significantly size-dependent behavior. Spherical nanoparticle, as an important element in nano-devices and nano-composites, has attracted many interesting studies on size effect, most of which are molecular dynamics (MD) simulations. However, the existing MD calculations yield two opposite size-dependent trends of surface energy density of nanoparticles. In order to clarify such a real underlying problem, atomistic calculations are carried out in the present paper for various spherical face-centered-cubic (fcc) metallic nanoparticles. Both the embedded atom method (EAM) potential and the modified embedded atom method (MEAM) one are adopted. It is found that the size-dependent trend of surface energy density of nanoparticles is not governed by the chosen potential function or variation trend of surface energy, but by the defined radius of spherical nanoparticles in MD models. The finding in the present paper should be helpful for further theoretical studies on surface/interface effect of nanoparticles and nanoparticle-reinforced composites.

Wear resistance of a metal surface modified with minerals

NASA Astrophysics Data System (ADS)

Kislov, S. V.; Kislov, V. G.; Balasch, P. V.; Skazochkin, A. V.; Bondarenko, G. G.; Tikhonov, A. N.

2016-02-01

The article describes the advantages of the new technology of mineral coating of metal products for the friction pair of mechanical systems. It presents the research results of the wear rate of the samples made of 12X13 steel (X12Cr13) with mineral layers, in the experiments with a piston ring sliding inside a cylinder liner with grease. The wear rate of the samples with mineral layers is lower almost by two factors than that of the samples made of grey foundry iron and untreated samples. As the result of slip/rolling abrasion tests of parts with mineral layers under conditions of high contact pressure, a suggestion was made concerning probable mechanics of surface wear.

New materials based on polylactide modified with silver and carbon ions

NASA Astrophysics Data System (ADS)

Kurzina, I. A.; Pukhova, I. V.; Botvin, V. V.; Davydova, D. V.; Filimoshkin, A. G.; Savkin, K. P.; Oskomov, K. V.; Oks, E. M.

2015-11-01

An integrated study of poly-L-lactide (PL) synthesis and the physicochemical properties of film surfaces, both modified by silver and carbon ion implantation and also unmodified PL surfaces, has been carried out. Surface modification was done using aMevva-5.Ru metal ion source with ion implantation doses of 1.1014, 1.1015 and 1.1016 ion/cm2. Material characterization was done using NMR, IRS, XPS and AFM. The molecular weight (MW), micro-hardness, surface resistivity, and limiting wetting angle of both un-implanted and implanted samples were measured. The results reveal that degradation of PL macromolecules occurs during ion implantation, followed by CO or CO2 removal and MW decrease. With increasing implantation dose, the glycerol wettability of the PL surface increases but the water affinity decreases (hydrophobic behavior). After silver and carbon ion implantation into the PL samples, the surface resistivity is reduced by several orders of magnitude and a tendency to micro-hardness reductionis induced.

Dynamic Model of Basic Oxygen Steelmaking Process Based on Multizone Reaction Kinetics: Modeling of Decarburization

NASA Astrophysics Data System (ADS)

Rout, Bapin Kumar; Brooks, Geoffrey; Akbar Rhamdhani, M.; Li, Zushu; Schrama, Frank N. H.; Overbosch, Aart

2018-06-01

In a previous study by the authors (Rout et al. in Metall Mater Trans B 49:537-557, 2018), a dynamic model for the BOF, employing the concept of multizone kinetics was developed. In the current study, the kinetics of decarburization reaction is investigated. The jet impact and slag-metal emulsion zones were identified to be primary zones for carbon oxidation. The dynamic parameters in the rate equation of decarburization such as residence time of metal drops in the emulsion, interfacial area evolution, initial size, and the effects of surface-active oxides have been included in the kinetic rate equation of the metal droplet. A modified mass-transfer coefficient based on the ideal Langmuir adsorption equilibrium has been proposed to take into account the surface blockage effects of SiO2 and P2O5 in slag on the decarburization kinetics of a metal droplet in the emulsion. Further, a size distribution function has been included in the rate equation to evaluate the effect of droplet size on reaction kinetics. The mathematical simulation indicates that decarburization of the droplet in the emulsion is a strong function of the initial size and residence time. A modified droplet generation rate proposed previously by the authors has been used to estimate the total decarburization rate by slag-metal emulsion. The model's prediction shows that about 76 pct of total carbon is removed by reactions in the emulsion, and the remaining is removed by reactions at the jet impact zone. The predicted bath carbon by the model has been found to be in good agreement with the industrially measured data.

Dynamic Model of Basic Oxygen Steelmaking Process Based on Multizone Reaction Kinetics: Modeling of Decarburization

NASA Astrophysics Data System (ADS)

Rout, Bapin Kumar; Brooks, Geoffrey; Akbar Rhamdhani, M.; Li, Zushu; Schrama, Frank N. H.; Overbosch, Aart

2018-03-01

In a previous study by the authors (Rout et al. in Metall Mater Trans B 49:537-557, 2018), a dynamic model for the BOF, employing the concept of multizone kinetics was developed. In the current study, the kinetics of decarburization reaction is investigated. The jet impact and slag-metal emulsion zones were identified to be primary zones for carbon oxidation. The dynamic parameters in the rate equation of decarburization such as residence time of metal drops in the emulsion, interfacial area evolution, initial size, and the effects of surface-active oxides have been included in the kinetic rate equation of the metal droplet. A modified mass-transfer coefficient based on the ideal Langmuir adsorption equilibrium has been proposed to take into account the surface blockage effects of SiO2 and P2O5 in slag on the decarburization kinetics of a metal droplet in the emulsion. Further, a size distribution function has been included in the rate equation to evaluate the effect of droplet size on reaction kinetics. The mathematical simulation indicates that decarburization of the droplet in the emulsion is a strong function of the initial size and residence time. A modified droplet generation rate proposed previously by the authors has been used to estimate the total decarburization rate by slag-metal emulsion. The model's prediction shows that about 76 pct of total carbon is removed by reactions in the emulsion, and the remaining is removed by reactions at the jet impact zone. The predicted bath carbon by the model has been found to be in good agreement with the industrially measured data.

Surface characterization of nickel titanium orthodontic arch wires

PubMed Central

Krishnan, Manu; Seema, Saraswathy; Tiwari, Brijesh; Sharma, Himanshu S.; Londhe, Sanjay; Arora, Vimal

2015-01-01

Background Surface roughness of nickel titanium orthodontic arch wires poses several clinical challenges. Surface modification with aesthetic/metallic/non metallic materials is therefore a recent innovation, with clinical efficacy yet to be comprehensively evaluated. Methods One conventional and five types of surface modified nickel titanium arch wires were surface characterized with scanning electron microscopy, energy dispersive analysis, Raman spectroscopy, Atomic force microscopy and 3D profilometry. Root mean square roughness values were analyzed by one way analysis of variance and post hoc Duncan's multiple range tests. Results Study groups demonstrated considerable reduction in roughness values from conventional in a material specific pattern: Group I; conventional (578.56 nm) > Group V; Teflon (365.33 nm) > Group III; nitride (301.51 nm) > Group VI (i); rhodium (290.64 nm) > Group VI (ii); silver (252.22 nm) > Group IV; titanium (229.51 nm) > Group II; resin (158.60 nm). It also showed the defects with aesthetic (resin/Teflon) and nitride surfaces and smooth topography achieved with metals; titanium/silver/rhodium. Conclusions Resin, Teflon, titanium, silver, rhodium and nitrides were effective in decreasing surface roughness of nickel titanium arch wires albeit; certain flaws. Findings have clinical implications, considering their potential in lessening biofilm adhesion, reducing friction, improving corrosion resistance and preventing nickel leach and allergic reactions. PMID:26843749

Bio-inspired immobilization of metal oxides on monolithic microreactor for continuous Knoevenagel reaction.

PubMed

Song, Wentong; Shi, Da; Tao, Shengyang; Li, Zhaoliang; Wang, Yuchao; Yu, Yongxian; Qiu, Jieshan; Ji, Min; Wang, Xinkui

2016-11-01

A facile method is reported to construct monolithic microreactor with high catalytic performance for Knoevenagel reaction. The microreactor is based on hierarchically porous silica (HPS) which has interconnected macro- and mesopores. Then the HPS is surface modified by pyrogallol (PG) polymer. Al(NO3)3 and Mg(NO3)2 are loaded on the surface of HPS through coordination with -OH groups of PG. After thermal treatment, Al(NO3)3 and Mg(NO3)2 are converted Al2O3 and MgO. The as-synthesized catalytic microreactor shows a high and stable performance in Knoevenagel reaction. The microreactor possess large surface area and interconnected pore structures which are beneficial for reactions. Moreover, this economic, facile and eco-friendly surface modification method can be used in loading more metal oxides for more reactions. Copyright © 2016 Elsevier Inc. All rights reserved.

Cell adhesion and proliferation on poly(tetrafluoroethylene) with plasma-metal and plasma-metal-carbon interfaces

NASA Astrophysics Data System (ADS)

Reznickova, Alena; Kvitek, Ondrej; Kolarova, Katerina; Smejkalova, Zuzana; Svorcik, Vaclav

2017-06-01

The aim of this article is to investigate the effect of the interface between plasma activated, gold and carbon coated poly(tetrafluoroethylene) (PTFE) on in vitro adhesion and spreading of mouse fibroblasts (L929). Surface properties of pristine and modified PTFE were studied by several experimental techniques. The thickness of a deposited gold film is an increasing function of the sputtering time, conversely thickness of carbon layer decreases with increasing distance between carbon source and the substrate. Because all the used surface modification techniques take place in inert Ar plasma, oxidized degradation products are formed on the PTFE surface, which affects wettability of the polymer surface. Cytocompatibility tests indicate that on samples with Au/C interface, the cells accumulate on the part of sample with evaporated carbon. Number of L929 cells proliferated on the studied samples is comparable to tissue culture polystyrene standard.

Heterogeneous catalysis with lasers

NASA Astrophysics Data System (ADS)

George, T. F.

1986-06-01

Theoretical techniques have been developed to describe a variety of laser-induced molecular rate processes occurring at solid surfaces which are involved in heterogeneous catalysis. Such processes include adsorption, migration, chemical reactions and desorption. The role of surface phonons in laser-selective processes and laser heating has been analyzed. The importance of electronic degrees of freedom has been considered for semiconductor and metal substrates, with special emphasis on the laser excitation of surface states. Surface-modified photochemistry has also been investigated, where the effect of a metal surface on the resonance fluorescence spectrum of a laser-driven atom/molecule has been assessed by means of surface-dressed optical Bloch equations. It is seen that the spectrum can be significantly different from the gas-phase case. Two related gas-surface collision processes have also been studied. First, the feasibility of the formation of the electron-hole pairs in a semiconductor by vibrationally excited molecules has been explored. Second, charge transfer in ion-surface collisions has been examined for both one-electron and two-electron transfer processes. Work has been initiated on microstructures and rough structures, including clusters and surface gratings.

Theoretical model of gravitational perturbation of current collector axisymmetric flow field

NASA Astrophysics Data System (ADS)

Walker, John S.; Brown, Samuel H.; Sondergaard, Neal A.

1990-05-01

Some designs of liquid-metal current collectors in homopolar motors and generators are essentially rotating liquid-metal fluids in cylindrical channels with free surfaces and will, at critical rotational speeds, become unstable. An investigation at David Taylor Research Center is being performed to understand the role of gravity in modifying this ejection instability. Some gravitational effects can be theoretically treated by perturbation techniques on the axisymmetric base flow of the liquid metal. This leads to a modification of previously calculated critical-current-collector ejection values neglecting gravity effects. The purpose of this paper is to document the derivation of the mathematical model which determines the perturbation of the liquid-metal base flow due to gravitational effects. Since gravity is a small force compared with the centrifugal effects, the base flow solutions can be expanded in inverse powers of the Froude number and modified liquid-flow profiles can be determined as a function of the azimuthal angle. This model will be used in later work to theoretically study the effects of gravity on the ejection point of the current collector.

Laboratory Study of MHD Effects on Stability of Free-surface Liquid Metal Flow

NASA Astrophysics Data System (ADS)

Burin, M. J.; Ji, H.; McMurtry, K.; Peterson, L.; Giannakis, D.; Rosner, R.; Fischer, P.

2006-10-01

The dynamics of free-surface MHD shear flows is potentially important to both astrophysics (e.g. in the mixing of dense plasma accreted upon neutron star surfaces) and fusion reactors (e.g. in liquid metal ‘first walls’). To date however few relevant experiments exist. In order to study the fundamental physics of such flows, a small-scale laboratory experiment is being built using a liquid gallium alloy flowing in an open- channel geometry. The flow dimensions are nominally 10cm wide, 1cm deep, and 70cm long under an imposed magnetic field up to 7kG, leading to maximum Hartman number of 2000 and maximum Reynolds number of 4x10^5. Two basic physics issues will ultimately be addressed: (1) How do MHD effects modify the stability of the free surface? For example, is the flow more stable (through the suppression of cross-field motions), or less stable (through the introduction of new boundary layers)? We also investigate whether internal shear layers and imposed electric currents can control the surface stability. (2) How do MHD effects modify free-surface convection driven by a vertical and/or horizontal temperature gradient? We discuss aspects of both of these issues, along with detailed descriptions of the experimental device. Pertinent theoretical stability analyses and initial hydrodynamic results are presented in companion posters. This work is supported by DoE under contract #DE-AC02-76-CH03073.

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

Predicting heavy metals' adsorption edges and adsorption isotherms on MnO2 with the parameters determined from Langmuir kinetics.

PubMed

Hu, Qinghai; Xiao, Zhongjin; Xiong, Xinmei; Zhou, Gongming; Guan, Xiaohong

2015-01-01

Although surface complexation models have been widely used to describe the adsorption of heavy metals, few studies have verified the feasibility of modeling the adsorption kinetics, edge, and isotherm data with one pH-independent parameter. A close inspection of the derivation process of Langmuir isotherm revealed that the equilibrium constant derived from the Langmuir kinetic model, KS-kinetic, is theoretically equivalent to the adsorption constant in Langmuir isotherm, KS-Langmuir. The modified Langmuir kinetic model (MLK model) and modified Langmuir isotherm model (MLI model) incorporating pH factor were developed. The MLK model was employed to simulate the adsorption kinetics of Cu(II), Co(II), Cd(II), Zn(II) and Ni(II) on MnO2 at pH3.2 or 3.3 to get the values of KS-kinetic. The adsorption edges of heavy metals could be modeled with the modified metal partitioning model (MMP model), and the values of KS-Langmuir were obtained. The values of KS-kinetic and KS-Langmuir are very close to each other, validating that the constants obtained by these two methods are basically the same. The MMP model with KS-kinetic constants could predict the adsorption edges of heavy metals on MnO2 very well at different adsorbent/adsorbate concentrations. Moreover, the adsorption isotherms of heavy metals on MnO2 at various pH levels could be predicted reasonably well by the MLI model with the KS-kinetic constants. Copyright © 2014. Published by Elsevier B.V.

Adsorption of Pb(II) using silica gel composite from rice husk ash modified 3-aminopropyltriethoxysilane (APTES)-activated carbon from coconut shell

NASA Astrophysics Data System (ADS)

Yusmaniar, Purwanto, Agung; Putri, Elfriyana Awalita; Rosyidah, Dzakiyyatur

2017-03-01

Silica gel modified by 3-aminopropyltriethoxysilane (APTES) was synthesized from rice husk ash combined with activated carbon from coconut shell yielded the composite adsorbent. The composite was characterized by Fourier Transform Infra Red spectroscopy (FT-IR), Electron Dispersive X-Ray (EDX), Surface Area Analyzer (SAA) and adsorption test by Atomic Absorption Spectrometry (AAS). This composite adsorbent has been used moderately for the removal of lead ions from metal solutions and compared with silica gel modified APTES and activated carbon. The adsorption experiments of Pb -ions by adsorbents were performed at different pH and contact time with the same metal solutions concentration, volume solution, and adsorbent dosage. The optimum pH for the adsorption was found to be 5.0 and the equilibrium was achieved for Pb with 20 min of contact time. Pb ions adsorption by composite silica gel modified APTES-activated carbon followed by Langmuir isotherm model with qmax value of 46.9483 mg/g that proved an adsorbent mechanism consistent to the mechanism of monolayer formation.

40 CFR 721.10044 - Metal oxide, modified with alkyl and vinyl terminated polysiloxanes (generic).

Code of Federal Regulations, 2011 CFR

2011-07-01

... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Metal oxide, modified with alkyl and... SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.10044 Metal oxide, modified with alkyl... to reporting. (1) The chemical substance identified generically as metal oxide, modified with alkyl...

Progress Report on Rotating Liquid Liner Implosion Experiment, 1 June to 31 December 1975.

DTIC Science & Technology

A critical question in the use of imploding liner flux compression for controlled fusion has been the stability of the inner surface of the liner ...To study the problem experimentally, the existing NRL Imploding Liner Facility was modified to allow the implosion of rotating liquid metal liners ...Rotational stabilization of lthe inner surface of a decelerating liquid sodium-potassium liner has been demonstrated, with excellent circularity of the

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

Design of nanocoatings by in situ phosphatizing reagent catalyzed polysilsesquioxane for corrosion inhibition and adhesion promotion on metal alloys

NASA Astrophysics Data System (ADS)

Henderson, Kimberly B.

When a metal reacts with oxygen and water, a redox reaction happens, which will cause corrosion. Current surface pretreatment for inhibiting corrosion on metal alloys is a phosphate conversion bath. The phosphate conversion bath will generate a phosphate-chromate layer to adhere strongly to a metal substrate. However, it is toxic and unfriendly to the environment. Our group proposed an innovative coating that contains a phosphate component (ISPR-In-situ Phosphatizing Reagent) within a protective coating. The ISPR coating will form a bound phosphate layer on the metal surface acting as the corrosion barrier and enhancing adhesion into the metal surface; moreover, it is low in cost and non-toxic. Within this dissertation, there are four projects that investigate design of ISPR nanocoatings for the use of corrosion inhibition and adhesion promotion. Surface modification and adjusting concentrations of materials with the different formulations are explored. The first project focuses on the adhesion enhancement of a coating created by modifying the surface of an aluminum panel. Secondly, the next project will discuss and present the use of three rare earth element formulations as a replacement for phosphate conversion coatings on magnesium alloy, AZ61. The third project is the design of a nanocoating by using heat dissipating materials to fill in small vacant spaces in the ISPR network coating on various metal alloys. The last project, studies the strategic selection of incorporating metal components into ISPR network by the reduction potential values on several different alloys. Many methods of analysis are used; SEM, TEM, ASTM B117, ASTM D1308, ASTM D3359, EIS, and thickness probe. It was found that the addition of ISPR in the nanocoatings dramatically improves the vitality of metal alloys and these results will be presented during this dissertation.

Atomically-thin molecular layers for electrode modification of organic transistors

NASA Astrophysics Data System (ADS)

Gim, Yuseong; Kang, Boseok; Kim, Bongsoo; Kim, Sun-Guk; Lee, Joong-Hee; Cho, Kilwon; Ku, Bon-Cheol; Cho, Jeong Ho

2015-08-01

Atomically-thin molecular layers of aryl-functionalized graphene oxides (GOs) were used to modify the surface characteristics of source-drain electrodes to improve the performances of organic field-effect transistor (OFET) devices. The GOs were functionalized with various aryl diazonium salts, including 4-nitroaniline, 4-fluoroaniline, or 4-methoxyaniline, to produce several types of GOs with different surface functional groups (NO2-Ph-GO, F-Ph-GO, or CH3O-Ph-GO, respectively). The deposition of aryl-functionalized GOs or their reduced derivatives onto metal electrode surfaces dramatically enhanced the electrical performances of both p-type and n-type OFETs relative to the performances of OFETs prepared without the GO modification layer. Among the functionalized rGOs, CH3O-Ph-rGO yielded the highest hole mobility of 0.55 cm2 V-1 s-1 and electron mobility of 0.17 cm2 V-1 s-1 in p-type and n-type FETs, respectively. Two governing factors: (1) the work function of the modified electrodes and (2) the crystalline microstructures of the benchmark semiconductors grown on the modified electrode surface were systematically investigated to reveal the origin of the performance improvements. Our simple, inexpensive, and scalable electrode modification technique provides a significant step toward optimizing the device performance by engineering the semiconductor-electrode interfaces in OFETs.Atomically-thin molecular layers of aryl-functionalized graphene oxides (GOs) were used to modify the surface characteristics of source-drain electrodes to improve the performances of organic field-effect transistor (OFET) devices. The GOs were functionalized with various aryl diazonium salts, including 4-nitroaniline, 4-fluoroaniline, or 4-methoxyaniline, to produce several types of GOs with different surface functional groups (NO2-Ph-GO, F-Ph-GO, or CH3O-Ph-GO, respectively). The deposition of aryl-functionalized GOs or their reduced derivatives onto metal electrode surfaces dramatically enhanced the electrical performances of both p-type and n-type OFETs relative to the performances of OFETs prepared without the GO modification layer. Among the functionalized rGOs, CH3O-Ph-rGO yielded the highest hole mobility of 0.55 cm2 V-1 s-1 and electron mobility of 0.17 cm2 V-1 s-1 in p-type and n-type FETs, respectively. Two governing factors: (1) the work function of the modified electrodes and (2) the crystalline microstructures of the benchmark semiconductors grown on the modified electrode surface were systematically investigated to reveal the origin of the performance improvements. Our simple, inexpensive, and scalable electrode modification technique provides a significant step toward optimizing the device performance by engineering the semiconductor-electrode interfaces in OFETs. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr03307a

Determining the Catalytic Activity of Transition Metal-Doped TiO2 Nanoparticles Using Surface Spectroscopic Analysis

NASA Astrophysics Data System (ADS)

Yang, Sena; Lee, Hangil

2017-11-01

The modified TiO2 nanoparticles (NPs) to enhance their catalytic activities by doping them with the five transition metals (Cr, Mn, Fe, Co, and Ni) have been investigated using various surface analysis techniques such as scanning electron microscopy (SEM), Raman spectroscopy, scanning transmission X-ray microscopy (STXM), and high-resolution photoemission spectroscopy (HRPES). To compare catalytic activities of these transition metal-doped TiO2 nanoparticles (TM-TiO2) with those of TiO2 NPs, we monitored their performances in the catalytic oxidation of 2-aminothiophenol (2-ATP) by using HRPES and on the oxidation of 2-ATP in aqueous solution by taking electrochemistry (EC) measurements. As a result, we clearly investigate that the increased defect structures induced by the doped transition metal are closely correlated with the enhancement of catalytic activities of TiO2 NPs and confirm that Fe- and Co-doped TiO2 NPs can act as efficient catalysts.

Evaluation of Heavy Metal Removal from Wastewater in a Modified Packed Bed Biofilm Reactor

PubMed Central

Azizi, Shohreh; Kamika, Ilunga; Tekere, Memory

2016-01-01

For the effective application of a modified packed bed biofilm reactor (PBBR) in wastewater industrial practice, it is essential to distinguish the tolerance of the system for heavy metals removal. The industrial contamination of wastewater from various sources (e.g. Zn, Cu, Cd and Ni) was studied to assess the impacts on a PBBR. This biological system was examined by evaluating the tolerance of different strengths of composite heavy metals at the optimum hydraulic retention time (HRT) of 2 hours. The heavy metal content of the wastewater outlet stream was then compared to the source material. Different biomass concentrations in the reactor were assessed. The results show that the system can efficiently treat 20 (mg/l) concentrations of combined heavy metals at an optimum HRT condition (2 hours), while above this strength there should be a substantially negative impact on treatment efficiency. Average organic reduction, in terms of the chemical oxygen demand (COD) of the system, is reduced above the tolerance limits for heavy metals as mentioned above. The PBBR biological system, in the presence of high surface area carrier media and a high microbial population to the tune of 10 000 (mg/l), is capable of removing the industrial contamination in wastewater. PMID:27186636

Microstructure Characterization of Al-TiC Surface Composite Fabricated by Friction Stir Processing

NASA Astrophysics Data System (ADS)

Shiva, Apireddi; Cheepu, Muralimohan; Charan Kantumuchu, Venkata; Kumar, K. Ravi; Venkateswarlu, D.; Srinivas, B.; Jerome, S.

2018-03-01

Titanium carbide (TiC) is an exceedingly hard and wear refractory ceramic material. The surface properties of the material are very important and the corrosion, wear and fatigue resistance behaviour determines its ability and applications. It is necessary to modify the surface properties of the materials to enhance their performance. The present work aims on developing a new surface composite using commercially pure aluminum and TiC reinforcement powder with a significant fabrication technique called friction stir processing (FSP). The metal matrix composite of Al/TiC has been developed without any defects formation to investigate the particles distribution in the composite, microstructural changes and mechanical properties of the material. The microstructural observations exhibited that the grain refinement in the nugget compared to the base metal and FSP without TiC particles. The developed composite properties showed substantial improvement in micro-hardness, friction factor, wear resistance and microstructural characteristics in comparison to parent metal. On the other side, the ductility of the composite specimens was diminished over the substrate. The FSPed specimens were characterised using X-ray diffraction technique and revealed that the formation of AlTi compounds and the presence of Ti phases in the matrix. The microstructures of the samples illustrated the uniform distribution of particles in the newly developed metal matrix composite.

Surface Grafting of Ru(II) Diazonium-Based Sensitizers on Metal Oxides Enhances Alkaline Stability for Solar Energy Conversion.

PubMed

Bangle, Rachel; Sampaio, Renato N; Troian-Gautier, Ludovic; Meyer, Gerald J

2018-01-24

The electrografting of [Ru(ttt)(tpy-C 6 H 4 -N 2 + )] 3+ , where "ttt" is 4,4',4″-tri-tert-butyl-2,2':6',2″-terpyridine, was investigated on several wide band gap metal oxide surfaces (TiO 2 , SnO 2 , ZrO 2 , ZnO, In 2 O 3 :Sn) and compared to structurally analogous sensitizers that differed only by the anchoring group, i.e., -PO 3 H 2 and -COOH. An optimized procedure for diazonium electrografting to semiconductor metal oxides is presented that allowed surface coverages that ranged between 4.7 × 10 -8 and 10.6 × 10 -8 mol cm -2 depending on the nature of the metal oxide. FTIR analysis showed the disappearance of the diazonium stretch at 2266 cm -1 after electrografting. XPS analysis revealed a characteristic peak of Ru 3d at 285 eV as well as a peak at 531.6 eV that was attributed to O 1s in Ti-O-C bonds. Photocurrents were measured to assess electron injection efficiency of these modified surfaces. The electrografted sensitizers exhibited excellent stability across a range of pHs spanning from 1 to 14, where classical binding groups such as carboxylic and phosphonic derivatives were hydrolyzed.

Surface Properties of Titanium dioxide and its Structural Modifications by Reactions with Transition Metals

NASA Astrophysics Data System (ADS)

Halpegamage, Sandamali

Surfaces of metal oxides play a vital role in many technologically important applications. The surfaces of titanium dioxide, in particular, show quite promising properties that can be utilized in solid-state gas sensing and photocatalysis applications. In the first part of this dissertation we investigate these properties of TiO2 surfaces through a vigorous surface scientific approach. In the second part, we investigate the possibilities of modifying the TiO2 surfaces by depositing multi-component transition metal oxide monolayers so that the properties of bare TiO2 surface can be influenced in a beneficial way. For instance, via formation of new surface sites or cations that have different valance states, the chemisorption and catalytic properties can be modified. We use sophisticated experimental surface science techniques that are compatible with ultra-high vacuum technology for surface characterization. All the experimental results, except for the photocatalysis experiments, were compared to and verified by supporting DFT-based theoretical results produced by our theory collaborators. TiO2 based solid-state gas sensors have been used before for detecting trace amounts of explosives such as 2,4-dinitrololuene (DNT), a toxic decomposition product of the explosive 2,4,6-trinitrotoluene (TNT) that have very low vapor pressure. However, the adsorption, desorption and reaction mechanism were not well- understood. Here, we investigate 2,4-DNT adsorption on rutile-TiO2(110) surface in order to gain insight about these mechanisms in an atomistic level and we propose an efficient way of desorbing DNT from the surface through UV-light induced photoreactions. TiO2 exists in different polymorphs and the photocatalytic activity differs from one polymorph to another. Rutile and anatase are the most famous forms of TiO2 in photocatalysis and anatase is known to show higher activity than rutile. The photoactivity also varies depending on the surface orientation for the same polymorph. So far, a reasonable explanation as to why these differences exist was not reported. In our studies, we used high quality epitaxial rutile and anatase thin films which enabled isolating the surface effects from the bulk effects and show that it is the difference between the charge carrier diffusion lengths that causes this difference in activities. In addition to that, using different surface orientations of rutile-TiO 2, we show that the anisotropic bulk charge carrier mobility may contribute to the orientation dependent photoactivity. Moreover, we show that different surface preparation methods also affect the activity of the sample and vacuum reduction results in an enhanced activity. In an effort to modify the TiO2 surfaces with monolayer/mixed monolayer oxides, we carried out experiments on (011) orientation of single crystal rutile TiO2 with few of the selected transition metal oxides namely Fe, V, Cr and Ni. We found that for specific oxidation conditions a monolayer mixed oxide is formed for all M (M= Fe, V, Cr, Ni), with one common structure with the composition MTi2O5. For small amounts of M the surface segregates into pure TiO2(011)-2x1 and into domains of MTi2O5 indicating that this mixed monolayer oxide is a low energy line phase in a compositional surface phase diagram. The oxygen pressure required for the formation of this unique monolayer structure increases in the order of V

Quantification of confocal images of biofilms grown on irregular surfaces

PubMed Central

Ross, Stacy Sommerfeld; Tu, Mai Han; Falsetta, Megan L.; Ketterer, Margaret R.; Kiedrowski, Megan R.; Horswill, Alexander R.; Apicella, Michael A.; Reinhardt, Joseph M.; Fiegel, Jennifer

2014-01-01

Bacterial biofilms grow on many types of surfaces, including flat surfaces such as glass and metal and irregular surfaces such as rocks, biological tissues and polymers. While laser scanning confocal microscopy can provide high-resolution images of biofilms grown on any surface, quantification of biofilm-associated bacteria is currently limited to bacteria grown on flat surfaces. This can limit researchers studying irregular surfaces to qualitative analysis or quantification of only the total bacteria in an image. In this work, we introduce a new algorithm called modified connected volume filtration (MCVF) to quantify bacteria grown on top of an irregular surface that is fluorescently labeled or reflective. Using the MCVF algorithm, two new quantification parameters are introduced. The modified substratum coverage parameter enables quantification of the connected-biofilm bacteria on top of the surface and on the imaging substratum. The utility of MCVF and the modified substratum coverage parameter were shown with Pseudomonas aeruginosa and Staphylococcus aureus biofilms grown on human airway epithelial cells. A second parameter, the percent association, provides quantified data on the colocalization of the bacteria with a labeled component, including bacteria within a labeled tissue. The utility of quantifying the bacteria associated with the cell cytoplasm was demonstrated with Neisseria gonorrhoeae biofilms grown on cervical epithelial cells. This algorithm provides more flexibility and quantitative ability to researchers studying biofilms grown on a variety of irregular substrata. PMID:24632515

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

Effects of self-assembly of 3-phosphonopropionic acid, 3-aminopropyltrimethoxysilane and dopamine on the corrosion behaviors and biocompatibility of a magnesium alloy.

PubMed

Pan, Chang-Jiang; Hou, Yu; Wang, Ya-Nan; Gao, Fei; Liu, Tao; Hou, Yan-Hua; Zhu, Yu-Fu; Ye, Wei; Wang, Ling-Ren

2016-10-01

Magnesium based alloys are attracting tremendous interests as the novel biodegradable metallic biomaterials. However, the rapid in vivo degradation and the limited surface biocompatibility restrict their clinical applications. Surface modification represents one of the important approaches to control the corrosion rate of Mg based alloys and to enhance the biocompatibility. In the present study, in order to improve the corrosion resistance and surface biocompatibility, magnesium alloy (AZ31B) was modified by the alkali heating treatment followed by the self-assembly of 3-phosphonopropionic acid, 3-aminopropyltrimethoxysilane (APTMS) and dopamine, respectively. The results of attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR) and X-ray photoelectron spectra (XPS) indicated that the molecules were successfully immobilized on the magnesium alloy surface by the self-assembly. An excellent hydrophilic surface was obtained after the alkali heating treatment and the water contact angle increased to some degree after the self-assembly of dopamine, APTMS and 3-phosphonopropionic acid, however, the hydrophilicity of the modified samples was better than that of the pristine magnesium substrate. Due to the formation of the passivation layer after the alkali heating treatment, the corrosion resistance of the magnesium alloy was obviously improved. The corrosion rate further decreased to varying degrees after the self-assembly surface modification. The blood compatibility of the pristine magnesium was significantly improved after the surface modification. The hemolysis rate was reduced from 56% of the blank magnesium alloy to 18% of the alkali heating treated sample and the values were further reduced to about 10% of dopamine-modified sample and 7% of APTMS-modified sample. The hemolysis rate was below 5% for the 3-phosphonopropionic acid modified sample. As compared to the pristine magnesium alloy, fewer platelets were attached and activated on the modified surfaces and the activated partial thromboplastin times (APTT) were prolonged to some degree. Furthermore, the modified samples showed good cytocompatibility. Endothelial cells exhibited the improved proliferative profiles in terms of CCK-8 assay as compared to those on the pristine magnesium alloy. The modified samples showed better endothelial cell adhesion and spreading than the pristine magnesium alloy. Taking all these results into consideration, the method of this study can be used to modify the magnesium alloy surface to improve the corrosion resistance and biocompatibility simultaneously. Copyright © 2016 Elsevier B.V. All rights reserved.

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.

Do dielectric nanostructures turn metallic in high-electric dc fields?

PubMed

Silaeva, E P; Arnoldi, L; Karahka, M L; Deconihout, B; Menand, A; Kreuzer, H J; Vella, A

2014-11-12

Three-dimensional dielectric nanostructures have been analyzed using field ion microscopy (FIM) to study the electric dc field penetration inside these structures. The field is proved to be screened within a few nanometers as theoretically calculated taking into account the high-field impact ionization process. Moreover, the strong dc field of the order of 0.1 V/Å at the surface inside a dielectric nanostructure modifies its band structure leading to a strong band gap shrinkage and thus to a strong metal-like optical absorption near the surface. This metal-like behavior was theoretically predicted using first-principle calculations and experimentally proved using laser-assisted atom probe tomography (APT). This work opens up interesting perspectives for the study of the performance of all field-effect nanodevices, such as nanotransistor or super capacitor, and for the understanding of the physical mechanisms of field evaporation of dielectric nanotips in APT.

[Preparation of polyacrylonitrile/natural sand composite materials and analysis of adsorption properties of Pb(II) on it by FAAS].

PubMed

Abduwayit, Medine; Nurulla, Ismayil; Abliz, Shawket

2015-02-01

Surfaces of natural sand particles were modified with (3-chloropropyl) trichlorosilane, so that bridging groups were introduced on the surfaces of natural sand particles; By grafting polyacrylonitrile onto the modified surfaces of the natural sand particles, a novelpolyacrylonitrile/natural sand composite material was prepared from the acrylonitrile, the azobisisobutyronitrile, the divinylbenzene and the modified natural sand particles, which are as functional monomer, initiator, either skeleton monomer or cross-linking agent and carrier respectively; the composite materials were characterized by using infrared spectroscopy and scanning electron microscopy; On the FTIR spectrum, the main characteristic peaks of various functional groups including nitrile, benzene ring, and silicon hydroxyl, which were from functional monomer, cross-linking agent and carrier respectively, were observed. On the SEM, two different cross section morphologies having different density which were from acrylonitrile and modified sand particles were observed; This proved that the polyacrylonitrile was decorated on modified sand particles during our preparation process. After preparing the composite materials, micro-column of separation and preconcentration was prepared using the composite materials as filler; the adsorption of some toxic heavy metal ions onto the composite materials was observed by flame atomic absorption spectrometry (FAAS); The results show that the adsorption of Pb2+ onto the composite materials was more stronger than the absorption of other toxic heavy metal ions, therefore, in this paper, the adsorption of Pb2+ onto the composite materials was mainly studied, at room temperature, when pH and flow rate of solution were 5. 4 and 4 mL x min(-1) respectively, the trace Pb(II) ions could be quantitatively adsorbed onto the composite materials; the maximum adsorption capacity of Pb(II) on the composite materials can reach 62.9 mg x g(-1). The column was eluted by 0.5 mol x L(-1) HCl and recovery of Pb(II) was more than 96%.

Bioactivity of sol-gel-derived TiO2 coating on polyetheretherketone: In vitro and in vivo studies.

PubMed

Shimizu, Takayoshi; Fujibayashi, Shunsuke; Yamaguchi, Seiji; Yamamoto, Koji; Otsuki, Bungo; Takemoto, Mitsuru; Tsukanaka, Masako; Kizuki, Takashi; Matsushita, Tomiharu; Kokubo, Tadashi; Matsuda, Shuichi

2016-04-15

A polyetheretherketone (PEEK) surface was modified using a sol-gel-derived TiO2 coating in order to confer bone-bonding ability. To enhance the bonding strength of the coating layer, pretreatment with either O2 plasma or sandblasting was performed prior to sol-gel coating. Additionally, post-treatment with acid was carried out to confer apatite (calcium phosphate)-forming ability to the surface. Biomechanical and histological analyses performed using an in vivo rabbit tibia model showed that PEEK surfaces modified with sol-gel-derived TiO2 and acid post-treatment had better bone-bonding properties than uncoated PEEK surfaces. These modified surfaces also performed well in terms of their in vitro cell responses due to their modified surface chemistries and topographies. Although O2 plasma or sandblasting treatment were, for the most part, equivocal in terms of performance, we conclude that sol-gel-derived TiO2 coating followed by acid post-treatment significantly improves the bone bonding ability of PEEK surfaces, thus rendering them optimal for their use in surgical implants. The role of polyetheretherketone (PEEK) as an alternative biomaterial to conventional metallic implant materials has become increasingly important. However, its low bone bonding ability is yet to be resolved. This in vivo and in vitro investigation on the functionalization of PEEK surfaces highlights the utility of this material in clinical interventions that require implants, and may extend range of applications of PEEK. Copyright © 2016 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Establishing Antibacterial Multilayer Films on the Surface of Direct Metal Laser Sintered Titanium Primed with Phase-Transited Lysozyme

PubMed Central

Guan, Binbin; Wang, Haorong; Xu, Ruiqing; Zheng, Guoying; Yang, Jie; Liu, Zihao; Cao, Man; Wu, Mingyao; Song, Jinhua; Li, Neng; Li, Ting; Cai, Qing; Yang, Xiaoping; Li, Yanqiu; Zhang, Xu

2016-01-01

Direct metal laser sintering is a technology that allows the fabrication of titanium (Ti) implants with a functional gradation of porosity and surface roughness according to three-dimensional (3D) computer data. The surface roughness of direct metal laser sintered titanium (DMLS-Ti) implants may provide abundant binding sites for bacteria. Bacterial colonization and subsequent biofilm formation can cause unsatisfactory cell adhesion and implant-related infections. To prevent such infections, a novel phase-transited lysozyme (PTL) was utilized as an initial functional layer to simply and effectively prime DMLS-Ti surfaces for subsequent coating with antibacterial multilayers. The purpose of the present study was to establish a surface with dual biological functionality. The minocycline-loaded polyelectrolyte multilayers of hyaluronic acid (HA) and chitosan (CS) formed via a layer-by-layer (LbL) self-assembly technique on PTL-functionalized DMLS-Ti were designed to inhibit pathogenic microbial infections while allowing the DMLS-Ti itself and the modified coatings to retain acceptable biocompatibility. The experimental results indicate that the DMLS-Ti and the hydrogel treated surfaces can inhibit early bacterial adhesion while completely preserving osteoblast functions. This design is expected to gain considerable interest in the medical field and to have good potential for applications in multifunctional DMLS-Ti implants. PMID:27821857

Establishing Antibacterial Multilayer Films on the Surface of Direct Metal Laser Sintered Titanium Primed with Phase-Transited Lysozyme.

PubMed

Guan, Binbin; Wang, Haorong; Xu, Ruiqing; Zheng, Guoying; Yang, Jie; Liu, Zihao; Cao, Man; Wu, Mingyao; Song, Jinhua; Li, Neng; Li, Ting; Cai, Qing; Yang, Xiaoping; Li, Yanqiu; Zhang, Xu

2016-11-08

Direct metal laser sintering is a technology that allows the fabrication of titanium (Ti) implants with a functional gradation of porosity and surface roughness according to three-dimensional (3D) computer data. The surface roughness of direct metal laser sintered titanium (DMLS-Ti) implants may provide abundant binding sites for bacteria. Bacterial colonization and subsequent biofilm formation can cause unsatisfactory cell adhesion and implant-related infections. To prevent such infections, a novel phase-transited lysozyme (PTL) was utilized as an initial functional layer to simply and effectively prime DMLS-Ti surfaces for subsequent coating with antibacterial multilayers. The purpose of the present study was to establish a surface with dual biological functionality. The minocycline-loaded polyelectrolyte multilayers of hyaluronic acid (HA) and chitosan (CS) formed via a layer-by-layer (LbL) self-assembly technique on PTL-functionalized DMLS-Ti were designed to inhibit pathogenic microbial infections while allowing the DMLS-Ti itself and the modified coatings to retain acceptable biocompatibility. The experimental results indicate that the DMLS-Ti and the hydrogel treated surfaces can inhibit early bacterial adhesion while completely preserving osteoblast functions. This design is expected to gain considerable interest in the medical field and to have good potential for applications in multifunctional DMLS-Ti implants.

Establishing Antibacterial Multilayer Films on the Surface of Direct Metal Laser Sintered Titanium Primed with Phase-Transited Lysozyme

NASA Astrophysics Data System (ADS)

Guan, Binbin; Wang, Haorong; Xu, Ruiqing; Zheng, Guoying; Yang, Jie; Liu, Zihao; Cao, Man; Wu, Mingyao; Song, Jinhua; Li, Neng; Li, Ting; Cai, Qing; Yang, Xiaoping; Li, Yanqiu; Zhang, Xu

2016-11-01

Direct metal laser sintering is a technology that allows the fabrication of titanium (Ti) implants with a functional gradation of porosity and surface roughness according to three-dimensional (3D) computer data. The surface roughness of direct metal laser sintered titanium (DMLS-Ti) implants may provide abundant binding sites for bacteria. Bacterial colonization and subsequent biofilm formation can cause unsatisfactory cell adhesion and implant-related infections. To prevent such infections, a novel phase-transited lysozyme (PTL) was utilized as an initial functional layer to simply and effectively prime DMLS-Ti surfaces for subsequent coating with antibacterial multilayers. The purpose of the present study was to establish a surface with dual biological functionality. The minocycline-loaded polyelectrolyte multilayers of hyaluronic acid (HA) and chitosan (CS) formed via a layer-by-layer (LbL) self-assembly technique on PTL-functionalized DMLS-Ti were designed to inhibit pathogenic microbial infections while allowing the DMLS-Ti itself and the modified coatings to retain acceptable biocompatibility. The experimental results indicate that the DMLS-Ti and the hydrogel treated surfaces can inhibit early bacterial adhesion while completely preserving osteoblast functions. This design is expected to gain considerable interest in the medical field and to have good potential for applications in multifunctional DMLS-Ti implants.

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.

In vitro biocompatibility of plasma-aided surface-modified 316L stainless steel for intracoronary stents.

PubMed

Bayram, Cem; Mizrak, Alpay Koray; Aktürk, Selçuk; Kurşaklioğlu, Hurkan; Iyisoy, Atila; Ifran, Ahmet; Denkbaş, Emir Baki

2010-10-01

316L-type stainless steel is a raw material mostly used for manufacturing metallic coronary stents. The purpose of this study was to examine the chemical, wettability, cytotoxic and haemocompatibility properties of 316L stainless steel stents which were modified by plasma polymerization. Six different polymeric compounds, polyethylene glycol, 2-hydroxyethyl methacrylate, ethylenediamine, acrylic acid, hexamethyldisilane and hexamethyldisiloxane, were used in a radio frequency glow discharge plasma polymerization system. As a model antiproliferative drug, mitomycin-C was chosen for covalent coupling onto the stent surface. Modified SS 316L stents were characterized by water contact angle measurements (goniometer) and x-ray photoelectron spectroscopy. C1s binding energies showed a good correlation with the literature. Haemocompatibility tests of coated SS 316L stents showed significant latency (t-test, p < 0.05) with respect to SS 316L and control groups in each test.

Demonstration of near infrared gas sensing using gold nanodisks on functionalized silicon.

PubMed

Rodríguez-Cantó, P J; Martínez-Marco, M; Rodríguez-Fortuño, F J; Tomás-Navarro, B; Ortuño, R; Peransí-Llopis, S; Martínez, A

2011-04-11

In this work, we demonstrate experimentally the use of an array of gold nanodisks on functionalized silicon for chemosensing purposes. The metallic nanostructures are designed to display a very strong plasmonic resonance in the infrared regime, which results in highly sensitive sensing. Unlike usual experiments which are based on the functionalization of the metal surface, we functionalized here the silicon substrate. This silicon surface was modified chemically by buildup of an organosilane self-assembled monolayer (SAM) containing isocyanate as functional group. These groups allow for an easy surface regeneration by simple heating, thanks to the thermally reversible interaction isocyanate-analyte, which allows the cyclic use of the sensor. The technique showed a high sensitivity to surface binding events in gas and allowed the surface regeneration by heating of the sensor at 150 °C. A relative wavelength shift ∆λ(max)λ(0)=0.027 was obtained when the saturation level was reached. © 2011 Optical Society of America

Equilibrium, Kinetic, and Thermodynamic Studies on the Adsorption of Cadmium from Aqueous Solution by Modified Biomass Ash

PubMed Central

Zheng, Xuebo; Cui, Hongbiao; Zhu, Zhenqiu; Liang, Jiani

2017-01-01

Natural biomass ash of agricultural residuals was collected from a power plant and modified with hexagonal mesoporous silica and functionalized with 3-aminopropyltriethoxysilane. The physicochemical and morphological properties of the biomass ash were analyzed by ICP-OES, SEM, TEM-EDS, FTIR, and BET analysis. The adsorption behavior of the modified product for Cd2+ in aqueous solution was studied as a function of pH, initial metal concentration, equilibrium time, and temperature. Results showed that the specific surface area of the modified product was 9 times that of the natural biomass ash. The modified biomass ash exhibited high affinity for Cd2+ and its adsorption capacity increased sharply with increasing pH from 4.0 to 6.0. The maximum adsorption capacity was 23.95 mg/g in a pH 5 solution with an initial metal concentration of 50 mg/L and a contact time of 90 min. The adsorption of Cd2+ onto the modified biomass ash was well fitted to the Langmuir model and it followed pseudo-second-order kinetics. Thermodynamic analysis results showed that the adsorption of Cd2+ was spontaneous and endothermic in nature. The results suggest that the modified biomass ash is promising for use as an inexpensive and effective adsorbent for Cd2+ removal from aqueous solution. PMID:28348509

Silane surface modification for improved bioadhesion of esophageal stents

NASA Astrophysics Data System (ADS)

Karakoy, Mert; Gultepe, Evin; Pandey, Shivendra; Khashab, Mouen A.; Gracias, David H.

2014-08-01

Stent migration occurs in 10-40% of patients who undergo placement of esophageal stents, with higher migration rates seen in those treated for benign esophageal disorders. This remains a major drawback of esophageal stent therapy. In this paper, we propose a new surface modification method to increase the adhesion between self-expandable metallic stents (SEMS) and tissue while preserving their removability. Taking advantage of the well-known affinity between epoxide and amine terminated silane coupling agents with amine and carboxyl groups that are abundant in proteins and related molecules in the human body; we modified the surfaces of silicone coated esophageal SEMS with these adhesive self-assembled monolayers (SAMs). We utilized vapor phase silanization to modify the surfaces of different substrates including PDMS strips and SEMS, and measured the force required to slide these substrates on a tissue piece. Our results suggest that surface modification of esophageal SEMS via covalent attachment of protein-binding coupling agents improves adhesion to tissue and could offer a solution to reduce SEMS migration while preserving their removability.

Uranium passivation by C + implantation: A photoemission and secondary ion mass spectrometry study

NASA Astrophysics Data System (ADS)

Nelson, A. J.; Felter, T. E.; Wu, K. J.; Evans, C.; Ferreira, J. L.; Siekhaus, W. J.; McLean, W.

2006-03-01

Implantation of 33 keV C + ions into polycrystalline U 238 with a dose of 4.3 × 10 17 cm -2 produces a physically and chemically modified surface layer that prevents further air oxidation and corrosion. X-ray photoelectron spectroscopy and secondary ion mass spectrometry were used to investigate the surface chemistry and electronic structure of this C + ion implanted polycrystalline uranium and a non-implanted region of the sample, both regions exposed to air for more than a year. In addition, scanning electron microscopy was used to examine and compare the surface morphology of the two regions. The U 4f, O 1s and C 1s core-level and valence band spectra clearly indicate carbide formation in the modified surface layer. The time-of-flight secondary ion mass spectrometry depth profiling results reveal an oxy-carbide surface layer over an approximately 200 nm thick UC layer with little or no residual oxidation at the carbide layer/U metal transitional interface.

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

Effect of alkaline earth metals on the liquid-phase hydrogenation of hydroquinone over Ru-based catalysts

NASA Astrophysics Data System (ADS)

Li, Hongwei; Ji, Dong; Li, Yu; Liang, Yalan; Li, Gui Xian

2015-12-01

A series of Ru-based catalysts modified by alkaline earth metals were prepared by the impregnation-precipitation method and characterized using transmission electron microscopy, X-ray diffraction, ICP optical emission spectroscopy, Infrared Spectroscopy of adsorbed pyridine analysis and surface area analysis. The performance of the catalysts was measured via liquid-phase hydroquinone hydrogenation reaction. Results show that the Ru-Sr/NaY catalyst has the best activity and selectivity among those Ru-based catalysts. The conversion of hydroquinone and the selectivity to 1,4-cyclohexanediol reached up to 99.6% and 89.6% at optimum reaction condition (700 r/min, 423 K and 5 MPa pressure of H2 in 3 h). This may be attributed to the fact that the right amount of Strontium is beneficial to the good dispersion of the ruthenium nanoclusters on the surface of NaY and modify the acidic properties of the catalyst. Moreover, IR of adsorbed pyridine analysis suggested the proper ratio of L/B acid of the catalysts played an important role in the performance of the hydroquinone hydrogenation reaction.

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.

Synthesis of Stable Interfaces on SnO2 Surfaces for Charge-Transfer Applications

NASA Astrophysics Data System (ADS)

Benson, Michelle C.

The commercial market for solar harvesting devices as an alternative energy source requires them to be both low-cost and efficient to replace or reduce the dependence on fossil fuel burning. Over the last few decades there has been promising efforts towards improving solar devices by using abundant and non-toxic metal oxide nanomaterials. One particular metal oxide of interest has been SnO2 due to its high electron mobility, wide-band gap, and aqueous stability. However SnO2 based solar cells have yet to reach efficiency values of other metal oxides, like TiO2. The advancement of SnO2 based devices is dependent on many factors, including improved methods of surface functionalization that can yield stable interfaces. This work explores the use of a versatile functionalization method through the use of the Cu(I)-catalyzed azide-alkyne cycloaddition (CuAAC) reaction. The CuAAC reaction is capable of producing electrochemically, photochemically, and electrocatalytically active surfaces on a variety of SnO2 materials. The resulting charge-transfer characteristics were investigated as well as an emphasis on understanding the stability of the resulting molecular linkage. We determined the CuAAC reaction is able to proceed through both azide-modified and alkyne-modified surfaces. The resulting charge-transfer properties showed that the molecular tether was capable of supporting charge separation at the interface. We also investigated the enhancement of electron injection upon the introduction of an ultra-thin ZrO2 coating on SnO2. Several complexes were used to fully understand the charge-transfer capabilities, including model systems of ferrocene and a ruthenium coordination complex, a ruthenium mononuclear water oxidation catalyst, and a commercial ruthenium based dye.

Coupled metal partitioning dynamics and toxicodynamics at biointerfaces: a theory beyond the biotic ligand model framework.

PubMed

Duval, Jérôme F L

2016-04-14

A mechanistic understanding of the processes governing metal toxicity to microorganisms (bacteria, algae) calls for an adequate formulation of metal partitioning at biointerfaces during cell exposure. This includes the account of metal transport dynamics from bulk solution to biomembrane and the kinetics of metal internalisation, both potentially controlling the intracellular and surface metal fractions that originate cell growth inhibition. A theoretical rationale is developed here for such coupled toxicodynamics and interfacial metal partitioning dynamics under non-complexing medium conditions with integration of the defining cell electrostatic properties. The formalism explicitly considers intertwined metal adsorption at the biointerface, intracellular metal excretion, cell growth and metal depletion from bulk solution. The theory is derived under relevant steady-state metal transport conditions on the basis of coupled Nernst-Planck equation and continuous logistic equation modified to include metal-induced cell growth inhibition and cell size changes. Computational examples are discussed to identify limitations of the classical Biotic Ligand Model (BLM) in evaluating metal toxicity over time. In particular, BLM is shown to severely underestimate metal toxicity depending on cell exposure time, metal internalisation kinetics, cell surface electrostatics and initial cell density. Analytical expressions are provided for the interfacial metal concentration profiles in the limit where cell-growth is completely inhibited. A rigorous relationship between time-dependent cell density and metal concentrations at the biosurface and in bulk solution is further provided, which unifies previous equations formulated by Best and Duval under constant cell density and cell size conditions. The theory is sufficiently flexible to adapt to toxicity scenarios with involved cell survival-death processes.

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

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.

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

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

The chemical and catalytic properties of nanocrystalline metal oxides prepared through modified sol-gel synthesis

NASA Astrophysics Data System (ADS)

Carnes, Corrie Leigh

The goal of this research was to synthesize, characterize and study the chemical properties of nanocrystalline metal oxides. Nanocrystalline (NC) ZnO, CuO, NiO, Al2O3, and the binary Al2O 3/MgO and ZnO/CuO were prepared through modified sol gel methods. These NC metal oxides were studied in comparison to the commercial (CM) metal oxides. The samples were characterized by XRD, TGA, FTIR, BET, and TEM. The NC samples were all accompanied by a significant increase in surface area and decrease in crystallite size. Several chemical reactions were studied to compare the NC samples to the CM samples. One of the reactions involved a high temperature reaction between carbon tetrachloride and the oxide to form carbon dioxide and the corresponding metal chloride. A similar high temperature reaction was conducted between the metal oxide and hydrogen sulfide to form water and the corresponding metal sulfide. A room temperature gas phase adsorption was studied where SO2 was adsorbed onto the oxide. A liquid phase adsorption conducted at room temperature was the destructive adsorption of paraoxon (a toxic insecticide). In all reactions the NC samples exhibited greater activity, destroying or adsorbing a larger amount of the toxins compared to the CM samples. To better study surface area effects catalytic reactions were also studied. The catalysis of methanol was studied over the nanocrystalline ZnO, CuO, NiO, and ZnO/CuO samples in comparison to their commercial counterparts. In most cases the NC samples proved to be more active catalysts, having higher percent conversions and turnover numbers. A second catalytic reaction was also studied, this reaction was investigated to look at the support effects. The catalysis of cyclopropane to propane was studied over Pt and Co catalysts. These catalysts were supported onto NC and CM alumina by impregnation. By observing differences in the catalytic behavior, support effects have become apparent.

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.

Excimer laser irradiation of metal surfaces

NASA Astrophysics Data System (ADS)

Kinsman, Grant

In this work a new method of enhancing CO2 laser processing by modifying the radiative properties of a metal surface is studied. In this procedure, an excimer laser (XeCl) or KrF) exposes the metal surface to overlapping pulses of high intensity, 10(exp 8) - 10(exp 9) W cm(exp -2), and short pulse duration, 30 nsec FWHM (Full Width Half Maximum), to promote structural and chemical change. The major processing effect at these intensities is the production of a surface plasma which can lead to the formation of a laser supported detonation wave (LSD wave). This shock wave can interact with the thin molten layer on the metal surface influencing to a varying degree surface oxidation and roughness features. The possibility of the expulsion, oxidation and redeposition of molten droplets, leading to the formation of micron thick oxide layers, is related to bulk metal properties and the incident laser intensity. A correlation is found between the expulsion of molten droplets and a Reynolds number, showing the interaction is turbulent. The permanent effects of these interactions on metal surfaces are observed through scanning electron microscopy (SEM), transient calorimetric measurements and Fourier transform infrared (FTIR) spectroscopy. Observed surface textures are related to the scanning procedures used to irradiate the metal surface. Fundamental radiative properties of a metal surface, the total hemispherical emissivity, the near-normal spectral absorptivity, and others are examined in this study as they are affected by excimer laser radiation. It is determined that for heavily exposed Al surface, alpha' (10.6 microns) can be increased to values close to unity. Data relating to material removal rates and chemical surface modification for excimer laser radiation is also discussed. The resultant reduction in the near-normal reflectivity solves the fundamental problem of coupling laser radiation into highly reflective and conductive metals such as copper and aluminum. The increased absorption at 10.6 microns enables enhanced CO2 laser drilling and cutting rates in electrolytic Cu at incident intensities, I(0) of approximately 10(exp 6) W cm(exp -2). Data showing enhanced drilling rates in Al 1100-H14 is also presented. In these regimes the majority of material is removed in the liquid state. The amount of molten material formed can be directly attributed to the enhanced initial coupling of the excimer laser irradiated surface. Previously, to process Cu and Al it has been required to increase I(0) until material removal occurs through vaporization. This fundamental data and analysis provides a basic framework for further work in this new field of study.

Enhanced Lifetime of Polymer Solar Cells by Surface Passivation of Metal Oxide Buffer Layers.

PubMed

Venkatesan, Swaminathan; Ngo, Evan; Khatiwada, Devendra; Zhang, Cheng; Qiao, Qiquan

2015-07-29

The role of electron selective interfaces on the performance and lifetime of polymer solar cells were compared and analyzed. Bilayer interfaces consisting of metal oxide films with cationic polymer modification namely poly ethylenimine ethoxylated (PEIE) were found to enhance device lifetime compared to bare metal oxide films when used as an electron selective cathode interface. Devices utilizing surface-modified metal oxide layers showed enhanced lifetimes, retaining up to 85% of their original efficiency when stored in ambient atmosphere for 180 days without any encapsulation. The work function and surface potential of zinc oxide (ZnO) and ZnO/PEIE interlayers were evaluated using Kelvin probe and Kelvin probe force microscopy (KPFM) respectively. Kelvin probe measurements showed a smaller reduction in work function of ZnO/PEIE films compared to bare ZnO films when aged in atmospheric conditions. KPFM measurements showed that the surface potential of the ZnO surface drastically reduces when stored in ambient air for 7 days because of surface oxidation. Surface oxidation of the interface led to a substantial decrease in the performance in aged devices. The enhancement in the lifetime of devices with a bilayer interface was correlated to the suppressed surface oxidation of the metal oxide layers. The PEIE passivated surface retained a lower Fermi level when aged, which led to lower trap-assisted recombination at the polymer-cathode interface. Further photocharge extraction by linearly increasing voltage (Photo-CELIV) measurements were performed on fresh and aged samples to evaluate the field required to extract maximum charges. Fresh devices with a bare ZnO cathode interlayer required a lower field than devices with ZnO/PEIE cathode interface. However, aged devices with ZnO required a much higher field to extract charges while aged devices with ZnO/PEIE showed a minor increase compared to the fresh devices. Results indicate that surface modification can act as a suitable passivation layer to suppress oxidation in metal oxide thin films for enhanced lifetime in inverted organic solar cells.

Modification of Structure and Tribological Properties of the Surface Layer of Metal-Ceramic Composite under Electron Irradiation in the Plasmas of Inert Gases

NASA Astrophysics Data System (ADS)

Ovcharenko, V. E.; Ivanov, K. V.; Mohovikov, A. A.; Yu, B.; Xu, Yu; Zhong, L.

2018-01-01

Metal-ceramic composites are the main materials for high-load parts in tribomechanical systems. Modern approaches to extend the operation life of tribomechanical systems are based on increasing the strength and tribological properties of the surface layer having 100 to 200 microns in depth. The essential improvement of the properties occurs when high dispersed structure is formed in the surface layer using high-energy processing. As a result of the dispersed structure formation the more uniform distribution of elastic stresses takes place under mechanical or thermal action, the energy of stress concentrators emergence significantly increases and the probability of internal defects formation reduces. The promising method to form the dispersed structure in the surface layer is pulse electron irradiation in the plasmas of inert gases combining electron irradiation and ion bombardment in one process. The present work reports upon the effect of pulse electron irradiation in plasmas of different inert gases with different atomic mass and ionization energy on the structure and tribological properties of the surface layer of TiC/(Ni-Cr) metal-ceramic composite with the volume ratio of the component being 50:50. It is experimentally shown that high-dispersed heterophase structure with a fraction of nanosized particles is formed during the irradiation. Electron microscopy study reveals that refining of the initial coarse TiC particles occurs via their dissolution in the molten metal binder followed by the precipitation of secondary fine particles in the interparticle layers of the binder. The depth of modified layer and the fraction of nanosized particles increase when the atomic number of the plasma gas increases and ionization energy decreases. The wear resistance of metal-ceramic composite improves in accordance to the formation of nanocrystalline structure in the surface layer.

Tartrazine modified activated carbon for the removal of Pb(II), Cd(II) and Cr(III).

PubMed

Monser, Lotfi; Adhoum, Nafaâ

2009-01-15

A two in one attempt for the removal of tartrazine and metal ions on activated carbon has been developed. The method was based on the modification of activated carbon with tartrazine then its application for the removal of Pb(II), Cd(II) and Cr(III) ions at different pH values. Tartrazine adsorption data were modelled using both Langmuir and Freundlich classical adsorption isotherms. The adsorption capacities qm were 121.3, 67 and 56.7mgg(-1) at initial pH values of 1.0, 6.0 and 10, respectively. The adsorption of tartrazine onto activated carbon followed second-order kinetic model. The equilibrium time was found to be 240min at pH 1.0 and 120min at pH 10 for 500mgL(-1) tartrazine concentration. A maximum removal of 85% was obtained after 1h of contact time. The presence of tartrazine as modifier enhances attractive electrostatic interactions between metal ions and carbon surface. The adsorption capacity for Pb(II), Cd(II) and Cr(III) ions has been improved with respect to non-modified carbon reaching a maximum of 140%. The adsorption capacity was found to be a pH dependent for both modified and non-modified carbon with a greater adsorption at higher pH values except for Cr(III). The enhancement percent of Pb(II), Cd(II) and Cr(III) at different pH values was varied from 28% to 140% with respect to non-modified carbon. The amount of metal ions adsorbed using static regime was 11-40% higher than that with dynamic mode. The difference between adsorption capacities could be attributed to the applied flow rate.

Reversible cobalt ion binding to imidazole-modified nanopipettes

PubMed Central

Sa, Niya; Fu, Yaqin; Baker, Lane A.

2010-01-01

In this report, we demonstrate that quartz nanopipettes modified with an imidazole-terminated silane respond to metal ions (Co2+) in solution. The response of nanopipettes is evaluated through examination of the ion current rectification response. By cycling nanopipettes between solutions of different pH, adsorbed Co2+ can be released from the nanopipette surface, to regenerate binding sites of the nanopipette. These results demonstrate that rectification-based sensing strategies for nanopore sensors can benefit from selection of recognition elements with intermediate binding affinities, such that reversible responses to be attained. PMID:21090777

Reversible cobalt ion binding to imidazole-modified nanopipettes.

PubMed

Sa, Niya; Fu, Yaqin; Baker, Lane A

2010-12-15

In this report, we demonstrate that quartz nanopipettes modified with an imidazole-terminated silane respond to metal ions (Co(2+)) in solution. The response of nanopipettes is evaluated through examination of the ion current rectification ratio. When nanopipettes are cycled between solutions of different pH, adsorbed Co(2+) can be released from the nanopipette surface, to regenerate binding sites of the nanopipette. These results demonstrate that rectification-based sensing strategies for nanopore sensors can benefit from selection of recognition elements with intermediate binding affinities, such that reversible responses can be attained.

Inhibiting Metal Oxide Atomic Layer Deposition: Beyond Zinc Oxide

DOE PAGES

Sampson, Matthew D.; Emery, Jonathan D.; Pellin, Michael J.; ...

2017-04-05

The atomic layer deposition (ALD) of several metal oxides is selectivity inhibited on alkanethiol self-assembled monolayers (SAMs) on Au and the eventual nucleation mechanism is investigated. The inhibition ability of the SAM is significantly improved by the in situ H 2-plasma pretreatment of the Au substrate prior to gas-phase deposition of a long-chain alkanethiol, 1-dodecanethiol (DDT). This more rigorous surface preparation inhibits even aggressive oxide ALD precursors, including trimethylaluminum and water, for at least 20 cycles. We study the effect that ALD precursor purge times, growth temperature, alkanethiol chain length, alkanethiol deposition time, and plasma treatment time have on Almore » 2O 3 ALD inhibition. This is the first example of Al 2O 3 ALD inhibition from a vapor-deposited SAM. Inhibition of Al 2O 3, ZnO, and MnO ALD processes are compared, revealing the versatility of this selective surface treatment. As a result, atomic force microscopy (AFM) and grazing incidence x-ray fluorescence (GIXRF) further reveals insight into the mechanism by which the well-defined surface chemistry of ALD may eventually be circumvented to allow metal oxide nucleation and growth on SAM-modified surfaces.« less

Inhibiting Metal Oxide Atomic Layer Deposition: Beyond Zinc Oxide

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

Sampson, Matthew D.; Emery, Jonathan D.; Pellin, Michael J.

The atomic layer deposition (ALD) of several metal oxides is selectivity inhibited on alkanethiol self-assembled monolayers (SAMs) on Au and the eventual nucleation mechanism is investigated. The inhibition ability of the SAM is significantly improved by the in situ H 2-plasma pretreatment of the Au substrate prior to gas-phase deposition of a long-chain alkanethiol, 1-dodecanethiol (DDT). This more rigorous surface preparation inhibits even aggressive oxide ALD precursors, including trimethylaluminum and water, for at least 20 cycles. We study the effect that ALD precursor purge times, growth temperature, alkanethiol chain length, alkanethiol deposition time, and plasma treatment time have on Almore » 2O 3 ALD inhibition. This is the first example of Al 2O 3 ALD inhibition from a vapor-deposited SAM. Inhibition of Al 2O 3, ZnO, and MnO ALD processes are compared, revealing the versatility of this selective surface treatment. As a result, atomic force microscopy (AFM) and grazing incidence x-ray fluorescence (GIXRF) further reveals insight into the mechanism by which the well-defined surface chemistry of ALD may eventually be circumvented to allow metal oxide nucleation and growth on SAM-modified surfaces.« less

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).

Controlling the surface photovoltage on WSe2 by surface chemical modification

NASA Astrophysics Data System (ADS)

Liu, Ro-Ya; Ozawa, Kenichi; Terashima, Naoya; Natsui, Yuto; Feng, Baojie; Ito, Suguru; Chen, Wei-Chuan; Cheng, Cheng-Maw; Yamamoto, Susumu; Kato, Hiroo; Chiang, Tai-Chang; Matsuda, Iwao

2018-05-01

The surface photovoltage (SPV) effect is key to the development of opto-electronic devices such as solar-cells and photo-detectors. For the prototypical transition metal dichalcogenide WSe2, core level and valence band photoemission measurements show that the surface band bending of pristine cleaved surfaces can be readily modified by adsorption with K (an electron donor) or C60 (an electron acceptor). Time-resolved pump-probe photoemission measurements reveal that the SPV for pristine cleaved surfaces is enhanced by K adsorption, but suppressed by C60 adsorption, and yet the SPV relaxation time is substantially shortened in both cases. Evidently, adsorbate-induced electronic states act as electron-hole recombination centers that shorten the carrier lifetime.

Chemically-modified activated carbon with ethylenediamine for selective solid-phase extraction and preconcentration of metal ions.

PubMed

Li, Zhenhua; Chang, Xijun; Zou, Xiaojun; Zhu, Xiangbing; Nie, Rong; Hu, Zheng; Li, Ruijun

2009-01-26

A new method that utilizes ethylenediamine-modified activated carbon (AC-EDA) as a solid-phase extractant has been developed for simultaneous preconcentration of trace Cr(III), Fe(III), Hg(II) and Pb(II) prior to the measurement by inductively coupled plasma optical emission spectrometry (ICP-OES). The new sorbent was prepared by oxidative surface modification. Experimental conditions for effective adsorption of trace levels of Cr(III), Fe(III), Hg(II) and Pb(II) were optimized with respect to different experimental parameters using batch and column procedures in detail. The optimum pH value for the separation of metal ions simultaneously on the new sorbent was 4.0. Complete elution of absorbed metal ions from the sorbent surface was carried out using 3.0 mL of 2% (%w/w) thiourea and 0.5 mol L(-1) HCl solution. Common coexisting ions did not interfere with the separation and determination of target metal ions. The maximum static adsorption capacity of the sorbent at optimum conditions was found to be 39.4, 28.9, 60.5 and 49.9 mg g(-1) for Cr(III), Fe(III), Hg(II) and Pb(II), respectively. The time for 94% adsorption of target metal ions was less than 2 min. The detection limits of the method was found to be 0.28, 0.22, 0.09 and 0.17 ng mL(-1) for Cr(III), Fe(III), Hg(II) and Pb(II), respectively. The precision (R.S.D.) of the method was lower 4.0% (n=8). The prepared sorbent as solid-phase extractant was successfully applied for the preconcentration of trace Cr(III), Fe(III), Hg(II) and Pb(II) in natural and certified samples with satisfactory results.

Adsorption of benzyldimethylhexadecylammonium chloride at the hydrophobic silica-water interface studied by total internal reflection Raman spectroscopy: effects of silica surface properties and metal salt addition.

PubMed

Grenoble, Zlata; Baldelli, Steven

2013-08-29

The adsorption of the cationic surfactant benzyldimethylhexadecylammonium (BDMHA(+)) chloride was studied at an octadecyltrichlorosilane (OTS)-monolayer-modified silica-water interface by Raman spectroscopy in total internal reflection (TIR) geometry. The present study demonstrates the capabilities of this spectroscopic technique to evaluate thermodynamic and kinetic BDMHA(+)Cl(-) adsorption properties at the hydrophobic silica surface. The surface coverage of BDMHA(+) decreased by 50% at the hydrophobic OTS-silica surface relative to the surface coverage on bare silica; the dominating driving mechanisms for surfactant adsorption were identified as hydrophobic effects and head group charge screening by the electrolyte counterions. Addition of magnesium metal salt (MgCl2) to the aqueous solution (∼ neutral pH) lowered the surface coverage and moderately increased the Langmuir adsorption constants relative to those of the pure surfactant. These trends were previously observed at the hydrophilic, negatively charged silica surface but with a smaller change in the Gibbs free energy of adsorption at the hydrophobic silica surface. The hydrophobic OTS-silica surface properties resulted in shorter times for the surfactant to reach steady-state adsorption conditions compared to the slow adsorption kinetics previously seen with the surfactant at the hydrophilic surface. Adsorption isotherms, based on Raman signal intensities from spectral analysis, were developed according to the Langmuir adsorption model for the pure surfactant at the OTS-silica-water interface; the modified Langmuir model was applied to the surfactant adsorption in the presence of 5, 10, 50, and 100 mM magnesium chloride. Spectral analysis of the Raman scattering intensities and geometric considerations suggests a hemimicelle-type surface aggregate as the most likely surfactant structure at the OTS-silica surface. The different kinetics observed at the hydrophilic versus the hydrophobic silica surface further indicate that the surface charge and potential influence the surfactant diffusion and kinetic rates of adsorption at the silica-water interface.

Investigation of gas surface interactions at self-assembled silicon surfaces acting as gas sensors

NASA Astrophysics Data System (ADS)

Narducci, Dario; Bernardinello, Patrizia; Oldani, Matteo

2003-05-01

This paper reports the results of an investigation aimed at using self-assembled monolayers to modify the supramolecular interactions between Si surfaces and gaseous molecules. The specific goal is that of employing molecularly imprinted silicon surfaces to develop a new class of chemical sensors capable to detect species with enhanced selectivity. Single-crystal p-type (0 0 1) silicon has been modified by grafting organic molecules onto its surface by using wet chemistry synthetic methods. Silicon has been activated toward nucleophilic attack by brominating its surface using a modified version of the purple etch, and aromatic fragments have been bonded through the formation of direct Si-C bonds onto it using Grignard reagents or lithium aryl species. Formation of self-assembled monolayers (SAMs) was verified by using vibrational spectroscopy. Porous metal-SAM-Si diodes have been successfully tested as resistive chemical sensors toward NO x, SO x, CO, NH 3 and methane. Current-voltage characteristics measured at different gas compositions showed that the mechanism of surface electron density modulation involves a modification of the junction barrier height upon gas adsorption. Quantum-mechanical simulations of the interaction mechanism were carried out using different computational methods to support such an interaction mechanism. The results obtained appear to open up new relevant applications of the SAM techniques in the area of gas sensing.

Modified biopolymers as sorbents for the removal of naphthenic acids from oil sands process affected water (OSPW).

PubMed

Arshad, Muhammad; Khosa, M A; Siddique, Tariq; Ullah, Aman

2016-11-01

Oil sands operations consume large volumes of water in bitumen extraction process and produce tailings that express pore water to the surface of tailings ponds known as oil sands process-affected water (OSPW). The OSPW is toxic and cannot be released into the environment without treatment. In addition to metals, dissolved solids, dissolved gases, hydrocarbons and polyaromatic compounds etc., OSPW also contains a complex mixture of dissolved organic acids, referred to as naphthenic acids (NAs). The NAs are highly toxic and react with metals to develop highly corrosive functionalities which cause corrosion in the oil sands processing and refining processes. We have chemically modified keratin biopolymer using polyhedral oligomeric silsesquioxanes (POSS) nanocages and goethite dopant to unfold keratinous structure for improving functionality. The untreated neat keratin and two modified sorbents were characterized to investigate structural, morphological, dimensional and thermal properties. These sorbents were then tested for the removal of NAs from OSPW. The NAs were selectively extracted and quantified before and after sorption process. The biosorption capacity (Q), rejection percentage (R%) and isotherm models were studied to investigate NAs removal efficiency of POSS modified keratin biopolymer (PMKB) and goethite modified keratin biopolymer (GMKB) from aliquots of OSPW. Copyright © 2016 Elsevier Ltd. All rights reserved.

Tea stains-inspired initiator primer for surface grafting of antifouling and antimicrobial polymer brush coatings.

PubMed

Pranantyo, Dicky; Xu, Li Qun; Neoh, Koon-Gee; Kang, En-Tang; Ng, Ying Xian; Teo, Serena Lay-Ming

2015-03-09

Inspired by tea stains, plant polyphenolic tannic acid (TA) was beneficially employed as the primer anchor for functional polymer brushes. The brominated TA (TABr) initiator primer was synthesized by partial modification of TA with alkyl bromide functionalities. TABr with trihydroxyphenyl moieties can readily anchor on a wide range of substrates, including metal, metal oxide, polymer, glass, and silicon. Concomitantly, the alkyl bromide terminals serve as initiation sites for atom transfer radical polymerization (ATRP). Cationic [2-(methacryloyloxy)ethyl]trimethylammonium chloride (META) and zwitterionic 2-methacryloyloxyethyl phosphorylcholine (MPC) and N-(3-sulfopropyl)-N-(methacryloxyethyl)-N,N-dimethylammonium betaine (SBMA) were graft-polymerized from the TABr-anchored stainless steel (SS) surface. The cationic polymer brushes on the modified surfaces are bactericidal, while the zwitterionic coatings exhibit resistance against bacterial adhesion. In addition, microalgal attachment (microfouling) and barnacle cyprid settlement (macrofouling) on the functional polymer-grafted surfaces were significantly reduced, in comparison to the pristine SS surface. Thus, the bifunctional TABr initiator primer provides a unique surface anchor for the preparation of functional polymer brushes for inhibiting both microfouling and macrofouling.

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.

Self-assembled Monolayer Mediated Surface Environment Modification of Poly(vinylpyrrolidone)-Coated Hollow Au-Ag Nanoshells for Enhanced Loading of Hydrophobic Drug and Efficient Multimodal Therapy.

PubMed

Jang, Hongje; Kim, Dong-Eun; Min, Dal-Hee

2015-06-17

Hollow Au-Ag bimetallic nanoshell possessing hydrophobic interior space and hydrophilic exterior surface was prepared and its application as a chemo-thermo-gene therapeutic agent based on its high payload of multiple drugs having different water solubility was demonstrated. The multifunctional drug delivery system is based on the hydrophobic interior created by the self-assembled monolayer (SAM) of hexanethiol onto the inner surface of the hollow metallic nanoshells whereas the outer surface was mostly coated by hydrophilic biocompatible polymer. The nanoshells having surface environment modified by hexanethiol SAMs provided high capacity both for hydrophilic DNAzyme (Dz) to induce gene silencing and for hydrophobic SN38 (7-ethyl-10-hydroxycamptothecin), anticancer drug. The release of the loaded Dz and SN38 was independently triggered by an acidic environment and by photothermal temperature elevation upon irradiation, respectively. The chemo-thermo-gene multitherapy based on the present nanoshells having modified surface environment showed high efficacy in quantitative cell-based assays using Huh7 human liver cell containing hepatitis C viral NS3 gene replicon RNA.

Electrochemical and density functional theory investigation on the differential behaviors of core-ring structured NiCo2O4 nanoplatelets toward heavy metal ions.

PubMed

Liao, Jianjun; Zhang, Junping; Wang, Cai-Zhuang; Lin, Shiwei

2018-08-31

In order to further improve the electroanalytical performance toward heavy metal ions, core-ring structured NiCo 2 O 4 nanoplatelets were used to modify glass carbon electrode (GCE) for the determination of heavy metal ions in water. Owing to the high surface area of NiCo 2 O 4 nanoplatelets, the Pb(II) sensitivity increased by a factor of 1.70, and the detection limit decreased by a factor of 2.64 as compared to solid NiCo 2 O 4 nanoparticles modified GCE. Interestingly, NiCo 2 O 4 nanoplatelets showed different sensitivities toward heavy metal ions with the same valence states, following the order Pb(II) > Cd(II) > Hg(II) > Cu(II). To better and scientifically understand the difference in sensitivity, adsorption and desorption abilities were integrated into account. Density functional theory calculations verified that the adsorption capability of NiCo 2 O 4 toward Pb(II) was strongest among all heavy metal ions, thereby resulting in the largest sensitivity. Further desorption current measurements indicated the large desorption barrier of Cu(II) was another important factor leading to its lowest sensitivity. Finally, the applicability of the proposed method was demonstrated by the detection of heavy metal ions in real seawater. Copyright © 2018 Elsevier B.V. All rights reserved.

Ru-decorated Pt surfaces as model fuel cell electrocatalysts for CO electrooxidation.

PubMed

Maillard, F; Lu, G-Q; Wieckowski, A; Stimming, U

2005-09-01

This feature article concerns Pt surfaces modified (decorated) by ruthenium as model fuel cell electrocatalysts for electrooxidation processes. This work reveals the role of ruthenium promoters in enhancing electrocatalytic activity toward organic fuels for fuel cells, and it particularly concerns the methanol decomposition product, surface CO. A special focus is on surface mobility of the CO as it is catalytically oxidized to CO(2). Different methods used to prepare Ru-decorated Pt single crystal surfaces as well as Ru-decorated Pt nanoparticles are reviewed, and the methods of characterization and testing of their activity are discussed. The focus is on the origin of peak splitting involved in the voltammetric electrooxidation of CO on Ru-decorated Pt surfaces, and on the interpretative consequences of the splitting for single crystal and nanoparticle Pt/Ru bimetallic surfaces. Apparently, screening through the literature allows formulating several models of the CO stripping reaction, and the validity of these models is discussed. Major efforts are made in this article to compare the results reported by the Urbana-Champaign group and the Munich group, but also by other groups. As electrocatalysis is progressively more and more driven by theory, our review of the experimental findings may serve to summarize the state of the art and clarify the roads ahead. Future studies will deal with highly dispersed and reactive nanoscale surfaces and other more advanced catalytic materials for fuel cell catalysis and related energy applications. It is expected that the metal/metal and metal/substrate interactions will be increasingly investigated on atomic and electronic levels, with likewise increasing participation of theory, and the structure and reactivity of various monolayer catalytic systems involving more than two metals (that is ternary and quaternary systems) will be interrogated.

Higher Order Multipole Potentials and Electrostatic Screening Effects on Cohesive Energy and Bulk Modulus of Metallic Nanoparticles

NASA Astrophysics Data System (ADS)

Barakat, T.

2011-12-01

Higher order multipole potentials and electrostatic screening effects are introduced to incorporate the dangling bonds on the surface of a metallic nanopaticle and to modify the coulomb like potential energy terms, respectively. The total interaction energy function for any metallic nanoparticle is represented in terms of two- and three-body potentials. The two-body part is described by dipole-dipole interaction potential, and in the three-body part, triple-dipole (DDD) and dipole-dipole-quadrupole (DDQ) terms are included. The size-dependent cohesive energy and bulk modulus are observed to decrease with decreasing sizes, a result which is in good agreement with the experimental values of Mo and W nanoparticles.

Continuous leaching modifies the surface properties and metal(loid) sorption of sludge-derived biochar.

PubMed

Feng, Mingyu; Zhang, Weihua; Wu, Xueyong; Jia, Yanming; Jiang, Chixiao; Wei, Hang; Qiu, Rongliang; Tsang, Daniel C W

2018-06-01

After the application of sludge derived biochar (SDBC) for soil stabilization, it is subjected to continuous leaching that may change its surface properties and metal(loid) immobilization performance. This study simulated the continuous leaching through the fresh SDBC sample in columns with unsaturated and saturated zones under flushing with 0.01M NaNO 3 solution (pH5.5) and acidic solution (pH adjusted to 3.2 by HNO 3 :H 2 SO 4 =1:2), respectively. The resultant changes were assessed in terms of the SDBC surface characteristics and metal(loid) sorption capacities. Continuous leaching was found to gradually decrease the density of basic functional groups and increase the density of carboxyl groups as well as cation exchange capacity on the SDBC surface. It was attributed to the surface acidification and oxidation process by the leaching process, yet it occurred to a lesser extent than the atmospheric exposure. Continuous leaching increased Pb(II), Cr(VI), and As(III) sorption capacity of the SDBC, probably because the increase in carboxyl groups promoted inner-sphere complexation and Fe oxidation as revealed by spectroscopic analysis. It was noteworthy that the SDBC in the unsaturated and saturated zones under continuous leaching displayed distinctive effects on metal(loid) sorption capacity than the atmospheric exposure. Future investigations are needed for understanding the fate and interactions of the SDBC under varying redox conditions and intermittent leaching process. Copyright © 2017. Published by Elsevier B.V.

Pb(II) and Cd(II) removal from aqueous solution, shipyard wastewater, and landfill leachate by modified Rhizopus oryzae biomass

NASA Astrophysics Data System (ADS)

Naeimi, Behrouz; Foroutan, Rauf; Ahmadi, Bahram; Sadeghzadeh, Farzaneh; Ramavandi, Bahman

2018-04-01

This study was designed to remove Pb(II) and Cd(II) from aqueous solution, shipyard wastewater, and sanitary landfill leachate using an alkaline-modified Rhizopus oryzae biomass. According to the Fourier transform infrared test, different functional groups like O–H, N–H, C=O, and P–O were detected in the bioadsorbent. The x-ray fluorescence (XRF) analysis showed that CaO, P2O3, and SO3 oxides have the highest content in the bioadsorbent. The surface area of modified Rhizopus oryzae was obtained as 20.32 m2 g‑1. The effect of initial pH, temperature, contact time, and bioadsorbent dose on the metals removal was discussed. At optimal conditions, maximum Pb(II) and Cd(II) removal was obtained 95.66% and 94.55%, respectively. Freundlich model was well- accurately described the equilibrium data. Among four studied models, the pseudo-second-order was better able to describe the kinetic behavior of the bioadsorption process. The amount of enthalpy, free energy of Gibbs, and entropy parameters indicated that the bioadsorption process of studied heavy metals is negative, exothermic, and spontaneous. The amount of heavy metals in a shipyard wastewater and sanitary landfill leachate was significantly decreased by using the developed bioadsorbent.

Electrochemical response of carbon paste electrode modified with mixture of titanium dioxide/zirconium dioxide in the detection of heavy metals: lead and cadmium.

PubMed

Nguyen, Phuong Khanh Quoc; Lunsford, Suzanne K

2012-11-15

A novel carbon modified electrode was developed by incorporating titanium dioxide/zirconium dioxide into the graphite carbon paste electrode to detect heavy metals-cadmium and lead. In this work, the development of the novel titanium dioxide/zirconium dioxide modified carbon paste electrode was studied to determine the optimum synthesis conditions related to the temperature, heating duration, amount and ratio of titanium dioxide/zirconium dioxide, and amount of surfactant, to create the most reproducible results. Using cyclic voltammetric (CV) analysis, this study has proven that the novel titanium dioxide/zirconium dioxide can be utilized to detect heavy metals-lead and cadmium, at relatively low concentrations (7.6×10(-6) M and 1.1×10(-5) M for Pb and Cd, respectively) at optimum pH value (pH=3). From analyzing CV data the optimal electrodes surface area was estimated to be 0.028 (±0.003) cm(2). Also, under the specific experimental conditions, electron transfer coefficients were estimated to be 0.44 and 0.33 along with the heterogeneous electron transfer rate constants of 5.64×10(-3) and 2.42×10(-3) (cm/s) for Pb and Cd, respectively. Copyright © 2012 Elsevier B.V. All rights reserved.

DOE Award No. DE-FC36-03GO13108 NOVEL NON-PRECIOUS METAL CATALYSTS FOR PEMFC: CATALYST SELECTION THROUGH MOLECULAR MODELING AND DURABILITY STUDIES Final Report (September 2003 – October 2008)

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

Branko N. Popov

2009-03-03

The objective of this project is to develop novel non-precious metal electrocatalysts for oxygen reduction reaction (ORR), and demonstrate the potential of the catalysts to perform at least as good as conventional Pt catalysts currently in use in polymer electrolyte membrane fuel cell (PEMFC) with a cost at least 50 % less than a target of 0.2 g (Pt loading)/peak kW and with durability > 2,000 h operation with less than 10 % power degradation. A novel nitrogen-modified carbon-based catalyst was obtained by modifying carbon black with nitrogen-containing organic precursor in the absence of transition metal precursor. The catalyst showsmore » the onset potential of approximately 0.76 V (NHE) for ORR and the amount of H2O2 of approximately 3% at 0.5 V (NHE). Furthermore, a carbon composite catalyst was achieved through the high-temperature pyrolysis of the precursors of transition metal (Co and Fe) and nitrogen supported on the nitrogen-modified carbon-based catalyst, followed by chemical post-treatment. This catalyst showed an onset potential for ORR as high as 0.87 V (NHE), and generated less than 1 % of H2O2. The PEM fuel cell exhibited a current density of 2.3 A cm-2 at 0.2 V for a catalyst loading of 6.0 mg cm-2. No significant performance degradation was observed for 480 h continuous operation. The characterization studies indicated that the metal-nitrogen chelate complexes decompose at the temperatures above 800 oC. During the pyrolysis, the transition metals facilitate the incorporation of pyridinic and graphitic nitrogen groups into the carbon matrix, and the carbon surface modified with nitrogen is active for ORR. In order to elucidate the role of transition metal precursor played in the formation of active sites in the non-precious metal catalysts, a novel ruthenium-based chelate (RuNx) catalyst was synthesized by using RuCl3 and propylene diammine as the Ru and N precursors, respectively, followed by high-temperature pyrolysis. This catalyst exhibited comparable catalytic activity and selectivity for ORR as the Pt catalyst. A theoretical analysis is made of the four-electron reduction reaction of oxygen to water over the mixed anion and cation (202) surface of pentlandite structure Co9Se8, one of several selenide phases. Reversible potentials for forming adsorbed reaction intermediates in acid are predicted using adsorption energies calculated with the Vienna ab initio simulation program (VASP) and the known bulk solution values together in a linear Gibbs energy relationship. The effect of hydrophobic and structural properties of a single/dual-layer cathode gas diffusion layer on mass transport in PEM fuel cells was studied using an analytical expression. The simulations indicated that liquid water transport at the cathode is controlled by the fraction of hydrophilic surface and the average pore diameter in the cathode gas diffusion layer. The optimized hydrophobicity and pore geometry in a dual-layer cathode GDL leads to an effective water management, and enhances the oxygen diffusion kinetics.« less

DOE Award No. DE-FC36-03GO13108 NOVEL NON-PRECIOUS METAL CATALYSTS FOR PEMFC: CATALYST SELECTION THROUGH MOLECULAR MODELING AND DURABILITY STUDIES Final Report (September 2003 – October 2008)

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

Branko N. Popov

2009-02-20

The objective of this project is to develop novel non-precious metal electrocatalysts for oxygen reduction reaction (ORR), and demonstrate the potential of the catalysts to perform at least as good as conventional Pt catalysts currently in use in polymer electrolyte membrane fuel cell (PEMFC) with a cost at least 50 % less than a target of 0.2 g (Pt loading)/peak kW and with durability > 2,000 h operation with less than 10 % power degradation. A novel nitrogen-modified carbon-based catalyst was obtained by modifying carbon black with nitrogen-containing organic precursor in the absence of transition metal precursor. The catalyst showsmore » the onset potential of approximately 0.76 V (NHE) for ORR and the amount of H2O2 of approximately 3% at 0.5 V (NHE). Furthermore, a carbon composite catalyst was achieved through the high-temperature pyrolysis of the precursors of transition metal (Co and Fe) and nitrogen supported on the nitrogen-modified carbon-based catalyst, followed by chemical post-treatment. This catalyst showed an onset potential for ORR as high as 0.87 V (NHE), and generated less than 1 % of H2O2. The PEM fuel cell exhibited a current density of 2.3 A cm-2 at 0.2 V for a catalyst loading of 6.0 mg cm-2. No significant performance degradation was observed for 480 h continuous operation. The characterization studies indicated that the metal-nitrogen chelate complexes decompose at the temperatures above 800 oC. During the pyrolysis, the transition metals facilitate the incorporation of pyridinic and graphitic nitrogen groups into the carbon matrix, and the carbon surface modified with nitrogen is active for ORR. In order to elucidate the role of transition metal precursor played in the formation of active sites in the non-precious metal catalysts, a novel ruthenium-based chelate (RuNx) catalyst was synthesized by using RuCl3 and propylene diammine as the Ru and N precursors, respectively, followed by high-temperature pyrolysis. This catalyst exhibited comparable catalytic activity and selectivity for ORR as the Pt catalyst. A theoretical analysis is made of the four-electron reduction reaction of oxygen to water over the mixed anion and cation (202) surface of pentlandite structure Co9Se8, one of several selenide phases. Reversible potentials for forming adsorbed reaction intermediates in acid are predicted using adsorption energies calculated with the Vienna ab initio simulation program (VASP) and the known bulk solution values together in a linear Gibbs energy relationship. The effect of hydrophobic and structural properties of a single/dual-layer cathode gas diffusion layer on mass transport in PEM fuel cells was studied using an analytical expression. The simulations indicated that liquid water transport at the cathode is controlled by the fraction of hydrophilic surface and the average pore diameter in the cathode gas diffusion layer. The optimized hydrophobicity and pore geometry in a dual-layer cathode GDL leads to an effective water management, and enhances the oxygen diffusion kinetics.« less

Nanoparticles Formed Onto/Into Halloysite Clay Tubules: Architectural Synthesis and Applications.

PubMed

Vinokurov, Vladimir A; Stavitskaya, Anna V; Glotov, Aleksandr P; Novikov, Andrei A; Zolotukhina, Anna V; Kotelev, Mikhail S; Gushchin, Pawel A; Ivanov, Evgenii V; Darrat, Yusuf; Lvov, Yuri M

2018-01-04

Nanoparticles, being objects with high surface area are prone to agglomeration. Immobilization onto solid supports is a promising method to increase their stability and it allows for scalable industrial applications, such as metal nanoparticles adsorbed to mesoporous ceramic carriers. Tubular nanoclay - halloysite - can be an efficient solid support, enabling the fast and practical architectural (inside / outside) synthesis of stable metal nanoparticles. The obtained halloysite-nanoparticle composites can be employed as advanced catalysts, ion-conducting membrane modifiers, inorganic pigments, and optical markers for biomedical studies. Here, we discuss the possibilities to synthesize halloysite decorated with metal, metal chalcogenide, and carbon nanoparticles, and to use these materials in various fields, especially in catalysis and petroleum refinery. © 2018 The Chemical Society of Japan & Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Three-year clinical evaluation of two ceramic crown systems: a preliminary study.

PubMed

Etman, Maged K; Woolford, M J

2010-02-01

The clinical performance and failure mechanisms of recently introduced ceramic crown systems used to restore posterior teeth have not been adequately examined. The purpose of this prospective clinical study was to evaluate and compare the clinical performance of 2 new ceramic crown systems with that of metal ceramic crowns using modified United States Public Health Services (USPHS) criteria. Ninety posterior teeth requiring crown restorations in 48 patients were randomized into 3 equal groups (n=30) for which different crown systems were used: an experimental hot-pressed glass ceramic based on a modified lithium disilicate ceramic (IPS e.max Press), an alumina-coping-based ceramic (Procera AllCeram), and a metal ceramic (Simidur S 2 veneered with IPS Classic Porcelain). The crowns were assessed over 3 years using the modified USPHS criteria. Crowns that developed visible cracks were sectioned and removed, and the surfaces were analyzed using a scanning electron microscope (SEM). The data were analyzed using the Kruskal-Wallis nonparametric statistical test, followed by the Mann-Whitney test with Bonferroni correction (alpha=.05). USPHS evaluation showed that the IPS e.max Press and metal ceramic crowns experienced fewer clinical changes than Procera AllCeram. Visible roughness, wear, and deformity were noticed in occlusal contact areas of Procera AllCeram crowns. SEM images showed well defined wear facets in both ceramic crown systems. Kruskal-Wallis tests showed a significant difference (P<.05) in Alpha scores among the 3 crown systems. Mann-Whitney tests showed significant differences among groups. IPS e.max Press crowns demonstrated clinical behavior comparable to Procera AllCeram and metal ceramic crowns, but the wear resistance of this crown type was superior to the Procera AllCeram crowns, according to modified USPHS criteria.

Tuning Surface Energy Landscapes in Metallic Quantum Films using Alkali Adsorbates

NASA Astrophysics Data System (ADS)

Khajetoorians, Alexander; Qin, Shengyong; Zhu, Wenguang; Eisele, Holger; Zhang, Zhenyu; Shih, Chih-Kang

2008-03-01

Quantum confinement shows a strong interplay with growth and kinetics in thin metal systems where the Fermi wavelength has a special relationship to the surface normal lattice constant. In the case of Pb/Si(111) systems, this relationship reveals an interesting thickness-dependent bilayer oscillation in the density of states and surface energy up to a phase. In this paper, we report on a novel effect: tuning of the energy landscape of a flat-top quantum Pb mesa using Cs adsorbates. Using STM/STS, we show that depositing Cs adsorbates on a thin Pb mesa promotes quantum stable Pb nanoislands on preferentially unstable thicknesses. Thickness-dependent nanoisland densities show a strong bilayer oscillation correlating with quantum stability. By modifying the Cs coverage on the mesa surface, we can tune the lateral size distribution of the nanoislands and the overall amplitude of the island density oscillation. Nanoisland formation is linked to a step decoration of Cs adatoms along the step edge of the nanoisland.

Electronic Interactions of Size-Selected Oxide Clusters on Metallic and Thin Film Oxide Supports

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

Xue, Meng; Nakayama, Miki; Liu, Ping

The interfacial electronic structure of various size-selected metal oxide nanoclusters (M 3O x; M = Mo, Nb, Ti) on Cu(111) and a thin film of Cu 2O supports were investigated in this paper by a combination of experimental methods and density functional theory (DFT). These systems explore electron transfer at the metal–metal oxide interface which can modify surface structure, metal oxidation states, and catalytic activity. Electron transfer was probed by measurements of surface dipoles derived from coverage dependent work function measurements using two-photon photoemission (2PPE) and metal core level binding energy spectra from X-ray photoelectron spectroscopy (XPS). The measured surfacemore » dipoles are negative for all clusters on Cu(111) and Cu 2O/Cu(111), but those on the Cu 2O surface are much larger in magnitude. In addition, sub-stoichiometric or “reduced” clusters exhibit smaller surface dipoles on both the Cu(111) and Cu 2O surfaces. Negative surface dipoles for clusters on Cu(111) suggest Cu → cluster electron transfer, which is generally supported by DFT-calculated Bader charge distributions. For Cu 2O/Cu(111), calculations of the surface electrostatic potentials show that the charge distributions associated with cluster adsorption structures or distortions at the cluster–Cu 2O–Cu(111) interface are largely responsible for the observed negative surface dipoles. Changes observed in the XPS spectra for the Mo 3d, Nb 3d, and Ti 2p core levels of the clusters on Cu(111) and Cu 2O/Cu(111) are interpreted with help from the calculated Bader charges and cluster adsorption structures, the latter providing information about the presence of inequivalent cation sites. Finally, the results presented in this work illustrate how the combined use of different experimental probes along with theoretical calculations can result in a more realistic picture of cluster–support interactions and bonding.« less

Electronic Interactions of Size-Selected Oxide Clusters on Metallic and Thin Film Oxide Supports

DOE PAGES

Xue, Meng; Nakayama, Miki; Liu, Ping; ...

2017-09-13

The interfacial electronic structure of various size-selected metal oxide nanoclusters (M 3O x; M = Mo, Nb, Ti) on Cu(111) and a thin film of Cu 2O supports were investigated in this paper by a combination of experimental methods and density functional theory (DFT). These systems explore electron transfer at the metal–metal oxide interface which can modify surface structure, metal oxidation states, and catalytic activity. Electron transfer was probed by measurements of surface dipoles derived from coverage dependent work function measurements using two-photon photoemission (2PPE) and metal core level binding energy spectra from X-ray photoelectron spectroscopy (XPS). The measured surfacemore » dipoles are negative for all clusters on Cu(111) and Cu 2O/Cu(111), but those on the Cu 2O surface are much larger in magnitude. In addition, sub-stoichiometric or “reduced” clusters exhibit smaller surface dipoles on both the Cu(111) and Cu 2O surfaces. Negative surface dipoles for clusters on Cu(111) suggest Cu → cluster electron transfer, which is generally supported by DFT-calculated Bader charge distributions. For Cu 2O/Cu(111), calculations of the surface electrostatic potentials show that the charge distributions associated with cluster adsorption structures or distortions at the cluster–Cu 2O–Cu(111) interface are largely responsible for the observed negative surface dipoles. Changes observed in the XPS spectra for the Mo 3d, Nb 3d, and Ti 2p core levels of the clusters on Cu(111) and Cu 2O/Cu(111) are interpreted with help from the calculated Bader charges and cluster adsorption structures, the latter providing information about the presence of inequivalent cation sites. Finally, the results presented in this work illustrate how the combined use of different experimental probes along with theoretical calculations can result in a more realistic picture of cluster–support interactions and bonding.« less

Enhancing the reactivity of gold: Nanostructured Au(111) adsorbs CO

DOE PAGES

Hoffmann, F. M.; Hrbek, J.; Ma, S.; ...

2015-12-02

Low-coordinated sites are surface defects whose presence can transform a surface of inert or noble metal such as Au into an active catalyst. We prepared gold surfaces modified by pits, starting with a well-ordered Au(111) surface; we then used microscopy (STM) for their structural characterization and CO spectroscopy (IRAS and NEXAFS) for probing reactivity of surface defects. In contrast to the Au(111) surface CO adsorbs readily on the pitted surfaces bonding to low-coordinated sites identified as step atoms forming {111} and {100} microfacets. Finally, pitted nanostructured surfaces can serve as interesting and easily prepared models of catalytic surfaces with definedmore » defects that offer an attractive alternative to vicinal surfaces or nanoparticles commonly employed in catalysis science.« less

Numerical investigation of melting and solidification processes in modified surface layers of metal at induction heating

NASA Astrophysics Data System (ADS)

Shchukin, V. G.; Popov, V. N.

2017-10-01

One of the perspective ways to improve the operational properties of parts of machines during induction treatment of their surfaces is the modification of the melt by specially prepared nanoscale particles of refractory compounds (carbides, nitrides, carbonitrides, etc.). This approach allows us to increase the number of crystallization centers and to refine the structural components of the solidified metal. The resulting high dispersity and homogeneity of crystalline grains favorably affect the quality of the treated surfaces. 3D numerical simulation of thermophysical processes in the modification of the surface layer of metal in a moving substrate was carried out. It is assumed that the surface of the substrate is covered with a layer of specially prepared nanoscale particles of a refractory compound, which, upon penetration into the melt, are uniformly distributed in it. The possibility of applying a high-frequency electromagnetic field of high power for heating and melting of a metal (iron) for the purpose of its subsequent modification is investigated. The distribution of electromagnetic energy in the metal is described by empirical formulas. Melting of the metal is considered in the Stefan approximation, and upon solidification it is assumed that all nanoparticles serve as centers for volume-sequential crystallization. Calculations were carried out with the following parameters: specific power p0 = 35 and 40 kW/cm2 at frequency f = 440 and 1200 kHz, the substrate velocity V = 0.5-2.5 cm/s, the nanoparticles' size is 50 nm and concentration Np = 2.0 . 109 cm-3. Based on the results obtained in a quasi-stationary formulation, the distribution of the temperature field, the dimensions of the melting and crystallization zones, the change in the solid fraction in the two-phase zone, the area of the treated substrate surface, depending on the speed of its movement and induction heating characteristics were estimated.

Silica-bound copper(II)triazacyclononane as a phosphate esterase: effect of linker length and surface hydrophobicity.

PubMed

Bodsgard, Brett R; Clark, Robert W; Ehrbar, Anthony W; Burstyn, Judith N

2009-04-07

A series of silica-bound Cu(ii) triazacyclononane materials was prepared to study the effect of linker length and surface hydrophobicity on the hydrolysis of phosphate esters. The general synthetic approach for these heterogeneous reagents was rhodium-catalyzed hydrosilation between an alkenyl-modified triazacyclononane and hydride-modified silica followed by metallation with a Cu(ii) salt. Elemental analysis confirmed that organic functionalization of the silica gel was successful and provided an estimate of the surface concentration of triazacyclononane. EPR spectra were consistent with square pyramidal Cu(ii), indicating that Cu(ii) ions were bound to the immobilized macrocycles. The hydrolytic efficacies of these heterogeneous reagents were tested with bis(p-nitrophenyl)phosphate (BNPP) and diethyl 4-nitrophenyl phosphate (paraoxon). The agent that performed best was an octyl-linked, propanol-blocked material. This material had the most hydrophilic surface and the most accessible active site, achieving a rate maximum on par with the other materials, but in fewer cycles and without an induction period.

Fabrication of an artificial nanosucker device with a large area nanotube array of metallic glass.

PubMed

Chen, Wei-Ting; Manivannan, Karthikeyan; Yu, Chia-Chi; Chu, Jinn P; Chen, Jem-Kun

2018-01-18

The concurrent attachment and detachment movements of geckos on virtually any type of surface via their foot pads have inspired us to develop a thermal device with numerous arrangements of a multi-layer thin film together with electrodes that can help modify the temperature of the surface via application of a voltage. A sequential fabrication process was employed on a large-scale integration to generate well-defined contact hole arrays of photoresist for use as templates on the electrode-based device. The photoresist templates were then subjected to sputter deposition of the metallic glass Zr 55 Cu 30 Al 10 Ni 5 . Consequently, a metallic glass nanotube (MGNT) array having a nominal wall thickness of 100 nm was obtained after removal of the photoresist template. When a water droplet was placed on the MGNT array, close nanochambers of metallic glass were formed. By applying voltage, the surface was heated to increase the pressure inside the nanochambers; this generated an expanding force that raised the droplet; thus, the static water contact angle (SWCA) was increased. In contrast, a sucking force was generated during surface cooling, which decreased the SWCA. Our fabrication strategy exploits the MGNT array surface as nanosuckers, which can mimic the climbing aptitude of geckos as they attach to (>10 N m -2 ) and detach from (0.26 N m -2 ) surfaces at 0.5 and 3 V of applied voltage, respectively. Thus, the climbing aptitude of geckos can be mimicked by employing the processing strategy presented herein for the development of artificial foot pads.

Technology of Strengthening Steel Details by Surfacing Composite Coatings

NASA Astrophysics Data System (ADS)

Burov, V. G.; Bataev, A. A.; Rakhimyanov, Kh M.; Mul, D. O.

2016-04-01

The article considers the problem of forming wear resistant meal ceramic coatings on steel surfaces using the results of our own investigations and the analysis of achievements made in the country and abroad. Increasing the wear resistance of surface layers of steel details is achieved by surfacing composite coatings with carbides or borides of metals as disperse particles in the strengthening phase. The use of surfacing on wearing machine details and mechanisms has a history of more than 100 years. But still engineering investigations in this field are being conducted up to now. The use of heating sources which provide a high density of power allows ensuring temperature and time conditions of surfacing under which composites with peculiar service and functional properties are formed. High concentration of energy in the zone of melt, which is created from powder mixtures and the hardened surface layer, allows producing the transition zone between the main material and surfaced coating. Surfacing by the electron beam directed from vacuum to the atmosphere is of considerable technological advantages. They give the possibility of strengthening surface layers of large-sized details by surfacing powder mixtures without their preliminary compacting. A modified layer of the main metal with ceramic particles distributed in it is created as a result of heating surfaced powders and the detail surface layer by the electron beam. Technology of surfacing allows using powders of refractory metals and graphite in the composition of powder mixtures. They interact with one another and form the particles of the hardening phase of the composition coating. The chemical composition of the main and surfaced materials is considered to be the main factor which determines the character of metallurgical processes in local zones of melt as well as the structure and properties of surfaced composition.

A model of Martian surface chemistry

NASA Technical Reports Server (NTRS)

Oyama, V. I.; Berdahl, B. J.

1979-01-01

Alkaline earth and alkali metal superoxides and peroxides, gamma-Fe2O3 and carbon suboxide polymer, are proposed to be constituents of the Martian surface material. These reactive substances explain the water modified reactions and thermal behaviors of the Martian samples demonstrated by all of the Viking Biology Experiments. It is also proposed that the syntheses of these substances result mainly from electrical discharges between wind-mobilized particles at Martian pressures; plasmas are initiated and maintained by these discharges. Active species in the plasma either combine to form or react with inorganic surfaces to create the reactive constituents.

Effect of gold subsurface layer on the surface activity and segregation in Pt/Au/Pt3M (where M = 3d transition metals) alloy catalyst from first-principles.

PubMed

Kim, Chang-Eun; Lim, Dong-Hee; Jang, Jong Hyun; Kim, Hyoung Juhn; Yoon, Sung Pil; Han, Jonghee; Nam, Suk Woo; Hong, Seong-Ahn; Soon, Aloysius; Ham, Hyung Chul

2015-01-21

The effect of a subsurface hetero layer (thin gold) on the activity and stability of Pt skin surface in Pt3M system (M = 3d transition metals) is investigated using the spin-polarized density functional theory calculation. First, we find that the heterometallic interaction between the Pt skin surface and the gold subsurface in Pt/Au/Pt3M system can significantly modify the electronic structure of the Pt skin surface. In particular, the local density of states projected onto the d states of Pt skin surface near the Fermi level is drastically decreased compared to the Pt/Pt/Pt3M case, leading to the reduction of the oxygen binding strength of the Pt skin surface. This modification is related to the increase of surface charge polarization of outmost Pt skin atoms by the electron transfer from the gold subsurface atoms. Furthermore, a subsurface gold layer is found to cast the energetic barrier to the segregation loss of metal atoms from the bulk (inside) region, which can enhance the durability of Pt3M based catalytic system in oxygen reduction condition at fuel cell devices. This study highlights that a gold subsurface hetero layer can provide an additional mean to tune the surface activity toward oxygen species and in turn the oxygen reduction reaction, where the utilization of geometric strain already reaches its practical limit.

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.

Surface modification of medical implant materials with hydrophilic polymers for enhanced biocompatibility and delivery of therapeutic agents

NASA Astrophysics Data System (ADS)

Urbaniak, Daniel J.

2004-11-01

In the research reported here, the surface modification of medical grade poly(dimethyl siloxane), polyetherurethane, and stainless steel through gamma-radiation grafting of hydrophilic polymers was investigated. Emphasis was placed on developing improved and simplified surface modification methods that produce more stable and more bioacceptible hydrophilic graft surfaces. As a result of this research, new surface modification techniques were developed that yield significantly improved surface stability unachievable using previous surface modification techniques. The surface modification of poly(dimethyl siloxane) with hydrophilic polymers was carried out using gamma radiation initiated graft polymerization. The addition of alkali metal hydroxides afforded a unique way to enhance the grafting of N-vinyl-2 pyrrolidone, dimethylacryamide, 2-methacryloyloxyethyl phosphoryl choline, N,N-dimethyl-N-(methacryloyloxyethyl)-N-(3-sulfopropyl)-ammonium-betaine, N,N-dimethyl-N-(methacrylamidopropyl)-N-(3-sulfopropyl)-ammonium-betaine, and copolymers thereof to silicones. Ethanolamine was found to further enhance the grafting of some hydrophilic polymers to silicone. The resulting hydrophilic surface grafts were resistant to hydrophobic surface rearrangement. This process overcomes previous problems inherent in silicone surface modification. The technique was also found to moderately enhance the grafting of hydrophilic monomers to polyetherurethane and to 316-L stainless steel. The surface modification of 316-L stainless steel was further enhanced by treating the substrates with a chromium III methacrylate bonding agent prior to irradiation. The coatings were evaluated for their potential use as depots for delivering therapeutic agents. The release of ofloxacin from surface-modified poly(dimethyl siloxane) and dexamethasone from surface-modified 316-L stainless steel was evaluated by in-vitro experiments. Therapeutic levels of drugs were released from surface-modified specimens via a burst effect. Improved surface characterization methods were another aspect of this research. New nanomechanical testing techniques were developed and used to evaluate the viscoelastic surface mechanical properties of low modulus surface-modified specimens. Dynamic nanoindentation characterization techniques were designed to measure the storage modulus and loss modulus of compliant viscoelastic substrate surfaces. The results of these experiments were compared with modulus data obtained by conventional dynamic mechanical spectroscopy. Nanoscratch testing methods were also developed that qualitatively compared the abrasion resistance of surface-modified substrates. (Abstract shortened by UMI.)

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.

Characterization of a multi-metal binding biosorbent: Chemical modification and desorption studies.

PubMed

Abdolali, Atefeh; Ngo, Huu Hao; Guo, Wenshan; Zhou, John L; Du, Bin; Wei, Qin; Wang, Xiaochang C; Nguyen, Phuoc Dan

2015-10-01

This work attends to preparation and characterization of a novel multi-metal binding biosorbent after chemical modification and desorption studies. Biomass is a combination of tea waste, maple leaves and mandarin peels with a certain proportion to adsorb cadmium, copper, lead and zinc ions from aqueous solutions. The mechanism involved in metal removal was investigated by SEM, SEM/EDS and FTIR. SEM/EDS showed the presence of different chemicals and adsorbed heavy metal ions on the surface of biosorbent. FTIR of both unmodified and modified biosorbents revealed the important role of carboxylate groups in heavy metal biosorption. Desorption using different eluents and 0.1 M HCl showed the best desorption performance. The effectiveness of regeneration step by 1 M CaCl2 on five successive cycles of sorption and desorption displays this multi-metal binding biosorbent (MMBB) can effectively be utilized as an adsorbent to remove heavy metal ions from aqueous solutions in five cycles of sorption/desorption/regeneration. Copyright © 2015 Elsevier Ltd. All rights reserved.

Large area ultraviolet photodetector on surface modified Si:GaN layers

NASA Astrophysics Data System (ADS)

Anitha, R.; R., Ramesh; Loganathan, R.; Vavilapalli, Durga Sankar; Baskar, K.; Singh, Shubra

2018-03-01

Unique features of semiconductor based heterostructured photoelectric devices have drawn considerable attention in the recent past. In the present work, large area UV photodetector has been fabricated utilizing interesting Zinc oxide microstructures on etched Si:GaN layers. The surface of Si:GaN layer grown by metal organic chemical vapor deposition method on sapphire has been modified by chemical etching to control the microstructure. The photodetector exhibits response to Ultraviolet light only. Optimum etching of Si:GaN was required to exhibit higher responsivity (0.96 A/W) and detectivity (∼4.87 × 109 Jones), the two important parameters for a photodetector. Present method offers a tunable functionality of photodetector through modification of top layer microstructure. A comparison with state of art materials has also been presented.

Synthesis and Transport Properties of Novel MOF/PIM-1/MOF Sandwich Membranes for Gas Separation

PubMed Central

Fuoco, Alessio; Khdhayyer, Muhanned R.; Attfield, Martin P.; Esposito, Elisa; Jansen, Johannes C.; Budd, Peter M.

2017-01-01

Metal-organic frameworks (MOFs) were supported on polymer membrane substrates for the fabrication of composite polymer membranes based on unmodified and modified polymer of intrinsic microporosity (PIM-1). Layers of two different MOFs, zeolitic imidazolate framework-8 (ZIF-8) and Copper benzene tricarboxylate ((HKUST-1), were grown onto neat PIM-1, amide surface-modified PIM-1 and hexamethylenediamine (HMDA) -modified PIM-1. The surface-grown crystalline MOFs were characterized by a combination of several techniques, including powder X-ray diffraction, infrared spectroscopy and scanning electron microscopy to investigate the film morphology on the neat and modified PIM-1 membranes. The pure gas permeabilities of He, H2, O2, N2, CH4, CO2 were studied to understand the effect of the surface modification on the basic transport properties and evaluate the potential use of these membranes for industrially relevant gas separations. The pure gas transport was discussed in terms of permeability and selectivity, highlighting the effect of the MOF growth on the diffusion coefficients of the gas in the new composite polymer membranes. The results confirm that the growth of MOFs on polymer membranes can enhance the selectivity of the appropriately functionalized PIM-1, without a dramatic decrease of the permeability. PMID:28208658

In Situ, High-Resolution Profiles of Labile Metals in Sediments of Lake Taihu

PubMed Central

Wang, Dan; Gong, Mengdan; Li, Yangyang; Xu, Lv; Wang, Yan; Jing, Rui; Ding, Shiming; Zhang, Chaosheng

2016-01-01

Characterizing labile metal distribution and biogeochemical behavior in sediments is crucial for understanding their contamination characteristics in lakes, for which in situ, high-resolution data is scare. The diffusive gradient in thin films (DGT) technique was used in-situ at five sites across Lake Taihu in the Yangtze River delta in China to characterize the distribution and mobility of eight labile metals (Fe, Mn, Zn, Ni, Cu, Pb, Co and Cd) in sediments at a 3 mm spatial resolution. The results showed a great spatial heterogeneity in the distributions of redox-sensitive labile Fe, Mn and Co in sediments, while other metals had much less marked structure, except for downward decreases of labile Pb, Ni, Zn and Cu in the surface sediment layers. Similar distributions were found between labile Mn and Co and among labile Ni, Cu and Zn, reflecting a close link between their geochemical behaviors. The relative mobility, defined as the ratio of metals accumulated by DGT to the total contents in a volume of sediments with a thickness of 10 mm close to the surface of DGT probe, was the greatest for Mn and Cd, followed by Zn, Ni, Cu and Co, while Pb and Fe had the lowest mobility; this order generally agreed with that defined by the modified BCR approach. Further analyses showed that the downward increases of pH values in surface sediment layer may decrease the lability of Pb, Ni, Zn and Cu as detected by DGT, while the remobilization of redox-insensitive metals in deep sediment layer may relate to Mn cycling through sulphide coprecipitation, reflected by several corresponding minima between these metals and Mn. These in situ data provided the possibility for a deep insight into the mechanisms involved in the remobilization of metals in freshwater sediments. PMID:27608033

Aerosol-spray diverse mesoporous metal oxides from metal nitrates.

PubMed

Kuai, Long; Wang, Junxin; Ming, Tian; Fang, Caihong; Sun, Zhenhua; Geng, Baoyou; Wang, Jianfang

2015-04-21

Transition metal oxides are widely used in solar cells, batteries, transistors, memories, transparent conductive electrodes, photocatalysts, gas sensors, supercapacitors, and smart windows. In many of these applications, large surface areas and pore volumes can enhance molecular adsorption, facilitate ion transfer, and increase interfacial areas; the formation of complex oxides (mixed, doped, multimetallic oxides and oxide-based hybrids) can alter electronic band structures, modify/enhance charge carrier concentrations/separation, and introduce desired functionalities. A general synthetic approach to diverse mesoporous metal oxides is therefore very attractive. Here we describe a powerful aerosol-spray method for synthesizing various mesoporous metal oxides from low-cost nitrate salts. During spray, thermal heating of precursor droplets drives solvent evaporation and induces surfactant-directed formation of mesostructures, nitrate decomposition and oxide cross-linking. Thirteen types of monometallic oxides and four groups of complex ones are successfully produced, with mesoporous iron oxide microspheres demonstrated for photocatalytic oxygen evolution and gas sensing with superior performances.

Sol-gel Synthesis, Photo- and Electrocatalytic Properties of Mesoporous TiO2 Modified with Transition Metal Ions

NASA Astrophysics Data System (ADS)

Smirnova, N.; Petrik, I.; Vorobets, V.; Kolbasov, G.; Eremenko, A.

2017-03-01

Mesoporous nanosized titania films modified with Co2+, Ni2+, Mn3+, and Cu2+ ions have been produced by templated sol-gel method and characterized by optical spectroscopy, X-ray diffraction (XRD), and Brunauer, Emmett, and Teller (BET) surface area measurement. Band gap energy and the position of flat band potentials were estimated by photoelectrochemical measurements. The films doped with transition metals possessed higher photocurrent quantum yield, as well as photo- and electrochemical activity compared to undoped samples. Mn+/TiO2 (M-Co, Ni, Mn, Cu) electrodes with low dopant content demonstrate high efficiency in electrocatalytic reduction of dissolved oxygen. Polarization curves of TiO2, TiO2/Ni2+, TiO2/Co2+/3+, and TiO2/Mn3+ electrodes contain only one current wave (oxygen reduction current). It means that reaction proceeds without the formation of an intermediate product H2O2.

Metal oxide composite enabled nanotextured Si photoanode for efficient solar driven water oxidation.

PubMed

Sun, Ke; Pang, Xiaolu; Shen, Shaohua; Qian, Xueqiang; Cheung, Justin S; Wang, Deli

2013-05-08

We present a study of a transition metal oxide composite modified n-Si photoanode for efficient and stable water oxidation. This sputter-coated composite functions as a protective coating to prevent Si from photodecomposition, a Schottky heterojunction, a hole conducting layer for efficient charge separation and transportation, and an electrocatalyst to reduce the reaction overpotential. The formation of mixed-valence oxides composed of Ni and Ru effectively modifies the optical, electrical, and catalytic properties of the coating material, as well as the interfaces with Si. The successful application of this oxide composite on nanotextured Si demonstrates improved conversion efficiency due to enhanced catalytic activity, minimized reflection, and increased surface reaction sites. Although the coated nanotextured Si shows a noticeable degradation from 500 cycles of operation, the oxide composite provides a simple method to enable unstable photoanode materials for solar fuel conversion.

Effects of surface treatments and bonding types on the interfacial behavior of fiber metal laminate based on magnesium alloy

NASA Astrophysics Data System (ADS)

Zhang, Xi; Ma, Quanyang; Dai, Yu; Hu, Faping; Liu, Gang; Xu, Zouyuan; Wei, Guobing; Xu, Tiancai; Zeng, Qingwen; Xie, Weidong

2018-01-01

Fiber metal laminates based on magnesium alloys (MgFML) with different surface treatments and different bonding types were tested and analyzed. By using dynamic contact angle measurement and scanning electron microscopy (SEM), it was found that phosphating treatment can significantly improve the surface energy and wettability of magnesium alloy, and the surface energy of phosphated magnesium alloy was approximately 50% higher than that of abraded-only magnesium alloy. The single cantilever beam (SCB) test showed that the interfacial fracture energies of directly bonded MgFMLs based on abraded-only magnesium and abraded + phosphated magnesium were 650 J/m2 and 1030 J/m2, respectively, whereas the interfacial fracture energies of indirectly bonded MgFMLs were 1650 J/m2 and 2260 J/m2, respectively. Phosphating treatment and modified polypropylene interleaf were observed to improve the tensile strength and interfacial fracture toughness of MgFML. In addition, the rougher surface was more conducive to enhance the bonding strength and interfacial fracture toughness of MgFML.

Influence of annealing on the photodeposition of silver on periodically poled lithium niobate

DOE PAGES

Carville, N. Craig; Neumayer, Sabine M.; Manzo, Michele; ...

2016-02-03

Here, the preferential deposition of metal nanoparticles onto periodically poled lithium niobate surfaces, whereby photogenerated electrons accumulate in accordance with local electric fields and reduce metal ions from solution, is known to depend on the intensity and wavelength of the illumination and the concentration of the solution used. Here, it is shown that for identical deposition conditions (wavelength, intensity, concentration), post-poling annealing for 10 h at 200 °C modifies the surface reactivity through the reorientation of internal defect fields. Whereas silver nanoparticles deposit preferentially on the +z domains on unannealed crystals, the deposition occurs preferentially along 180 degrees domain wallsmore » for annealed crystals. In neither case is the deposition selective; limited deposition occurs also on the unannealed -z domain surface and on both annealed domain surfaces. The observed behavior is attributed to a relaxation of the poling-induced defect frustration mediated by Li + ion mobility during annealing, which affects the accumulation of electrons, thereby changing the surface reactivity. The evolution of the defect field with temperature is corroborated using Raman spectroscopy.« less

A voltammetric method for Fe(iii) in blood serum using a screen-printed electrode modified with a Schiff base ionophore.

PubMed

Mittal, Susheel K; Rana, Sonia; Kaur, Navneet; Banks, Craig E

2018-05-23

Herein, a potent electrochemical ionophore (SMS-2) based on a Schiff base has been used for the modification of a screen-printed electrode (SPE). The modified disposable electrode can selectively detect ferric ions in an aqueous medium. Redox behavior of the proposed strip was characterized using cyclic voltammetry (CV) and differential pulse voltammetry (DPV). Incorporation of the ligand in the ink of the SPE enhanced the analytical performance of the electrode, and its surface modification was confirmed by SEM and EDX analysis. Shifting/quenching of the cathodic peak potential of the ionophore after binding with Fe(iii) ions was used to detect and measure the ferric ion concentration. This sensor can identify Fe(iii) in the detection range from 0.625 μM to 7.5 μM. The modified SPE can selectively detect ferric ions in the presence of many other interfering ions and has been successfully used to determine the Fe(iii) content in blood serum samples. The metal-ionophore complex structure was optimized using DFT calculations to study the energetics of the metal-ionophore interactions.

Enhancement of chromate reduction in soils by surface modified biochar.

PubMed

Mandal, Sanchita; Sarkar, Binoy; Bolan, Nanthi; Ok, Yong Sik; Naidu, Ravi

2017-01-15

Chromium (Cr) is one of the common metals present in the soils and may have an extremely deleterious environmental impact depending on its redox state. Among two common forms, trivalent Cr(III) is less toxic than hexavalent Cr(VI) in soils. Carbon (C) based materials including biochar could be used to alleviate Cr toxicity through converting Cr(VI) to Cr(III). Incubation experiments were conducted to examine Cr(VI) reduction in different soils (Soil 1: pH 7.5 and Soil 2: pH 5.5) with three manures from poultry (PM), cow (CM) and sheep (SM), three respective manure-derived biochars (PM biochar (PM-BC), CM biochar (CM-BC) and SM biochar (SM-BC)) and two modified biochars (modified PM-BC (PM-BC-M) and modified SM-BC (SM-BC-M)). Modified biochar was synthesized by incorporating chitosan and zerovalent iron (ZVI) during pyrolysis. Among biochars, highest Cr(VI) reduction was observed with PM-BC application (5%; w/w) (up to 88.12 mg kg -1 ; 45% reduction) in Soil 2 (pH 5.5). The modified biochars enhanced Cr(VI) reduction by 55% (SM-BC-M) compared to manure (29%, SM) and manure-derived biochars (40% reduction, SM-BC). Among the modified biochars, SM-BC-M showed a higher Cr(VI) reduction rate (55%) than PM-BC-M (48%) in Soil 2. Various oxygen-containing surface functional groups such as phenolic, carboxyl, carbonyl, etc. on biochar surface might act as a proton donor for Cr(VI) reduction and subsequent Cr(III) adsorption. This study underpins the immense potential of modified biochar in remediation of Cr(VI) contaminated soils. Copyright © 2016 Elsevier Ltd. All rights reserved.

Silane surface modification for improved bioadhesion of esophageal stents

PubMed Central

Karakoy, Mert; Gultepe, Evin; Pandey, Shivendra; Khashab, Mouen A.; Gracias, David H.

2014-01-01

Stent migration occurs in 10-40% of patients who undergo placement of esophageal stents, with higher migration rates seen in those treated for benign esophageal disorders. This remains a major drawback of esophageal stent therapy. In this paper, we propose a new surface modification method to increase the adhesion between self-expandable metallic stents (SEMS) and tissue while preserving their removability. Taking advantage of the well-known affinity between epoxide and amine terminated silane coupling agents with amine and carboxyl groups that are abundant in proteins and related molecules in the human body; we modified the surfaces of silicone coated esophageal SEMS with these adhesive self-assembled monolayers (SAMs). We utilized vapor phase silanization to modify the surfaces of different substrates including PDMS strips and SEMS, and measured the force required to slide these substrates on a tissue piece. Our results suggest that surface modification of esophageal SEMS via covalent attachment of protein-binding coupling agents improves adhesion to tissue and could offer a solution to reduce SEMS migration while preserving their removability. PMID:25663731

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.

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

Li, Lidong; Zhou, Lu; Ould-Chikh, Samy

Surface composition and structure are of vital importance for heterogeneous catalysts, especially for bimetallic catalysts, which often vary as a function of reaction conditions (known as surface segregation). The preparation of bimetallic catalysts with controlled metal surface composition and structure is very challenging. In this study, we synthesize a series of Ni/Pt bimetallic catalysts with controlled metal surface composition and structure using a method derived from surface organometallic chemistry. The evolution of the surface composition and structure of the obtained bimetallic catalysts under simulated reaction conditions is investigated by various techniques, which include CO-probe IR spectroscopy, high-angle annular dark-field scanningmore » transmission electron microscopy, energy-dispersive X-ray spectroscopy, extended X-ray absorption fine structure analysis, X-ray absorption near-edge structure analysis, XRD, and X-ray photoelectron spectroscopy. It is demonstrated that the structure of the bimetallic catalyst is evolved from Pt monolayer island-modified Ni nanoparticles to core–shell bimetallic nanoparticles composed of a Ni-rich core and a Ni/Pt alloy shell upon thermal treatment. As a result, these catalysts are active for the dry reforming of methane, and their catalytic activities, stabilities, and carbon formation vary with their surface composition and structure.« less

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

Li, Lidong; Zhou, Lu; Ould-Chikh, Samy

The surface composition and structure are of vital importance for heterogeneous catalysts, especially for bimetallic catalysts, which often vary as a function of reaction conditions (known as surface segregation). The preparation of bimetallic catalysts with controlled metal surface composition and structure is very challenging. In this study, we synthesize a series of Ni/Pt bimetallic catalysts with controlled metal surface composition and structure using a method derived from surface organometallic chemistry. Moreover, the evolution of the surface composition and structure of the obtained bimetallic catalysts under simulated reaction conditions is investigated by various techniques, which include CO-probe IR spectroscopy, high-angle annularmore » dark-field scanning transmission electron microscopy, energy-dispersive X-ray spectroscopy, extended X-ray absorption fine structure analysis, X-ray absorption near-edge structure analysis, XRD, and X-ray photoelectron spectroscopy. It is demonstrated that the structure of the bimetallic catalyst is evolved from Pt monolayer island-modified Ni nanoparticles to core–shell bimetallic nanoparticles composed of a Ni-rich core and a Ni/Pt alloy shell upon thermal treatment. The catalysts are active for the dry reforming of methane, and their catalytic activities, stabilities, and carbon formation vary with their surface composition and structure.« less

Contact Killing of Bacteria on Copper Is Suppressed if Bacterial-Metal Contact Is Prevented and Is Induced on Iron by Copper Ions

PubMed Central

Mathews, Salima; Hans, Michael

2013-01-01

Bacteria are rapidly killed on copper surfaces, and copper ions released from the surface have been proposed to play a major role in the killing process. However, it has remained unclear whether contact of the bacteria with the copper surface is also an important factor. Using laser interference lithography, we engineered copper surfaces which were covered with a grid of an inert polymer which prevented contact of the bacteria with the surface. Using Enterococcus hirae as a model organism, we showed that the release of ionic copper from these modified surfaces was not significantly reduced. In contrast, killing of bacteria was strongly attenuated. When E. hirae cells were exposed to a solid iron surface, the loss of cell viability was the same as on glass. However, exposing cells to iron in the presence of 4 mM CuSO4 led to complete killing in 100 min. These experiments suggest that contact killing proceeds by a mechanism whereby the metal-bacterial contact damages the cell envelope, which, in turn, makes the cells susceptible to further damage by copper ions. PMID:23396344

Synthetic phytochelatin surface display in Cupriavidus metallidurans CH34 for enhanced metals bioremediation.

PubMed

Biondo, Ronaldo; da Silva, Felipe Almeida; Vicente, Elisabete José; Souza Sarkis, Jorge Eduardo; Schenberg, Ana Clara Guerrini

2012-08-07

This work describes the effects of the cell surface display of a synthetic phytochelatin in the highly metal tolerant bacterium Cupriavidus metallidurans CH34. The EC20sp synthetic phytochelatin gene was fused between the coding sequences of the signal peptide (SS) and of the autotransporter β-domain of the Neisseria gonorrhoeae IgA protease precursor (IgAβ), which successfully targeted the hybrid protein toward the C. metallidurans outer membrane. The expression of the SS-EC20sp-IgAβ gene fusion was driven by a modified version of the Bacillus subtilis mrgA promoter showing high level basal gene expression that is further enhanced by metal presence in C. metallidurans. The recombinant strain showed increased ability to immobilize Pb(2+), Zn(2+), Cu(2+), Cd(2+), Mn(2+), and Ni(2+) ions from the external medium when compared to the control strain. To ensure plasmid stability and biological containment, the MOB region of the plasmid was replaced by the E. coli hok/sok coding sequence.

Theoretical analysis of field emission from a metal diamond cold cathode emitter

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

Lerner, P.; Cutler, P.H.; Miskovsky, N.M.

Recently, Geis {ital et al.} [J. Vac. Sci. Technol. B {bold 14}, 2060 (1996)] proposed a cold cathode emitter based on a Spindt-type design using a diamond film doped by substitutional nitrogen. The device is characterized by high field emission currents at very low power. Two properties, the rough surface of the metallic injector and the negative electron affinity of the (111) surface of the diamond are essential for its operation. We present a first consistent quantitative theory of the operation of a Geis{endash}Spindt diamond field emitter. Its essential features are predicated on nearly {ital zero-field conditions} in the diamondmore » beyond the depletion layer, {ital quasiballistic transport} in the conduction band, and applicability of a modified {ital Fowler{endash}Nordheim equation} to the transmission of electrons through the Schottky barrier at the metal-diamond interface. Calculated results are in good qualitative and quantitative agreement with the experimental results of Geis {ital et al.} {copyright} {ital 1997 American Vacuum Society.}« less

Selective Functionalization of Arbitrary Nanowires

DTIC Science & Technology

2006-11-02

3-mercaptopropyl)- trimethoxysilane (MPTMS). The wires were grown electrochemically in anodic aluminum oxide ( AAO ) templates. Selective deposition...In the past, templates composed of polycarbonate track-etched membranes or anodic aluminum oxide materials have been used for the construction of...modifier MPTMS was used to function- alize the AAO template because it can form covalent bonds with silanes and metal oxide surfaces21 and because of

INTERACTION OF LASER RADIATION WITH MATTER AND OTHER LASER APPLICATIONS: Changes in the emission properties of metal targets during pulse-periodic laser irradiation

NASA Astrophysics Data System (ADS)

Konov, Vitalii I.; Pimenov, S. M.; Prokhorov, A. M.; Chapliev, N. I.

1988-02-01

A scanning electron microscope was used with a pulse-periodic CO2 laser to discover the laws governing the correlation of the modified microrelief of metal surfaces, subjected to the action of multiple laser pulses, with the emission of charged particles and the luminescence of the irradiated zone. It was established that the influence of sorption and laser-induced desorption on the emission signals may be manifested differently depending on the regime of current generation in the "target-vacuum chamber" circuit.

Testing of an actively damped boring bar featuring structurally integrated PZT stack actuators

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

Redmond, J.; Barney, P.

This paper summarizes the results of cutting tests performed using an actively damped boring bar to minimize chatter in metal cutting. A commercially available 2 inch diameter boring bar was modified to incorporate PZT stack actuators for controlling tool bending vibrations encountered during metal removal. The extensional motion of the actuators induce bending moments in the host structure through a two-point preloaded mounting scheme. Cutting tests performed at various speeds and depths of cuts on a hardened steel workpiece illustrate the bar`s effectiveness toward eliminating chatter vibrations and improving workpiece surface finish.

The growth of protective ultra-thin alumina layers on γ-TiAl(1 1 1) intermetallic single-crystal surfaces

NASA Astrophysics Data System (ADS)

Maurice, V.; Despert, G.; Zanna, S.; Josso, P.; Bacos, M.-P.; Marcus, P.

2005-12-01

An XPS and AES study of the early stages of oxidation of γ-TiAl(1 1 1) surfaces at 650 °C under 1.0 × 10 -7-1.0 × 10 -6 mbar O 2 is reported. The data evidence a first regime of oxidation characterized by the growth of a pure alumina layer followed by a second regime of simultaneous oxidation of both alloying elements. In the first regime, continuous alumina layers from ˜0.4 to ˜1.5 nm thick have been observed by angle-resolved XPS. The composition of the metallic phase underneath the growing oxide is modified by a depletion of Al and the injection of Al vacancies in the metal during the growth of the transient alumina formed at 650 °C. The onset of Ti oxidation was repeatedly observed for a critical concentration in the modified region of the alloy underneath the alumina layer: Ti 75±2Al 25±2 (Ti 50Al 17±2V(Al) 33±2), showing that decreasing the number of Ti-Al bonds in the modified intermetallic region increases the activity of Ti up to a critical point where its oxidation at the oxide/metal interface becomes competitive with that of Al. The growth of Ti 3+ and Ti 4+ oxide particles observed above the alumina layer by angle-resolved XPS indicates the transport of titanium cations trough the alumina layer and their subsequent reaction with oxygen at the outer gas/oxide interface. Improving structural ordering in the intermetallic phase slows down the growth kinetics of the alumina layer and the related Al-depletion of the substrate, and increases the resistance of the alloy to the subsequent oxidation of Ti. This is assigned to two combined effects: a slower diffusion of Al in the better ordered metallic phase and the growth of less defective alumina layers allowing to slow down the ionic transport through the oxide. Highly stable and corrosion resistant alloy surfaces covered by a 0.4 nm thick alumina layer have been obtained by slowly oxidizing the alloy at lower partial pressure (<5.0 × 10 -10 mbar O 2).

Design and use of a servo-controlled high pressure window bomb in spectroscopic studies of solid propellant combustion

NASA Technical Reports Server (NTRS)

Goetz, F.; Mann, D. M.

1980-01-01

The feasibility of using a high pressure window bomb as a laboratory scale model of actual motor conditions. The design and operation of a modified high pressure window bomb is discussed. An optical servocontrol mechanism has been designed to hold the burning surface of a propellant strand at a fixed position within the bomb chamber. This mechanism permits the recording of visible and infrared emission spectra from various propellants. Preliminary visible emission spectra of a nonmetalized and metalized propellant are compared with spectra recorded using the modified bomb.

Development of ion-exchange properties of bamboo charcoal modified with concentrated nitric acid

NASA Astrophysics Data System (ADS)

Khandaker, S.; Kuba, T.; Toyohara, Y.; Kamida, S.; Uchikawa, Y.

2017-08-01

The surface chemistry and the structural properties of activated carbon can be altered by the acidic modification. The objective of this study is to investigate the changes occurring in bamboo charcoal (BC) during activation with concentrated nitric acid. Low temperature (500°C) carbonized BC has been prepared and oxidized with 70% concentrated boiling nitric acid (BC-AC). The porous properties of the BC are analyzed with nitrogen adsorption isotherm at 77 K. The surface structure is observed by Field emission scanning electronic microscope (FESEM) and the surface functional groups are examined by Fourier transform infrared (FTIR) spectroscopy, X-ray photoelectron spectroscopy (XPS) and the pH of the point of zero charge (pHPZC). The results reveal that severe oxidation with HNO3 considerably decreases the surface area of BC with enhanced pore widening and FESEM observation demonstrates the erosive effect of oxidation. The FTIR analysis detects that some absorption bands are assigned for carboxyl, aldehyde and ketone groups on BC-AC. The XPS analysis also clearly shows that the ratio of oxygen and acidic functional groups has been enriched significantly on the BC-AC. The low pHPZC value of BC-AC confirms that the surface is highly acidic for the fixation of acidic functional groups on surface. In general, the existence of the abundant amount of acidic functional groups on adsorbents enhances the sorption of heavy metals ions in aqueous solution. Therefore, it is strongly expected that the modified BC, activated under the proposed conditions would be a promising ion exchanger in aqueous solution and can be applied for the adsorption of different heavy metal ions and radioactive materials from effluent.

Modified natural diatomite and its enhanced immobilization of lead, copper and cadmium in simulated contaminated soils.

PubMed

Ye, Xinxin; Kang, Shenghong; Wang, Huimin; Li, Hongying; Zhang, Yunxia; Wang, Guozhong; Zhao, Huijun

2015-05-30

Natural diatomite was modified through facile acid treatment and ultrasonication, which increased its electronegativity, and the pore volume and surface area achieved to 0.211 cm(3) g(-1) and 76.9 m(2) g(-1), respectively. Modified diatomite was investigated to immobilize the potential toxic elements (PTEs) of Pb, Cu and Cd in simulated contaminated soil comparing to natural diatomite. When incubated with contaminated soils at rates of 2.5% and 5.0% by weight for 90 days, modified diatomite was more effective in immobilizing Pb, Cu and Cd than natural diatomite. After treated with 5.0% modified diatomite for 90 days, the contaminated soils showed 69.7%, 49.7% and 23.7% reductions in Pb, Cu and Cd concentrations after 0.01 M CaCl2 extraction, respectively. The concentrations of Pb, Cu and Cd were reduced by 66.7%, 47.2% and 33.1% in the leaching procedure, respectively. The surface complexation played an important role in the immobilization of PTEs in soils. The decreased extractable metal content of soil was accompanied by improved microbial activity which significantly increased (P<0.05) in 5.0% modified diatomite-amended soils. These results suggested that modified diatomite with micro/nanostructured characteristics increased the immobilization of PTEs in contaminated soil and had great potential as green and low-cost amendments. Copyright © 2015 Elsevier B.V. All rights reserved.

Preparation of dumbbell manganese dioxide/gelatin composites and their application in the removal of lead and cadmium ions.

PubMed

Wang, Xiu; Huang, Kai; Chen, Ying; Liu, Jiafa; Chen, Shan; Cao, Jianlei; Mei, Surong; Zhou, Yikai; Jing, Tao

2018-05-15

The nano-sized sorbents restrict their practical application in flow-through system due to excessive pressure. In this study, dumbbell MnO 2 /gelatin composites were synthesized based on the protein-assisted synthesis technology. Then they were immobilized on the amino-modified polymethyl methacrylate (PMMA) plate. SEM, TEM, XRD, XPS and FT-IR were employed to study the surface properties and the adsorption mechanism of MnO 2 /gelatin composites. Adsorption experiments for Pb(II) and Cd(II) ions were performed to study the adsorption isotherms, kinetics, and thermodynamics as well as the influencing factors. The maximum adsorption capacities of Pb(II) and Cd(II) ions were 318.7 mg g -1 and 105.1 mg g -1 respectively. The adsorption process met the pseudo-second-order kinetic model. Subsequently, MnO 2 /gelatin composites modified plates were used to remove the heavy metal ions in surface water and wastewater samples. The removal efficiencies of Pb(II) ion was changed from 83% (wastewater) to 100% (surface water), when the initial concentration was 10 mg L -1 . This device exhibited great application prospect in the removal of heavy metals taking advantage of its high removal efficiency, excellent stability and reusability and ease of operation. Copyright © 2018 Elsevier B.V. All rights reserved.

Noble Metal Immersion Spectroscopy of Silica Alcogels and Aerogels

NASA Technical Reports Server (NTRS)

Smith, David D.; Sibille, Laurent; Cronise, Raymond J.; Noever, David A.

1998-01-01

We have fabricated aerogels containing gold and silver nanoparticles for gas catalysis applications. By applying the concept of an average or effective dielectric constant to the heterogeneous interlayer surrounding each particle, we extend the technique of immersion spectroscopy to porous or heterogeneous media. Specifically, we apply the predominant effective medium theories for the determination of the average fractional composition of each component in this inhomogeneous layer. Hence, the surface area of metal available for catalytic gas reaction is determined. The technique is satisfactory for statistically random metal particle distributions but needs further modification for aggregated or surfactant modified systems. Additionally, the kinetics suggest that collective particle interactions in coagulated clusters are perturbed during silica gelation resulting in a change in the aggregate geometry.

Crystalline hydroxyapatite coatings synthesized under hydrothermal conditions on modified titanium substrates.

PubMed

Suchanek, Katarzyna; Bartkowiak, Amanda; Gdowik, Agnieszka; Perzanowski, Marcin; Kąc, Sławomir; Szaraniec, Barbara; Suchanek, Mateusz; Marszałek, Marta

2015-06-01

Hydroxyapatite coatings were successfully produced on modified titanium substrates via hydrothermal synthesis in a Ca(EDTA)(2-) and (NH4)2HPO4 solution. The morphology of modified titanium substrates as well as hydroxyapatite coatings was studied using scanning electron microcopy and phase identification by X-ray diffraction, and Raman and FTIR spectroscopy. The results show that the nucleation and growth of hydroxyapatite needle-like crystals with hexagonal symmetry occurred only on titanium substrates both chemically and thermally treated. No hydroxyapatite phase was detected on only acid etched Ti metal. This finding demonstrates that only a particular titanium surface treatment can effectively induce the apatite nucleation under hydrothermal conditions. Copyright © 2015 Elsevier B.V. All rights reserved.

Catechol-grafted poly(ethylene glycol) for PEGylation on versatile substrates.

PubMed

Lee, Hyukjin; Lee, Kang Dae; Pyo, Kyung Bo; Park, Sung Young; Lee, Haeshin

2010-03-16

We report on catechol-grafted poly(ethylene) glycol (PEG-g-catechol) for the preparation of nonfouling surfaces on versatile substrates including adhesion-resistant PTFE. PEG-g-catechol was prepared by the step-growth polymerization of PEO to which dopamine, a mussel-derived adhesive molecule, was conjugated. The immersion of substrates into an aqueous solution of PEG-g-catechol resulted in robust PEGylation on versatile surfaces of noble metals, oxides, and synthetic polymers. Surface PEGylation was unambiguously confirmed by various surface analytical tools such as ellipsometry, goniometry, infrared spectroscopy, and X-ray photoelectron spectroscopy. Contrary to existing PEG derivatives that are difficult-to-modify synthetic polymer surfaces, PEG-g-catechol can be considered to be a new class of PEGs for the facile surface PEGylation of various types of surfaces.

PTFE-nanocomposites structure and wear-resistance changing in various methods of structural modification

NASA Astrophysics Data System (ADS)

Mashkov, Yu K.; Ruban, A. S.; Rogachev, E. A.; Chemisenko, O. V.

2018-01-01

Conditions of polymer materials usage containing nanoelements as modifiers significantly affect the requirements for their physic-mechanical and tribological properties. However, the mechanisms of nanoparticles effect to the polymers tribotechnical properties have not been studied enough. The article aim is to analyze the results of studying polytetrafluoroethylene modified with cryptocrystalline graphite and silicon dioxide and to determine the effectiveness of the modification methods used and methods for further improving filled PTFE mechanical and tribotechnical properties. The effect of modifiers to PCM supramolecular structure was analyzed with SEM methods. The results of modifying the PCM samples surface by depositing a copper film with ion-vacuum deposition methods and changing the structural-phase composition and tribological characteristics are considered. The findings make possible to characterize the physicochemical processes under frictional interaction in metal polymer tribosystems.

Adenoviral vector tethering to metal surfaces via hydrolysable cross-linkers for the modulation of vector release and transduction

PubMed Central

Fishbein, Ilia; Forbes, Scott P.; Chorny, Michael; Connolly, Jeanne M.; Adamo, Richard F.; Corrales, Ricardo; Alferiev, Ivan S.; Levy, Robert J.

2013-01-01

The use of arterial stents and other medical implants as a delivery platform for surface immobilized gene vectors allows for safe and efficient localized expression of therapeutic transgenes. In this study we investigate the use of hydrolysable cross-linkers with distinct kinetics of hydrolysis for delivery of gene vectors from polyallylamine bisphosphonate-modified metal surfaces. Three cross-linkers with the estimated t1/2 of ester bonds hydrolysis of 5, 12 and 50 days demonstrated a cumulative 20%, 39% and 45% vector release, respectively, after 30 days exposure to physiological buffer at 37°C. Transgene expression in endothelial and smooth muscles cells transduced with substrate immobilized adenovirus resulted in significantly different expression profiles for each individual cross-linker. Furthermore, immobilization of adenoviral vectors effectively extended their transduction effectiveness beyond the initial phase of release. Transgene expression driven by adenovirus-tethered stents in rat carotid arteries demonstrated that a faster rate of cross-linker hydrolysis resulted in higher expression levels at day 1, which declined by day 8 after stent implantation, while inversely, slower hydrolysis was associated with increased arterial expression at day 8 in comparison with day 1. In conclusion, adjustable release of transduction-competent adenoviral vectors from metallic surfaces can be achieved, both in vitro and in vivo, through surface immobilization of adenoviral vectors using hydrolysable cross-linkers with structure-specific release kinetics. PMID:23777912

ATOMIC-SCALE DESIGN OF IRON FISCHER-TROPSCH CATALYSTS: A COMBINED COMPUTATIONAL CHEMISTRY, EXPERIMENTAL, AND MICROKINETIC MODELING APPROACH

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

Manos Mavrikakis; James A. Dumesic; Amit A. Gokhale

2005-03-22

Efforts during this first year focused on four areas: (1) searching/summarizing published FTS mechanistic and kinetic studies of FTS reactions on iron catalysts; (2) construction of mass spectrometer-TPD and Berty CSTR reactor systems; (3) preparation and characterization of unsupported iron and alumina-supported iron catalysts at various iron loadings (4) Determination of thermochemical parameters such as binding energies of reactive intermediates, heat of FTS elementary reaction steps, and kinetic parameters such as activation energies, and frequency factors of FTS elementary reaction steps on a number of model surfaces. Literature describing mechanistic and kinetic studies of Fischer-Tropsch synthesis on iron catalysts wasmore » compiled in a draft review. Construction of the mass spectrometer-TPD system is 90% complete and of a Berty CSTR reactor system 98% complete. Three unsupported iron catalysts and three alumina-supported iron catalysts were prepared by nonaqueous-evaporative deposition (NED) or aqueous impregnation (AI) and characterized by chemisorption, BET, extent-of-reduction, XRD, and TEM methods. These catalysts, covering a wide range of dispersions and metal loadings, are well-reduced and relatively thermally stable up to 500-600 C in H{sub 2}, thus ideal for kinetic and mechanistic studies. The alumina-supported iron catalysts will be used for kinetic and mechanistic studies. In the coming year, adsorption/desorption properties, rates of elementary steps, and global reaction rates will be measured for these catalysts, with and without promoters, providing a database for understanding effects of dispersion, metal loading, and support on elementary kinetic parameters and for validation of computational models that incorporate effects of surface structure and promoters. Furthermore, using state-of-the-art self-consistent Density Functional Theory (DFT) methods, we have extensively studied the thermochemistry and kinetics of various elementary steps on three different model surfaces: (1) Fe(110), (2) Fe(110) modified by subsurface C, and (3) Fe surface modified with Pt adatoms. These studies have yielded valuable insights into the reactivity of Fe surfaces for FTS, and provided accurate estimates for the effect of Fe modifiers such as subsurface C and surface Pt.« less

Physicochemical of pillared clays prepared by several metal oxides

NASA Astrophysics Data System (ADS)

Rinaldi, Nino; Kristiani, Anis

2017-03-01

Natural clays could be modified by the pillarization method, called as Pillared Clays (PILCs). PILCs have been known as porous materials that can be used for many applications, one of the fields is catalysis. PILCs as two dimensional materials are interesting because their structures and textural properties can be controlled by using a metal oxide as the pillar. Different metal oxide used as the pillar causes different properties results of pillared clays. Usually, natural smectite clays/bentonites are used as a raw material. Therefore, a series of bentonite pillared by metal oxides was prepared through pillarization method. Variation of metals pillared into bentonite are aluminium, chromium, zirconium, and ferro. The physicochemical properties of catalysts were characterized by using X-ray Diffraction (XRD), Thermo Gravimetric Analysis (TGA), Brunauer-Emmett-Teller (BET) and Barret-Joyner-Halenda (BJH) analysis, and Fourier transform infrared spectroscopy (FTIR) measurement. Noteworthy characterization results showed that different metals pillared into bentonite affected physical and chemical properties, i.e. basal spacing, surface area, pore size distribution, thermal stability and acidity.

Dimensional and compositional dependent analysis of plasmonic bimetallic nanorods

NASA Astrophysics Data System (ADS)

Bansal, Amit; Singh Sekhon, Jagmeet; Verma, S. S.

2015-11-01

The individual noble metal nanoparticles (NPs) are combined to form alloys with improved optical response, cost effectiveness and better stability. The selection of noble metal alloy NPs for their better use in plasmonic applications is being made on the bases of surface plasmon resonance peak position, its intensity and full width at half maxima (FWHM). Presently, the effect of metal composition (x), aspect ratio (R), size and metal type on the longitudinal plasmon resonance (LPR) of noble metal Ag-Au alloy nanorods (NRs) has been studied by applying modified Gans theory including finite wavelength effects and found that the LPR shifts towards the longer wavelength region with increase in aspect ratio and size of the NR. Moreover, a linear relationship which is in good agreement to the experimental results between the plasmon resonance and aspect ratio has been obtained. The aspect ratio and NR width-dependent absorption efficiency and FWHM have also been calculated. Further, a negligible effect of metal composition and its type is found on the LPR.

Handheld Delivery System for Modified Boron-Type Fire Extinguishment Agent

DTIC Science & Technology

1993-11-01

was to develop and test a handheld portable delivery system for use with the modified boron-type fire extinguishing agent for metal fires . B...BACKGROUND A need exists for an extinguishing agent and accompanying delivery system that are effective against complex geometry metal fires . A modified...agent and its delivery system have proven effective against complex geometry metal fires containing up to 200 pounds of magnesium metal. Further

Corrosion resistance and biocompatibility of magnesium alloy modified by alkali heating treatment followed by the immobilization of poly (ethylene glycol), fibronectin and heparin.

PubMed

Pan, Changjiang; Hu, Youdong; Hou, Yu; Liu, Tao; Lin, Yuebin; Ye, Wei; Hou, Yanhua; Gong, Tao

2017-01-01

In recent years, magnesium alloys are attracting more and more attention as a kind of biodegradable metallic biomaterials, however, their uncontrollable biodegradation speed in vivo and the limited surface biocompatibility hinder their clinical applications. In the present study, with the aim of improving the corrosion resistance and biocompatibility, the magnesium alloy (AZ31B) surface was modified by alkali heating treatment followed by the self-assembly of 3-aminopropyltrimethoxysilane (APTMS). Subsequently, poly (ethylene glycol) (PEG) and fibronectin or fibronectin/heparin complex were sequentially immobilized on the modified surface. The results of attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR) and X-ray photoelectron spectroscopy (XPS) confirmed that the above molecules were successfully immobilized on the magnesium alloy surface. An excellent hydrophilic surface was obtained after the alkali heating treatment while the hydrophilicity decreased to some degree after the self-assembly of APTMS, the surface hydrophilicity was gradually improved again after the immobilization of PEG, fibronectin or fibronectin/heparin complex. The corrosion resistance of the control magnesium alloy was significantly improved by the alkali heating treatment. The self-assembly of APTMS and the following immobilization of PEG further enhanced the corrosion resistance of the substrates, however, the grafting of fibronectin or fibronectin/heparin complex slightly lowered the corrosion resistance. As compared to the pristine magnesium alloy, the samples modified by the immobilization of PEG and fibronectin/heparin complex presented better blood compatibility according to the results of hemolysis assay and platelet adhesion as well as the activated partial thromboplastin time (APTT). In addition, the modified substrates had better cytocompatibility to endothelial cells due to the improved anticorrosion and the introduction of fibronectin. The substrates modified by fibronectin or fibronectin/heparin complex can significantly promote endothelial cell adhesion and proliferation. Taking all these results into consideration, the method of the present study can be used for the surface modification of the magnesium alloy to simultaneously impart it better corrosion resistance, favorable blood compatibility and good cytocompatibility to endothelial cells. Copyright © 2016 Elsevier B.V. All rights reserved.

Adsorption Equilibrium and Kinetics at Goethite-Water and Related Interfaces

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

Katz, Lynn Ellen

This research study is an important component of a broader comprehensive project, “Geochemistry of Interfaces: From Surfaces to Interlayers to Clusters,” which sought to identify and evaluate the critical molecular phenomena at metal-oxide interfaces that control many geochemical and environmental processes. The primary goal of this research study was to better understand and predict adsorption of metal ions at mineral/water surfaces. Macroscopic data in traditional batch experiments was used to develop predictive models that characterize sorption in complex systems containing a wide range of background solution compositions. Our studies focused on systems involving alkaline earth metal (Mg 2+, Ca 2+,more » Sr 2+, Ba 2+) and heavy metal (Hg 2+, Co 2+, Cd 2+, Cu 2+, Zn 2+, Pb 2+) cations. The anions we selected for study included Cl -, NO 3 -, ClO 4 -, SO 4 2-, CO 3 2- and SeO 3 2- and the background electrolyte cations we examined included (Na +, K +, Rb + and Cs +) because these represent a range of ion sizes and have varying potentials for forming ion-pairs or ternary complexes with the metal ions studied. The research led to the development of a modified titration congruency approach for estimating site densities for mineral oxides such as goethite. The CD-MUSIC version of the surface complexation modeling approach was applied to potentiometric titration data and macroscopic adsorption data for single-solute heavy metals, oxyanions, alkaline earth metals and background electrolytes over a range of pH and ionic strength. The model was capable of predicting sorption in bi-solute systems containing multiple cations, cations and oxyanions, and transition metal cations and alkaline earth metal ions. Incorporation of ternary complexes was required for modeling Pb(II)-Se(IV) and Cd(II)-Se(IV) systems. -Both crystal face contributions and capacitance values were shown to be sensitive to varying specific surface area but were successfully accounted for in the modeling strategy. The insights gained from the macroscopic, spectroscopic and CD-MUSIC modeling developed in this study can be used to guide the implementation of less complex models which may be more applicable to field conditions. The findings of this research suggest that surface complexation models can be used as a predictive tool for fate and transport modeling of metal ions and oxyanions in fresh and saline systems typical of energy production waters and wastewaters.« less

Highly reusability surface loaded metal particles magnetic catalyst microspheres (MCM-MPs) for treatment of dye-contaminated water

NASA Astrophysics Data System (ADS)

Liu, Ying; Zhang, Kun; Yin, Xiaoshuang; Yang, Wenzhong; Zhu, Hongjun

2016-04-01

The metal-deposited magnetic catalyst microspheres (MCM-MPs) were successfully synthesized by one facile, high yield and controllable approach. Here, the bare magnetic microspheres were firstly synthesized according to the solvothermal method. Then silica shell were coated on the surface of the magnetic microspheres via sol-gel method, and subsequently with surface modifying with amino in the purpose to form SiO2-NH2 shell. Thus, metal particles were easily adsorbed into the SiO2-NH2 shell and in-situ reduced by NaBH4 solution. All the obtained products (MCM-Cu, MCM-Ag, MCM-Pd) which were monodisperse and constitutionally stable were exhibited high magnetization and excellent catalytic activity towards dyes solution reduction. The catalytic rate ratio of MCM-Pd: MCM-Cu: MCM-Ag could be 10:3:1. Besides, some special coordination compound Cu2(OH)3Br had been generated in the in-situ reduced process of MCM-Cu, which produced superior cyclical stability (>20 times) than that of MCM-Ag and MCM-Pd. In all, those highly reusability and great catalytic efficiency of MCM-MPs show promising and great potential for treatment of dye-contaminated water.

Electric Field-Assisted Orientation of Short Phosphate Glass Fibers on Stainless Steel for Biomedical Applications.

PubMed

Chen, Qiang; Jing, Jiajia; Qi, Hongfei; Ahmed, Ifty; Yang, Haiou; Liu, Xianhu; Lu, T L; Boccaccini, Aldo R

2018-04-11

Structural and compositional modifications of metallic implant surfaces are being actively investigated to achieve improved bone-to-implant bonding. In this study, a strategy to modify bulk metallic surfaces by electrophoretic deposition (EPD) of short phosphate glass fibers (sPGF) is presented. Random and aligned orientation of sPGF embedded in a poly(acrylic acid) matrix is achieved by vertical and horizontal EPD, respectively. The influence of EPD parameters on the degree of alignment is investigated to pave the way for the fabrication of highly aligned sPGF structures in large areas. Importantly, the oriented sPGF structure in the coating, owing to the synergistic effects of bioactive composition and fiber orientation, plays an important role in directional cell migration and enhanced proliferation. Moreover, gene expression of MC3T3-E1 cells cultured with different concentrations of sPGF is thoroughly assessed to elucidate the potential stimulating effect of sPGF on osteogenic differentiation. This study represents an innovative exploitation of EPD to develop textured surfaces by orientation of fibers in the macroscale, which shows great potential for directional functionalization of metallic implants.

Electronic Structure and Band Gap of Fullerenes on Tungsten Surfaces: Transition from a Semiconductor to a Metal Triggered by Annealing.

PubMed

Monazami, Ehsan; McClimon, John B; Rondinelli, James; Reinke, Petra

2016-12-21

The understanding and control of molecule-metal interfaces is critical to the performance of molecular electronics and photovoltaics devices. We present a study of the interface between C 60 and W, which is a carbide-forming transition metal. The complex solid-state reaction at the interface can be exploited to adjust the electronic properties of the molecule layer. Scanning tunneling microscopy/spectroscopy measurements demonstrate the progression of this reaction from wide band gap (>2.5 eV) to metallic molecular surface during annealing from 300 to 800 K. Differential conduction maps with 10 4 scanning tunneling spectra are used to quantify the transition in the density of states and the reduction of the band gap during annealing with nanometer spatial resolution. The electronic transition is spatially homogeneous, and the surface band gap can therefore be adjusted by a targeted annealing step. The modified molecules, which we call nanospheres, are quite resistant to ripening and coalescence, unlike any other metallic nanoparticle of the same size. Densely packed C 60 and isolated C 60 molecules show the same transition in electronic structure, which confirms that the transformation is controlled by the reaction at the C 60 -W interface. Density functional theory calculations are used to develop possible reaction pathways in agreement with experimentally observed electronic structure modulation. Control of the band gap by the choice of annealing temperature is a unique route to tailoring molecular-layer electronic properties.

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.

Competitive adsorption of Cd2+, Pb2+ and Ni2+ onto Fe3+-modified argillaceous limestone: Influence of pH, ionic strength and natural organic matters.

PubMed

He, Shuran; Li, Yongtao; Weng, Liping; Wang, Jinjin; He, Jinxian; Liu, Yonglin; Zhang, Kun; Wu, Qihong; Zhang, Yulong; Zhang, Zhen

2018-10-01

In present study, the feasibility of applying a natural adsorbent with Fe 3+ modification (Fe 3+ -modified argillaceous limestone, FAL) on the competitive adsorption of heavy metals (i.e., Cd 2+ , Pb 2+ and Ni 2+ ) was evaluated. The current results revealed an efficient adsorption on Cd 2+ , Pb 2+ and Ni 2+ in mono-metal system. Further experiments demonstrated a high selectivity of Pb 2+ during the competitive adsorption of Cd 2+ , Pb 2+ and Ni 2+ . The adsorption selectivity of the metal ions followed the order of Pb ≫ Cd > Ni. In addition, both pH and ionic strength are important factors affecting the metal adsorptions. It is interestingly that various NOMs (i.e., humic acid (HA) and glycine (Gly)) exerted different effects on the adsorption behaviors, probably due to the different affinities for Pb 2+ , Cd 2+ and Ni 2+ and the redistribution of newly-formed metal-DOM complexes. X-ray photoelectron spectroscopy (XPS) analysis together with X-ray diffraction (XRD) and energy dispersive spectrometer (EDS) analysis revealed that the metal adsorptions were mainly regulated via the synergistic mechanisms of ion exchange by Na + , Ca 2+ , and Al 3+ , precipitation to form CdCO 3 and Pb 2 (OH) 2 (CO 3 ) 2 , as well as complexes of FAL-OPb and FAL-ONi by hydroxyl groups on the surface of FAL. The application of FAL would be a promising option in leading to an efficient heavy metal removal. Copyright © 2018 Elsevier B.V. All rights reserved.

In-situ Raman and X-ray photoelectron spectroscopic studies on the pitting corrosion of modified 9Cr-1Mo steel in neutral chloride solution

NASA Astrophysics Data System (ADS)

Ramya, S.; Nanda Gopala Krishna, D.; Mudali, U. Kamachi

2018-01-01

In-situ Raman and X-ray photoelectron spectroscopic studies were performed for the identification of native and corroded surface oxide layers of modified 9Cr-1Mo steel. The Raman data obtained for native oxide layer of modified 9Cr-1Mo steel revealed that it was mainly composed of oxides of Fe and Cr. The presence of alloying element Mo was found to be less significant in the native oxide film. The oxides of Cr were dominant at the surface and were found to be decreasing closer to metal/oxide layer interface. The changes in the chemical composition of the native films upon in-situ pitting during potentiostatic polarization experiment were characterized by in-situ Raman analysis. The corrosion products of potentiostatically polarized modified 9Cr-1Mo steel was composed of dominant Fe (III) phases viz., γ- Fe2O3, α and γ - FeOOH along with the oxides of chromium. The results from Raman analysis were corroborated with the XPS experiments on as received and pitted samples of modified 9Cr-1Mo steel specimens. It was observed that the oxides of Cr and Mo contributed for the stability of the surface layer by forming Cr2O3 and MoO3. Also, the study attempted to find out the intermediate corrosion products inside the metastable pits to account for the pseudo passive behavior of modified 9Cr-1Mo steel in 0.1 M NaCl solution.

Metal modified tungsten carbide (WC) for catalytic and electrocatalytic applications

NASA Astrophysics Data System (ADS)

Mellinger, Zachary J.

One of the major challenges in the commercialization of proton exchange membrane fuel cells (PEMFC) is the cost, and low CO tolerance of the anode electrocatalyst material. The anode typically requires a high loading of precious metal electrocatalyst (Pt or Pt--Ru) to obtain a useful amount of electrical energy from the electrooxidation of methanol (CH3OH) or ethanol (C2H5OH). The complete electro--oxidation of methanol or ethanol on these catalysts produces strongly adsorbed CO on the surface, which reduces the activity of the Pt or Pt--Ru catalysts. Another major disadvantage of these electrocatalyst components is the scarcity and consequently high price of both Pt and Ru. Tungsten monocarbide (WC) has shown similar catalytic properties to Pt, leading to the utilization of WC and metal modified WC as replacements to Pt and Pt--Ru. In this thesis we investigated WC and Pt--modified WC as a potentially more CO--tolerant electrocatalysts as compared to pure Pt. These catalysts would reduce or remove the high loading of Pt used industrially. The binding energy of CO, estimated using temperature programmed desorption, is weaker on WC and Pt/WC than on Pt, suggesting that it should be easier to oxidize CO on WC and Pt/WC. This hypothesis was verified using cyclic voltammetry to compare the electro--oxidation of CO on WC, Pt/WC, and Pt supported on carbon substrates, which showed a lower voltage for the onset of oxidation of CO on WC and Pt/WC than on Pt. After observing these improved properties on the Pt/WC catalysts, we decided to expand our studies to investigate Pd--modified WC as Pd is less expensive than Pt and has shown more ideal properties for alcohol electrocatalysis in alkaline media. Pd/WC showed a lower binding energy of CO than both its parent metal Pd as well as Pt. Then, density functional theory (DFT) calculations were performed to determine how the presence of Pd affected the bonding of methanol and ethanol on the WC surface. The DFT studies showed that the binding energies for methanol and methoxy as well as ethanol and ethoxy on one monolayer (ML) Pd/WC are more similar to Pd than to WC. This predicts that the ML Pd/WC surface should have catalytic properties more similar to Pd than to WC. Ultra--high vacuum (UHV) experiments were then performed to determine the reaction products and pathways for methanol and ethanol on Pd(111), WC, and Pd/WC surfaces. These studies showed that the WC surface was very active toward the O--H bond cleavage to produce a methoxy intermediate, although WC was also undesirable because it was active for C--O bond scission and less active for the C--H bond scission. Adding Pd on WC enhanced the scission of the C--H bonds of methoxy while removing the C--O bond scission reaction pathway, suggesting a synergistic effect of using Pd/WC as electrocatalysts for methanol and ethanol decomposition. Dissociation of water, which is important for CO tolerance, was also investigated using UHV techniques with the conclusion that both the WC and Pd/WC surfaces dissociated water. The predictions from UHV studies was verified in electrochemical experiments using cyclic voltammetry (CV) and chronoamperometry (CA) measurements of electro--oxidation of methanol and ethanol in an alkaline environment. These experiments showed that Pd/WC was electrochemically active towards methanol and ethanol decomposition and has greater electrochemical stability over time than pure Pd, potentially due to higher CO tolerance for Pd/WC.

Surface tailored organobentonite enhances bacterial proliferation and phenanthrene biodegradation under cadmium co-contamination.

PubMed

Mandal, Asit; Biswas, Bhabananda; Sarkar, Binoy; Patra, Ashok K; Naidu, Ravi

2016-04-15

Co-contamination of soil and water with polycyclic aromatic hydrocarbon (PAH) and heavy metals makes biodegradation of the former extremely challenging. Modified clay-modulated microbial degradation provides a novel insight in addressing this issue. This study was conducted to evaluate the growth and phenanthrene degradation performance of Mycobacterium gilvum VF1 in the presence of a palmitic acid (PA)-grafted Arquad® 2HT-75-based organobentonite in cadmium (Cd)-phenanthrene co-contaminated water. The PA-grafted organobentonite (ABP) adsorbed a slightly greater quantity of Cd than bentonite at up to 30mgL(-1) metal concentration, but its highly negative surface charge imparted by carboxylic groups indicated the potential of being a significantly superior adsorbent of Cd at higher metal concentrations. In systems co-contained with Cd (5 and 10mgL(-1)), the Arquad® 2HT-75-modified bentonite (AB) and PA-grafted organobentonite (ABP) resulted in a significantly higher (72-78%) degradation of phenanthrene than bentonite (62%) by the bacterium. The growth and proliferation of bacteria were supported by ABP which not only eliminated Cd toxicity through adsorption but also created a congenial microenvironment for bacterial survival. The macromolecules produced during ABP-bacteria interaction could form a stable clay-bacterial cluster by overcoming the electrostatic repulsion among individual components. Findings of this study provide new insights for designing clay modulated PAH bioremediation technologies in mixed-contaminated water and soil. Copyright © 2016 Elsevier B.V. All rights reserved.

Estimation of Enthalpy of Formation of Liquid Transition Metal Alloys: A Modified Prescription Based on Macroscopic Atom Model of Cohesion

NASA Astrophysics Data System (ADS)

Raju, Subramanian; Saibaba, Saroja

2016-09-01

The enthalpy of formation Δo H f is an important thermodynamic quantity, which sheds significant light on fundamental cohesive and structural characteristics of an alloy. However, being a difficult one to determine accurately through experiments, simple estimation procedures are often desirable. In the present study, a modified prescription for estimating Δo H f L of liquid transition metal alloys is outlined, based on the Macroscopic Atom Model of cohesion. This prescription relies on self-consistent estimation of liquid-specific model parameters, namely electronegativity ( ϕ L) and bonding electron density ( n b L ). Such unique identification is made through the use of well-established relationships connecting surface tension, compressibility, and molar volume of a metallic liquid with bonding charge density. The electronegativity is obtained through a consistent linear scaling procedure. The preliminary set of values for ϕ L and n b L , together with other auxiliary model parameters, is subsequently optimized to obtain a good numerical agreement between calculated and experimental values of Δo H f L for sixty liquid transition metal alloys. It is found that, with few exceptions, the use of liquid-specific model parameters in Macroscopic Atom Model yields a physically consistent methodology for reliable estimation of mixing enthalpies of liquid alloys.

Ion exchange materials, method of forming ion exchange materials, and methods of treating liquids

DOEpatents

Wertsching, Alan K.; Peterson, Eric S.; Wey, John E.

2007-12-25

The invention includes an ion affinity material having an organic component which is sulfonated and which is chemically bonded to an inorganic substrate component. The invention includes a method of forming a metal binding material. A solid support material comprising surface oxide groups is provided and an organic component having at least one alkyl halide is covalently linked to at least some of the surface oxide groups to form a modified support material. The at least one alkyl halide is subsequently converted into an alkyl sulfonate. The invention further includes a method and system for extracting ions from a liquid. An ion exchange material having a sulfonated alkyl silane component covalently bonded to a metal oxide support material is provided and a liquid is exposed to the ion exchange material.

High-Yield Excited Triplet States in Pentacene Self-Assembled Monolayers on Gold Nanoparticles through Singlet Exciton Fission.

PubMed

Kato, Daiki; Sakai, Hayato; Tkachenko, Nikolai V; Hasobe, Taku

2016-04-18

One of the major drawbacks of organic-dye-modified self-assembled monolayers on metal nanoparticles when employed for efficient use of light energy is the fact that singlet excited states on dye molecules can be easily deactivated by means of energy transfer to the metal surface. In this study, a series of 6,13-bis(triisopropylsilylethynyl)pentacene-alkanethiolate monolayer protected gold nanoparticles with different particle sizes and alkane chain lengths were successfully synthesized and were employed for the efficient generation of excited triplet states of the pentacene derivatives by singlet fission. Time-resolved transient absorption measurements revealed the formation of excited triplet states in high yield (172±26 %) by suppressing energy transfer to the gold surface. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Soft-Templating Synthesis of Mesoporous Silica-Based Materials for Environmental Applications

NASA Astrophysics Data System (ADS)

Gunathilake, Chamila Asanka

Dissertation research is mainly focus on: 1) the development of mesoporous silica materials with organic pendant and bridging groups (isocyanurate, amidoxime, benzene) and incorporated metal (aluminum, zirconium, calcium, and magnesium) species for high temperature carbon dioxide (CO2) sorption, 2) phosphorous-hydroxy functionalized mesoporous silica materials for water treatment, and 3) amidoxime-modified ordered mesoporous silica materials for uranium sorption under seawater conditions. The goal is to design composite materials for environmental applications with desired porosity, surface area, and functionality by selecting proper metal oxide precursors, organosilanes, tetraethylorthosilicate, (TEOS), and block copolymer templates and by adjusting synthesis conditions. The first part of dissertation presents experimental studies on the merge of aluminum, zirconium, calcium, and magnesium oxides with mesoporous silica materials containing organic pendant (amidoxime) and bridging groups (isocyanurate, benzene) to obtain composite sorbents for CO2 sorption at ambient (0-25 °C) and elevated (60-120 °C) temperatures. These studies indicate that the aforementioned composite sorbents are fairly good for CO2 capture at 25 °C via physisorption mechanism and show a remarkably high affinity toward CO2 chemisorption at 60-120 °C. The second part of dissertation is devoted to silica-based materials with organic functionalities for removal of heavy metal ions such as lead from contaminated water and for recovery of metal ions such as uranium from seawater. First, ordered mesoporous organosilica (OMO) materials with diethylphosphatoethyl and hydroxyphosphatoethyl surface groups were examined for Pb2+ adsorption and showed unprecedented adsorption capacities up to 272 mg/g and 202 mg/g, respectively However, the amidoxime-modified OMO materials were explored for uranium extraction under seawater conditions and showed remarkable capacities reaching 57 mg of uranium per gram of adsorbent.

Nanocellulose-Based Materials for Water Purification

PubMed Central

Voisin, Hugo; Bergström, Lennart; Liu, Peng; Mathew, Aji P.

2017-01-01

Nanocellulose is a renewable material that combines a high surface area with high strength, chemical inertness, and versatile surface chemistry. In this review, we will briefly describe how nanocellulose is produced, and present—in particular, how nanocellulose and its surface modified versions affects the adsorption behavior of important water pollutants, e.g., heavy metal species, dyes, microbes, and organic molecules. The processing of nanocellulose-based membranes and filters for water purification will be described in detail, and the uptake capacity, selectivity, and removal efficiency will also be discussed. The processing and performance of nanocellulose-based membranes, which combine a high removal efficiency with anti-fouling properties, will be highlighted. PMID:28336891

Quantitative Hydrocarbon Surface Analysis

NASA Technical Reports Server (NTRS)

Douglas, Vonnie M.

2000-01-01

The elimination of ozone depleting substances, such as carbon tetrachloride, has resulted in the use of new analytical techniques for cleanliness verification and contamination sampling. The last remaining application at Rocketdyne which required a replacement technique was the quantitative analysis of hydrocarbons by infrared spectrometry. This application, which previously utilized carbon tetrachloride, was successfully modified using the SOC-400, a compact portable FTIR manufactured by Surface Optics Corporation. This instrument can quantitatively measure and identify hydrocarbons from solvent flush of hardware as well as directly analyze the surface of metallic components without the use of ozone depleting chemicals. Several sampling accessories are utilized to perform analysis for various applications.

Quantitative analysis of enamel on debonded orthodontic brackets.

PubMed

Cochrane, Nathan J; Lo, Thomas W G; Adams, Geoffrey G; Schneider, Paul M

2017-09-01

Iatrogenic damage to the tooth surface in the form of enamel tearouts can occur during removal of fixed orthodontic appliances. The aim of this study was to assess debonded metal and ceramic brackets attached with a variety of bonding materials to determine how frequently this type of damage occurs. Eighty-one patients close to finishing fixed orthodontic treatment were recruited. They had metal brackets bonded with composite resin and a 2-step etch-and-bond technique or ceramic brackets bonded with composite resin and a 2-step etch-and- bond technique, and composite resin with a self-etching primer or resin-modified glass ionomer cement. Debonded brackets were examined by backscattered scanning electron microscopy with energy dispersive x-ray spectroscopy to determine the presence and area of enamel on the base pad. Of the 486 brackets collected, 26.1% exhibited enamel on the bonding material on the bracket base pad. The incidences of enamel tearouts for each group were metal brackets, 13.3%; ceramic brackets, 30.2%; composite resin with self-etching primer, 38.2%; and resin-modified glass ionomer cement, 21.2%. The percentage of the bracket base pad covered in enamel was highly variable, ranging from 0% to 46.1%. Enamel damage regularly occurred during the debonding process with the degree of damage being highly variable. Damage occurred more frequently when ceramic brackets were used (31.9%) compared with metal brackets (13.3%). Removal of ceramic brackets bonded with resin-modified glass ionomer cement resulted in less damage compared with the resin bonding systems. Copyright © 2017 American Association of Orthodontists. Published by Elsevier Inc. All rights reserved.

Excited-state potential-energy surfaces of metal-adsorbed organic molecules from linear expansion Δ-self-consistent field density-functional theory (ΔSCF-DFT).

PubMed

Maurer, Reinhard J; Reuter, Karsten

2013-07-07

Accurate and efficient simulation of excited state properties is an important and much aspired cornerstone in the study of adsorbate dynamics on metal surfaces. To this end, the recently proposed linear expansion Δ-self-consistent field method by Gavnholt et al. [Phys. Rev. B 78, 075441 (2008)] presents an efficient alternative to time consuming quasi-particle calculations. In this method, the standard Kohn-Sham equations of density-functional theory are solved with the constraint of a non-equilibrium occupation in a region of Hilbert-space resembling gas-phase orbitals of the adsorbate. In this work, we discuss the applicability of this method for the excited-state dynamics of metal-surface mounted organic adsorbates, specifically in the context of molecular switching. We present necessary advancements to allow for a consistent quality description of excited-state potential-energy surfaces (PESs), and illustrate the concept with the application to Azobenzene adsorbed on Ag(111) and Au(111) surfaces. We find that the explicit inclusion of substrate electronic states modifies the topologies of intra-molecular excited-state PESs of the molecule due to image charge and hybridization effects. While the molecule in gas phase shows a clear energetic separation of resonances that induce isomerization and backreaction, the surface-adsorbed molecule does not. The concomitant possibly simultaneous induction of both processes would lead to a significantly reduced switching efficiency of such a mechanism.

Vertical Carbon Nanotube Device in Nanoporous Templates

NASA Technical Reports Server (NTRS)

Sands, Timothy (Inventor); Fisher, Timothy Scott (Inventor); Bashir, Rashid (Inventor); Maschmann, Matthew Ralph (Inventor)

2014-01-01

A modified porous anodic alumina template (PAA) containing a thin CNT catalyst layer directly embedded into the pore walls. CNT synthesis using the template selectively catalyzes SWNTs and DWNTs from the embedded catalyst layer to the top PAA surface, creating a vertical CNT channel within the pores. Subsequent processing allows for easy contact metallization and adaptable functionalization of the CNTs and template for a myriad of applications.

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

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

Rath, Swagat S., E-mail: swagat.rath@gmail.com; Nayak, Pradeep; Mukherjee, P.S.

2012-03-15

Highlights: Black-Right-Pointing-Pointer Sentences/phrases were modified. Black-Right-Pointing-Pointer Necessary discussions for different figures were included. Black-Right-Pointing-Pointer More discussion have been included on the flue gas analysis. Black-Right-Pointing-Pointer Queries to both the reviewers have been given. - Abstract: 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 asmore » 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.« less

Controlled surface segregation leads to efficient coke-resistant nickel/platinum bimetallic catalysts for the dry reforming of methane

DOE PAGES

Li, Lidong; Zhou, Lu; Ould-Chikh, Samy; ...

2015-02-03

Surface composition and structure are of vital importance for heterogeneous catalysts, especially for bimetallic catalysts, which often vary as a function of reaction conditions (known as surface segregation). The preparation of bimetallic catalysts with controlled metal surface composition and structure is very challenging. In this study, we synthesize a series of Ni/Pt bimetallic catalysts with controlled metal surface composition and structure using a method derived from surface organometallic chemistry. The evolution of the surface composition and structure of the obtained bimetallic catalysts under simulated reaction conditions is investigated by various techniques, which include CO-probe IR spectroscopy, high-angle annular dark-field scanningmore » transmission electron microscopy, energy-dispersive X-ray spectroscopy, extended X-ray absorption fine structure analysis, X-ray absorption near-edge structure analysis, XRD, and X-ray photoelectron spectroscopy. It is demonstrated that the structure of the bimetallic catalyst is evolved from Pt monolayer island-modified Ni nanoparticles to core–shell bimetallic nanoparticles composed of a Ni-rich core and a Ni/Pt alloy shell upon thermal treatment. As a result, these catalysts are active for the dry reforming of methane, and their catalytic activities, stabilities, and carbon formation vary with their surface composition and structure.« less

Systems and Methods of Laser Texturing of Material Surfaces and Their Applications

NASA Technical Reports Server (NTRS)

Gupta, Mool C. (Inventor); Nayak, Barada K. (Inventor)

2014-01-01

The surface of a material is textured and by exposing the surface to pulses from an ultrafast laser. The laser treatment causes pillars to form on the treated surface. These pillars provide for greater light absorption. Texturing and crystallization can be carried out as a single step process. The crystallization of the material provides for higher electric conductivity and changes in optical and electronic properties of the material. The method may be performed in vacuum or a gaseous environment. The gaseous environment may aid in texturing and/or modifying physical and chemical properties of the surfaces. This method may be used on various material surfaces, such as semiconductors, metals and their alloys, ceramics, polymers, glasses, composites, as well as crystalline, nanocrystalline, polycrystalline, microcrystalline, and amorphous phases.

Influence of the sulfur species reactivity on biofilm conformation during pyrite colonization by Acidithiobacillus thiooxidans.

PubMed

Lara, René H; García-Meza, J Viridiana; Cruz, Roel; Valdez-Pérez, Donato; González, Ignacio

2012-08-01

Massive pyrite (FeS₂) electrodes were potentiostatically modified by means of variable oxidation pulse to induce formation of diverse surface sulfur species (S(n)²⁻, S⁰). The evolution of reactivity of the resulting surfaces considers transition from passive (e.g., Fe(1-x )S₂) to active sulfur species (e.g., Fe(1-x )S(2-y ), S⁰). Selected modified pyrite surfaces were incubated with cells of sulfur-oxidizing Acidithiobacillus thiooxidans for 24 h in a specific culture medium (pH 2). Abiotic control experiments were also performed to compare chemical and biological oxidation. After incubation, the attached cells density and their exopolysaccharides were analyzed by confocal laser scanning microscopy (CLMS) and atomic force microscopy (AFM) on bio-oxidized surfaces; additionally, S(n)²⁻/S⁰ speciation was carried out on bio-oxidized and abiotic pyrite surfaces using Raman spectroscopy. Our results indicate an important correlation between the evolution of S(n)²⁻/S⁰ surface species ratio and biofilm formation. Hence, pyrite surfaces with mainly passive-sulfur species were less colonized by A. thiooxidans as compared to surfaces with active sulfur species. These results provide knowledge that may contribute to establishing interfacial conditions that enhance or delay metal sulfide (MS) dissolution, as a function of the biofilm formed by sulfur-oxidizing bacteria.

Optical properties study of silicone polymer PDMS substrate surfaces modified by plasma treatment

NASA Astrophysics Data System (ADS)

Zahid, A.; Dai, B.; Hong, R.; Zhang, D.

2017-10-01

In this study, PDMS (polydimethylsiloxane) substrates with a half-plain, half-rough surface were prepared on a plain and rough fused silica glass substrate using a molding technique. The molded PDMS surface morphology was changed into a half-smooth and half-rough surface after peeling. The modified PDMS surfaces’ optical properties were inspected with and without treatment. The treatment is exposed by oxygen plasma (15 W) for 3 min in a vacuum, down to a pressure of six torr, using a vacuum pump. An atomic force microscope (AMF) and interferometer (white light) indicated that the plasma O2 treatment increased the formation of the plain surface and decreased the formation of the rough surface. The optical properties via a spectrophotometer (lambda) show the resonance from 300 nm to 1200 nm on the rough surface, which is considered to be a faithful reproduction for transmittance and reflectance. The Raman spectra and FDTD simulation results are in excellent agreement; not to be confused with metal local surface plasmon resonances (LSPRs). The Raman spectra peaks and hotspot are the results of the PDMS Si-O backbone. The PDMS substrate presented the diversity of the optical properties, which makes the substrate complementary to various optical applications.

Covalent Functionalization of NiTi Surfaces with Bioactive Peptide Amphiphile Nanofibers

PubMed Central

Sargeant, Timothy D.; Rao, Mukti S.; Koh, Chung-Yan

2009-01-01

Surface modification enables the creation of bioactive implants using traditional material substrates without altering the mechanical properties of the bulk material. For applications such as bone plates and stents, it is desirable to modify the surface of metal alloy substrates to facilitate cellular attachment, proliferation, and possibly differentiation. In this work we present a general strategy for altering the surface chemistry of nickel-titanium shape memory alloy (NiTi) in order to covalently attach self-assembled peptide amphiphile (PA) nanofibers with bioactive functions. Bioactivity in the systems studied here includes biological adhesion and proliferation of osteoblast and endothelial cell types. The optimized surface treatment creates a uniform TiO2 layer with low levels of Ni on the NiTi surface, which is subsequently covered with an aminopropylsilane coating using a novel, lower temperature vapor deposition method. This method produces an aminated surface suitable for covalent attachment of PA molecules containing terminal carboxylic acid groups. The functionalized NiTi surfaces have been characterized by X-ray photoelectron spectroscopy (XPS), time-of-flight secondary ion mass spectroscopy (ToF-SIMS), and atomic force microscopy (AFM). These techniques offer evidence that the treated metal surfaces consist primarily of TiO2 with very little Ni, and also confirm the presence of the aminopropylsilane overlayer. Self-assembled PA nanofibers presenting the biological peptide adhesion sequence Arg-Gly-Asp-Ser are capable of covalently anchoring to the treated substrate, as demonstrated by spectrofluorimetry and AFM. Cell culture and scanning electron microscopy (SEM) demonstrate cellular adhesion, spreading, and proliferation on these functionalized metal surfaces. Furthermore, these experiments demonstrate that covalent attachment is crucial for creating robust PA nanofiber coatings, leading to confluent cell monolayers. PMID:18083225

Modified local diatomite as potential functional drug carrier--A model study for diclofenac sodium.

PubMed

Janićijević, Jelena; Krajišnik, Danina; Čalija, Bojan; Vasiljević, Bojana Nedić; Dobričić, Vladimir; Daković, Aleksandra; Antonijević, Milan D; Milić, Jela

2015-12-30

Diatomite makes a promising candidate for a drug carrier because of its high porosity, large surface area, modifiable surface chemistry and biocompatibility. Herein, refined diatomite from Kolubara coal basin, which complied with the pharmacopoeial requirements for heavy metals content and microbiological quality, was used as a starting material. Inorganic modification of the starting material was performed through a simple, one-step procedure. Significant increase in adsorbent loading with diclofenac sodium (DS) was achieved after the modification process (∼373mg/g) which enabled the preparation of comprimates containing therapeutic dose of the adsorbed drug. Adsorption of DS onto modified diatomite resulted in the alteration of the drug's XRD pattern and FTIR spectrum. In vitro drug release studies in phosphate buffer pH 7.5 demonstrated prolonged DS release over 8h from comprimates containing DS adsorbed on modified diatomite (up to 37% after 8h) and those containing physical mixture of the same composition (up to 45% after 8h). The results of in vivo toxicity testing on mice pointed on potential safety of both unmodified (starting) and modified diatomite. All these findings favor the application of diatomite as a potential functional drug carrier. Copyright © 2015 Elsevier B.V. All rights reserved.

Seed-induced growth of flower-like Au-Ni-ZnO metal-semiconductor hybrid nanocrystals for photocatalytic applications.

PubMed

Chen, Yuanzhi; Zeng, Deqian; Cortie, Michael B; Dowd, Annette; Guo, Huizhang; Wang, Junbao; Peng, Dong-Liang

2015-03-25

The combination of metal and semiconductor components in nanoscale to form a hybrid nanocrystal provides an important approach for achieving advanced functional materials with special optical, magnetic and photocatalytic functionalities. Here, a facile solution method is reported for the synthesis of Au-Ni-ZnO metal-semiconductor hybrid nanocrystals with a flower-like morphology and multifunctional properties. This synthetic strategy uses noble and magnetic metal Au@Ni nanocrystal seeds formed in situ to induce the heteroepitaxial growth of semiconducting ZnO nanopyramids onto the surface of metal cores. Evidence of epitaxial growth of ZnO{0001} facets on Ni {111} facets is observed on the heterojunction, even though there is a large lattice mismatch between the semiconducting and magnetic components. Adjustment of the amount of Au and Ni precursors can control the size and composition of the metal core, and consequently modify the surface plasmon resonance (SPR) and magnetic properties. Room-temperature superparamagnetic properties can be achieved by tuning the size of Ni core. The as-prepared Au-Ni-ZnO nanocrystals are strongly photocatalytic and can be separated and re-cycled by virtue of their magnetic properties. The simultaneous combination of plasmonic, semiconducting and magnetic components within a single hybrid nanocrystal furnishes it multifunctionalities that may find wide potential applications. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Cleavage fracture in high strength low alloy weld metal

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

Bose, W.W.; Bowen, P.; Strangwood, M.

1996-12-31

The present investigation gives an evaluation of the effect of microstructure on the cleavage fracture process of High Strength Low Alloy (HSLA) multipass weld metals. With additions of alloying elements, such as Ti, Ni, Mo and Cr, the microstructure of C-Mn weld metal changes from the classical composition, i.e., allotriomorphic ferrite with acicular ferrite and Widmanstaetten ferrite, to bainite and low carbon martensite. Although the physical metallurgy of some HSLA weld metals has been studied before, more work is necessary to correlate the effect of the microstructure on the fracture behavior of such weld metals. In this work detailed microstructuralmore » analysis was carried out using optical and electron (SEM and TEM) microscopy. Single edge notched (SEN) bend testpieces were used to assess the cleavage fracture stress, {sigma}{sub F}. Inclusions beneath the notch surface were identified as the crack initiators of unstable cleavage fracture. From the size of such inclusions and the value of tensile stress predicted at the initiation site, the effective surface energy for cleavage was calculated using a modified Griffth energy balance for a penny shape crack. The results suggest that even though inclusions initiate cleavage fracture, the local microstructure may play an important role in the fracture process of these weld metals. The implications of these observations for a quantitative theory of the cleavage fracture of ferritic steels is discussed.« less

Extremely durable biofouling-resistant metallic surfaces based on electrodeposited nanoporous tungstite films on steel

PubMed Central

Tesler, Alexander B.; Kim, Philseok; Kolle, Stefan; Howell, Caitlin; Ahanotu, Onye; Aizenberg, Joanna

2015-01-01

Formation of unwanted deposits on steels during their interaction with liquids is an inherent problem that often leads to corrosion, biofouling and results in reduction in durability and function. Here we report a new route to form anti-fouling steel surfaces by electrodeposition of nanoporous tungsten oxide (TO) films. TO-modified steels are as mechanically durable as bare steel and highly tolerant to compressive and tensile stresses due to chemical bonding to the substrate and island-like morphology. When inherently superhydrophilic TO coatings are converted to superhydrophobic, they remain non-wetting even after impingement with yttria-stabilized-zirconia particles, or exposure to ultraviolet light and extreme temperatures. Upon lubrication, these surfaces display omniphobicity against highly contaminating media retaining hitherto unseen mechanical durability. To illustrate the applicability of such a durable coating in biofouling conditions, we modified naval construction steels and surgical instruments and demonstrated significantly reduced marine algal film adhesion, Escherichia coli attachment and blood staining. PMID:26482559

Extremely durable biofouling-resistant metallic surfaces based on electrodeposited nanoporous tungstite films on steel

NASA Astrophysics Data System (ADS)

Tesler, Alexander B.; Kim, Philseok; Kolle, Stefan; Howell, Caitlin; Ahanotu, Onye; Aizenberg, Joanna

2015-10-01

Formation of unwanted deposits on steels during their interaction with liquids is an inherent problem that often leads to corrosion, biofouling and results in reduction in durability and function. Here we report a new route to form anti-fouling steel surfaces by electrodeposition of nanoporous tungsten oxide (TO) films. TO-modified steels are as mechanically durable as bare steel and highly tolerant to compressive and tensile stresses due to chemical bonding to the substrate and island-like morphology. When inherently superhydrophilic TO coatings are converted to superhydrophobic, they remain non-wetting even after impingement with yttria-stabilized-zirconia particles, or exposure to ultraviolet light and extreme temperatures. Upon lubrication, these surfaces display omniphobicity against highly contaminating media retaining hitherto unseen mechanical durability. To illustrate the applicability of such a durable coating in biofouling conditions, we modified naval construction steels and surgical instruments and demonstrated significantly reduced marine algal film adhesion, Escherichia coli attachment and blood staining.

Extremely durable biofouling-resistant metallic surfaces based on electrodeposited nanoporous tungstite films on steel

DOE PAGES

Tesler, Alexander B.; Kim, Philseok; Kolle, Stefan; ...

2015-10-20

Formation of unwanted deposits on steels during their interaction with liquids is an inherent problem that often leads to corrosion, biofouling and results in reduction in durability and function. Here we report a new route to form anti-fouling steel surfaces by electrodeposition of nanoporous tungsten oxide (TO) films. TO-modified steels are as mechanically durable as bare steel and highly tolerant to compressive and tensile stresses due to chemical bonding to the substrate and island-like morphology. When inherently superhydrophilic TO coatings are converted to superhydrophobic, they remain non-wetting even after impingement with yttria-stabilized-zirconia particles, or exposure to ultraviolet light and extrememore » temperatures. Upon lubrication, these surfaces display omniphobicity against highly contaminating media retaining hitherto unseen mechanical durability. Furthermore, to illustrate the applicability of such a durable coating in biofouling conditions, we modified naval construction steels and surgical instruments and demonstrated significantly reduced marine algal film adhesion, Escherichia coli attachment and blood staining.« less

Effect of sandblasting intensity on microstructures and properties of pure titanium micro-arc oxidation coatings in an optimized composite technique

NASA Astrophysics Data System (ADS)

Wang, Hong-Yuan; Zhu, Rui-Fu; Lu, Yu-Peng; Xiao, Gui-Yong; He, Kun; Yuan, Y. F.; Ma, Xiao-Ni; Li, Ying

2014-02-01

Sandblasting is one of the most effective methods to modify a metal surface and improve its properties for application. Micro-arc oxidation (MAO) could produce a ceramic coating on a dental implant, facilitating cellular differentiation and osseocomposite on it. This study aims to deposit bioceramic Ca- and P-containing coatings on sandblasted commercially pure titanium by an optimum composite technique to improve the bioactive performance. The effect of sandblasting intensity on microstructures and properties of the implant coatings is examined, and the modified surfaces are characterized in terms of their topography, phase, chemical composition, mechanical properties and hydroxyapatite (HA)-inducing ability. The results show that a moderate sandblasting micromachines the substrate in favorable combination of rough and residual stresses; its MAO coating deposits nano-hydroxyapatite after immersion in simulated body fluid (SBF) for 5 days exhibiting better bioactivity. The further improvement of the implant surface performance is attributed to an optimized composite technique.

Detonation nanodiamonds biofunctionalization and immobilization to titanium alloy surfaces as first steps towards medical application.

PubMed

Gonçalves, Juliana P L; Shaikh, Afnan Q; Reitzig, Manuela; Kovalenko, Daria A; Michael, Jan; Beutner, René; Cuniberti, Gianaurelio; Scharnweber, Dieter; Opitz, Jörg

2014-01-01

Due to their outstanding properties nanodiamonds are a promising nanoscale material in various applications such as microelectronics, polishing, optical monitoring, medicine and biotechnology. Beyond the typical diamond characteristics like extreme hardness or high thermal conductivity, they have additional benefits as intrinsic fluorescence due to lattice defects without photobleaching, obtained during the high pressure high temperature process. Further the carbon surface and its various functional groups in consequence of the synthesis, facilitate additional chemical and biological modification. In this work we present our recent results on chemical modification of the nanodiamond surface with phosphate groups and their electrochemically assisted immobilization on titanium-based materials to increase adhesion at biomaterial surfaces. The starting material is detonation nanodiamond, which exhibits a heterogeneous surface due to the functional groups resulting from the nitrogen-rich explosives and the subsequent purification steps after detonation synthesis. Nanodiamond surfaces are chemically homogenized before proceeding with further functionalization. Suspensions of resulting surface-modified nanodiamonds are applied to the titanium alloy surfaces and the nanodiamonds subsequently fixed by electrochemical immobilization. Titanium and its alloys have been widely used in bone and dental implants for being a metal that is biocompatible with body tissues and able to bind with adjacent bone during healing. In order to improve titanium material properties towards biomedical applications the authors aim to increase adhesion to bone material by incorporating nanodiamonds into the implant surface, namely the anodically grown titanium dioxide layer. Differently functionalized nanodiamonds are characterized by infrared spectroscopy and the modified titanium alloys surfaces by scanning and transmission electron microscopy. The process described shows an adsorption and immobilization of modified nanodiamonds on titanium; where aminosilanized nanodiamonds coupled with O-phosphorylethanolamine show a homogeneous interaction with the titanium substrate.

A novel surface-enhanced Raman scattering nanosensor for detecting multiple heavy metal ions based on 2-mercaptoisonicotinic acid functionalized gold nanoparticles.

PubMed

Tan, Enzhong; Yin, Penggang; Lang, Xiufeng; Zhang, Hongyan; Guo, Lin

2012-11-01

A novel, effective and simple surface-enhanced Raman scattering (SERS) nanosensor for selectively and sensitively detecting heavy metal ions in aqueous solution has been developed in the form of 2-mercaptoisonicotinic acid (2 MNA)-modified gold nanoparticles (AuNPs). Multiple heavy metal ions can be identified and quantified by using relative peak intensity ratios of selected vibrational bands in the SERS spectra of 2 MNA. Especially, concentration of Hg(2+) and Pb(2+) ions are determined by comparing the intensity ratios of the bands 1160/1230 cm(-1) for Hg(2+) and 861/815 cm(-1) (or 815/1392 cm(-1)) for Pb(2+), with detection limits of 3.4×10(-8) and 1.0×10(-7)M, respectively. 2 MNA-AuNPs sensors show a high selectivity for Hg(2+) without masking reagent, and they can also be highly selective for Pb(2+) when using sodium thiosulphate and l-cysteine as masking reagents. These results demonstrate that these 2 MNA-AuNPs nanosensors are promising candidates for in situ heavy metal ions detection and quantification, maybe even inside living cells. Copyright © 2012 Elsevier B.V. All rights reserved.

Noble metal-modified titania with visible-light activity for the decomposition of microorganisms

PubMed Central

Endo, Maya; Wei, Zhishun; Wang, Kunlei; Karabiyik, Baris; Yoshiiri, Kenta; Rokicka, Paulina; Ohtani, Bunsho

2018-01-01

Commercial titania photocatalysts were modified with silver and gold by photodeposition, and characterized by diffuse reflectance spectroscopy (DRS), X-ray powder diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and scanning transmission electron microscopy (STEM). It was found that silver co-existed in zero valent (core) and oxidized (shell) forms, whereas gold was mainly zero valent. The obtained noble metal-modified samples were examined with regard to antibacterial (Escherichia coli (E. coli)) and antifungal (Aspergillus niger (A. niger), Aspergillus melleus (A. melleus), Penicillium chrysogenum (P. chrysogenum), Candida albicans (C. albicans)) activity under visible-light irradiation and in the dark using disk diffusion, suspension, colony growth (“poisoned food”) and sporulation methods. It was found that silver-modified titania, besides remarkably high antibacterial activity (inhibition of bacterial proliferation), could also decompose bacterial cells under visible-light irradiation, possibly due to an enhanced generation of reactive oxygen species and the intrinsic properties of silver. Gold-modified samples were almost inactive against bacteria in the dark, whereas significant bactericidal effect under visible-light irradiation suggested that the mechanism of bacteria inactivation was initiated by plasmonic excitation of titania by localized surface plasmon resonance of gold. The antifungal activity tests showed efficient suppression of mycelium growth by bare titania, and suppression of mycotoxin generation and sporulation by gold-modified titania. Although, the growth of fungi was hardly inhibited through disc diffusion (inhibition zones around discs), it indicates that gold does not penetrate into the media, and thus, a good stability of plasmonic photocatalysts has been confirmed. In summary, it was found that silver-modified titania showed superior antibacterial activity, whereas gold-modified samples were very active against fungi, suggesting that bimetallic photocatalysts containing both gold and silver should exhibit excellent antimicrobial properties. PMID:29600144

Approach to Rapid Synthesis and Functionalization of Iron Oxide Nanoparticles for High Gene Transfection.

PubMed

Stephen, Zachary R; Dayringer, Christopher J; Lim, Josh J; Revia, Richard A; Halbert, Mackenzie V; Jeon, Mike; Bakthavatsalam, Arvind; Ellenbogen, Richard G; Zhang, Miqin

2016-03-01

Surface functionalization of theranostic nanoparticles (NPs) typically relies on lengthy, aqueous postsynthesis labeling chemistries that have limited ability to fine-tune surface properties and can lead to NP heterogeneity. The need for a rapid, simple synthesis approach that can provide great control over the display of functional moieties on NP surfaces has led to increased use of highly selective bioorthoganol chemistries including metal-affinity coordination. Here we report a simple approach for rapid production of a superparamagnetic iron oxide NPs (SPIONs) with tunable functionality and high reproducibility under aqueous conditions. We utilize the high affinity complex formed between catechol and Fe((III)) as a means to dock well-defined catechol modified polymer modules on the surface of SPIONs during sonochemical coprecipitation synthesis. Polymer modules consisted of chitosan and poly(ethylene glycol) (PEG) copolymer (CP) modified with catechol (CCP), and CCP functionalized with cationic polyethylenimine (CCP-PEI) to facilitate binding and delivery of DNA for gene therapy. This rapid synthesis/functionalization approach provided excellent control over the extent of PEI labeling, improved SPION magnetic resonance imaging (MRI) contrast enhancement and produced an efficient transfection agent.

Hydrodynamic Simulations of Ejecta Production From Shocked Metallic Surfaces

NASA Astrophysics Data System (ADS)

Karkhanis, Varad Abhimanyu

The phenomenon of mass ejection into vacuum from a shocked metallic free surfaces can have a deleterious effect on the implosion phase of the Inertial Confinement Fusion (ICF) process. Often, the ejecta take the form of a cloud of particles that are the result of microjetting sourced from imperfections on the metallic free surface. Significant progress has been achieved in the understanding of ejecta dynamics by treating the process as a limiting case of the baroclinically-driven Richtmyer-Meshkov Instability (RMI). This conceptual picture is complicated by several practical considerations including breakup of spikes due to surface tension and yield strength of the metal. Thus, the problem involves a wide range of physical phenomena, occurring often under extreme conditions of material behavior. We describe an approach in which continuum simulations using ideal gases can be used to capture key aspects of ejecta growth associated with the RMI. The approach exploits the analogy between the Rankine-Hugoniot jump conditions for ideal gases and the linear relationship between the shock velocity and particle velocity governing shocked metals. Such simulations with Upsilon-law fluids have been successful in accurately predicting the velocity and mass of ejecta for different shapes, and in excellent agreement with experiments. We use the astrophysical FLASH code, developed at the University of Chicago to model this problem. Based on insights from our simulations, we suggest a modified expression for ejecta velocities that is valid for large initial perturbation amplitudes. The expression for velocities is extended to ejecta originating from cavities with any arbitrary shape. The simulations are also used to validate a recently proposed source model for ejecta that predicts the ejected mass per unit area for sinusoidal and non-standard shapes. Such simulations and theoretical models play an important role in the design of target experiment campaigns.

Superhydrophobic Copper Surfaces with Anticorrosion Properties Fabricated by Solventless CVD Methods.

PubMed

Vilaró, Ignasi; Yagüe, Jose L; Borrós, Salvador

2017-01-11

Due to continuous miniaturization and increasing number of electrical components in electronics, copper interconnections have become critical for the design of 3D integrated circuits. However, corrosion attack on the copper metal can affect the electronic performance of the material. Superhydrophobic coatings are a commonly used strategy to prevent this undesired effect. In this work, a solventless two-steps process was developed to fabricate superhydrophobic copper surfaces using chemical vapor deposition (CVD) methods. The superhydrophobic state was achieved through the design of a hierarchical structure, combining micro-/nanoscale domains. In the first step, O 2 - and Ar-plasma etchings were performed on the copper substrate to generate microroughness. Afterward, a conformal copolymer, 1H,1H,2H,2H-perfluorodecyl acrylate-ethylene glycol diacrylate [p(PFDA-co-EGDA)], was deposited on top of the metal via initiated CVD (iCVD) to lower the surface energy of the surface. The copolymer topography exhibited a very characteristic and unique nanoworm-like structure. The combination of the nanofeatures of the polymer with the microroughness of the copper led to achievement of the superhydrophobic state. AFM, SEM, and XPS were used to characterize the evolution in topography and chemical composition during the CVD processes. The modified copper showed water contact angles as high as 163° and hysteresis as low as 1°. The coating withstood exposure to aggressive media for extended periods of time. Tafel analysis was used to compare the corrosion rates between bare and modified copper. Results indicated that iCVD-coated copper corrodes 3 orders of magnitude slower than untreated copper. The surface modification process yielded repeatable and robust superhydrophobic coatings with remarkable anticorrosion properties.

STM/STS Study of Surface Modification Effect on Bandgap Structure of Ti2C with -OH, -F, and -H

NASA Astrophysics Data System (ADS)

Jung, Seong Jun; Lai, Shen; Jeong, Taehwan; Lee, Sungjoo; Song, Young Jae

In this presentation, we present Scanning Tunneling Microscopy (STM) and Spectroscopy (STS) study of bandgap structures of surface-modified Ti2C with -OH, -F, and -O in atomic scale. Since the discovery of new two dimensional (2D) materials like graphene, various 2D materials including transition metal dichalcogenide (TMD) have been intensively investigated. There are, however, still scientific issues to apply them to the device fabrications for controlling the appropriate bandgap structure with high field effect mobility. Recently another 2D materials of transition metal carbide (TMC), Ti2CTx with modifiable surface group Tx(-OH, -F, and -O) was suggested. [S. Lai et. al, Nanoscale (2015), DOI: 10.1039/C5NR06513E]. This 2D material shows that the mobility at room temperature is less sensitive to the measured transport bandgap, which can imply that Ti2CTx can be a strong candidate of 2D TMC for application to the future electronic devices. Surface modification on the electronic structure of Ti2C by -OH, -F, and -O is, therefore, investigated by STM and STS in atomic scale. More scientific results will be further discussed in the presentation. This research was supported by Basic Science Research Program through the National Research Foundation of Korea funded by the Korean government (Grant Numbers: 2015R1A1A1A05027585, 2011­0030046, IBS- R011­D1, 2014M3C1A3053024 and 2015M3A7B4050455).

Electrochemical sensors and devices for heavy metals assay in water: the French groups' contribution

PubMed Central

Pujol, Luca; Evrard, David; Groenen-Serrano, Karine; Freyssinier, Mathilde; Ruffien-Cizsak, Audrey; Gros, Pierre

2014-01-01

A great challenge in the area of heavy metal trace detection is the development of electrochemical techniques and devices which are user-friendly, robust, selective, with low detection limits and allowing fast analyses. This review presents the major contribution of the French scientific academic community in the field of electrochemical sensors and electroanalytical methods within the last 20 years. From the well-known polarography to the up-to-date generation of functionalized interfaces, the different strategies dedicated to analytical performances improvement are exposed: stripping voltammetry, solid mercury-free electrode, ion selective sensor, carbon based materials, chemically modified electrodes, nano-structured surfaces. The paper particularly emphasizes their advantages and limits face to the last Water Frame Directive devoted to the Environmental Quality Standards for heavy metals. Recent trends on trace metal speciation as well as on automatic “on line” monitoring devices are also evoked. PMID:24818124

Rapid detection and identification of energetic materials with surface enhanced raman spectrometry (SERS)

DOEpatents

Han, Thomas Yong-Jin; Valdez, Carlos A; Olson, Tammy Y; Kim, Sung Ho; Satcher, Jr., Joe H

2015-04-21

In one embodiment, a system includes a plurality of metal nanoparticles functionalized with a plurality of organic molecules tethered thereto, wherein the plurality of organic molecules preferentially interact with one or more analytes when placed in proximity therewith. According to another embodiment, a method for detecting analytes includes contacting a fluid having one or more analytes of interest therein with a plurality of metal nanoparticles, each metal nanoparticle having a plurality of organic molecules tethered thereto, and detecting Raman scattering from an analyte of interest from the fluid, the analyte interacting with one or more of the plurality of organic molecules. In another embodiment, a method includes chemically modifying a plurality of cyclodextrin molecules at a primary hydroxyl moiety to create a chemical handle, and tethering the plurality of cyclodextrin molecules to a metal nanoparticle using the chemical handle. Other systems and methods for detecting analytes are also described.

Significant improvement in the electrical characteristics of Schottky barrier diodes on molecularly modified Gallium Nitride surfaces

NASA Astrophysics Data System (ADS)

Garg, Manjari; Naik, Tejas R.; Pathak, C. S.; Nagarajan, S.; Rao, V. Ramgopal; Singh, R.

2018-04-01

III-Nitride semiconductors face the issue of localized surface states, which causes fermi level pinning and large leakage current at the metal semiconductor interface, thereby degrading the device performance. In this work, we have demonstrated the use of a Self-Assembled Monolayer (SAM) of organic molecules to improve the electrical characteristics of Schottky barrier diodes (SBDs) on n-type Gallium Nitride (n-GaN) epitaxial films. The electrical characteristics of diodes were improved by adsorption of SAM of hydroxyl-phenyl metallated porphyrin organic molecules (Zn-TPPOH) onto the surface of n-GaN. SAM-semiconductor bonding via native oxide on the n-GaN surface was confirmed using X-ray photoelectron spectroscopy measurements. Surface morphology and surface electronic properties were characterized using atomic force microscopy and Kelvin probe force microscopy. Current-voltage characteristics of different metal (Cu, Ni) SBDs on bare n-GaN were compared with those of Cu/Zn-TPPOH/n-GaN and Ni/Zn-TPPOH/n-GaN SBDs. It was found that due to the molecular monolayer, the surface potential of n-GaN was decreased by ˜350 mV. This caused an increase in the Schottky barrier height of Cu and Ni SBDs from 1.13 eV to 1.38 eV and 1.07 eV to 1.22 eV, respectively. In addition to this, the reverse bias leakage current was reduced by 3-4 orders of magnitude for both Cu and Ni SBDs. Such a significant improvement in the electrical performance of the diodes can be very useful for better device functioning.

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

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

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

2016-06-17

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

Photochemical Hydrogen Doping Induced Embedded Two-Dimensional Metallic Channel Formation in InGaZnO at Room Temperature.

PubMed

Kim, Myeong-Ho; Lee, Young-Ahn; Kim, Jinseo; Park, Jucheol; Ahn, Seungbae; Jeon, Ki-Joon; Kim, Jeong Won; Choi, Duck-Kyun; Seo, Hyungtak

2015-10-27

The photochemical tunability of the charge-transport mechanism in metal-oxide semiconductors is of great interest since it may offer a facile but effective semiconductor-to-metal transition, which results from photochemically modified electronic structures for various oxide-based device applications. This might provide a feasible hydrogen (H)-radical doping to realize the effectively H-doped metal oxides, which has not been achieved by thermal and ion-implantation technique in a reliable and controllable way. In this study, we report a photochemical conversion of InGaZnO (IGZO) semiconductor to a transparent conductor via hydrogen doping to the local nanocrystallites formed at the IGZO/glass interface at room temperature. In contrast to thermal or ionic hydrogen doping, ultraviolet exposure of the IGZO surface promotes a photochemical reaction with H radical incorporation to surface metal-OH layer formation and bulk H-doping which acts as a tunable and stable highly doped n-type doping channel and turns IGZO to a transparent conductor. This results in the total conversion of carrier conduction property to the level of metallic conduction with sheet resistance of ∼16 Ω/□, room temperature Hall mobility of 11.8 cm(2) V(-1) sec(-1), the carrier concentration at ∼10(20) cm(-3) without any loss of optical transparency. We demonstrated successful applications of photochemically highly n-doped metal oxide via optical dose control to transparent conductor with excellent chemical and optical doping stability.

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.

Synergic adsorption in the simultaneous removal of acid blue 25 and heavy metals from water using a Ca(PO3)2-modified carbon.

PubMed

Tovar-Gómez, R; Rivera-Ramírez, D A; Hernández-Montoya, V; Bonilla-Petriciolet, A; Durán-Valle, C J; Montes-Morán, M A

2012-01-15

We report the simultaneous adsorption of acid blue 25 dye (AB25) and heavy metals (Zn(2+), Ni(2+) and Cd(2+)) on a low-cost activated carbon, whose adsorption properties have been improved via a surface chemistry modification using a calcium solution extracted from egg shell wastes. Specifically, we have studied the removal performance of this adsorbent using the binary aqueous systems: AB25-Cd(2+), AB25-Ni(2+) and AB25-Zn(2+). Multi-component kinetic and equilibrium experiments have been performed and used to identify and characterize the synergic adsorption in the simultaneous removal of these pollutants. Our results show that the presence of AB25 significantly favors the removal of heavy metals and may increase the adsorption capacities up to six times with respect to the results obtained using the mono-cationic metallic systems, while the adsorption capacities of AB25 are not affected by the presence of metallic ions. It appears that this anionic dye favors the electrostatic interactions with heavy metals or may create new specific sites for adsorption process. In particular, heavy metals may interact with the -SO(3)(-) group of AB25 and to the hydroxyl and phosphoric groups of this adsorbent. A response surface methodology model has been successfully used for fitting multi-component adsorption data. Copyright © 2011 Elsevier B.V. All rights reserved.

Acousto-optical Transducer with Surface Plasmons

NASA Astrophysics Data System (ADS)

Kolomenskii, A. A.; Surovic, E.; Schuessler, H. A.

2018-04-01

The surface plasmon resonance (SPR) is a sensitive technique for the detection of changes in dielectric parameters in close proximity to a metal film supporting surface plasmon waves. Here we study the application of the SPR effect to an efficient conversion of an acoustic signal into an optical one. Such a transducer potentially has a large bandwidth and good sensitivity. When an acoustic wave is incident onto a receiving plate positioned within the penetration depth of the surface plasmons, it creates displacements of the surface of the plate and, thus, modulates the dielectric properties in the proximity of the gold film. This modulation, in turn, modifies the light reflection under surface plasmon resonance conditions. We simulate characteristics of this acousto-optical transducer with surface plasmons and provide sets of parameters at the optical wavelength of 800 nm and 633 nm for its realization.

Activity of N-coordinated multi-metal-atom active site structures for Pt-free oxygen reduction reaction catalysis: Role of *OH ligands

DOE PAGES

Holby, Edward F.; Taylor, Christopher D.

2015-03-19

We report calculated oxygen reduction reaction energy pathways on multi-metal-atom structures that have previously been shown to be thermodynamically favorable. We predict that such sites have the ability to spontaneously cleave the O₂ bond and then will proceed to over-bind reaction intermediates. In particular, the *OH bound state has lower energy than the final 2 H₂O state at positive potentials. Contrary to traditional surface catalysts, this *OH binding does not poison the multi-metal-atom site but acts as a modifying ligand that will spontaneously form in aqueous environments leading to new active sites that have higher catalytic activities. These *OH boundmore » structures have the highest calculated activity to date.« less

Characterization of chemical interactions during chemical mechanical polishing (CMP) of copper

NASA Astrophysics Data System (ADS)

Lee, Seung-Mahn

2003-10-01

Chemical mechanical polishing (CMP) has received much attention as an unique technique to provide a wafer level planarization in semiconductor manufacturing. However, despite the extensive use of CMP, it still remains one of the least understood areas in semiconductor processing. The lack of the fundamental understanding is a significant barrier to further advancements in CMP technology. One critical aspect of metal CMP is the formation of a thin surface layer on the metal surface. The formation and removal of this layer controls all the aspects of the CMP process, including removal rate, surface finish, etc. In this dissertation, we focus on the characterization of the formation and removal of the thin surface layer on the copper surface. The formation dynamics was investigated using static and dynamic electrochemical techniques, including potentiodynamic scans and chronoamperometry. The results were validated using XPS measurements. The mechanical properties of the surface layer were investigated using nanoindentation measurements. The electrochemical investigation showed that the thickness of the surface layer is controlled by the chemicals such as an oxidizer (hydrogen peroxide), a corrosion inhibitor (benzotriazole), a complexing agent (citric acid), and their concentrations. The dynamic electrochemical measurements indicated that the initial layer formation kinetics is unaffected by the corrosion inhibitors. The passivation due to the corrosion inhibitor becomes important only on large time scales (>200 millisecond). The porosity and the density of the chemically modified surface layer can be affected by additives of other chemicals such as citric acid. An optimum density of the surface layer is required for high polishing rate while at the same time maintaining a high degree of surface finish. Nanoindentation measurements indicated that the mechanical properties of the surface layer are strongly dependent on the chemical additives in the slurry. The CMP removal rates were found to be in good agreement with the initial reaction kinetics as well as the mechanical properties of the chemically modified surface layer. In addition, the material removal model based on the micro- and nano-scale interactions, which were measured experimentally, has been developed.

Surface modification induced by UV nanosecond Nd:YVO4 laser structuring on biometals

NASA Astrophysics Data System (ADS)

Fiorucci, M. Paula; López, Ana J.; Ramil, Alberto

2014-08-01

Laser surface texturing is a promising tool for improving metallic biomaterials performance in dental and orthopedic bone-replacing applications. Laser ablation modifies the topography of bulk material and might alter surface properties that govern the interactions with the surrounding tissue. This paper presents a preliminary evaluation of surface modifications in two biometals, stainless steel 316L and titanium alloy Ti6Al4V by UV nanosecond Nd:YVO4. Scanning electron microscopy of the surface textured by parallel micro-grooves reveals a thin layer of remelted material along the grooves topography. Furthermore, X-ray diffraction allowed us to appreciate a grain refinement of original crystal structure and consequently induced residual strain. Changes in the surface chemistry were determined by means of X-ray photoelectron spectroscopy; in this sense, generalized surface oxidation was observed and characterization of the oxides and other compounds such hydroxyl groups was reported. In case of titanium alloy, oxide layer mainly composed by TiO2 which is a highly biocompatible compound was identified. Furthermore, laser treatment produces an increase in oxide thickness that could improve the corrosion behavior of the metal. Otherwise, laser treatment led to the formation of secondary phases which might be detrimental to physical and biocompatibility properties of the material.

EFFECT OF SOIL MODIFYING FACTORS ON THE BIOAVAILABILITY AND TOXICITY OF METAL CONTAMINATED SOILS

EPA Science Inventory

Heavy metal and organic chemical contamination of soils is a worldwide problem posing a risk to humans and more directly, soil organisms. Metal toxicity is often not directly related to the total concentration of metals present due to a number of modifying factors that depend,...

Bacterial adhesion on conventional and self-ligating metallic brackets after surface treatment with plasma-polymerized hexamethyldisiloxane.

PubMed

Tupinambá, Rogerio Amaral; Claro, Cristiane Aparecida de Assis; Pereira, Cristiane Aparecida; Nobrega, Celestino José Prudente; Claro, Ana Paula Rosifini Alves

2017-01-01

Plasma-polymerized film deposition was created to modify metallic orthodontic brackets surface properties in order to inhibit bacterial adhesion. Hexamethyldisiloxane (HMDSO) polymer films were deposited on conventional (n = 10) and self-ligating (n = 10) stainless steel orthodontic brackets using the Plasma-Enhanced Chemical Vapor Deposition (PECVD) radio frequency technique. The samples were divided into two groups according to the kind of bracket and two subgroups after surface treatment. Scanning Electron Microscopy (SEM) analysis was performed to assess the presence of bacterial adhesion over samples surfaces (slot and wings region) and film layer integrity. Surface roughness was assessed by Confocal Interferometry (CI) and surface wettability, by goniometry. For bacterial adhesion analysis, samples were exposed for 72 hours to a Streptococcus mutans solution for biofilm formation. The values obtained for surface roughness were analyzed using the Mann-Whitney test while biofilm adhesion were assessed by Kruskal-Wallis and SNK test. Significant statistical differences (p< 0.05) for surface roughness and bacterial adhesion reduction were observed on conventional brackets after surface treatment and between conventional and self-ligating brackets; no significant statistical differences were observed between self-ligating groups (p> 0.05). Plasma-polymerized film deposition was only effective on reducing surface roughness and bacterial adhesion in conventional brackets. It was also noted that conventional brackets showed lower biofilm adhesion than self-ligating brackets despite the absence of film.

Surface acidity scales: Experimental measurements of Brønsted acidities on anatase TiO2 and comparison with coinage metal surfaces

NASA Astrophysics Data System (ADS)

Silbaugh, Trent L.; Boaventura, Jaime S.; Barteau, Mark A.

2016-08-01

The first quantitative surface acidity scale for Brønsted acids on a solid surface is presented through the use of titration-displacement and equilibrium experiments on anatase TiO2. Surface acidities of species on TiO2 correlated with gas phase acidities, as was previously observed in qualitative studies of Brønsted acid displacement on Ag(110), Cu(110) and Au(111). A 90% compression of the surface acidity scale relative to the gas phase was observed due to compensation from the covalent component of the conjugate base - surface bond. Adsorbed conjugate bases need not be completely anionic for correlations with gas phase acidities to hold. Positive and negative substituent effects, such as substituted fluorine and hydrocarbon sidechain dispersion interactions with the surface, may modify the surface acidity scale, in agreement with previous experimental and theoretical work on Au(111).

Aerosol-spray diverse mesoporous metal oxides from metal nitrates

PubMed Central

Kuai, Long; Wang, Junxin; Ming, Tian; Fang, Caihong; Sun, Zhenhua; Geng, Baoyou; Wang, Jianfang

2015-01-01

Transition metal oxides are widely used in solar cells, batteries, transistors, memories, transparent conductive electrodes, photocatalysts, gas sensors, supercapacitors, and smart windows. In many of these applications, large surface areas and pore volumes can enhance molecular adsorption, facilitate ion transfer, and increase interfacial areas; the formation of complex oxides (mixed, doped, multimetallic oxides and oxide-based hybrids) can alter electronic band structures, modify/enhance charge carrier concentrations/separation, and introduce desired functionalities. A general synthetic approach to diverse mesoporous metal oxides is therefore very attractive. Here we describe a powerful aerosol-spray method for synthesizing various mesoporous metal oxides from low-cost nitrate salts. During spray, thermal heating of precursor droplets drives solvent evaporation and induces surfactant-directed formation of mesostructures, nitrate decomposition and oxide cross-linking. Thirteen types of monometallic oxides and four groups of complex ones are successfully produced, with mesoporous iron oxide microspheres demonstrated for photocatalytic oxygen evolution and gas sensing with superior performances. PMID:25897988

Retardation of surface corrosion of biodegradable magnesium-based materials by aluminum ion implantation

NASA Astrophysics Data System (ADS)

Wu, Guosong; Xu, Ruizhen; Feng, Kai; Wu, Shuilin; Wu, Zhengwei; Sun, Guangyong; Zheng, Gang; Li, Guangyao; Chu, Paul K.

2012-07-01

Aluminum ion implantation is employed to modify pure Mg as well as AZ31 and AZ91 magnesium alloys and their surface degradation behavior in simulated body fluids is studied. Polarization tests performed in conjunction with scanning electron microscopy (SEM) reveal that the surface corrosion resistance after Al ion implantation is improved appreciably. This enhancement can be attributed to the formation of a gradient surface structure with a gradual transition from an Al-rich oxide layer to Al-rich metal layer. Compared to the high Al-content magnesium alloy (AZ91), a larger reduction in the degradation rate is achieved from pure magnesium and AZ31. Our results reveal that the surface corrosion resistance of Mg alloys with no or low Al content can be improved by Al ion implantation.

Recent progress on magnetic iron oxide nanoparticles: synthesis, surface functional strategies and biomedical applications

PubMed Central

Wu, Wei; Wu, Zhaohui; Yu, Taekyung; Jiang, Changzhong; Kim, Woo-Sik

2015-01-01

This review focuses on the recent development and various strategies in the preparation, microstructure, and magnetic properties of bare and surface functionalized iron oxide nanoparticles (IONPs); their corresponding biological application was also discussed. In order to implement the practical in vivo or in vitro applications, the IONPs must have combined properties of high magnetic saturation, stability, biocompatibility, and interactive functions at the surface. Moreover, the surface of IONPs could be modified by organic materials or inorganic materials, such as polymers, biomolecules, silica, metals, etc. The new functionalized strategies, problems and major challenges, along with the current directions for the synthesis, surface functionalization and bioapplication of IONPs, are considered. Finally, some future trends and the prospects in these research areas are also discussed. PMID:27877761

Preparation of superhydrophobic copper surface by a novel silk-screen printing aided electrochemical machining method

NASA Astrophysics Data System (ADS)

Yan, X. Y.; Chen, G. X.; Liu, J. W.

2018-03-01

A kind of superhydrophobic copper surface with micro-nanocomposite structure has been successfully fabricated by employing a silk-screen printing aided electrochemical machining method. At first silk-screen printing technology has been used to form a column point array mask, and then the microcolumn array would be fabricated by electrochemical machining (ECM) effect. In this study, the drop contact angles have been studied and scanning electron microscopy (SEM) has been used to study the surface characteristic of the workpiece. The experiment results show that the micro-nanocomposite structure with cylindrical array can be successfully fabricated on the metal surface. And the maximum contact angle is 151° when the fluoroalkylsilane ethanol solution was used to modify the machined surface in this study.

Adhesive Bonding for Shelters

DTIC Science & Technology

1980-12-01

Durability Stress-Durability Metal Etching Eqvironmental Aging Failure Mode Shelter Panel Modified Epoxy Surface Preparation 20 UYSTRACT (Coriot,. on...and two adherend alloys (6061T6 and 50521!34) , ind tested at two tent conditions [720F (22C) and 200%F ()3’C) after hot- burri~l ag ing,. 7...assembly in an elevated temperature, high humidity aging environment until the specimen failed as the exposure period reached a preselected limit (1000 hours

Materials and Techniques for Implantable Nutrient Sensing Using Flexible Sensors Integrated with Metal-Organic Frameworks.

PubMed

Ling, Wei; Liew, Guoguang; Li, Ya; Hao, Yafeng; Pan, Huizhuo; Wang, Hanjie; Ning, Baoan; Xu, Hang; Huang, Xian

2018-06-01

The combination of novel materials with flexible electronic technology may yield new concepts of flexible electronic devices that effectively detect various biological chemicals to facilitate understanding of biological processes and conduct health monitoring. This paper demonstrates single- or multichannel implantable flexible sensors that are surface modified with conductive metal-organic frameworks (MOFs) such as copper-MOF and cobalt-MOF with large surface area, high porosity, and tunable catalysis capability. The sensors can monitor important nutriments such as ascorbicacid, glycine, l-tryptophan (l-Trp), and glucose with detection resolutions of 14.97, 0.71, 4.14, and 54.60 × 10 -6 m, respectively. In addition, they offer sensing capability even under extreme deformation and complex surrounding environment with continuous monitoring capability for 20 d due to minimized use of biological active chemicals. Experiments using live cells and animals indicate that the MOF-modified sensors are biologically safe to cells, and can detect l-Trp in blood and interstitial fluid. This work represents the first effort in integrating MOFs with flexible sensors to achieve highly specific and sensitive implantable electrochemical detection and may inspire appearance of more flexible electronic devices with enhanced capability in sensing, energy storage, and catalysis using various properties of MOFs. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Preparation and characterization of magnetic allylamine modified graphene oxide-poly(vinyl acetate-co-divinylbenzene) nanocomposite for vortex assisted magnetic solid phase extraction of some metal ions.

PubMed

Khan, Mansoor; Yilmaz, Erkan; Sevinc, Basak; Sahmetlioglu, Ertugrul; Shah, Jasmin; Jan, Muhammad Rasul; Soylak, Mustafa

2016-01-01

Magnetic allylamine modified graphene oxide-poly(vinyl acetate-co-divinylbenzene) (MGO-DVB-VA) was synthesized and used for magnetic solid phase extraction of Pb(II), Cd(II), Cu(II), Ni(II) and Co(II) prior to their determination by flame atomic absorption spectroscopy. The adsorbent surface functional group was characterized by using FT-IR and Raman spectroscopy. XRD pattern was used to determine the layers of GO. Surface morphology and elemental composition of the adsorbent were evaluated by using SEM and EDX analysis. Various parameters, effecting adsorption efficiency like initial solution pH, adsorbent dose, type and volume of eluent, volume of sample and diverse ions effects were optimized. The preconcentration factor (PF) is 40 for all the metals and the limits of detection for Pb, Cd, Cu, Ni and Co are in the range of 0.37-2.39 µg L(-1) and relative standard deviation below 3.1%. The method was validated by using the method for certified reference materials (Tobacco Leaves (INCT-OBTL-5), Tomato Leaves (1573a), Certified Water (SPS-ww2) and Certified Water (TMDA 64-2)). The method was successfully applied for natural water and food samples. Copyright © 2015 Elsevier B.V. All rights reserved.

Infrared absorption spectroscopy characterization of liquid-solid interfaces: The case of chiral modification of catalysts

NASA Astrophysics Data System (ADS)

Zaera, Francisco

2018-03-01

An overview is provided here of our work on the characterization of chiral modifiers for the bestowing of enantioselectivity to metal-based hydrogenation catalysts, with specific reference to the so-called Orito reaction. We start with a brief discussion of the use of infrared absorption spectroscopy (IR) for the characterization of chemical species at liquid-solid interfaces, describing the options available as well as the information that can be extracted from such experiments and the advantages and disadvantages associated with the technique. We then summarize the main results that we have reported to date from our IR study of the adsorption of cinchona alkaloids and related compounds from solutions onto platinum surfaces. Several observations are highlighted and placed in context in terms of the existing knowledge and their relevance to catalysis. Key conclusions include the uniqueness of the nature of the adsorbed species when in the presence of the solvent (versus when the uptake is done under vacuum, or versus the pure or dissolved molecules), the fact that each modifier adopts unique and distinct adsorption geometries on the surface and that those change with the concentration of the solution in ways that correlate well with the performance of the catalyst, the potential tendency of at least some of these chiral modifiers to bind to the surface primarily via the nitrogen atom of the amine group, not the aromatic ring as it is often assumed, and the observation that the ability of one modifier to dominate the catalytic chemistry in solutions containing mixtures of two or more of those is linked to their capacity for displacing each other from the surface, which in turn is determined by a balance between the strength of their binding to the surface and their solubility in the liquid solvent.

Photo-reduction of bromate in drinking water by metallic Ag and reduced graphene oxide (RGO) jointly modified BiVO4 under visible light irradiation.

PubMed

Chen, Fei; Yang, Qi; Zhong, Yu; An, Hongxue; Zhao, Jianwei; Xie, Ting; Xu, Qiuxiang; Li, Xiaoming; Wang, Dongbo; Zeng, Guangming

2016-09-15

Bromate (BrO3(-)), an oxyhalide disinfection by-product (DBP) in drinking water, has been demonstrated to be carcinogenic and genotoxic. In the current work, metallic Ag and reduced graphene oxide (RGO) co-modified BiVO4 was successfully synthesized by a stepwise chemical method coupling with a photo-deposition process and applied in the photo-reduction of BrO3(-) under visible light irradiation. In this composite, metallic Ag acted as an electron donor or mediator and RGO enhanced the BrO3(-) adsorption onto the surface of catalysts as well as an electron acceptor to restrict the recombination of photo-generated electron-hole pairs. The Ag@BiVO4@RGO composite exhibited greater photo-reduction BrO3(-) performance than pure BiVO4, Ag@BiVO4 and RGO@BiVO4 under identical experimental conditions: initial BrO3(-) concentration 150 μg/L, catalyst dosage 0.5 g/L, pH 7.0 and visible light (λ > 420 nm). The photoluminescence spectra (PL), electron-spin resonance (ESR), photocurrent density (PC) and electrochemical impedance spectroscopy (EIS) measurements indicated that the modified BiVO4 enhanced the photo-generated electrons and separated the electron-hole pairs. The photocatalytic reduction efficiency for BrO3(-) removal decreased with the addition of electron quencher K2S2O8, suggesting that electrons were the primary factor in this photo-reduction process. The declining photo-reduction efficiency of BrO3(-) in tap water should attribute to the consumption of photo-generated electrons by coexisting anions and the adsorption of dissolved organic matter (DOM) on graphene surface. The overall results indicate a promising application potential for photo-reduction in the DBPs removal from drinking water. Copyright © 2016 Elsevier Ltd. All rights reserved.

Level, source identification, and risk analysis of heavy metal in surface sediments from river-lake ecosystems in the Poyang Lake, China.

PubMed

Zhang, Hua; Jiang, Yinghui; Ding, Mingjun; Xie, Zhenglei

2017-09-01

The concentrations, sources, and risks of heavy metals (Fe, Al, Mn, Cr, Co, Ni, Cu, Zn, As, Cd, W, Pb, and Tl) in sediments in five river-lake ecosystems in the Poyang Lake region were studied. The concentrations of the heavy metals varied spatially, with most of the highest concentrations in the Raohe river-lake ecosystem (RH). All heavy metals except As, Cd, W, and Tl were enriched in sediments possessing high total organic carbon contents or in finer sediments. Based on enrichment factors and statistical methods, it was found that Cd in sediments in the Xiushui (XS), Ganjiang (GJ), Xinjiang (XJ) river-lake ecosystems, and RH; Mn in the XS, GJ, and RH; and W in the XS and GJ were greatly affected by anthropogenic inputs. Moreover, the origins of Cu, Zn, and As require more attention due to the high concentrations found. The high enrichment factor of Cd in the sediments indicated that this metal might cause significant pollution in the environment. The results of the modified potential ecological risk index revealed that the XS, GJ, RH, and XJ were at considerable ecological risk, while the sediments in the Fuhe river-lake ecosystem (FH) were at moderate ecological risk, with Cd contributing the highest proportion of risk. The hazard score fundamentally validated the modified potential ecological risk analysis and revealed a mean toxicity of 57.80% to the benthic organisms in the RH.

Electrocatalytic oxidation of small organic molecules in acid medium: enhancement of activity of noble metal nanoparticles and their alloys by supporting or modifying them with metal oxides.

PubMed

Kulesza, Pawel J; Pieta, Izabela S; Rutkowska, Iwona A; Wadas, Anna; Marks, Diana; Klak, Karolina; Stobinski, Leszek; Cox, James A

2013-11-01

Different approaches to enhancement of electrocatalytic activity of noble metal nanoparticles during oxidation of small organic molecules (namely potential fuels for low-temperature fuel cells such as methanol, ethanol and formic acid) are described. A physical approach to the increase of activity of catalytic nanoparticles (e.g. platinum or palladium) involves nanostructuring to obtain highly dispersed systems of high surface area. Recently, the feasibility of enhancing activity of noble metal systems through the formation of bimetallic (e.g. PtRu, PtSn, and PdAu) or even more complex (e.g. PtRuW, PtRuSn) alloys has been demonstrated. In addition to possible changes in the electronic properties of alloys, specific interactions between metals as well as chemical reactivity of the added components have been postulated. We address and emphasize here the possibility of utilization of noble metal and alloyed nanoparticles supported on robust but reactive high surface area metal oxides (e.g. WO 3 , MoO 3 , TiO 2 , ZrO 2 , V 2 O 5 , and CeO 2 ) in oxidative electrocatalysis. This paper concerns the way in which certain inorganic oxides and oxo species can act effectively as supports for noble metal nanoparticles or their alloys during electrocatalytic oxidation of hydrogen and representative organic fuels. Among important issues are possible changes in the morphology and dispersion, as well as specific interactions leading to the improved chemisorptive and catalytic properties in addition to the feasibility of long time operation of the discussed systems.

Electrocatalytic oxidation of small organic molecules in acid medium: enhancement of activity of noble metal nanoparticles and their alloys by supporting or modifying them with metal oxides

PubMed Central

Kulesza, Pawel J.; Pieta, Izabela S.; Rutkowska, Iwona A.; Wadas, Anna; Marks, Diana; Klak, Karolina; Stobinski, Leszek; Cox, James A.

2013-01-01

Different approaches to enhancement of electrocatalytic activity of noble metal nanoparticles during oxidation of small organic molecules (namely potential fuels for low-temperature fuel cells such as methanol, ethanol and formic acid) are described. A physical approach to the increase of activity of catalytic nanoparticles (e.g. platinum or palladium) involves nanostructuring to obtain highly dispersed systems of high surface area. Recently, the feasibility of enhancing activity of noble metal systems through the formation of bimetallic (e.g. PtRu, PtSn, and PdAu) or even more complex (e.g. PtRuW, PtRuSn) alloys has been demonstrated. In addition to possible changes in the electronic properties of alloys, specific interactions between metals as well as chemical reactivity of the added components have been postulated. We address and emphasize here the possibility of utilization of noble metal and alloyed nanoparticles supported on robust but reactive high surface area metal oxides (e.g. WO3, MoO3, TiO2, ZrO2, V2O5, and CeO2) in oxidative electrocatalysis. This paper concerns the way in which certain inorganic oxides and oxo species can act effectively as supports for noble metal nanoparticles or their alloys during electrocatalytic oxidation of hydrogen and representative organic fuels. Among important issues are possible changes in the morphology and dispersion, as well as specific interactions leading to the improved chemisorptive and catalytic properties in addition to the feasibility of long time operation of the discussed systems. PMID:24443590

Oxygen Vacancy Engineering of Co3 O4 Nanocrystals through Coupling with Metal Support for Water Oxidation.

PubMed

Zhang, Jun-Jun; Wang, Hong-Hui; Zhao, Tian-Jian; Zhang, Ke-Xin; Wei, Xiao; Jiang, Zhi-Dong; Hirano, Shin-Ichi; Li, Xin-Hao; Chen, Jie-Sheng

2017-07-21

Oxygen vacancies can help to capture oxygen-containing species and act as active centers for oxygen evolution reaction (OER). Unfortunately, effective methods for generating a high amount of oxygen vacancies on the surface of various nanocatalysts are rather limited. Here, we described an effective way to generate oxygen-vacancy-rich surface of transition metal oxides, exemplified with Co 3 O 4 , simply by constructing highly coupled interface of ultrafine Co 3 O 4 nanocrystals and metallic Ti. Impressively, the amounts of oxygen vacancy on the surface of Co 3 O 4 /Ti surpassed the reported values of the Co 3 O 4 modified even under highly critical conditions. The Co 3 O 4 /Ti electrode could provide a current density of 23 mA cm -2 at an OER overpotential of 570 mV, low Tafel slope, and excellent durability in neutral medium. Because of the formation of a large amount of oxygen vacancies as the active centers for OER on the surface, the TOF value of the Co 3 O 4 @Ti electrode was optimized to be 3238 h -1 at an OER overpotential of 570 mV, which is 380 times that of the state-of-the-art non-noble nanocatalysts in the literature. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Medium-induced change of the optical response of metal clusters in rare-gas matrices

NASA Astrophysics Data System (ADS)

Xuan, Fengyuan; Guet, Claude

2017-10-01

Interaction with the surrounding medium modifies the optical response of embedded metal clusters. For clusters from about ten to a few hundreds of silver atoms, embedded in rare-gas matrices, we study the environment effect within the matrix random phase approximation with exact exchange (RPAE) quantum approach, which has proved successful for free silver clusters. The polarizable surrounding medium screens the residual two-body RPAE interaction, adds a polarization term to the one-body potential, and shifts the vacuum energy of the active delocalized valence electrons. Within this model, we calculate the dipole oscillator strength distribution for Ag clusters embedded in helium droplets, neon, argon, krypton, and xenon matrices. The main contribution to the dipole surface plasmon red shift originates from the rare-gas polarization screening of the two-body interaction. The large size limit of the dipole surface plasmon agrees well with the classical prediction.

Heavy Metals in Soil and Salad in the Proximity of Historical Ferroalloy Emission

PubMed Central

Ferri, Roberta; Donna, Filippo; Smith, Donald R.; Guazzetti, Stefano; Zacco, Annalisa; Rizzo, Luigi; Bontempi, Elza; Zimmerman, Neil J.; Lucchini, Roberto G.

2016-01-01

Emissions of manganese (Mn), lead (Pb), iron (Fe), zinc (Zn), copper (Cu) from ferro-alloy operations has taken place in Valcamonica, a pre-Alp valley in the province of Brescia, Italy, for about a century until 2001. Metal concentrations were measured in the soil of local home gardens and in the cultivated vegetables. Soil analysis was carried out using a portable X-Ray Fluorescence (XRF) spectrometer in both surface soil and at 10 cm depth. A subset of soil samples (n = 23) additionally was analysed using the modified BCR sequential extraction method and ICP-OES for intercalibration with XRF (XRF Mn = 1.33 * total OES Mn – 71.8; R = 0.830, p < 0.0001). Samples of salads (Lactuca sativa and Chichorium spp.) were analyzed with a Total Reflection X-Ray Fluorescence (TXRF) technique. Vegetable and soil metal measurements were performed in 59 home gardens of Valcamonica, and compared with 23 gardens from the Garda Lake reference area. Results indicate significantly higher levels of soil Mn (median 986 ppm vs 416 ppm), Pb (median 46.1 ppm vs 30.2 ppm), Fe (median 19,800 ppm vs 13,100 ppm) in the Valcamonica compared to the reference area. Surface soil levels of all metals were significantly higher in surface soil compared to deeper soil, consistent with atmospheric deposition. Significantly higher levels of metals were shown also in lettuce from Valcamonica for Mn (median 53.6 ppm vs 30.2) and Fe (median 153 vs 118). Metals in Chichorium spp. did not differ between the two areas. Surface soil metal levels declined with increasing distance from the closest ferroalloy plant, consistent with plant emissions as the source of elevated soil metal levels. A correlation between Mn concentrations in soil and lettuce was also observed. These data show that historic ferroalloy plant activity, which ended nearly a decade before this study, has contributed to the persistence of increased Mn levels in locally grown vegetables. Further research is needed to assess whether this increase can lead to adverse effects in humans and plants especially for Mn, an essential element that can be toxic in humans when exceeding the homeostatic ranges. PMID:27818841

Understanding charge transfer of Li+ and Na+ ions scattered from metal surfaces with high work function

NASA Astrophysics Data System (ADS)

Chen, Lin; Wu, Wen-Bin; Liu, Pin-Yang; Xiao, Yun-Qing; Li, Guo-Peng; Liu, Yi-Ran; Jiang, Hao-Yu; Guo, Yan-Ling; Chen, Xi-Meng

2016-08-01

For Li+ and Na+ ions scattered from high work function metal surfaces, efficient neutralization is observed, and it cannot be explained by the conventional free electron model. In order to explain these experimental data, we investigate the velocity-dependent neutral fraction with the modified Brako-Newns (BN) model. The calculated results are in agreement with the experimental data. We find that the parallel velocity effect plays an important role in neutralizing the Li+ and Na+ ions for large angle scattering. The nonmonotonic velocity behavior of neutral fraction is strongly related to the distance-dependent coupling strength between the atomic level and metal states. Project supported by the National Natural Science Foundation of China (Grant Nos. 11405078 and 11474140), the Fundamental Research Funds for the Central Universities, China (Grant Nos. lzujbky-2014-169 and lzujbky-2015-244), the Project sponsored by the Scientific Research Foundation for the Returned Overseas Chinese Scholars, the State Education Ministry, and the National Students’ Innovation and Entrepreneurship Training Program (Grant Nos. 201410730069 and 201510730078).

Optical response of nanostructured metal/dielectric composites and multilayers

NASA Astrophysics Data System (ADS)

Smith, Geoffrey B.; Maaroof, Abbas I.; Allan, Rodney S.; Schelm, Stefan; Anstis, Geoffrey R.; Cortie, Michael B.

2004-08-01

The homogeneous optical response in conducting nanostructured layers, and in insulating layers containing dense arrays of self assembled conducting nanoparticles separated by organic linkers, is examined experimentally through their effective complex indices (n*, k*). Classical effective medium models, modified to account for the 3-phase nanostructure, are shown to explain (n*, k*) in dense particulate systems but not inhomogeneous layers with macroscopic conductance for which a different approach to homogenisation is discussed. (n*, k*) data on thin granular metal films, thin mesoporous gold, and on thin metal layers containing ordered arrays of voids, is linked to properties of the surface plasmon states which span the nanostructured film. Coupling between evanescent waves at either surface counterbalanced by electron scattering losses must be considered. Virtual bound states for resonant photons result, with the associated transit delay leading to a large rise in n* in many nanostructures. Overcoating n-Ag with alumina is shown to alter (n*, k*) through its impact on the SP coupling. In contrast to classical optical homogenisation, effective indices depend on film thickness. Supporting high resolution SEM images are presented.

Advanced cathode materials for polymer electrolyte fuel cells based on pt/ metal oxides: from model electrodes to catalyst systems.

PubMed

Fabbri, Emiliana; Pătru, Alexandra; Rabis, Annett; Kötz, Rüdiger; Schmidt, Thomas J

2014-01-01

The development of stable catalyst systems for application at the cathode side of polymer electrolyte fuel cells (PEFCs) requires the substitution of the state-of-the-art carbon supports with materials showing high corrosion resistance in a strongly oxidizing environment. Metal oxides in their highest oxidation state can represent viable support materials for the next generation PEFC cathodes. In the present work a multilevel approach has been adopted to investigate the kinetics and the activity of Pt nanoparticles supported on SnO2-based metal oxides. Particularly, model electrodes made of SnO2 thin films supporting Pt nanoparticles, and porous catalyst systems made of Pt nanoparticles supported on Sb-doped SnO2 high surface area powders have been investigated. The present results indicate that SnO2-based supports do not modify the oxygen reduction reaction mechanism on the Pt nanoparticle surface, but rather lead to catalysts with enhanced specific activity compared to Pt/carbon systems. Different reasons for the enhancement in the specific activity are considered and discussed.

Electroless Plating of Copper on Polyimide Film Modified by 50 Hz Plasma Graft Polymerization with 1-Vinylimidazole

NASA Astrophysics Data System (ADS)

Wong, Chiow San; Lem, Hon Pong; Goh, Boon Tong; Wong, Cin Wie

2009-03-01

This paper reports on the proof of concept work on the novel process of producing metalized polyimide (PI) film by coating a layer of copper (Cu) thin film on the surface of the PI film without using any adhesive. The method which is employed to produce a metalized PI film used in flexible printed circuit (FPC) is based on plasma graft polymerization of 1-vinlyimidazole (VIDz) on plasma pre-treated PI surface. The plasma grafted PI film (VIDz-g-PI) surfaces are characterized by X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM), and scanning electron microscopy (SEM). AFM results show that the PI film surface has been successfully treated and grafted with VIDz. As post-thermal treatment is known to promote adhesion strength between the metallic film and the PI surface, the effects of post-thermal treatment environment and temperature on the adhesion property of Cu plated VIDz-g-PI (Cu/VIDz-g-PI) are evaluated. Post-thermal treatment in air shows better adhesion strength than in vacuum. The adhesion strength decreases as the post-thermal treatment temperature is increased. In the present development work, the adhesion strength obtained has met the initial market targeted 9-10 N/cm adhesion strength. Samples obtained at a pre-selected plasma power and time window are able to maintain their adhesion strength after being subjected to ageing at 100 °C for 168 h.

Enhanced photocatalytic degradation of methylene blue by metal-modified silicon nanowires

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

Brahiti, N., E-mail: dihiabrahiti@yahoo.fr; Université Mouloud MAMMERI de TiziOuzou, Département de Physique, Bastos; Hadjersi, T., E-mail: hadjersi@gmx.com

2015-02-15

Highlights: • SiNWs modified with Pd, Au and Pt were used as photocatalysts to degrade MB. • Yield of photodegardation increases with UV irradiation time. • SiNWs modified with Pd nanoparticles show the best photocatalytic activity. • A degradation of 97% was obtained after 200 min of UV irradiation. - Abstract: Silicon nanowires (SiNWs) modified with Au, Pt and Pd nanoparticles were used as heterogeneous photocatalysts for the photodegradation of methylene blue in water under UV light irradiation. The modification of SiNWs was carried out by deposition of metal nanoparticles using the electroless metal deposition (EMD) technique. The effect ofmore » metal nanoparticles deposition time on the photocatalytic activity was studied. It was found that the photocatalytic activity of modified SiNWs was enhanced when the deposition time of metal nanoparticles was increased. In addition of modified SiNWs with Pt, Au and Pd nanoparticles, oxidized silicon substrate (Ox-Si), oxidized silicon nanowires (Ox-SiNWs) and hydrogen-terminated silicon nanowires (H-SiNWs) were also evaluated for the photodegradation of methylene blue.« less

Effect of specific surface microstructures on substrate endothelialisation and thrombogenicity: Importance for stent design.

PubMed

Lutter, Christoph; Nothhaft, Matthias; Rzany, Alexander; Garlichs, Christoph D; Cicha, Iwona

2015-01-01

In coronary artery disease, highly stenosed arteries are frequently treated by stent implantation, which thereafter necessitates a dual-antiplatelet therapy (DAPT) in order to prevent stent-thrombosis. We hypothesized that specific patterns of microstructures on stents can accelerate endothelialisation thereby reducing their thrombogenicity and the DAPT duration. Differently designed, 2-5 μm high elevations or hollows were lithographically etched on silicon plates, subsequently coated with silicon carbide. Smooth silicon plates and bare metal substrates were used as controls. To assess attachment and growth of human umbilical vein endothelial cells under static or flow conditions, actin cytoskeleton was visualised with green phalloidin. Endothelial migration was assessed in a modified barrier assay. To investigate surface thrombogenicity, platelets were incubated on the structured surfaces in static and flow conditions, and visualised with fluorescein-conjugated P-selectin antibody. Images were taken with incident-light fluorescent microscope for non-transparent objects. Compared to smooth surface, flat cubic elevations (5 μm edge length) improved endothelial cell attachment and growth under static and dynamic conditions, whereas smaller, spiky structures (2 μm edge length) had a negative influence on endothelialisation. Endothelial cell migration was fastest on flat cubic elevations, hollows, and smooth surfaces, whereas spiky structures and bare metal had a negative effect on endothelial migration. Thrombogenicity assays under static and flow conditions showed that platelet adhesion was reduced on the flat elevations and the smooth surface, as compared to the spiky structures, the hollow design and the bare metal substrates. Surface microstructures strongly influence endothelialisation of substrates. Designing stents with surface topography which accelerates endothelialisation and reduces thrombogenicity may be of clinical benefit by improving the safety profile of coronary interventions.

Comparison of the effect of different surface treatments on the bond strength of different cements with nickel chromium metal alloy: An in vitro study

PubMed Central

Kapoor, Saumya; Balakrishnan, Dhanasekar

2017-01-01

Background For success of any indirect metal restoration, a strong bond between cement and the intaglio surface of metal is imperative. The aim of this study is to evaluate and compare the effect of different surface treatment on the tensile and shear bond strength of different cements with nickel–chromium alloy. Material and Methods 120 premolars were sectioned horizontally parallel to the occlusal surface to expose the dentin. Wax patterns were fabricated for individual tooth followed by casting them in nickel chromium alloy. 60 samples were tested for tensile bond strength, and the remaining 60 for shear bond strength. The samples were divided into three groups (of 20 samples each) as per the following surface treatment: oxidation only, oxidation and sandblasting, or oxidation, sandblasting followed by application of alloy primer. Each group was subdivided into 2 subgroups of 10 samples each, according to the bonding cement i.e RM-GIC and resin cement. Samples were subjected to thermocycling procedure followed by evaluation of bond strength. Results Two-way analyses of variance (ANOVA) was performed to compare the means of tensile and shear bond strength across type of surface treatment and cement, followed by post hoc parametric analysis. For all tests ‘p’ value of less than 0.05 was considered statistically significant. Conclusions The surface treatment of oxidation and sandblasting followed by application of alloy primer offered the maximum tensile and shear bond strength for both RM GIC and resin cement. Resin cement exhibited greater tensile and shear bond strength than RM-GIC for all the three surface treatment methods. Key words:Resin cement, resin modified glass ionomer cement, oxidation, sandblasting, alloy primer, tensile bond strength, shear bond strength, universal testing machine. PMID:28828160

In-situ surface science studies of the interaction between sulfur dioxide and two-dimensional palladium loaded-cerium/zirconium mixed metal oxide model catalysts

NASA Astrophysics Data System (ADS)

Romano, Esteban Javier

2005-07-01

Cerium and zirconium oxides are important materials in industrial catalysis. Particularly, the great advances attained in the past 30 years in controlling levels of gaseous pollutants released from internal combustion engines can be attributed to the development of catalysts employing these materials. Unfortunately, oxides of sulfur are known threats to the longevity of many catalytic systems by irreversibly interacting with catalytic materials. In this work, polycrystalline cerium-zirconium mixed-metal-oxide (MMO) solid solutions were synthesized. High resolution x-ray photoelectron spectroscopy (XPS) spectral data was collected and examined for revelation of the surface species that form on these metal oxides after in-situ exposures to sulfur dioxide. The model catalysts were exposed to sulfur dioxide using a custom modified in-situ reaction cell and platen heater. The results of this study demonstrate the formation of sulfate and sulfite surface sulfur species. Temperature and compositional dependencies were displayed, with higher temperatures and ceria molar ratios displaying a larger propensity for forming surface sulfur species. In addition to analysis of sulfur photoemission, the photoemission regions of oxygen, zirconium, and cerium were examined for the materials used in this study before and after the aforementioned treatments with sulfur dioxide. The presence of surface hydroxyl groups was observed and metal oxidation state changes were probed to further enhance the understanding of sulfur dioxide adsorption on the synthesized materials. Palladium loaded mixed-metal oxides were synthesized using a unique solid-state methodology to probe the effect of palladium addition on sulfur dioxide adsorption. The addition of palladium to this model system is shown to have a strong effect on the magnitude of adsorption for sulfur dioxide on some material/exposure condition combinations. Ceria/zirconia sulfite and sulfate species are identified on the palladium-loaded MMO materials with adsorption sites located on the exposed oxide sites.

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).

Preparation and adsorption behavior of aminated electrospun polyacrylonitrile nanofiber mats for heavy metal ion removal.

PubMed

Kampalanonwat, Pimolpun; Supaphol, Pitt

2010-12-01

Polyacrylonitrile (PAN) nanofiber mats were prepared by electrospinning and they were further modified to contain amidino diethylenediamine chelating groups on their surface via heterogeneous reaction with diethylenetriamine (DETA). The obtained aminated PAN (APAN) nanofiber mats were evaluated for their chelating property with four types of metal ions, namely Cu(II), Ag(I), Fe(II), and Pb(II) ions. The amounts of the metal ions adsorbed onto the APAN nanofiber mats were influenced by the initial pH and the initial concentration of the metal ion solutions. Increasing the contact time also resulted in a monotonous increase in the adsorbed amounts of the metal ions, which finally reached equilibria at about 10 h for Cu(II) ions and about 5 h for Ag(I), Fe(II), and Pb(II) ions. The maximal adsorption capacities of the metal ions on the APAN nanofiber mats, as calculated from the Langmuir model, were 150.6, 155.5, 116.5, and 60.6 mg g(-1), respectively. Lastly, the spent APAN nanofiber mats could be facilely regenerated with a hydrochloric acid (HCl) aqueous solution.

Structured copolymers and their use as absorbents, gels and carriers of metal ions

DOEpatents

Hedstrand, David M.; Helmer, Bradley J.; Tomalia, Donald A.

1996-01-01

Dense star polymers or dendrimers having a highly branched interior structure capable of associating or chelating with metal ions are modified by capping with a hydrophobic group capable of providing a hydrophobic outer shell. The modified dendrimers are useful for dispersing metal ions in a non-aqueous polymer matrix. Also dense star polymers or dendrimers having a highly branched hydrophilic interior structure are modified by capping with a hydrophobic group capable of providing a hydrophobic outer shell, which modified polymers are useful as gels and surfactants.

Structured copolymers and their use as absorbents, gels and carriers of metal ions

DOEpatents

Hedstrand, D.M.; Helmer, B.J.; Tomalia, D.A.

1996-10-01

Dense star polymers or dendrimers having a highly branched interior structure capable of associating or chelating with metal ions are modified by capping with a hydrophobic group capable of providing a hydrophobic outer shell. The modified dendrimers are useful for dispersing metal ions in a non-aqueous polymer matrix. Also dense star polymers or dendrimers having a highly branched hydrophilic interior structure are modified by capping with a hydrophobic group capable of providing a hydrophobic outer shell, which modified polymers are useful as gels and surfactants.

Hollow metal nanostructures for enhanced plasmonics (Conference Presentation)

NASA Astrophysics Data System (ADS)

Genç, Aziz; Patarroyo, Javier; Sancho-Parramon, Jordi; Duchamp, Martial; Gonzalez, Edgar; Bastus, Neus G.; Houben, Lothar; Dunin-Borkowski, Rafal; Puntes, Victor F.; Arbiol, Jordi

2016-03-01

Complex metal nanoparticles offer a great playground for plasmonic nanoengineering, where it is possible to cover plasmon resonances from ultraviolet to near infrared by modifying the morphologies from solid nanocubes to nanoframes, multiwalled hollow nanoboxes or even nanotubes with hybrid (alternating solid and hollow) structures. We experimentally show that structural modifications, i.e. void size and final morphology, are the dominant determinants for the final plasmonic properties, while compositional variations allow us to get a fine tuning. EELS mappings of localized surface plasmon resonances (LSPRs) reveal an enhanced plasmon field inside the voids of hollow AuAg nanostructures along with a more homogeneous distributions of the plasmon fields around the nanostructures. With the present methodology and the appropriate samples we are able to compare the effects of hybridization at the nanoscale in hollow nanostructures. Boundary element method (BEM) simulations also reveal the effects of structural nanoengineering on plasmonic properties of hollow metal nanostructures. Possibility of tuning the LSPR properties of hollow metal nanostructures in a wide range of energy by modifying the void size/shell thickness is shown by BEM simulations, which reveals that void size is the dominant factor for tuning the LSPRs. As a proof of concept for enhanced plasmonic properties, we show effective label free sensing of bovine serum albumin (BSA) with some of our hollow nanostructures. In addition, the different plasmonic modes observed have also been studied and mapped in 3D.

Surface properties, crystallinity and optical properties of anodised titanium in mixture of β-glycerophosphate (β-GP) and calcium acetate (CA)

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

Chuan, Lee Te, E-mail: gd130079@siswa.uthm.edu.my; Abdullah, Hasan Zuhudi, E-mail: hasan@uthm.edu.my; Idris, Maizlinda Izwana, E-mail: izwana@uthm.edu.my

Anodic oxidation is an electrochemical method for the production of ceramic films on a metallic substrate. It had been widely used to deposit the ceramic coatings on the metals surface. This method has been widely used in surface modification of biomaterials especially for dental implants. In this study, the surface morphology, crystallinity and optical properties of titanium foil was modified by anodising in mixture of β-glycerophosphate disodium salt pentahydrate (β-GP) and calcium acetate monohydrate (CA). The experiments were carried out at high voltage (350 V), different anodising time (5 and 10 minutes) and current density (10-70 mA.cm{sup −2}) at room temperature. Anodisedmore » titanium was characterised by using field emission scanning electron microscopy (FESEM), X-ray diffractometer (XRD), and UV-Vis spectrometry. The result of the experiment showed that surface morphology, crystallinity and optical properties depended strongly on the current density and anodising time. More porous surface and large amount of anatase and rutile was produced at higher current density and longer anodising time. Apart from that, it is also revealed that the energy band gap of anodised titanium increases as the increase in current density due to the presence of anatase and rutile TiO{sub 2}.« less

Activated Carbon Fibers "Thickly Overgrown" by Ag Nanohair Through Self-Assembly and Rapid Thermal Annealing

NASA Astrophysics Data System (ADS)

Yan, Xuefeng; Xu, Sijun; Wang, Qiang; Fan, Xuerong

2017-11-01

Anisotropic nanomaterial-modified carbon fibers attract increasing attention because of their superior properties over traditional ones. In this study, activated carbon fibers (ACFs) "thickly overgrown" by Ag nanohair were prepared through self-assembly and rapid thermal annealing. Viscose fibers with well-dispersed silver nanoparticles (AgNPs) on surfaces were first prepared through self-assembly of hyperbranched poly(amino-amine) (HBPAA)-capped AgNPs on viscose surfaces. HBPAA endowed the AgNP surfaces with negative charges and abundant amino groups, allowing AgNPs to monodispersively self-assemble to fiber surfaces. Ag nanohair-grown ACFs were prepared by sequential pre-oxidation and carbonization. Because the carbonization furnace was open-ended, ACFs are immediately transferrable to the outside of the furnace. Therefore, the Ag liquid adsorbed by ACF pores squeezed out to form Ag nanowires through thermal contraction. FESEM characterization indicated that Ag nanohairs stood on ACF surface and grew from ACF caps. XPS and XRD characterization showed that Ag successfully assembled to fiber surfaces and retained its metallic state even after high-temperature carbonization. TG analysis suggested that Ag nanohair-grown ACFs maintained their excellent thermal stabilities. Finally, the fabricated ACFs showed excellent and durable antibacterial activities, and the developed method may provide a potential strategy for preparing metal nanowire-grown ACFs.

Surface properties, crystallinity and optical properties of anodised titanium in mixture of β-glycerophosphate (β-GP) and calcium acetate (CA)

NASA Astrophysics Data System (ADS)

Chuan, Lee Te; Abdullah, Hasan Zuhudi; Idris, Maizlinda Izwana

2015-07-01

Anodic oxidation is an electrochemical method for the production of ceramic films on a metallic substrate. It had been widely used to deposit the ceramic coatings on the metals surface. This method has been widely used in surface modification of biomaterials especially for dental implants. In this study, the surface morphology, crystallinity and optical properties of titanium foil was modified by anodising in mixture of β-glycerophosphate disodium salt pentahydrate (β-GP) and calcium acetate monohydrate (CA). The experiments were carried out at high voltage (350 V), different anodising time (5 and 10 minutes) and current density (10-70 mA.cm-2) at room temperature. Anodised titanium was characterised by using field emission scanning electron microscopy (FESEM), X-ray diffractometer (XRD), and UV-Vis spectrometry. The result of the experiment showed that surface morphology, crystallinity and optical properties depended strongly on the current density and anodising time. More porous surface and large amount of anatase and rutile was produced at higher current density and longer anodising time. Apart from that, it is also revealed that the energy band gap of anodised titanium increases as the increase in current density due to the presence of anatase and rutile TiO2.

Magnetic separation of heavy metal ions and evaluation based on surface-enhanced Raman spectroscopy: copper(II) ions as a case study.

PubMed

Yan, Xue; Zhang, Xue-Jiao; Yuan, Ya-Xian; Han, San-Yang; Xu, Min-Min; Gu, Ren'ao; Yao, Jian-Lin

2013-11-01

A new approach was developed for the magnetic separation of copper(II) ions with easy operation and high efficiency. p-Mercaptobenzoic acid served as the modified tag of Fe2O3@Au nanoparticles both for the chelation ligand and Raman reporter. Through the chelation between the copper(II) ions and carboxyl groups on the gold shell, the Fe2O3@Au nanoparticles aggregated to form networks that were enriched and separated from the solution by a magnet. A significant decrease in the concentration of copper(II) ions in the supernatant solution was observed. An extremely sensitive method based on surface-enhanced Raman spectroscopy was employed to detect free copper(II) ions that remained after the magnetic separation, and thus to evaluate the separation efficiency. The results indicated the intensities of the surface-enhanced Raman spectroscopy bands from p-mercaptobenzoic acid were dependent on the concentration of copper(II) ions, and the concentration was decreased by several orders of magnitude after the magnetic separation. The present protocol effectively decreased the total amount of heavy metal ions in the solution. This approach opens a potential application in the magnetic separation and highly sensitive detection of heavy metal ions. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Antibacterial and antifouling properties of a polyurethane surface modified with perfluoroalkyl and silver nanoparticles.

PubMed

Xu, Deqiu; Su, Yuling; Zhao, Lili; Meng, Fancui; Liu, Chang; Guan, Yayuan; Zhang, Jiya; Luo, Jianbin

2017-02-01

Inspired by mussel-adhesion phenomena in nature, a simple, mild surface modification process was elaborated to endow the polyurethane (PU) substrate with antibacterial/antifouling properties. In the present study, polydopamine was coated directly onto polyurethane surfaces. AgNO 3 was then added and absorbed onto the surface by the active catechol and amine groups of the polydopamine coating. Meanwhile, the adsorbed Ag + ions were reduced in situ into metallic silver nanoparticles by the "bridge" of the polydopamine coating which yielded a coating with good antimicrobial properties. Finally, 1H, 1H, 2H, 2H-perfluorodecanethiol (CF 3 (CF 2 ) 7 CH 2 CH 2 SH, F-SH) was attached on the PDA coating via the Michael addition reaction. The hydrophobic F-SH layer above the antibacterial layer yielded a surface with excellent antifouling properties. Preliminary antibacterial assays indicate that the coated surfaces show enhanced antibacterial activity against Escherichia coli (Gram-negative bacteria) and Staphylococcus aureus (Gram-positive bacteria). Platelet adhesion was significantly reduced for the F-SH-coated PU film. These results suggest that the modified PU could be used as an antibacterial material for future biomedical applications. © 2016 Wiley Periodicals, Inc. J Biomed Mater Res Part A: 105A: 531-538, 2017. © 2016 Wiley Periodicals, Inc.

The effect of metal cluster deposition route on structure and photocatalytic activity of mono- and bimetallic nanoparticles supported on TiO2 by radiolytic method

NASA Astrophysics Data System (ADS)

Klein, Marek; Nadolna, Joanna; Gołąbiewska, Anna; Mazierski, Paweł; Klimczuk, Tomasz; Remita, Hynd; Zaleska-Medynska, Adriana

2016-08-01

TiO2 (P25) was modified with small and relatively monodisperse mono- and bimetallic clusters (Ag, Pd, Pt, Ag/Pd, Ag/Pt and Pd/Pt) induced by radiolysis to improve its photocatalytic activity. The as-prepared samples were characterized by X-ray fluorescence spectrometry (XRF), photoluminescence spectrometry (PL), diffuse reflectance spectroscopy (DRS), X-ray powder diffractometry (XRD), scanning transition electron microscopy (STEM) and BET surface area analysis. The effect of metal type (mono- and bimetallic modification) as well as deposition method (simultaneous or subsequent deposition of two metals) on the photocatalytic activity in toluene removal in gas phase under UV-vis irradiation (light-emitting diodes- LEDs) and phenol degradation in liquid phase under visible light irradiation (λ > 420 nm) were investigated. The highest photoactivity under Vis light was observed for TiO2 co-loaded with platinum (0.1%) and palladium (0.1%) clusters. Simultaneous addition of metal precursors results in formation of larger metal nanoparticles (15-30 nm) on TiO2 surface and enhances the Vis-induced activity of Ag/Pd-TiO2 up to four times, while the subsequent metal ions addition results in formation of metal particle size ranging from 4 to 20 nm. Subsequent addition of metal precursors results in formation of BNPs (bimetallic nanoparticle) composites showing higher stability in four cycles of toluene degradation under UV-vis. Obtained results indicated that direct electron transfer from the BNPs to the conduction band of the semiconductor is responsible for visible light photoactivity, whereas superoxide radicals (such as O2rad- and rad OOH) are responsible for pollutants degradation over metal-TiO2 composites.

Performance enhancement in organic photovoltaic solar cells using iridium (Ir) ultra-thin surface modifier (USM)

NASA Astrophysics Data System (ADS)

Pandey, Rina; Lim, Ju Won; Kim, Jung Hyuk; Angadi, Basavaraj; Choi, Ji Won; Choi, Won Kook

2018-06-01

In this study, Iridium (Ir) metallic layer as an ultra-thin surface modifier (USM) was deposited on ITO coated glass substrate using radio frequency magnetron sputtering for improving the photo-conversion efficiency of organic photovoltaic cells. Ultra-thin Ir acts as a surface modifier replacing the conventional hole transport layer (HTL) PEDOT:PSS in organic photovoltaic (OPV) cells with two different active layers P3HT:PC60BM and PTB7:PC70BM. The Ir USM (1.0 nm) coated on ITO glass substrate showed transmittance of 84.1% and work function of >5.0 eV, which is higher than that of ITO (4.5-4.7 eV). The OPV cells with Ir USM (1.0 nm) exhibits increased power conversion efficiency of 3.70% (for P3HT:PC60BM active layer) and 7.28% (for PTB7:PC70BM active layer) under 100 mW/cm2 illumination (AM 1.5G) which are higher than those of 3.26% and 6.95% for the same OPV cells but with PEDOT:PSS as HTL instead of Ir USM. The results reveal that the chemically stable Ir USM layer could be used as an alternative material for PEDOT:PSS in organic photovoltaic cells.

Fabrication and characterization of superhydrophobic copper fiber sintered felt with a 3D space network structure and their oil-water separation

NASA Astrophysics Data System (ADS)

Hu, Jinyi; Yuan, Wei; Chen, Wenjun; Xu, Xiaotian; Tang, Yong

2016-12-01

This study reports the fabrication of a novel stable superhydrophobic and superoleophylic porous metal material on a copper fiber sintered felt (CFSF) substrate via a simple solution-immersion method. Oxidation and modification times are two important factors related to the level of hydrophobicity; oxidation for 1 h and modification for 24 h are appropriate to build a superhydrophobic CFSF surface with a water contact angle of 152.83° and a kerosene contact angle of 0°. The stability and high temperature resistance of superhydrophobic CFSF were studied. A novel device was designed to measure the water repellent ability of the treated CFSF. The results indicated that the water repellent ability of superhydrophobic CFSF was almost constant after 40 cycles of sanding. Both the water contact angle and the microstructure of the modified CFSF surface remained nearly unchanged after experiencing ultrasonic vibration for 1 min. The modified CFSF surface maintains super hydrophobicity after being treated at 180 °C for 1 h. The separation efficiencies for different types of oils and organic solvents (kerosene, chloroform, n-hexane and gasoline) are more than 96%. The modified CFSF retains a high robustness of separation efficiency even after it is recycled for the separation of kerosene and water for more than 10 times.

Aminopyridine modified Spirulina platensis biomass for chromium(VI) adsorption in aqueous solution.

PubMed

Bayramoglu, Gulay; Akbulut, Aydin; Arica, M Yakup

Chemical modification of Spirulina platensis biomass was realized by sequential treatment of algal surface with epichlorohydrin and aminopyridine. Adsorptive properties of Cr(VI) ions on native and aminopyridine modified algal biomass were investigated by varying pH, contact time, ionic strength, initial Cr(VI) concentration, and temperature. FTIR and analytical analysis indicated that carboxyl and amino groups were the major functional groups for Cr(VI) ions adsorption. The optimum adsorption was observed at pH 3.0 for native and modified algal biomasses. The adsorption capacity was found to be 79.6 and 158.7 mg g(-1), for native and modified algal biomasses, respectively. For continuous system studies, the experiments were conducted to study the effect of important design parameters such as flow rate and initial concentration of metal ions, and the maximum sorption capacity was observed at a flow rate of 50 mL h(-1), and Cr(VI) ions concentration 200 mg L(-1) with modified biomass. Experimental data fitted a pseudo-second-order equation. The regeneration performance was observed to be 89.6% and 94.3% for native and modified algal biomass, respectively.

Natural sorbents modified by divalent Cu2+- and Zn2+- ions and their corresponding antimicrobial activity.

PubMed

Đolić, Maja B; Rajaković-Ognjanović, Vladana N; Štrbac, Svetlana B; Dimitrijević, Suzana I; Mitrić, Miodrag N; Onjia, Antonije E; Rajaković, Ljubinka V

2017-10-25

The objective of this study was to investigate the modification of materials used in wastewater treatment for possible antimicrobial application(s). Granulated activated carbon (GAC) and natural clinoptilolite (CLI) were activated using Cu 2+ - and Zn 2+ - ions and the disinfection ability of the resulting materials was tested. Studies of the sorption and desorption kinetics were performed in order to determine and clarify the antimicrobial activity of the metal-activated sorbents. The exact sorption capacities of the selected sorbents, GAC and CLI, activated through use of Cu 2+ - ions, were 15.90 and 3.60mg/g, respectively, while for the materials activated by Zn 2+ - ions, the corresponding capacities were 14.00 and 4.72mg/g,. The desorption rates were 2 and 3 orders of magnitude lower than their sorption efficacy for the Cu 2+ -, and Zn 2+ -activated sorbents, respectively. The intermediate sorption capacity and low desorption rate indicated that the overall antimicrobial activity of the metal-modified sorbents was a result of metal ions immobilized onto surface sites. The effect of antimicrobial activity of free ions desorbed from the metal-activated surface may thus be disregarded. The antimicrobial activities of Cu/GAC, Zn/GAC, Cu/CLI and Zn/CLI were also tested against Escherichia coli, Staphylococcus aureus, and Candida albicans. After 15min exposure, the highest levels of cell inactivation were obtained through the Cu/CLI and the Cu/GAC against E. coli, 100.0 and 98.24%, respectively. However, for S. aureus and yeast cell inactivation, all Cu 2+ - and Zn 2+ -activated sorbents proved to be unsatisfactory. A characterization of the sorbents was performed by X-ray diffraction (XRD), X-ray photo electron spectroscopy (XPS), and field emission scanning electron microscopy (FE-SEM). A concentration of the adsorbed and released ions was determined by inductively coupled plasma-optical emission spectroscopy (ICP-OES) and mass spectrometry (ICP-MS). The results showed that the antimicrobial performance of the activated sorbents depended on the surface characteristics of the material, which itself designates the distribution and the bioavailability of the activating agent. Copyright © 2017 Elsevier B.V. All rights reserved.

Electron- and photon-stimulated desorption of atomic hydrogen from radiation-modified alkali halide surfaces

NASA Astrophysics Data System (ADS)

Hudson, L. T.; Tolk, N. H.; Bao, C.; Nordlander, P.; Russell, D. P.; Xu, J.

2000-10-01

The desorption yields of excited hydrogen atoms from the surfaces of KCl, KBr, NaCl, NaF, and LiF have been measured as a function of incident photon and electron energy and flux, time of irradiation, dosing pressure of H2 and sample temperature. As these surfaces are exposed to H2 gas during electron or photon bombardment, the fluorescence from excited hydrogen atoms ejected from the surface is monitored. The desorption yields are found to be contingent upon surface damage induced by the incident particle radiation, leading to dissociative adsorption at surface sites containing an excess of alkali metal. A desorption mechanism is presented in which incident electrons or photons induce a valence excitation to a neutral, antibonding state of the surface alkali hydride molecule complex, leading to the desorption of hydrogen atoms possessing several eV of kinetic energy.

Synthesis and comparative photocatalytic activity of Pt/WO 3 and Au/WO 3 nanocomposites under sunlight-type excitation

NASA Astrophysics Data System (ADS)

Qamar, M.; Yamani, Z. H.; Gondal, M. A.; Alhooshani, K.

2011-09-01

The article deals with the synthesis of highly active visible-light-driven nanocomposite for the decontamination of water hazards under sunlight-type excitation. The surface of visible-light-active nanostructured photocatalyst tungsten oxide (WO 3) was modified with noble metals, such as platinum (Pt) and gold (Au) nanoparticles, and the resulting photocatalytic activity of the nanocomposites was investigated by studying the removal of Methyl Orange and 2,4-Dichlorophenoxyacetic acid (2,4-D) under sunlight-type excitation. The study revealed that the deposited noble metals are not always favorable for the enhancement of photocatalytic response of catalysts; the activity of WO 3 was enhanced manyfold (˜8 times) by depositing an optimum amount of Pt nanoparticles after certain photodeposition time whereas the presence of Au nanoparticles onto the WO 3 surface, under identical experimental conditions, affected the removal process negatively. The variation in the photocatalytic activity of nanocomposites was attributed to the size of the deposited metals; Pt nanoparticles were uniformly dispersed with narrow size distribution (2-4 nm) while the size distribution of Au nanoparticles was found to be 10-15 nm for similar preparation conditions. The effects of critical parameters, such as metal deposition time and metal contents, on the photocatalytic activity of WO 3 were investigated. Furthermore, Pt/WO 3 nanocomposites showed good stability and recyclability under the conditions studied.

Methods for and products of processing nanostructure nitride, carbonitride and oxycarbonitride electrode power materials by utilizing sol gel technology for supercapacitor applications

DOEpatents

Huang, Yuhong; Wei, Oiang; Chu, Chung-tse; Zheng, Haixing

2001-01-01

Metal nitride, carbonitride, and oxycarbonitride powder with high surface area (up to 150 m.sup.2 /g) is prepared by using sol-gel process. The metal organic precursor, alkoxides or amides, is synthesized firstly. The metal organic precursor is modified by using unhydrolyzable organic ligands or templates. A wet gel is formed then by hydrolysis and condensation process. The solvent in the wet gel is then be removed supercritically to form porous amorphous hydroxide. This porous hydroxide materials is sintered to 725.degree. C. under the ammonia flow and porous nitride powder is formed. The other way to obtain high surface area nitride, carbonitride, and oxycarbonitride powder is to pyrolyze polymerized templated metal amides aerogel in an inert atmosphere. The electrochemical capacitors are prepared by using sol-gel prepared nitride, carbonitride, and oxycarbonitride powder. Two methods are used to assemble the capacitors. Electrode is formed either by pressing the mixture of nitride powder and binder to a foil, or by depositing electrode coating onto metal current collector. The binder or coating is converted into a continuous network of electrode material after thermal treatment to provide enhanced energy and power density. Liquid electrolyte is soaked into porous electrode. The electrochemical capacitor assembly further has a porous separator layer between two electrodes/electrolyte and forming a unit cell.

Comparison on surface properties and desulfurization of MnO2 and pyrolusite blended activated carbon by steam activation.

PubMed

Zhang, Guochen; Zhao, Xin; Ning, Ping; Yang, Danni; Jiang, Xia; Jiang, Wenju

2018-04-18

In this study, MnO 2 and pyrolusite were used as the catalysts to prepare modified activated carbon, i.e., AC-Mn and AC-P, respectively, from coals by blending method and steam activation. The BET results indicated that the AC-P had higher surface areas and micropore volumes than the AC-Mn with the same blending ratio. The relative contents of basic functional groups (i.e. C = O, π-π*) on AC-P were slightly lower than those on AC-Mn, while both contained the same main metal species, i.e. MnO. The desulfurization results showed that with 3 wt% of blending ratio, AC-Mn3 and AC-P3 had higher sulfur capacities at 220 and 205 mg/g, respectively, which were much higher than blank one (149.6 mg/g). Moreover, the AC-P had relatively higher sulfur capacity than the AC-Mn with the same contents of Mn, which might be attributed to the existence of other metals in pyrolusite. After desulfurization process, MnO were gradually transferred into MnSO 4 , and the relative contents of basic functional groups decreased evidently for both AC-Mn3 and AC-P3. The results demonstrated that pyrolusite could be one good alternative of MnO 2 to prepare modified activated carbon for desulfurization. Implication statement MnO 2 and pyrolusite were used as the additives to prepare the modified activated carbon from coals by blending method and steam activation, i.e., AC-Mn and AC-P, respectively. The AC-P had higher surface areas and micropore volumes than the AC-Mn with the same blending ratio. The AC-Mn and AC-P had higher sulfur capacities than blank one. Moreover, the AC-P had relatively higher sulfur capacity than the AC-Mn with the same contents of Mn. The results demonstrated that pyrolusite could be one good alternative of MnO 2 to prepare modified activated carbon for desulfurization.

Metal-chelating active packaging film enhances lysozyme inhibition of Listeria monocytogenes.

PubMed

Roman, Maxine J; Decker, Eric A; Goddard, Julie M

2014-07-01

Several studies have demonstrated that metal chelators enhance the antimicrobial activity of lysozyme. This study examined the effect of metal-chelating active packaging film on the antimicrobial activity of lysozyme against Listeria monocytogenes. Polypropylene films were surface modified by photoinitiated graft polymerization of acrylic acid (PP-g-PAA) from the food contact surface of the films to impart chelating activity based on electrostatic interactions. PP-g-PAA exhibited a carboxylic acid density of 113 ± 5.4 nmol cm(-2) and an iron chelating activity of 53.7 ± 9.8 nmol cm(-2). The antimicrobial interaction of lysozyme and PP-g-PAA depended on growth media composition. PP-g-PAA hindered lysozyme activity at low ionic strength (2.48-log increase at 64.4 mM total ionic strength) and enhanced lysozyme activity at moderate ionic strength (5.22-log reduction at 120 mM total ionic strength). These data support the hypothesis that at neutral pH, synergy between carboxylate metal-chelating films (pKa(bulk) 6.45) and lysozyme (pI 11.35) is optimal in solutions of moderate to high ionic strength to minimize undesirable charge interactions, such as lysozyme absorption onto film. These findings suggest that active packaging, which chelates metal ions based on ligand-specific interactions, in contrast to electrostatic interactions, may improve antimicrobial synergy. This work demonstrates the potential application of metal-chelating active packaging films to enhance the antimicrobial activity of membrane-disrupting antimicrobials, such as lysozyme.

Dispersed metal cluster catalysts by design. Synthesis, characterization, structure, and performance

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

Arslan, Ilke; Dixon, David A.; Gates, Bruce C.

2015-09-30

To understand the class of metal cluster catalysts better and to lay a foundation for the prediction of properties leading to improved catalysts, we have synthesized metal catalysts with well-defined structures and varied the cluster structures and compositions systematically—including the ligands bonded to the metals. These ligands include supports and bulky organics that are being tuned to control both the electron transfer to or from the metal and the accessibility of reactants to influence catalytic properties. We have developed novel syntheses to prepare these well-defined catalysts with atomic-scale control the environment by choice and placement of ligands and applied state-of-themore » art spectroscopic, microscopic, and computational methods to determine their structures, reactivities, and catalytic properties. The ligands range from nearly flat MgO surfaces to enveloping zeolites to bulky calixarenes to provide controlled coverages of the metal clusters, while also enforcing unprecedented degrees of coordinative unsaturation at the metal site—thereby facilitating bonding and catalysis events at exposed metal atoms. With this wide range of ligand properties and our arsenal of characterization tools, we worked to achieve a deep, fundamental understanding of how to synthesize robust supported and ligand-modified metal clusters with controlled catalytic properties, thereby bridging the gap between active site structure and function in unsupported and supported metal catalysts. We used methods of organometallic and inorganic chemistry combined with surface chemistry for the precise synthesis of metal clusters and nanoparticles, characterizing them at various stages of preparation and under various conditions (including catalytic reaction conditions) and determining their structures and reactivities and how their catalytic properties depend on their compositions and structures. Key characterization methods included IR, NMR, and EXAFS spectroscopies to identify ligands on the metals and their reactions; EXAFS spectroscopy and high-resolution STEM to determine cluster framework structures and changes resulting from reactant treatment and locations of metal atoms on support surfaces; X-ray diffraction crystallography to determine full structures of cluster-ligand combinations in the absence of a support, and TEM with tomographic methods to observe individual metal atoms and determine three-dimensional structures of catalysts. Electronic structure calculations were used to verify and interpret spectra and extend the understanding of reactivity beyond what is measurable experimentally.« less

Magnetic evidence for heavy metal pollution of topsoil in Shanghai, China

NASA Astrophysics Data System (ADS)

Wang, Guan; Liu, Yuan; Chen, Jiao; Ren, Feifan; Chen, Yuying; Ye, Fangzhou; Zhang, Weiguo

2018-03-01

This study presents the results obtained from magnetic susceptibility and heavy metal (Cu, Zn, Pb, and Cr) concentration measurements of soil profiles collected from arable land and urban parks in Baoshan District, an industrial district of Shanghai, China. The study focuses on the investigation of vertical variations in magnetic susceptibilities and heavy metal concentrations and on correlations between magnetic susceptibilities and heavy metal concentrations in soil profiles. The results demonstrate that magnetic enhancement in the surface layer of the soil profile is associated with increased heavy metal pollution. The enrichment factors (EF) and the Tomlinson Pollution Load Index (PLI-EF) are calculated for estimating the level of heavy metal pollution of soil profiles in the study. The significant positive correlations between heavy metal contents, enrichment factors (EF), Tomlinson pollution load index (PLI-CF), modified Tomlinson pollution load index (PLI-EF), and magnetic susceptibility (c) indicate that much of the heavy metal contamination in the study area is linked to combustion derived particulate emissions. The results confirm that the combined magnetic measurement and heavy metal concentration analysis could provide useful information for soil monitoring in urban environments. However, the use of magnetic technique to locate the heavy metal pollution boundary in the soil profile of this studied area should be confirmed by further geochemical analysis.

The effect of the carbon nanotube buffer layer on the performance of a Li metal battery

NASA Astrophysics Data System (ADS)

Zhang, Ding; Zhou, Yi; Liu, Changhong; Fan, Shoushan

2016-05-01

Lithium (Li) metal is one of the most promising candidates as an anode for the next-generation energy storage systems because of its high specific capacity and lowest negative electrochemical potential. But the growth of Li dendrites limits the application of the Li metal battery. In this work, a type of modified Li metal battery with a carbon nanotube (CNT) buffer layer inserted between the separator and the Li metal electrode was reported. The electrochemical results show that the modified batteries have a much better rate capability and cycling performance than the conventional Li metal batteries. The mechanism study by electrochemical impedance spectroscopy reveals that the modified battery has a smaller charge transfer resistance and larger Li ion diffusion coefficient during the deposition process on the Li electrode than the conventional Li metal batteries. Symmetric battery tests show that the interfacial behavior of the Li metal electrode with the buffer layer is more stable than the naked Li metal electrode. The morphological characterization of the CNT buffer layer and Li metal lamina reveals that the CNT buffer layer has restrained the growth of Li dendrites. The CNT buffer layer has great potential to solve the safety problem of the Li metal battery.Lithium (Li) metal is one of the most promising candidates as an anode for the next-generation energy storage systems because of its high specific capacity and lowest negative electrochemical potential. But the growth of Li dendrites limits the application of the Li metal battery. In this work, a type of modified Li metal battery with a carbon nanotube (CNT) buffer layer inserted between the separator and the Li metal electrode was reported. The electrochemical results show that the modified batteries have a much better rate capability and cycling performance than the conventional Li metal batteries. The mechanism study by electrochemical impedance spectroscopy reveals that the modified battery has a smaller charge transfer resistance and larger Li ion diffusion coefficient during the deposition process on the Li electrode than the conventional Li metal batteries. Symmetric battery tests show that the interfacial behavior of the Li metal electrode with the buffer layer is more stable than the naked Li metal electrode. The morphological characterization of the CNT buffer layer and Li metal lamina reveals that the CNT buffer layer has restrained the growth of Li dendrites. The CNT buffer layer has great potential to solve the safety problem of the Li metal battery. Electronic supplementary information (ESI) available. See DOI: 10.1039/c6nr00465b

Processing of catalysts by atomic layer epitaxy: modification of supports

NASA Astrophysics Data System (ADS)

Lindblad, Marina; Haukka, Suvi; Kytökivi, Arla; Lakomaa, Eeva-Liisa; Rautiainen, Aimo; Suntola, Tuomo

1997-11-01

Different supports were modified with titania, zirconia and chromia by the atomic layer epitaxy technique (ALE). In ALE, a metal precursor is bound to the support in saturating gas-solid reactions. Surface oxides are grown by alternating reactions of the metal precursor and an oxidizing agent. Growth mechanisms differ depending on the precursor-support pair and the processing conditions. In this work, the influences of the support, precursor and reaction temperature were investigated by comparing the growth of titania from Ti(OCH(CH 3) 2) 4 on silica and alumina, titania from TiCl 4 and Ti(OCH(CH 3) 2) 4 on silica, and zirconia from ZrCl 4 on silica and alumina. The modification of porous oxides supported on metal substrates (monoliths) was demonstrated for the growth of chromia from Cr(acac) 3.

Biological Nanoplatforms for Self-Assembled Electronics

DTIC Science & Technology

2015-03-24

as M13 , a virus that infects Escherichia coli. Approximately one billion different amino acid sequences are displayed on different viruses in the...sequence when contained within a phage M13 coat protein sequence, not chemically linked to the surface of phage MS2 VLPs. Thus, binding properties may...gallium arsenide in a bacteriophage M13 phage display library, MS2 VLPs modified with the metal binding peptides do not display the same activity

Nanoengineered Plasmonic Hybrid Systems for Bio-nanotechnology

NASA Astrophysics Data System (ADS)

Leong, Kirsty

Plasmonic hybrid systems are fabricated using a combination of lithography and layer-by-layer directed self-assembly approaches to serve as highly sensitive nanosensing devices. This layer-by-layer directed self-assembly approach is utilized as a hybrid methodology to control the organization of quantum dots (QDs), nanoparticles, and biomolecules onto inorganic nanostructures with site-specific attachment and functionality. Here, surface plasmon-enhanced nanoarrays are fabricated where the photoluminescence of quantum dots and conjugated polymer nanoarrays are studied. This study was performed by tuning the localized surface plasmon resonance and the distance between the emitter and the metal surface using genetically engineered polypeptides as binding agents and biotin-streptavidin binding as linker molecules. In addition, these nanoarrays were also chemically modified to support the immobilization and label-free detection of DNA using surface enhanced Raman scattering. The surface of the nanoarrays was chemically modified using an acridine containing molecule which can act as an intercalating agent for DNA. The self-assembled monolayer (SAM) showed the ability to immobilize and intercalate DNA onto the surface. This SAM system using surface enhanced Raman scattering (SERS) serves as a highly sensitive methodology for the immobilization and label-free detection of DNA applicable into a wide range of bio-diagnostic platforms. Other micropatterned arrays were also fabricated using a combination of soft lithography and surface engineering. Selective single cell patterning and adhesion was achieved through chemical modifications and surface engineering of poly(dimethylsiloxane) surface. The surface of each microwell was functionally engineered with a SAM which contained an aldehyde terminated fused-ring aromatic thiolated molecule. Cells were found to be attracted and adherent to the chemically modified microwells. By combining soft lithography and surface engineering, a simple methodology produced single cell arrays on biocompatible substrates. Thus the design of plasmonic devices relies heavily on the nature of the plasmonic interactions between nanoparticles in the devices which can potentially be fabricated into lab-on-a-chip devices for multiplex sensing capabilities.

A theoretical study on metal atom-modified BC3 sheets for effects of gas molecule adsorptions

NASA Astrophysics Data System (ADS)

Tang, Yanan; Cui, Xiao; Chen, Weiguang; Zhu, Dalei; Chai, Huaduo; Dai, Xianqi

2018-06-01

Based on the first-principle calculations, the chemical reactivity of transition metal (Fe, Co, Ni, and Cu) dopants within BC3 sheets toward toxic gas molecules (CO, NO, NO2, SO2, and HCN) is comparably investigated. First, the adsorbed gases on metal-modified BC3 sheets exhibit the different stability. Compared with other gases, the metal-modified BC3 substrates exhibit the stronger affinity toward the NO and NO2 molecules (> 1.0 eV), while the adsorbed HCN has the smallest adsorption energy, illustrating that the NO and NO2 as specific toxic gas molecule can be easily detected. Second, the adsorbed gas molecules can effectively regulate the electronic structure and magnetic property of BC3 systems. Fox example, the strong adsorption of NO and NO2 on Fe-modified BC3 systems exhibits non-magnetic property, yet these gases on Co modified BC3 systems exhibit the magnetic character. In addition, the adsorbed NO and SO2 can induce and turn the degree of magnetic moments of Ni- and Cu-modified BC3 systems. Therefore, the different kinds of adsorbed gases on metal-modified BC3 sheets can be distinguished through investigating the changed magnetic moments of system, which would provide important information for designing the functional BC3-based materials.

Characterization, sorption, and exhaustion of metal oxide nanoparticles as metal adsorbents

NASA Astrophysics Data System (ADS)

Engates, Karen Elizabeth

Safe drinking water is paramount to human survival. Current treatments do not adequately remove all metals from solution, are expensive, and use many resources. Metal oxide nanoparticles are ideal sorbents for metals due to their smaller size and increased surface area in comparison to bulk media. With increasing demand for fresh drinking water and recent environmental catastrophes to show how fragile water supplies are, new approaches to water conservation incorporating new technologies like metal oxide nanoparticles should be considered as an alternative method for metal contaminant adsorbents from typical treatment methods. This research evaluated the potential of manufactured iron, anatase, and aluminum nanoparticles (Al2O3, TiO2, Fe2O3) to remove metal contaminants (Pb, Cd, Cu, Ni, Zn) in lab-controlled and natural waters in comparison to their bulk counterparts by focusing on pH, contaminant and adsorbent concentrations, particle size, and exhaustive capabilities. Microscopy techniques (SEM, BET, EDX) were used to characterize the adsorbents. Adsorption experiments were performed using 0.01, 0.1, or 0.5 g/L nanoparticles in pH 8 solution. When results were normalized by mass, nanoparticles adsorbed more than bulk particles but when surface area normalized the opposite was observed. Adsorption was pH-dependent and increased with time and solid concentration. Aluminum oxide was found to be the least acceptable adsorbent for the metals tested, while titanium dioxide anatase (TiO2) and hematite (alpha-Fe2O3) showed great ability to remove individual and multiple metals from pH 8 and natural waters. Intraparticle diffusion was likely part of the complex kinetic process for all metals using Fe2O3 but not TiO 2 nanoparticles within the first hour of adsorption. Adsorption kinetics for all metals tested were described by a modified first order rate equation used to consider the diminishing equilibrium metal concentrations with increasing metal oxides, showing faster adsorption rates for nanoparticles compared to bulk particles. Isotherms were best fit with most correlations of r=0.99 or better using the Langmuir-Freundlich equation which describes a heterogeneous surface with monolayer adsorption. Calculated rate constants and distribution coefficients (Kd) showed TiO2 nanoparticles were very good sorbents and more rapid in removing metals than other nanoparticles studied here and reported in the literature. Desorption studies concluded Pb, Cd, and Zn appear to be irreversibly sorbed to TiO2 surfaces at pH 8. TiO2 and Fe2O3 nanoparticles were capable of multiple metal loadings, with exhaustion for both adsorbents at pH 6. Exhaustion studies at pH 8 showed hematite exhausted after four consecutive cycles while anatase showed no exhaustion after 8 cycles. Their bulk counterparts exhausted in earlier cycles indicating the lack of ability to adsorb much of the multiple metals in solution. The increased surface area of TiO2 and Fe 2O3 nanoparticles, coupled with strong adsorption at the pH of most natural waters and resistance to desorption of some metals, may offer a potential remediation method for removal of metals from water in the future.

Modification of Ti6Al4V implant surfaces by biocompatible TiO2/PCL hybrid layers prepared via sol-gel dip coating: Structural characterization, mechanical and corrosion behavior.

PubMed

Catauro, Michelina; Bollino, Flavia; Giovanardi, Roberto; Veronesi, Paolo

2017-05-01

Surface modification of metallic implants is a promising strategy to improve tissue tolerance, osseointegration and corrosion resistance of them. In the present work, bioactive and biocompatible organic-inorganic hybrid coatings were prepared using a sol-gel dip coating route. They consist of an inorganic TiO 2 matrix in which different percentages of poly(ε-caprolactone) (PCL), a biodegradable and biocompatible polymer, were incorporated. The coatings were used to modify the surface of Ti6Al4V substrates in order to improve their wear and corrosion resistance. The chemical structure of the coatings was analyzed by attenuated total reflectance (ATR) Fourier transform infrared (FTIR) spectroscopy. Coating microstructure, mechanical properties and ability to inhibit the corrosion of the substrates were evaluated as a function of the PCL amount. Scanning electron microscopy (SEM) showed that the polymer allows to obtain crack-free coatings, but when high percentages were added uncoated areas appear. Nano-indentation tests revealed that, as expected, surface hardness and elastic modulus decrease as the percentage of polymeric matrix increases, but scratch testing demonstrated that the coatings are effective in preventing scratching of the underlying metallic substrate, at least for PCL contents up to 20wt%. The electrochemical tests (polarization curves acquired in order to evaluate the corrosion resistance) allowed to asses that the coatings have a significant effect in term of corrosion potential (E corr ) but they do not significantly affect the passivation process that titanium undergoes in contact with the test solution used (modified Dulbecco's phosphate-buffered saline or DPBS). Copyright © 2016 Elsevier B.V. All rights reserved.

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

Gallegos, N.G.; Alvarez, A.M.; Cagnoli, M.V.

SiO{sub 2} covered with MgO has been used as support of iron catalysts in the Fischer-Tropsch reaction. Catalysts of 5% (w/w) iron concentration and 2, 4, and 8% (w/w) of MgO on SiO{sub 2} were prepared. Selective chemisorption of CO, volumetric oxidation, and Moessbauer spectroscopy were used to characterize the type of iron species and the metallic crystal sizes. MgO covers the SiO{sub 2} surface and modifies the metallic crystal size. The activity to total hydrocarbons increases with the amount of MgO added. An optimal concentration of about 4% (w/w) was found to have the highest selectivity to olefins. 45more » refs., 13 figs., 3 tabs.« less

Nano-particle modified stationary phases for high-performance liquid chromatography.

PubMed

Nesterenko, Ekaterina P; Nesterenko, Pavel N; Connolly, Damian; He, Xiaoyun; Floris, Patrick; Duffy, Emer; Paull, Brett

2013-08-07

This review covers the latest developments and applications of nano-materials in stationary phase development for various modes of high-performance liquid chromatography. Specific attention is placed upon the development of new composite phases, including the synthetic and immobilisation strategies used, to produce either encapsulated nano-particles, or surface attached nano-particles, layers, coatings and other structures. The resultant chromatographic applications, where applicable, are discussed with comment upon enhanced selectivity and/or efficiency of the nano-particle modified phases, where such effects have been identified. In the main this review covers developments over the past five years and is structured according to the nature of the nano-particles themselves, including carbonaceous, metallic, inorganic, and organopolymer based materials.

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

Rana, Vijay Kumar; Department of Chemical Technology, North Maharashtra University Jalgaon-425001; Division of Polymer Science and Engineering, National Chemical Laboratory, Pune-411 008

To achieve a high level of heavy metal adsorption, 1,1 Prime ,1 Double-Prime -(1,3,5-triazine-2,4,6-triyl)tris(3-(3-(triethoxysilyl)propyl)urea) (TTPU) was synthesized as a novel melamine precursor and incorporated on the silica surface of periodic mesoporous organosilica (PMO). The melamine modified PMOs (MPMOs) were synthesized under acidic conditions using TTPU, tetraethylorthosilicate (TEOS) and Pluronic P123 as a template and the modified PMOs were characterized using the relevant instrumental techniques. The characteristic materials were used as adsorbents for the adsorption of Fe(III) ions. Fe(III) adsorption studies revealed MPMO-7.5 to be a good absorbent with higher adsorption efficiency than other MPMOs. - Graphical Abstract: A new organosilicamore » precursor, TTPU, has been successfully synthesized and characterized to incorporate on the silica surface of periodic mesoporous organosilica (PMO). The melamine modified PMOs (MPMOs), in particular, the MPMO-7.5 was found to exhibit good adsorption efficiency for Fe(III). Highlights: Black-Right-Pointing-Pointer Synthesis of new melamine modified periodic mesoporous organosilicas (MPMOs). Black-Right-Pointing-Pointer A new organosilica precursor, TTPU, has been successfully synthesized for the MPMOs. Black-Right-Pointing-Pointer The MPMOs were characterized by the relevant instrumental techniques. Black-Right-Pointing-Pointer MPMO-7.5 exhibits higher adsorption efficiency for Fe(III) ions than other MPMOs.« less

Shear bond strength of brackets on restorative materials: Comparison on various dental restorative materials using the universal primer Monobond® Plus.

PubMed

Ebert, Thomas; Elsner, Laura; Hirschfelder, Ursula; Hanke, Sebastian

2016-03-01

The purpose of this work was to analyze surfaces consisting of different restorative materials for shear bond strength (SBS) and failure patterns of metal and ceramic brackets. Bonding involved the use of a universal primer (Monobond® Plus, Ivoclar Vivadent). Six restorative materials were tested, including one composite resin (Clearfil Majesty™ Posterior, Kuraray Noritake Dental), one glass-ceramic material (IPS Empress® Esthetic, Ivoclar Vivadent), one oxide-ceramic material (CORiTEC Zr transpa Disc, imes-icore), two base-metal alloys (remanium® star, Dentaurum; Colado® CC, Ivoclar Vivadent), and one palladium-based alloy (Callisto® 75 Pd, Ivoclar Vivadent). Bovine incisors served as controls. Both metal and ceramic brackets (discovery®/discovery® pearl; Dentaurum) were bonded to the restorative surfaces after sandblasting and pretreatment with Monobond® Plus. A setup modified from DIN 13990-2 was used for SBS testing and adhesive remnant index (ARI)-based analysis of failure patterns. The metal brackets showed the highest mean SBS values on the glass-ceramic material (68.61 N/mm(2)) and the composite resin (67.58 N/mm(2)) and the lowest mean SBS on one of the base-metal alloys (Colado® CC; 14.01 N/mm(2)). The ceramic brackets showed the highest mean SBS on the glass-ceramic material (63.36 N/mm(2)) and the lowest mean SBS on the palladium-based alloy (38.48 N/mm(2)). Significant differences between the metal and ceramic brackets were observed in terms of both SBS values and ARI scores (p < 0.05). Under both bracket types, fractures of the composite-resin and the glass-ceramic samples were observed upon debonding. Opaque restorative materials under metal brackets were found to involve undercuring of the adhesive. Monobond® Plus succeeded in generating high bond strengths of both bracket types on all restorative surfaces. Given our observations of cohesive fracture (including cases of surface avulsion) of the composite-resin and the glass-ceramic samples, we recommend against using these material combinations in clinical practice.

Nanometric Surface Oscillation Spectroscopy of Water-Poor Microemulsions.

PubMed

Corti, Mario; Raudino, Antonio; Cantù, Laura; Theisen, Johannes; Pleines, Maximilian; Zemb, Thomas N

2018-06-18

Selectively exchanging metal complexes between emulsified water-poor microemulsions and concentrated solutions of mixed electrolytes is the core technology for strategic metal recycling. Nanostructuration triggered by solutes present in the organic phase is understood, but little is known about fluctuations of the microemulsion-water interface. We use here a modified version of an opto-electric device initially designed for air bubbles, in order to evidence resonant electrically induced surface waves of an oily droplet suspended in an aqueous phase. Resonant waves of nanometer amplitude of a millimeter-sized microemulsion droplet containing a common ion-specific extractant diluted by dodecane and suspended in a solution of rare earth nitrate are evidenced for the first time with low excitation fields (5 V/cm). From variation of the surface wave spectrum with rare earth concentration, we evidence up-take of rare-earth ions at the interface and at higher concentration the formation of a thin "crust" of liquid crystal forming at unusually low concentration, indicative of a surface induced phase transition. The effect of the liquid crystal structure on the resonance spectrum is backed up by a model, which is used to estimate crust thickness.

Enhanced removal of nitrate from water using surface modification of adsorbents--a review.

PubMed

Loganathan, Paripurnanda; Vigneswaran, Saravanamuthu; Kandasamy, Jaya

2013-12-15

Elevated concentration of nitrate results in eutrophication of natural water bodies affecting the aquatic environment and reduces the quality of drinking water. This in turn causes harm to people's health, especially that of infants and livestock. Adsorbents with the high capacity to selectively adsorb nitrate are required to effectively remove nitrate from water. Surface modifications of adsorbents have been reported to enhance their adsorption of nitrate. The major techniques of surface modification are: protonation, impregnation of metals and metal oxides, grafting of amine groups, organic compounds including surfactant coating of aluminosilicate minerals, and heat treatment. This paper reviews current information on these techniques, compares the enhanced nitrate adsorption capacities achieved by the modifications, and the mechanisms of adsorption, and presents advantages and drawbacks of the techniques. Most studies on this subject have been conducted in batch experiments. These studies need to include continuous mode column trials which have more relevance to real operating systems and pilot-plant trials. Reusability of adsorbents is important for economic reasons and practical treatment applications. However, only limited information is available on the regeneration of surface modified adsorbents. Copyright © 2013 Elsevier Ltd. All rights reserved.

Bacterial adhesion on conventional and self-ligating metallic brackets after surface treatment with plasma-polymerized hexamethyldisiloxane

PubMed Central

Tupinambá, Rogerio Amaral; Claro, Cristiane Aparecida de Assis; Pereira, Cristiane Aparecida; Nobrega, Celestino José Prudente; Claro, Ana Paula Rosifini Alves

2017-01-01

ABSTRACT Introduction: Plasma-polymerized film deposition was created to modify metallic orthodontic brackets surface properties in order to inhibit bacterial adhesion. Methods: Hexamethyldisiloxane (HMDSO) polymer films were deposited on conventional (n = 10) and self-ligating (n = 10) stainless steel orthodontic brackets using the Plasma-Enhanced Chemical Vapor Deposition (PECVD) radio frequency technique. The samples were divided into two groups according to the kind of bracket and two subgroups after surface treatment. Scanning Electron Microscopy (SEM) analysis was performed to assess the presence of bacterial adhesion over samples surfaces (slot and wings region) and film layer integrity. Surface roughness was assessed by Confocal Interferometry (CI) and surface wettability, by goniometry. For bacterial adhesion analysis, samples were exposed for 72 hours to a Streptococcus mutans solution for biofilm formation. The values obtained for surface roughness were analyzed using the Mann-Whitney test while biofilm adhesion were assessed by Kruskal-Wallis and SNK test. Results: Significant statistical differences (p< 0.05) for surface roughness and bacterial adhesion reduction were observed on conventional brackets after surface treatment and between conventional and self-ligating brackets; no significant statistical differences were observed between self-ligating groups (p> 0.05). Conclusion: Plasma-polymerized film deposition was only effective on reducing surface roughness and bacterial adhesion in conventional brackets. It was also noted that conventional brackets showed lower biofilm adhesion than self-ligating brackets despite the absence of film. PMID:28902253

Ultralow-power complementary metal-oxide-semiconductor inverters constructed on Schottky barrier modified nanowire metal-oxide-semiconductor field-effect-transistors.

PubMed

Ma, R M; Peng, R M; Wen, X N; Dai, L; Liu, C; Sun, T; Xu, W J; Qin, G G

2010-10-01

We show that the threshold voltages of both n- and p-channel metal-oxide-semiconductor field-effect-transistors (MOSFETs) can be lowered to close to zero by adding extra Schottky contacts on top of nanowires (NWs). Novel complementary metal-oxide-semiconductor (CMOS) inverters are constructed on these Schottky barrier modified n- and p-channel NW MOSFETs. Based on the high performances of the modified n- and p-channel MOSFETs, especially the low threshold voltages, the as-fabricated CMOS inverters have low operating voltage, high voltage gain, and ultra-low static power dissipation.

Ion exchanger from chemically modified banana leaves.

PubMed

El-Gendy, Ahmed A; Mohamed, Samar H; Abd-Elkader, Amal H

2013-07-25

Cation exchangers from chemically modified banana leaves have been prepared. Banana leaves were treated with different molarities of KMnO4 and cross linked with epichlorohydrin and their effect on metal ion adsorption was investigated. Phosphorylation of chemically modified banana leaves was also studied. The metal ion uptake by these modified banana leaves was clarified. Effect of different varieties, e.g. activation of produced cation exchanger, concentration of metal ions was also investigated. Characterization of the prepared ion exchangers by using infrared and thermal analysis was also taken in consideration. Copyright © 2013 Elsevier Ltd. All rights reserved.

Adsorption Behavior of Selective Recognition Functionalized Biochar to Cd(II) in Wastewater

PubMed Central

Zhang, Shiqiu; Yang, Xue; Liu, Le; Ju, Meiting; Zheng, Kui

2018-01-01

Biochar is an excellent absorbent for most heavy metal ions and organic pollutants with high specific surface area, strong aperture structure, high stability, higher cation exchange capacity and rich surface functional groups. To improve the selective adsorption capacity of biochar to designated heavy metal ions, biochar prepared by agricultural waste is modified via Ionic-Imprinted Technique. Fourier transform infrared (FT-IR) spectra analysis and X-ray photoelectron spectroscopy (XPS) analysis of imprinted biochar (IB) indicate that 3-Mercaptopropyltrimethoxysilane is grafted on biochar surface through Si–O–Si bonds. The results of adsorption experiments indicate that the suitable pH range is about 3.0–8.0, the dosage is 2.0 g·L−1, and the adsorption equilibrium is reached within 960 min. In addition, the data match pseudo-second-order kinetic model and Langmuir model well. The computation results of adsorption thermodynamics and stoichiometric displacement theory of adsorption (SDT-A) prove that the adsorption process is spontaneous and endothermic. Finally, IB possesses a higher selectivity adsorption to Cd(II) and a better reuse capacity. The functionalized biochar could solidify designated ions stably. PMID:29443954

Bowl Inversion and Electronic Switching of Buckybowls on Gold.

PubMed

Fujii, Shintaro; Ziatdinov, Maxim; Higashibayashi, Shuhei; Sakurai, Hidehiro; Kiguchi, Manabu

2016-09-21

Bowl-shaped π-conjugated compounds, or buckybowls, are a novel class of sp(2)-hybridized nanocarbon materials. In contrast to tubular carbon nanotubes and ball-shaped fullerenes, the buckybowls feature structural flexibility. Bowl-to-bowl structural inversion is one of the unique properties of the buckybowls in solutions. Bowl inversion on a surface modifies the metal-molecule interactions through bistable switching between bowl-up and bowl-down states on the surface, which makes surface-adsorbed buckybowls a relevant model system for elucidation of the mechano-electronic properties of nanocarbon materials. Here, we report a combination of scanning tunneling microscopy (STM) measurements and ab initio atomistic simulations to identify the adlayer structure of the sumanene buckybowl on Au(111) and reveal its unique bowl inversion behavior. We demonstrate that the bowl inversion can be induced by approaching the STM tip toward the molecule. By tuning the local metal-molecule interaction using the STM tip, the sumanene buckybowl exhibits structural bistability with a switching rate that is two orders of magnitude faster than that of the stochastic inversion process.

Surface and Interface Engineering of Noble-Metal-Free Electrocatalysts for Efficient Energy Conversion Processes.

PubMed

Zhu, Yun Pei; Guo, Chunxian; Zheng, Yao; Qiao, Shi-Zhang

2017-04-18

Developing cost-effective and high-performance electrocatalysts for renewable energy conversion and storage is motivated by increasing concerns regarding global energy security and creating sustainable technologies dependent on inexpensive and abundant resources. Recent achievements in the design and synthesis of efficient non-precious-metal and even non-metal electrocatalysts make the replacement of noble metal counterparts for the hydrogen evolution reaction (HER), oxygen evolution reaction (OER), and oxygen reduction reaction (ORR) with earth-abundant elements, for example, C, N, Fe, Mn, and Co, a realistic possibility. It has been found that surface atomic engineering (e.g., heteroatom-doping) and interface atomic or molecular engineering (e.g., interfacial bonding) can induce novel physicochemical properties and strong synergistic effects for electrocatalysts, providing new and efficient strategies to greatly enhance the catalytic activities. In this Account, we discuss recent progress in the design and fabrication of efficient electrocatalysts based on carbon materials, graphitic carbon nitride, and transition metal oxides or hydroxides for efficient ORR, OER, and HER through surface and interfacial atomic and molecular engineering. Atomic and molecular engineering of carbon materials through heteroatom doping with one or more elements of noticeably different electronegativities can maximally tailor their electronic structures and induce a synergistic effect to increase electrochemical activity. Nonetheless, the electrocatalytic performance of chemically modified carbonaceous materials remains inferior to that of their metallic counterparts, which is mainly due to the relatively limited amount of electrocatalytic active sites induced by heteroatom doping. Accordingly, coupling carbon substrates with other active electrocatalysts to produce composite structures can impart novel physicochemical properties, thereby boosting the electroactivity even further. Although the majority of carbon-based materials remain uncompetitive with state-of-the-art metal-based catalysts for the aforementioned catalytic processes, non-metal carbon hybrids have already shown performance that typically only conventional noble metals or transition metal materials can achieve. The idea of hybridized carbon-based catalysts possessing unique active surfaces and macro- or nanostructures is addressed herein. For metal-carbon couples, the incorporation of carbon can effectively compensate for the intrinsic deficiency in conductivity of the metallic components. Chemical modification of carbon frameworks, such as nitrogen doping, not only can change the electron-donor character, but also can introduce anchoring sites for immobilizing active metallic centers to form metal-nitrogen-carbon (M-N-C) species, which are thought to facilitate the electrocatalytic process. With thoughtful material design, control over the porosity of composites, the molecular architecture of active metal moieties and macromorphologies of the whole catalysts can be achieved, leading to a better understanding structure-activity relationships. We hope that we can offer new insight into material design, particularly the role of chemical composition and structural properties in electrochemical performance and reaction mechanisms.

Controlled Synthesis of Pd/Pt Core Shell Nanoparticles Using Area-selective Atomic Layer Deposition

PubMed Central

Cao, Kun; Zhu, Qianqian; Shan, Bin; Chen, Rong

2015-01-01

We report an atomic scale controllable synthesis of Pd/Pt core shell nanoparticles (NPs) via area-selective atomic layer deposition (ALD) on a modified surface. The method involves utilizing octadecyltrichlorosilane (ODTS) self-assembled monolayers (SAMs) to modify the surface. Take the usage of pinholes on SAMs as active sites for the initial core nucleation, and subsequent selective deposition of the second metal as the shell layer. Since new nucleation sites can be effectively blocked by surface ODTS SAMs in the second deposition stage, we demonstrate the successful growth of Pd/Pt and Pt/Pd NPs with uniform core shell structures and narrow size distribution. The size, shell thickness and composition of the NPs can be controlled precisely by varying the ALD cycles. Such core shell structures can be realized by using regular ALD recipes without special adjustment. This SAMs assisted area-selective ALD method of core shell structure fabrication greatly expands the applicability of ALD in fabricating novel structures and can be readily applied to the growth of NPs with other compositions. PMID:25683469

Enhanced visible light-induced photocatalytic activity of surface-modified BiOBr with Pd nanoparticles

NASA Astrophysics Data System (ADS)

Meng, Xiangchao; Li, Zizhen; Chen, Jie; Xie, Hongwei; Zhang, Zisheng

2018-03-01

Palladium nanoparticles well-dispersed on BiOBr surfaces were successfully prepared via a two-step process, namely hydrothermal synthesis of BiOBr followed by photodeposition of palladium. Surface-exposed palladium nanoparticles may improve the harvesting capacity of visible light photons via the surface plasmonic resonance effect to produce extra electrons. Palladium is an excellent electron acceptor, and therefore favours the separation of photogenerated electron/hole pairs. As a result, palladium significantly improves the photocatalytic activity of BiOBr in the removal of organic pollutants (phenol) under visible light irradiation. In addition to as-prepared samples which were comprehensively characterized, the mechanism for the enhancement via the deposition of palladium nanoparticles was also proposed based on results. This work may serve as solid evidence to confirm that surface-deposited palladium nanoparticles are capable of improving photocatalytic activity, and that photodeposition may be an effective approach to load metal nanoparticles onto a surface.

Surface wettability of an atomically heterogeneous system and the resulting intermolecular forces

NASA Astrophysics Data System (ADS)

Chatterjee, Sanghamitro; Bhattacharjee, Sudeep; Maurya, Sanjeev K.; Srinivasan, Vyas; Khare, Krishnacharya; Khandekar, Sameer

2017-06-01

We present the effect of 0.5 keV Ar+ beam irradiation on the wetting properties of metallic thin films. Observations reveal a transition from hydrophilic to hydrophobic nature at higher beam fluences which can be attributed to a reduction in net surface free energy. In this low-energy regime, ion beams do not induce significant surface roughness and chemical heterogeneity. However, they cause implantation of atomic impurities in the near surface region of the target and thus form a heterogeneous system at atomic length scales. Interestingly, the presence of implanted Ar atoms in the near surface region modifies the dispersive intermolecular interaction near the surface but induces no chemical modification due to their inert nature. On this basis, we have developed a theoretical model consistent with the experimental observations that reproduces the effective Hamaker constant with a reasonable accuracy.

Surface modification of poly(dimethylsiloxane) for microfluidic assay applications

NASA Astrophysics Data System (ADS)

Séguin, Christine; McLachlan, Jessica M.; Norton, Peter R.; Lagugné-Labarthet, François

2010-02-01

The surface of a poly(dimethylsiloxane) (PDMS) film was imparted with patterned functionalities at the micron-scale level. Arrays of circles with diameters of 180 and 230 μm were functionalized using plasma oxidation coupled with aluminum deposition, followed by silanization with solutions of 3-aminopropyltrimethoxy silane (3-APTMS) and 3-mercaptopropyltrimethoxy silane (3-MPTMS), to obtain patterned amine and thiol functionalities, respectively. The modification of the samples was confirmed using X-ray photoelectron spectroscopy (XPS), gold nanoparticle adhesion coupled with optical microscopy, as well as by derivatization with fluorescent dyes. To further exploit the novel surface chemistry of the modified PDMS, samples with surface amine functionalities were used to develop a protein assay as well as an array capable of cellular capture and patterning. The modified substrate was shown to successfully selectively immobilize fluorescently labeled immunoglobulin G (IgG) by tethering Protein A to the surface, and, for the cellular arrays, C2C12 rat endothelial cells were captured. Finally, this novel method of patterning chemical functionalities onto PDMS has been incorporated into microfluidic channels. Finally, we demonstrate the in situ chemical modification of the protected PDMS oxidized surface within a microfluidic device. This emphasizes the potential of our method for applications involving micron-scale assays since the aluminum protective layer permits to functionalize the oxidized PDMS surface several weeks after plasma treatment simply after etching away the metallic thin film.

Application of carbohydrate polymers as corrosion inhibitors for metal substrates in different media: A review.

PubMed

Umoren, Saviour A; Eduok, Ubong M

2016-04-20

Naturally occurring polysaccharides are biopolymers existing as products of biochemical processes in living systems. A wide variety of them have been employed for various material applications; as binders, coatings, drug delivery, corrosion inhibitors etc. This review describes the application of some green and benign carbohydrate biopolymers and their derivatives for inhibition of metal corrosion. Their modes and mechanisms of protection have also been described as directly related to their macromolecular weights, chemical composition and their unique molecular and electronic structures. For instance, cellulose and chitosan possess free amine and hydroxyl groups capable of metal ion chelation and their lone pairs of electrons are readily utilized for coordinate bonding at the metal/solution interface. Some of the carbohydrate polymers reviewed in this work are either pure or modified forms; their grafted systems and nanoparticle composites with multitude potentials for metal protection applications have also been highlighted. Few inhibitors grafted to introduce more compact structures with polar groups capable of increasing the total energy of the surface have also been mentioned. Exudate gums, carboxymethyl and hydroxyethyl cellulose, starch, pectin and pectates, substituted/modified chitosans, carrageenan, dextrin/cyclodextrins and alginates have been elaborately reviewed, including the effects of halide additives on their anticorrosion performances. Aspects of computational/theoretical approach to corrosion monitoring have been recommended for future studies. This non-experimental approach to corrosion could foster a better understanding of the corrosion inhibition processes by correlating actual inhibition mechanisms with molecular structures of these carbohydrate polymers. Copyright © 2015 Elsevier Ltd. All rights reserved.

Nanoporous metals for biodegradable implants: Initial bone mesenchymal stem cell adhesion and degradation behavior.

PubMed

Heiden, Michael; Huang, Sabrina; Nauman, Eric; Johnson, David; Stanciu, Lia

2016-07-01

Nanostructured Fe-Mn and Fe-Mn-Zn metal scaffolds were generated through a well-controlled selective leaching process in order to fulfill the growing demand for adjustable degradation rates and improved cellular response of resorbable materials. Mouse bone marrow mesenchymal stem cells (D1 ORL UVA) were seeded onto eleven, carefully chosen nanoporous surfaces for 24 h in vitro. Using a combination of fluorescence microscopy, scanning electron microscopy (SEM), and an MTS assay, it was discovered that scaffolds with nanoscale roughened surfaces had increased cell attachment by up to 123% compared to polished smooth Fe-Mn surfaces. Significant cell spreading and construction of cell multilayers were also apparent after 24 h, suggesting better adhesion. Additionally, static electrochemical polarization experiments revealed an improvement of up to 26% in the actual rate of biodegradation for Fe-Mn surface-modified materials. However, any residual concentration of zinc after leaching was shown to slightly increase corrosion resistance. The results demonstrate that selectively leached, nanostructured Fe-Mn surfaces have the potential of being tailored to a diverse set of transient implant scenarios, while also effectively boosting overall biocompatibility, initial cell attachment, and degradation rate. © 2016 Wiley Periodicals, Inc. J Biomed Mater Res Part A: 104A: 1747-1758, 2016. © 2016 Wiley Periodicals, Inc.

Controlled assembly of high-order nanoarray metal structures on bulk copper surface by femtosecond laser pulses

NASA Astrophysics Data System (ADS)

Qin, Wanwan; Yang, Jianjun

2017-07-01

We report a new one-step maskless method to fabricate high-order nanoarray metal structures comprising periodic grooves and particle chains on a single-crystal Cu surface using femtosecond laser pulses at the central wavelength of 400 nm. Remarkably, when a circularly polarized infrared femtosecond laser pulse (spectrally centered at 800 nm) pre-irradiates the sample surface, the geometric dimensions of the composite structure can be well controlled. With increasing the energy fluence of the infrared laser pulse, both the groove width and particle diameter are observed to reduce, while the measured spacing-to-diameter ratio of the nanoparticles tends to present an increasing tendency. A physical scenario is proposed to elucidate the underlying mechanisms: as the infrared femtosecond laser pulse pre-irradiates the target, the copper surface is triggered to display anomalous transient physical properties, on which the subsequently incident Gaussian blue laser pulse is spatially modulated into fringe-like energy depositions via the excitation of ultrafast surface plasmon. During the following relaxation processes, the periodically heated thin-layer regions can be transferred into the metastable liquid rivulets and then they break up into nanodroplet arrays owing to the modified Rayleigh-like instability. This investigation indicates a simple integrated approach for active designing and large-scale assembly of complexed functional nanostructures on bulk materials.

Membrane technology for treating of waste nanofluids coolant: A review

NASA Astrophysics Data System (ADS)

Mohruni, Amrifan Saladin; Yuliwati, Erna; Sharif, Safian; Ismail, Ahmad Fauzi

2017-09-01

The treatment of cutting fluids wastes concerns a big number of industries, especially from the machining operations to foster environmental sustainability. Discharging cutting fluids, waste through separation technique could protect the environment and also human health in general. Several methods for the separation emulsified oils or oily wastewater have been proposed as three common methods, namely chemical, physicochemical and mechanical and membrane technology application. Membranes are used into separate and concentrate the pollutants in oily wastewater through its perm-selectivity. Meanwhile, the desire to compensate for the shortcomings of the cutting fluid media in a metal cutting operation led to introduce the using of nanofluids (NFs) in the minimum quantity lubricant (MQL) technique. NFs are prepared based on nanofluids technology by dispersing nanoparticles (NPs) in liquids. These fluids have potentially played to enhance the performance of traditional heat transfer fluids. Few researchers have studied investigation of the physical-chemical, thermo-physical and heat transfer characteristics of NFs for heat transfer applications. The use of minimum quantity lubrication (MQL) technique by NFs application is developed in many metal cutting operations. MQL did not only serve as a better alternative to flood cooling during machining operation and also increases better-finished surface, reduces impact loads on the environment and fosters environmental sustainability. Waste coolant filtration from cutting tools using membrane was treated by the pretreated process, coagulation technique and membrane filtration. Nanomaterials are also applied to modify the membrane structure and morphology. Polyvinylidene fluoride (PVDF) is the better choice in coolant wastewater treatment due to its hydrophobicity. Using of polyamide nanofiltration membranes BM-20D and UF-PS-100-100, 000, it resulted in the increase of permeability of waste coolant filtration. Titanium dioxide is nanomaterials additive to modify the Nanopores of the surface membrane. Contact angle and average pore size were used in the investigation of the surface morphology of membranes. An adequate choice in modifying the membrane surface in waste coolant filtration may bring a promised alternative as a solution in waste coolant remediation.

The structure of epitaxial V2O3 films and their surfaces: A medium energy ion scattering study

NASA Astrophysics Data System (ADS)

Window, A. J.; Hentz, A.; Sheppard, D. C.; Parkinson, G. S.; Woodruff, D. P.; Unterberger, W.; Noakes, T. C. Q.; Bailey, P.; Ganduglia-Pirovano, M. V.; Sauer, J.

2012-11-01

Medium energy ion scattering, using 100 keV H+ incident ions, has been used to investigate the growth of epitaxial films, up to thicknesses of ~ 200 Å, of V2O3 on both Pd(111) and Au(111). Scattered-ion energy spectra provide a measure of the average film thickness and the variations in this thickness, and show that, with suitable annealing, the crystalline quality is good. Plots of the scattering yield as a function of scattering angle, so-called blocking curves, have been measured for two different incidence directions and have been used to determine the surface structure. Specifically, scattering simulations for a range of different model structures show poor agreement with experiment for half-metal (….V'O3V) and vanadyl (….V'O3V=O) terminations, with and without surface interlayer relaxations. However, good agreement with experiment is found for the modified oxygen-termination structure, first proposed by Kresse et al., in which a subsurface V half-metal layer is moved up into the outermost V buckled metal layer to produce a VO2 overlayer on the underlying V2O3, with an associated layer structure of ….O3VV''V 'O3. This result is consistent with the predictions of thermodynamic equilibrium at the surface under the surface preparation conditions, but is at variance with the conclusions of earlier studies of this system that have favoured the vanadyl termination. The results of these previous studies are re-evaluated in the light of the new result.

Surface and bulk modified high capacity layered oxide cathodes with low irreversible capacity loss

NASA Technical Reports Server (NTRS)

Manthiram, Arumugam (Inventor); Wu, Yan (Inventor)

2010-01-01

The present invention includes compositions, surface and bulk modifications, and methods of making of (1-x)Li[Li.sub.1/3Mn.sub.2/3]O.sub.2.xLi[Mn.sub.0.5-yNi.sub.0.5-yCo.sub.2- y]O.sub.2 cathode materials having an O3 crystal structure with a x value between 0 and 1 and y value between 0 and 0.5, reducing the irreversible capacity loss in the first cycle by surface modification with oxides and bulk modification with cationic and anionic substitutions, and increasing the reversible capacity to close to the theoretical value of insertion/extraction of one lithium per transition metal ion (250-300 mAh/g).

Plasma effect on weld pool surface reconstruction by shape-from-polarization analysis

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

Coniglio, N.; Mathieu, A., E-mail: alexandre.mathieu@u-bourgogne.fr; Aubreton, O.

2014-03-31

The polarimetric state of the thermal radiations emitted by the weld metal contains geometric information about the emitting surface. Even though the analysed thermal radiation has a wavelength corresponding to a blind spectral window of the arc plasma, the physical presence of the arc plasma itself interferes with the rays radiated by the weld pool surface before attaining the polarimeter, thus modifying the geometric information transported by the ray. In the present work, the effect of the arc plasma-surrounding zone on the polarimetric state and propagation direction of the radiated ray is analyzed. The interaction with the arc plasma zonemore » induces a drop in ray intensity and a refraction of ray optical path.« less

Characterization of the modified nickel-zinc ferrite nanoparticles coated with APTES by salinization reaction

NASA Astrophysics Data System (ADS)

Zainal, Israa G.; Al-Shammari, Ahmed Majeed; Kachi, Wjeah

2018-05-01

Surface functionalization of magnetic iron oxide nanoparticles (NPs) is a kind of functional materials, which have been widely used in the biotechnology and catalysis. In this study, Nickel-Zinc ferrite nanoparticles was functionalized with amino propyl triethoxy silane (APTES) by silanization reaction and both non coated and organosilane-coated magnetite characterized by energy-dispersive X-ray spectroscopy (EDX), X-ray diffractometry, Fourier transformed infrared spectroscopy (FTIR) and atomic force microscopy. Basic groups of amino anchored on the external surface of the coated magnetite were observed. Our study procedure nanoparticles which have surface with free - NH2 groups which can carry out ionic interaction with carboxylic groups and act as a carrier of biological molecules, drugs and metals.

Surface and bulk modified high capacity layered oxide cathodes with low irreversible capacity loss

DOEpatents

Manthiram, Arumugam; Wu, Yan

2010-03-16

The present invention includes compositions, surface and bulk modifications, and methods of making of (1-x)Li[Li.sub.1/3Mn.sub.2/3]O.sub.2.xLi[Mn.sub.0.5-yNi.sub.0.5-yCo.sub.2- y]O.sub.2 cathode materials having an O3 crystal structure with a x value between 0 and 1 and y value between 0 and 0.5, reducing the irreversible capacity loss in the first cycle by surface modification with oxides and bulk modification with cationic and anionic substitutions, and increasing the reversible capacity to close to the theoretical value of insertion/extraction of one lithium per transition metal ion (250-300 mAh/g).

Electrochemical characterisation and anodic stripping voltammetry at mesoporous platinum rotating disc electrodes.

PubMed

Lozano-Sanchez, Pablo; Elliott, Joanne M

2008-02-01

Using the technique of liquid crystal templating a rotating disc electrode (RDE) was modified with a high surface area mesoporous platinum film. The surface area of the electrode was characterised by acid voltammetry, and found to be very high (ca. 86 cm(2)). Acid characterisation of the electrode produced distorted voltammograms was interpreted as being due to the extremely large surface area which produced a combination of effects such as localised pH change within the pore environment and also ohmic drop effects. Acid voltammetry in the presence of two different types of surfactant, namely Tween 20 and Triton X-100, suggested antifouling properties associated with the mesoporous deposit. Further analysis of the modified electrode using a redox couple in solution showed typical RDE behaviour although extra capacitive currents were observed due to the large surface area of the electrode. The phenomenon of underpotential deposition was exploited for the purpose of anodic stripping voltammetry and results were compared with data collected for microelectrodes. Underpotential deposition of metal ions at the mesoporous RDE was found to be similar to that at conventional platinum electrodes and mesoporous microelectrodes although the rate of surface coverage was found to be slower at a mesoporous RDE. It was found that a mesoporous RDE forms a suitable system for quantification of silver ions in solution.

NOx Direct Decomposition: Potentially Enhanced Thermodynamics and Kinetics on Chemically Modified Ferroelectric Surfaces

NASA Astrophysics Data System (ADS)

Kakekhani, Arvin; Ismail-Beigi, Sohrab

2014-03-01

NOx are regulated pollutants produced during automotive combustion. As part of an effort to design catalysts for NOx decomposition that operate in oxygen rich environment and permit greater fuel efficiency, we study chemistry of NOx on (001) ferroelectric surfaces. Changing the polarization at such surfaces modifies electronic properties and leads to switchable surface chemistry. Using first principles theory, our previous work has shown that addition of catalytic RuO2 monolayer on ferroelectric PbTiO3 surface makes direct decomposition of NO thermodynamically favorable for one polarization. Furthermore, the usual problem of blockage of catalytic sites by strong oxygen binding is overcome by flipping polarization that helps desorb the oxygen. We describe a thermodynamic cycle for direct NO decomposition followed by desorption of N2 and O2. We provide energy barriers and transition states for key steps of the cycle as well as describing their dependence on polarization direction. We end by pointing out how a switchable order parameter of substrate,in this case ferroelectric polarization, allows us to break away from some standard compromises for catalyst design(e.g. the Sabatier principle). This enlarges the set of potentially catalytic metals. Primary support from Toyota Motor Engineering and Manufacturing, North America, Inc.

Preparation of bone-implants by coating hydroxyapatite nanoparticles on self-formed titanium dioxide thin-layers on titanium metal surfaces.

PubMed

Wijesinghe, W P S L; Mantilaka, M M M G P G; Chathuranga Senarathna, K G; Herath, H M T U; Premachandra, T N; Ranasinghe, C S K; Rajapakse, R P V J; Rajapakse, R M G; Edirisinghe, Mohan; Mahalingam, S; Bandara, I M C C D; Singh, Sanjleena

2016-06-01

Preparation of hydroxyapatite coated custom-made metallic bone-implants is very important for the replacement of injured bones of the body. Furthermore, these bone-implants are more stable under the corrosive environment of the body and biocompatible than bone-implants made up of pure metals and metal alloys. Herein, we describe a novel, simple and low-cost technique to prepare biocompatible hydroxyapatite coated titanium metal (TiM) implants through growth of self-formed TiO2 thin-layer (SFTL) on TiM via a heat treatment process. SFTL acts as a surface binder of HA nanoparticles in order to produce HA coated implants. Colloidal HA nanorods prepared by a novel surfactant-assisted synthesis method, have been coated on SFTL via atomized spray pyrolysis (ASP) technique. The corrosion behavior of the bare and surface-modified TiM (SMTiM) in a simulated body fluid (SBF) medium is also studied. The highest corrosion rate is found to be for the bare TiM plate, but the corrosion rate has been reduced with the heat-treatment of TiM due to the formation of SFTL. The lowest corrosion rate is recorded for the implant prepared by heat treatment of TiM at 700 °C. The HA-coating further assists in the passivation of the TiM in the SBF medium. Both SMTiM and HA coated SMTiM are noncytotoxic against osteoblast-like (HOS) cells and are in high-bioactivity. The overall production process of bone-implant described in this paper is in high economic value. Copyright © 2016 Elsevier B.V. All rights reserved.

Heavy metals and metalloids in the surface sediments of the Xiangjiang River, Hunan, China: distribution, contamination, and ecological risk assessment.

PubMed

Chai, Liyuan; Li, Huan; Yang, Zhihui; Min, Xiaobo; Liao, Qi; Liu, Yi; Men, Shuhui; Yan, Yanan; Xu, Jixin

2017-01-01

Here, we aim to determine the distribution, ecological risk and sources of heavy metals and metalloids in the surface sediments of the Xiangjiang River, Hunan Province, China. Sixty-four surface sediment samples were collected in 16 sites of the Xiangjiang River, and the concentrations of ten heavy metals and metalloids (Mn, Zn, Cr, V, Pb, Cu, As, Ni, Co, and Cd) in the sediment samples were investigated using an inductively coupled plasma mass spectrometer (ICP-MS) and an atomic fluorescence spectrophotometer (AFS), respectively. The results showed that the mean concentrations of the ten heavy metals and metalloids in the sediment samples followed the order Mn > Zn > Cr > V > Pb > Cu > As ≈ Ni >Co > Cd. The geoaccumulation index (I geo ), enrichment factor (EF), modified degree of contamination (mC d ), and potential ecological risk index (RI) revealed that Cd, followed by Pb, Zn, and Cu, caused severely contaminated and posed very highly potential ecological risk in the Xiangjiang River, especially in Shuikoushan of Hengyang, Xiawan of Zhuzhou, and Yijiawan of Xiangtan. The Pearson's correlation coefficient (PCC) analysis, principal component analysis (PCA), and hierarchical cluster analysis (HCA) indicated that the ten heavy metals and metalloids in the sampling sediments of the Xiangjiang River were classified into three groups: (1) Cd, Pb, Zn, and Cu which possibly originated from Shuikoushan, Xiawan, and Yijiawan clustering Pb-Zn mining and smelting industries; (2) Co, V, Ni, Cr, and Al from natural resources; and (3) Mn and As. Therefore, our results suggest that anthropogenic activities, especially mining and smelting, have caused severe contamination of Cd, Pb, Zn, and Cu and posed very high potential ecological risk in the Xiangjiang River.

Grain refinement in heavy rare earth element-free sintered Nd–Fe–B magnets by addition of a small amount of molybdenum

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

Kim, Jin Woo; Lee, Won Suk; Byun, Jong Min

2015-05-07

We employed a modified refractory-metal-addition method to achieve higher coercivity and remanence in heavy rare earth element (HREE)-free Nd–Fe–B sintered magnets. This process involved inducing the formation of a homogeneous secondary phase at the grain boundaries during sintering, making it possible to control the intergrain diffusion by adding small amounts of Mo, a refractory metal. To control the microstructure of the secondary phase effectively, a metal organic compound of the refractory metal was coated on the surfaces of the particles of an HREE-free Nd–Fe–B powder. The average grain size after this process was 5.60 μm, which was approximately 1.8 μm smaller thanmore » that of the HREE-free sintered Nd–Fe–B magnets (7.4 μm). The coercivity of the magnets prepared through this process could be increased from 11.88 kOe to 13.91 kOe without decreasing their remanence.« less

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.

Rapid preparation of biosorbents with high ion exchange capacity from rice straw and bagasse for removal of heavy metals.

PubMed

Rungrodnimitchai, Supitcha

2014-01-01

This work describes the preparation of the cellulose phosphate with high ion exchange capacity from rice straw and bagasse for removal of heavy metals. In this study, rice straw and bagasse were modified by the reaction with phosphoric acid in the presence of urea. The introduced phosphoric group is an ion exchangeable site for heavy metal ions. The reaction by microwave heating yielded modified rice straw and modified bagasse with greater ion exchange capacities (∼3.62 meq/g) and shorter reaction time (1.5-5.0 min) than the phosphorylation by oil bath heating. Adsorption experiments towards Pb²⁺, Cd²⁺, and Cr³⁺ ions of the modified rice straw and the modified bagasse were performed at room temperature (heavy metal concentration 40 ppm, adsorbent 2.0 g/L). The kinetics of adsorption agreed with the pseudo-second-order model. It was shown that the modified rice straw and the modified bagasse could adsorb heavy metal ions faster than the commercial ion exchange resin (Dowax). As a result of Pb²⁺ sorption test, the modified rice straw (RH-NaOH 450W) removed Pb²⁺ much faster in the initial step and reached 92% removal after 20 min, while Dowax (commercial ion exchange resin) took 90 min for the same removal efficiency.

Facile synthesis of reduced graphene oxide/peroxomolybdate(VI)-citrate composite and its potential energy storage application

NASA Astrophysics Data System (ADS)

Ciszewski, Mateusz; Benke, Grzegorz; Leszczyńska-Sejda, Katarzyna; Kopyto, Dorota

2017-11-01

A new energy storage material based on molybdate active species has been presented. Molybdenum seems to be a perspective material in supercapacitors because of numerous possible metal oxidation states, electrolyte storage by means of various chemical reactions and availability in comparison to other refractory metals. Material synthesized within this research was composed of reduced graphene oxide matrix and peroxomolybdate(VI)-citrate active dimers. It was showed that peroxomolybdate(VI)-citrate structure enhanced electrochemical activity of symmetric supercapacitor. Simple methodology was used to synthesize a composite with pH adjustment as the key step. The specific capacity calculated from galvanostatic charge/discharge curves was as high as 250 F/g. Material was distinguished by good cyclability with 5% capacity loss after 1000 cycles. The increase in charge transfer resistance, induced by metal-oxygen compound within the carbon matrix was relatively low, compared to parent reduced graphene oxide. Amorphous structure of peroxomolybdate(VI)-modified material was observed with slight increase in the interlayer distance in comparison to parent reduced graphene oxide. The height and lateral size of crystallites were also determined. Significant decrease in the specific surface area of peroxomolybdate(VI)-modified composite was observed, in comparison to the parent reduced graphene oxide.

Interfaces of electrical contacts in organic semiconductor devices

NASA Astrophysics Data System (ADS)

Demirkan, Korhan

Progress in organic semiconductor devices relies on better understanding of interfaces as well as material development. The engineering of interfaces that exhibit low resistance, low operating voltage and long-term stability to minimize device degradation is one of the crucial requirements. Photoelectron spectroscopy is a powerful technique to study the metal-semiconductor interfaces, allowing: (i) elucidation of the energy levels of the semiconductor and the contacts that determine Schottky barrier height, (ii) inspection of electrical interactions (such as charge transfer, dipole formation, formation of induced density of states or formation of polaron/bi-polaron states) that effect the energy level alignment, (iii) determination of interfacial chemistry, and (iv) estimation of interface morphology. In this thesis, we have used photoelectron spectroscopy extensively for detailed analysis of the metal organic semiconductor interfaces. In this study, we demonstrate the use of photoelectron spectroscopy for construction of energy level diagrams and display some results related to chemical tailoring of materials for engineering interfaces with lowered Schottky barriers. Following our work on the energy level alignment of poly(p-phenyene vinylene) based organic semiconductors on various substrates [Au, indium tin oxide, Si (with native oxide) and Al (with native oxide)], we tested controlling the energy level alignment by using polar self assembled molecules (SAMs). Photoelectron spectroscopy showed that, by introducing SAMs on the Au surface, we successfully changed the effective work function of Au surface. We found that in this case, the change in the effective work function of the metal surface was not reflected as a shift in the energy levels of the organic semiconductor, as opposed to the results achieved with different substrate materials. To investigate the chemical interactions at the metal/organic interface, we studied the metallization of poly(2-methoxy-5,2'-ethyl-hexyloxy-phenylene vinylene) (MEH-PPV), polystyrene (PS) and ozone treated polystyrene (PS-O3) surfaces by thermal deposition of aluminum. Photoelectron spectroscopy showed the degree of chemical interaction between Al and each polymer, for MEH-PPV, the chemical interactions were mainly through the C-O present in the side chain of the polymer structure. The chemical interaction of Al with polystyrene was less significant, but it showed a dramatic increase after ozone treatment of the polystyrene surface (due to the formation of exposed oxygen sites). Formation of metal oxide and metal-organic compound is detected during the Al metallization of MEH-PPV and ozone-treated PS surfaces. Our results showed that the condensation of Al on polymer surfaces is highly dependent on surface reactivity. Enormous differences were observed for the condensation coefficient of Al on PS and PS-O3 surfaces. For the inert PS surface, results showed that Al atoms poorly wet the polymer surface and form distributed clusters at the surface. Results on reactive polymer surfaces suggest morphology reminiscent of a Stranski-Krastanov-type growth and high contact area. Many studies have shown that the insertion of a thin interlayer of the oxide or fluoride of alkali or alkaline metals between the low work function electrode and the organic semiconductor layers dramatically lowers the onset voltage and increases the efficiency compared to identical devices without the insulating layer. Various modes have been suggested for the mechanism of device performance enhancement. We have investigated the chemical and electrical interaction of (i) LiF with MEH-PPV, (ii) Al with MEH-PPV in the presence of a thin LiF layer at the interface, and finally (iii) the interaction of Al with LiF. AFM and XPS data showed that LiF forms island on the surface. Our data in agreement with various existing models suggested the (i) alteration in the electronic properties under applied bias, (ii) doping of the organic semiconductor, (iii) formation of metal alloy (Au-Li). In addition to the possible electrical modifications at the interface suggested previously, our data also suggest a change in the film growth on LiF modified surfaces.

PdCo nanoparticles supported on carbon fibers derived from cotton: Maximum utilization of Pd atoms for efficient reduction of nitroarenes.

PubMed

Yang, Jin; Wang, Wei David; Dong, Zhengping

2018-08-15

In the present work, a facile and environment-friendly route is illustrated for the efficient fabrication of highly dispersed PdCo nanoparticles (NPs) by modified cotton-derived carbon fibers (PdCo/CCF). Firstly, commercial cotton was impregnated with CoCl 2 , followed by pyrolysis under high calcination temperature to obtain the Co NPs modified CCF sample (Co/CCF). Secondly, Co/CCF was treated with Pd(AcO) 2 aqueous solution, wherein, through a spontaneous replacement reaction process, Pd 2+ is reduced to metallic Pd and mostly covered on the surface of the Co NPs. Thus, the PdCo/CCF catalyst was obtained avoiding the use of toxic reductants like NaBH 4 , NH 2 NH 2 and HCHO. The PdCo/CCF catalyst exhibits excellent catalytic activity and recyclability for the reduction of 4-nitrophenol and other nitroarenes compared with Pd/CCF, PdCo NPs and many other noble metals based catalysts. The reasons could be attributed to the uniformly dispersed and accessible PdCo NPs on the surface of the CCF, and the Pd atoms deposited on the Co NPs surface that makes the Pd active sites available for optimum use. The PdCo/CCF catalyst also exhibits potential application for catalytic reduction of nitroarenes in a fixed bed reactor under mild reaction conditions. Furthermore, the PdCo/CCF catalyst can be magnetically recycled and reused for at least ten cycles without either losing catalytic activity or leaching of Pd active sites, thereby confirming its superior stability. Copyright © 2018 Elsevier Inc. All rights reserved.

Progress in Protective Coatings for Aircraft Gas Turbines: A Review of NASA Sponsored Research

NASA Technical Reports Server (NTRS)

Merutka, J. P.

1981-01-01

Problems associated with protective coatings for advanced aircraft gas turbines are reviewed. Metallic coatings for preventing titanium fires in compressors are identified. Coatings for turbine section are also considered, Ductile aluminide coatings for protecting internal turbine-blade cooling passage surface are also identified. Composite modified external overlay MCrAlY coatings deposited by low-pressure plasma spraying are found to be better in surface protection capability than vapor deposited MCrAlY coatings. Thermal barrier coating (TBC), studies are presented. The design of a turbine airfoil is integrated with a TBC, and computer-aided manufacturing technology is applied.

Development of an active boring bar for increased chatter immunity

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

Redmond, J.; Barney, P.; Smith, D.

The development and initial evaluation of a prototype boring bar featuring active vibration control for increased chatter immunity is described. The significance of active damping both normal and tangential to the workpiece surface is evaluated, indicating the need for two axis control to ensure adequate performance over expected variations in tool mounting procedures. The prototype tool features a commercially available boring bar modified to accommodate four PZT stack actuators for two axis bending control. Measured closed-loop dynamics are combined with a computer model of the boring process to simulate increased metal removal rate and improved workpiece surface finish through activemore » control.« less