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Sample records for well-defined silica-supported tungsten

  1. Hydro-Metathesis of Long-Chain Olefin (1-decene) using Well-Defined Silica-Supported Tungsten (VI), Molybdenum (VI) and Tantalum (V) Catalysts

    KAUST Repository

    Saidi, Aya

    2016-11-01

    Nowadays, catalysis lies at the heart of economy growth mainly in the petroleum industry. Catalysis can offer real and potential solutions to the current challenges for a long-term sustainable energy, green chemistry, and environmental protection. In this context, one of the most important and future prosperity promising catalytic applications in the petrochemical field is hydrocarbons metathesis; it consists on the conversion of both renewable and non-petroleum fossil carbon sources to transportation fuels. Olefin metathesis has become one of the standard methodologies for constructing C-C bonds in many organic transformation reactions. This owed to the numerous types of metathesis reactions that have been developed, for example, enyne, ring-opening and closing, self and cross metathesis, etc. But the one step conversion of olefin to alkanes has not been studied much. Recently, only one such a work has been published for the hydro-metathesis of propylene by tantalum hydride supported on KCC-1 in dynamic reactor. With this knowledge, we thought to study the hydro-metathesis using liquid olefin (1-decene). Another aspect of using 1-decene comes from our previous experience on metathesis of n-decane where the first step is the conversion of decane to 1-decene and subsequently to different chain length alkanes with W-alkyl/alkylidene catalyst. In this way, it would be easy for us to use different catalysts and compare them with parent catalyst concerning TON. We found 100% conversion with TON of 1010 using supported WMe6 onto SiO2-700 [(≡Si-O-)WMe5] against the previous results for n-decane showing 20% conversion and TON of 153. In this work, we disclose the hydro-metathesis reaction of 1-decene using well-defined silica supported W(VI), Mo(VI) and Ta(V) alkyl catalysts in batch reactor condition. This work is divided into three major sections; first chapter contains an introduction to the field of catalysis and surface organometallic chemistry. In second chapter

  2. Well-defined single-site monohydride silica-supported zirconium from azazirconacyclopropane

    KAUST Repository

    Hamzaoui, Bilel

    2015-01-13

    The silica-supported azazirconacyclopropane ≡SiOZr(HNMe2)(η2-NMeCH2)(NMe2) (1) leads exclusively under hydrogenolysis conditions (H2, 150°C) to the single-site monopodal monohydride silica-supported zirconium species ≡SiOZr(HNMe2)(NMe2)2H (2). Reactivity studies by contacting compound 2 with ethylene, hydrogen/ethylene, propene, or hydrogen/propene, at a temperature of 200°C revealed alkene hydrogenation.

  3. Well-defined silica-supported zirconium–imido complexes mediated heterogeneous imine metathesis

    KAUST Repository

    Hamzaoui, Bilel

    2016-02-15

    Upon prolonged thermal exposure under vacuum, a well-defined single-site surface species [(≡Si-O-)Zr(NEt2)3] (1) evolves into an ethylimido complex [(≡Si-O-)Zr(=NEt)NEt2] (2). Reactions of 2 with an imine substrate result in imido/imine (=NRi, R: Et, Ph) exchange (metathesis) with the formation of [(≡Si-O-)Zr(=NPh)NEt2] (3). Compounds 2 and 3 effectively catalyze imine/imine cross-metathesis and are thus considered as the first heterogeneous catalysts active for imine metathesis. © The Royal Society of Chemistry 2016.

  4. Well-Defined Silica Supported Aluminum Hydride: Another Step Towards the Utopian Single Site Dream?

    KAUST Repository

    Werghi, Baraa

    2015-07-17

    Reaction of triisobutylaluminum with SBA15700 at room temperature occurs by two parallel pathways involving either silanol or siloxane bridges. It leads to the formation of a well-defined bipodal [(≡SiO)2Al-CH2CH(CH3)2] 1a, silicon isobutyl [≡Si-CH2CH(CH3)2] 1b and a silicon hydride [≡Si-H] 1c. Their structural identity was characterized by FT-IR and advance solid-state NMR spectroscopies (1H, 13C, 29Si, 27Al and 2D multiple quantum), elemental and gas phase analysis, and DFT calculations. The reaction involves the formation of a highly reactive monopodal intermediate: [≡SiO-Al-[CH2CH(CH3)2]2], with evolution of isobutane. This intermediate undergoes two parallel routes: Transfer of either one isobutyl fragment or of one hydride to an adjacent silicon atom. Both processes occur by opening of a strained siloxane bridge, ≡Si-O-Si≡ but with two different mechanisms, showing that the reality of “single site” catalyst may be an utopia: DFT calculations indicate that isobutyl transfer occurs via a simple metathesis between the Al-isobutyl and O-Si bonds, while hydride transfer occurs via a two steps mechanism, the first one is a ß-H elimination to Al with elimination of isobutene, whereas the second is a metathesis step between the formed Al-H bond and a O-Si bond. Thermal treatment of 1a (at 250 °C) under high vacuum (10-5 mbar) generates Al-H through a ß-H elimination of isobutyl fragment. These supported well-defined Al-H which are highly stable with time, are tetra, penta and octa coordinated as demonstrated by IR and 27Al–1H J-HMQC NMR spectroscopy. All these observations indicate that surfaces atoms around the site of grafting play a considerable role in the reactivity of a single site system.

  5. Isolation and Characterization of Well-Defined Silica-Supported Azametallacyclopentane: A Key Intermediate in Catalytic Hydroaminoalkylation Reactions

    KAUST Repository

    Hamzaoui, Bilel

    2015-09-25

    Intermolecular catalytic hydroaminoalkylation of unactivated alkene occurs with silica-supported azazirconacyclopropane [[TRIPLE BOND]Si[BOND]O[BOND]Zr(HNMe2)(η2-NMeCH2)(NMe2)]. Mechanistic studies were conducted using surface organometallic chemistry (SOMC) concepts to identify the key surface intermediates. The azametallacyclopentene intermediate {[TRIPLE BOND]Si[BOND]O[BOND]Zr(HNMe2)[η2-NMeCH2CH(Me)CH2](NMe2)} was isolated after treating with 1-propylene and characterized by FT-IR spectroscopy, elemental analysis, 1H 13C HETCOR, DARR SS-NMR and DQ TQ SS-NMR. The regeneration of the catalyst was conducted by dimethylamine protonolysis to yield the pure amine.

  6. Solid-State NMR and DFT Studies on the Formation of Well-Defined Silica-Supported Tantallaaziridines: From Synthesis to Catalytic Application

    KAUST Repository

    Hamzaoui, Bilel

    2016-01-27

    Single-site, well-defined, silica-supported tantallaaziridine intermediates [≡Si-O-Ta(η2-NRCH2)(NMe2)2] [R=Me (2), Ph (3)] were prepared from silica-supported tetrakis(dimethylamido)tantalum [≡Si-O-Ta(NMe2)4] (1) and fully characterized by FTIR spectroscopy, elemental analysis, and 1H,13C HETCOR and DQ TQ solid-state (SS) NMR spectroscopy. The formation mechanism, by β-H abstraction, was investigated by SS NMR spectroscopy and supported by DFT calculations. The C-H activation of the dimethylamide ligand is favored for R=Ph. The results from catalytic testing in the hydroaminoalkylation of alkenes were consistent with the N-alkyl aryl amine substrates being more efficient than N-dialkyl amines. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. Well-defined silica supported bipodal molybdenum oxo alkyl complexes: a model of the active sites of industrial olefin metathesis catalysts

    KAUST Repository

    Merle, Nicolas

    2017-09-25

    A well-defined, silica-supported molybdenum oxo alkyl species, ([triple bond, length as m-dash]SiO-)2Mo([double bond, length as m-dash]O)(CH2tBu)2, was prepared by the selective grafting of Mo([double bond, length as m-dash]O)(CH2tBu)3Cl onto a silica partially dehydroxylated at 200 °C using a rigorous surface organometallic chemistry approach. The immobilized bipodal surface species, partly resembling the active species of industrial MoO3/SiO2 olefin metathesis catalysts, exhibited excellent functional group tolerance in conjunction with its high activity in homocoupling, self and ring closing olefin metathesis.

  8. Well-defined silica supported bipodal molybdenum oxo alkyl complexes: a model of the active sites of industrial olefin metathesis catalysts.

    Science.gov (United States)

    Merle, Nicolas; Le Quéméner, Frédéric; Barman, Samir; Samantaray, Manoja K; Szeto, Kai C; De Mallmann, Aimery; Taoufik, Mostafa; Basset, Jean-Marie

    2017-10-12

    A well-defined, silica-supported molybdenum oxo alkyl species, ([triple bond, length as m-dash]SiO-)2Mo([double bond, length as m-dash]O)(CH2(t)Bu)2, was prepared by the selective grafting of Mo([double bond, length as m-dash]O)(CH2(t)Bu)3Cl onto a silica partially dehydroxylated at 200 °C using a rigorous surface organometallic chemistry approach. The immobilized bipodal surface species, partly resembling the active species of industrial MoO3/SiO2 olefin metathesis catalysts, exhibited excellent functional group tolerance in conjunction with its high activity in homocoupling, self and ring closing olefin metathesis.

  9. Development of the first well-defined tungsten oxo alkyl derivatives supported on silica by SOMC: towards a model of WO3/SiO2 olefin metathesis catalyst

    KAUST Repository

    Mazoyer, Etienne

    2010-01-01

    A well-defined, silica-supported tungsten oxo alkyl species prepared by the surface organometallic chemistry approach displays high and sustained activity in propene metathesis. Remarkably, its catalytic performances outpace those of the parent imido derivative, underlining the importance of the oxo ligand in the design of robust catalysts. © 2010 The Royal Society of Chemistry.

  10. Understanding the Hydro-metathesis Reaction of 1-decene by Using Well-defined Silica Supported W, Mo, Ta Carbene/Carbyne Complexes

    KAUST Repository

    Saidi, Aya

    2017-12-21

    Direct conversion of 1-decene to petroleum range alkanes was obtained using hydro-metathesis reaction. To understand this reaction we employed three different well-defined single site catalysts precursors; [(≡Si-O-)W(CH3)5] 1, [(≡Si-O-)Mo(≡CtBu)(CH2tBu)2] 2 and [(≡Si-O)Ta(=CHtBu)(CH2tBu)2] 3. We witnessed that in our conditions olefin metathesis/isomerization of 1-decene occurs much faster followed by reduction of the newly formed olefins rather than reduction of the 1-decene to decane, followed by metathesis of decane. We found that Mo-based catalyst favors 2+2 cycloaddition of 1-decene forming metallocarbene, followed by reduction of the newly formed olefins to alkanes. However, in the case of W and Ta-based catalysts, a rapid isomerization (migration) of the double bond followed by olefin metathesis and reduction of the newly formed olefins were observed. We witnessed that silica supported W catalyst precursor 1 and Mo catalyst precursor 2 are better catalysts for hydro-metathesis reaction with TONs of 818 and 808 than Ta-based catalyst 3 (TON of 334). This comparison of the catalysts provides us a better understanding that, if a catalyst is efficient in olefin metathesis reaction it would be a better catalyst for hydro-metathesis reaction.

  11. [(≢SiO)TaVCl2Me2]: A well-defined silica-supported tantalum(V) surface complex as catalyst precursor for the selective cocatalyst-free trimerization of ethylene

    KAUST Repository

    Chen, Yin

    2012-10-22

    On the surface of it: In the absence of co-catalyst, a well-defined silica-supported surface organometallic complex [(≢SiO)Ta VCl2Me2] selectively catalyzes the oligomerization of ethylene. The use of surface organometallic species allows three different pathways to be determined for the reduction of TaV to TaIII species under pressure of ethylene. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Cationic Silica-Supported N-Heterocyclic Carbene Tungsten Oxo Alkylidene Sites: Highly Active and Stable Catalysts for Olefin Metathesis.

    Science.gov (United States)

    Pucino, Margherita; Mougel, Victor; Schowner, Roman; Fedorov, Alexey; Buchmeiser, Michael R; Copéret, Christophe

    2016-03-18

    Designing supported alkene metathesis catalysts with high activity and stability is still a challenge, despite significant advances in the last years. Described herein is the combination of strong σ-donating N-heterocyclic carbene ligands with weak σ-donating surface silanolates and cationic tungsten sites leading to highly active and stable alkene metathesis catalysts. These well-defined silica-supported catalysts, [(≡SiO)W(=O)(=CHCMe2 Ph)(IMes)(OTf)] and [(≡SiO)W(=O)(=CHCMe2 Ph)(IMes)(+) ][B(Ar(F) )4 (-) ] [IMes=1,3-bis(2,4,6-trimethylphenyl)-imidazol-2-ylidene, B(Ar(F) )4 =B(3,5-(CF3 )2 C6 H3 )4 ] catalyze alkene metathesis, and the cationic species display unprecedented activity for a broad range of substrates, especially for terminal olefins with turnover numbers above 1.2 million for propene. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. A well-defined silica-supported aluminium alkyl through an unprecedented, consecutive two-step protonolysis–alkyl transfer mechanism

    KAUST Repository

    Pelletier, Jérémie

    2011-01-01

    Impregnation of [(AliBu3)(Et2O)] on partially dehydroxylated SBA-15 affords a mesoporous material bearing the well-defined single site surface aluminium species [(≡SiO)2Al(iBu)(Et 2O)]. © The Royal Society of Chemistry.

  14. Controlling the hydrogenolysis of silica-supported tungsten pentamethyl leads to a class of highly electron deficient partially alkylated metal hydrides

    KAUST Repository

    Maity, Niladri

    2015-11-30

    The well-defined single-site silica-supported tungsten complex [([triple bond, length as m-dash]Si–O–)W(Me)5], 1, is an excellent precatalyst for alkane metathesis. The unique structure of 1 allows the synthesis of unprecedented tungsten hydrido methyl surface complexes via a controlled hydrogenolysis. Specifically, in the presence of molecular hydrogen, 1 is quickly transformed at −78 °C into a partially alkylated tungsten hydride, 4, as characterized by 1H solid-state NMR and IR spectroscopies. Species 4, upon warming to 150 °C, displays the highest catalytic activity for propane metathesis yet reported. DFT calculations using model systems support the formation of [([triple bond, length as m-dash]Si–O–)WH3(Me)2], as the predominant species at −78 °C following several elementary steps of hydrogen addition (by σ-bond metathesis or α-hydrogen transfer). Rearrangement of 4 occuring between −78 °C and room temperature leads to the formation of an unique methylidene tungsten hydride [([triple bond, length as m-dash]Si–O–)WH3([double bond, length as m-dash]CH2)], as determined by solid-state 1H and 13C NMR spectroscopies and supported by DFT. Thus for the first time, a coordination sphere that incorporates both carbene and hydride functionalities has been observed.

  15. SOMC-Designed Silica Supported Tungsten Oxo Imidazolin-2-iminato Methyl Precatalyst for Olefin Metathesis Reactions.

    Science.gov (United States)

    Qureshi, Ziyauddin S; Hamieh, Ali; Barman, Samir; Maity, Niladri; Samantaray, Manoja K; Ould-Chikh, Samy; Abou-Hamad, Edy; Falivene, Laura; D'Elia, Valerio; Rothenberger, Alexander; Llorens, Isabelle; Hazemann, Jean-Louis; Basset, Jean-Marie

    2017-01-17

    Synthesis, structure, and olefin metathesis activity of a surface complex [(≡Si-O-)W(═O)(CH3)2-Im(Dipp)N] (4) (Im(Dipp) = 1,3-bis(2,6-diisopropylphenyl)imidazolin-2-iminato) supported on silica by a surface organometallic chemistry (SOMC) approach are reported. The reaction of N-silylated 2-iminoimidazoline with tungsten(VI) oxytetrachloride generated the tungsten oxo imidazolin-2-iminato chloride complex [Im(Dipp)NW(═O)Cl3] (2). This was grafted on partially dehydroxylated silica pretreated at 700 °C (SiO2-700) to afford a well-defined monopodal surface complex [(≡Si-O-)W(═O)Cl2-Im(Dipp)N] (3). 3 underwent alkylation by ZnMe2 to produce [(≡Si-O-)W(═O)(CH3)2-Im(Dipp)N] (4). The alkylated surface complex was thoroughly characterized by solid-state NMR, elemental microanalysis, Raman, FT-IR spectroscopies, and XAS analysis. 4 proved to be an active precatalyst for self-metathesis of terminal olefins such as propylene and 1-hexene.

  16. SOMC-Designed Silica Supported Tungsten Oxo Imidazolin-2-iminato Methyl Precatalyst for Olefin Metathesis Reactions

    KAUST Repository

    Qureshi, Ziyauddin

    2017-01-05

    Synthesis, structure, and olefin metathesis activity of a surface complex [(≡Si-O-)W(═O)(CH3)2-ImDippN] (4) (ImDipp = 1,3-bis(2,6-diisopropylphenyl)imidazolin-2-iminato) supported on silica by a surface organometallic chemistry (SOMC) approach are reported. The reaction of N-silylated 2-iminoimidazoline with tungsten(VI) oxytetrachloride generated the tungsten oxo imidazolin-2-iminato chloride complex [ImDippNW(═O)Cl3] (2). This was grafted on partially dehydroxylated silica pretreated at 700 °C (SiO2-700) to afford a well-defined monopodal surface complex [(≡Si-O-)W(═O)Cl2-ImDippN] (3). 3 underwent alkylation by ZnMe2 to produce [(≡Si-O-)W(═O)(CH3)2-ImDippN] (4). The alkylated surface complex was thoroughly characterized by solid-state NMR, elemental microanalysis, Raman, FT-IR spectroscopies, and XAS analysis. 4 proved to be an active precatalyst for self-metathesis of terminal olefins such as propylene and 1-hexene.

  17. Synthesis and characterization of a homogeneous and silica supported homoleptic cationic tungsten(vi) methyl complex: application in olefin metathesis

    KAUST Repository

    Dey, Raju

    2016-08-19

    A method for the synthesis of a homogeneous cationic tungsten(VI)penta-methyl complex [(WMe5)(+)(C6F5)(3)BMe-] from neutral tungstenhexamethyl (WMe6) and a silica supported cationic tungstentetramethyl complex [( Si-O-)WMe4+ (C6F5)(3)BMe-] from a neutral silica supported tungstenpentamethyl complex [( Si-O-)WMe5] is described. In both cases a direct demethylation using the B(C6F5)(3) reagent was used. The aforesaid complexes were characterized by liquid or solid state NMR spectroscopy. Interestingly, the homogeneous cationic complex [(WMe5)(+)(C6F5)(3)BMe-] shows moderate activity whereas the supported cationic complex [( Si-O-)WMe4+(C6F5)(3)BMe-] exhibits good activity in olefin metathesis reactions.

  18. Synthesis and characterization of a homogeneous and silica supported homoleptic cationic tungsten(vi) methyl complex: application in olefin metathesis.

    Science.gov (United States)

    Dey, Raju; Samantaray, Manoja K; Poater, Albert; Hamieh, Ali; Kavitake, Santosh; Abou-Hamad, Edy; Callens, Emmanuel; Emwas, Abdul-Hamid; Cavallo, Luigi; Basset, Jean-Marie

    2016-09-13

    A method for the synthesis of a homogeneous cationic tungsten(vi)pentamethyl complex [(WMe5)(+)(C6F5)3BMe(-)] from neutral tungstenhexamethyl (WMe6) and a silica supported cationic tungstentetramethyl complex [([triple bond, length as m-dash]Si-O-)WMe4(+) (C6F5)3BMe(-)] from a neutral silica supported tungstenpentamethyl complex [([triple bond, length as m-dash]Si-O-)WMe5] is described. In both cases a direct demethylation using the B(C6F5)3 reagent was used. The aforesaid complexes were characterized by liquid or solid state NMR spectroscopy. Interestingly, the homogeneous cationic complex [(WMe5)(+)(C6F5)3BMe(-)] shows moderate activity whereas the supported cationic complex [([triple bond, length as m-dash]Si-O-)WMe4(+)(C6F5)3BMe(-)] exhibits good activity in olefin metathesis reactions.

  19. Photodeposition of platinum nanoparticles on well-defined Tungsten oxide: controlling oxidation state, particle size and geometrical distribution

    NARCIS (Netherlands)

    Wenderich, Kasper

    2016-01-01

    In this thesis, structure-directed photodeposition of the cocatalyst platinum (Pt) on monoclinic tungsten oxide (WO3) nanoplates is described, both considering fundamental aspects, as well as usefulness for applications in photocatalytic propane oxidation. Before such studies are described, the

  20. Investigation of Surface Alkylation Strategy in SOMC: In Situ Generation of a Silica-Supported Tungsten Methyl Catalyst for Cyclooctane Metathesis

    KAUST Repository

    Hamieh, Ali Imad Ali

    2016-07-28

    An efficient and potentially scalable method is described for the synthesis of the silica-supported complexes [(≡Si-O-)WMe5] and [(≡Si-O-)WMe2(≡CH)] obtained by in situ alkylation of the surface-grafted tungsten chloride [(≡Si-O-)WCl5] (1). [(≡Si-O-)WCl5] can be readily prepared by the reaction of commercially available and stable tungsten hexachloride WCl6 with partially dehydroxylated silica at 700 °C (SiO2-700). Further reaction with ZnMe2 at room temperature rapidly forms a mixture of surface-alkylated tungsten complexes. They were fully characterized by microanalysis, FTIR, mass balance, and solid-state NMR (1H, 13C, 1H-13C HETCOR, 1H-1H double quantum and triple quantum) and identified as [(≡Si-O-)WMe5] and another product, [(≡Si-O-)WMe2(≡CH)]. The latter might have been generated by partial decomposition of the tungsten methyl chloride compound, which is formed during the stepwise alkylation of [(≡Si-O-)WCl5]. DFT calculations were carried out to check the relative stability of the tungsten methyl chloride intermediates and the feasibility of the reaction and corroborate the experimental results. This tungsten complex and its derivative were found to be active catalysts for the metathesis of cyclooctane. © 2016 American Chemical Society.

  1. Silica-supported tungsten carbynes (≡SiO)xW(≡CH)(Me)y (x = 1, y = 2; X = 2, y = 1): New efficient catalysts for alkyne cyclotrimerization

    KAUST Repository

    Riache, Nassima

    2015-02-23

    The activity of silica-supported tungsten carbyne complexes (≡SiO)xW(≡CH)(Me)y (x = 1, y = 2; x = 2, y = 1) toward alkynes is reported. We found that they are efficient precatalysts for terminal alkyne cyclotrimerization with high TONs. We also demonstrate that this catalyst species is active for alkyne cyclotrimerization without the formation of significant alkyne metathesis products. Additional DFT calculations highlight the importance of the W coordination sphere in supporting this experimental behavior.

  2. Well-Defined Molybdenum Oxo Alkyl Complex Supported on Silica by Surface Organometallic Chemistry: A Highly Active Olefin Metathesis Precatalyst

    KAUST Repository

    Merle, Nicolas

    2016-12-05

    The well-defined silica-supported molybdenum oxo alkyl species (SiO−)MoO(CH Bu) was selectively prepared by grafting of MoO(CH Bu)Cl onto partially dehydroxylated silica (silica) using the surface organometallic chemistry approach. This surface species was fully characterized by elemental analysis and DRIFT, solid-state NMR, and EXAFS spectroscopy. This new material is related to the active species of industrial supported MoO/SiO olefin metathesis catalysts. It displays very high activity in propene self-metathesis at mild (turnover number = 90 000 after 25 h). Remarkably, its catalytic performance outpaces those of the parent imido derivative and its tungsten oxo analogue.

  3. Well-Defined Molybdenum Oxo Alkyl Complex Supported on Silica by Surface Organometallic Chemistry: A Highly Active Olefin Metathesis Precatalyst.

    Science.gov (United States)

    Merle, Nicolas; Le Quéméner, Frédéric; Bouhoute, Yassine; Szeto, Kai C; De Mallmann, Aimery; Barman, Samir; Samantaray, Manoja K; Delevoye, Laurent; Gauvin, Régis M; Taoufik, Mostafa; Basset, Jean-Marie

    2017-02-15

    The well-defined silica-supported molybdenum oxo alkyl species (≡SiO-)MoO(CH2tBu)3 was selectively prepared by grafting of MoO(CH2tBu)3Cl onto partially dehydroxylated silica (silica700) using the surface organometallic chemistry approach. This surface species was fully characterized by elemental analysis and DRIFT, solid-state NMR, and EXAFS spectroscopy. This new material is related to the active species of industrial supported MoO3/SiO2 olefin metathesis catalysts. It displays very high activity in propene self-metathesis at mild (turnover number = 90 000 after 25 h). Remarkably, its catalytic performance outpaces those of the parent imido derivative and its tungsten oxo analogue.

  4. Controlled interactions between anhydrous keggin-type heteropolyacids and silica support: Preparation and characterization of well-defined silica-supported polyoxometalate species

    KAUST Repository

    Grinenval, Eva

    2010-11-11

    Anhydrous Keggin-type phosphorus heteropolyacids were deposited on partially dehydroxylated silica by using the surface organometallic chemistry (SOMC) strategy. The resulting solids were characterized by a combination of physicochemical methods including IR, Raman, 1D and 2D 1H, and 31P MAS NMR, electron microscopy experiments and density functional theory (DFT) calculations. It is shown that the main surface species is [ - Si(OH...H+)]2[H+]1[PM 12O403-] where the polyoxometalate is linked to the support by proton interaction with two silanols. Two other minor species (10% each) are formed by coordination of the polyoxometalate to the surface via the interaction between all three protons with three silanol groups or via three covalent bonds formed by dehydroxylation of the above species. Comparison of the reactivity of these solids and of compounds prepared by a classical way shows that the samples prepared by the SOMC approach contain ca. 7 times more acid sites. © 2010 American Chemical Society.

  5. Synergy between Two Metal Catalysts: A Highly Active Silica Supported Bimetallic W/Zr Catalyst for Metathesis of n-Decane

    KAUST Repository

    Samantaray, Manoja

    2016-06-01

    A well-defined, silica supported, bimetallic precatalyst [≡Si-O-W(Me)5 ≡Si-O-Zr(Np)3](4) has been synthesized for the first time via successively grafting two organometallic complexes [W(CH3)6 (1) followed by ZrNp4 (2)] on a single silica support. Surprisingly, multiple quantum NMR characterization demonstrates that W and Zr species are in close proximity to each other. Hydrogenation of this bimetallic catalyst at room temperature showed the easy formation of Zirconium hydride, probably facilitated by tungsten hydride which was formed at this temperature. This bimetallic W/Zr hydride precatalyst proved to be more efficient (TON: 1436) than the monometallic W hydride (TON: 650) in metathesis of n-decane at 150 0C. This synergy between Zr and W suggests that the slow step of alkane metathesis is the C-H bond activation which occurs on Zr. The produced olefin resulting from a ß–H elimination undergoes easy metathesis on W.

  6. Well-Defined Surface Species [(≡Si - O -)W(=O)Me3] Prepared by Direct Methylation of [(≡Si - O -)W(=O)Cl3], a Catalyst for Cycloalkane Metathesis and Transformation of Ethylene to Propylene

    KAUST Repository

    Hamieh, Ali Imad Ali

    2015-04-03

    The silica-supported tungsten oxo-trimethyl complex [(≡Si - O -)W(=O)Me3] was synthesized using a novel SOMC synthetic approach. By grafting the inexpensive stable compound WOCl4 on the surface of silica, partially dehydroxylated at 700 °C (SiO2-700), a well-defined monopodal surface complex [(≡Si - O -)W(=O)Cl3] was produced. The supported complex directly methylated with ZnMe2 and transformed into [(≡Si - O -)W(=O)Me3], which we fully characterized by microanalysis, IR, mass balance and SS NMR (1H, 13C, 1H-13C HETCOR, 1H-1H DQ and TQ). [(≡Si - O)W(=O)Me3] has two conformational isomers on the surface at room temperature. The conversion of one to the other was observed at 318 K by variable-temperature 13C CP/MAS and 1H spin echo MAS solid-state NMR; this was also confirmed by NMR and DFT calculations. [(≡Si - O)W(=O)Me3] was found to be active in cyclooctane metathesis and to have a wide distribution range in ring-contracted and ring-expanded products. In addition, [(≡Si - O)W(=O)Me3] proved to be highly active for selective transformation of ethylene to propylene compared to other silica-supported organometallic complexes. (Chemical Equation Presented). © 2015 American Chemical Society.

  7. PREPARATION OF CHEMICALLY WELL-DEFINED CARBOHYDRATE DENDRIMER CONJUGATES

    DEFF Research Database (Denmark)

    2004-01-01

    A method for the synthesis of dendrimer conjugates having a well-defined chemical structure, comprising one or more carbohydrate moieties and one or more immunomodulating substances coupled to a dendrimer, is presented. First, the carbohydrate is bound to the dendrimer in a chemoselective manner....... Subsequently, the immunomodulating substance is also bound in a chemoselective manner, to give a dendrimer conjugate with a well-defined structure and connectivity and containing a precise, pre-determined ratio of carbohydrate to immunomodulating substance. The invention also relates to novel dendrimer...

  8. Well-defined transition metal hydrides in catalytic isomerizations.

    Science.gov (United States)

    Larionov, Evgeny; Li, Houhua; Mazet, Clément

    2014-09-07

    This Feature Article intends to provide an overview of a variety of catalytic isomerization reactions that have been performed using well-defined transition metal hydride precatalysts. A particular emphasis is placed on the underlying mechanistic features of the transformations discussed. These have been categorized depending upon the nature of the substrate and in most cases discussed following a chronological order.

  9. Well-defined side-chain liquid-crystalline polysiloxanes

    NARCIS (Netherlands)

    Hempenius, Mark A.; Lammertink, Rob G.H.; Vancso, Gyula J.

    1996-01-01

    A route to well-defined side-chain liquid-crystalline polysiloxanes (ratio of weight-to number-average molar masses Mw/Mn < 1.2 is reported. Anionic ring-opening polymerization of pentamethylvinylcyclotrisiloxane yielded a poly(dimethylsiloxane-co-methylvinylsiloxane) backbone. A flexible disiloxane

  10. A generic synthesis algorithm for well-defined parametric design

    NARCIS (Netherlands)

    Schotborgh, W.O.; Kokkeler, Frans; Tragter, Hendrik; Bomhoff, M.J.; van Houten, Frederikus J.A.M.; van Houten, F.J.A.M.; Miedema, J.; Lutters, D.

    2008-01-01

    This paper aims to improve the way synthesis tools can be built by formalizing: 1) the design artefact, 2) related knowledge and 3) an algorithm to generate solutions. This paper focuses on well-defined parametric engineering design, ranging from machine elements to industrial products. A design

  11. A well-defined rhenium(VII) olefin metathesis catalyst

    Energy Technology Data Exchange (ETDEWEB)

    Toreki, R.; Schrock, R.R. (Massachusetts Institute of Technology, Cambridge (USA))

    1990-03-14

    Molybdenum tungsten, and rhenium are the three most active metals in classical olefin metathesis systems. Molybdenum (VI){sup 2} and tungsten(VI){sup 3} alkylidene complexes of the type M-(CHR{prime})(NAr)(OR){sub 2} (Ar = 2,6-C{sub 6}H{sub 3}-i-Pr{sub 2}) have been shown to be well-behaved olefin metathesis catalysts with an activity that can be controlled through the choice of OR. Although several rhenium alkylidene complexes have been reported, none has shown any confirmable metathesis activity, even toward strained cyclic olefins such as norbornene. Since Re{triple bond}CR{double prime} and M{double bond}NR{double prime} (M = Mo or W) can be regarded as isoelectronic units, plausible candidates as olefin metathesis catalysts are complexes of the type Re(CHR{prime})(CR{double prime})(OR){sub 2}. The authors report here that such a complex in which OR = OCMe(CF{sub 3}){sub 2} is a well-behaved olefin metathesis catalyst.

  12. Silica-supported Preyssler Nanoparticles as New Catalysts in the ...

    African Journals Online (AJOL)

    A new and efficient method for the preparation of 4(3H)-quinazolinones from the condensation of anthranilic acid, orthoester and substituted anilines, in the presence of catalytic amounts of silica-supported Preyssler nanoparticles is reported. The catalyst performs very well in comparison with other catalysts reported before.

  13. Silica-Supported Yttrium Nitrate Hexahydrate as a Heterogeneous ...

    African Journals Online (AJOL)

    NICO

    Silica-Supported Yttrium Nitrate Hexahydrate as a. Heterogeneous Catalyst for the Synthesis of. 2-Amino-4H-Chromenes in Water. Bahador Karami*, Mahnaz Farahi, Masoomeh Bazrafshan and Saeed Khodabakhshi. Department of Chemistry, Yasouj University, Yasouj 75918-74831, Iran. Recieved 4 February 2014, ...

  14. Well-defined (co)polypeptides bearing pendant alkyne groups

    KAUST Repository

    Zhao, Wei

    2016-03-18

    A novel metal-free strategy, using hydrogen-bonding catalytic ring opening polymerization of acetylene-functionalized N-carboxy anhydrites of α-amino acids, was developed for the synthesis of well-defined polypeptides bearing pendant alkyne groups. This method provides an efficient way to synthesize novel alkyne-functionalized homopolypeptides (A) and copolypeptides, such as AB diblock (B: non-functionalized), ABA triblock and star-AB diblock, as well as linear and star random copolypeptides, precursors of a plethora complex macromolecular architectures by click chemistry.

  15. WMe6 tamed by silica: Si-O-WMe5 as an efficient, well-defined species for alkane metathesis, leading to the observation of a supported W-methyl/methylidyne species

    KAUST Repository

    Samantaray, Manoja

    2014-01-22

    The synthesis and full characterization of a well-defined silica-supported ≡Si-O-W(Me)5 species is reported. Under an inert atmosphere, it is a stable material at moderate temperature, whereas the homoleptic parent complex decomposes above -20 °C, demonstrating the stabilizing effect of immobilization of the molecular complex. Above 70 °C the grafted complex converts into the two methylidyne surface complexes [(≡SiO-)W(≡CH) Me2] and [(≡SiO-)2W(≡CH)Me]. All of these silica-supported complexes are active precursors for propane metathesis reactions. © 2013 American Chemical Society.

  16. Molybdenum species on alumina and silica supports for soot combustion

    OpenAIRE

    Braun, Silvana; Appel, Lúcia Gorenstin; Schmal,Martin

    2010-01-01

    Mo/A1203 and Mo/Si02 catalysts with different molybdenum species were tested in diesel soot combustion. These catalysts have shown different performances due to the presence of different species, being the most active those dispersed onto silica surface. which are similar to M020~- ion. The thermal stability was evaluated by differential thermal analyses and the results have shown that Mo species formed on silica-supported catalysts are thermally stable under the reaction conditions....

  17. Supramolecular Diblock Copolymers Featuring Well-defined Telechelic Building Blocks.

    Science.gov (United States)

    Elacqua, Elizabeth; Croom, Anna; Manning, Kylie B; Pomarico, Scott K; Lye, Diane; Young, Lauren; Weck, Marcus

    2016-12-19

    We report supramolecular AB diblock copolymers comprised of well-defined telechelic building blocks. Helical motifs, formed via reversible addition-fragmentation chain-transfer (RAFT) or anionic polymerization, are assembled with coil-forming and sheet-featuring blocks obtained via atom-transfer radical polymerization (ATRP) or ring-opening metathesis polymerization (ROMP). Interpolymer hydrogen bonding or metal-coordination achieves dynamic diblock architectures featuring hybrid topologies of coils, helices, and/or π-stacked sheets that, on a basic level, mimic protein structural motifs in fully synthetic systems. The intrinsic properties of each block (e.g., circular dichroism and fluorescence) remain unaffected in the wake of self-assembly. This strategy to develop complex synthetic polymer scaffolds from functional building blocks is significant in a field striving to produce architectures reminiscent of biosynthesis, yet fully synthetic in nature. This is the first plug-and-play approach to fabricate hybrid π-sheet/helix, π-sheet/coil, and helix/coil architectures via directional self-assembly. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Unearthing a Well-Defined Highly Active Bimetallic W/Ti Precatalyst Anchored on a Single Silica Surface for Metathesis of Propane

    KAUST Repository

    Samantaray, Manoja

    2017-02-10

    Two compatible organometallic complexes, W(Me)(6) (1) and TiNp4 (2), were successively anchored on a highly dehydroxylated single silica support (SiO2-700) to synthesize the well-defined bimetallic precatalyst [(equivalent to Si-O-)W(Me)(5)(equivalent to Si-O-)Ti(Np)(3)] (4). Precatalyst 4 was characterized at the molecular level using advanced surface organometallic chemistry (SOMC) characterization techniques. The strong autocorrelation observed between methyl of W and Ti in H-1-H-1 multiple-quantum NMR spectra demonstrates that W and Ti species are in close proximity to each other. The bimetallic precatalyst 4, with a turnover number (TON) of 9784, proved to be significantly more efficient than the silica-supported monometallic catalyst [(equivalent to Si-O-)W(Me)(5)] (3), with a TON of 98, for propane metathesis at 150 degrees C in a flow reactor. The dramatic improvement in the activity signifies the cooperativity between Ti and W and indicates that the key step of alkane metathesis (C-H bond activation followed by beta-H elimination) occurs on Ti, followed by olefin metathesis, which occurs on W. We have demonstrated the influence and importance of proximity of Ti to W for achieving such a significantly high activity. This is the first report demonstrating the considerably high activity (TON = 9784) in propane metathesis at moderate temperature (150 degrees C) using a well-defined bimetallic system prepared via the SOMC approach.

  19. Unearthing a Well-Defined Highly Active Bimetallic W/Ti Precatalyst Anchored on a Single Silica Surface for Metathesis of Propane.

    Science.gov (United States)

    Samantaray, Manoja K; Kavitake, Santosh; Morlanés, Natalia; Abou-Hamad, Edy; Hamieh, Ali; Dey, Raju; Basset, Jean-Marie

    2017-03-08

    Two compatible organometallic complexes, W(Me)6 (1) and TiNp4 (2), were successively anchored on a highly dehydroxylated single silica support (SiO2-700) to synthesize the well-defined bimetallic precatalyst [(≡Si-O-)W(Me)5(≡Si-O-)Ti(Np)3] (4). Precatalyst 4 was characterized at the molecular level using advanced surface organometallic chemistry (SOMC) characterization techniques. The strong autocorrelation observed between methyl of W and Ti in (1)H-(1)H multiple-quantum NMR spectra demonstrates that W and Ti species are in close proximity to each other. The bimetallic precatalyst 4, with a turnover number (TON) of 9784, proved to be significantly more efficient than the silica-supported monometallic catalyst [(≡Si-O-)W(Me)5] (3), with a TON of 98, for propane metathesis at 150 °C in a flow reactor. The dramatic improvement in the activity signifies the cooperativity between Ti and W and indicates that the key step of alkane metathesis (C-H bond activation followed by β-H elimination) occurs on Ti, followed by olefin metathesis, which occurs on W. We have demonstrated the influence and importance of proximity of Ti to W for achieving such a significantly high activity. This is the first report demonstrating the considerably high activity (TON = 9784) in propane metathesis at moderate temperature (150 °C) using a well-defined bimetallic system prepared via the SOMC approach.

  20. Catalysis by Design: Well-Defined Single-Site Heterogeneous Catalysts.

    Science.gov (United States)

    Pelletier, Jérémie D A; Basset, Jean-Marie

    2016-04-19

    Heterogeneous catalysis, a field important industrially and scientifically, is increasingly seeking and refining strategies to render itself more predictable. The main issue is due to the nature and the population of catalytically active sites. Their number is generally low to very low, their "acid strengths" or " redox properties" are not homogeneous, and the material may display related yet inactive sites on the same material. In many heterogeneous catalysts, the discovery of a structure-activity reationship is at best challenging. One possible solution is to generate single-site catalysts in which most, if not all, of the sites are structurally identical. Within this context and using the right tools, the catalyst structure can be designed and well-defined, to reach a molecular understanding. It is then feasible to understand the structure-activity relationship and to develop predictable heterogeneous catalysis. Single-site well-defined heterogeneous catalysts can be prepared using concepts and tools of surface organometallic chemistry (SOMC). This approach operates by reacting organometallic compounds with surfaces of highly divided oxides (or of metal nanoparticles). This strategy has a solid track record to reveal structure-activity relationship to the extent that it is becoming now quite predictable. Almost all elements of the periodical table have been grafted on surfaces of oxides (from simple oxides such as silica or alumina to more sophisticated materials regarding composition or porosity). Considering catalytic hydrocarbon transformations, heterogeneous catalysis outcome may now be predicted based on existing mechanistic proposals and the rules of molecular chemistry (organometallic, organic) associated with some concepts of surface sciences. A thorough characterization of the grafted metal centers must be carried out using tools spanning from molecular organometallic or surface chemistry. By selection of the metal, its ligand set, and the support taken

  1. Catalysis by Design: Well-Defined Single-Site Heterogeneous Catalysts

    KAUST Repository

    Pelletier, Jeremie

    2016-03-09

    ConspectusHeterogeneous catalysis, a field important industrially and scientifically, is increasingly seeking and refining strategies to render itself more predictable. The main issue is due to the nature and the population of catalytically active sites. Their number is generally low to very low, their "acid strengths" or " redox properties" are not homogeneous, and the material may display related yet inactive sites on the same material. In many heterogeneous catalysts, the discovery of a structure-activity reationship is at best challenging. One possible solution is to generate single-site catalysts in which most, if not all, of the sites are structurally identical. Within this context and using the right tools, the catalyst structure can be designed and well-defined, to reach a molecular understanding. It is then feasible to understand the structure-activity relationship and to develop predictable heterogeneous catalysis. Single-site well-defined heterogeneous catalysts can be prepared using concepts and tools of surface organometallic chemistry (SOMC). This approach operates by reacting organometallic compounds with surfaces of highly divided oxides (or of metal nanoparticles). This strategy has a solid track record to reveal structure-activity relationship to the extent that it is becoming now quite predictable. Almost all elements of the periodical table have been grafted on surfaces of oxides (from simple oxides such as silica or alumina to more sophisticated materials regarding composition or porosity).Considering catalytic hydrocarbon transformations, heterogeneous catalysis outcome may now be predicted based on existing mechanistic proposals and the rules of molecular chemistry (organometallic, organic) associated with some concepts of surface sciences. A thorough characterization of the grafted metal centers must be carried out using tools spanning from molecular organometallic or surface chemistry. By selection of the metal, its ligand set, and the

  2. On oxygen chemisorption for characterization of silica-supported vanadium oxide catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Faraldos, M.; Banares, M.A.; Fierro, J.L.G. [Instituto de Catalysis y Petroleoquimica, Madrid (Spain)] [and others

    1997-05-01

    Oxygen chemisorption experiments on prereduced silica- supported vanadia catalysts have been performed in order to determine the optimum conditions for measuring the relative dispersion of vanadium oxide on the silica substrate. By following the extent of vanadia reduction microgravimetrically, it is shown that an appropriate prereduction of the catalyst at 823 K under hydrogen is fundamental in obtaining a reproducible well-defined stoichiometrically reduced vanadium oxide system (V{sup 3+}). AT 643 K the reduction process is very much slower and requires very long times in order to approach a plateau. Measurement of the binding energies of the V{sub 2}p{sub 3/2} core level spectra indicates that high-temperature oxygen chemisorption (643 K) results in a reoxidation of the prereduced vanadium oxide species within crystallites leading to an overestimation of the number of exposed vanadium sites. Chemisorption at low temperatures (298 or 195 K) does not affect the stoichiometrically reduced vanadium oxide species within crystallites, thus allowing the number of exposed surface vanadium sites to be measured. 25 refs., 5 figs., 1 tab.

  3. Studies of Immobilized Homogeneous Metal Catalysts on Silica Supports

    Energy Technology Data Exchange (ETDEWEB)

    Stanger, Keith James [Iowa State Univ., Ames, IA (United States)

    2003-01-01

    The tethered, chiral, chelating diphosphine rhodium complex, which catalyzes the enantioselective hydrogenation of methyl-α-acetamidocinnamate (MAC), has the illustrated structure as established by 31P NMR and IR studies. Spectral and catalytic investigations also suggest that the mechanism of action of the tethered complex is the same as that of the untethered complex in solution. The rhodium complexes, [Rh(COD)H]4, [Rh(COD)2]+BF4-, [Rh(COD)Cl]2, and RhCl3• 3H2O, adsorbed on SiO2 are optimally activated for toluene hydrogenation by pretreatment with H2 at 200 C. The same complexes on Pd-SiO2 are equally active without pretreatments. The active species in all cases is rhodium metal. The catalysts were characterized by XPS, TEM, DRIFTS, and mercury poisoning experiments. Rhodium on silica catalyzes the hydrogenation of fluorobenzene to produce predominantly fluorocyclohexane in heptane and 1,2-dichloroethane solvents. In heptane/methanol and heptane/water solvents, hydrodefluorination to benzene and subsequent hydrogenation to cyclohexane occurs exclusively. Benzene inhibits the hydrodefluorination of fluorobenzene. In DCE or heptane solvents, fluorocyclohexane reacts with hydrogen fluoride to form cyclohexene. Reaction conditions can be chosen to selectively yield fluorocyclohexane, cyclohexene, benzene, or cyclohexane. The oxorhenium(V) dithiolate catalyst [-S(CH2)3s-]Re(O)(Me)(PPh3) was modified by linking it to a tether that could be attached to a silica support. Spectroscopic investigation and catalytic oxidation reactivity showed the heterogenized catalyst's structure and reactivity to be similar to its homogeneous analog. However, the immobilized catalyst offered additional advantages of recyclability, extended stability, and increased resistance to deactivation.

  4. Well-Defined Silica Grafted Molybdenum Bis(imido) Catalysts for Imine Metathesis Reactions

    KAUST Repository

    Barman, Samir

    2017-04-06

    Novel site-isolated tetracoordinated molybdenum complexes possessing bis(imido) ligands, [(≡Si–O)2Mo(═NR)2] (R = t-Bu, 2,6-C6H3-i-Pr2), were immobilized on partially dehydroxylated silica (SiO2-200) by a rigorous surface organometallic chemistry protocol. The newly developed materials adorned with bis(imido) functional units, which were previously exploited mainly as spectator ligands on silica-supported olefin metathesis molybdenum catalysts, are found to be efficient heterogeneous catalytic systems for imine cross metathesis under mild conditions.

  5. Efficient Construction of Well-Defined Multicompartment Porous Systems in a Modular and Chemically Orthogonal Fashion.

    Science.gov (United States)

    Gao, Ning; Tian, Tian; Cui, Jiecheng; Zhang, Wanlin; Yin, Xianpeng; Wang, Shiqiang; Ji, Jingwei; Li, Guangtao

    2017-03-27

    A microfluidic assembly approach was developed for efficiently producing hydrogel spheres with reactive multidomains that can be employed as an advantageous platform to create spherical porous networks in a facile manner with well-defined multicompartments and spatiotemporally controlled functions. This strategy allows for not only large scale fabrication of various robust hydrogel microspheres with controlled size and porosity, but also the domains embedded in hydrogel network could be introduced in a modular manner. Additionally, the number of different domains and their ratio could be widely variable on demand. More importantly, the reactive groups distributed in individual domains could be used as anchor sites to further incorporate functional units in an orthogonal fashion, leading to well-defined multicompartment systems. The strategy provides a new and efficient route to construct well-defined functional multicompartment systems with great flexibility and extendibility. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. Selective oxidation of propylene to acrolein by silica-supported bismuth molybdate catalysts

    DEFF Research Database (Denmark)

    Duc, Duc Truong; Ha, Hanh Nguyen; Fehrmann, Rasmus

    2011-01-01

    Silica-supported bismuth molybdate catalysts have been prepared by impregnation, structurally characterized and examined as improved catalysts for the selective oxidation of propylene to acrolein. Catalysts with a wide range of loadings (from 10 to 90 wt%) of beta bismuth molybdate (β-Bi2Mo2O9...

  7. Magnetic Silica Supported Copper: A Modular Approach to Aqueous Ullmann-type Amination of Aryl Halides

    Science.gov (United States)

    One-pot synthesis of magnetic silica supported copper catalyst has been described via in situ generated magnetic silica (Fe3O4@SiO2); the catalyst can be used for the efficacious amination of aryl halides in aqueous medium under microwave irradiation.

  8. Magnetic silica supported palladium catalyst: synthesis of allyl aryl ethers in water

    Science.gov (United States)

    A simple and benign procedure for the synthesis of aryl allyl ethers has been developed using phenols, allyl acetates and magnetically recyclable silica supported palladium catalyst in water; performance of reaction in air and easy separation of the catalyst using an external mag...

  9. One-pot synthesis of well-defined oligo- butadiynylene-naphthalene diimides.

    Science.gov (United States)

    Yue, Wan; Zhen, Yonggang; Li, Yan; Jiang, Wei; Lv, Aifeng; Wang, Zhaohui

    2010-08-06

    A homogeneous series of well-defined oligo-butadiynylene-NDIs containing up to five naphthalene diimides (NDIs) moieties have been efficiently synthesized in one pot by oxidative homocoupling of 1,6-di((trimethylsilyl)ethynyl)naphthalene diimides in good yields.

  10. Synthesis of well-defined catechol polymers for surface functionalization of magnetic nanoparticles

    OpenAIRE

    Zhang, Qiang; Nurumbetov, Gabit; Simula, Alexandre; Zhu, Chongyu; Li, Muxiu; Wilson, Paul; Kempe, Kristian; Yang, Bin; tao, lei; Haddleton, David M.

    2016-01-01

    In order to obtain dual-modal fluorescent magnetic nanoparticles, well-defined fluorescent functional polymers with terminal catechol groups were synthesized by single electron transfer living radical polymerization (SET-LRP) under aqueous conditions for “grafting to” modification of iron oxide nanoparticles. Acrylamide, N-isopropylacrylamide, poly(ethylene glycol) methyl ether acrylate, 2-hydroxyethyl acrylate, glycomonomer and rhodamine B piperazine acrylamide were homo-polymerized or block...

  11. Pengaruh Pendekatan Pengajaran dan Tipe Masalah Terhadap Kemampuan Pemecahan Masalah Tipe ILL dan WELL-DEFINED

    OpenAIRE

    Demitra Demitra

    2016-01-01

    This study focuses on examining the effects of teaching approaches (problem-based learning v.s. regular) and types of problem (ill defined v.s. well defined) on Matematical problem solving abilities. This quasi-experimental study involved 107 elementary school students, who had been randomly selected from 635 clustered students. MANCOVA analysis of pretest and posttest result indicates that there is an interactional effect of teaching approaches and types of problem on problem solving abiliti...

  12. Pengaruh Pendekatan Pengajaran dan Tipe Masalah terhadap Kemampuan Pemecahan Masalah Tipe ILL dan WELL-DEFINED

    OpenAIRE

    Demitra, Demitra

    2006-01-01

    This study focuses on examining the effects of teaching approaches (problem-based learning v.s. regular) and types of problem (ill defined v.s. well defined) on Matematical problem solving abilities. This quasi-experimental study involved 107 elementary school students, who had been randomly selected from 635 clustered students. MANCOVA analysis of pretest and posttest result indicates that there is an interactional effect of teaching approaches and types of problem on problem solving abiliti...

  13. Well-defined polyethylene molecular brushes by polyhomologation and ring opening metathesis polymerization

    KAUST Repository

    Zhang, Hefeng

    2014-01-01

    A novel strategy using polyhomologation and ring opening metathesis polymerization (ROMP) has been developed for the synthesis of well-defined polyethylene (PE) molecular brushes. Polyhomologation was used to afford an OH-terminated PE, which after transformation to the norbornyl PE macromonomer was subjected to ROMP. Kinetics of ROMP of the PE macromonomer was studied by in situ1H NMR monitoring. The brush structure was proved from HT-GPC, 1H NMR and DSC results.

  14. Living Polycondensation: Synthesis of Well-Defined Aromatic Polyamide-Based Polymeric Materials

    KAUST Repository

    Alyami, Mram Z.

    2016-11-01

    Chain growth condensation polymerization is a powerful tool towards the synthesis of well-defined polyamides. This thesis focuses on one hand, on the synthesis of well-defined aromatic polyamides with different aminoalkyl pendant groups with low polydispersity and controlled molecular weights, and on the other hand, on studying their thermal properties. In the first project, well-defined poly (N-octyl-p-aminobenzoate) and poly (N-butyl-p-aminobenzoate) were synthesized, and for the first time, their thermal properties were studied. In the second project, ethyl4-aminobenzoate, ethyl 4-octyl aminobenzoate and 4-(hydroxymethyl) benzoic acid were used as novel efficient initiators of ε-caprolactone with t-BuP2 as a catalyst. Macroinitiator and Macromonomer of poly (ε-caprolactone) were synthesized with ethyl 4-octyl aminobenzoate and ethyl 4-aminobenzoate as initiators to afford polyamide-block-poly (ε-caprolactone) and polyamide-graft-poly (ε-caprolactone) by chain growth condensation polymerization (CGCP). In the third project, a new study has been done on chain growth condensation polymerization to discover the probability to synthesize new polymers and studied their thermal properties. For this purpose, poly (N-cyclohexyl-p-aminobenzoate) and poly (N-hexyl-p-aminobenzoate) were synthesized with low polydispersity and controlled molecular weights.

  15. Cyclooctane metathesis catalyzed by silica-supported tungsten pentamethyl [(ΞSiO)W(Me)5]: Distribution of macrocyclic alkanes

    KAUST Repository

    Riache, Nassima

    2014-10-03

    Metathesis of cyclic alkanes catalyzed by the new surface complex [(ΞSiO)W(Me)5] affords a wide distribution of cyclic and macrocyclic alkanes. The major products with the formula CnH2n are the result of either a ring contraction or ring expansion of cyclooctane leading to lower unsubstituted cyclic alkanes (5≤n≤7) and to an unprecedented distribution of unsubstituted macrocyclic alkanes (12≤n≤40), respectively, identified by GC/MS and by NMR spectroscopies.

  16. Well-Defined Copper(I) Fluoroalkoxide Complexes for Trifluoroethoxylation of Aryl and Heteroaryl Bromides

    KAUST Repository

    Huang, Ronglu

    2015-03-17

    © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim. Copper(I) fluoroalkoxide complexes bearing dinitrogen ligands were synthesized and the structure and reactivity of the complexes toward trifluoroethoxylation, pentafluoropropoxylation, and tetrafluoropropoxylation of aryl and heteroaryl bromides were investigated. Efficiency drive: A series of copper(I) fluoroalkoxide complexes bearing N,N ligands have been prepared and structurally characterized. These well-defined complexes serve as efficient reagents for the fluoroalkoxylation of aryl and heteroaryl bromides to produce a wide range of trifluoroethyl, pentafluoropropyl, and tetrafluoropropyl (hetero)aryl ethers in good to excellent yields.

  17. Alkane metathesis with the tantalum methylidene [(≡SiO)Ta(=CH2)Me2]/[(≡SiO)2Ta(=CH2)Me] generated from well-defined surface organometallic complex [(≡SiO)TaVMe4

    KAUST Repository

    Chen, Yin

    2015-01-21

    By grafting TaMe5 on Aerosil700, a stable, well-defined, silica-supported tetramethyl tantalum(V) complex, [(≡SiO)TaMe4], is obtained on the silica surface. After thermal treatment at 150 °C, the complex is transformed into two surface tantalum methylidenes, [(≡SiO)2Ta(=CH2)Me] and [(≡SiO)Ta(=CH2)Me2], which are active in alkane metathesis and comparable to the previously reported [(≡SiO)2TaHx]. Here we present the first experimental study to isolate and identify a surface tantalum carbene as the intermediate in alkane metathesis. A systematic experimental study reveals a new reasonable pathway for this reaction.

  18. Dichotomous Well-defined Nanostructure with Weakly Arranged Ion Packing Explains the Solvency of Pyrrolidinium Acetate.

    Science.gov (United States)

    Jiang, Haihui Joy; Imberti, Silvia; Atkin, Rob; Warr, Gregory G

    2017-07-13

    Pyrrolidinium ionic liquids, especially pyrrolidinium acetate (PyrrAc), have demonstrated outstanding capacity for extracting lignin from biomass, as electrolytes for fuel cells and lithium ion batteries and as solvents for acid-catalyzed reactions. In this work we show that the unusual liquid nanostructure of PyrrAc is the key to its versatility as a solvent compared to other ionic liquids. Neutron diffraction with multiple H/D isotopic substitutions reveals that the bulk nanostructure of PyrrAc is a bicontinuous network of interpenetrating polar and apolar domains. However, the arrangement of groups in both domains is strikingly different from that found in other ionic liquids. In the apolar regions, the pyrrolidinium rings are highly intercalated and disordered, with no preferred alignment between adjacent pyrrolidinium rings, which distinguishes it from both π-π stacking seen in imidazolium or pyridinium ionic liquids, and the tail-tail bilayer-like arrangements in linear alkylammonium ionic liquids. The H-bond network within the polar domain extends only to form finite clusters, with long bent H-bonds to accommodate electrostatics. Therefore, while PyrrAc unquestionably has well-defined amphiphilic nanostructure, the disordered arrangement of groups in the polar and apolar domains enables it to accommodate a wide variety of solutes. The combination of well-defined polar/apolar nanostructure, but disordered arrangements of groups within domains, is therefore the origin of PyrrAc's capacity for lignin extraction and as an electrolyte.

  19. Large and well-defined Rabi splitting in a semiconductor nanogap cavity.

    Science.gov (United States)

    Uemoto, Mitsuharu; Ajiki, Hiroshi

    2014-09-22

    We propose a nanogap structure composed of semiconductor nanoparticles forming an optical cavity. The resonant excitation of excitons in the nanoparticles can generate a localized strong light field in the gap region, also called "hot spot". The spectral width of the hot spot is significantly narrow because of the small exciton damping and the dephasing at low temperature, so the semiconductor nanogap structure acts as a high-Q cavity. In addition, the interaction between light and matter at the nanogap is significantly larger than that in a conventional microcavity, because the former has a small cavity-mode volume beyond the diffraction limit. We theoretically demonstrate the large and well-defined vacuum-Rabi splitting of a two-level emitter placed inside the semiconductor nanogap cavity: the Rabi splitting energy of 1.7 meV for the transition dipole moment of the emitter (25 Debye) is about 6.3 times larger than the spectral width. An optical cavity providing such a large and well-defined Rabi splitting is highly suited for studying characteristic features of the cavity quantum electrodynamics and for the development of new applications.

  20. Challenging nature's monopoly on the creation of well-defined nanoparticles.

    Science.gov (United States)

    Jeong, Wonhee; Napier, Mary E; DeSimone, Joseph M

    2010-06-01

    Nature has selected and fine-tuned the physical and chemical properties of natural objects, such as size, shape, mechanical properties and surface chemistry, at the molecular level in order to modulate biological functions. A new particle fabrication process, particle replication in nonwetting templates (PRINT), has recently begun to attempt to emulate nature's ability to control those physical and chemical traits. The PRINT technology, which combines modern soft lithography with the unique properties of perfluoropolyether molds, enables the production of nanoparticles with unprecedented control of size, shape, chemical composition, deformability and surface functionality. This scalable 'top-down' fabrication process allows for the generation of well-defined nanostructures without the need for molecular assembly. The ability to flexibly engineer various matrix materials offers unique opportunities for the development of nanomedicines with desired functionality. The strength and versatility of PRINT makes it a powerful platform in nanomedicine for elucidating the role of physical and chemical properties of nanodelivery vehicles on the behavior and fate at the cellular, tissue and whole organism level. Utilizing the PRINT technology, we are generating well-defined nanomedicines with tailored properties for preclinical studies against a variety of human diseases.

  1. Well-defined and biocompatible hydrogels with toughening and reversible photoresponsive properties.

    Science.gov (United States)

    Sun, Zhiqiang; Liu, Shunli; Li, Kewen; Tan, Linhua; Cen, Lian; Fu, Guodong

    2016-02-21

    In the present study, novel hydrogels with extremely high strength, reversible photoresponsive and excellent biocompatible properties were prepared. The functional hydrogels were synthesized from a well-defined poly (ethylene glycol) polymer with spiropyran groups at a given position (PEG-SP) via a Cu(i)-catalyst Azide-Alkyne Cycloaddition (CuAAC) reaction. The molecular structures of the sequential intermediates for PEG-SP hydrogel preparation were verified by (1)HNMR and FT-IR. The mechanical property, swelling ratio, compression strength, surface hydrophilicity, and biocompatibility of the resulting hydrogel were characterized. Since spiropyran is pivotal to the switch in hydrophilicity on the hydrogel surface, the swelling ratio of PEG-SP hydrogel under Vis irradiation has a major decrease (155%). Before and after UV light irradiation, the contact angle of the hydrogel has a change of 13.8°. The photoresponsive property of this hydrogel was thus demonstrated, and such a property was also shown to be reversible. The well-defined PEG-SP hydrogel can also sustain a compressive stress of 49.8 MPa without any macro- or micro-damage, indicating its outstanding mechanical performance. Furthermore, it possessed excellent biocompatibility as demonstrated by its performance in an in vivo porcine subcutaneous implantation environment. No inflammation was observed and it got along well with the adjacent tissue. The above features indicate that PEG-SP hydrogels are promising as an implantable matrix for potential applications in biomaterial.

  2. Amphiphilic conjunct of methyl cellulose and well-defined polyvinyl acetate.

    Science.gov (United States)

    Xiao, Congming; Xia, Cunping

    2013-01-01

    Tailor-made conjunct of methyl cellulose (MC) and polyvinyl acetate (PVAc) was synthesized through the combination of reversible addition-fragmentation chain transfer (RAFT) polymerization and thiol-ene click reaction. MC was firstly transferred into unsaturated MC (UMC), and then covalently connected with well-defined PVAc obtained by RAFT polymerization of vinyl acetate. The structure of the conjunct polymer (MCV) was confirmed with Fourier transform infrared spectra (FTIR) and proton nuclear magnetic resonance ((1)H NMR). Well-defined MCV was amphiphilic and able to self-assemble into size controllable micelles, which was verified with transmission electron microscopy (TEM) and size distribution analysis. It was found that the mean diameters of the micelles in aqueous solution were 105.6, 96.0 and 75.9 nm when the number average molecular weights of PVAc segments of MCV were 49,300, 32,500 and 18,200, respectively. Copyright © 2012 Elsevier B.V. All rights reserved.

  3. Formation and stability of small well-defined Cu- and Ni oxide particles

    Energy Technology Data Exchange (ETDEWEB)

    Thalinger, Ramona [Institute of Physical Chemistry, University of Innsbruck, A-6020 Innsbruck (Austria); Heggen, Marc; Stroppa, Daniel G. [Ernst Ruska Zentrum und Peter Grünberg Institut, Forschungszentrum Jülich GmbH, 52425 Jülich (Germany); Stöger-Pollach, Michael [University Service Facility for Transmission Electron Microscopy (USTEM), Vienna University of Technology, A-1040 Vienna (Austria); Klötzer, Bernhard [Institute of Physical Chemistry, University of Innsbruck, A-6020 Innsbruck (Austria); Penner, Simon, E-mail: simon.penner@uibk.ac.at [Institute of Physical Chemistry, University of Innsbruck, A-6020 Innsbruck (Austria)

    2013-12-16

    Well-defined and -structured Cu/Cu{sub 2}O and Ni/NiO composite nanoparticles have been prepared by physical-vapor deposition on vacuum-cleaved NaCl(001) single crystal facets. Epitaxial growth has been observed due to the close crystallographic matching of the respective cubic crystal lattices. Distinct particle morphologies have only been obtained for the Ni/NiO particles, comprising truncated half-octahedral, rhombohedral- and pentagonal-shaped outlines. Oxidation of the particles in the temperature range 473–673 K in both cases led to the formation of well-defined CuO and NiO particles with distinct morphologies. Whereas CuO possibly adopts its thermodynamical equilibrium shape, NiO formation is accompanied by entering a Kirkendall-like state, that is, a hollow core–shell structure is obtained. The difference in the formation of the oxides is also reflected by their stability under reducing conditions. CuO transforms back to a polycrystalline mixture of Cu metal, Cu{sub 2}O and CuO after reduction in hydrogen at 673 K. In contrast, as expected from theoretical stability considerations, the formation of the hollow NiO structure is reversed upon annealing in hydrogen at 673 K and moreover results in the formation of a Ni-rich silicide structure Ni{sub 3}Si{sub 2}. The discussed systems present a convenient way to tackle and investigate various problems in nanotechnology or catalysis, including phase transformations, establishing structure/activity relationships or monitoring intermetallic particles, starting from well-defined and simple models. - Highlights: • Preparation of epitaxial Cu/Cu{sub 2}O and Ni/NiO composite nanoparticles on NaCl(001). • Distinct Ni/NiO particle morphologies. • Formation of well-shaped CuO and NiO particles upon oxidation. • Reversal of Kirkendall-NiO-state upon reduction/annealing in hydrogen.

  4. Well-Defined Cyclic Triblock Terpolymers: A Missing Piece of the Morphology Puzzle

    KAUST Repository

    Polymeropoulos, George

    2016-10-27

    Two well-defined cyclic triblock terpolymers, missing pieces of the terpolymer morphology puzzle, consisting of poly(isoprene), polystyrene, and poly(2-vinylpyridine), were synthesized by combining the Glaser coupling reaction with anionic polymerization. An α,ω-dihydroxy linear triblock terpolymer (OH-PI1,4-b-PS-b-P2VP-OH) was first synthesized followed by transformation of the OH to alkyne groups by esterification with pentynoic acid and cyclization by Glaser coupling. The size exclusion chromatography (SEC) trace of the linear terpolymer precursor was shifted to lower elution time after cyclization, indicating the successful synthesis of the cyclic terpolymer. Additionally, the SEC trace of the cyclic terpolymer produced, after cleavage of the ester groups, shifted again practically to the position corresponding to the linear precursor. The first exploratory results on morphology showed the tremendous influence of the cyclic structure on the morphology of terpolymers. © 2016 American Chemical Society.

  5. Well-defined Cationic Shell Crosslinked Nanoparticles for Efficient Delivery of DNA or Peptide Nucleic Acids

    Science.gov (United States)

    Zhang, Ke; Fang, Huafeng; Shen, Gang; Taylor, John-Stephen A.; Wooley, Karen L.

    2009-01-01

    This mini-review highlights developments that have been made over the past year to advance the construction of well-defined nanoscale objects to serve as devices for cell transfection. Design of the nanoscale objects originated from biomimicry concepts, using histones as the model, to afford cationic shell crosslinked knedel-like (cSCK) nanoparticles. Packaging and delivery of plasmid DNA, oligonucleotides, and peptide nucleic acids were studied by dynamic light scattering, transmission electron microscopy, gel electrophoresis, biological activity assays, RT-PCR measurements, flow cytometry, and confocal fluorescence microscopy. With the demonstration of more efficient cell transfection in vitro than that achieved using commercially-available transfection agents, together with the other features offered by the robust nanostructural framework, work continues toward the application of these cSCKs for in vivo molecular recognition of genetic material, for imaging and therapy targeted specifically to pulmonary injury and disease. PMID:19687218

  6. A Green function approach to graphene-superconductor junctions with well-defined edges

    Energy Technology Data Exchange (ETDEWEB)

    Herrera, William J [Departamento de Fisica, Universidad Nacional de Colombia, Bogota (Colombia); Burset, P; Levy Yeyati, A [Departamento de Fisica Teorica de la Materia Condensada C-V, Facultad de Ciencias, Universidad Autonoma de Madrid, E-28049 Madrid (Spain)

    2010-07-14

    This work presents a novel approach to describing spectral properties of graphene layers with well-defined edges. We microscopically analyze the boundary problem for the continuous Bogoliubov-de Gennes-Dirac equations and derive the Green functions for normal and superconducting graphene layers. Importing the idea used in tight-binding models of a microscopic hopping that couples different regions, we are able to set up and solve an algebraic Dyson equation describing a graphene-superconductor junction. For this coupled system we analytically derive the Green functions and use them to calculate the local density of states and the spatial variation of the induced pairing correlations in the normal region. Signatures of specular Andreev reflections are identified.

  7. A Green function approach to graphene-superconductor junctions with well-defined edges.

    Science.gov (United States)

    Herrera, William J; Burset, P; Levy Yeyati, A

    2010-07-14

    This work presents a novel approach to describing spectral properties of graphene layers with well-defined edges. We microscopically analyze the boundary problem for the continuous Bogoliubov-de Gennes-Dirac equations and derive the Green functions for normal and superconducting graphene layers. Importing the idea used in tight-binding models of a microscopic hopping that couples different regions, we are able to set up and solve an algebraic Dyson equation describing a graphene-superconductor junction. For this coupled system we analytically derive the Green functions and use them to calculate the local density of states and the spatial variation of the induced pairing correlations in the normal region. Signatures of specular Andreev reflections are identified.

  8. Well-defined porous membranes for robust omniphobic surfaces via microfluidic emulsion templating

    Science.gov (United States)

    Zhu, Pingan; Kong, Tiantian; Tang, Xin; Wang, Liqiu

    2017-06-01

    Durability is a long-standing challenge in designing liquid-repellent surfaces. A high-performance omniphobic surface must robustly repel liquids, while maintaining mechanical/chemical stability. However, liquid repellency and mechanical durability are generally mutually exclusive properties for many omniphobic surfaces--improving one performance inevitably results in decreased performance in another. Here we report well-defined porous membranes for durable omniphobic surfaces inspired by the springtail cuticle. The omniphobicity is shown via an amphiphilic material micro-textured with re-entrant surface morphology; the mechanical durability arises from the interconnected microstructures. The innovative fabrication method--termed microfluidic emulsion templating--is facile, cost-effective, scalable and can precisely engineer the structural topographies. The robust omniphobic surface is expected to open up new avenues for diverse applications due to its mechanical and chemical robustness, transparency, reversible Cassie-Wenzel transition, transferability, flexibility and stretchability.

  9. Malignant transformation of non-neoplastic Barrett's epithelial cells through well-defined genetic manipulations.

    Directory of Open Access Journals (Sweden)

    Xi Zhang

    2010-09-01

    Full Text Available Human Barrett's cancer cell lines have numerous, poorly-characterized genetic abnormalities and, consequently, those lines have limited utility as models for studying the early molecular events in carcinogenesis. Cell lines with well-defined genetic lesions that recapitulate various stages of neoplastic progression in Barrett's esophagus would be most useful for such studies.To develop such model cell lines, we started with telomerase-immortalized, non-neoplastic Barrett's epithelial (BAR-T cells, which are spontaneously deficient in p16, and proceeded to knock down p53 using RNAi, to activate Ras by introducing oncogenic H-Ras(G12V, or both. BAR-T cells infected with either p53 RNAi or oncogenic H-Ras(G12V alone maintained cell-to-cell contact inhibition and did not exhibit anchorage-independent growth in soft agar. In contrast, the combination of p53 RNAi knockdown with expression of oncogenic H-Ras(G12V transformed the p16-deficient BAR-T cells, as evidenced by their loss of contact inhibition, by their formation of colonies in soft agar, and by their generation of tumors in immunodeficient mice.Through these experiments, we have generated a number of transformed and non-transformed cell lines with well-characterized genetic abnormalities recapitulating various stages of carcinogenesis in Barrett's esophagus. These lines should be useful models for the study of carcinogenesis in Barrett's esophagus, and for testing the efficacy of chemopreventive and chemotherapeutic agents.

  10. Synthesis and Complexation of Well-Defined Labeled Poly(N,N-dimethylaminoethyl methacrylates (PDMAEMA

    Directory of Open Access Journals (Sweden)

    Mark Billing

    2015-11-01

    Full Text Available We present the synthesis and characterization of well-defined polycationic copolymers containing thiazole dyes in the side chain. Atom transfer radical polymerization (ATRP was used for the copolymerization of 3-azidopropyl methacrylate (AzPMA and N,N-dimethylaminoethyl methacrylate (DMAEMA of different composition. Thiazole-based alkyne-functionalized dyes (e.g., 5-methyl-4-(prop-2-yn-1-yloxy-2-(pyridin-2-ylthiazole, (MPPT were afterwards covalently attached using copper catalyzed azide alkyne cycloadditions (CuAAC reaching contents of up to 9 mol % dye. Subsequent quaternization of the tertiary nitrogen of DMAEMA with strong methylation agents (e.g., methyl iodide led to permanently charged polyelectrolytes. The materials were characterized by size exclusion chromatography, as well as NMR- and UV/VIS-spectroscopy. Particular attention is paid to the spectroscopic properties of the dyes in the side chain upon environmental changes such as pH and salinity. We anticipate the application of such precisely functionalized polyelectrolytes as temperature- and pH-responsive sensors in biomedical applications, e.g., within interpolyelectrolyte complexes. Concerning the latter, first complex formation results are demonstrated.

  11. Synthesis, characterization and self-assembly of well-defined linear heptablock quaterpolymers

    KAUST Repository

    Ntaras, Christos

    2016-05-17

    Two well-defined heptablock quaterpolymers of the ABCDCBA type [Α: polystyrene (PS), B: poly(butadiene) with ∼90% 1,4-microstructure (PB1,4), C: poly(isoprene) with ∼55% 3,4-microstructure (PI3,4) and D: poly(dimethylsiloxane) (PDMS)] were synthesized by combining anionic polymerization high vacuum techniques and hydrosilylation/chlorosilane chemistry. All intermediates and final products were characterized by size exclusion chromatography, membrane osmometry, and proton nuclear magnetic resonance spectroscopy. Fourier transform infrared spectroscopy was used to further verify the chemical modification reaction of the difunctional PDMS. The self-assembly in bulk of these novel heptablock quarterpolymers, studied by transmission electron microscopy and small angle X-ray scattering, revealed 3-phase 4-layer alternating lamellae morphology of PS, PB1,4, and mixed PI3,4/PDMS domains. Differential scanning calorimetry was used to further confirm the miscibility of PI3,4 and PDMS blocks. It is the first time that PDMS is the central segment in such multiblock polymers (≥3 chemically different blocks). © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016, 54, 1443–1449. © 2016 Wiley Periodicals, Inc.

  12. Comparative Evaluation of the Chemical Stability of 4 Well-Defined Immunoglobulin G1-Fc Glycoforms.

    Science.gov (United States)

    Mozziconacci, Olivier; Okbazghi, Solomon; More, Apurva S; Volkin, David B; Tolbert, Thomas; Schöneich, Christian

    2016-02-01

    As part of a series of articles in this special issue evaluating model IgG1-Fc glycoforms for biosimilarity analysis, 3 well-defined IgG1-Fc glycoforms (high mannose-Fc, Man5-Fc, and N-acetylglucosamine-Fc) and a nonglycosylated Fc protein (N297Q-Fc) were examined in this work to elucidate chemical degradation pathways. The 4 proteins underwent a combination of accelerated thermal stability studies and 4 independent forced degradation studies (UV light, metal-catalyzed oxidation, peroxyl radicals, and hydrogen peroxide) at pH 6.0. Our results highlight chemical degradations at Asn315, Met428, Trp277, and Trp313. A cross-comparison of the different Fc glycoforms, stress conditions, and the observed chemical reactions revealed that both the deamidation of Asn315 and the transformation of Trp277 into glycine hydroperoxide were glycan dependent during incubation for 3 months at 40 °C. Our data will show that different glycans not only affect chemical degradation differently but also do lead to different impurity profiles, which can affect chemical degradation. Copyright © 2016 American Pharmacists Association®. Published by Elsevier Inc. All rights reserved.

  13. Well-Defined Polyethylene-Based Random, Block, and Bilayered Molecular Cobrushes

    KAUST Repository

    Zhang, Hefeng

    2015-06-09

    Novel well-defined polyethylene-based random, block, and bilayered molecular cobrushes were synthesized through the macromonomer strategy. Two steps were involved in this approach: (i) synthesis of norbornyl-terminated macromonomers of polyethylene (PE), polycaprolactone (PCL), poly(ethylene oxide) (PEO), and polystyrene (PS), as well as polyethylene-b-polycaprolactone (PE-b-PCL), by esterification of the hydroxyl-terminated precursors (PE, PCL, PEO, PS, and PE-b-PCL) with 5-norbornene-2-carboxylic acid and (ii) ring-opening metathesis (co)polymerization of the resulting macromonomers to afford the PE-based molecular cobrushes. The PE-macromonomers were synthesized by polyhomologation of dimethylsulfoxonium methylide, while the others by anionic polymerization. Proton nuclear magnetic resonance spectroscopy (1H NMR) and high-temperature gel permeation chromatography (HT-GPC) were used to imprint the molecular characteristics of all macromonomers and molecular brushes and differential scanning calorimetry (DSC) for the thermal properties. The bilayered molecular cobrushes of P(PE-b-PCL) adopt a wormlike morphology on silica wafer as visualized by atomic force microscopy (AFM). © 2015 American Chemical Society.

  14. Co-aggregation of two anionic azo dyestuffs at a well-defined stoichiometry.

    Science.gov (United States)

    Michels, Rolf; Sinemus, Thomas; Hoffmann, Jan; Brutschy, Bernhard; Huber, Klaus

    2013-07-18

    The present work investigates the formation of well-defined heteroaggregates from a binary mixture of a red and a yellow azo-dyestuff in the presence of Mg(2+) ions. Combined static and dynamic light scattering together with laser induced liquid bead ion desorption mass spectrometry (LILBID-MS) has been applied to characterize the states of the pure red dye and the pure yellow dye as well as of their mixture in aqueous solution without Mg(2+). These experiments indicated that a structural reorganization on a molecular scale takes place as soon as the two dyes are combined. Solutions of the combined red and yellow dye contain micelle-like mixed entities with a size of a few tenths of nanometers. Upon the addition of Mg(2+), these micelles vanish in favor of elongated heteroaggregates, which grow by a stepwise addition of smaller building units. As unraveled by UV/vis spectroscopy, the heteroaggregates that are formed from the red and yellow azo dye in the presence of Mg(2+) obey a stoichiometric ratio of the two components of 1:1. A new multiangle scattering instrument allowed us for the first time to follow this aggregation process at the stoichiometric ratio by time-resolved combined static and dynamic light scattering, thereby providing further aspects of the worm-like nature of the growing heteroaggregates.

  15. Design of porous silica supported tantalum oxide hollow spheres showing enhanced photocatalytic activity.

    Science.gov (United States)

    Sharma, Manu; Das, Debashree; Baruah, Arabinda; Jain, Archana; Ganguli, Ashok K

    2014-03-25

    Silica-supported tantalum oxide (ST) hollow spheres were designed for photocatalytic applications in the UV range of 4.1 to 4.8 eV. These nanostructures with a variable diameter of 100-250 nm and shell thickness of 24-58 nm were obtained by the hydrothermal treatment of tantalum isopropoxide and tetraethylorthosilicate at 120 °C for 48 h in the presence of cetyl trimethyl ammonium bromide, which was used as a capping agent. The maximum observed surface area was found to be 610 m(2)/g and pore size distribution of ST hollow spheres varied from 13.4 to 19.0 nm. Lewis acidity of silica and the contact area between SiO2 and Ta2O5 plays a crucial role in controlling the photocatalytic properties of the ST hollow spheres. We observe a remarkable 6× enhancement in the photoactivity of silica-supported tantalum oxide hollow spheres compared to pure Ta2O5.

  16. thesis of high-purity carbon nanotubes over alumina and silica supported bimetallic catalysts

    Directory of Open Access Journals (Sweden)

    Sanja Ratković

    2009-10-01

    Full Text Available Carbon nanotubes (CNTs were synthesized by a catalytic chemical vapor deposition method (CCVD of ethylene over alumina and silica supported bimetallic catalysts based on Fe, Co and Ni. The catalysts were prepared by a precipitation method, calcined at 600 °C and in situ reduced in hydrogen flow at 700 °C. The CNTs growth was carried out by a flow the mixture of C2H4 and nitrogen over the catalyst powder in a horizontal oven. The structure and morphology of as-synthesized CNTs were characterized using SEM. The as-synthesized nanotubes were purified by acid and basic treatments in order to remove impurities such as amorphous carbon, graphite nanoparticles and metal catalysts. XRD and DTA/TG analyses showed that the amounts of by-products in the purified CNTs samples were reduced significantly. According to the observed results, ethylene is an active carbon source for growing high-density CNTs with high yield but more on alumina-supported catalysts than on their silica- supported counterparts. The last might be explained by SMSI formed in the case of alumina-supported catalysts, resulting in higher active phase dispersion.

  17. Sorption and diffusion of phenols onto well-defined ordered nanoporous monolithic silicas.

    Science.gov (United States)

    El-Safty, S A

    2003-04-01

    The sorption of phenol, and o-, m-, and p-aminophenol (o-, m-, and p-AP) onto highly ordered mesoporous silicas (HOM) with cubic Im3m (HOM-1), hexagonal H(I) (HOM-2), 3-D hexagonal p6(3)/mmc (HOM-3), cubic Ia3d (HOM-5), lamellar L( infinity ) (HOM-6), and solid phase S (HOM-8) materials has been investigated kinetically. Nanostructured silica molecular sieves have been prepared at 25 and 60 degrees C with lyotropic liquid-crystalline phases of the nonionic surfactant (Brij 76) that was used as a structure-directing agent. Such nanostructured silicas have been studied by 29Si nuclear magnetic resonance (29Si NMR), powder X-ray diffraction (XRD), the Brunauer-Emmett-Teller (BET) method for nitrogen adsorption and surface area measurements, and transmission electron microscopy (TEM) techniques after synthesis and sorption. It was found that all materials exhibit well-defined long-range porous architectures without significant loss of the ordered texture during phenol sorption. The kinetics of phenol sorption has been studied spectrophotometrically at different temperatures (25-40 degrees C; +/-0.1 range). The sorption rate is zero order in all phenols sorbed, and increases directly in the pattern P >m-AP > o-AP > p-AP, which reflects the mobility of the phenol compounds on the particle pores. The isothermal sorption and the kinetic parameters were discussed and it was established that a diffusion-controlled process characterizes phenol sorption. Furthermore, the mechanism of phenol sorption was deduced to be predominantly particle diffusion. The diffusion coefficients were determined using Fick's equation. The trend of diffusion of all phenols onto nanoporous silica was HOM-8 > HOM-2 > HOM-6 > HOM-5 > HOM-1 > HOM-3, reflecting the effect of the uniform pore size distribution and the internal surface area of the nanostructured silicas on the diffusion process.

  18. A Well-Defined Osmium-Cupin Complex: Hyperstable Artificial Osmium Peroxygenase.

    Science.gov (United States)

    Fujieda, Nobutaka; Nakano, Takumi; Taniguchi, Yuki; Ichihashi, Haruna; Sugimoto, Hideki; Morimoto, Yuma; Nishikawa, Yosuke; Kurisu, Genji; Itoh, Shinobu

    2017-04-03

    Thermally stable TM1459 cupin superfamily protein from Thermotoga maritima was repurposed as an osmium (Os) peroxygenase by metal-substitution strategy employing the metal-binding promiscuity. This novel artificial metalloenzyme bears a datively bound Os ion supported by the 4-histidine motif. The well-defined Os center is responsible for not only the catalytic activity but also the thermodynamic stability of the protein folding, leading to the robust biocatalyst (Tm ≈ 120 °C). The spectroscopic analysis and atomic resolution X-ray crystal structures of Os-bound TM1459 revealed two types of donor sets to Os center with octahedral coordination geometry. One includes trans-dioxide, OH, and mer-three histidine imidazoles (O3N3 donor set), whereas another one has four histidine imidazoles plus OH and water molecule in a cis position (O2N4 donor set). The Os-bound TM1459 having the latter donor set (O2N4 donor set) was evaluated as a peroxygenase, which was able to catalyze cis-dihydroxylation of several alkenes efficiently. With the low catalyst loading (0.01% mol), up to 9100 turnover number was achieved for the dihydroxylation of 2-methoxy-6-vinyl-naphthalene (50 mM) using an equivalent of H2O2 as oxidant at 70 °C for 12 h. When octene isomers were dihydroxylated in a preparative scale for 5 h (2% mol cat.), the terminal alkene octene isomers was converted to the corresponding diols in a higher yield as compared with the internal alkenes. The result indicates that the protein scaffold can control the regioselectivity by the steric hindrance. This protein scaffold enhances the efficiency of the reaction by suppressing disproportionation of H2O2 on Os reaction center. Moreover, upon a simple site-directed mutagenesis, the catalytic activity was enhanced by about 3-fold, indicating that Os-TM1459 is evolvable nascent osmium peroxygenase.

  19. Physics and chemistry on well-defined semiconductor and oxide surfaces

    Energy Technology Data Exchange (ETDEWEB)

    Chen, Peijun

    1992-12-31

    High resolution electron energy loss spectroscopy (HREELS) and other surface spectroscopic techniques have been employed to investigate the following two classes of surface/interface phenomena on well-defined semiconductor and oxide surfaces: (i) the fundamental physical and chemical processes involved in gas-solid interaction on silicon single crystal surfaces, and (ii) the physical and chemical properties of metal-oxide interfaces. The particular systems reported in this dissertation are: NH{sub 3}, PH{sub 3} and B{sub 10}H{sub 14} on Si(111)-(7 x 7); NH{sub 3} on Si(100)-(2 x 1); atomic H on Si(111)-(7 x 7) and boron-modified Si(111); Al on Al{sub 2}O{sub 3} and Sn on SiO{sub 2}. On silicon surfaces, the surface dangling bonds function as the primary adsorption sites where surface chemical processes take place. The unambiguous identification of surface species by vibrational spectroscopy allow the elementary steps involved in these surface chemical processes to be followed on a molecular level. For adsorbate such as NH{sub 3} and PH{sub 3}, the nature of the initial low temperature (100-300 K) adsorption is found to be dissociative, while that for B{sub 10}H{sub 14} is non-dissociative. This has been deduced based upon the presence (or absence) of specific characteristic vibrational mode(s) on surface. By following the evolution of surface species as a function of temperature, the elementary steps leading to silicon nitride thin film growth and doping of silicon are elucidated. In the case of NH{sub 3} on Si(111)-(7 x7) and Si(100)-(2 x 1), a detailed understanding on the role of substrate surface structure is controlling the surface reactivity has been gained on the basis of a Si adatom backbond-strain relief mechanism on the Si(111)-(7 x 7). The electronic modification to Si(111) surface by subsurface boron doping has been shown to quench its surface chemistry, even for the most aggressive atomic H.

  20. Unsaturated Fatty Acid Esters Metathesis Catalyzed by Silica Supported WMe5

    KAUST Repository

    Riache, Nassima

    2015-11-14

    Metathesis of unsaturated fatty acid esters (FAEs) by silica supported multifunctional W-based catalyst is disclosed. This transformation represents a novel route towards unsaturated di-esters. Especially, the self-metathesis of ethyl undecylenate results almost exclusively on the homo-coupling product whereas with such catalyst, 1-decene gives ISOMET (isomerization and metathesis olefin) products. The olefin metathesis in the presence of esters is very selective without any secondary cross-metathesis products demonstrating that a high selective olefin metathesis could operate at 150 °C. Additionally, a cross-metathesis of unsaturated FAEs and α-olefins allowed the synthesis of the corresponding ester with longer hydrocarbon skeleton without isomerisation.

  1. Progress of the Application of Mesoporous Silica-Supported Heteropolyacids in Heterogeneous Catalysis and Preparation of Nanostructured Metal Oxides

    Directory of Open Access Journals (Sweden)

    Heyong He

    2010-01-01

    Full Text Available Mesoporous silica molecular sieves are a kind of unique catalyst support due to their large pore size and high surface area. Several methods have been developed to immobilize heteropolyacids (HPAs inside the channels of these mesoporous silicas. The mesoporous silica-supported HPA materials have been widely used as recyclable catalysts in heterogeneous systems. They have shown high catalytic activities and shape selectivities in some reactions, compared to the parent HPAs in homogeneous systems. This review summarizes recent progress in the field of mesoporous silica-supported HPAs applied in the heterogeneous catalysis area and preparation of nanostructured metal oxides using HPAs as precursors and mesoporous silicas as hard templates.

  2. Progress of the Application of Mesoporous Silica-Supported Heteropolyacids in Heterogeneous Catalysis and Preparation of Nanostructured Metal Oxides

    Science.gov (United States)

    Ren, Yuanhang; Yue, Bin; Gu, Min; He, Heyong

    2010-01-01

    Mesoporous silica molecular sieves are a kind of unique catalyst support due to their large pore size and high surface area. Several methods have been developed to immobilize heteropolyacids (HPAs) inside the channels of these mesoporous silicas. The mesoporous silica-supported HPA materials have been widely used as recyclable catalysts in heterogeneous systems. They have shown high catalytic activities and shape selectivities in some reactions, compared to the parent HPAs in homogeneous systems. This review summarizes recent progress in the field of mesoporous silica-supported HPAs applied in the heterogeneous catalysis area and preparation of nanostructured metal oxides using HPAs as precursors and mesoporous silicas as hard templates.

  3. Immobilization of β-glucosidase onto mesoporous silica support: Physical adsorption and covalent binding of enzyme

    Directory of Open Access Journals (Sweden)

    Ivetić Darjana Ž.

    2014-01-01

    Full Text Available This paper investigates β-glucosidase immobilization onto mesoporous silica support by physical adsorption and covalent binding. The immobilization was carried out onto micro-size silica aggregates with the average pore size of 29 nm. During physical adsorption the highest yield of immobilized β-glucosidase was obtained at initial protein concentration of 0.9 mg ml-1. Addition of NaCl increased 1.7-fold, while Triton X-100 addition decreased 6-fold yield of adsorption in comparison to the one obtained without any addition. Covalently bonded β-glucosidase, via glutaraldehyde previously bonded to silanized silica, had higher yield of immobilized enzyme as well as higher activity and substrate affinity in comparison to the one physically adsorbed. Covalent binding did not considerably changed pH and temperature stability of obtained biocatalyst in range of values that are commonly used in reactions in comparison to unbounded enzyme. Furthermore, covalent binding provided biocatalyst which retained over 70% of its activity after 10 cycles of reuse. [Projekat Ministarstva nauke Republike Srbije, br. III 45021

  4. Porous silica supports for micro-Raman spectroscopic studies of individual living cells

    Science.gov (United States)

    Cristini-Robbe, O.; Raulin, K.; Dubart, F.; Bernard, R.; Kinowski, C.; Damene, N.; El Yazidi, I.; Boed, A.; Turrell, S.

    2013-10-01

    A work was undertaken to explore the possibility of using porous silica gels as support materials for in vitro studies of individual living cells. Accordingly, tetra methyl orthosilicate-derived silica xerogels were prepared and tested as substrates for human breast adenocarcinoma MCF-7 cells. Micro-Raman spectra and BET measurements were used to determine the effect of sol-pH and autoclave sterilization on the substrate. MCF-7 cells were then seeded and grown on the resulting silica gels. Combined techniques show that (a) sol-pH affects substrate porosity and (b) autoclave conditions affect only the substrate surface thus increasing the surface porosity. Micro-Raman spectra of in situ grown MCF-7 cells indicate that they proliferate well on these xerogel surfaces with a preference for base-catalyzed substrates and that the surface morphology of supports can have a definite effect on the adherence and on the life time of human cells. Spectral evolutions observed for cells over a period of 48 h have made it possible to show that these substrates enable the easy maintenance of cell viability for over 36 h and that micro-Raman techniques make it possible to study individual cells and to characterize evolutional changes at different stages of their life-times. Results point to these new porous silica supports as promising substrates for rapid screening of drug toxicity.

  5. Investigation of Hexagonal Mesoporous Silica-Supported Composites for Trace Moisture Adsorption

    Science.gov (United States)

    Li, Li; Tang, Nian; Wang, Yaxue; Cen, Wanglai; Liu, Jie; Zhou, Yongyan

    2015-11-01

    Moisture control is an important part of effective maintenance program for gas-insulated switchgear (GIS). Herein, hexagonal mesoporous silica (HMS) materials were synthesized by adopting dodecylamine as a structure directing agent, which was then employed as a host for supporting polyethylenimine (PEI) without further calcinations or extraction treatment. The physicochemical properties of the silica support and composites were characterized, and the moisture adsorption capacity of these composites was determined. The reserved template agents resulted in a dramatic improvement in moisture adsorption amount. Among them, 50PEI/DHMS showed the highest adsorption value. The enhanced adsorption could be attributed to the generated hydrogen bonding between amino groups and H2O molecules and the improved diffusion of moisture into the bulk networks of PEI polymers due to its better spatial dispersion imposed by the long alkyl chains of template agents, which was confirmed by thermogravimetry results and hydrogen efficiency analysis. Moreover, the maintained terminal amino groups of templates could also function as active sites for moisture adsorption. The results herein imply that the PEI/DHMS composites could be appealing materials for capturing moisture in GIS.

  6. Photocatalytic Decolorization of Methyl Orange by Silica-Supported TiO2 Composites

    Directory of Open Access Journals (Sweden)

    mohammad ghorbanpour

    2017-06-01

    Full Text Available Immobilization of TiO2 on silica gel has been proposed to enable easy separation of the catalyst in aqueous systems after photocatalytic reaction. Our simple synthesizing method reduces production cost, and the photocatalyst could find economical application in wastewater treatment. Silica-supported TiO2 composites were prepared by molten salt method at 500, 600 and 700 °C for 60 min. The obtained samples were characterized by scanning electron microscopy (SEM, X-ray diffraction (XRD, diffuse reflectance spectroscopy and X-ray fluorescence. SEM results showed a heterogeneous surface covered with spherical particles. According to XRD findings, the only phase of the prepared TiO2/SG nanocomposites at all temperatures was pure anatase. The average crystallite size of anatase was roughly 25, 42, 44 and 53 nm for nanocomposites prepared at 550, 600, 700 and 800 °C, respectively. The samples taken at 500 and 600 ºC showed a band gap value of 2.98 eV, and for sample synthesized at 700 ºC the band gap was 2.95 eV. The decolorization activity has been evaluated by Methyl orange (MO oxidation in liquid phase. The results showed that the sample obtained at 700 °C had the highest photocatalytic decolorization efficiency activity, and the sample prepared at 500 °C had the lowest. The decolorization activity of photocatalyst prepared at 700 °C did not change during stability experiment.

  7. The Effect of Nitrogen Surface Ligands on Propane Metathesis: Design and Characterizations of N-modified SBA15-Supported Schrock-type Tungsten Alkylidyne

    KAUST Repository

    Eid, Ahmed A.

    2014-04-01

    Catalysis, which is primarily a molecular phenomenon, is an important field of chemistry because it requires the chemical conversion of molecules into other molecules. It also has an effect on many fields, including, but not limited to, industry, environment and life Science[1]. Surface Organometallic Chemistry is an effective methodology for Catalysis as it imports the concept and mechanism of organometallic chemistry, to surface science and heterogeneous catalysis. So, it bridges the gap between homogenous and heterogeneous catalysis[1]. The aim of the present research work is to study the effect of Nitrogen surface ligands on the activity of Alkane, Propane in particular, metathesis. Our approach is based on the preparation of selectively well-defined group (VI) transition metal complexes supported onto mesoporous materials, SBA15 and bearing amido and/or imido ligands. We choose nitrogen ligands because, according to the literature, they showed in some cases better catalytic properties in homogenous catalysis in comparison with their oxygen counterparts[2]. The first section covers the modification of a highly dehydroxylated SBA15 surface using a controlled ammonia treatment. These will result in the preparation of two kind of Nitrogen surface ligands: -\\tOne with vicinal silylamine/silanol, (≡SiNH2)(≡SiOH), noted [N,O]SBA15 and, -\\tAnother\\tone\\twith\\tvicinal\\tbis-silylamine moieties (≡SiNH2)2, noted [N,N]SBA15[3]. The second section covers the reaction of Schrock type Tungsten Carbyne [W(≡C- tBu)(CH2-tBu)3] with those N-surface ligands and their characterizations by FT-IR, multiple quantum solid state NMR (1H, 13C), elemental analysis and gas phase analysis. The third section covers the generation of the active site, tungsten hydride species. Their performance toward propane metathesis reaction using the dynamic reactor technique PID compared toward previous well-known catalysts supported on silica oxide or mesoporous materials[4]. A fairly good

  8. Structure of branching enzyme- and amylomaltase modified starch produced from well-defined amylose to amylopectin substrates

    DEFF Research Database (Denmark)

    Sorndecha, Waraporn; Sagnelli, Domenico; Meier, Sebastian

    2016-01-01

    constituent in starch and the effect of amylose on enzyme catalysis was investigated using amylose-only barley starch (AO) and waxy maize starch (WX) in well-defined ratios. All products were analysed for amylopectin chain length distribution, α-1,6 glucosidic linkages content, molar mass distribution...... and digestibility by using rat intestinal α-glucosidases. For each enzyme treatment series, increased AO content resulted in a higher rate of α-1,6 glucosidic linkage formation but as an effect of the very low initial branching of the AO, the final content of α-1,6 glucosidic linkages was slightly lower as compared...

  9. Efficient hydrogen liberation from formic acid catalyzed by a well-defined iron pincer complex under mild conditions.

    Science.gov (United States)

    Zell, Thomas; Butschke, Burkhard; Ben-David, Yehoshoa; Milstein, David

    2013-06-17

    Hydrogen liberation: An attractive approach to reversible hydrogen storage applications is based on the decomposition of formic acid. The efficient and selective hydrogen liberation from formic acid is catalyzed by an iron pincer complex in the presence of trialkylamine. Turnover frequencies up to 836 h⁻¹ and turnover numbers up to 100,000 were achieved at 40 °C. A mechanism including well-defined intermediates is suggested on the basis of experimental and computational data. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Tungsten Filament Fire

    Science.gov (United States)

    Ruiz, Michael J.; Perkins, James

    2016-01-01

    We safely remove the outer glass bulb from an incandescent lamp and burn up the tungsten filament after the glass is removed. This demonstration dramatically illustrates the necessity of a vacuum or inert gas for the environment surrounding the tungsten filament inside the bulb. Our approach has added historical importance since the incandescent…

  11. Textbook tests with tungsten

    CERN Multimedia

    Barbara Warmbein

    2010-01-01

    CERN's linear collider detector group joins forces with CALICE in building the world's first tungsten hadronic calorimeter.   Hadronic calorimeter prototype made of tungsten for the linear collider detector being equipped with CALICE scintillators. In a hall for test beam experiments at CERN, next to the CLOUD climate experiment and an irradiation facility, sits a detector prototype that is in many ways a first. It's the first ever hadronic sandwich calorimeter (HCal) prototype made of tungsten. It's the first prototype for a detector for the Compact Linear Collider Study CLIC, developed by the linear collider detector R&D group (LCD group) at CERN. And it's the first piece of hardware that results directly from the cooperation between CLIC and ILC detector study groups. Now its makers are keen to see first particle showers in their detector. The tungsten calorimeter has just moved from a workshop at CERN, where it was assembled from finely polished tungsten squares and triangles, into the ...

  12. Physical degradation of proteins in well-defined fluid flows studied within a four-roll apparatus.

    Science.gov (United States)

    Simon, S; Krause, H J; Weber, C; Peukert, W

    2011-12-01

    In most applications of biotechnology and downstream processing proteins are exposed to fluid stresses in various flow configurations which often lead to the formation of unwanted protein aggregates. In this paper we present physical degradation experiments for proteins under well-defined flow conditions in a four-roll apparatus. The flow field was characterized numerically by computational fluid dynamics (CFD) and experimentally by particle image velocimetry (PIV). The local shear strain rate as well as the local shear and elongation rate was used to characterize the hydrodynamic stress environment acting on the proteins. Lysozyme was used as a model protein and subjected to well-defined fluid stresses in high and low stress environment. By using in situ turbidity measurements during stressing the aggregate formation was monitored directly in the fluid flow. An increase in absorbance at 350 nm was attributed to a higher content of visible particles (>1 µm). In addition to lysozyme, the formation of aggregates was confirmed for two larger proteins (bovine serum albumin and alcohol dehydrogenase). Thus, the presented experimental setup is a helpful tool to monitor flow-induced protein aggregation with high reproducibility. For instance, screening experiments for formulation development of biopharmaceuticals for fill and finish operations can be performed in the lab-scale in a short time-period if the stress distributions in the application are transferred and applied in the four-roll mill. Copyright © 2011 Wiley Periodicals, Inc.

  13. Synthesis and evaluation of a well-defined HPMA copolymer-dexamethasone conjugate for effective treatment of rheumatoid arthritis.

    Science.gov (United States)

    Liu, Xin-Ming; Quan, Ling-Dong; Tian, Jun; Alnouti, Yazen; Fu, Kai; Thiele, Geoffrey M; Wang, Dong

    2008-12-01

    To develop a pH-sensitive dexamethasone (Dex)-containing N-(2-hydroxypropyl)methacrylamide (HPMA) copolymer conjugate with well-defined structure for the improved treatment of rheumatoid arthritis (RA). A new pH-sensitive Dex-containing monomer (MA-Gly-Gly-NHN=Dex) was synthesized and copolymerized with HPMA using reversible addition-fragmentation transfer (RAFT) polymerization. The structure of the resulting HPMA copolymer-Dex conjugate (P-Dex) was analyzed and its therapeutic efficacy was evaluated on adjuvant-induced arthritis (AIA) rats. P-Dex was synthesized with controllable molecular weight and polydispersity index (PDI). The Dex content can be controlled by the feed-in ratio of MA-Gly-Gly-NHN=Dex. The P-Dex used for in vitro and in vivo evaluation has a average molecular weight (M (w)) of 34 kDa and a PDI of 1.34. The in vitro drug-release studies showed that the Dex release from the conjugate was triggered by low pH. Clinical measurements, endpoint bone mineral density (BMD) test and histology grading from the in vivo evaluation all suggest that newly synthesized P-Dex has strong and long-lasting anti-inflammatory and joint protection effects. A HPMA copolymer-dexamethasone conjugate with a well-defined structure has been synthesized and proved to be an effective anti-arthritis therapy. It may have a unique clinical application in the treatment of rheumatoid arthritis.

  14. In Situ SIMS and IR Spectroscopy of Well-Defined Surfaces Prepared by Soft Landing of Mass-Selected Ions

    Energy Technology Data Exchange (ETDEWEB)

    Johnson, Grant E.; Gunaratne, Kalupathirannehelage Don D.; Laskin, Julia

    2014-06-16

    Soft landing of mass-selected ions onto surfaces is a powerful approach for the highly-controlled preparation of materials that are inaccessible using conventional synthesis techniques. Coupling soft landing with in situ characterization using secondary ion mass spectrometry (SIMS) and infrared reflection absorption spectroscopy (IRRAS) enables analysis of well-defined surfaces under clean vacuum conditions. The capabilities of three soft-landing instruments constructed in our laboratory are illustrated for the representative system of surface-bound organometallics prepared by soft landing of mass-selected ruthenium tris(bipyridine) dications, [Ru(bpy)3]2+, onto carboxylic acid terminated self-assembled monolayer surfaces on gold (COOH-SAMs). In situ time-of-flight (TOF)-SIMS provides insight into the reactivity of the soft-landed ions. In addition, the kinetics of charge reduction, neutralization and desorption occurring on the COOH-SAM both during and after ion soft landing are studied using in situ Fourier transform ion cyclotron resonance (FT-ICR)-SIMS measurements. In situ IRRAS experiments provide insight into how the structure of organic ligands surrounding metal centers is perturbed through immobilization of organometallic ions on COOH-SAM surfaces by soft landing. Collectively, the three instruments provide complementary information about the chemical composition, reactivity and structure of well-defined species supported on surfaces.

  15. Silica-supported sulfonic acids as recyclable catalyst for esterification of levulinic acid with stoichiometric amounts of alcohols

    Directory of Open Access Journals (Sweden)

    Raimondo Maggi

    2016-10-01

    Full Text Available Converting biomass into value-added chemicals holds the key to sustainable long-term carbon resource management. In this context, levulinic acid, which is easily obtained from cellulose, is valuable since it can be transformed into a variety of industrially relevant fine chemicals. Here we present a simple protocol for the selective esterification of levulinic acid using solid acid catalysts. Silica supported sulfonic acid catalysts operate under mild conditions and give good conversion and selectivity with stoichiometric amounts of alcohols. The sulfonic acid groups are tethered to the support using organic tethers. These tethers may help in preventing the deactivation of the active sites in the presence of water.

  16. Comparison of Catalysts Preyssler and Silica-Supported Nano Preyssler in the Synthesis of Acetyl Salicylic Acid

    Directory of Open Access Journals (Sweden)

    H. Nazari

    2012-01-01

    Full Text Available The extensive demand for cleaner environment is forcing chemical industry to use less hazardous materials. In this regard, heteropolyacids attracted considerable amount of interest due to the less toxic behavior in addition of possessing higher acidity. Heteropoly acids have been used as catalysts for the reaction of salicylic acid with acetic anhydride. The performance of different forms of heteropoly acids in the presence of acetic anhydride as acetylating agent for acetylation of salicylic acid was compared. The best conditions were observed using Preyssler and Silica-supported Preyssler Nanoparticles as catalysts. The catalyst is recyclable and reusable.

  17. Preparation of well-defined erythromycin imprinted non-woven fabrics via radiation-induced RAFT-mediated grafting

    Science.gov (United States)

    Söylemez, Meshude Akbulut; Barsbay, Murat; Güven, Olgun

    2018-01-01

    Radiation-induced RAFT polymerization technique was applied to synthesize well-defined molecularly imprinted polymers (MIPs) of erythromycin (ERY). Methacrylic acid (MAA) was grafted onto porous polyethylene (PE)/polypropylene (PP) nonwoven fabrics, under γ-irradiation by employing 2-pheny-2-propyl benzodithioate as the RAFT agent and ethylene glycol dimethacrylate (EGDMA) as the crosslinker. MAA/erythromycin ratios of 2/1, 4/1, 6/1 were tested to optimize the synthesis of MIPs. The highest binding capacity was encountered at a MAA/ERY ratio of 4/1. Non-imprinted polymers (NIPs) were also synthesized in the absence of ERY. The MIPs synthesized by RAFT method presented a better binding capacity compared to those prepared by conventional method where no RAFT agent was employed.

  18. Acyclic Diene Metathesis (ADMET Polymerization for Precise Synthesis of Defect-Free Conjugated Polymers with Well-Defined Chain Ends

    Directory of Open Access Journals (Sweden)

    Tahmina Haque

    2015-03-01

    Full Text Available This accounts introduces unique characteristics by adopting the acyclic diene metathesis (ADMET polymerization for synthesis of conjugated polymers, poly(arylene vinylenes, known as promising molecular electronics. The method is more suitable than the other methods in terms of atom efficiency affording defect-free, stereo-regular (exclusive trans polymers with well-defined chain ends; the resultant polymers possess better property than those prepared by the conventional methods. The chain ends (vinyl group in the resultant polymer prepared by ruthenium-carbene catalyst(s can be modified by treating with molybdenum-alkylidene complex (olefin metathesis followed by addition of various aldehyde (Wittig type cleavage, affording the end-functionalized polymers exclusively. An introduction of initiating fragment, the other conjugated segment, and one-pot synthesis of end-functionalized block copolymers, star shape polymers can be achieved by adopting this methodology.

  19. Stable aqueous based Cu nanoparticle ink for printing well-defined highly conductive features on a plastic substrate.

    Science.gov (United States)

    Jeong, Sunho; Song, Hae Chun; Lee, Won Woo; Lee, Sun Sook; Choi, Youngmin; Son, Wonil; Kim, Eui Duk; Paik, Choon Hoon; Oh, Seok Heon; Ryu, Beyong-Hwan

    2011-03-15

    With the aim of inkjet printing highly conductive and well-defined Cu features on plastic substrates, aqueous based Cu ink is prepared for the first time using water-soluble Cu nanoparticles with a very thin surface oxide layer. Owing to the specific properties, high surface tension and low boiling point, of water, the aqueous based Cu ink endows a variety of advantages over conventional Cu inks based on organic solvents in printing narrow conductive patterns without irregular morphologies. It is demonstrated how the design of aqueous based ink affects the basic properties of printed conductive features such as surface morphology, microstructure, conductivity, and line width. The long-term stability of aqueous based Cu ink against oxidation is analyzed through an X-ray photoelectron spectroscopy (XPS) based investigation on the evolution of the surface oxide layer in the aqueous based ink.

  20. Self-assembly behavior of well-defined polymethylene-block-poly(ethylene glycol) copolymers in aqueous solution

    KAUST Repository

    Alkayal, Nazeeha

    2016-09-22

    A series of well-defined amphiphilic polymethylene-b-poly(ethylene glycol) (PM-b-PEG) diblock copolymers, with different hydrophobic chain length, were synthesized by combining Diels-Alder reaction with polyhomologation. The successful synthetic procedure was confirmed by size-exclusion chromatography (SEC) and 1H NMR spectroscopy. These block copolymers self-assembled into spherical micelles in aqueous solutions and exhibit low critical micelle concentration (CMC) of 2–4 mg/mL, as determined by fluorescence spectroscopy using pyrene as a probe. Measurements of the micelle hydrodynamic diameters, performed by dynamic light scattering (DLS), cryo-transmission electron microscopy (cryo-TEM) and atomic force microscopy (AFM), revealed a direct dependence of the micelle size from the polymethylene block length.

  1. Synthesis of Well-Defined Polybenzamide-block-Polystyrene by Combination of Chain-Growth Condensation Polymerization and RAFT Polymerization.

    Science.gov (United States)

    Masukawa, Tomohiro; Yokoyama, Akihiro; Yokozawa, Tsutomu

    2009-08-18

    Well-defined diblock copolymers composed of poly(N-octylbenzamide) and polystyrene were synthesized by reversible addition-fragmentation chain transfer (RAFT) polymerization of styrene with a polyamide chain transfer agent (CTA) prepared via chain-growth condensation polymerization. Synthesis of a dithioester-type macro-CTA possessing the polyamide segment as an activating group was unsatisfactory due to side reactions and incomplete introduction of the benzyl dithiocarbonyl unit. On the other hand, a dithiobenzoate-CTA containing poly(N-octylbenzamide) as a radical leaving group was easily synthesized, and the RAFT polymerization of styrene with this CTA afforded poly(N-octylbenzamide)-block-polystyrene with controlled molecular weight and narrow polydispersity. Copyright © 2009 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Synthesis and Characterization of Well-Defined Regular Star Polyisoprenes with 3, 4, 6 and 8 Arms

    KAUST Repository

    Ratkanthwar, Kedar R.

    2013-01-01

    Three series of regular well-defined star polyisoprenes (PIs) with 3, 4 and 6 arms (each series: same arm molecular weight) have been synthesized by anionic polymerization high vacuum techniques and chlorosilane chemistry. In addition, three linear PIs with practically the double arm molecular weight of the corresponding series (2-arm star PIs) have been synthesized, as well as one 8-arm star PI. All intermediate (arms) and final (stars) products have been characterized by size exclusion chromatography (SEC), SEC-multi-angle laser light scattering (SEC-MALLS) and nuclear magnetic resonance (NMR) spectroscopy. The Tg of the star PIs was determined by differential scanning calorimetry. These model polymeric materials are essential for polymer physics and polymer physical chemistry in order to establish the structure/property relationships.

  3. Well-defined and high resolution Pt nanowire arrays for a high performance hydrogen sensor by a surface scattering phenomenon.

    Science.gov (United States)

    Yoo, Hae-Wook; Cho, Soo-Yeon; Jeon, Hwan-Jin; Jung, Hee-Tae

    2015-02-03

    Developing hydrogen (H2) sensors with a high sensitivity, rapid response, long-term stability, and high throughput is one of the critical issues in energy and environmental technology [Hübert et al. Sens. Actuators, B 2011, 157, 329]. To date, H2 sensors have been mainly developed using palladium (Pd) as the channel material because of its high selectivity and strong affinity to the H2 molecule [(Xu et al. Appl. Phys. Lett. 2005, 86, 203104), (Offermans et al. Appl. Phys. Lett. 2009, 94, 223110), (Yang et al. Nano Lett. 2009, 9, 2177), (Yang et al. ACS Nano 2010, 4, 5233), and (Zou et al. Chem. Commun. 2012, 48, 1033)]. Despite significant progress in this area, Pd based H2 sensors suffer from fractures on their structure due to hydrogen adsorption induced volumetric swelling during the α → β phase transition, leading to poor long-term stability and reliability [(Favier et al. Science 2001, 293, 2227), (Walter et al. Microelectron. Eng. 2002, 61–62, 555), and (Walter et al. Anal. Chem. 2002, 74, 1546)]. In this study, we developed a platinum (Pt) nanostructure based H2 sensor that avoids the stability limitations of Pd based sensors. This sensor exhibited an excellent sensing performance, low limit of detection (LOD, 1 ppm), reproducibility, and good recovery behavior at room temperature. This Pt based H2 sensor relies on a highly periodic, small cross sectional dimension (10–40 nm) and a well-defined configuration of Pt nanowire arrays over a large area. The resistance of the Pt nanowire arrays significantly decreased upon exposure to H2 due to reduced electron scattering in the cross section of the hydrogen adsorbed Pt nanowires, as compared to the oxygen terminated original state. Therefore, these well-defined Pt nanowire arrays prepared using advanced lithographic techniques can facilitate the production of high performance H2 sensors.

  4. Well-defined block copolymers for gene delivery to dendritic cells: probing the effect of polycation chain-length.

    Science.gov (United States)

    Tang, Rupei; Palumbo, R Noelle; Nagarajan, Lakshmi; Krogstad, Emily; Wang, Chun

    2010-03-03

    The development of safe and efficient polymer carriers for DNA vaccine delivery requires mechanistic understanding of structure-function relationship of the polymer carriers and their interaction with antigen-presenting cells. Here we have synthesized a series of diblock copolymers with well-defined chain-length using atom transfer radical polymerization and characterized the influence of polycation chain-length on the physico-chemical properties of the polymer/DNA complexes as well as the interaction with dendritic cells. The copolymers consist of a hydrophilic poly(ethylene glycol) block and a cationic poly(aminoethyl methacrylate) (PAEM) block. The average degree of polymerization (DP) of the PAEM block was varied among 19, 39, and 75, with nearly uniform distribution. With increasing PAEM chain-length, polyplexes formed by the diblock copolymers and plasmid DNA had smaller average particle size and showed higher stability against electrostatic destabilization by salt and heparin. The polymers were not toxic to mouse dendritic cells (DCs) and only displayed chain-length-dependent toxicity at a high concentration (1mg/mL). In vitro gene transfection efficiency and polyplex uptake in DCs were also found to correlate with chain-length of the PAEM block with the longer polymer chain favoring transfection and cellular uptake. The polyplexes induced a modest up-regulation of surface markers for DC maturation that was not significantly dependent on PAEM chain-length. Finally, the polyplex prepared from the longest PAEM block (DP of 75) achieved an average of 20% enhancement over non-condensed anionic dextran in terms of uptake by DCs in the draining lymph nodes 24h after subcutaneous injection into mice. Insights gained from studying such structurally well-defined polymer carriers and their interaction with dendritic cells may contribute to improved design of practically useful DNA vaccine delivery systems. Copyright 2009 Elsevier B.V. All rights reserved.

  5. Mesoporous Silica Supported Pd-MnOx Catalysts with Excellent Catalytic Activity in Room-Temperature Formic Acid Decomposition

    Science.gov (United States)

    Jin, Min-Ho; Oh, Duckkyu; Park, Ju-Hyoung; Lee, Chun-Boo; Lee, Sung-Wook; Park, Jong-Soo; Lee, Kwan-Young; Lee, Dong-Wook

    2016-09-01

    For the application of formic acid as a liquid organic hydrogen carrier, development of efficient catalysts for dehydrogenation of formic acid is a challenging topic, and most studies have so far focused on the composition of metals and supports, the size effect of metal nanoparticles, and surface chemistry of supports. Another influential factor is highly desired to overcome the current limitation of heterogeneous catalysis for formic acid decomposition. Here, we first investigated the effect of support pore structure on formic acid decomposition performance at room temperature by using mesoporous silica materials with different pore structures such as KIE-6, MCM-41, and SBA-15, and achieved the excellent catalytic activity (TOF: 593 h-1) by only controlling the pore structure of mesoporous silica supports. In addition, we demonstrated that 3D interconnected pore structure of mesoporous silica supports is more favorable to the mass transfer than 2D cylindrical mesopore structure, and the better mass transfer provides higher catalytic activity in formic acid decomposition. If the pore morphology of catalytic supports such as 3D wormhole or 2D cylinder is identical, large pore size combined with high pore volume is a crucial factor to achieve high catalytic performance.

  6. Well-defined Polymethylene-Based Co/Terpolymers by Combining Anthracene/Maleimide Diels-Alder Reaction with Polyhomologation

    KAUST Repository

    Hadjichristidis, Nikolaos

    2015-05-26

    A novel strategy towards well-defined polymethylene-based co/terpolymers, by combining anthracene/maleimide Diels-Alder reaction with polyhomologation, is presented. For the synthesis of diblock copolymers the following approach was applied: a) synthesis of α-anthracene-ω-hydroxy- polymethylene by polyhomologation using tri (9-anthracene-methyl propyl ether) borane as initiator, b) synthesis of furan-protected-maleimide-terminated poly (ε-caprolactone) or polyethylene glycol and c). Diels-Alder reaction between the anthracene and maleimide-terminated polymers. In the case of triblock terpolymers the α-anthracene-ω-hydroxy-polymethylene was used as macroinitiator for the ring-opening polymerization of D, L-lactide to afford an anthracene-terminated PM-b-PLA copolymer, followed by Diels-Alder reaction with furan-protected maleimide-terminated poly (ε-caprolactone) or polyethylene glycol to give the triblock terpolymers. All intermediate and final products were characterized by SEC, 1H NMR, UV-VIS spectroscopy and DSC.

  7. Well-defined triblock copolymers of polyethylene with polycaprolactone or polystyrene using a novel difunctional polyhomologation initiator

    KAUST Repository

    Hadjichristidis, Nikolaos

    2017-08-04

    α,ω-Dihydroxy polyethylene was synthesized by polyhomologation of dimethylsulfoxonium methylide with 9-thexyl-9-BBN (9-BNN: 9-Borabicyclo[3.3.1]nonane), a novel difunctional initiator produced from 9-BBN and 2,3-dimethylbut-2-ene, with two active and one blocked sites, followed by hydrolysis/oxidation. The terminal hydroxy groups were either used directly as initiators, in the presence of 1-tert-butyl-2,2,4,4,4-pentakis(dimethylamino)-2λ5,4λ5-catenadi(phosphazene) (t-BuP2), for the ring opening polymerization of ɛ-caprolactone to afford polycaprolactone-b-polyethylene-b-polycaprolactone (PCL-b-PE-b-PCL) or after transformation to atom transfer radical polymerization initiating sites, for the polymerization of styrene to produce polystyrene-b-polyethylene-b-polystyrene (PSt-b-PE-b-PSt) triblock copolymers. Molecular characterization by 11B, 13C and 1H NMR as well as FTIR, and high temperature GPC (HT-GPC) confirmed the well-defined nature of the synthesized new difunctional initiator and triblock copolymers. Differential scanning calorimetry was used to determine the melting points of PE and PCL.

  8. A New Synthetic Route to Microporous Silica with Well-Defined Pores by Replication of a Metal-Organic Framework.

    Science.gov (United States)

    Kondo, Atsushi; Hall, Anthony Shoji; Mallouk, Thomas E; Maeda, Kazuyuki

    2015-08-17

    Microporous amorphous hydrophobic silica materials with well-defined pores were synthesized by replication of the metal-organic framework (MOF) [Cu3 (1,3,5-benzenetricarboxylate)2 ] (HKUST-1). The silica replicas were obtained by using tetramethoxysilane or tetraethoxysilane as silica precursors and have a micro-meso binary pore system. The BET surface area, the micropore volume, and the mesopore volume of the silica replica, obtained by means of hydrothermal treatment at 423 K with tetraethoxysilane, are 620 m(2) g(-1) , 0.18 mL g(-1) , and 0.55 mL g(-1) , respectively. Interestingly, the silica has micropores with a pore size of 0.55 nm that corresponds to the pore-wall thickness of the template MOF. The silica replica is hydrophobic, as confirmed by adsorption analyses, although the replica has a certain amount of silanol groups. This hydrophobicity is due to the unique condensation environment of the silica precursors in the template MOF. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. Syntheses and Post-Polymerization Modifications of Well-Defined Styrenic Polymers Containing Three-Membered Heterocyclic Functionalities

    Science.gov (United States)

    McLeod, David Charles

    Macromolecules that contain electrophilic moieties, such as benzyl halides, activated esters, and epoxides, will readily undergo efficient nucleophilic substitution reactions with a wide variety of compounds under mild conditions, and are therefore ideally suited to act as "universal" precursors to functional materials. Epoxide-containing polymers derived from the radical polymerization of commercially-available glycidyl methacrylate are often employed in this role; however, methacrylic polymers suffer from certain limitations as a result of the incorporated ester groups, which are not stabile in the presence of strong nucleophiles, acids, bases, or esterase enzymes. Styrenic polymers that do not contain labile carbonyl moieties are usually the precursors of choice when high chemical stability is desired in the end product, but the production of functional materials from epoxide-containing styrenic polymers is relatively unexplored. In this dissertation, improved methods were developed for synthesizing 4-vinylphenyloxirane (4VPO) and 4-vinylphenyl glycidyl ether (4VPGE), two of the better-known epoxide-containing styrenic monomers, in high-yield and purity. Well-defined, epoxide-containing styrenic polymers with targeted molecular weights, narrow molecular weight distributions, and controlled architectures (specifically, linear and star-shaped homopolymers, as well as linear block copolymers with styrene) were produced from 4VPO and 4VPGE for the first time using reversible-deactivation radical polymerization techniques, such as low-catalyst-concentration atom transfer radical polymerization (LCC ATRP) and reversible addition-fragmentation chain-transfer (RAFT) polymerization. The robust nature and utility of poly4VPO and poly4VPGE were then demonstrated by the efficient, ring-opening modification of the pendant epoxide groups with a structurally- and functionally-diverse array of alcohols under acidic conditions at ambient temperature. The macromolecular

  10. Synthesis and characterization of well-defined hydrogel matrices and their application to intestinal stem cell and organoid culture.

    Science.gov (United States)

    Gjorevski, Nikolce; Lutolf, Matthias P

    2017-11-01

    Growing cells within an extracellular matrix-like 3D gel is required for, or can improve, the growth of many cell types ex vivo. Here, we describe a protocol for the generation of well-defined matrices for the culture of intestinal stem cells (ISCs) and intestinal organoids. These matrices comprise a poly(ethylene glycol) (PEG) hydrogel backbone functionalized with minimal adhesion cues including RGD (Arg-Gly-Asp), which is sufficient for ISC expansion, and laminin-111, which is required for organoid formation. As such, the hydrogels present a defined and reproducible, but also tunable, environment, allowing researches to manipulate physical and chemical parameters, and examine their influence on ISC and organoid growth. Hydrogels are formed by an enzymatic cross-linking reaction of multiarm PEG precursors bearing glutamine- and lysine-containing peptides. PEG precursors containing either stable or hydrolytically degradable moieties are used to produce mechanically softening hydrogels, which are used for the expansion of ISCs or the formation of organoids, respectively. We also provide protocols for immunofluorescence analysis of cellular structures grown within these matrices, as well as for their dissociation and retrieval of cells for downstream use. Hydrogel precursors can be produced and their mechanical properties characterized to ascertain stiffness within 5-7 d. Hydrogel formation for ISC expansion or organoid formation takes 1-2 h. The materials described here can be readily adapted for the culture of other types of normal or transformed organoid structures.

  11. Well-Defined Bilayered Molecular Cobrushes with Internal Polyethylene Blocks and ω-Hydroxyl-Functionalized Polyethylene Homobrushes

    KAUST Repository

    Zhang, Hefeng

    2016-02-15

    Novel well-defined bilayered molecular cobrushes with internal polyethylene blocks, P(PEcore-b-PScorona) (PE: polyethylene; PS: polystyrene), and ω-hydroxyl-functionalized polyethylene homobrushes, P(PE-OH), were synthesized through the macromonomer strategy. Two main steps were involved in the synthesis of the P(PEcore-b-PScorona) bilayered cobrushes: (i) formation of norbornyl-terminated macromonomer (Nor-PE-b-PS) by esterification of PS-b-PE-OH (combination of anionic polymerization, hydroboration, and polyhomologation) with 5-norbornene-2-carboxylic acid and (ii) ring-opening metathesis polymerization (ROMP) of Nor-PE-b-PS. The synthesis of P(PE-OH) was achieved by (i) hydroboration of tert-butyldimethylsilyl-protected allyl alcohol, followed by polyhomologation of dimethylsulfoxoniun methylide with the formed tri[3-(tert-butyldimethylsilyloxyl)propyl]borane initiator, oxidation/hydrolysis, and esterification of the TBDMS-O-PE-OH with 5-norbornene-2-carboxylic acid to afford the macromonomer TBDMS-O-PE-Nor, and (ii) ROMP of TBDMS-O-PE-Nor, followed by deprotection. Nuclear magnetic resonance spectroscopy (1H and 13C NMR) and high temperature gel permeation chromatography (HT-GPC) were used to characterize all macromonomers/molecular brushes and differential scanning calorimetry (DSC) to study the thermal properties. The molecular brush P(PE-b-PS) showed lower melting point (Tm) and better solubility in toluene than the corresponding macromonomer PS-b-PE-Nor. In the case of homobrushes, the thermal properties were strongly affected by the presence of the PE end-groups. © 2016 American Chemical Society.

  12. Optimization of the alpha image reconstruction - an iterative CT-image reconstruction with well-defined image quality metrics.

    Science.gov (United States)

    Lebedev, Sergej; Sawall, Stefan; Knaup, Michael; Kachelrieß, Marc

    2017-09-01

    Optimization of the AIR-algorithm for improved convergence and performance. The AIR method is an iterative algorithm for CT image reconstruction. As a result of its linearity with respect to the basis images, the AIR algorithm possesses well defined, regular image quality metrics, e.g. point spread function (PSF) or modulation transfer function (MTF), unlike other iterative reconstruction algorithms. The AIR algorithm computes weighting images α to blend between a set of basis images that preferably have mutually exclusive properties, e.g. high spatial resolution or low noise. The optimized algorithm uses an approach that alternates between the optimization of rawdata fidelity using an OSSART like update and regularization using gradient descent, as opposed to the initially proposed AIR using a straightforward gradient descent implementation. A regularization strength for a given task is chosen by formulating a requirement for the noise reduction and checking whether it is fulfilled for different regularization strengths, while monitoring the spatial resolution using the voxel-wise defined modulation transfer function for the AIR image. The optimized algorithm computes similar images in a shorter time compared to the initial gradient descent implementation of AIR. The result can be influenced by multiple parameters that can be narrowed down to a relatively simple framework to compute high quality images. The AIR images, for instance, can have at least a 50% lower noise level compared to the sharpest basis image, while the spatial resolution is mostly maintained. The optimization improves performance by a factor of 6, while maintaining image quality. Furthermore, it was demonstrated that the spatial resolution for AIR can be determined using regular image quality metrics, given smooth weighting images. This is not possible for other iterative reconstructions as a result of their non linearity. A simple set of parameters for the algorithm is discussed that provides

  13. Optimization of the alpha image reconstruction. An iterative CT-image reconstruction with well-defined image quality metrics

    Energy Technology Data Exchange (ETDEWEB)

    Lebedev, Sergej; Sawall, Stefan; Knaup, Michael; Kachelriess, Marc [German Cancer Research Center, Heidelberg (Germany).

    2017-10-01

    Optimization of the AIR-algorithm for improved convergence and performance. TThe AIR method is an iterative algorithm for CT image reconstruction. As a result of its linearity with respect to the basis images, the AIR algorithm possesses well defined, regular image quality metrics, e.g. point spread function (PSF) or modulation transfer function (MTF), unlike other iterative reconstruction algorithms. The AIR algorithm computes weighting images α to blend between a set of basis images that preferably have mutually exclusive properties, e.g. high spatial resolution or low noise. The optimized algorithm uses an approach that alternates between the optimization of rawdata fidelity using an OSSART like update and regularization using gradient descent, as opposed to the initially proposed AIR using a straightforward gradient descent implementation. A regularization strength for a given task is chosen by formulating a requirement for the noise reduction and checking whether it is fulfilled for different regularization strengths, while monitoring the spatial resolution using the voxel-wise defined modulation transfer function for the AIR image. The optimized algorithm computes similar images in a shorter time compared to the initial gradient descent implementation of AIR. The result can be influenced by multiple parameters that can be narrowed down to a relatively simple framework to compute high quality images. The AIR images, for instance, can have at least a 50% lower noise level compared to the sharpest basis image, while the spatial resolution is mostly maintained. The optimization improves performance by a factor of 6, while maintaining image quality. Furthermore, it was demonstrated that the spatial resolution for AIR can be determined using regular image quality metrics, given smooth weighting images. This is not possible for other iterative reconstructions as a result of their non linearity. A simple set of parameters for the algorithm is discussed that provides

  14. Poisoning Experiments Aimed at Discriminating Active and Less-Active Sites of Silica-Supported Tantalum Hydride for Alkane Metathesis

    KAUST Repository

    Saggio, Guillaume

    2010-10-04

    Only 50% of the silica-supported tantalum hydride sites are active in the metathesis of propane. Indeed, more than 45% of the tantalum hydride can be eliminated by a selective oxygen poisoning of inactive sites with no significant decrease in the global turnover. Conversely, cyclopentane induces no such selective poisoning. Hence, the active tantalum hydride sites that show greater resistance to oxygen poisoning correspond to the νTa-H bands of higher wavenumbers, particularly that at 1860cm-1. These active tantalum hydride sites should correspond to tris- or monohydride species relatively far from silica surface oxygen atoms. © 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Point Defect Calculations in Tungsten

    National Research Council Canada - National Science Library

    Danilowicz, Ronald

    1968-01-01

    .... The vacancy migration energy for tungsten was calculated. The calculated value of 1.73 electron volts, together with experimental data, suggests that vacancies migrate in stage III recovery in tungsten...

  16. Silica-Supported Co3O4 Nanoparticles as a Recyclable Catalyst for Rapid Degradation of Azodye

    Directory of Open Access Journals (Sweden)

    Ali Baghban

    2016-10-01

    Full Text Available In this paper, silica nanoparticles with particle size of ~ 10-20 nm were selected as a support for the synthesis of Co3O4 nanoparticles by impregnation of silica nanoparticles in solution of Co(II in a specific concentrations and then calcination to 800 oC. This nanocomposite was then, used as a catalyst for oxidative degradation of methyl orange (MO with ammonium persulfate in aqueous media. Effect of pH, temperature, contact time, amount of oxidant and catalyst were studied in the presence of manuscript. Scanning electron microscope (SEM, electron dispersive spectroscopy (EDS, FT-IR, and ICP-AES analyses were used for analysis of silica-supported Co3O4 (Co3O4/SiO2. Treating MO with ammonium persulfate in the presence of Co3O4/SiO2 led to complete degradation of MO under the optimized conditions. Also, the catalyst exhibited recyclability at least over 10 consecutive runs. Copyright © 2016 BCREC GROUP. All rights reserved Received: 12nd December 2015; Revised: 27th January 2016; Accepted: 27th January 2016 How to Cite: Baghban, A., Doustkhah, E., Rostamnia, S., Aghbash, K.O. (2016. Silica-Supported Co3O4 Nanoparticles as a Recyclable Catalyst for Rapid Degradation of Azodye. Bulletin of Chemical Reaction Engineering & Catalysis, 11 (3: 284-291 (doi:10.9767/bcrec.11.3.568.284-291 Permalink/DOI: http://doi.org/10.9767/bcrec.11.3.568.284-291

  17. Surface modification with well-defined biocompatible triblock copolymers Improvement of biointerfacial phenomena on a poly(dimethylsiloxane) surface.

    Science.gov (United States)

    Iwasaki, Yasuhiko; Takamiya, Mika; Iwata, Ryoko; Yusa, Shin-Ichi; Akiyoshi, Kazunari

    2007-06-15

    To improve interfacial phenomena of poly(dimethylsiloxane) (PDMS) as biomaterials, well-defined triblock copolymers were prepared as coating materials by reversible addition-fragmentation chain transfer (RAFT) controlled polymerization. Hydroxy-terminated poly(vinylmethylsiloxane-co-dimethylsiloxane) (HO-PV(l)D(m)MS-OH) was synthesized by ring-opening polymerization. The copolymerization ratio of vinylmethylsiloxane to dimethylsiloxane was 1/9. The molecular weight of HO-PV(l)D(m)MS-OH ranged from (1.43 to 4.44)x10(4), and their molecular weight distribution (M(w)/M(n)) as determined by size-exclusion chromatography equipped with multiangle laser light scattering (SEC-MALS) was 1.16. 4-Cyanopentanoic acid dithiobenzoate was reacted with HO-PV(l)D(m)MS-OH to obtain macromolecular chain transfer agents (macro-CTA). 2-Methacryloyloxyethyl phosphorylcholine (MPC) was polymerized with macro-CTAs. The gel-permeation chromatography (GPC) chart of synthesized polymers was a single peak and M(w)/M(n) was relatively narrow (1.3-1.6). Then the poly(MPC) (PMPC)-PV(l)D(m)MS-PMPC triblock copolymers were synthesized. The molecular weight of PMPC in a triblock copolymer was easily controllable by changing the polymerization time or the composition of the macro-CTA to a monomer in the feed. The synthesized block copolymers were slightly soluble in water and extremely soluble in ethanol and 2-propanol. Surface modification was performed via hydrosilylation. The block copolymer was coated on the PDMS film whose surface was pretreated with poly(hydromethylsiloxane). The surface wettability and lubrication of the PDMS film were effectively improved by immobilization with the block copolymers. In addition, the number of adherent platelets from human platelet-rich plasma (PRP) was dramatically reduced by surface modification. Particularly, the triblock copolymer having a high composition ratio of MPC units to silicone units was effective in improving the surface properties of PDMS. By

  18. OPAL Silicon Tungsten Luminometer

    CERN Multimedia

    OPAL was one of the four experiments installed at the LEP particle accelerator from 1989 - 2000. The Silicon Tungsten Luminometer was part of OPAL's calorimeter which was used to measure the energy of particles. Most particles end their journey in calorimeters. These detectors measure the energy deposited when particles are slowed down and stopped.

  19. How NO affects nickel and cobalt nitrates at low temperatures to arrive at highly dispersed silica-supported nickel and cobalt catalysts

    NARCIS (Netherlands)

    Wolters, M.|info:eu-repo/dai/nl/304829560; Munnik, P.|info:eu-repo/dai/nl/328228524; Bitter, J.H.|info:eu-repo/dai/nl/160581435; de Jongh, P.E.|info:eu-repo/dai/nl/186125372; de Jong, K.P.|info:eu-repo/dai/nl/06885580X

    2011-01-01

    Impregnation of porous silica supports with cobalt and nickel nitrate precursor solutions is a convenient method to prepare supported nickel and cobalt (oxide) catalysts. However, the metal (oxide) dispersion obtained is highly dependent on the gas atmosphere during thermal treatment to convert the

  20. Amine grafted silica supported CrAuPd alloy nanoparticles: superb heterogeneous catalysts for the room temperature dehydrogenation of formic acid.

    Science.gov (United States)

    Yurderi, Mehmet; Bulut, Ahmet; Caner, Nurdan; Celebi, Metin; Kaya, Murat; Zahmakiran, Mehmet

    2015-07-21

    Herein we show that a previously unappreciated combination of CrAuPd alloy nanoparticles and amine-grafted silica support facilitates the liberation of CO-free H2 from dehydrogenation of formic acid with record activity in the absence of any additives at room temperature. Furthermore, their excellent catalytic stability makes them isolable and reusable heterogeneous catalysts in the formic acid dehydrogenation.

  1. Hydration effects on the molecular structure of silica-supported vanadium oxide catalysts: A combined IR, Raman, UV–vis and EXAFS study

    NARCIS (Netherlands)

    Keller, D.E.; Visser, T.|info:eu-repo/dai/nl/110288327; Soulimani, F.|info:eu-repo/dai/nl/313889449; Koningsberger, D.C.|info:eu-repo/dai/nl/073704342; Weckhuysen, B.M.|info:eu-repo/dai/nl/285484397

    2007-01-01

    The effect of hydration on the molecular structure of silica-supported vanadium oxide catalysts with loadings of 1–16 wt.% V has been systematically investigated by infrared, Raman, UV–vis and EXAFS spectroscopy. IR and Raman spectra recorded during hydration revealed the formation of V–OH groups,

  2. Macromolecular Engineering: New Routes Towards the Synthesis of Well-??Defined Polyethers/Polyesters Co/Terpolymers with Different Architectures

    KAUST Repository

    Alamri, Haleema

    2016-05-18

    The primary objective of this research was to develop a new and efficient pathway for well-defined multicomponent homo/co/terpolymers of cyclic esters/ethers using an organocatalytic approach with an emphasis on the macromolecular engineering aspects of the overall synthesis. Macromolecular engineering (as discussed in the first chapter) of homo/copolymers refers to the specific tailoring of these materials for achieving an easy and reproducible synthesis that results in precise molecular characteristics, i.e. molecular weight and polydispersity, as well as specific structure and end?group choices. Precise control of these molecular characteristics will provide access to new materials that can be used for pre-targeted purposes such as biomedical applications. Among the most commonly used engineering materials are polyesters (biocompatible and biodegradable) and polyethers (biocompatible), either as homopolymers or when or copolymers with linear structures. The ability to create non-linear structures, for example stars, will open new horizons in the applications of these important polymeric materials. The second part of this thesis describes the synthesis of aliphatic polyesters, particularly polycaprolactone and polylactide, using a metal-free initiator/catalyst system. A phosphazene base (t?BuP2) was used as the catalyst for the ring-opening copolymerization of ?-aprolactone (??CL) and L,Lactide (LLA) at room temperature with a variety of protic initiators in different solvents. These studies provided important information for the design of a metal-free route toward the synthesis of polyester?based (bio) materials. The third part of the thesis describes a novel route for the one?pot synthesis of polyether-b polyester block copolymers with either a linear or a specific macromolecular architecture. Poly (styrene oxide)?b?poly(caprolactone)?b?poly(L,lactide) was prepared using this method with the goal of synthesizing poly(styrene oxide)-based materials since this

  3. Cationic Tungsten(VI) Penta-Methyl Complex: Synthesis, Characterization and its Application in Olefin Metathesis Reaction

    OpenAIRE

    Dey Raju; Samantaray Manoja K.; Callens Emmanuel; Hamieh Ali; Emwas Abdul-Hamid M.; Abou-hamad Edy; Kavitake Santosh; Basset Jean-Marie

    2016-01-01

    Tungsten-hexa-methyl readily reacts with B(C6F5)3 in dichloromethane and generates the corresponding well-defined cationic tungsten-penta-methyl complex which was identified precisely by 1H NMR, 13C NMR, 1H-13C NMR correlation spectroscopy. Unlike WMe6, this cationic complex has low energy barrier to form tungsten carbene intermediate, which was further supported by the fact that WMe6 alone has no activity in olefin metathesis reaction whereas the cationic complex shows catalytic activity for...

  4. Cationic Tungsten(VI Penta-Methyl Complex: Synthesis, Characterization and its Application in Olefin Metathesis Reaction

    Directory of Open Access Journals (Sweden)

    Dey Raju

    2016-03-01

    Full Text Available Tungsten-hexa-methyl readily reacts with B(C6F53 in dichloromethane and generates the corresponding well-defined cationic tungsten-penta-methyl complex which was identified precisely by 1H NMR, 13C NMR, 1H-13C NMR correlation spectroscopy. Unlike WMe6, this cationic complex has low energy barrier to form tungsten carbene intermediate, which was further supported by the fact that WMe6 alone has no activity in olefin metathesis reaction whereas the cationic complex shows catalytic activity for self-metathesis of 1-octene.

  5. Cationic Tungsten(VI) Penta-Methyl Complex: Synthesis, Characterization and its Application in Olefin Metathesis Reaction

    KAUST Repository

    Dey, Raju

    2016-04-13

    Tungsten-hexa-methyl readily reacts with B(C6F5)3 in dichloromethane and generates the corresponding well-defined cationic tungsten-penta-methyl complex which was identified precisely by 1H NMR, 13C NMR, 1H-13C NMR correlation spectroscopy. Unlike WMe6, this cationic complex has low energy barrier to form tungsten carbene intermediate, which was further supported by the fact that WMe6 alone has no activity in olefin metathesis reaction whereas the cationic complex shows catalytic activity for self-metathesis of 1-octene.

  6. Support effects and reaction mechanism of acetylene trimerization over silica-supported Cu4 clusters: A DFT study

    Science.gov (United States)

    Maleki, Farahnaz; Schlexer, Philomena; Pacchioni, Gianfranco

    2018-02-01

    Oxide-supported Cu nanoparticles and clusters catalyze a variety of important reactions, such as CO/CO2 hydrogenation to methanol. Recent studies demonstrate that also sub-nanometer clusters consisting of only a few atoms can actively catalyze chemical reactions. In this study, we investigate the interaction between Cu4 clusters and silica-surfaces, considering the de-hydroxylated and the fully hydroxylated α-quartz surfaces. We also considered various dopants such as Ti- and Nb-ions substitutional to Si, respectively, in order to see if an electronic change of the support has an effect on the reaction of the supported cluster. We find that hydroxyl groups can enhance the adsorption energy of the cluster, whereas the dopants have only little effects on the adsorption mode of the Cu cluster. On the fully hydroxylated surface, the cluster may react with the hydroxyl groups via reverse hydrogen spillover. Finally, we explore the reactivity of the silica-supported Cu4 cluster in terms of acetylene trimerization, for which extended Cu surfaces have shown catalytic activity. We find that this reaction should occur with activation barriers below 0.8 eV; Nb-doping of the support does not seem to produce any direct effect on the reactivity of the Cu tetramer.

  7. Selective formation of tungsten nanowires

    Directory of Open Access Journals (Sweden)

    Bien Daniel

    2011-01-01

    Full Text Available Abstract We report on a process for fabricating self-aligned tungsten (W nanowires with polycrystalline silicon core. Tungsten nanowires as thin as 10 nm were formed by utilizing polysilicon sidewall transfer technology followed by selective deposition of tungsten by chemical vapor deposition (CVD using WF6 as the precursor. With selective CVD, the process is self-limiting whereby the tungsten formation is confined to the polysilicon regions; hence, the nanowires are formed without the need for lithography or for additional processing. The fabricated tungsten nanowires were observed to be perfectly aligned, showing 100% selectivity to polysilicon and can be made to be electrically isolated from one another. The electrical conductivity of the nanowires was characterized to determine the effect of its physical dimensions. The conductivity for the tungsten nanowires were found to be 40% higher when compared to doped polysilicon nanowires of similar dimensions.

  8. Hydration effects on the molecular structure of silica-supported vanadium oxide catalysts: A combined IR, Raman, UV–vis and EXAFS study

    OpenAIRE

    Keller, D.E.; Visser, T; Soulimani, F.; Koningsberger, D. C.; Weckhuysen, B.M.

    2007-01-01

    The effect of hydration on the molecular structure of silica-supported vanadium oxide catalysts with loadings of 1–16 wt.% V has been systematically investigated by infrared, Raman, UV–vis and EXAFS spectroscopy. IR and Raman spectra recorded during hydration revealed the formation of V–OH groups, characterized by a band at 3660 cm−1. Hydroxylation was found to start instantaneously upon exposure to traces of water, reflecting a very high sensitivity of the supported vanadium oxide catalysts ...

  9. Model arenes hydrogenation with silica-supported rhodium nanoparticles:The role of the silica grains and of the solvent on catalytic activities

    OpenAIRE

    Barthe, Laurie; Denicourt-Nowicki, Audrey; Roucoux, Alain; Philippot, Karine; Chaudret, Bruno; Hemati, Mehrdji

    2009-01-01

    Silica-supported rhodium-based nanoheterogeneous catalysts were easily prepared by impregnation with a pre-stabilized colloidal suspension. The resulting catalysts contain rhodium nanoparticles well-dispersed in the silica pores with a mean size of 5 nm. Influence of the silica grains size and of the solvent was investigated in arenes hydrogenation. It appeared that the size of the silica grains has a minimal influence on the reaction rate but the supported nanocatalysts displayed higher TOFs...

  10. Cooperative effect by monopodal silica-supported niobium com-plexes pairs enhancing catalytic cyclic carbonate production

    KAUST Repository

    D'Elia, Valerio

    2015-05-07

    Recent discoveries highlighted the activity and the intriguing mechanistic features of NbCl5 as a molecular catalyst for the cycloaddition of CO2 and epoxides under ambient conditions. This has inspired the preparation of novel silica supported Nb-species by reacting a molecular niobium precursor [NbCl5•OEt2] with silica dehydroxylated at 700 °C (SiO2-700) or at 200 oC (SiO2-200) to generate diverse surface complexes. The product of the reaction between SiO2-700 and [NbCl5•OEt2] was identified as a monopodal supported surface species [≡SiONbCl4•OEt2] (1a). The reactions of SiO2-200 with the niobium precursor, according to two different protocols, generated surface complexes 2a and 3a presenting significant, but different, populations of the monopodal surface complex along with bipodal [(≡SiO)2NbCl3•OEt2]. 93Nb SSNMR spectra of 1a-3a and 31P SSNMR on their PMe3 derivatives (1b-3b) led to the unambiguous assignment of 1a as a single site, monopodal Nb-species while 2a and 3a were found to present two distinct surface-supported components, with 2a being mostly monopodal [≡SiONbCl4•OEt2] and 3a being mostly bipodal [≡S ONbCl3•OEt2]. Double-quantum/single-quantum 31P NMR correlation experiment carried out on 2b supported the existence of vicinal Nb centers on the silica surface for this species. 1a-3a were active heterogeneous catalysts for the synthesis of propylene carbonate from CO2 and propylene oxide under mild catalytic conditions; the performance of 2a was found to significantly surpass that of 1a and 3a. With the support of a systematic DFT study carried out on model silica surfaces, the observed differences in catalytic efficiency were correlated with an unprece-dented cooperative effect between two neighboring Nb centers on the surface of 2a. This is in an excellent agreement with our previous discoveries regarding the mechanism of the NbCl5 catalyzed cycloaddition in the homogeneous phase.

  11. Successive heterolytic cleavages of H2 achieve N2 splitting on silica-supported tantalum hydrides: A DFT proposed mechanism

    KAUST Repository

    Soláns, Xavier Luis

    2012-07-02

    DFT(B3PW91) calculations have been carried out to propose a pathway for the N2 cleavage by H2 in the presence of silica-supported tantalum hydride complexes [(≡ SiO)2TaHx] that forms [(≡SiO)2Ta(NH)(NH2)] (Science2007, 317, 1056). The calculations, performed on the cluster models {μ-O[(HO)2SiO] 2}TaH1 and {μ-O[(HO)2SiO] 2}TaH3, labelled as (≡SiO)2TaH x (x = 1, 3), show that the direct hydride transfers to coordinated N-based ligands in (≡SiO)2TaH(η2-N2) and (≡SiO)2TaH(η2-HNNH) have high energy barrier barriers. These high energy barriers are due in part to a lack of energetically accessible empty orbitals in the negatively charged N-based ligands. It is shown that a succession of proton transfers and reduction steps (hydride transfer or 2 electron reduction by way of dihydride reductive coupling) to the nitrogen-based ligands leads to more energetically accessible pathways. These proton transfers, which occur by way of heterolytic activation of H2, increase the electrophilicity of the resulting ligand (diazenido, N 2H-, and hydrazido, NHNH2-, respectively) that can thus accept a hydride with a moderate energy barrier. In the case of (≡SiO)2TaH(η2-HNNH), the H 2 molecule that is adding across the Ta-N bond is released after the hydride transfer step by heterolytic elimination from (≡SiO) 2TaH(NH2)2, suggesting that dihydrogen has a key role in assisting the final steps of the reaction without itself being consumed in the process. This partly accounts for the experimental observation that the addition of H2 is needed to convert an intermediate, identified as a diazenido complex [(≡SiO)2TaH(η 2-HNNH)] from its ν(N-H) stretching frequency of 3400 cm -1, to the final product. Throughout the proposed mechanism, the tantalum remains in its preferred high oxidation state and avoids redox-type reactions, which are more energetically demanding. © 2012 American Chemical Society.

  12. A Simple and Universal Gel Permeation Chromatography Technique for Precise Molecular Weight Characterization of Well-Defined Poly(ionic liquid)s

    Energy Technology Data Exchange (ETDEWEB)

    He, Hongkun; Zhong, Mingjiang; Adzima, Brian; Luebke, David; Nulwala, Hunaid; Matyjaszewski, Krzysztof

    2013-03-20

    Poly(ionic liquid)s (PILs) are an important class of technologically relevant materials. However, characterization of well-defined polyionic materials remains a challenge. Herein, we have developed a simple and versatile gel permeation chromatography (GPC) methodology for molecular weight (MW) characterization of PILs with a variety of anions. PILs with narrow MW distributions were synthesized via atom transfer radical polymerization, and the MWs obtained from GPC were further confirmed via nuclear magnetic resonance end group analysis.

  13. PHEA-g-PMMA Well-Defined Graft Copolymer: ATRP Synthesis, Self-Assembly, and Synchronous Encapsulation of Both Hydrophobic and Hydrophilic Guest Molecules.

    Science.gov (United States)

    Ding, Aishun; Xu, Jie; Gu, Guangxin; Lu, Guolin; Huang, Xiaoyu

    2017-10-03

    A series of well-defined amphiphilic graft copolymer bearing a hydrophilic poly(2-hydroxyethyl acrylate) (PHEA) backbone and hydrophobic poly(methyl methacrylate) (PMMA) side chains was synthesized by successive reversible addition-fragmentation chain transfer (RAFT) polymerization and atom transfer radical polymerization (ATRP) through the grafting-from strategy. A well-defined PHEA-based backbone with Cl-containing ATRP initiating group in every repeated unit (M w /M n  = 1.08), poly(2-hydroxyethyl 2-((2-chloropropanoyloxy)methyl)acrylate) (PHECPMA), was first prepared by RAFT homopolymerization of 2-hydroxyethyl 2-((2-chloropropanoyloxy)methyl)acrylate (HECPMA), a Cl-containing trifunctional acrylate. ATRP of methyl methacrylate was subsequently initiated by PHECPMA homopolymer to afford the target well-defined poly(2-hydroxyethyl acrylate)-graft-poly(methyl methacrylate) (PHEA-g-PMMA) graft copolymers (M w /M n  ≤ 1.36) with 34 PMMA side chains and 34 pendant hydroxyls in PHEA backbone using CuCl/dHbpy as catalytic system. The critical micelle concentration (cmc) of the obtained graft copolymer was determined by fluorescence spectroscopy using N-phenyl-1-naphthylamine as probe while micellar morphologies in aqueous media were visualized by transmission electron microscopy. Interestingly, PHEA-g-PMMA graft copolymer could self-assemble into large compound micelles rather than common spherical micelles, which can encapsulate hydrophilic rhodamine 6 G and hydrophobic pyrene separately or simultaneously.

  14. A well-defined Pd hybrid material for the Z-selective semihydrogenation of alkynes characterized at the molecular level by DNP SENS.

    Science.gov (United States)

    Conley, Matthew P; Drost, Ruben M; Baffert, Mathieu; Gajan, David; Elsevier, Cornelis; Franks, W Trent; Oschkinat, Hartmut; Veyre, Laurent; Zagdoun, Alexandre; Rossini, Aaron; Lelli, Moreno; Lesage, Anne; Casano, Gilles; Ouari, Olivier; Tordo, Paul; Emsley, Lyndon; Copéret, Christophe; Thieuleux, Chloé

    2013-09-09

    Direct evidence of the conformation of a Pd-N heterocyclic carbene (NHC) moiety imbedded in a hybrid material and of the Pd-NHC bond were obtained by dynamic nuclear polarization surface-enhanced NMR spectroscopy (DNP SENS) at natural abundance in short experimental times (hours). Overall, this silica-based hybrid material containing well-defined Pd-NHC sites in a uniform environment displays high activity and selectivity in the semihydrogenation of alkynes into Z-alkenes (see figure). Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. A combined UHV-STM-flow cell set-up for electrochemical/electrocatalytic studies of structurally well-defined UHV prepared model electrodes

    DEFF Research Database (Denmark)

    Schnaidt, J.; Beckord, S.; Engstfeld, Albert Kilian

    2017-01-01

    We describe the construction and discuss the performance of a novel combined ultrahigh vacuum (UHV)-electrochemistry set-up, allowing the controlled preparation and structural characterization of complex nanostructured electrode surfaces by high resolution scanning tunnelling microscopy (STM) under...... collector electrode or by differential electrochemical mass spectrometry (DEMS). The potential of the set-up will be illustrated in two electrocatalytic reactions on complex, but structurally well-defined bimetallic electrode surfaces, O-2 reduction on PtxAg1-x/Pt(111) monolayer surface alloys and bulk CO...

  16. Tailor-made starch-based conjugates containing well-defined poly(vinyl acetate and its derivative poly(vinyl alcohol

    Directory of Open Access Journals (Sweden)

    2011-06-01

    Full Text Available Reversible addition-fragmentation chain transfer (RAFT polymerization was adopted to synthesize starch-based conjugates that possessed controllable architecture and properties. Starch-based xanthate agent was prepared and applied as chain transfer agent to conduct the living/controlled polymerization (LCP of vinyl acetate, which generated tailor-made conjugates of starch and well-defined poly(vinyl acetate (SVAc. The relevant derivatives, conjugates of starch and chain length-controlled poly(vinyl alcohol (SVA, were obtained subsequently. Various characterizations such as Fourier transform infrared spectra (FTIR, ultraviolet-visible spectroscopy (UV, proton nuclear magnetic resonance (1H NMR, gel permeation chromatography (GPC, X-ray diffraction (XRD, Thermogravimetric analysis (TGA, and dynamic mechanical thermal analysis (DMTA were performed to examine the structure of intermediates and the starch-based conjugates. Static contact angle measurements revealed that the hydrophilic character of starch-based conjugates was tunable. Well-defined SVAc was amphiphilic and it was able to self-assemble into size controllable micelles, which was verified by contact angles, transmission electron microscopy (TEM and dynamic light scattering (DLS tests. SVA exhibited much higher capability to form physically cross-linked hydrogel than starch did. Both the characteristic of SVAc and SVA were chain length-dependent.

  17. Further development of the tungsten-fibre reinforced tungsten composite

    Energy Technology Data Exchange (ETDEWEB)

    Gietl, Hanns; Hoeschen, Till; Riesch, Johann [Max-Planck-Institut fuer Plasmaphysik, 85748 Garching (Germany); Aumann, Martin; Coenen, Jan [Forschungszentrum Juelich, IEK4, 52425 Juelich (Germany); Huber, Philipp [Lehrstuhl fuer Textilmaschinenbau und Institut fuer Textiltechnik (ITA), 52062 Aachen (Germany); Neu, Rudolf [Max-Planck-Institut fuer Plasmaphysik, 85748 Garching (Germany); Technische Universitaet Muenchen, 85748 Garching (Germany)

    2016-07-01

    For the use in a fusion device tungsten has a unique property combination. The brittleness below the ductile-to-brittle transition temperature and the embrittlement during operation e.g. by overheating, neutron irradiation are the main drawbacks for the use of pure tungsten. Tungsten fibre-reinforced tungsten composites utilize extrinsic mechanisms to improve the toughness. After proofing that this idea works in principle the next step is the conceptual proof for the applicability in fusion reactors. This will be done by producing mock-ups and testing them in cyclic high heat load tests. For this step all constituents of the composite, which are fibre, matrix and interface, and all process steps need to be investigated. Tungsten fibres are investigated by means of tension tests to find the optimum diameter and pretreatment. New interface concepts are investigated to meet the requirements in a fusion reactor, e.g. high thermal conductivity, low activation. In addition weaving processes are evaluated for their use in the fibre preform production. This development is accompanied by an extensive investigation of the materials properties e.g. single fibre tension tests.

  18. A Rare Case of Primary Intrapulmonary Neurilemmoma Diagnosed in a 43-Year-Old Asymptomatic Man with a Well-defined Intrapulmonary Mass.

    Science.gov (United States)

    Chrysikos, Serafeim; Kaponi, Maria; Triantafillidou, Christina; Karampitsakos, Theodoros; Tzouvelekis, Argyrios; Anyfanti, Maria; Marossis, Konstantinos; Konstantinou, Marios; Tringidou, Rodoula; Bouros, Demosthenes; Dimakou, Katerina

    2018-01-01

    Neurilemmoma (NL), also termed schwannoma, presents as a well-circumscribed and encapsulated mass in the human body and is almost always solitary. CT scan of a patient with NL shows a round, ovoid, or lobulated well-demarcated solid mass of soft tissue density. Primary intrathoracic neurogenic tumors location varies. However, the development of such tumors is by far more common in the costovertebral angle of the posterior mediastinum. Here, we report a rare case of a 43-year-old patient, never smoker and previously healthy, who presented with a mass adjacent to the right pulmonary hilum. This was an incidental finding on a chest X-ray after annual checkup at his workplace. The diagnosis was primary intrapulmonary NL. Primary intrapulmonary NL is an extremely rare tumor. However, based on the above, chest CT findings of a well-defined solid mass in an asymptomatic patient should raise the suspicion of NL, irrespective of the tumor localization.

  19. The tungsten metallome of Pyrococcus furiosus

    NARCIS (Netherlands)

    Sevcenco, A.M.; Pinkse, M.W.H.; Bol, E.; Krijger, G.C.; Wolterbeek, H.T.; Verhaert, P.; Hagedoorn, P.L.; Hagen, W.R.

    2009-01-01

    The tungsten metallome of the hyperthermophilic archaeon Pyrococcus furiosus has been investigated using electroanalytical metal analysis and native-native 2D-PAGE with the radioactive tungsten isotope W-187 (t(1/2) = 23.9 h). P. furiosus cells have an intracellular tungsten concentration of 29 mu

  20. The tungsten metallome of Pyrococcus furiosus

    NARCIS (Netherlands)

    Sevcenco, A.M.; Pinkse, M.; Bol, E.; Krijgen, G.; Wolterbeek, H.; Verhaert, P.D.E.M.; Hagedoorn, P.L.; Hagen, W.R.

    2009-01-01

    The tungsten metallome of the hyperthermophilic archaeon Pyrococcus furiosus has been investigated using electroanalytical metal analysis and native–native 2D-PAGE with the radioactive tungsten isotope W-187 (t1/2 = 23.9 h). P. furiosus cells have an intracellular tungsten concentration of 29 mM, of

  1. Method of synthesizing tungsten nanoparticles

    Science.gov (United States)

    Thoma, Steven G; Anderson, Travis M

    2013-02-12

    A method to synthesize tungsten nanoparticles has been developed that enables synthesis of nanometer-scale, monodisperse particles that can be stabilized only by tetrahydrofuran. The method can be used at room temperature, is scalable, and the product concentrated by standard means. Since no additives or stabilizing surfactants are required, this method is particularly well suited for producing tungsten nanoparticles for dispersion in polymers. If complete dispersion is achieved due to the size of the nanoparticles, then the optical properties of the polymer can be largely maintained.

  2. Single Site Silica Supported Tetramethyl Niobium by the SOMC Strategy: Synthesis, Characterization and Structure-Activity Relationship in Ethylene Oligomerization Reaction

    KAUST Repository

    Hamieh, Ali Imad Ali

    2017-06-06

    Silica supported Tetramethyl niobium complex [(≡SiO)NbMe4] 2 has been isolated by surface alkylation of [(≡SiO-)NbCl3Me] 1 with dimethyl zinc in pentane. 1 can be easily synthesized by grafting of NbCl3Me2 on to the surface of partially dehydroxylated silica by the SOMC strategy. Precise structural analysis was carried out by the FTIR, advance solid state NMR, elemental analysis and mass balance techniques (gas quantification after treating 2 with degassed water) . Complex 1 was found to be active in the ethylene oligomerization to produce up to C30, whereas to our surprise complex 2 selectively dimerizes ethylene into 1-butene in the absence of a co-catalyst at the same conversion levels.

  3. HYDROGEN VACANCY INTERACTION IN TUNGSTEN

    NARCIS (Netherlands)

    FRANSENS, [No Value; ELKERIEM, MSA; PLEITER, F

    1991-01-01

    Hydrogen-vacancy interaction in tungsten was investigated by means of the perturbed angular correlation technique, using the isotope In-111 as a probe. Hydrogen trapping at an In-111-vacancy cluster manifests itself as a change of the local electric field gradient, which gives rise to an observable

  4. Tungsten biochemistry of Pyrococcus furiosus

    NARCIS (Netherlands)

    Bevers, L.E.

    2008-01-01

    Tungsten is the heaviest element that exhibits biological activity (atomic number 74), when it is present in an enzyme. It is taken up by cells in the form of tungstate, and it is subsequently processed into an organic cofactor referred to as tungstopterin, which is found as active center in several

  5. Controllable assembly of well-defined monodisperse Au nanoparticles on hierarchical ZnO microspheres for enhanced visible-light-driven photocatalytic and antibacterial activity.

    Science.gov (United States)

    Wang, Yuan; Fang, Hua-Bin; Zheng, Yan-Zhen; Ye, Rongqin; Tao, Xia; Chen, Jian-Feng

    2015-12-07

    A high-efficiency visible-light-driven photocatalyst composed of homogeneously distributed Au nanoparticles (AuNPs) well-defined on hierarchical ZnO microspheres (ZMS) via a controllable layer-by-layer self-assembly technique is demonstrated. The gradual growth of the characteristic absorption bands of Au loaded on ZnO in the visible light region with an increasing number of assemblies indicates the enhancement of the light harvesting ability of the ZMS/Au composites as well as the reproducibility and controllability of the entire assembly process. Results on the photoelectrochemical performance characterized by EIS and transient photocurrent response spectra indicate that the ZMS/Au composites possess increased photoinduced charge separation and transfer efficiency compared to the pure ZMS film. As a result, the hybrid composites exhibited enhanced decomposition activity for methylene blue and salicylic acid as well as antibacterial activity in killing S. aureus and E. coli under visible light irradiation. It can be noted that well-distributed Au components even at a rather low Au/ZnO weight ratio of ∼1.2% also exhibited extraordinary photocatalysis. Such a facile and controllable self-assembly approach may be viable for preparing high-performance visible-light-driven ZMS/Au photocatalysts in a simple and controllable way, and consequently, the technology may extend to other plasmon-enhanced heterostructures made of nanostructured semiconductors and noble metals for great potential application in environmental protection.

  6. A cuboctahedral platinum (Pt79) nanocluster enclosed by well defined facets favours di-sigma adsorption and improves the reaction kinetics for methanol fuel cells.

    Science.gov (United States)

    Mahata, Arup; Choudhuri, Indrani; Pathak, Biswarup

    2015-08-28

    The methanol dehydrogenation steps are studied very systematically on the (111) facet of a cuboctahedral platinum (Pt79) nanocluster enclosed by well-defined facets. The various intermediates formed during the methanol decompositions are adsorbed at the edge and bridge site of the facet either vertically (through C- and O-centres) or in parallel. The di-sigma adsorption (in parallel) on the (111) facet of the nanocluster is the most stable structure for most of the intermediates and such binding improves the interaction between the substrate and the nanocluster and thus the catalytic activity. The reaction thermodynamics, activation barrier, and temperature dependent reaction rates are calculated for all the successive methanol dehydrogenation steps to understand the methanol decomposition mechanism, and these values are compared with previous studies to understand the catalytic activity of the nanocluster. We find the catalytic activity of the nanocluster is excellent while comparing with any previous reports and the methanol dehydrogenation thermodynamics and kinetics are best when the intermediates are adsorbed in a di-sigma manner.

  7. Rational and practical exfoliation of graphite using well-defined poly(3-hexylthiophene) for the preparation of conductive polymer/graphene composite.

    Science.gov (United States)

    Iguchi, Hiroki; Higashi, Chisato; Funasaki, Yuichi; Fujita, Keisuke; Mori, Atsunori; Nakasuga, Akira; Maruyama, Tatsuo

    2017-01-06

    Processing and manipulation of highly conductive pristine graphene in large quantities are still major challenges in the practical application of graphene for electric device. In the present study, we report the liquid-phase exfoliation of graphite in toluene using well-defined poly(3-hexylthiophene) (P3HT) to produce a P3HT/graphene composite. We synthesize and use regioregular P3HT with controlled molecular weights as conductive dispersants for graphene. Simple ultrasonication of graphite flakes with the P3HT successfully produces single-layer and few-layer graphene sheets dispersed in toluene. The produced P3HT/graphene composite can be used as conductive graphene ink, indicating that the P3HT/graphene composite has high electrical conductivity owing to the high conductivity of P3HT and graphene. The P3HT/graphene composite also works as an oxidation-resistant and conductive film for a copper substrate, which is due to the high gas-barrier property of graphene.

  8. A Well-Defined Silicon Nanocone-Carbon Structure for Demonstrating Exclusive Influences of Carbon Coating on Silicon Anode of Lithium-Ion Batteries.

    Science.gov (United States)

    Wang, Chao; Luo, Fei; Lu, Hao; Rong, Xiaohui; Liu, Bonan; Chu, Geng; Sun, Yu; Quan, Baogang; Zheng, Jieyun; Li, Junjie; Gu, Changzhi; Qiu, Xinping; Li, Hong; Chen, Liquan

    2017-01-25

    Nanotechnology and carbon coating have been applied to silicon anodes to achieve excellent lithium-ion batteries, but the exclusive influence of carbon coating on solid-electrolyte interphase (SEI) formation is difficult to exhibit distinctly because of the impurity and morphological irregularity of most nanostructured anodes. Here, we design a silicon nanocone-carbon (SNC-C) composite structure as a model anode to demonstrate the significant influences of carbon coating on SEI formation and electrochemical performance, unaffectedly as a result of pure electrode component and distinctly due to regular nanocone morphology. As demonstrated by morphological and elemental analysis, compared to the SNC electrode, the SNC-C electrode maintains a thinner SEI layer (∼10 nm) and more stable structure during cycling as well as longer cycle life (>725 cycles), higher Coulombic efficiency (>99%), and lower electrode polarization. This well-defined structure clearly shows the interface stability attributed to carbon coating and is promising in fundamental research of the silicon anode.

  9. Magnetic fluid control for viscous loss reduction of high-speed MRF brakes and clutches with well-defined fail-safe behavior

    Science.gov (United States)

    Güth, Dirk; Schamoni, Markus; Maas, Jürgen

    2013-09-01

    No-load losses within brakes and clutches based on magnetorheological fluids are unavoidable and represent a major barrier towards their wide-spread commercial adoption. Completely torque free rotation is not yet possible due to persistent fluid contact within the shear gap. In this paper, a novel concept is presented that facilitates the controlled movement of the magnetorheological fluid from an active, torque-transmitting region into an inactive region of the shear gap. This concept enables complete decoupling of the fluid engaging surfaces such that viscous drag torque can be eliminated. In order to achieve the desired effect, motion in the magnetorheological fluid is induced by magnetic forces acting on the fluid, which requires an appropriate magnetic circuit design. In this investigation, we propose a methodology to determine suitable magnetic circuit designs with well-defined fail-safe behavior. The magnetically induced motion of magnetorheological fluids is modeled by the use of the Kelvin body force, and a multi-physics domain simulation is performed to elucidate various transitions between an engaged and disengaged operating mode. The modeling approach is validated by captured high-speed video frames which show the induced motion of the magnetorheological fluid due to the magnetic field. Finally, measurements performed with a prototype actuator prove that the induced viscous drag torque can be reduced significantly by the proposed magnetic fluid control methodology.

  10. Amphiphilic Fluorescent Well-Defined Living Polymer from Indole-3-Carboxaldehyde and 4-Bromo-1, 8-Naphthalic Anhydride: Synthesis and Characterization

    Directory of Open Access Journals (Sweden)

    Ambika Srivastava

    2014-01-01

    Full Text Available We reported a well-defined amphiphilic fluorescent polymer bearing indole repeating units with naphthalimide pendants obtained by ATRP followed by chemical modification. The obtained polymer poly (N-allyl indole-2-(4-hydroxybutyl-1, 8-naphthalimide (PAIHN was characterized by 1H NMR, FTIR, and GPC. The polymer showed a specific fluorescence emission maximum at 538 nm excited at 435 nm in aqueous solution. The amphiphilic nature of the polymer was investigated in aqueous solution using two spectroscopic methods, namely, absorption and emission spectroscopy. The Critical Miceller Concentration values obtained by UV-visible and fluorescence are in good agreement with each other. The micelles were characterized by TEM at concentration of 0.014 mg/mL. The polymer PAIHN prepared after tweaking exhibits green fluorescence at 538 nm due to the significant effect of naphthalimide moieties, whereas before tweaking the polymer poly (1-allyl indole-3-carbaldehyde (PAIC exhibits blue fluorescence at 425 nm due to indole repeating units of the polymer.

  11. Structural Analysis and Anticoagulant Activities of the Novel Sulfated Fucan Possessing a Regular Well-Defined Repeating Unit from Sea Cucumber

    Directory of Open Access Journals (Sweden)

    Mingyi Wu

    2015-04-01

    Full Text Available Sulfated fucans, the complex polysaccharides, exhibit various biological activities. Herein, we purified two fucans from the sea cucumbers Holothuria edulis and Ludwigothurea grisea. Their structures were verified by means of HPGPC, FT-IR, GC–MS and NMR. As a result, a novel structural motif for this type of polymers is reported. The fucans have a unique structure composed of a central core of regular (1→2 and (1→3-linked tetrasaccharide repeating units. Approximately 50% of the units from L. grisea (100% for H. edulis fucan contain sides of oligosaccharides formed by nonsulfated fucose units linked to the O-4 position of the central core. Anticoagulant activity assays indicate that the sea cucumber fucans strongly inhibit human blood clotting through the intrinsic pathways of the coagulation cascade. Moreover, the mechanism of anticoagulant action of the fucans is selective inhibition of thrombin activity by heparin cofactor II. The distinctive tetrasaccharide repeating units contribute to the anticoagulant action. Additionally, unlike the fucans from marine alga, although the sea cucumber fucans have great molecular weights and affluent sulfates, they do not induce platelet aggregation. Overall, our results may be helpful in understanding the structure-function relationships of the well-defined polysaccharides from invertebrate as new types of safer anticoagulants.

  12. Well-defined 4-arm stars with hydroxy-terminated polyethylene, polyethylene-b-polycaprolactone and polyethylene-b-(polymethyl methacrylate) 2 arms

    KAUST Repository

    Zhang, Zhen

    2016-07-20

    Bis-boron-thexyl-silaboracycle was prepared by hydroboration of 1,4-bis(methyldivinylsilyl)butane with thexylborane and used to initiate the polyhomologation of dimethylsulfoxonium methylide to afford well-defined hydroxy-terminated 4-arm polyethylene (PE) stars. The synthesized PE stars were transformed to (PE-b-PCL)4 starblock copolymers via the ring-opening polymerization of ϵ-caprolactone (CL) initiated by the hydroxyl end groups of (PE-OH)4 in the presence of P2-tBu phosphazene base. Esterification of the hydroxyl groups of the OH-terminated PE star with 2,2-dichloroacetyl chloride led to (PE-Cl2)4 which was used as initiator (eight initiating atom transfer radical polymerization, ATRP, sites) for the synthesis of (PE-b-PMMA2)4 dendrimer-like stars by the ATRP of methyl methacrylate (MMA). All intermediates and final products were characterized by high temperature gel permeation chromatography and proton nuclear magnetic resonance spectroscopy. © 2016 The Royal Society of Chemistry.

  13. Facile Synthesis of Multiblock Copolymers Containing Sequence-Controlled Peptides and Well-Defined Vinyl Polymers by Nitroxide-Mediated Polymerization.

    Science.gov (United States)

    Nishimura, Shin-Nosuke; Higashi, Nobuyuki; Koga, Tomoyuki

    2017-08-10

    Precisely incorporating a wide range of structural and functional multiblocks along a polymer backbone is a significant challenge in polymer chemistry and offers promising opportunities to design highly ordered materials, including controlled polymer folding. Herein, a facile and versatile strategy for preparing functional multiblock copolymers composed of sequential peptides and well-defined vinyl polymers with a narrow polydispersity is reported. Cyclic oligopeptides have been developed that contain an alkoxyamine bond in the framework. By using this type of cyclic initiator, peptide-containing multiblock copolymers are successfully synthesized by nitroxide-mediated polymerization of styrene. To demonstrate the versatility of this method, radical (co)polymerizations were carried out for different monomers (p-chlorostyrene, 4-vinylpyridine, and styrene/acrylonitrile) and by three different cyclic peptide initiators with specific amino acid sequences. The resultant multiblock copolymer is foldable through intramolecular interactions between peptide blocks. It is believed that this approach will significantly advance the field of controlled polymer synthesis for complex structures and single-chain folding. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. Amine-functionalized SBA-15 with uniform morphology and well-defined mesostructure for highly sensitive chemosensors to detect formaldehyde vapor.

    Science.gov (United States)

    Zhu, Yongheng; Li, Hui; Zheng, Qi; Xu, Jiaqiang; Li, Xinxin

    2012-05-22

    Amine-functionalized SBA-15 with uniform morphology and well-defined mesostructure was prepared using a postgrafting route. The morphology, mesostructure, and functionality of the materials were characterized by scanning electron microscopy, transmission electron microscopy, small-angle X-ray scattering, nitrogen adsorption-desorption, Fourier transform infrared spectroscopy, and solid-state nuclear magnetic resonance spectroscopy techniques. The results show that hexagonal lamelliform SBA-15 with a uniform particle size and short vertical channels plays two significant roles in uniformly dispersing amine-functionalizing groups and effectively adjusting the loadings of the functional groups within the mesopore channels. To confirm the potential application of the hybrids in gas sensors, using amine-functionalized SBA-15 as a sensing material and a quartz crystal microbalance as a transducer, a parts per billion level formaldehyde sensor with high sensitivity (response time about 11 s, recovery time about 15 s) and good chemoselectivity was achieved. This material holds great potential in the area of rapid, sensitive, and highly convenient formaldehyde detection.

  15. Well-defined copolymers synthesized by RAFT polymerization as effective modifiers to enhance the photocatalytic performance of TiO{sub 2}

    Energy Technology Data Exchange (ETDEWEB)

    Vasilaki, E., E-mail: euavasilakh@gmail.com [Department of Chemistry, University of Crete, 710 03, Heraklion, Crete (Greece); Center of Materials Technology and Photonics, School of Applied Technology, Technological Educational Institute of Crete, 710 04 Heraklion, Crete (Greece); Kaliva, M. [Institute of Electronic Structure and Laser, Foundation for Research & Technology-Hellas, P.O. Box 1385, Vassilika Vouton, 711 10 Heraklion, Crete (Greece); Department of Materials Science and Technology, University of Crete, 710 03, Heraklion, Crete (Greece); Katsarakis, N. [Center of Materials Technology and Photonics, School of Applied Technology, Technological Educational Institute of Crete, 710 04 Heraklion, Crete (Greece); Institute of Electronic Structure and Laser, Foundation for Research & Technology-Hellas, P.O. Box 1385, Vassilika Vouton, 711 10 Heraklion, Crete (Greece); Vamvakaki, M. [Institute of Electronic Structure and Laser, Foundation for Research & Technology-Hellas, P.O. Box 1385, Vassilika Vouton, 711 10 Heraklion, Crete (Greece); Department of Materials Science and Technology, University of Crete, 710 03, Heraklion, Crete (Greece)

    2017-03-31

    Highlights: • Well-defined, random functional copolymers were synthesized by RAFT polymerization. • Novel TiO{sub 2} particles in-situ modified with copolymers were synthesized. • The hybrid catalysts exhibited reduced aggregation and particle size. • The photocatalytic removal of methylene blue was higher for the hybrid catalysts. - Αbstract: The enhancement of the photocatalytic performance of anatase TiO{sub 2} nanoparticles is demonstrated by a facile route, involving their in-situ surface modification with preformed polymer chains. Random copolymers of poly(ethylene glycol) methyl ether acrylate-co-methacrylic acid (PEGA-co-MAA) or poly(ethylene glycol) methyl ether acrylate-co-dopamine methacrylamide (PEGA-co-DMA) were synthesized by reversible addition−fragmentation chain-transfer (RAFT) polymerization and were bound onto the surface of anatase titania nanoparticles via the “grafting to” method. The hybrid nanocatalysts were characterized by fourier transform infrared spectroscopy, zeta-potential measurements, X-ray powder diffraction, thermogravimetric analysis and transmission electron microscopy. Their photocatalytic performance was evaluated by the decoloration of methylene blue (MB) dye in aqueous media under UV–vis light irradiation. The enhanced photoactivity and reusability of the polymer modified photocatalysts compared to that of bare TiO{sub 2} nanoparticles was attributed to their improved dispersability and colloidal stability, the smaller particle size that leads to a larger surface area and the increased adsorption capacity of the dye onto the polymer modified nanoparticles.

  16. Chitosan encapsulation of essential oil "cocktails" with well-defined binary Zn(II)-Schiff base species targeting antibacterial medicinal nanotechnology.

    Science.gov (United States)

    Halevas, Eleftherios; Nday, Christiane M; Chatzigeorgiou, Evanthia; Varsamis, Vasileios; Eleftheriadou, Despoina; Jackson, Graham E; Litsardakis, Georgios; Lazari, Diamanto; Ypsilantis, Konstantinos; Salifoglou, Athanasios

    2017-11-01

    The advent of biodegradable nanomaterials with enhanced antibacterial activity stands as a challenge to the global research community. In an attempt to pursue the development of novel antibacterial medicinal nanotechnology, we herein a) synthesized ionic-gelated chitosan nanoparticles, b) compared and evaluated the antibacterial activity of essential oils extracted from nine different herbs (Greek origin) and their combinations with a well-defined antibacterial Zn(II)-Schiff base compound, and c) encapsulated the most effective hybrid combination of Zn(II)-essential oils inside the chitosan matrix, thereby targeting well-formulated nanoparticles of distinct biological impact. The empty and loaded chitosan nanoparticles were physicochemically characterized by FT-IR, Thermogravimetric Analysis (TGA), Scanning Electron Microscopy (SEM), with the entrapment and drug release studies being conducted through UV-Visible and atomic absorption techniques. The antimicrobial properties of the novel hybrid materials were demonstrated against Gram positive (S. aureus, B. subtilis, and B. cereus) and Gram negative (E. coli and X. campestris) bacteria using modified agar diffusion methods. The collective physicochemical profile of the hybrid Zn(II)-essential oil cocktails, formulated so as to achieve optimal activity when loaded to chitosan nanoparticles, signifies the importance of design in the development of efficient nanomedicinal pharmaceuticals a) based on both natural products and biogenic metal ionic cofactors, and b) targeting bacterial infections and drug resistance. Copyright © 2017 Elsevier Inc. All rights reserved.

  17. High-Hall-Mobility Al-Doped ZnO Films Having Textured Polycrystalline Structure with a Well-Defined (0001) Orientation.

    Science.gov (United States)

    Nomoto, Junichi; Makino, Hisao; Yamamoto, Tetsuya

    2016-12-01

    Five hundred-nanometer-thick ZnO-based textured polycrystalline films consisting of 490-nm-thick Al-doped ZnO (AZO) films deposited on 10-nm-thick Ga-doped ZnO (GZO) films exhibited a high Hall mobility (μ H) of 50.1 cm(2)/Vs with a carrier concentration (N) of 2.55 × 10(20) cm(-3). Firstly, the GZO films were prepared on glass substrates by ion plating with dc arc discharge, and the AZO films were then deposited on the GZO films by direct current magnetron sputtering (DC-MS). The GZO interface layers with a preferential c-axis orientation play a critical role in producing AZO films with texture development of a well-defined (0001) orientation, whereas 500-nm-thick AZO films deposited by only DC-MS showed a mixture of the c-plane and the other plane orientation, to exhibit a μ H of 38.7 cm(2)/Vs with an N of 2.22 × 10(20) cm(-3).

  18. Bidimensional analysis of the phase behavior of a well-defined surfactant (C10E4)/oil (n-octane)/water-temperature system.

    Science.gov (United States)

    Pizzino, Aldo; Molinier, Valérie; Catté, Marianne; Salager, Jean-Louis; Aubry, Jean-Marie

    2009-12-17

    The equilibrium phase behavior of the well-defined system tetraethyleneglycol decyl ether (C(10)E(4))/n-octane/water (SOW) at variable temperature (T) was revisited by careful analysis of the three bidimensional cuts, namely, the gamma (at constant water-oil ratio), chi (at constant surfactant concentration), and Delta (at constant temperature) plots. A straightforward methodology is reported to determine the frontiers of the triphasic (Winsor III) domain on any cut of the SOW-T phase prism. It comes from the systematic analysis of another cut, here gamma at different water-oil ratios and chi at different surfactant concentrations from the knowledge of Delta cuts at different temperatures. The method has been validated through comparison with experimental results. It enables one to show, for the first time, the evolution of a SOW system three-phase body contours with (i) water-oil ratio, (ii) surfactant concentration, and (iii) temperature. It exhibits a strong impact of the surfactant affinity for the pure oil and water phases on the shape of the phase diagrams. The systematic study of the effect of the surfactant concentration on the aspect of the chi plot sheds light on an unusual shape found at low surfactant concentration.

  19. Rational and practical exfoliation of graphite using well-defined poly(3-hexylthiophene) for the preparation of conductive polymer/graphene composite

    Science.gov (United States)

    Iguchi, Hiroki; Higashi, Chisato; Funasaki, Yuichi; Fujita, Keisuke; Mori, Atsunori; Nakasuga, Akira; Maruyama, Tatsuo

    2017-01-01

    Processing and manipulation of highly conductive pristine graphene in large quantities are still major challenges in the practical application of graphene for electric device. In the present study, we report the liquid-phase exfoliation of graphite in toluene using well-defined poly(3-hexylthiophene) (P3HT) to produce a P3HT/graphene composite. We synthesize and use regioregular P3HT with controlled molecular weights as conductive dispersants for graphene. Simple ultrasonication of graphite flakes with the P3HT successfully produces single-layer and few-layer graphene sheets dispersed in toluene. The produced P3HT/graphene composite can be used as conductive graphene ink, indicating that the P3HT/graphene composite has high electrical conductivity owing to the high conductivity of P3HT and graphene. The P3HT/graphene composite also works as an oxidation-resistant and conductive film for a copper substrate, which is due to the high gas-barrier property of graphene.

  20. Longitudinal and shear wave velocities in pure tungsten and tungsten fiber-reinforced tungsten composites

    Science.gov (United States)

    Lee, H. T.; Ando, S.; Coenen, J. W.; Mao, Y.; Riesch, J.; Gietl, H.; Kasada, R.; Hamaji, Y.; Ibano, K.; Ueda, Y.

    2017-12-01

    Longitudinal and shear wave velocities in pure tungsten and tungsten fiber-reinforced tungsten (Wf/W) composites were studied by laser ultrasonic measurements. The samples were produced from powders or powder/fiber mixtures by spark plasma sintering process. It was found that sintering temperature, as a processing parameter, has the largest effect. Higher sintering temperatures result in faster wave velocities. For example, longitudinal wave velocities and their standard deviations in sintered W at 1800 °C and 2000 °C were 4834 ± 53 m s-1 and 5043 ± 47 m s-1. In comparison, the average longitudinal wave velocity for a polycrystalline reference W was 5227 ± 5 m s-1. The values for Wf/W composites fall between the two sintered samples. However, the thicker Yttria (Y2O3) fiber/matrix interface resulted in faster wave velocities. The elastic moduli were calculated from the sound velocities using average density measurements. The standard relations for isotropic, homogeneous material were used. It was found that the shear, bulk, Young’s modulus are 80%-90% of the values for polycrystalline tungsten, while the temperature dependency from 25 °C to 450 °C is similar.

  1. Tensile behaviour of drawn tungsten wire used in tungsten fibre-reinforced tungsten composites

    Science.gov (United States)

    Riesch, J.; Feichtmayer, A.; Fuhr, M.; Almanstötter, J.; Coenen, J. W.; Gietl, H.; Höschen, T.; Linsmeier, Ch; Neu, R.

    2017-12-01

    In tungsten fibre-reinforced tungsten composites (Wf/W) the brittleness problem of tungsten is solved by utilizing extrinsic toughening mechanisms. The properties of the composite are very much related to the properties of the drawn tungsten wire used as fibre reinforcements. Its high strength and capability of ductile deformation are ideal properties facilitating toughening of Wf/W. Tensile tests have been used for determining mechanical properties and study the deformation and the fracture behaviour of the wire. Tests of as-fabricated and straightened drawn wires with a diameter between 16 and 150 μm as well as wire electrochemically thinned to a diameter of 5 μm have been performed. Engineering stress–strain curves and a microscopic analysis are presented with the focus on the ultimate strength. All fibres show a comparable stress–strain behaviour comprising necking followed by a ductile fracture. A reduction of the diameter by drawing leads to an increase of strength up to 4500 MPa as a consequence of a grain boundary hardening mechanism. Heat treatment during straightening decreases the strength whereas electrochemical thinning has no significant impact on the mechanical behaviour.

  2. Facile preparation of well-defined hydrophilic core-shell upconversion nanoparticles for selective cell membrane glycan labeling and cancer cell imaging.

    Science.gov (United States)

    Zhang, Wanjun; Peng, Bo; Tian, Fang; Qin, Weijie; Qian, Xiaohong

    2014-01-07

    Molecular imaging enables in situ visualization of biomolecules in living organisms and creates numerous opportunities for basic biological research and early disease diagnosis. As luminescent probes for molecular imaging, lanthanide-doped upconversion nanoparticles (UCNPs) exhibit superior performance compared to conventional fluorescent dyes in many ways, including high tissue penetration depth and minimized autofluorescence and photobleaching, making them particularly advantageous for imaging analysis. Although various synthesis methods have been reported, the preparation of high quality, water-soluble UCNPs remains challenging. For in situ imaging, glycans on the cell surface are particularly attractive due to their key roles in cellular activity and disease occurrence and development. However, glycan imaging is a challenging task due to their diverse structures and incompatibility with genetically encoded fluorescent tagging techniques. Herein, we report a new type of highly water-soluble, lectin-functionalized core-shell UCNP synthesized by surface-initiated atom transfer radical polymerization (SI-ATRP) for selective cell membrane glycan labeling and cancer cell imaging. SI-ATRP modification results in controlled growth of hydrophilic polymers on the UCNP surface and well-defined core-shell structure, producing UCNPs with improved biocompatibility and intact luminance property. Furthermore, the numerous functional groups on the polymer brush shell provide a large number of binding sites and 3D support for lectin immobilization. The increased loading density and diversified architecture of the immobilized lectins facilitates multivalent binding between the lectins and the glycans on the cell surface and leads to selective labeling of highly metastatic hepatocellular carcinoma cells (HCCHM3) in vitro and successful in vivo imaging of HCCHM3 inoculated mice.

  3. Surfactant-Free RAFT Emulsion Polymerization of Styrene Using Thermoresponsive macroRAFT Agents: Towards Smart Well-Defined Block Copolymers with High Molecular Weights

    Directory of Open Access Journals (Sweden)

    Steffen Eggers

    2017-12-01

    Full Text Available The combination of reversible addition–fragmentation chain transfer (RAFT and emulsion polymerization has recently attracted much attention as a synthetic tool for high-molecular-weight block copolymers and their micellar nano-objects. Up to recently, though, the use of thermoresponsive polymers as both macroRAFT agents and latex stabilizers was impossible in aqueous media due to their hydrophobicity at the usually high polymerization temperatures. In this work, we present a straightforward surfactant-free RAFT emulsion polymerization to obtain thermoresponsive styrenic block copolymers with molecular weights of around 100 kDa and their well-defined latexes. The stability of the aqueous latexes is achieved by adding 20 vol % of the cosolvent 1,4-dioxane (DOX, increasing the phase transition temperature (PTT of the used thermoresponsive poly(N-acryloylpyrrolidine (PAPy macroRAFT agents above the polymerization temperature. Furthermore, this cosolvent approach is combined with the use of poly(N,N-dimethylacrylamide-block-poly(N-acryloylpiperidine-co-N-acryloylpyrrolidine (PDMA-b-P(APi-co-APy as the macroRAFT agent owning a short stabilizing PDMA end block and a widely adjustable PTT of the P(APi-co-APy block in between 4 and 47 °C. The temperature-induced collapse of the latter under emulsion polymerization conditions leads to the formation of RAFT nanoreactors, which allows for a very fast chain growth of the polystyrene (PS block. In dynamic light scattering (DLS, as well as cryo-transmission electron microscopy (cryoTEM, moreover, all created latexes indeed reveal a high (temperature stability and a reversible collapse of the thermoresponsive coronal block upon heating. Hence, this paper pioneers a versatile way towards amphiphilic thermoresponsive high-molecular-weight block copolymers and their nano-objects with tailored corona switchability.

  4. Solvent-Controlled Branching of Localized versus Delocalized Singlet Exciton States and Equilibration with Charge Transfer in a Structurally Well-Defined Tetracene Dimer

    Energy Technology Data Exchange (ETDEWEB)

    Cook, Jasper D. [Department; Carey, Thomas J. [Department; Arias, Dylan H. [National Renewable Energy Laboratory, Golden, Colorado 80401, United States; Johnson, Justin C. [National Renewable Energy Laboratory, Golden, Colorado 80401, United States; Damrauer, Niels H. [Department

    2017-11-21

    A detailed photophysical picture is elaborated for a structurally well-defined and symmetrical bis-tetracene dimer in solution. The molecule was designed for interrogation of the initial photophysical steps (S1 - 1TT) in intramolecular singlet fission (SF). (Triisopropylsilyl)acetylene substituents on the dimer TIPS-BT1 as well as a monomer model TIPS-Tc enable a comparison of photophysical properties, including transient absorption dynamics, as solvent polarity is varied. In nonpolar toluene solutions, TIPS-BT1 decays via radiative and nonradiative pathways to the ground state with no evidence for dynamics related to the initial stages of SF. This contrasts with the behavior of the previously reported unsubstituted dimer BT1 and is likely a consequence of energetic perturbations to the singlet excited-state manifold of TIPS-BT1 by the (trialkylsilyl)acetylene substituents. In polar benzonitrile, two key findings emerge. First, photoexcited TIPS-BT1 shows a bifurcation into both arm-localized (S1-loc) and dimer-delocalized (S1-dim) singlet exciton states. The S1-loc decays to the ground state, and weak temperature dependence of its emissive signatures suggests that once it is formed, it is isolated from S1-dim. Emissive signatures of the S1-dim state, on the other hand, are strongly temperature-dependent, and transient absorption dynamics show that S1-dim equilibrates with an intramolecular charge-transfer state in 50 ps at room temperature. This equilibrium decays to the ground state with little evidence for formation of long-lived triplets nor 1TT. These detailed studies spectrally characterize many of the key states in intramolecular SF in this class of dimers but highlight the need to tune electronic coupling and energetics for the S1 - 1TT photoreaction.

  5. Gender-specific association between serotonin transporter polymorphisms (5-HTTLPR and rs25531) and neuroticism, anxiety and depression in well-defined healthy Han Chinese.

    Science.gov (United States)

    Chang, Chuan-Chia; Chang, Hsin-An; Fang, Wen-Hui; Chang, Tieh-Ching; Huang, San-Yuan

    2017-01-01

    A tri-allelic serotonin transporter promoter polymorphism (5-HTTLPR/rs25531) more effectively determines the levels of transcriptional efficacy than that with the bi-allelic 5-HTTLPR polymorphism in vitro. Both are reportedly associated with personality traits of negative emotionality, but with conflicting findings. One explanation for this is that a gender difference may play a role in genetic contribution. Here, we hypothesized that the tri-allelic genotype of the serotonin transporter is more closely linked to neuroticism, an anxiety- and depression-related trait, than the bi-allelic variation, particularly in a gender-dependent way. The genotypes of the 5-HTTLPR and rs25531 loci were determined in 1139 well-defined physically and mentally healthy Han Chinese (550 men, 589 women; mean age 38.3±10.3 years). All participants completed the neuroticism measure of the short-form Maudsley Personality Inventory (MPI). The levels of anxiety and depression were assessed by the Beck Anxiety Inventory (BAI) and the Beck Depression Inventory (BDI), respectively. A significant tri-allelic genotype-by-gender interaction effect was found in the MPI-neuroticism measure. S'S' homozygotes were associated with higher neuroticism than L' allele carriers in men. Also, both the BAI and BDI scores were higher in the S'S' homozygotic men. In the bi-allelic analyses, however, there was only an association between SS genotype and MPI-neuroticism in men. Sub-analyses by gender-stratification may reduce the statistical power. Our findings confirm that gender differences exist in the genetic contributions of the serotonin transporter in human neuroticism, and anxiety/depression. Our data provide further support for rs25531, strengthening the effects of 5-HTTLPR. Copyright © 2016 Elsevier B.V. All rights reserved.

  6. A facile approach to TiO2 colloidal spheres decorated with Au nanoparticles displaying well-defined sizes and uniform dispersion.

    Science.gov (United States)

    Damato, Tatiana C; de Oliveira, Caio C S; Ando, Rômulo A; Camargo, Pedro H C

    2013-02-05

    This paper describes a straightforward approach for the synthesis of hybrid materials composed of titanium dioxide (TiO(2)) colloidal spheres decorated with gold nanoparticles (Au NPs). In the reported method, monodisperse TiO(2) colloidal spheres (∼220 nm in diameter) could be directly employed as templates for the nucleation and growth of Au NPs over their surface using AuCl(4)(-)(aq) as the Au precursor, ascorbic acid as the reducing agent, PVP as the stabilizer, and water as the solvent. The Au NPs presented a uniform distribution over the TiO(2) surface. Interestingly, the size of the Au NPs could be controlled by performing sequential reduction steps with AuCl(4)(-)(aq). This method could also be adapted for the production of TiO(2) colloidal spheres decorated with other metal NPs including silver (Ag), palladium (Pd), and platinum (Pt). The catalytic activities of the TiO(2)-Au materials as a function of composition and NPs size were investigated toward the reduction of 4-nitrophenol to 4-aminophenol under ambient conditions. An increase of up to 10.3-fold was observed for TiO(2)-Au relative to TiO(2). A surface-enhanced Raman scattering application for TiO(2)-Au was also demonstrated employing 4-mercaptopyridine as the probe molecule. The results presented herein indicate that our approach may serve as a platform for the synthesis of hybrid materials containing TiO(2) and metal NPs displaying well-defined morphologies, compositions, and sizes. This can have important implications for the design of TiO(2)-based materials with improved performances for photocatalysis and photovoltaic applications.

  7. High field electron paramagnetic resonance spectroscopy under ultrahigh vacuum conditions—A multipurpose machine to study paramagnetic species on well defined single crystal surfaces

    Science.gov (United States)

    Rocker, J.; Cornu, D.; Kieseritzky, E.; Seiler, A.; Bondarchuk, O.; Hänsel-Ziegler, W.; Risse, T.; Freund, H.-J.

    2014-08-01

    A new ultrahigh vacuum (UHV) electron paramagnetic resonance (EPR) spectrometer operating at 94 GHz to investigate paramagnetic centers on single crystal surfaces is described. It is particularly designed to study paramagnetic centers on well-defined model catalysts using epitaxial thin oxide films grown on metal single crystals. The EPR setup is based on a commercial Bruker E600 spectrometer, which is adapted to ultrahigh vacuum conditions using a home made Fabry Perot resonator. The key idea of the resonator is to use the planar metal single crystal required to grow the single crystalline oxide films as one of the mirrors of the resonator. EPR spectroscopy is solely sensitive to paramagnetic species, which are typically minority species in such a system. Hence, additional experimental characterization tools are required to allow for a comprehensive investigation of the surface. The apparatus includes a preparation chamber hosting equipment, which is required to prepare supported model catalysts. In addition, surface characterization tools such as low energy electron diffraction (LEED)/Auger spectroscopy, temperature programmed desorption (TPD), and infrared reflection absorption spectroscopy (IRAS) are available to characterize the surfaces. A second chamber used to perform EPR spectroscopy at 94 GHz has a room temperature scanning tunneling microscope attached to it, which allows for real space structural characterization. The heart of the UHV adaptation of the EPR experiment is the sealing of the Fabry-Perot resonator against atmosphere. To this end it is possible to use a thin sapphire window glued to the backside of the coupling orifice of the Fabry Perot resonator. With the help of a variety of stabilization measures reducing vibrations as well as thermal drift it is possible to accumulate data for a time span, which is for low temperature measurements only limited by the amount of liquid helium. Test measurements show that the system can detect paramagnetic

  8. Synthesis and property investigations of well-defined polymer/inorganic core-shell nanomaterials with structural, optical, electronic and magnetic properties

    Science.gov (United States)

    Gravano, Stefanie Marie

    (methyl methacrylate) (pMMA) which can function as strength enhancers in a material, (2) as wave-guides in electro-optical applications by grafting a non-linear optical (NLO) molecule to a nano-sized core, (3) as a conductive medium by developing a conductive poly(thiophene) (pT) polymerization method to functionalize an core structure, and (4) as a nano-sized magnetic core encased in a well-defined poly(styrene) (pS) matrix.

  9. High field electron paramagnetic resonance spectroscopy under ultrahigh vacuum conditions—A multipurpose machine to study paramagnetic species on well defined single crystal surfaces

    Energy Technology Data Exchange (ETDEWEB)

    Rocker, J.; Cornu, D.; Kieseritzky, E.; Hänsel-Ziegler, W.; Freund, H.-J. [Fritz-Haber-Institut der MPG, Faradayweg 4-6, 14195 Berlin (Germany); Seiler, A. [Fritz-Haber-Institut der MPG, Faradayweg 4-6, 14195 Berlin (Germany); Laboratorium für Applikationen der Synchrotronstrahlung, KIT Campus Süd, Kaiserstr. 12, 76131 Karlsruhe (Germany); Bondarchuk, O. [Fritz-Haber-Institut der MPG, Faradayweg 4-6, 14195 Berlin (Germany); CIC energiGUNE, Parque Tecnologico, C/Albert Einstein 48, CP 01510 Minano (Alava) (Spain); Risse, T., E-mail: risse@chemie.fu-berlin.de [Fritz-Haber-Institut der MPG, Faradayweg 4-6, 14195 Berlin (Germany); Institut für Chemie und Biochemie, Freie Universität Berlin, Takustr. 3, 14195 Berlin (Germany)

    2014-08-01

    A new ultrahigh vacuum (UHV) electron paramagnetic resonance (EPR) spectrometer operating at 94 GHz to investigate paramagnetic centers on single crystal surfaces is described. It is particularly designed to study paramagnetic centers on well-defined model catalysts using epitaxial thin oxide films grown on metal single crystals. The EPR setup is based on a commercial Bruker E600 spectrometer, which is adapted to ultrahigh vacuum conditions using a home made Fabry Perot resonator. The key idea of the resonator is to use the planar metal single crystal required to grow the single crystalline oxide films as one of the mirrors of the resonator. EPR spectroscopy is solely sensitive to paramagnetic species, which are typically minority species in such a system. Hence, additional experimental characterization tools are required to allow for a comprehensive investigation of the surface. The apparatus includes a preparation chamber hosting equipment, which is required to prepare supported model catalysts. In addition, surface characterization tools such as low energy electron diffraction (LEED)/Auger spectroscopy, temperature programmed desorption (TPD), and infrared reflection absorption spectroscopy (IRAS) are available to characterize the surfaces. A second chamber used to perform EPR spectroscopy at 94 GHz has a room temperature scanning tunneling microscope attached to it, which allows for real space structural characterization. The heart of the UHV adaptation of the EPR experiment is the sealing of the Fabry-Perot resonator against atmosphere. To this end it is possible to use a thin sapphire window glued to the backside of the coupling orifice of the Fabry Perot resonator. With the help of a variety of stabilization measures reducing vibrations as well as thermal drift it is possible to accumulate data for a time span, which is for low temperature measurements only limited by the amount of liquid helium. Test measurements show that the system can detect paramagnetic

  10. Terminal uranium(V/VI) nitride activation of carbon dioxide and carbon disulfide. Factors governing diverse and well-defined cleavage and redox reactions

    Energy Technology Data Exchange (ETDEWEB)

    Cleaves, Peter A.; Gardner, Benedict M.; Liddle, Stephen T. [School of Chemistry, The University of Manchester (United Kingdom); Kefalidis, Christos E.; Maron, Laurent [LPCNO, CNRS and INSA, Universite Paul Sabatier, Toulouse (France); Tuna, Floriana; McInnes, Eric J.L. [School of Chemistry and Photon Science Institute, The University of Manchester (United Kingdom); Lewis, William [School of Chemistry, The University of Nottingham (United Kingdom)

    2017-02-24

    The reactivity of terminal uranium(V/VI) nitrides with CE{sub 2} (E=O, S) is presented. Well-defined C=E cleavage followed by zero-, one-, and two-electron redox events is observed. The uranium(V) nitride [U(Tren{sup TIPS})(N)][K(B15C5){sub 2}] (1, Tren{sup TIPS}=N(CH{sub 2}CH{sub 2}NSiiPr{sub 3}){sub 3}; B15C5=benzo-15-crown-5) reacts with CO{sub 2} to give [U(Tren{sup TIPS})(O)(NCO)][K(B15C5){sub 2}] (3), whereas the uranium(VI) nitride [U(Tren{sup TIPS})(N)] (2) reacts with CO{sub 2} to give isolable [U(Tren{sup TIPS})(O)(NCO)] (4); complex 4 rapidly decomposes to known [U(Tren{sup TIPS})(O)] (5) with concomitant formation of N{sub 2} and CO proposed, with the latter trapped as a vanadocene adduct. In contrast, 1 reacts with CS{sub 2} to give [U(Tren{sup TIPS})(κ{sup 2}-CS{sub 3})][K(B15C5){sub 2}] (6), 2, and [K(B15C5){sub 2}][NCS] (7), whereas 2 reacts with CS{sub 2} to give [U(Tren{sup TIPS})(NCS)] (8) and ''S'', with the latter trapped as Ph{sub 3}PS. Calculated reaction profiles reveal outer-sphere reactivity for uranium(V) but inner-sphere mechanisms for uranium(VI); despite the wide divergence of products the initial activation of CE{sub 2} follows mechanistically related pathways, providing insight into the factors of uranium oxidation state, chalcogen, and NCE groups that govern the subsequent divergent redox reactions that include common one-electron reactions and a less-common two-electron redox event. Caution, we suggest, is warranted when utilising CS{sub 2} as a reactivity surrogate for CO{sub 2}. (copyright 2017 Wiley-VCH Verlag GmbH and Co. KGaA, Weinheim)

  11. Generation of Well-Defined Pairs of Silylamine on Highly Dehydroxylated SBA-15: Application to the Surface Organometallic Chemistry of Zirconium

    KAUST Repository

    Azzi, Joachim

    2012-11-01

    Design of a new well-defined surface organometallic species [O-(=Si–NH)2Zr(IV)Np2] has been obtained by reaction of tetraneopentyl zirconium (ZrNp4) on SBA-15 surface displaying mainly silylamine pairs [O-(=Si–NH2)2]. These surface species have been achieved by an ammonia treatment of a highly dehydroxylated SBA-15 at 1000°C (SBA-151000). This support is known to contain mainly strained reactive siloxane bridges (≡Si-O-Si≡)[1] along with a small amount of isolated plus germinal silanols =Si(OH)2. Chemisorption of ammonia occurs primarily by opening these siloxane bridges[2] to generate silanol/silylamine pairs [O-(=Si–NH2)(=SiOH)] followed by substitution of the remaining silanol. Further treatment using hexamethyldisilazane (HMDS) results in the protection of the isolated remaining silanol groups by formation of ≡Si-O-SiMe3 and =Si(OSiMe3)2 but leaves ≡SiNH2 untouched. After reaction of this functionalized surface with ZrNp4, this latter displays mainly a bi-podal zirconium neopentyl organometallic complex [O-(=Si–NH)2Zr(IV)Np2] which has been fully characterized by diverse methods such as infrared transmission spectroscopy, magic angle spinning solid state nuclear magnetic resonance, surface elemental analysis, small angle X-ray powder diffraction (XRD), nitrogen adsorption and energy filtered transmission electron microscopy (EFTEM). These different characterization tools unambiguously prove that the zirconium organometallic complex reacts mostly with silylamine pairs to give a bi-podal zirconium bis-neopentyl complex, uniformly distributed into the channels of SBA-151000. Therefore this new material opens a new promising research area in Surface Organometallic Chemistry which, so far, was dealing mainly with O containing surface. It is expected that vicinal amine functions may play a very different role as compared with classical inorganic supports. Given the importance in the last decades of N containing ligands in catalysis, one may expect

  12. Tungsten foil laminate for structural divertor applications – Joining of tungsten foils

    Energy Technology Data Exchange (ETDEWEB)

    Reiser, Jens, E-mail: jens.reiser@kit.edu [Karlsruhe Institute of Technology (KIT), Institute for Applied Materials (IAM-AWP) (Germany); Rieth, Michael; Möslang, Anton; Dafferner, Bernhard; Hoffmann, Jan [Karlsruhe Institute of Technology (KIT), Institute for Applied Materials (IAM-AWP) (Germany); Mrotzek, Tobias; Hoffmann, Andreas [PLANSEE SE, Reutte (Austria); Armstrong, D.E.J.; Yi, Xiaoou [University of Oxford, Department of Materials (United Kingdom)

    2013-05-15

    This paper is the fourth in our series on tungsten laminates. The aim of this paper is to discuss laminate synthesis, meaning the joining of tungsten foils. It is obvious that the properties of the tungsten laminate strongly depend on the combination of (i) interlayer and (ii) joining technology, as this combination defines (i) the condition of the tungsten foil after joining (as-received or recrystallised) as well as (ii) the characteristics of the interface between the tungsten foil and the interlayer (wettability or diffusion leading to a solid solution or the formation of intermetallics). From the example of tungsten laminates joined by brazing with (i) an eutectic silver copper brazing filler, (ii) copper, (iii) titanium, and (iv) zirconium, the microstructure will be discussed, with special focus on the interface. Based on our assumptions of the mechanism of the extraordinary ductility of tungsten foil we present three syntheses strategies and make recommendations for the synthesis of high temperature tungsten laminates.

  13. One-pot preparation of N,N′-alkylidene bisamide derivatives catalyzed by silica supported polyphosphoric acid (SiO2-PPA

    Directory of Open Access Journals (Sweden)

    Mohammad Reza Mohammad Shafiee

    2014-04-01

    Full Text Available Silica supported polyphosphoric acid (SiO2-PPA as an efficient heterogeneous catalyst was found to be effective for the one-pot three-component condensation reaction of phenyl acetylene/1-hexyne, aromatic aldehyde and benzamide/acetamide to produce a series of N,N′-alkylidene bisamides. The desired products were obtained in good to high yields. The assistance of alkynes has been confirmed by using thin layer chromatographic (TLC studies. All the reactions were done at 100 °C using 0.025 g of catalyst. The developed method is valid for either substituted aldehyde, thus it constitutes a general synthetic method for these kinds of compounds. In all the cases aromatic aldehydes containing electron-withdrawing groups gave shorter time than that with electron-donating groups. Additionally, the reaction of butyraldehyde with benzamide failed to have any product in the presence of phenyl acetylene but with 1-hexyne the product was formed in moderate yield.

  14. High-energy, high-rate consolidation of tungsten and tungsten-based composite powders

    Energy Technology Data Exchange (ETDEWEB)

    Raghunathan, S.K.; Persad, C.; Bourell, D.L.; Marcus, H.L. (Center for Materials Science and Engineering, Univ. of Texas, Austin (USA))

    1991-01-20

    Tungsten and tungsten-based heavy alloys are well known for their superior mechanical properties at elevated temperatures. However, unalloyed tungsten is difficult to consolidate owing to its very high melting temperature (3683 K). The additions of small amounts of low-melting elements such as iron, nickel, cobalt and copper, facilitate the powder processing of dense heavy alloys at moderate temperatures. Energetic high-current pulses have been used recently for powder consolidation. In this paper, the use of a homopolar generator as a power source to consolidate selected tungsten and tungsten-based alloys is examined. Various materials were consolidated including unalloyed tungsten, W-Nb, W-Ni, and tungsten heavy alloy with boron carbide. The effect of process parameters such as pressure and specific energy input on the consolidation of different alloy systems is described in terms of microstructure and property relationships. (orig.).

  15. Tungsten: A Preliminary Environmental Risk Assessment

    Science.gov (United States)

    2011-05-01

    Effects on Flora & Fauna • Geochemistry • Soil microbial communities • Plants • Soil invertebrates • Higher order animals • Additional studies BUILDING...Bioaccumulation of Tungsten in Plants Natural Sources • Trees & shrubs in Rocky Mountain region, USA • Siberian pine, willows, mosses & lichen in tungsten

  16. International strategic mineral issues summary report: tungsten

    Science.gov (United States)

    Werner, Antony B.T.; Sinclair, W. David; Amey, Earle B.

    1998-01-01

    Scheelite and wolframite are the principal minerals currently mined for tungsten. Both occur in hard-rock deposits; wolframite is also recovered from placer deposits. Most current mine production of tungsten is from vein/stockwork, skarn, porphyry, and strata-bound deposits. Minor amounts are produced from disseminated, pegmatite, breccia, and placer deposits.

  17. Structures and transitions in tungsten grain boundaries

    Energy Technology Data Exchange (ETDEWEB)

    Frolov, T. [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States); Zhu, Q. [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States); Marian, J. [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States); Rudd, R. E. [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)

    2017-02-07

    The objective of this study is to develop a computational methodology to predict structure, energies of tungsten grain boundaries as a function of misorientation and inclination. The energies and the mobilities are the necessary input for thermomechanical model of recrystallization of tungsten for magnetic fusion applications being developed by the Marian Group at UCLA.

  18. Development of Tungsten Based Composites

    Science.gov (United States)

    1992-02-01

    CONTENTS Section Title Page 1 INTRODUCTION & SUMMARY .............................. 1 2 MATERIAL SELECTION .................................. 3 3...Metallographic Examination .. 41 - iv - 1. INTRODUCTION & SUMMARY This is the. Final Report on a Phase I SBIR Program entitled "Development of Tungsten Based...m = - -𔃺 S (l- 1- =11 = (t) 011CU ’a . 4) woj .- :2 01w c L .0 u .-. 0C 0 goa - L 0d MCDM . 3 -X - z 1 m- L. S.1 MCDM -z3-2: S - m 1 o. 01 In 0,10Lnw

  19. A silica-supported double-decker silsesquioxane provides a second skin for the selective generation of bipodal surface organometallic complexes

    KAUST Repository

    Espinas, Jeff

    2012-11-12

    A well-defined silica-based material with a homogeneous nanolayer presenting identical pairs of vicinal silanols has been prepared by reaction of the surface organometallic species [≡SiOZr(CH 2CMe 3) 3], obtained on a silica dehydroxylated at 900 °C, with the double-decker-shaped silsesquioxane (OH) 2DD(OH) 2. The surface structure has been established using extensive NMR characterization ( 1H, 13C, 29Si, HETCOR, double-quantum, triple-quantum). Treatment with Zr(CH 2CMe 3) 4 leads to the first well-defined single-site bipodal grafted bis-neopentyl zirconium complex. © 2012 American Chemical Society.

  20. The DAMPE silicon tungsten tracker

    CERN Document Server

    Gallo, Valentina; Asfandiyarov, R; Azzarello, P; Bernardini, P; Bertucci, B; Bolognini, A; Cadoux, F; Caprai, M; Domenjoz, M; Dong, Y; Duranti, M; Fan, R; Franco, M; Fusco, P; Gargano, F; Gong, K; Guo, D; Husi, C; Ionica, M; Lacalamita, N; Loparco, F; Marsella, G; Mazziotta, M N; Mongelli, M; Nardinocchi, A; Nicola, L; Pelleriti, G; Peng, W; Pohl, M; Postolache, V; Qiao, R; Surdo, A; Tykhonov, A; Vitillo, S; Wang, H; Weber, M; Wu, D; Wu, X; Zhang, F; De Mitri, I; La Marra, D

    2017-01-01

    The DArk Matter Particle Explorer (DAMPE) satellite has been successfully launched on the 17th December 2015. It is a powerful space detector designed for the identification of possible Dark Matter signatures thanks to its capability to detect electrons and photons with an unprecedented energy resolution in an energy range going from few GeV up to 10 TeV. Moreover, the DAMPE satellite will contribute to a better understanding of the propagation mechanisms of high energy cosmic rays measuring the nuclei flux up to 100 TeV. DAMPE is composed of four sub-detectors: a plastic strip scintillator, a silicon-tungsten tracker-converter (STK), a BGO imaging calorimeter and a neutron detector. The STK is made of twelve layers of single-sided AC-coupled silicon micro-strip detectors for a total silicon area of about 7 $m^2$ . To promote the conversion of incident photons into electron-positron pairs, tungsten foils are inserted into the supporting structure. In this document, a detailed description of the STK constructi...

  1. A kinetic study on the adsorption and reaction of hydrogen over silica-supported ruthenium and silver-ruthenium catalysts during the hydrogenation of carbon monoxide

    Energy Technology Data Exchange (ETDEWEB)

    VanderWiel, David P. [Iowa State Univ., Ames, IA (United States)

    1999-02-12

    Although the catalytic hydrogenation of carbon monoxide has been a subject of considerable investigation for many years, its increasing economical attractiveness as an industrial source of hydrocarbons has recently led to a search for more active and selective catalysts. A fundamental problem in the development of such catalysts is an incomplete knowledge of the operative surface processes, due in large part to the inability to accurately measure surface concentrations of reactant species during reaction. Specifically, the concentration of surface hydrogen proves difficult to estimate using normally revealing techniques such as transient isotopic exchange due to kinetic isotope effects. Knowledge of such concentrations is essential to the determination of the mechanisms of adsorption and reaction, since many kinetic parameters are concentration dependent. It is the aim of this research to investigate the mechanism and kinetics of the adsorption and reaction of hydrogen on silica-supported ruthenium and silver-ruthenium catalysts during the hydrogenation of carbon monoxide. By preadsorbing carbon monoxide onto the surface of ruthenium and silver-ruthenium catalysts, the kinetics of hydrogen adsorption and reaction can be monitored upon exposure of this surface to ambient hydrogen gas. This is accomplished by conducting identical experiments on two separate systems. First, the formation of methane is monitored using mass spectroscopy, and specific reaction rates and apparent activation energies are measured. Next, in situ 1H-NMR is used to monitor the amount of hydrogen present on the catalyst surface during adsorption and reaction. The results for these two sets of experiments are then combined to show a correlation between the rate of reaction and the surface hydrogen concentration. Finally, transition state theory is applied to this system and is used to explain the observed change in the apparent activation energy. The structure sensitivity of hydrogen

  2. Investigation of Silica-Supported Vanadium Oxide Catalysts by High-Field 51 V Magic-Angle Spinning NMR

    Energy Technology Data Exchange (ETDEWEB)

    Jaegers, Nicholas R.; Wan, Chuan; Hu, Mary Y.; Vasiliu, Monica; Dixon, David A.; Walter, Eric; Wachs, Israel E.; Wang, Yong; Hu, Jian Zhi

    2017-03-14

    Supported V2O5/SiO2 catalysts were studied using solid state 51V MAS NMR at a sample spinning rate of 36 kHz and at a magnetic field of 19.975 T for a better understanding of the coordination of the vanadium oxide as a function of environmental conditions . Structural transformations of the supported vanadium oxide species between the catalyst in the dehydrated state and hydrated state under an ambient environment were revisited to examine the degree of oligomerization and the effect of water. The experimental results indicate the existence of a single dehydrated surface vanadium oxide species that resonates at -675 ppm and two vanadium oxide species under ambient conditions that resonate at -566 and -610 ppm, respectively. No detectable structural difference was found as a function of vanadium oxide loading on SiO2 (3% V2O5/SiO2 and 8% V2O5/SiO2). Quantum chemistry simulations of the 51V NMR chemical shifts on predicted surface structures were used as an aide in understanding potential surface vanadium oxide species on the silica support. The results suggest the formation of isolated surface VO4 units for the dehydrated catalysts with the possibility of dimer and cyclic trimer presence. The absence of bridging V-O-V vibrations (~200-300 cm-1) in the Raman spectra [Gao et al. J. Phys. Chem. B 1998, 102, 10842-10852], however, indicates that the isolated surface VO4 sites are the dominant dehydrated surface vanadia species on silica. Upon exposure to water, hydrolysis of the bridging V-O-Si bonds is most likely responsible for the decreased electron shielding experienced by vanadium. No indicators for the presence of hydrated decavanadate clusters or hydrated vanadia gels previously proposed in the literature were detected in this study.

  3. Environmental fate of tungsten from military use

    Energy Technology Data Exchange (ETDEWEB)

    Clausen, Jay L. [Research and Development Center, Cold Regions Research and Engineering Laboratory, 72 Lyme Road, Hanover, New Hampshire, 03755 (United States)], E-mail: Jay.L.Clausen@erdc.usace.army.mil; Korte, Nic [1946 Clover Ct., Grand Junction, Colorado, 81506 (United States)

    2009-04-01

    This manuscript describes the distribution, fate and transport of tungsten used in training rounds at three small arms ranges at Camp Edwards on the Massachusetts Military Reservation (MMR), USA. Practice with tungsten/nylon rounds began in 2000 subsequent to a 1997 US Environmental Protection Agency ban on training with lead. Training with the tungsten rounds was halted in 2005 because of concerns regarding tungsten's environmental mobility and potential toxicity. This study, therefore, examines how tungsten partitions in the environment when fired on a small arms training range. Soil sampling revealed surface soil concentrations, highest at the berm face, up to 2080 mg/kg. Concentrations decreased rapidly with depth-at least by an order of magnitude by 25 cm. Nonetheless, tungsten concentrations remained above background to at least 150 cm. Pore-water samples from lysimeters installed in berm areas revealed a range of concentrations (< 1-400 mg/L) elevated with respect to background although there was no discernable trend with depth. Groundwater monitoring well samples collected approximately 30 m below ground surface showed tungsten (0.001-0.56 mg/L) attributable to range use.

  4. Tungsten foil laminate for structural divertor applications – Tensile test properties of tungsten foil

    Energy Technology Data Exchange (ETDEWEB)

    Reiser, Jens, E-mail: jens.reiser@kit.edu [Karlsruhe Institute of Technology (KIT), Institute for Applied Materials (IAM-AWP) (Germany); Rieth, Michael; Möslang, Anton; Dafferner, Bernhard [Karlsruhe Institute of Technology (KIT), Institute for Applied Materials (IAM-AWP) (Germany); Hoffmann, Andreas [PLANSEE SE, Reutte (Austria); Yi, Xiaoou; Armstrong, D.E.J. [University of Oxford, Department of Materials (United Kingdom)

    2013-03-15

    This paper is the third part of our series on tungsten foil laminates. Within the tungsten laminate project we have succeeded in ductilizing tungsten by synthesizing a tungsten laminate made of tungsten foil, which is ductile. By assembling and joining several layers of tungsten foil, the ductile properties of the foil can be extended to the bulk. The aim of this paper is to present the results of tensile tests on 100-μm-thick tungsten foil in as-received and recrystallized conditions (1 h at 2000 °C). The results show that the mechanical properties of tungsten foil are anisotropic and can be explained by considering (i) the texture of the tungsten foil of {1 0 0}〈0 1 1〉, (ii) the anisotropic grain shape (0.5 μm × 3 μm × 15 μm), (iii) the preferred slip direction of body-centered cubic (bcc) metals, the 〈1 1 1〉 direction, as well as the preferred cleavage plane of tungsten at room temperature, the {1 0 0} plane. Furthermore, the results give further hints for the sources and mechanism of the extraordinary ductility of tungsten foil such as the ‘foil effect’, which is the dislocation annihilation at the free surface. In particular, the ductile material behavior of tungsten foil in the recrystallized condition seems to benefit from the foil effect and this is how a plastic strain of about 30% in a tensile test at 600 °C can be explained.

  5. Tungsten oxide thin films grown by thermal evaporation with high resistance to leaching

    Energy Technology Data Exchange (ETDEWEB)

    Correa, Diogo S. [Universidade Federal de Pelotas (UFPel), RS (Brazil). Centro de Ciencias Quimicas, Farmaceuticas e de Alimentos; Pazinato, Julia C.O.; Freitas, Mauricio A. de; Radtke, Claudio; Garcia, Irene T.S., E-mail: irene@iq.ufrgs.br [Universidade Federal do Rio Grande do Sul (UFRGS), Porto Alegre, RS (Brazil). Instituto de Quimica; Dorneles, Lucio S. [Universidade Federal de Santa Maria (UFSM), RS (Brazil). Centro de Ciencias Naturais e Exatas

    2014-05-15

    Tungsten oxides show different stoichiometries, crystal lattices and morphologies. These characteristics are important mainly when they are used as photocatalysts. In this work tungsten oxide thin films were obtained by thermal evaporation on (100) silicon substrates covered with gold and heated at 350 and 600 °C, with different deposition times. The stoichiometry of the films, morphology, crystal structure and resistance to leaching were characterized through X-ray photoelectron spectroscopy, micro-Raman spectroscopy, scanning and transmission electron microscopy, X-ray diffractometry, Rutherford backscattering spectrometry and O{sup 16} (α,α')O{sup 16} resonant nuclear reaction. Films obtained at higher temperatures show well-defined spherical nanometric structure; they are composed of WO{sub 3.1} and the presence of hydrated tungsten oxide was also observed. The major crystal structure observed is the hexagonal. Thin films obtained through thermal evaporation present resistance to leaching in aqueous media and excellent performance as photocatalysts, evaluated through the degradation of the methyl orange dye. (author)

  6. Direct Electrochemical Preparation of Cobalt, Tungsten, and Tungsten Carbide from Cemented Carbide Scrap

    Science.gov (United States)

    Xiao, Xiangjun; Xi, Xiaoli; Nie, Zuoren; Zhang, Liwen; Ma, Liwen

    2017-02-01

    A novel process of preparing cobalt, tungsten, and tungsten carbide powders from cemented carbide scrap by molten salt electrolysis has been investigated in this paper. In this experiment, WC-6Co and NaCl-KCl salt were used as sacrificial anode and electrolyte, respectively. The dissolution potential of cobalt and WC was determined by linear sweep voltammetry to be 0 and 0.6 V ( vs Ag/AgCl), respectively. Furthermore, the electrochemical behavior of cobalt and tungsten ions was investigated by a variety of electrochemical techniques. Results of cyclic voltammetry (CV) and square-wave voltammetry show that the cobalt and tungsten ions existed as Co2+ and W2+ on melts, respectively. The effect of applied voltage, electrolysis current, and electrolysis times on the composition of the product was studied. Results showed that pure cobalt powder can be obtained when the electrolysis potential is lower than 0.6 V or during low current and short times. Double-cathode and two-stage electrolysis was utilized for the preparation of cobalt, tungsten carbide, and tungsten powders. Additionally, X-ray diffraction results confirm that the product collected at cathodes 1 and 2 is pure Co and WC, respectively. Pure tungsten powder was obtained after electrolysis of the second part. Scanning electron microscope results show that the diameters of tungsten, tungsten carbide, and cobalt powder are smaller than 100, 200, and 200 nm, respectively.

  7. Characterization of a Cobalt-Tungsten Interconnect

    DEFF Research Database (Denmark)

    Harthøj, Anders; Holt, Tobias; Caspersen, Michael

    2012-01-01

    A ferritic steel interconnect for a solid oxide fuel cell must be coated in order to prevent chromium evaporation from the steel substrate. The Technical University of Denmark and Topsoe Fuel Cell have developed an interconnect coating based on a cobalt-tungsten alloy. The purpose of the coating...... is to act both as a diffusion barrier for chromium and provide better protection against high temperature oxidation than a pure cobalt coating. This work presents a characterization of a cobalt-tungsten alloy coating electrodeposited on the ferritic steel Crofer 22 H which subsequently was oxidized in air...... of oxidation time. The coating had completely oxidized during the 300 h oxidation time. GDOES measurements showed that the tungsten was located in an inner zone in the coating/substrate interface. The outer layer of the coating did not contain any tungsten after oxidation but consisted mainly of cobalt...

  8. Hydrogen sulfide removal from hot coal gas by various mesoporous silica supported Mn{sub 2}O{sub 3} sorbents

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Z.F.; Liu, B.S., E-mail: bingsiliu@tju.edu.cn; Wang, F.; Wang, W.S.; Xia, C.; Zheng, S.; Amin, R.

    2014-09-15

    Graphical abstract: - Highlights: • Mn{sub 2}O{sub 3}/KIT-1 presented the best desulfurization performance at 600–850 °C. • High sulfur capacity of Mn{sub 2}O{sub 3}/KIT-1 correlated closely with 3-D channel of KIT-1. • Desulfurization character depended strongly on framework structure of sorbents. • High steam content suppressed greatly the occurrence of sulfidation reaction. - Abstract: A series of 50 wt% Mn{sub 2}O{sub 3} sorbents was prepared using various mesoporous silica, MCM-41, HMS, and KIT-1 as support. The influence of textural parameters of mesoporous silica, especially type of channel on the desulfurization performance of Mn{sub 2}O{sub 3} sorbents was investigated at 600–850 °C using hot coal gas containing 0.33 vol.% H{sub 2}S. The fresh and used sorbents were characterized by means of N{sub 2}-adsorption, x-ray diffraction (XRD), high resolution transmission microscopy (HRTEM) and H{sub 2} temperature- programmed reduction (H{sub 2}-TPR) techniques. The results confirmed that the manganese oxide was dispersed highly in regular pore channel of the mesoporous supports due to high surface area. Compared with the Mn{sub 2}O{sub 3}/diatomite, all mesoporous silica supported Mn{sub 2}O{sub 3} sorbents exhibited high breakthrough sulfur capacity and a sharp deactivation rate after the breakthrough point. Compared to Mn{sub 2}O{sub 3}/MCM-41 and Mn{sub 2}O{sub 3}/HMS sorbent, the Mn{sub 2}O{sub 3}/KIT-1 showed better desulfurization performance because of the 3D wormhole-like channel. The high sulfur capacity of the Mn{sub 2}O{sub 3}/KIT-1 sorbent was maintained during the eight consecutive desulfurization-regeneration cycles. The Mn{sub 2}O{sub 3}/KIT-1 still presented high desulfurization activity when hot coal gas contained low steam (<5%)

  9. Tungsten metallizing alumina--yttria ceramics

    Energy Technology Data Exchange (ETDEWEB)

    Cowan, R.E.; Stoddard, S.D.

    1977-03-01

    The ease with which high-alumina bodies may be metallized with tungsten is improved by additions of yttria to the alumina. Mechanisms of this bonding process were studied by use of optical and electron microscopy, electron microprobe, and tensile tests. Variables studied included yttria content of the body and the firing temperature during metallizing. The study showed that a reaction between the tungsten and the yttrogarnet grain boundary phase markedly improved adherence.

  10. Synthesis of Well-Defined Copper "N"-Heterocyclic Carbene Complexes and Their Use as Catalysts for a "Click Reaction": A Multistep Experiment that Emphasizes the Role of Catalysis in Green Chemistry

    Science.gov (United States)

    Ison, Elon A.; Ison, Ana

    2012-01-01

    A multistep experiment for an advanced synthesis lab course that incorporates topics in organic-inorganic synthesis and catalysis and highlights green chemistry principles was developed. Students synthesized two "N"-heterocyclic carbene ligands, used them to prepare two well-defined copper(I) complexes and subsequently utilized the complexes as…

  11. Tungsten foil laminate for structural divertor applications - Analyses and characterisation of tungsten foil

    Energy Technology Data Exchange (ETDEWEB)

    Reiser, Jens, E-mail: jens.reiser@kit.edu [Karlsruhe Institute of Technology (KIT), Institute for Applied Materials (IAM-AWP) (Germany); Rieth, Michael; Dafferner, Bernhard [Karlsruhe Institute of Technology (KIT), Institute for Applied Materials (IAM-AWP) (Germany); Hoffmann, Andreas [PLANSEE SE, Reutte (Austria); Yi Xiaoou; Armstrong, David E.J. [University of Oxford, Department of Materials (United Kingdom)

    2012-05-15

    It has been attempted for several years to synthesise a tungsten material with a low brittle-to-ductile transition temperature and a high fracture toughness that can be used for structural parts. It was shown in our previous work that tungsten foil is ductile at room temperature and that this ductility can be transformed to bulk by synthesising a tungsten laminate. In this work we want to focus on tungsten foil and assess the microstructure as well as the mechanical properties of the foil. The assessment of the microstructure of 0.1 mm tungsten foil will be performed using electron microscopy. It will be shown that the grains of the tungsten foil have a dimension of 0.5 {mu}m Multiplication-Sign 3 {mu}m Multiplication-Sign 15 {mu}m and a clear texture in (1 0 0) Left-Pointing-Angle-Bracket 0 1 1 Right-Pointing-Angle-Bracket . This texture becomes even more pronounced by annealing. Three-point-bending tests with tungsten foil, as-received, will define the barriers: ductile at room temperature and brittle in liquid nitrogen (-196 Degree-Sign C). This shows that the ductility is a thermally activated process. Recrystallised tungsten foil (annealed for 1 h/2700 Degree-Sign C) shows ductile material behaviour at 200 Degree-Sign C. The paper closes with a discussion on the reasons of the ductility of 0.1 mm tungsten foil. These might be the ultra fine grained (UFG) microstructure or, in other words, a nano microstructure (see tungsten foil as-received), the high amount of mobile edge dislocations, and/or the foil effect, which means that dislocations can move to the surface and are annihilated (see tungsten foil recrystallised).

  12. Extraction Factor Of Tungsten Sources From Tungsten Scraps By Zinc Decomposition Process

    Directory of Open Access Journals (Sweden)

    Pee J.-H.

    2015-06-01

    Full Text Available Decomposition promoting factors and extraction process of tungsten carbide and tungstic acid powders in the zinc decomposition process of tungsten scraps which are composed mostly of tungsten carbide and cobalt were evaluated. Zinc volatility was suppressed by the enclosed graphite crucible and zinc volatilization pressure was produced in the reaction graphite crucible inside an electric furnace for ZDP (Zinc Decomposition Process. Decomposition reaction was done for 2hours at 650°, which 100% decomposed the tungsten scraps that were over 30 mm thick. Decomposed scraps were pulverized under 75μm and were composed of tungsten carbide and cobalt identified by the XRD (X-ray Diffraction. To produce the WC(Tungsten Carbide powder directly from decomposed scraps, pulverized powders were reacted with hydrochloric acid to remove the cobalt binder. Also to produce the tungstic acid, pulverized powders were reacted with aqua regia to remove the cobalt binder and oxidize the tungsten carbide. Tungsten carbide and tungstic acid powders were identified by XRD and chemical composition analysis.

  13. Deuterium retention in tungsten and tungsten-tantalum alloys exposed to high-flux deuterium plasmas

    NARCIS (Netherlands)

    Zayachuk, Y.; Hoen, M. H. J. 't; van Emmichoven, P. A. Zeijlma; Uytdenhouwen, I.; Van Oost, G.

    2012-01-01

    A direct comparison of deuterium retention in samples of tungsten and two grades of tungsten-tantalum alloys-W-1% Ta and W-5% Ta, exposed to deuterium plasmas (ion flux similar to 10(24) m(-2) s(-1), ion energy at the biased target similar to 50 eV) at the plasma generator Pilot-PSI was performed

  14. Complete doping in solid-state by silica-supported perchloric acid as dopant solid acid: Synthesis and characterization of the novel chiral composite of poly [(±)-2-(sec-butyl) aniline

    Energy Technology Data Exchange (ETDEWEB)

    Farrokhzadeh, Abdolkarim; Modarresi-Alam, Ali Reza, E-mail: modaresi@chem.usb.ac.ir

    2016-05-15

    Poly [(±)-2-(sec-butyl) aniline]/silica-supported perchloric acid composites were synthesized by combination of poly[(±)-2-sec-butylaniline] base (PSBA) and the silica-supported perchloric acid (SSPA) as dopant solid acid in solid-state. The X-ray photoelectron spectroscopy (XPS) and CHNS results confirm nigraniline oxidation state and complete doping for composites (about 75%) and non-complete for the PSBA·HCl salt (about 49%). The conductivity of samples was (≈0.07 S/cm) in agreement with the percent of doping obtained of the XPS analysis. Also, contact resistance was determined by circular-TLM measurement. The morphology of samples by the scanning electron microscopy (SEM) and their coating were investigated by XPS, SEM-map and energy-dispersive X-ray spectroscopy (EDX). The key benefits of this work are the preparation of conductive chiral composite with the delocalized polaron structure under green chemistry and solid-state condition, the improvement of the processability by inclusion of the 2-sec-butyl group and the use of dopant solid acid (SSPA) as dopant. - Highlights: • The solid-state synthesis of the novel chiral composites of poly[(±)-2-(sec-butyl)aniline] (PSBA) and silica-supported perchloric acid (SSPA). • It takes 120 h for complete deprotonation of PSBA.HCl salt. • Use of SSPA as dopant solid acid for the first time to attain the complete doping of PSBA. • The coating of silica surface with PSBA.

  15. Synthesis, characterization and catalytic application of silica supported tin oxide nanoparticles for synthesis of 2,4,5-tri and 1,2,4,5-tetrasubstituted imidazoles under solvent-free conditions

    Directory of Open Access Journals (Sweden)

    Ashok V. Borhade

    2017-02-01

    Full Text Available Highly efficient and eco-friendly, one pot synthesis of 1,2,4,5-tetra substituted imidazoles and 2,4,5-trisubstituted imidazoles was reported under solvent free conditions using nanocrystalline silica supported tin oxide (SiO2:SnO2 as a catalyst with excellent yield. The present methodology offers several advantages such as mild reaction conditions, short reaction time, good yield, high purity of product, recyclable catalyst without a noticeable decrease in catalytic activity and can be used for large scale synthesis. The synthesized SiO2:SnO2 nanocrystalline catalyst was characterized by XRD, BET surface area and TEM techniques.

  16. Striking difference between alkane and olefin metathesis using the well-defined precursor [≡Si-O-WMe5]: Indirect evidence in favour of a bifunctional catalyst W alkylidene-hydride

    KAUST Repository

    Riache, Nassima

    2015-01-01

    Metathesis of linear alkanes catalyzed by the well-defined precursor (≡Si-O-WMe5) affords a wide distribution of linear alkanes from methane up to triacontane. Olefin metathesis using the same catalyst and under the same reaction conditions gives a very striking different distribution of linear α-olefins and internal olefins. This shows that olefin and alkane metathesis processes occur via very different pathways.

  17. Electroanalytical determination of tungsten and molybdenum in proteins

    NARCIS (Netherlands)

    Hagedoorn, P.L.; Slot, van 't P.; Leeuwen, van H.P.; Hagen, W.R.

    2001-01-01

    Recent crystal structure determinations accelerated the progress in the biochemistry of tungsten-containing enzymes. In order to characterize these enzymes, a sensitive determination of this metal in protein-containing samples is necessary. An electroanalytical tungsten determination has

  18. Element 74, the Wolfram Versus Tungsten Controversy

    Energy Technology Data Exchange (ETDEWEB)

    Holden,N.E.

    2008-08-11

    Two and a quarter centuries ago, a heavy mineral ore was found which was thought to contain a new chemical element called heavy stone (or tungsten in Swedish). A few years later, the metal was separated from its oxide and the new element (Z=74) was called wolfram. Over the years since that time, both the names wolfram and tungsten were attached to this element in various countries. Sixty years ago, IUPAC chose wolfram as the official name for the element. A few years later, under pressure from the press in the USA, the alternative name tungsten was also allowed by IUPAC. Now the original, official name 'wolfram' has been deleted by IUPAC as one of the two alternate names for the element. The history of this controversy is described here.

  19. Impact of residual by-products from tungsten film deposition on process integration due to nonuniformity of the tungsten film

    CERN Document Server

    Sidhwa, A; Gandy, T; Melosky, S; Brown, W; Ang, S; Naseem, H; Ulrich, R

    2002-01-01

    The effects of residual by products from a tungsten film deposition process and their impact on process integration due to the nonuniformity of the tungsten film were investigated in this work. The tungsten film deposition process involves three steps: nucleation, stabilization, and tungsten bulk fill. Six experiments were conducted in search for a solution to the problem. The resulting data suggest that excess nitrogen left in the chamber following the tungsten nucleation step, along with residual by products, causes a shift in the tungsten film uniformity during the tungsten bulk fill process. Data reveal that, due to the residual by products, an abnormal grain growth occurs causing a variation in the tungsten thickness across the wafer during the bulk fill step. Although several possible solutions were revealed by the experiments, potential integration problems limited the acceptable solutions to one. The solution chosen was the introduction of a 10 s pumpdown immediately following the nucleation step. Thi...

  20. Carcinogenicity of Embedded Tungsten Alloys in Mice

    Science.gov (United States)

    2011-03-01

    2010 ProofNo: 1 UN CO RR EC TE D PR OO F 228 cating that the observed DU effects were not the result of foreign-body carcinogen- esis ( Brand et al...describing adverse health effects due to exposure to tungsten and tungsten-based materials. As part of an initiation rite, a French artillery...soldier drank 250 ml of a beer and wine mixture that had been used to rinse a gun barrel. Shortly after, he suffered seizures and was comatose for 24 h

  1. Química organometálica de superfície aplicada à preparação de catalisadores heterogêneos bem definidos Surface organometallic chemistry applied to the preparation of well defined heterogeneous catalysts

    Directory of Open Access Journals (Sweden)

    Silvana I. Wolke

    2002-11-01

    Full Text Available The study of the reactions of organometallic complexes with the surfaces of inorganic oxides, zeolites and metals constitutes the basis of Surface Organometallic Chemistry (SOMC. The basic rules of organometallic chemistry are often valid when applied to surfaces and well-defined surface organometallic complexes can be obtained. These complexes can be used as heterogeneous catalysts or, by controlled reactions, can be transformed in other species useful for a given catalytic reaction. In some cases, these catalysts exhibit higher activity and/or selectivity than their analogous molecular complexes.

  2. CALICE silicon–tungsten electromagnetic calorimeter

    Indian Academy of Sciences (India)

    2015-11-27

    Nov 27, 2015 ... Abstract. A highly granular electromagnetic calorimeter prototype based on tungsten absorber and sampling units equipped with silicon pads as sensitive devices for signal collection is under construction. The full prototype will have in total 30 layers and be read out by about 10000 Si cells of 1 × 1 cm2.

  3. Superhard Rhenium/Tungsten Diboride Solid Solutions.

    Science.gov (United States)

    Lech, Andrew T; Turner, Christopher L; Lei, Jialin; Mohammadi, Reza; Tolbert, Sarah H; Kaner, Richard B

    2016-11-02

    Rhenium diboride (ReB 2 ), containing corrugated layers of covalently bonded boron, is a superhard metallic compound with a microhardness reaching as high as 40.5 GPa (under an applied load of 0.49 N). Tungsten diboride (WB 2 ), which takes a structural hybrid between that of ReB 2 and AlB 2 , where half of the boron layers are planar (as in AlB 2 ) and half are corrugated (as in ReB 2 ), has been shown not to be superhard. Here, we demonstrate that the ReB 2 -type structure can be maintained for solid solutions of tungsten in ReB 2 with tungsten content up to a surprisingly large limit of nearly 50 atom %. The lattice parameters for the solid solutions linearly increase along both the a- and c-axes with increasing tungsten content, as evaluated by powder X-ray and neutron diffraction. From micro- and nanoindentation hardness testing, all of the compositions within the range of 0-48 atom % W are superhard, and the bulk modulus of the 48 atom % solid solution is nearly identical to that of pure ReB 2 . These results further indicate that ReB 2 -structured compounds are superhard, as has been predicted from first-principles calculations, and may warrant further studies into additional solid solutions or ternary compounds taking this structure type.

  4. Gas tungsten arc welder with electrode grinder

    Science.gov (United States)

    Christiansen, David W.; Brown, William F.

    1984-01-01

    A welder for automated closure of fuel pins by a gas tungsten arc process in which a rotating length of cladding is positioned adjacent a welding electrode in a sealed enclosure. An independently movable axial grinder is provided in the enclosure for refurbishing the used electrode between welds.

  5. OPAL Example Segment of Silicon Tungsten Luminometer

    CERN Multimedia

    OPAL was one of the four experiments installed at the LEP particle accelerator from 1989 - 2000. The Silicon Tungsten Luminometer was part of OPAL's calorimeter which was used to measure the energy of particles. Most particles end their journey in calorimeters. These detectors measure the energy deposited when particles are slowed down and stopped.

  6. Titanium tungsten coatings for bioelectrochemical applications

    DEFF Research Database (Denmark)

    Wierzbicki, Rafal; Amato, Letizia; Łopacińska, J.

    2011-01-01

    This paper presents an assessment of titanium tungsten (TiW) coatings and their applicability as components of biosensing systems. The focus is put on using TiW as an electromechanical interface layer between carbon nanotube (CNT) forests and silicon nanograss (SiNG) cell scaffolds. Cytotoxicity...

  7. Electrokinetic treatment of firing ranges containing tungsten-contaminated soils

    Energy Technology Data Exchange (ETDEWEB)

    Braida, Washington [Center for Environmental Systems, Stevens Institute of Technology, Castle Point on Hudson, Hoboken, NJ 07030 (United States)], E-mail: wbraida@stevens.edu; Christodoulatos, Christos; Ogundipe, Adebayo; Dermatas, Dimitris [Center for Environmental Systems, Stevens Institute of Technology, Castle Point on Hudson, Hoboken, NJ 07030 (United States); O' Connor, Gregory [US Army, Environmental Technology Division, Picatinny, NJ 07806 (United States)

    2007-11-19

    Tungsten-based alloys and composites are being used and new formulations are being considered for use in the manufacturing of different types of ammunition. The use of tungsten heavy alloys (WHA) in new munitions systems and tungsten composites in small caliber ammunition could potentially release substantial amounts of this element into the environment. Although tungsten is widely used in industrial and military applications, tungsten's potential environmental and health impacts have not been thoroughly addressed. This necessitates the research and development of remedial technologies to contain and/or remove tungsten from soils that may serve as a source for water contamination. The current work investigates the feasibility of using electrokinetics for the remediation of tungsten-contaminated soils in the presence of other heavy metals of concern such as Cu and Pb with aim to removing W from the soil while stabilizing in situ, Pb and Cu.

  8. Computer simulations for thorium doped tungsten crystals

    Energy Technology Data Exchange (ETDEWEB)

    Eberhard, Bernd

    2009-07-17

    Tungsten has the highest melting point among all metals in the periodic table of elements. Furthermore, its equilibrium vapor pressure is by far the lowest at the temperature given. Thoria, ThO{sub 2}, as a particle dopant, results in a high temperature creep resistant material. Moreover, thorium covered tungsten surfaces show a drastically reduced electronic work function. This results in a tremendous reduction of tip temperatures of cathodes in discharge lamps, and, therefore, in dramatically reduced tungsten vapor pressures. Thorium sublimates at temperatures below those of a typical operating cathode. For proper operation, a diffusional flow of thorium atoms towards the surface has to be maintained. This atomic flux responds very sensitively on the local microstructure, as grain boundaries as well as dislocation cores offer ''short circuit paths'' for thorium atoms. In this work, we address some open issues of thoriated tungsten. A molecular dynamics scheme (MD) is used to derive static as well as dynamic material properties which have their common origin in the atomistic behavior of tungsten and thorium atoms. The interatomic interactions between thorium and tungsten atoms are described within the embedded atom model (EAM). So far, in literature no W-Th interaction potentials on this basis are described. As there is no alloying system known between thorium and tungsten, we have determined material data for the fitting of these potentials using ab-initio methods. This is accomplished using the full potential augmented plane wave method (FLAPW), to get hypothetical, i.e. not occurring in nature, ''alloy'' data of W-Th. In order to circumvent the limitations of classical (NVE) MD schemes, we eventually couple our model systems to external heat baths or volume reservoirs (NVT, NPT). For the NPT ensemble, we implemented a generalization of the variable cell method in combination with the Langevin piston, which results in a

  9. Gas-driven permeation of deuterium through tungsten and tungsten alloys

    Energy Technology Data Exchange (ETDEWEB)

    Buchenauer, Dean A., E-mail: dabuche@sandia.gov [Sandia National Laboratories, Energy Innovation Department, Livermore, CA 94550 (United States); Karnesky, Richard A. [Sandia National Laboratories, Energy Innovation Department, Livermore, CA 94550 (United States); Fang, Zhigang Zak; Ren, Chai [University of Utah, Department of Metallurgical Engineering, Salt Lake City, UT 84112 (United States); Oya, Yasuhisa [Shizuoka University, Graduate School of Science, Shizuoka (Japan); Otsuka, Teppei [Kyushu University, Department of Advanced Energy Engineering Science, Fukuoka (Japan); Yamauchi, Yuji [Hokkaido University, Third Division of Quantum Science and Engineering, Faculty of Engineering, Sapporo (Japan); Whaley, Josh A. [Sandia National Laboratories, Energy Innovation Department, Livermore, CA 94550 (United States)

    2016-11-01

    Highlights: • We have designed and performed initial studies on a high temperature gas-driven permeation cell capable of operating at temperatures up to 1150 °C and at pressures between 0.1–1 atm. • Permeation measurements on ITER grade tungsten compare well with past studies by Frauenfelder and Zahkarov in the temperature range from 500 to 1000 °C. • First permeation measurements on Ti dispersoid-strengthened ultra-fine grained tungsten show higher permeation at 500 °C, but very similar permeation with ITER tungsten at 1000 °C. Diffusion along grain boundaries may be playing a role for this type of material. - Abstract: To address the transport and trapping of hydrogen isotopes, several permeation experiments are being pursued at both Sandia National Laboratories (deuterium gas-driven permeation) and Idaho National Laboratories (tritium gas- and plasma-driven tritium permeation). These experiments are in part a collaboration between the US and Japan to study the performance of tungsten at divertor relevant temperatures (PHENIX). Here we report on the development of a high temperature (≤1150 °C) gas-driven permeation cell and initial measurements of deuterium permeation in several types of tungsten: high purity tungsten foil, ITER-grade tungsten (grains oriented through the membrane), and dispersoid-strengthened ultra-fine grain (UFG) tungsten being developed in the US. Experiments were performed at 500–1000 °C and 0.1–1.0 atm D{sub 2} pressure. Permeation through ITER-grade tungsten was similar to earlier W experiments by Frauenfelder (1968–69) and Zaharakov (1973). Data from the UFG alloy indicates marginally higher permeability (< 10×) at lower temperatures, but the permeability converges to that of the ITER tungsten at 1000 °C. The permeation cell uses only ceramic and graphite materials in the hot zone to reduce the possibility for oxidation of the sample membrane. Sealing pressure is applied externally, thereby allowing for elevation

  10. Hardening of self ion implanted tungsten and tungsten 5-wt% rhenium

    Energy Technology Data Exchange (ETDEWEB)

    Armstrong, D.E.J., E-mail: david.armstrong@materials.ox.ac.uk [Department of Materials, University of Oxford (United Kingdom); Yi, X. [Department of Materials, University of Oxford (United Kingdom); Marquis, E.A. [Department of Materials, University of Oxford (United Kingdom); Department of Materials Science and Engineering, University of Michigan, MI 48109 (United States); Roberts, S.G. [Department of Materials, University of Oxford (United Kingdom)

    2013-01-15

    Highlights: Black-Right-Pointing-Pointer W{sup +} ion implantation was used to simulate neutron damage in W and W-5 wt%Re. Black-Right-Pointing-Pointer A Hardness increase in pure tungsten was seen to saturate by 0.4 dpa. Black-Right-Pointing-Pointer TEM of pure W shows little change in damage levels between 0.4 and 33 dpa. Black-Right-Pointing-Pointer W-5 wt%Re alloy shows a hardness saturation between 0.07 dpa and 1.2 dpa. Black-Right-Pointing-Pointer Above 13 dpa rhenium clusters are seen by APT and hardness rapidly increases. - Abstract: Tungsten is one of the most promising materials for high temperature components in any future nuclear fusion tokamak. In this study tungsten-ion implantation has been used to simulate the damage caused by neutrons in pure tungsten and tungsten 5 wt% rhenium. This damaged layer is only 300 nm deep so conventional mechanical tests cannot be used to investigate it. Nanoindentation has been used to measure the change in hardness as a function of six damage levels (0 dpa, 0.07 dpa, 0.4 dpa, 1.2 dpa, 13 dpa and 33 dpa). In pure tungsten the hardness increase is seen to saturate by 0.4 dpa at Almost-Equal-To 0.8 GPa. Transmission electron microscopy of the damage structure sees a similar saturation of the loop volume number density at the same damage level. In the tungsten 5 wt% rhenium the increase in hardness is constant between 0.07 and 1.2 dpa, Almost-Equal-To 0.85 GPa. The loop volume number density as measured using TEM is also shows little change in this region. At a damage level of 33 dpa the hardness increase is 2.88 GPa; this corresponds with the formation of small 3-5 nm rhenium clusters as observed using atom probe tomography.

  11. Detection and reduction of tungsten contamination in ion implantation processes

    Energy Technology Data Exchange (ETDEWEB)

    Polignano, M.L.; Galbiati, A.; Grasso, S.; Mica, I.; Barbarossa, F.; Magni, D. [STMicroelectronics, Agrate Brianza (Italy)

    2016-12-15

    In this paper, we review the results of some studies addressing the problem of tungsten contamination in implantation processes. For some tests, the implanter was contaminated by implantation of wafers with an exposed tungsten layer, resulting in critical contamination conditions. First, DLTS (deep level transient spectroscopy) measurements were calibrated to measure tungsten contamination in ion-implanted samples. DLTS measurements of tungsten-implanted samples showed that the tungsten concentration increases linearly with the dose up to a rather low dose (5 x 10{sup 10} cm{sup -2}). Tungsten deactivation was observed when the dose was further increased. Under these conditions, ToF-SIMS revealed tungsten at the wafer surface, showing that deactivation was due to surface segregation. DLTS calibration could therefore be obtained in the linear dose regime only. This calibration was used to evaluate the tungsten contamination in arsenic implantations. Ordinary operating conditions and critical contamination conditions of the equipment were compared. A moderate tungsten contamination was observed in samples implanted under ordinary operating conditions. This contamination was easily suppressed by a thin screen oxide. On the contrary, implantations in critical conditions of the equipment resulted in a relevant tungsten contamination, which could be reduced but not suppressed even by a relatively thick screen oxide (up to 150 Aa). A decontamination process consisting of high dose implantations of dummy wafers was tested for its efficiency to remove tungsten and titanium contamination. This process was found to be much more effective for titanium than for tungsten. Finally, DLTS proved to be much more sensitive that TXRF (total reflection X-ray fluorescence) in detecting tungsten contamination. (copyright 2016 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  12. Structure-specific adipogenic capacity of novel, well-defined ternary Zn(II)-Schiff base materials. Biomolecular correlations in zinc-induced differentiation of 3T3-L1 pre-adipocytes to adipocytes.

    Science.gov (United States)

    Tsave, O; Halevas, E; Yavropoulou, M P; Kosmidis Papadimitriou, A; Yovos, J G; Hatzidimitriou, A; Gabriel, C; Psycharis, V; Salifoglou, A

    2015-11-01

    Among the various roles of zinc discovered to date, its exogenous activity as an insulin mimetic agent stands as a contemporary challenge currently under investigation and a goal to pursue in the form of a metallodrug against type 2 Diabetes Mellitus. Poised to investigate the adipogenic potential of Zn(II) and appropriately configure its coordination sphere into well-defined anti-diabetic forms, (a) a series of new well-defined ternary dinuclear Zn(II)-L (L=Schiff base ligands with a variable number of alcoholic moieties) compounds were synthesized and physicochemically characterized, (b) their cytotoxicity and migration effect(s) in both pre- and mature adipocytes were assessed, (c) their ability to effectively induce cell differentiation of 3T3-L1 pre-adipocytes into mature adipocytes was established, and (d) closely linked molecular targets involving or influenced by the specific Zn(II) forms were perused through molecular biological techniques, cumulatively delineating factors involved in Zn(II)-induced adipogenesis. Collectively, the results (a) reveal the significance of key structural features of Schiff ligands coordinated to Zn(II), thereby influencing its (a)toxicity behavior and insulin-like activity, (b) project molecular targets influenced by the specific forms of Zn(II) formulating its adipogenic potential, and (c) exemplify the interwoven relationship between Zn(II)-L structural speciation and insulin mimetic biological activity, thereby suggesting ways of fine tuning structure-specific zinc-induced adipogenicity in future efficient antidiabetic drugs. Copyright © 2015 Elsevier Inc. All rights reserved.

  13. Thermal stability of warm-rolled tungsten

    DEFF Research Database (Denmark)

    Alfonso Lopez, Angel

    , and recrystallization fitted to JMAK recrystallization kinetics, which in turn allowed thecalculation of recrystallization activation energies. Much faster recovery and recrystallizationkinetics were found for the plate warm-rolled to 90% thickness reduction, as compared to the platewarm-rolled to 67% thickness...... and recrystallization occur in tungsten, and quantifying the kinetics and microstructuralaspects of these restoration processes. Two warm-rolled tungsten plates are annealed attemperatures between 1100 °C and 1350 °C, under vacuum conditions or argon atmosphere. Theeffects of annealing on the microstructure...... reduction. An initial incubation time before recrystallization wasfound for both plates warm-rolled to 67% and 90% thickness reductions. The different Avramiexponents found for the two plates were explained microstructurally in terms of nucleation. The microstructural evolution during recovery...

  14. Femtosecond fiber laser additive manufacturing of tungsten

    Science.gov (United States)

    Bai, Shuang; Liu, Jian; Yang, Pei; Zhai, Meiyu; Huang, Huan; Yang, Lih-Mei

    2016-04-01

    Additive manufacturing (AM) is promising to produce complex shaped components, including metals and alloys, to meet requirements from different industries such as aerospace, defense and biomedicines. Current laser AM uses CW lasers and very few publications have been reported for using pulsed lasers (esp. ultrafast lasers). In this paper, additive manufacturing of Tungsten materials is investigated by using femtosecond (fs) fiber lasers. Various processing conditions are studied, which leads to desired characteristics in terms of morphology, porosity, hardness, microstructural and mechanical properties of the processed components. Fully dense Tungsten part with refined grain and increased hardness was obtained and compared with parts made with different pulse widths and CW laser. The results are evidenced that the fs laser based AM provides more dimensions to modify mechanical properties with controlled heating, rapid melting and cooling rates compared with a CW or long pulsed laser. This can greatly benefit to the make of complicated structures and materials that could not be achieved before.

  15. Stability of stacking faults in tungsten

    Energy Technology Data Exchange (ETDEWEB)

    Dranova, Z.I.; Ksenofontov, V.A.; Kul' ko, V.B.; Mikhailovskii, I.M.

    1979-12-01

    The atomic configuration of planar lattice defects in tungsten was investigated by field-ion microscopy and thermal etching. Stable stacking faults were observed throughout the investigated temperature range 78--1700/sup 0/K. These faults were studied by field-ion microscopy and mathematical modeling methods. It was found that the existence of stacking faults in bcc crystals was not associated with the action of strong omnidirectional tensile stresses. The crystallographic characteristics of the faults were determined.

  16. Pressures produced by gas tungsten arcs

    Science.gov (United States)

    Lin, M. L.; Eagar, T. W.

    1986-09-01

    The pressure of gas tungsten welding arcs has been measured for currents from 300 to 600 amperes using argon and helium gases. Although the measurements are generally consistent with previous results at lower currents, the present work shows that the pressure exerted by helium is a strong function of arc length. Several different scaling laws for the maximum pressure as a function of arc current and electrode tip angle are discussed.

  17. Epitaxial growth of tungsten nanoparticles on alumina and spinel surfaces

    Energy Technology Data Exchange (ETDEWEB)

    Rodriguez-Suarez, T; Lopez-Esteban, S; Pecharroman, C; Esteban-Cubillo, A; Moya, J S [Instituto de Ciencia de Materiales de Madrid (ICMM), Consejo Superior de Investigaciones Cientificas (CSIC), C/ Sor Juana Ines de la Cruz 3, 28049, Cantoblanco, Madrid (Spain); Diaz, L A; Torrecillas, R [Nanomaterials and Nanotechnology Research Center (CINN), Consejo Superior de Investigaciones CientIficas (CSIC), C/ Francisco Pintado Fe 26, 33011, Oviedo, Asturias (Spain); Gremillard, L [Universite de Lyon, INSA-Lyon, MATEIS, UMR CNRS 5510, 20 avenue Albert Einstein, Villeurbanne F-69621 (France)], E-mail: jsmoya@icmm.csic.es

    2008-05-28

    Isolated tungsten nanoparticles ({alpha}-W and {beta}-W phase) were synthesized and epitaxially grown on alumina and spinel particle surfaces with an average tungsten size of {<=}20 nm for a low tungsten content (of {<=}1.5 vol%). Using tungsten (VI) ethoxide alcoholic solutions, tungsten trioxide hydrated precursors were attached to a ceramic grains surface as a nanoparticle coating. High-resolution transmission electron microscopy (HRTEM) micrographs showed epitaxial interfaces between alumina, spinel and metallic tungsten. This epitaxial growth is assumed to be due to the effect of water vapour on the sublimation of ortho-tungstic acid during the reduction process in a hydrogen atmosphere. The planes involved in the epitaxy were found to be (22-bar 0){sub Al2O3} parallel (121){sub W} and (311){sub MgAl2O4} parallel (110){sub W}.

  18. Chemical vapour deposition of tungsten and tungsten silicide layers for applications in novel silicon technology

    CERN Document Server

    Li, F X

    2002-01-01

    This work was a detailed investigation into the Chemical Vapour Deposition (CVD) of tungsten and tungsten silicide for potential applications in integrated circuit (IC) and other microelectronic devices. These materials may find novel applications in contact schemes for transistors in advanced ICs, buried high conductivity layers in novel Silicon-On-Insulator (SOI) technology and in power electronic devices. The CVD techniques developed may also be used for metal coating of recessed or enclosed features which may occur in novel electronic or electromechanical devices. CVD of tungsten was investigated using the silicon reduction reaction of WF sub 6. W layers with an optimum self-limiting thickness of 100 nm and resistivity 20 mu OMEGA centre dot cm were produced self-aligned to silicon. A hydrogen passivation technique was developed as part of the wafer pre-clean schedule and proved essential in achieving optimum layer thickness. Layers produced by this approach are ideal for intimate contact to shallow junct...

  19. Electronic state of europium atoms on surface of oxidized tungsten

    CERN Document Server

    Davydov, S Y

    2001-01-01

    The energy scheme of the europium atoms adsorption system on the tungsten surface, coated with the oxygen monolayer, is considered. The evaluations of the europium adatoms charged state on the oxidized tungsten surface are performed. It is established, that europium, adsorbed at the oxidized tungsten surface, is a positive ion with the charge close to the unit. The zonal scheme of the Eu-O/W adsorption system for the europium low and high concentrations is proposed

  20. Characterization of tungsten tips for STM by SEM/AES/XPS

    NARCIS (Netherlands)

    Lisowski, W.F.; van den Berg, A.H.J.; Kip, Gerhardus A.M.; Hanekamp, L.J.; Hanekamp, L.J.

    1991-01-01

    For the first time, both X-ray Photoelectron Spectroscopy (XPS) and Auger Electron Spectroscopy (AES) techniques were applied in analysis of surface contamination of electrochemically etched Scanning Tunneling Microscope (STM) tungsten tips. Carbon monoxide, graphite, tungsten carbide and tungsten

  1. Room temperature one-step synthesis of microarrays of N-doped flower-like anatase TiO2 composed of well-defined multilayer nanoflakes by Ti anodization

    Science.gov (United States)

    Wang, Chenglin; Wang, Mengye; Xie, Kunpeng; Wu, Qi; Sun, Lan; Lin, Zhiqun; Lin, Changjian

    2011-07-01

    Microarrays of N-doped flower-like TiO2 composed of well-defined multilayer nanoflakes were synthesized at room temperature by electrochemical anodization of Ti in NH4F aqueous solution. The TiO2 flowers were of good anatase crystallinity. The effects of anodizing time, applied voltage and NH4F concentration on the flower-like morphology were systematically examined. It was found that the morphologies of the anodized Ti were related to the anodizing time and NH4F concentration. The size and density of the TiO2 flowers could be tuned by changing the applied voltage. The obtained N-doped flower-like TiO2 microarrays exhibited intense absorption in wavelengths ranging from 320 to 800 nm. Under both UV and visible light irradiation, the photocatalytic activity of the N-doped flower-like TiO2 microarrays in the oxidation of methyl orange showed a significant increase compared with that of commercial P25 TiO2 film.

  2. Investigation on the formation of tungsten carbide in tungsten-containing diamond like carbon coatings

    NARCIS (Netherlands)

    Strondl, C.; Carvalho, N.M.; Hosson, J.Th.M. De; Kolk, G.J. van der

    2003-01-01

    A series of tungsten-containing diamond-like carbon (Me-DLC) coatings have been produced by unbalanced magnetron sputtering using a Hauzer HTC-1000 production PVD system. Sputtering from WC targets has been used to form W-C:H coatings. The metal to carbon ratio has been varied to study changes in

  3. Tritium decay helium-3 effects in tungsten

    Directory of Open Access Journals (Sweden)

    M. Shimada

    2017-08-01

    Full Text Available Tritium (T implanted by plasmas diffuses into bulk material, especially rapidly at elevated temperatures, and becomes trapped in neutron radiation-induced defects in materials that act as trapping sites for the tritium. The trapped tritium atoms will decay to produce helium-3 (3He atoms at a half-life of 12.3 years. 3He has a large cross section for absorbing thermal neutrons, which after absorbing a neutron produces hydrogen (H and tritium ions with a combined kinetic energy of 0.76 MeV through the 3He(n,HT nuclear reaction. The purpose of this paper is to quantify the 3He produced in tungsten by tritium decay compared to the neutron-induced helium-4 (4He produced in tungsten. This is important given the fact that helium in materials not only creates microstructural damage in the bulk of the material but alters surface morphology of the material effecting plasma-surface interaction process (e.g. material evolution, erosion and tritium behavior of plasma-facing component materials. Effects of tritium decay 3He in tungsten are investigated here with a simple model that predicts quantity of 3He produced in a fusion DEMO FW based on a neutron energy spectrum found in literature. This study reveals that: (1 helium-3 concentration was equilibrated to ∼6% of initial/trapped tritium concentration, (2 tritium concentration remained approximately constant (94% of initial tritium concentration, and (3 displacement damage from 3He(n,HT nuclear reaction became >1 dpa/year in DEMO FW.

  4. Stress in tungsten carbide-diamond like carbon multilayer coatings

    NARCIS (Netherlands)

    Pujada, B.R.; Tichelaar, F.D.; Janssen, G.C.A.M.

    2007-01-01

    Tungsten carbide-diamond like carbon (WC-DLC) multilayer coatings have been prepared by sputter deposition from a tungsten-carbide target and periodic switching on and off of the reactive acetylene gas flow. The stress in the resulting WC-DLC multilayers has been studied by substrate curvature.

  5. Microstructure and tensile properties of tungsten at elevated temperatures

    Science.gov (United States)

    Shen, Tielong; Dai, Yong; Lee, Yongjoong

    2016-01-01

    In order to support the development of the 5 MW spallation target for the European Spallation Source, the effect of fabrication process on microstructure, ductile-to-brittle transition temperature (DBTT), tensile and fracture behaviour of powder-metallurgy pure tungsten materials has been investigated. A hot-rolled (HR) tungsten piece of 12 mm thickness and a hot-forged (HF) piece of about 80 mm thickness were used to simulate the thin and thick blocks in the target. The two tungsten pieces were characterized with metallography analysis, hardness measurement and tensile testing. The HR piece exhibits an anisotropic grain structure with an average size of about 330 × 140 × 40 μm in rolling, long transverse and short transverse (thickness) directions. The HF piece possesses a bimodal grain structure with about 310 × 170 × 70 μm grain size in deformed part and about 25 μm sized grains remained from sintering process. Hardness (HV0.2) of the HR piece is slightly greater than that of the HF one. The ductility of the HR tungsten specimens is greater than that of the HF tungsten. For the HF tungsten piece, specimens with small grains in gauge section manifest lower ductility but higher strength. The DBTT evaluated from the tensile results is 250-300 °C for the HR tungsten and about 350 °C for the HF tungsten.

  6. Page 1 Index Tungsten diselenide Photoelectrochemical solar cell ...

    Indian Academy of Sciences (India)

    Tungsten diselenide. Photoelectrochemical solar cell fabrication with tungsten diselenide single crystals 163. YBa2Cu3O7-3. Oxygen-enrichment of YBa2Cu307-; using the fluidization technique 63. YBazCu3O. Effect of oxide additives on the properties of high temperature superconductor, YBaCuO. 513. Zero-flux plane.

  7. Dioxobridged complexes of molybdenum (IV) and tungsten (IV) with ...

    Indian Academy of Sciences (India)

    Abstract. Six new dioxobridged complexes of molybdenum (IV) and tungsten (IV) with N-alkylphenothiazines having the general formula M2O4(L)2(H2O)2 [where M = molybdenum or tungsten and L = N-alkylphenothiazines] have been synthesised. The complexes have been characterised on the basis of analytical, molar ...

  8. New spectroscopic data for atomic tungsten XIV

    Science.gov (United States)

    Raineri, M.; Reyna Almandos, J.; Gallardo, M.; Pagan, C. J. B.

    2015-01-01

    The thirteen times ionized tungsten is isoelectronic with PmI. Wavelengths and transition probabilities for the 5s-5p and 5p-5d transitions of WXIV, identifying the ground state as 4f13 5s2 2F7/2 were calculated. Both, a relativistic Hartree Fock approach, including core-polarization effects, and a purely relativistic multiconfiguration Dirac-Fock method were used for the calculations. Particularly, 5s-5p transitions were compared with experimental results obtained with VUV electron beam ion trap (EBIT) spectroscopy.

  9. Synthesis and characterization of novel liquid-crystalline azo-dyes bearing two amino-nitro substituted azobenzene units and a well-defined, oligo(ethylene glycol) spacer

    Energy Technology Data Exchange (ETDEWEB)

    Caicedo, Carolina [Instituto de Investigaciones en Materiales, Universidad Nacional Autonoma de Mexico, Circuito Exterior, Ciudad Universitaria, C.P. 04510 Mexico D.F. (Mexico); Rivera, Ernesto, E-mail: riverage@iim.unam.mx [Instituto de Investigaciones en Materiales, Universidad Nacional Autonoma de Mexico, Circuito Exterior, Ciudad Universitaria, C.P. 04510 Mexico D.F. (Mexico); Valdez-Hernandez, Yazmin; Carreon-Castro, Maria del Pilar [Instituto de Ciencias Nucleares, Universidad Nacional Autonoma de Mexico, Circuito Exterior, Ciudad Universitaria, C.P. 04510 Mexico D.F. (Mexico)

    2011-10-17

    Highlights: {yields} Novel dyes containing azobenzene and oligo(ethylene glycol) were synthesized. {yields} Absorption spectra of RED-PEG dyes in CHCl{sub 3} showed {lambda}{sub max} = 440-480 nm. {yields} Absorption spectra of RED-PEG dyes in film revealed the formation of H-aggregates. {yields} Their liquid-crystalline behaviour was confirmed by light polarized microscopy. {yields} These liquid-crystalline dyes can form Langmuir films on the air-water interface. - Abstract: Four novel liquid-crystalline azo-dyes bearing two amino-nitro substituted azobenzene units linked by a well-defined oligo(ethylene glycol) spacer (DIRED-PEG series): (E)-N,N'-(2,2'-oxybis(ethane-2,1-diyl))bis(N-methyl-4-((E)-(4-nitrophenyl) diazenyl) benzenamine) (DIRED-PEG-2), (E)-N,N'-(2,2'-(ethane-1,2-diylbis(oxy)) bis(ethane-2,1-diyl)) bis(N-methyl-4-((E)-(4-nitrophenyl) diazenyl) benzenamine) (DIRED-PEG-3), (E)-N,N'-(2,2'-(2,2'-oxybis (ethane-2,1-diyl) bis(oxy)) bis(ethane-2,1-diyl)) bis(N-methyl-4-((E)-(4-nitrophenyl) diazenyl) benzenamine) (DIRED-PEG-4) and N1,N17-dimethyl-N1,N17-bis (4-((E)-(4-nitrophenyl) diazenyl) phenyl)-3,6,9,12,15-pentaoxaheptadecane-1,17-diamine (DIRED-PEG-6) have been synthesized. These dyes were fully characterized by FTIR, {sup 1}H and {sup 13}C NMR spectroscopies, and their thermal and optical properties were studied. Besides, the liquid-crystalline behaviour of these compounds was monitored in function of the temperature by light polarized microscopy. Finally, Langmuir films were prepared with these dyes.

  10. Study of properties of tungsten irradiated in hydrogen atmosphere

    Science.gov (United States)

    Tazhibayeva, I.; Skakov, M.; Baklanov, V.; Koyanbayev, E.; Miniyazov, A.; Kulsartov, T.; Ponkratov, Yu.; Gordienko, Yu.; Zaurbekova, Zh.; Kukushkin, I.; Nesterov, E.

    2017-12-01

    The paper presents the results of the experiments with DF (double forged) tungsten samples irradiated at the WWR-K research reactor in hydrogen and helium atmospheres. The irradiation time was 3255 h (135.6 d). After reactor irradiation, W samples have been subjected to investigations of their activity level, hardness, and microstructure, as well as x-ray and texture observations. The hydrogen yield released from irradiated tungsten samples have been measured using TDS-method. The hydrogen concentration in the tungsten samples irradiated in hydrogen was higher than that in the samples irradiated in helium atmosphere. It is shown that the surface microstructure of tungsten samples irradiated in hydrogen is characterized by micro-pits, inclusions and blisters in the form of bubbles, which were not observed earlier for tungsten irradiated in hydrogen.

  11. Tungsten recycling in the United States in 2000

    Science.gov (United States)

    Shedd, Kim B.

    2011-01-01

    This report, which is one of a series of reports on metals recycling, defines and quantifies the flow of tungsten-bearing materials in the United States from imports and stock releases through consumption and disposition in 2000, with particular emphasis on the recycling of industrial scrap (new scrap) and used products (old scrap). Because of tungsten's many diverse uses, numerous types of scrap were available for recycling by a wide variety of processes. In 2000, an estimated 46 percent of U.S. tungsten supply was derived from scrap. The ratio of tungsten consumed from new scrap to that consumed from old scrap was estimated to be 20:80. Of all the tungsten in old scrap available for recycling, an estimated 66 percent was either consumed in the United States or exported to be recycled.

  12. An experimental study of the influence of oxygen on silicide formation with tungsten deposited from tungsten hexafluoride

    Science.gov (United States)

    Zhang, S.-L.; Smith, U.; Buchta, R.; Östling, M.

    1991-01-01

    Tungsten disilicide (WSi2) was formed by annealing tungsten films deposited by low-pressure chemical vapor deposition on -silicon substrates. The influence of oxygen on the silicidation rate was studied. Si wafers with different oxygen content in the form of Czochralski, float-zone, and epitaxial wafers were used. Oxygen was also ion implanted into either the silicon substrate or the as-deposited tungsten film. The Rutherford backscattering technique was used to follow the progress of the silicidation. The silicidation rate was found to be dependent on the oxygen content of the Si substrates. The rate was lowest for Czochralski substrates and highest for float-zone substrates. Secondary ion mass spectroscopy was used to study the oxygen and fluorine profiles in the films prior to and after silicidation. Growth of WSi2 was found to be retarded concurrently with a pile-up of fluorine at the tungsten side of the W/WSi2 interface and a gettering of oxygen from the annealing atmosphere at the interface. Growth of WSi2 was then transferred to the tungsten surface. Oxygen implantation into silicon and tungsten, respectively, reduced the rate of silicide formation. Oxygen implantation into tungsten altered the distribution of fluorine and suppressed WSi2 growth at the tungsten surface. The observations led to a conceptual model, which ascribes the retardation in the growth of the inner WSi2 to a``poisoning'' effect caused by the increase of oxygen and fluorine levels at the interface.

  13. Deuterium desorption from tungsten using laser heating

    Directory of Open Access Journals (Sweden)

    J.H. Yu

    2017-08-01

    Full Text Available Retention and desorption of hydrogenic species need to be accurately modeled to predict the tritium inventory of next generation fusion devices, which is needed both for tritium fuel recovery and for tritium safety concerns. In this paper, experiments on thermal desorption of deuterium from intrinsic polycrystalline tungsten defects using laser heating are compared to TMAP-7 modeling. The samples during deuterium plasma exposure were at a temperature of 373K for this benchmark study with ion fluence of 0.7–1.0 ×1024Dm−2. Following plasma exposure, a fiber laser (λ= 1100nm heated the samples to peak surface temperatures ranging from ∼500 to 1400K with pulse widths from 10ms to 1s, and 1 to 10 pulses applied to each sample. The remaining deuterium retention was measured using temperature programmed desorption (TPD. Results show that > 95% of deuterium is desorbed when the peak surface temperature reached ∼950K for > 1s. TMAP-7 is used to predict deuterium desorption from tungsten for a range of surface temperatures and heating durations, and is compared to previous work on desorption from beryllium codeposits.

  14. Well-defined critical association concentration and rapid adsorption at the air/water interface of a short amphiphilic polymer, amphipol A8-35: a study by Förster resonance energy transfer and dynamic surface tension measurements.

    Science.gov (United States)

    Giusti, Fabrice; Popot, Jean-Luc; Tribet, Christophe

    2012-07-17

    Amphipols (APols) are short amphiphilic polymers designed to handle membrane proteins (MPs) in aqueous solutions as an alternative to small surfactants (detergents). APols adsorb onto the transmembrane, hydrophobic surface of MPs, forming small, water-soluble complexes, in which the protein is biochemically stabilized. At variance with MP/detergent complexes, MP/APol ones remain stable even at extreme dilutions. Pure APol solutions self-associate into well-defined micelle-like globules comprising a few APol molecules, a rather unusual behavior for amphiphilic polymers, which typically form ill-defined assemblies. The best characterized APol to date, A8-35, is a random copolymer of acrylic acid, isopropylacrylamide, and octylacrylamide. In the present work, the concentration threshold for self-association of A8-35 in salty buffer (NaCl 100 mM, Tris/HCl 20 mM, pH 8.0) has been studied by Förster resonance energy transfer (FRET) measurements and tensiometry. In a 1:1 mol/mol mixture of APols grafted with either rhodamine or 7-nitro-1,2,3-benzoxadiazole, the FRET signal as a function of A8-35 concentration is essentially zero below a threshold concentration of 0.002 g·L(-1) and increases linearly with concentration above this threshold. This indicates that assembly takes place in a narrow concentration interval around 0.002 g·L(-1). Surface tension measurements decreases regularly with concentration until a threshold of ca. 0.004 g·L(-1), beyond which it reaches a plateau at ca. 30 mN·m(-1). Within experimental uncertainties, the two techniques thus yield a comparable estimate of the critical self-assembly concentration. The kinetics of variation of the surface tension was analyzed by dynamic surface tension measurements in the time window 10 ms-100 s. The rate of surface tension decrease was similar in solutions of A8-35 and of the anionic surfactant sodium dodecylsulfate when both compounds were at a similar molar concentration of n-alkyl moieties. Overall, the

  15. Tungsten transport in the plasma edge at ASDEX upgrade

    Energy Technology Data Exchange (ETDEWEB)

    Janzer, Michael Arthur

    2015-04-30

    The Plasma Facing Components (PFC) will play a crucial role in future deuterium-tritium magnetically confined fusion power plants, since they will be subject to high energy and particle loads, but at the same time have to ensure long lifetimes and a low tritium retention. These requirements will most probably necessitate the use of high-Z materials such as tungsten for the wall materials, since their erosion properties are very benign and, unlike carbon, capture only little tritium. The drawback with high-Z materials is, that they emit strong line radiation in the core plasma, which acts as a powerful energy loss mechanism. Thus, the concentration of these high-Z materials has to be controlled and kept at low levels in order to achieve a burning plasma. Understanding the transport processes in the plasma edge is essential for applying the proper impurity control mechanisms. This control can be exerted either by enhancing the outflux, e.g. by Edge Localized Modes (ELM), since they are known to expel impurities from the main plasma, or by reducing the influx, e.g. minimizing the tungsten erosion or increasing the shielding effect of the Scrape Off Layer (SOL). ASDEX Upgrade (AUG) has been successfully operating with a full tungsten wall for several years now and offers the possibility to investigate these edge transport processes for tungsten. This study focused on the disentanglement of the frequency of type-I ELMs and the main chamber gas injection rate, two parameters which are usually linked in H-mode discharges. Such a separation allowed for the first time the direct assessment of the impact of each parameter on the tungsten concentration. The control of the ELM frequency was performed by adjusting the shape of the plasma, i.e. the upper triangularity. The radial tungsten transport was investigated by implementing a modulated tungsten source. To create this modulated source, the linear dependence of the tungsten erosion rate at the Ion Cyclotron Resonance

  16. Advanced smart tungsten alloys for a future fusion power plant

    Science.gov (United States)

    Litnovsky, A.; Wegener, T.; Klein, F.; Linsmeier, Ch; Rasinski, M.; Kreter, A.; Tan, X.; Schmitz, J.; Mao, Y.; Coenen, J. W.; Bram, M.; Gonzalez-Julian, J.

    2017-06-01

    The severe particle, radiation and neutron environment in a future fusion power plant requires the development of advanced plasma-facing materials. At the same time, the highest level of safety needs to be ensured. The so-called loss-of-coolant accident combined with air ingress in the vacuum vessel represents a severe safety challenge. In the absence of a coolant the temperature of the tungsten first wall may reach 1200 °C. At such a temperature, the neutron-activated radioactive tungsten forms volatile oxide which can be mobilized into atmosphere. Smart tungsten alloys are being developed to address this safety issue. Smart alloys should combine an acceptable plasma performance with the suppressed oxidation during an accident. New thin film tungsten-chromium-yttrium smart alloys feature an impressive 105 fold suppression of oxidation compared to that of pure tungsten at temperatures of up to 1000 °C. Oxidation behavior at temperatures up to 1200 °C, and reactivity of alloys in humid atmosphere along with a manufacturing of reactor-relevant bulk samples, impose an additional challenge in smart alloy development. First exposures of smart alloys in steady-state deuterium plasma were made. Smart tungsten-chroimium-titanium alloys demonstrated a sputtering resistance which is similar to that of pure tungsten. Expected preferential sputtering of alloying elements by plasma ions was confirmed experimentally. The subsequent isothermal oxidation of exposed samples did not reveal any influence of plasma exposure on the passivation of alloys.

  17. High Purity Tungsten Spherical Particle Preparation From WC-Co Spent Hard Scrap

    Directory of Open Access Journals (Sweden)

    Han Chulwoong

    2015-06-01

    Full Text Available Tungsten carbide-cobalt hard metal scrap was recycled to obtain high purity spherical tungsten powder by a combined hydrometallurgy and physical metallurgy pathway. Selective leaching of tungsten element from hard metal scrap occurs at solid / liquid interface and therefore enlargement of effective surface area is advantageous. Linear oxidation behavior of Tungsten carbide-cobalt and the oxidized scrap is friable to be pulverized by milling process. In this regard, isothermally oxidized Tungsten carbide-cobalt hard metal scrap was mechanically broken into particles and then tungsten trioxide particle was recovered by hydrometallurgical method. Recovered tungsten trioxide was reduced to tungsten particle in a hydrogen environment. After that, tungsten particle was melted and solidified to make a spherical one by RF (Ratio Frequency thermal plasma process. Well spherical tungsten micro-particle was successfully obtained from spent scrap. In addition to the morphological change, thermal plasma process showed an advantage for the purification of feedstock particle.

  18. Tungsten Stable Isotope Compositions of Ferromanganese Crusts

    Science.gov (United States)

    Abraham, K.; Barling, J.; Hein, J. R.; Schauble, E. A.; Halliday, A. N.

    2014-12-01

    We report the first accurate and precise data for mass-dependent fractionation of tungsten (W) stable isotopes, using a double spike technique and MC-ICPMS. Results are expressed relative to the NIST 3136 W isotope standard as per mil deviations in 186W/184W (δ186W). Although heavy element mass-dependent fractionations are expected to be small, Tl and U both display significant low temperature isotopic fractionations. Theoretical calculations indicate that W nuclear volume isotopic effects should be smaller than mass-dependent fractionations at low temperatures. Hydrogenetic ferromanganese (Fe-Mn) crusts precipitate directly from seawater and have been used as paleoceanographic recorders of temporal changes in seawater chemistry. Crusts are strongly enriched in W and other metals, and are a promising medium for exploring W isotopic variability. Tungsten has a relatively long residence time in seawater of ~61,000 years, mainly as the tungstate ion (WO42-). Water depth profiles show conservative behaviour. During adsorption on Fe-Mn crusts, W species form inner-sphere complexes in the hexavalent (W6+) state. The major host phase is thought to be Mn oxides and the lighter W isotope is expected to be absorbed preferentially. Surface scrapings of 13 globally distributed hydrogenetic Fe-Mn crusts display δ186W from -0.08 to -0.22‰ (±0.03‰, 2sd). A trend toward lighter W isotope composition exists with increasing water depth (~1500 to ~5200m) and W concentration. One hydrothermal Mn-oxide sample is anomalously light and Mn nodules are both heavy and light relative to Fe-Mn crusts. Tungsten speciation depends on concentration, pH, and time in solution and is not well understood because of the extremely slow kinetics of the reactions. In addition, speciation of aqueous and/or adsorbed species might be sensitive to pressure, showing similar thermodynamic stability but different effective volumes. Thus, W stable isotopes might be used as a water-depth barometer in

  19. Dense Pure Tungsten Fabricated by Selective Laser Melting

    Directory of Open Access Journals (Sweden)

    Dianzheng Wang

    2017-04-01

    Full Text Available Additive manufacturing using tungsten, a brittle material, is difficult because of its high melting point, thermal conductivity, and oxidation tendency. In this study, pure tungsten parts with densities of up to 18.53 g/cm3 (i.e., 96.0% of the theoretical density were fabricated by selective laser melting. In order to minimize balling effects, the raw polyhedral tungsten powders underwent a spheroidization process before laser consolidation. Compared with polyhedral powders, the spherical powders showed increased laser absorptivity and packing density, which helped in the formation of a continuous molten track and promoted densification.

  20. Thermal expansion method for lining tantalum alloy tubing with tungsten

    Science.gov (United States)

    Watson, G. K.; Whittenberger, J. D.; Mattson, W. F.

    1973-01-01

    A differential-thermal expansion method was developed to line T-111 (tantalum - 8 percent tungsten - 2 percent hafnium) tubing with a tungsten diffusion barrier as part of a fuel element fabrication study for a space power nuclear reactor concept. This method uses a steel mandrel, which has a larger thermal expansion than T-111, to force the tungsten against the inside of the T-111 tube. Variables investigated include lining temperature, initial assembly gas size, and tube length. Linear integrity increased with increasing lining temperature and decreasing gap size. The method should have more general applicability where cylinders must be lined with a thin layer of a second material.

  1. Remobilization of tungsten dust from castellated plasma-facing components

    Directory of Open Access Journals (Sweden)

    M. De Angeli

    2017-08-01

    Full Text Available Studies of tungsten dust remobilization from castellated plasma-facing components can shed light to whether gaps constitute a dust accumulation site with important implications for monitoring but also removal. Castellated structures of ITER relevant geometry that contained pre-adhered tungsten dust of controlled deposition profile have been exposed in the Pilot-PSI linear device. The experiments were performed under steady state and transient plasma conditions, as well as varying magnetic field topologies. The results suggest that dust remobilization from the plasma-facing monoblock surface can enhance dust trapping in the gaps and that tungsten dust is efficiently trapped inside the gaps.

  2. Electrode potentials of tungsten in fused alkali chlorides

    Science.gov (United States)

    Ivanov, A. B.; Volkovich, V. A.; Poskryakov, D. A.; Vasin, B. D.; Griffiths, T. R.

    2016-09-01

    Anodic dissolution of tungsten was studied at 823-1173 K in the melts based on NaCl-CsCl, NaCl-KCl-CsCl and LiCl-KCl-CsCl eutectic mixtures. The process results in the formation of W(IV) ions. Prolonged contact with silica results in oxidation W(IV) ions and decreasing tungsten concentration in the electrolyte due to formation of volatile higher oxidation state chloro- and oxychloro-species. Tungsten electrode potentials were measured in NaCl-CsCl and NaCl-KCl-CsCl based melts using potentiometry.

  3. Rhenium alloying of tungsten heavy alloys

    Energy Technology Data Exchange (ETDEWEB)

    Bose, A.; Jerman, G.; German, R.M.

    1989-06-01

    Alloying experiments have been performed using rhenium additions to a classic 90 mass% tungsten heavy alloy. The mixed powder system was liquid phase sintered to full density at 1500/sup 0/C in 60 min. The rhenium modified alloys exhibited a smaller grain size, higher hardness, higher strength, and lower ductility than the unalloyed system. For an alloy with a composition of 84W-6Re-8Ni-2Fe, the sintered density was 17,4 Mg/m/sup 3/ with a yield strength of 815 MPa, tensile strength of 1180 MPa, and elongation to failure of 13%. This property combination results from the aggregate effects of grain size reduction and solid solution hardening due to rhenium. In the unalloyed system these properties require post-sintering swaging and aging; thus, alloying with rhenium is most attractive for applications where netshaping is desired, such as by powder injection molding. (orig.).

  4. Rhenium alloying of tungsten heavy alloys

    Energy Technology Data Exchange (ETDEWEB)

    German, R.M.; Bose, A.; Jerman, G.

    1989-01-01

    Alloying experiments were performed using rhenium additions to a classic 90 mass % tungsten heavy alloy. The mixed-powder system was liquid phase sintered to full density at 1500 C in 60 min The rhenium-modified alloys exhibited a smaller grain size, higher hardness, higher strength, and lower ductility than the unalloyed system. For an alloy with a composition of 84W-6Re-8Ni-2Fe, the sintered density was 17, 4 Mg/m{sup 3} with a yield strength of 815 MPa, tensile strength of 1180 MPa, and elongation to failure of 13%. This property combination results from the aggregate effects of grain size reduction and solid solution hardening due to rhenium. In the unalloyed system these properties require post-sintering swaging and aging; thus, alloying with rhenium is most attractive for applications where net shaping is desired, such as by powder injection molding.

  5. On getter action of tungsten for methane

    Energy Technology Data Exchange (ETDEWEB)

    Kyoh, Bunkei; Uchida, Kumao (Kinki Univ., Higashi-Osaka, Osaka (Japan). Faculty of Science and Technology); Imoto, Shosuke

    1990-07-01

    The tungsten filament was electrically heated in methane atmosphere, and its getter action for methane has been investigated. The rapid adsorption of methane occurred during gettering at methane pressures between 10{sup -3} and 10{sup -5} Pa. When compared to the absorbed amount at higher temperature (above 200degC) was about 1/10 smaller than at room temperature. Desorption of methane from W getter film was hardly observed, but hydrogen was desorbed and the amount increased with temperature. About 16% carbon was found in the W film after gettering, of which the crystal structure differed according to the substrate ({beta}-W on glass sub., {alpha}-W on W sub.). (author).

  6. Hydrogen isotope recycling at a tungsten target

    Energy Technology Data Exchange (ETDEWEB)

    Sakamoto, M., E-mail: sakamoto@prc.tsukuba.ac.jp [Plasma Research Center, University of Tsukuba, Tsukuba, Ibaraki 305-8577 (Japan); Nakashima, Y. [Plasma Research Center, University of Tsukuba, Tsukuba, Ibaraki 305-8577 (Japan); Higashizono, Y. [Research Institute for Applied Mechanics, Kyushu University, Kasuga, Fukuoka 816-8580 (Japan); Ogawa, K. [Interdisciplinary Graduate School for Engineering Sciences, Kyushu University, Kasuga, Fukuoka 816-8580 (Japan); Hosoi, K. [Plasma Research Center, University of Tsukuba, Tsukuba, Ibaraki 305-8577 (Japan); Rusinov, A. [Interdisciplinary Graduate School for Engineering Sciences, Kyushu University, Kasuga, Fukuoka 816-8580 (Japan); Takeda, H.; Akabane, Y.; Kohagura, J.; Yoshikawa, M.; Ichimura, M.; Imai, T. [Plasma Research Center, University of Tsukuba, Tsukuba, Ibaraki 305-8577 (Japan)

    2013-07-15

    Hydrogen recycling has been studied focusing on the neutral behavior in front of tungsten target in the plasma–wall interaction simulator APSEDAS and the tandem mirror GAMMA 10. The line intensity of hydrogen Balmer series decreased toward the target corresponding to a decrease in the electron density in APSEDAS. The relative population of n = 3 and n = 4 increased and that of n = 5 and n = 6 decreased just in front of the target (Z < 5 mm). This might be attributed to the reflected atom or reemitted molecule from the target. In GAMMA 10, the intensity of hydrogen Balmer (H{sub α}) line decreased exponentially with distance from the target with two decay lengths: ∼16 mm and ∼53 mm. These two short decay lengths are attributed to the fact that a fraction of the reflected atoms and atoms dissociated from molecules are at excited energy states.

  7. A Study of Tungsten-Technetium Alloys

    Science.gov (United States)

    Maltz, J. W.

    1965-01-01

    Technetium is a sister element to rhenium and has many properties that are similar to rhenium. It is predicted that technetium will have about the same effects on tungsten as rhenium in regard to increase in workability, lowered ductile to brittle transition temperature, and improved ductility. The objectives of the current work are to recover technetium from fission product wastes at Hanford Atomic Products Operation and reduce to purified metal; prepare W-Tc alloys containing up to 50 atomic% Tc; fabricate the alloy ingots to sheet stock, assessing the effect of technetium on workability; and perform metallurgical and mechanical properties evaluation of the fabricated alloys. Previous reports have described the separation and purification of 800 g of technetium metal powder, melting of technetium and W-Tc alloys, and some initial observation of the alloy material.

  8. Ferromagnetism in exfoliated tungsten disulfide nanosheets

    Science.gov (United States)

    2013-01-01

    Two-dimensional-layered transition metal dichalcogenides nanosheets have attracted tremendous attention for their promising applications in spintronics because the atomic-thick nanosheets can not only enhance the intrinsic properties of their bulk counterparts, but also give birth to new promising properties. In this paper, ultrathin tungsten disulfide (WS2) nanosheets were gotten by liquid exfoliation route from its bulk form using dimethylformamide (DMF). Compared to the antiferromagnetism bulk WS2, ultrathin WS2 nanosheets show intrinsic room-temperature ferromagnetism (FM) with the maximized saturation magnetization of 0.004 emu/g at 10 K, where the appearance of FM in the nanosheets is partly due to the presence of zigzag edges in the magnetic ground state at the grain boundaries. PMID:24134699

  9. Fuzzy tungsten in a magnetron sputtering device

    Energy Technology Data Exchange (ETDEWEB)

    Petty, T.J., E-mail: tjpetty@liv.ac.uk [Department of Electrical Engineering and Electronics, University of Liverpool, Brownlow Hill, Liverpool, L69 3GJ (United Kingdom); Khan, A. [Pariser Building-G11, School of Mechanical, Aerospace and Civil Engineering, The University of Manchester, Manchester, M13 9PL (United Kingdom); Heil, T. [NiCaL, Block C Waterhouse Building, 1-3 Brownlow Street, Liverpool, L69 3GL (United Kingdom); Bradley, J.W., E-mail: j.w.bradley@liverpool.ac.uk [Department of Electrical Engineering and Electronics, University of Liverpool, Brownlow Hill, Liverpool, L69 3GJ (United Kingdom)

    2016-11-15

    Helium ion induced tungsten nanostructure (tungsten fuzz) has been studied in a magnetron sputtering device. Three parameters were varied, the fluence from 3.4 × 10{sup 23}–3.0 × 10{sup 24} m{sup −2}, the He ion energy from 25 to 70 eV, and the surface temperature from 900 to 1200 K. For each sample, SEM images were captured, and measurements of the fuzz layer thickness, surface roughness, reflectivity, and average structure widths are provided. A cross-over point from pre-fuzz to fully formed fuzz is found at 2.4 ± 0.4 × 10{sup 24} m{sup −2}, and a temperature of 1080 ± 60 K. No significant change was observed in the energy sweep. The fuzz is compared to low fluence fuzz created in the PISCES-A linear plasma device. Magnetron fuzz is less uniform than fuzz created by PISCES-A and with generally larger structure widths. The thicknesses of the magnetron samples follow the original Φ{sup 1/2} relation as opposed to the incubation fluence fit. - Highlights: • Fuzz has been created in a magnetron sputtering device. • Three parameters for fuzz formation have been swept. • A cross-over from pre-fuzz to fully formed fuzz is seen. • Evidence for annealing out at lower temperatures than has been seen before. • Evidence to suggest that fuzz grown in discrete exposures is not consistent with fuzz grown in one long exposure.

  10. Applications of silica supports in affinity chromatography.

    Science.gov (United States)

    Schiel, John E; Mallik, Rangan; Soman, Sony; Joseph, Krina S; Hage, David S

    2006-04-01

    The combined use of silica-based chromatographic supports with immobilized affinity ligands can be used in many preparative and analytical applications. One example is the use of silica-based affinity columns in HPLC, giving rise to a method known as high-performance affinity chromatography (HPAC). This review discusses the role that silica has played in the development of affinity chromatography and HPAC and the applications of silica in these methods. This includes a discussion of the types of ligands that have been employed with silica and the methods by which these ligands have been immobilized. Various formats have also been presented for the use of silica in affinity chromatographic methods, including assays involving direct or indirect analyte detection, on-line or off-line affinity extraction, and chiral separations. The use of silica-based affinity columns in studies of biological systems based on zonal elution and frontal analysis methods will also be considered.

  11. Refractory metals welded or brazed with tungsten inert gas equipment

    Science.gov (United States)

    Wisner, J. P.

    1965-01-01

    Appropriate brazing metals and temperatures facilitate the welding or brazing of base metals with tungsten inert gas equipment. The highest quality bond is obtained when TIG welding is performed in an inert atmosphere.

  12. Tungsten-induced carcinogenesis in human bronchial epithelial cells

    OpenAIRE

    Laulicht, Freda; Brocato, Jason; Cartularo, Laura; Vaughan, Joshua; Wu, Feng; Kluz, Thomas; Sun, Hong; Oksuz, Betul Akgol; Shen, Steven; Paena, Massimilano; Medici, Serenella; Zoroddu, Maria Antonietta; Costa, Max

    2015-01-01

    Metals such as arsenic, cadmium, beryllium, and nickel are known human carcinogens; however, other transition metals, such as tungsten (W), remain relatively uninvestigated with regard to their potential carcinogenic activity. Tungsten production for industrial and military applications has almost doubled over the past decade and continues to increase. Here, for the first time, we demonstrate tungsten’s ability to induce carcinogenic related endpoints including cell transformation, increased ...

  13. Metallic Tungsten Nanostructures and Highly Nanostructured Thin Films by Deposition of Tungsten Oxide and Subsequent Reduction in a Single Hot-Wire CVD Process

    NARCIS (Netherlands)

    Harks, P.P.R.M.L.; Houweling, Z.S.|info:eu-repo/dai/nl/251874486; de Jong, M.M.|info:eu-repo/dai/nl/325844208; Kuang, Y; Geus, J.W.; Schropp, R.E.I.|info:eu-repo/dai/nl/072502584

    2012-01-01

    The synthesis of metallic tungsten nanostructures and highly nanostructured thin films is presented. Crystalline tungsten oxide nanostructures are deposited on glassy carbon substrates kept at 700 100 8C by oxidizing resistively heated tungsten filaments in an air flow under subatmospheric

  14. Tungsten oxide thin films: detection and trapping of hazardous gases

    Science.gov (United States)

    Godbole, Rhushikesh; Vedpathak, Amol; Godbole, Vijay; Bhagwat, Sunita

    2017-07-01

    Synthesis of tungsten (W) and tungsten tri-oxide (WO3) thin films on alumina substrate by a peculiar Red-ox reaction route using hot-filament chemical vapor deposition technique is described. The resulting tungsten and tungsten oxide films were characterized using various techniques such as x-ray diffraction (XRD), Raman spectroscopy and Scanning electron microscopy (SEM). XRD results revealed the complete conversion of cubic phase of pure tungsten into monoclinic phase of tungsten oxide. Raman spectroscopic analysis also confirmed the formation of WO3. SEM images show considerable alteration in morphology from well faceted particles to wafers when pure W-film was converted to WO3 film. The wafer like morphology of WO3 films is found to be suitable for gas sensing towards hazardous gases such as NO2 and NH3. The WO3 films showcased their highly responsive nature towards NO2 gas with exceptionally high gas sensitivity ~32. WO3 film demonstrated longer recovery time towards NO2 gas unlike NH3 gas making them attractive for their utilization in ‘Newer application’ such as a catalyst support material in catalytic converter devices which are potential representatives to arrest pollutant gases (NO2) getting flown into the living environment.

  15. Irradiation effects in tungsten-copper laminate composite

    Science.gov (United States)

    Garrison, L. M.; Katoh, Y.; Snead, L. L.; Byun, T. S.; Reiser, J.; Rieth, M.

    2016-12-01

    Tungsten-copper laminate composite has shown promise as a structural plasma-facing component as compared to tungsten rod or plate. The present study evaluated the tungsten-copper composite after irradiation in the High Flux Isotope Reactor (HFIR) at temperatures of 410-780 °C and fast neutron fluences of 0.02-9.0 × 1025 n/m2, E > 0.1 MeV, 0.0039-1.76 displacements per atom (dpa) in tungsten. Tensile tests were performed on the composites, and the fracture surfaces were analyzed with scanning electron microscopy. Before irradiation, the tungsten layers had brittle cleavage failure, but the overall composite had 15.5% elongation at 22 °C. After only 0.0039 dpa this was reduced to 7.7% elongation, and no ductility was observed after 0.2 dpa at all irradiation temperatures when tensile tested at 22 °C. For elevated temperature tensile tests after irradiation, the composite only had ductile failure at temperatures where the tungsten was delaminating or ductile.

  16. Irradiation effects in tungsten-copper laminate composite

    Energy Technology Data Exchange (ETDEWEB)

    Garrison, L. M.; Katoh, Y.; Snead, L. L.; Byun, T. S.; Reiser, J.; Rieth, M.

    2016-12-01

    Tungsten-copper laminate composite has shown promise as a structural plasma-facing component as compared to tungsten rod or plate. The present study evaluated the tungsten-copper composite after irradiation in the High Flux Isotope Reactor (HFIR) at temperatures of 410-780°C and fast neutron fluences of 0.02-9.0×1025 n/m2, E>0.1 MeV, 0.0039-1.76 displacements per atom (dpa) in tungsten. Tensile tests were performed on the composites, and the fracture surfaces were analyzed with scanning electron microscopy. Before irradiation, the tungsten layers had brittle cleavage failure, but the overall composite had 15.5% elongation at 22°C. After only 0.0039 dpa this was reduced to 7.7% elongation, and no ductility was observed after 0.2 dpa at all irradiation temperatures when tensile tested at 22°C. For elevated temperature tensile tests after irradiation, the composite only had ductile failure at temperatures where the tungsten was delaminating or ductile.

  17. Development of Low Thermal Expansion Tungsten UO 2 Cermet Fuel

    Energy Technology Data Exchange (ETDEWEB)

    Marlowe, M O; Kaznoff, A I

    1970-03-31

    An attempt was made to develop a tungsten-uranium dioxide cermet of high fue 1 loading with thermal expansion approaching that of tungsten and with good dimensional stability on thermal cycling. These goals were sought through the use of tungsten-coated uranium dioxide particles with sufficient locally available void volume to accommodate the difference in thermal expansion between the uranium dioxide and the tungsten matrix and through limitation of plastic deformation in the particles during fabrication to avoid mechanical keying of the particles and the matrix. The particles were vibratorily compacted prior to hot pressing. The thermal expansion of the cermets was determined and they were thermal cycle tested. The thermal expansion of the cermets was considerably closer to that of tungsten than was observed with previously reported specimens of similar composition. However, the thermal cycling of the cermets resulted in intolerable growth. This growth could be accounted for by the agglomeration of gases trapped in the uranium dioxide particles during deposition of the tungsten coating.

  18. Growth and structure analysis of tungsten oxide nanorods using environmental TEM.

    Science.gov (United States)

    Tokunaga, Tomoharu; Kawamoto, Tadashi; Tanaka, Kenta; Nakamura, Naohiro; Hayashi, Yasuhiko; Sasaki, Katsuhiro; Kuroda, Kotaro; Yamamoto, Takahisa

    2012-01-25

    WO3 nanorods targeted for applications in electric devices were grown from a tungsten wire heated in an oxygen atmosphere inside an environmental transmission electron microscope, which allowed the growth process to be observed to reveal the growth mechanism of the WO3 nanorods. The initial growth of the nanorods did not consist of tungsten oxide but rather crystal tungsten. The formed crystal tungsten nanorods were then oxidized, resulting in the formation of the tungsten oxide nanorods. Furthermore, it is expected that the nanorods grew through cracks in the natural surface oxide layer on the tungsten wire.

  19. Nanomechanics of Single Crystalline Tungsten Nanowires

    Directory of Open Access Journals (Sweden)

    Volker Cimalla

    2008-01-01

    Full Text Available Single crystalline tungsten nanowires were prepared from directionally solidified NiAl-W alloys by a chemical release from the resulting binary phase material. Electron back scatter diffraction (EBSD proves that they are single crystals having identical crystallographic orientation. Mechanical investigations such as bending tests, lateral force measurements, and mechanical resonance measurements were performed on 100–300 nm diameter wires. The wires could be either directly employed using micro tweezers, as a singly clamped nanowire or in a doubly clamped nanobridge. The mechanical tests exhibit a surprisingly high flexibility for such a brittle material resulting from the small dimensions. Force displacement measurements on singly clamped W nanowires by an AFM measurement allowed the determination of a Young's modulus of 332 GPa very close to the bulk value of 355 GPa. Doubly clamped W nanowires were employed as resonant oscillating nanowires in a magnetomotively driven resonator running at 117 kHz. The Young's modulus determined from this setup was found to be higher 450 GPa which is likely to be an artefact resulting from the shift of the resonance frequency by an additional mass loading.

  20. Tungsten-enhanced growth of Methanosphaera stadtmanae

    Directory of Open Access Journals (Sweden)

    Dridi Bédis

    2012-05-01

    Full Text Available Abstract Background The methanogenic Archaea Methanosphaera stadtmanae has been detected in the human gut microbiota by both culture and culture-independent methods. Its growth reaches an exponential phase after 5 to 7-day culture in medium 322 (10% vol. Our recent successful isolation of Methanomassiliicoccus luminyensis, a tungstate-selenite-requiring Archaea sharing similar metabolism characteristics with M. stadtmanae prompted us to study the effects of tungsten and selenium on M. stadtmanae growth. Findings Addition of 0.2 mg/L sodium tungstate to medium 322 yielded, 48 hours after inoculation, a growth rate equivalent to that obtained after 6 days with control culture as measured by methane monitoring and optical density measurement. Addition of 50 μg/mL sodium selenate had no effect on M. stadtmanae growth. Quantitative real-time PCRs targeting the M. stadtmanae 16S rRNA confirmed these data. Conclusions These data provide new information regarding the poorly known nutritional requirements of the human gut colonizing organismsM. stadtmanae. Adding sodium tungstate to basal medium may facilitate phenotypic characterization of this organism and additionally aid the isolation of new Archaeafrom complex host microbiota.

  1. Signal Analysis of Gas Tungsten Arc Welds

    Science.gov (United States)

    Eagar, T. W.

    1985-01-01

    Gas tungsten arc welding is a process in which the input parameters such as current, voltage and travel speed, can be easily controlled and/or monitored. However, weld quality is not solely a function of these parameters. An adaptive method of observing weld quality is desired to improve weld quality assurance. The use of dynamic electrical properties of the welding arc as a weld quality monitor was studied. The electrical properties of the arc are characterized by the current voltage transfer function. The hardware and software necessary to collect the data at a maximum rate of 45 kHz and to allow the off-line processing of this data are tested. The optimum input current waveform is determined. Bead-on-plate welds to observe such characteristics of the weld as the fundamental frequency of the puddle are studied. Future work is planned to observe changes of the arc response with changes in joint geometry, base metal chemistry, and shielding gas composition are discussed.

  2. The DAMPE silicon–tungsten tracker

    Energy Technology Data Exchange (ETDEWEB)

    Azzarello, P., E-mail: philipp.azzarello@unige.ch [Département de Physique Nucléaire et Corpusculaire, University of Geneva, Geneva (Switzerland); Ambrosi, G. [Istituto Nazionale di Fisica Nucleare Sezione di Perugia, Perugia (Italy); Asfandiyarov, R. [Département de Physique Nucléaire et Corpusculaire, University of Geneva, Geneva (Switzerland); Bernardini, P. [Dipartimento di Matematica e Fisica “E. De Giorgi”, Università del Salento, Lecce (Italy); Istituto Nazionale di Fisica Nucleare Sezione di Lecce, Lecce (Italy); Bertucci, B.; Bolognini, A. [Istituto Nazionale di Fisica Nucleare Sezione di Perugia, Perugia (Italy); Dipartimento di Fisica e Geologia, Università di Perugia, Perugia (Italy); Cadoux, F. [Département de Physique Nucléaire et Corpusculaire, University of Geneva, Geneva (Switzerland); Caprai, M. [Istituto Nazionale di Fisica Nucleare Sezione di Perugia, Perugia (Italy); De Mitri, I. [Dipartimento di Matematica e Fisica “E. De Giorgi”, Università del Salento, Lecce (Italy); Istituto Nazionale di Fisica Nucleare Sezione di Lecce, Lecce (Italy); Domenjoz, M. [Département de Physique Nucléaire et Corpusculaire, University of Geneva, Geneva (Switzerland); Dong, Y. [Institute of High Energy Physics, Chinese Academy of Sciences, Beijing (China); Duranti, M. [Istituto Nazionale di Fisica Nucleare Sezione di Perugia, Perugia (Italy); Dipartimento di Fisica e Geologia, Università di Perugia, Perugia (Italy); Fan, R. [Institute of High Energy Physics, Chinese Academy of Sciences, Beijing (China); and others

    2016-09-21

    The DArk Matter Particle Explorer (DAMPE) is a spaceborne astroparticle physics experiment, launched on 17 December 2015. DAMPE will identify possible dark matter signatures by detecting electrons and photons in the 5 GeV–10 TeV energy range. It will also measure the flux of nuclei up to 100 TeV, for the study of the high energy cosmic ray origin and propagation mechanisms. DAMPE is composed of four sub-detectors: a plastic strip scintillator, a silicon–tungsten tracker–converter (STK), a BGO imaging calorimeter and a neutron detector. The STK is composed of six tracking planes of 2 orthogonal layers of single-sided micro-strip detectors, for a total detector surface of ca. 7 m{sup 2}. The STK has been extensively tested for space qualification. Also, numerous beam tests at CERN have been done to study particle detection at silicon module level, and at full detector level. After description of the DAMPE payload and its scientific mission, we will describe the STK characteristics and assembly. We will then focus on some results of single ladder performance tests done with particle beams at CERN.

  3. Anthocyanins facilitate tungsten accumulation in Brassica

    Energy Technology Data Exchange (ETDEWEB)

    Hale, K.L.

    2002-11-01

    Accumulation of molybdenum in Brassica was recently found to be correlated with anthocyanin content, involving the formation of a blue complex. Here the role of anthocyanins in tungsten sequestration was investigated using three species of Brassica: B. rapa (cv. Fast plants), B. juncea (Indian mustard) and B. oleracea (red cabbage). Seedlings of B. rapa and B. juncea turned blue when supplied with colourless tungstate. The blue compound co-localized with anthocyanins in the peripheral cell layers, and the degree of blueness was correlated with anthocyanin content. The direct involvement of anthocyanins in the blue coloration was evident when purified anthocyanins showed a colour change from pink to blue in vitro upon addition of tungstate, over a wide pH range. Anthocyanin production was upregulated 3-fold by W in B. juncea, possibly reflecting a function for anthocyanins in W tolerance or sequestration. The presence of anthocyanins facilitated W accumulation in B. rapa: anthocyanin-containing seedlings accumulated 3-fold more W than an anthocyaninless mutant. There was no correlation between anthocyanin content and W tolerance under these conditions. The nature of the interaction between anthocyanins and tungstate was investigated. X-ray absorption spectroscopy showed no change in the local chemical environment of Wupon uptake of tungstate by the plant; HPLC analysis of purified anthocyanin with or without tungstate showed no peak shift after metal treatment.

  4. Effect of tungsten and carbon surface mixed layer on deuterium permeation in tungsten

    Energy Technology Data Exchange (ETDEWEB)

    Peng, H.Y., E-mail: penghanyee_8388@st.eie.eng.osaka-u.ac.jp [Graduate School of Engineering, Osaka University, Suita, Osaka (Japan); Lee, H.T.; Ohtsuka, Y.; Ueda, Y. [Graduate School of Engineering, Osaka University, Suita, Osaka (Japan)

    2013-07-15

    Deuterium ion-driven permeation in tungsten under mixed deuterium and carbon irradiation at 1 keV was studied to investigate the incident flux dependency on deuterium permeation. Permeation experiments were performed at three temperatures (T{sub w} = 610 K, 710 K, 850 K) under incident flux of 10{sup 19}–10{sup 20} m{sup −2} s{sup −1}. The variation of incident flux leads to similar temperature-dependent increase in steady-state deuterium permeation flux under mixed deuterium and carbon irradiation as observed in previous study. It is also found that the rise in permeation at high temperature larger than 800 K cannot be explained by changes in front diffusivity of W–C mixed layer. Also, the incident flux dependency in deuterium permeation cannot be explained only by the hydrogen transport theory of Doyle and Brice. It is deducted that a mixed deuterium and carbon irradiation could cause an oversaturation state of deuterium in tungsten at temperature lower than 700 K.

  5. Chemically deposited tungsten fibre-reinforced tungsten – The way to a mock-up for divertor applications

    Directory of Open Access Journals (Sweden)

    J. Riesch

    2016-12-01

    Full Text Available The development of advanced materials is essential for sophisticated energy systems like a future fusion reactor. Tungsten fibre-reinforced tungsten composites (Wf/W utilize extrinsic toughening mechanisms and therefore overcome the intrinsic brittleness of tungsten at low temperature and its sensitivity to operational embrittlement. This material has been successfully produced and tested during the last years and the focus is now put on the technological realisation for the use in plasma facing components of fusion devices. In this contribution, we present a way to utilize Wf/W composites for divertor applications by a fabrication route based on the chemical vapour deposition (CVD of tungsten. Mock-ups based on the ITER typical design can be realized by the implementation of Wf/W tiles. A concept based on a layered deposition approach allows the production of such tiles in the required geometry. One fibre layer after the other is positioned and ingrown into the W-matrix until the final sample size is reached. Charpy impact tests on these samples showed an increased fracture energy mainly due to the ductile deformation of the tungsten fibres. The use of Wf/W could broaden the operation temperature window of tungsten significantly and mitigate problems of deep cracking occurring typically in cyclic high heat flux loading. Textile techniques are utilized to optimise the tungsten wire positioning and process speed of preform production. A new device dedicated to the chemical deposition of W enhances significantly, the available machine time for processing and optimisation. Modelling shows that good deposition results are achievable by the use of a convectional flow and a directed temperature profile in an infiltration process.

  6. Recovery of Tungsten and Molybdenum from Low-Grade Scheelite

    Science.gov (United States)

    Li, Yongli; Yang, Jinhong; Zhao, Zhongwei

    2017-10-01

    With most high-quality tungsten ores being exhausted, the enhancement of low-grade scheelite concentrates processing has attracted a great deal of attention. The objective of this study is to develop a method to maximize the recovery tungsten and molybdenum from a low-grade scheelite via a new acid leaching process followed by solvent extraction. Under optimal conditions (350 g/L H2SO4, 95°C, and 2 h), approximately 99.8% of tungsten and 98% of molybdenum were leached out. In the subsequent solvent extraction process, more than 99% of the tungsten and molybdenum were extracted with a co-extraction system (50% TBP, 30% HDEHP, and 10% 2-octanol in kerosene) using a three-stage cross-flow extraction. The raffinate can be recycled for the next leaching process after replenishing the H2SO4 to the initial value (approximately 350 g/L). Based on these results, a conceptual flowsheet is presented to recover tungsten and molybdenum from the low-grade scheelite.

  7. Tungsten materials as durable catalyst supports for fuel cell electrodes

    Science.gov (United States)

    Perchthaler, M.; Ossiander, T.; Juhart, V.; Mitzel, J.; Heinzl, C.; Scheu, C.; Hacker, V.

    2013-12-01

    Durable platinum catalyst support materials, e.g. tungsten carbide (WC), tungsten oxide (WOx) and self-synthesized tungsten oxide (WOxs) were evaluated for the use in High-Temperature Proton Exchange Fuel Cells (HT-PEM) based on phosphoric acid doped polybenzimidazole as electrolyte. The support materials and the catalyst loaded support materials were characterized ex-situ by cyclic voltammetry in HClO4, potential cycling, CO-stripping, electron microscopy and X-ray diffraction measurements. The tungsten oxide and tungsten carbide based supported catalysts were compared to High Surface Area Carbon (HSAC), each coated with platinum via the same in-house manufacturing procedures. The in-house manufacturing procedures resulted in catalyst particle sizes on HSAC of 3-4 nm with a uniform distribution. The in-situ Potential Cycling experiments of WOx or WOxs supported catalysts showed much lower degradation rates compared to High Surface Area Carbons. The formation of WOx species on WC was proven by ex- and in-situ cyclic voltammetric studies and thermogravimetric analyses. X-ray diffraction, ex-situ cyclic voltammetry and in-situ cyclic voltammetry showed that WOx is formed from WC as starting material under oxidizing conditions. Finally a 1000 h durability test with WOx as catalyst support material on the anode was done in a HT-PEM fuel cell with reformed methanol on the anode.

  8. 75 FR 75694 - Certain Semiconductor Integration Circuits Using Tungsten Metallization and Products Containing...

    Science.gov (United States)

    2010-12-06

    ... United States after importation of certain semiconductor integrated circuits using tungsten metallization... COMMISSION Certain Semiconductor Integration Circuits Using Tungsten Metallization and Products Containing... Manufacturing Corporation of China; Integrated Device Technology, Inc. of San Jose, California; and Nanya...

  9. Study of Tungsten effect on CFETR performance

    Science.gov (United States)

    Shi, Shengyu; Xiang Gao Collaboration; Guoqiang Li Collaboration; Nan Shi Collaboration; Vincent Chan Collaboration; Xiang Jian Collaboration

    2017-10-01

    An integrated modeling workflow using OMFIT/TGYRO is constructed to evaluate W impurity effects on China Fusion Engineering Test Reactor (CFETR) performance. Self-consistent modeling of tungsten(W) core density profile, accounting for turbulence and neoclassical transport, is performed based on the CFETR steady-state scenario developed by D.Zhao (ZhaoDeng, APS, 2016). It's found that the fusion performance degraded in a limited level with increasing W concentration. The main challenge arises in sustainment of H-mode with significant W radiation. Assuming the power threshold of H-L back transition is approximately the same as that of L-H transition, using the scaling law of Takizuka (Takizuka etc, Plasma Phys. Control. Fusion, 2004), it is found that the fractional W concentration should not exceed 3e-5 to stay in H-mode for CFETR phase I. A future step is to connect this requirement to W wall erosion modeling. We are grateful to Dr. Emiliano Fable and Dr. Thomas Pütterich and Ms. Emily Belli for very helpful discussions and comments. We also would like to express our thanks to all the members of the CFETR Physics Group, and we appreciate the General Atomic Theory Group for permission to use the OMFIT framework and GA code suite, and for their valuable technical support. Numerical computations were performed on the ShenMa High Performance Computing Cluster in the Institute of Plasma Physics, Chinese Academy of Sciences. This work was mainly supported by the National Magnetic Confinement Fusion Research Program of China (Grant Nos. 2014GB110001, 2014GB110002, 2014GB110003) and supported in part by the National ITER Plans Program of China (Grant Nos. 2013GB106001, 2013GB111002, 2015GB110001).

  10. Mathematical Modelling of the Process of Tungsten Fluorides Reduction by Hydrogen

    OpenAIRE

    Brendakov Roman; Shvab Alexander; Brendakov Vladimir

    2016-01-01

    The process of tungsten fluorides reduction by hydrogen is a component part of Fluoride technology of tungsten conversion. Nowadays the researchers are definitely interested in studying this process. It is connected with common use of metal tungsten products in different sectors of the economy, which is the result of unique qualities of this metal. With the help of physical and mathematical modelling of the process of tungsten hexafluoride reduction by hydrogen, it becomes possible to create ...

  11. Tungsten erosion at low energy impact under steady state plasma conditions

    Energy Technology Data Exchange (ETDEWEB)

    Antonov, N.V. [Institute of Nuclear Fusion, Russian Research Center `Kurchatov Inst.`, Moscow (Russian Federation); Khripunov, B.I. [Institute of Nuclear Fusion, Russian Research Center `Kurchatov Inst.`, Moscow (Russian Federation); Petrov, V.B. [Institute of Nuclear Fusion, Russian Research Center `Kurchatov Inst.`, Moscow (Russian Federation); Shapkin, V.V. [Institute of Nuclear Fusion, Russian Research Center `Kurchatov Inst.`, Moscow (Russian Federation); Pistunovich, V.I. [Institute of Nuclear Fusion, Russian Research Center `Kurchatov Inst.`, Moscow (Russian Federation)

    1995-04-01

    Tungsten is considered as one of the candidate materials for application in future fusion devices for plasma facing components. The calculated threshold energy of deuterium for physical sputtering of tungsten is rather high [3] (341 eV). Thus one could expect that tungsten surface sputtering would be absent in pure hydrogen edge plasma with low temperature. Continuous deuterium plasma conditions were used in these experiments to investigate the tungsten erosion characteristics. ((orig.)).

  12. Material properties of very thin electroless silver-tungsten films

    Energy Technology Data Exchange (ETDEWEB)

    Bogush, V.; Inberg, A.; Croitoru, N.; Dubin, V.; Shacham-Diamand, Y

    2003-02-24

    Thin electroless silver-tungsten (Ag-W) films were deposited on silicon dioxide substrate from the benzoate solution. The layer composition and microstructure as well as the film deposition rate were studied as a function of the bath formulation. The tungsten concentration in the deposit was up to {approx}2.1 atm% with corresponding oxygen concentration approximately 4 atm%. It was found that electrical, optical, and mechanical properties of Ag-W films depend on the W content in the deposit. Ag-W films of sub 120 nm thickness with {approx}0.6 atm% tungsten and 1.8 atm% oxygen have demonstrated the resistivity of {approx}4 {mu}{omega}{center_dot}cm. Finally, the possibility to use the Ag-W thin films for microelectronic metallization is discussed.

  13. [Radiation protection provided by tungsten bismuth caps during interventional cardiology].

    Science.gov (United States)

    Ramos-Avasola, Sergio; Díaz, Natalia; Roldán, Reynaldo; Gamarra, Jorge; Catalán, Mónica

    2016-07-01

    The effectiveness against radiation of tungsten bismuth caps, used in interventional cardiology is not well known. To determine the degree of radiation protection conferred by these caps in real work conditions. We compared the gross electric charges received at brain lobe levels by three occupationally exposed professionals who participated in 22 consecutive procedures, inside and outside of the tungsten bismuth cap. The median electric charges outside and inside the cap were 3.71 (range 1.46-5.62) and 2.2 (range 1.29-3.93) nC, which correspond to a 40% radiation attenuation. However, the protection was heterogeneous. Tungsten bismuth caps provide an adequate attenuation, but its degree is heterogeneous.

  14. Synthesis of Tungsten Diselenide Nanoparticles by Chemical Vapor Condensation Method

    Directory of Open Access Journals (Sweden)

    Oleg V. Tolochko

    2015-09-01

    Full Text Available Crystalline tungsten diselenide (WSe2 nanoparticles have been synthesized by a gas phase reaction using tungsten hexacarbonyl and elemental selenium as precursors. The WSe2 nanoparticle morphology varies from the spherical shape to flake-like layered structures. Mean size in smaller dimension are less than 5 nm and the number of layers decreased linearly with decreasing of reaction time and concentration of carbonyl in the gas phase. The mean value of interlayer distance in <0001> direction is comparable with the microscopic values. The selenium-to-tungsten atomic ratios of 2.07, 2.19 and 2.19 were determined respectively, approach to the stoichiometric ratio of 2:1. Main impurities are oxygen and carbon and strongly interrelated with carbonyl concentration in the gas phase.DOI: http://dx.doi.org/10.5755/j01.ms.21.3.7356

  15. Study of ion-irradiated tungsten in deuterium plasma

    Energy Technology Data Exchange (ETDEWEB)

    Khripunov, B.I., E-mail: boris@nfi.kiae.ru [National Research Center Kurchatov Institute, Kurchatov Sq. 1, Moscow 123182 (Russian Federation); Gureev, V.M.; Koidan, V.S.; Kornienko, S.N.; Latushkin, S.T.; Petrov, V.B.; Ryazanov, A.I.; Semenov, E.V.; Stolyarova, V.G.; Danelyan, L.S. [National Research Center Kurchatov Institute, Kurchatov Sq. 1, Moscow 123182 (Russian Federation); Kulikauskas, V.S.; Zatekin, V.V. [Institute of Nuclear Physics, Lomonosov University, Moscow 119991 (Russian Federation); Unezhev, V.N. [National Research Center Kurchatov Institute, Kurchatov Sq. 1, Moscow 123182 (Russian Federation)

    2013-07-15

    Experimental study aimed at investigation of neutron induced damage influence on fusion reactor plasma facing materials is reported. Displacement damage was produced in tungsten by high-energy helium and carbon ions at 3–10 MeV. The reached level of displacement damage ranged from several dpa to 600 dpa. The properties of the irradiated tungsten were studied in steady-state deuterium plasma on the LENTA linear divertor simulator. Plasma exposures were made at 250 eV of ion energy to fluence 10{sup 21}–10{sup 22} ion/cm{sup 2}. Erosion dynamics of the damaged layer and deuterium retention were observed. Surface microstructure modifications and important damage of the 5 μm layer shown. Deuterium retention in helium-damaged tungsten (ERD) showed its complex behavior (increase or decrease) depending on implanted helium quantity and the structure of the surface layer.

  16. Synthetic approaches toward tungsten photonic crystals for thermal emission

    Science.gov (United States)

    Denny, Nicholas R.; Han, Sangjin; Turgeon, Ryan T.; Lytle, Justin C.; Norris, David J.; Stein, Andreas

    2005-11-01

    The efficiency of standard incandescent light sources is limited by strong thermal emission in the infrared regime. It is possible that emission of light may be more efficient when the conventional tungsten filament is replaced by metallic photonic crystals that have large photonic band gaps in the infrared and can suppress the thermal emission of blackbody emitters. One approach toward fabricating photonic crystal structures with highly ordered periodic features on an optical length scale involves colloidal crystal templating to produce inverse opals. Metallic inverse opals were synthesized using chemical vapor deposition (CVD) and wet chemical methods capable of producing granules, thin films and monolithic pieces. Thin films were prepared by infiltrating silica opal films with tungsten hexacarbonyl in a CVD process, reducing tungsten in hydrogen and removing the silica template by HF etching. A range of soluble metal precursors, including tungsten(VI) chloride, tungsten(V) ethoxide and acetylated peroxotungstic acid, were infiltrated into self-assembled, colloidal crystal arrays comprised of monodisperse poly(methyl methacrylate) (PMMA) spheres. The infiltrated composites were processed under reducing conditions to produce metallic inverse replicas of the template. The influence of processing conditions on structural properties, including thickness of skeletal walls, window openings and solid filling fraction, was studied. A monolithic tungsten inverse opal with dimensions of 0.5 × 0.5 × 0.2 cm was resistively heated in an inert atmosphere and thermal emission was observed. The wet chemical methods provide a low cost alternative to expensive nanolithographic methods for the fabrication of three-dimensional periodic metallic structures.

  17. Effect of neon plasma pre-irradiation on surface morphology and deuterium retention of tungsten

    NARCIS (Netherlands)

    Cheng, L.; De Temmerman, G.; van Emmichoven, P. A. Zeijlma; Ji, G.; Zhou, H. B.; Wang, B.; Yuan, Y.; Zhang, Y.; Lu, G. H.

    2015-01-01

    Neon and deuterium plasma irradiation of polycrystalline tungsten targets have been performed at high fluxes of ∼1024 ions m−2 s−1 to study the interaction of neon with tungsten and the influence of neon on deuterium retention. Tungsten exposure to neon plasma leads to the

  18. Deuterium retention and surface modifications of nanocrystalline tungsten films exposed to high-flux plasma

    NARCIS (Netherlands)

    't Hoen, M.H.J.; Dellasega, D.; Pezzoli, A.; Passoni, M.; Kleyn, A.W.; Zeijlmans van Emmichoven, P.A.

    2015-01-01

    Deuterium retention studies are presented for nanostructured tungsten films exposed to high-flux deuterium plasmas. Thin tungsten films of similar to 1 mu m thickness were deposited with pulsed laser deposition (PLD) on bulk tungsten. Surface modifications were studied with scanning electron

  19. Characterisation of Tungsten Nitride Layers and their Erosion under Plasma Exposure in NANO-PSI

    NARCIS (Netherlands)

    Alegre, D.; Acsente, T.; Martin-Rojo, A. B.; Oyarzabal, E.; Tabares, F. L.; Dinescu, G.; De Temmerman, G.; Birjega, R.; Logofatu, C.; Kovac, J.; Mozetic, M.

    2015-01-01

    The properties of tungsten nitride thin films deposited by both reactive RF-magnetron sputtering from tungsten targets in Argon/N-2, and RF generated nitrogen ions bombardment of previously sequentially deposited tungsten layers have been investigated. Films exhibited smaller erosion than pure

  20. Deuterium retention and surface modifications of nanocrystalline tungsten films exposed to high-flux plasma

    NARCIS (Netherlands)

    Hoen, M. H. J. 't; Dellasega, D.; Pezzoli, A.; Passoni, M.; Kleyn, A. W.; van Emmichoven, P. A. Zeijlma

    2015-01-01

    Abstract Deuterium retention studies are presented for nanostructured tungsten films exposed to high-flux deuterium plasmas. Thin tungsten films of ∼1 μm thickness were deposited with pulsed laser deposition (PLD) on bulk tungsten. Surface modifications were studied with scanning electron

  1. Quantum-Accurate Molecular Dynamics Potential for Tungsten

    Energy Technology Data Exchange (ETDEWEB)

    Wood, Mitchell; Thompson, Aidan P.

    2017-03-01

    The purpose of this short contribution is to report on the development of a Spectral Neighbor Analysis Potential (SNAP) for tungsten. We have focused on the characterization of elastic and defect properties of the pure material in order to support molecular dynamics simulations of plasma-facing materials in fusion reactors. A parallel genetic algorithm approach was used to efficiently search for fitting parameters optimized against a large number of objective functions. In addition, we have shown that this many-body tungsten potential can be used in conjunction with a simple helium pair potential1 to produce accurate defect formation energies for the W-He binary system.

  2. Temperature and distortion transients in gas tungsten-arc weldments

    Energy Technology Data Exchange (ETDEWEB)

    Glickstein, S.S.; Friedman, E.

    1979-10-01

    An analysis and test program to develop a fundamental understanding of the gas tungsten-arc welding process has been undertaken at the Bettis Atomic Power Laboratory to develop techniques to determine and control the various welding parameters and weldment conditions so as to result in optimum weld response characteristics. These response characteristics include depth of penetration, weld bead configuration, weld bead sink and roll, distortion, and cracking sensitivity. The results are documented of that part of the program devoted to analytical and experimental investigations of temperatures, weld bead dimensions, and distortions for moving gas tungsten-arc welds applied to Alloy 600 plates.

  3. A review of chromium, molybdenum, and tungsten alloys

    Science.gov (United States)

    Klopp, W. D.

    1975-01-01

    The mechanical properties of chromium, molybdenum, and tungsten alloys are reviewed with particular emphasis on high-temperature strength and low-temperature ductility. Precipitate strengthening is highly effective at 0.4 to 0.8 times the melting temperature in these metals, with HfC being most effective in tungsten and molybdenum, and Ta(B,C) most effective in chromium. Low-temperature ductility can be improved by alloying to promote rhenium ductilizing or solution softening. The low-temperature mechanical properties of these alloys appear related to electronic interactions rather than to the usual metallurgical considerations.

  4. Dislocation mechanism of deuterium retention in tungsten under plasma implantation.

    Science.gov (United States)

    Dubinko, V I; Grigorev, P; Bakaev, A; Terentyev, D; van Oost, G; Gao, F; Van Neck, D; Zhurkin, E E

    2014-10-01

    We have developed a new theoretical model for deuterium (D) retention in tungsten-based alloys on the basis of its being trapped at dislocations and transported to the surface via the dislocation network with parameters determined by ab initio calculations. The model is used to explain experimentally observed trends of D retention under sub-threshold implantation, which does not produce stable lattice defects to act as traps for D in conventional models. Saturation of D retention with implantation dose and effects due to alloying of tungsten with, e.g. tantalum, are evaluated, and comparison of the model predictions with experimental observations under high-flux plasma implantation conditions is presented.

  5. Tool life of ceramic wedges during precise turning of tungsten

    Directory of Open Access Journals (Sweden)

    Legutko Stanislaw

    2017-01-01

    Full Text Available Properties, application and machinability of tungsten and its alloys have been demonstrated. The comparison of the tool life and wear of the wedges made of SiAlON and whisker ceramics during the precise turning at different cutting parameters have been presented. The CNC lathe DMG CTX 310 Ecoline and tungsten of 99.7 % purity were used during the experiments. Only the wedge of whisker ceramics has proved to be sufficiently suitable and only for relatively low cutting speeds.

  6. Effects of sequential tungsten and helium ion implantation on nano-indentation hardness of tungsten

    Energy Technology Data Exchange (ETDEWEB)

    Armstrong, D. E. J.; Edmondson, P. D.; Roberts, S. G. [Department of Materials, University of Oxford, Parks Road, Oxford OX1 3PH (United Kingdom)

    2013-06-24

    To simulate neutron and helium damage in a fusion reactor first wall sequential self-ion implantation up to 13 dpa followed by helium-ion implantation up to 3000 appm was performed to produce damaged layers of {approx}2 {mu}m depth in pure tungsten. The hardness of these layers was measured using nanoindentation and was studied using transmission electron microscopy. Substantial hardness increases were seen in helium implanted regions, with smaller hardness increases in regions which had already been self-ion implanted, thus, containing pre-existing dislocation loops. This suggests that, for the same helium content, helium trapped in distributed vacancies gives stronger hardening than helium trapped in vacancies condensed into dislocation loops.

  7. Tungsten-molybdenum fractionation in estuarine environments

    Science.gov (United States)

    Mohajerin, T. Jade; Helz, George R.; Johannesson, Karen H.

    2016-03-01

    Dissolved tungsten (W) and molybdenum (Mo) concentrations were measured in surface waters and sediment pore waters of Terrebonne Bay, a shallow estuary in the Mississippi River delta, to investigate the biogeochemical processes that fractionate these Group 6 elements relative to one another during transit from weathering to sedimentary environments. Although many of the chemical properties of W and Mo are similar, the two elements behave autonomously, and the fractionation mechanisms are only partly understood. In sulfidic pore waters, dissolved Mo is depleted relative to river water-seawater mixtures, whereas dissolved W is >10-fold enriched. Reductive dissolution of poorly crystalline phases like ferrihydrite, which is a preferential host of W relative to Mo in grain coatings on river-borne particles, can explain the dissolved W enrichment. Dissolved W becomes increasingly enriched as H2S(aq) rises above about 60 μM due to transformation of WO42- to thiotungstates as well as to additional reductive dissolution of phases that host W. In contrast, as rising sulfide transforms MoO42- to thiomolybdates in pore waters, dissolved Mo is suppressed, probably owing to equilibration with an Fe-Mo-S phase. This putative phase appears to control the aqueous ion product, Q = [Fe2+][MoS42-]0.6 [H2S0]0.4/[H+]0.8, at a value of 10-7.78. Concentrations of dissolved W and Mo in pore waters bear no relation to concentrations in surface waters of the same salinity. In surface waters, dissolved Mo is nearly conserved in the estuarine mixing zone. Dissolved W appears also to be conserved except for several cases where W may have been enhanced by exchange with underlying, W-rich pore waters. With increasing salinity, the molar Mo/W ratio rises from about 10 to about 1000 in surface waters whereas it is mostly sequestration on river-borne particles and its subsequent release to sulfidic pore waters after the particles are deposited in the delta and become subject to reductive

  8. Friedel-Crafts acylation of the 2-methoxynaphthalene using the silica-supported dodecatungstophosphoric acid (HPW/SiO{sub 2}) as catalyst and acetonitrile as solvent; Acilacao de Friedel-Crafts do 2-metoxinaftaleno usando o acido dodecafosfotungstico suportado em silica (HPW/SiO{sub 2}) como catalisador e acetonitrila como solvente

    Energy Technology Data Exchange (ETDEWEB)

    Santos, Gil Luciano Guedes dos; Silva, Creuza Souza; Cardoso, Luiz Augusto Martins [Universidade Estadual do Sudoeste da Bahia, Jequie, BA (Brazil). Dept. de Quimica e Exatas

    2010-07-01

    The synthesis of fine chemicals intermediates using Friedel-Crafts acylation is one of the most important methods in chemical technology. In this work, the acylation of 2-methoxynaphthalene with acetic anhydride using a silica-supported dodeca tungstophosphoric acid catalyst (HPW/SiO{sub 2}) and acetonitrile as solvent was studied, showing that this reaction is a feasible alternative to produce intermediaries to replace the current methods of production. The reactions using acetonitrile solvent showed yields greater than or equal to the reactions using traditional solvents such as nitrobenzene and dichloroethane. Finally, the modified Eley-Rideal mechanism was proposed to elucidate the experimental data obtained. (author)

  9. Acilação de Friedel-Crafts do 2-metoxinaftaleno usando o ácido dodecafosfotúngstico suportado em sílica (HPW/SiO2 como catalisador e acetonitrila como solvente Friedel-Crafts acylation of the 2-methoxynaphthalene using the silica-supported dodecatungstophosphoric acid (HPW/SiO2 as catalyst and acetonitrile as solvent

    Directory of Open Access Journals (Sweden)

    Gil Luciano Guedes dos Santos

    2010-01-01

    Full Text Available The synthesis of fine chemicals intermediates using Friedel-Crafts acylation is one of the most important methods in chemical technology. In this work, the acylation of 2-methoxynaphthalene with acetic anhydride using a silica-supported dodecatungstophosphoric acid catalyst (HPW/SiO2 and acetonitrila as solvent was studied, showing that this reaction is a feasible alternative to produce intermediaries to replace the current methods of production. The reactions using acetonitrile solvent showed yields greater than or equal to the reactions using traditional solvents such as nitrobenzene and dichloroethane. Finally, the modified Eley-Rideal mechanism was proposed to elucidate the experimental data obtained.

  10. Construction of a well-defined multifunctional dendrimer for theranostics.

    Science.gov (United States)

    Ornelas, Cátia; Pennell, Ryan; Liebes, Leonard F; Weck, Marcus

    2011-03-04

    A dendrimer-based building block for theranostics was designed. The multifunctional dendrimer is polyamide-based and contains nine azide termini, nine amine termini, and fifty-four terminal acid groups. Orthogonal functionalization of the multifunctional dendrimer with a near-infrared (NIR) cyanine dye afforded the final dendrimer that shows fluorescence in the NIR region and no toxicity toward T98G human cells. The synthetic strategy described here might be promising for fabricating the next generation of materials for theranostics.

  11. Electron transfer in systems of well-defined geometry

    Energy Technology Data Exchange (ETDEWEB)

    Overfield, R.E.; Kaufmann, K.J.; Wasielewski, M.R.

    1980-01-01

    Two mesopyropheophorbide macrocycles can be joined via two covalent linkages to produce a cyclophane. It is possible to insert one or two Mg atoms into the cyclophane. The Qy transitions of the macrocycles are nearly orthogonal. The visible absorption spectrum of the monometal cyclophane is nearly a superposition of the spectra of the monomers. Emission from the monometal cyclophane arises primarily from the red most absorbing chromophore. The excited state difference spectrum shows that both macrocycles are excited. Fluorescence lifetimes of the monometal cyclophane decrease with increasing dielectric strength. Changes in the fluorescence and the triplet yield parallel the shortening of the singlet lifetime. Thus the radiative rate is solvent independent. This is in contrast to what one would expect if the emitting state had charge transfer character. Since the fluorescence lifetime is dependent on dielectric, the nonradiative relaxation from the singlet state is due to formation of a radical pair. The decay rate of the postulated radical pair was monitored by observing the kinetics of ground state repopulation. For the geometry of this cyclophane, electron transfer proceeds relatively slowly (k = 3 x 10/sup 9/ sec/sup -1/) in the forward direction. Modeling calculations indicate that the rate of annihilation of the radical pair may decrease as the solvent dielectric decreases.

  12. Method of preparing well-defined polypeptides via rop

    KAUST Repository

    Hadjichristidis, Nikolaos

    2015-09-24

    A process for living ring-opening polymerization can include exposing an N- carboxyanhydride monomer to an initiator that includes a first primary amine covalently linked to a first electron donor by a first linking group to form a polyamide polymer. The initiator can include a second primary amine, optionally a second electron donor, and optionally a third electron donor.

  13. Well-Defined Microapertures for Ion Channel Biosensors

    NARCIS (Netherlands)

    Halza, Erik; Bro, Tobias Hedegaard; Bilenberg, Brian; Kocer, Armagan

    2013-01-01

    Gated ion channels are excitable nanopores in biological membranes. They sense and respond to different triggers in nature. The sensory characteristics of these channels can be modified by protein engineering tools and the channels can be functionally reconstituted into synthetic lipid bilayer

  14. Ichthyosis prematurity syndrome: a well-defined congenital ichthyosis subtype

    DEFF Research Database (Denmark)

    Bygum, Anette; Westermark, Per; Brandrup, Flemming

    2008-01-01

    Ichthyosis prematurity syndrome is a rare syndrome characterized by the clinical triad of premature birth, thick caseous desquamating epidermis, and neonatal asphyxia. We describe two siblings with ichthyosis prematurity syndrome. The index patient was born at gestational week 34. Immediately aft...

  15. Core tungsten radiation diagnostic calibration by small shell pellet injection in the DIII-D tokamak

    Science.gov (United States)

    Hollmann, E. M.; Commaux, N.; Shiraki, D.; Alexander, N.; Bykov, I.; Moser, A. L.; Thomas, D.; Victor, B. S.

    2017-10-01

    Injection of small (outer diameter = 0.8 mm) plastic pellets carrying embedded smaller (10 μg) tungsten grains is used to check calibrations of core tungsten line radiation diagnostics in support of the 2016 tungsten ring campaign in the DIII-D tokamak. Observed total brightness (1 eV-10 keV) and soft x-ray (1 keV-10 keV) brightness are found to be reasonably well (core (extreme ultra-violet/soft x-ray) tungsten line brightness appears to be somewhat less reliable (factor 2-4) for the prediction of core tungsten concentration.

  16. Comparative evaluation of tungsten inert gas and laser beam ...

    Indian Academy of Sciences (India)

    Abstract. In this study, the bead-on-plate welds were made on AA5083-H321 alloy plates using both tungsten inert gas (TIG) welding and laser beam (LB) welding pro- cesses to study the enhancement of mechanical properties such as weld yield strength and hardness. The low heat input of laser beam welding effectively ...

  17. Growth stress in tungsten carbide-diamond-like carbon coatings

    NARCIS (Netherlands)

    Pujada, B.R.; Tichelaar, F.D.; Arnoldbik, W.M.; Sloof, W.G.; Janssen, G.C.A.M.

    2009-01-01

    Growth stress in tungsten carbide-diamond-like carbon coatings, sputter deposited in a reactive argon/acetylene plasma, has been studied as a function of the acetylene partial pressure. Stress and microstructure have been investigated by wafer curvature and transmission electron microscopy (TEM)

  18. Measurements of tungsten migration in the DIII-D divertor

    Science.gov (United States)

    Wampler, W. R.; Rudakov, D. L.; Watkins, J. G.; McLean, A. G.; Unterberg, E. A.; Stangeby, P. C.

    2017-12-01

    An experimental study of migration of tungsten in the DIII-D divertor is described, in which the outer strike point of L-mode plasmas was positioned on a toroidal ring of tungsten-coated metal inserts. Net deposition of tungsten on the divertor just outside the strike point was measured on graphite samples exposed to various plasma durations using the divertor materials evaluation system. Tungsten coverage, measured by Rutherford backscattering spectroscopy (RBS), was found to be low and nearly independent of both radius and exposure time closer to the strike point, whereas farther from the strike point the W coverage was much larger and increased with exposure time. Depth profiles from RBS show this was due to accumulation of thicker mixed-material deposits farther from the strike point where the plasma temperature is lower. These results are consistent with a low near-surface steady-state coverage on graphite undergoing net erosion, and continuing accumulation in regions of net deposition. This experiment provides data needed to validate, and further improve computational simulations of erosion and deposition of material on plasma-facing components and transport of impurities in magnetic fusion devices. Such simulations are underway and will be reported later.

  19. Comparative evaluation of tungsten inert gas and laser beam ...

    Indian Academy of Sciences (India)

    In this study, the bead-on-plate welds were made on AA5083-H321 alloy plates using both tungsten inert gas (TIG) welding and laser beam (LB) welding processes to study the enhancement of mechanical properties such as weld yield strength and hardness. The low heat input of laser beam welding effectively reduced the ...

  20. Self-Passivation Tungsten Alloys for Plasma Facing Materials

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Seung Su; Ryu, Ho Jin [KAIST, Daejeon (Korea, Republic of)

    2016-05-15

    Compared with other materials, tungsten has many advantageous properties in a plasma environments. For examples, tungsten has the merit of very low sputter erosion under bombardment by energetic particles like D, T, He ions from the plasma. And it also is high melting point and high thermal conductivity which is good properties for resisting to high thermal load. A potential problem with using pure tungsten in a fusion reactor is the formation of WO3 which is radioactive and highly volatile compound and there is possibility that it may get released under accidental scenario. A feasible way for avoiding this is developing a self-passivating oxide layer at the surface of tungsten. W-based self-passivation bulk alloys were successfully fabricated by the high energy planetary ball milling and simple mixing. And also spark plasma sintering is good for fabricating them. As compared to simple mixing samples, mechanical alloying samples have better mechanical properties. Especially PCr10 sample exhibits impressive performance in terms of compressive strength. In oxidation test, there were no significant difference between simple mixing samples and mechanical alloying samples.

  1. Tungsten based anisotropic metamaterial as an ultra-broadband absorber

    DEFF Research Database (Denmark)

    Lin, Yinyue; Cui, Yanxia; Ding, Fei

    2017-01-01

    : We show theoretically that an array of tungsten/germanium anisotropic nano-cones placed on top of a reflective substrate can absorb light at the wavelength range from 0.3 μm to 9 μm with an average absorption efficiency approaching 98%. It is found that the excitation of multiple orders of slow...

  2. Effect of tempering after cryogenic treatment of tungsten carbide ...

    Indian Academy of Sciences (India)

    #Department of Industrial and Production Engineering, National Institute of Technology, Jalandhar 144 001, India. MS received 10 ... Tungsten carbide is the most commonly used cutting tool material in the industry and the tech- nique can also be ..... in the WC-Co inserts and was present in the form of clusters of particles ...

  3. New tungsten alloy has high strength at elevated temperatures

    Science.gov (United States)

    1966-01-01

    Tungsten-hafnium-carbon alloy has tensile strengths of 88,200 psi at 3000 deg F and 62,500 psi at 3500 deg F. Possible industrial applications for this alloy would include electrical components such as switches and spark plugs, die materials for die casting steels, and heating elements.

  4. Gas Tungsten Arc Welding and Plasma Arc Cutting. Teacher Edition.

    Science.gov (United States)

    Fortney, Clarence; And Others

    This welding curriculum guide treats two topics in detail: the care of tungsten electrodes and the entire concept of contamination control and the hafnium electrode and its importance in dual-air cutting systems that use compressed shop air for plasma arc cutting activities. The guide contains three units of instruction that cover the following…

  5. Volume and surface photoemission from tungsten. II. Experiment

    DEFF Research Database (Denmark)

    Feuerbacher, B.; Egede Christensen, N.

    1974-01-01

    Energy-distribution spectra of photoelectrons emitted normal to three single-crystal faces of tungsten have been measured for photon energies between 7.7 and 21.2 eV. The results are interpreted in terms of one-dimensional electronic properties along the symmetry lines in k space that correspond...

  6. Formation of nanoscale tungsten oxide structures and colouration ...

    Indian Academy of Sciences (India)

    In this work, pH dependent evolution of tungsten oxide (WO3) nanostructures is being reported along with physical characteristics. The synthesis was carried out via an inexpensive solvothermal cum chemical reduction route, with sodium tungstate (Na2WO4) and cetyl trimethyl ammonium bromide (C19H42NBr) as main ...

  7. Molybdenum incorporation in tungsten aldehyde oxidoreductase enzymes from Pyrococcus furiosus

    NARCIS (Netherlands)

    Sevcenco, A.M.; Bevers, L.E.; Pinkse, M.W.H.; Krijger, G.C.; Wolterbeek, H.T.; Verhaert, P.D.E.M.; Hagen, W.R.; Hagedoorn, P.L.

    2010-01-01

    The hyperthermophilic archaeon Pyrococcus furiosus expresses five aldehyde oxidoreductase (AOR) enzymes, all containing a tungsto-bispterin cofactor. The growth of this organism is fully dependent on the presence of tungsten in the growth medium. Previous studies have suggested that molybdenum is

  8. Effect of tempering after cryogenic treatment of tungsten carbide ...

    Indian Academy of Sciences (India)

    Cryogenic treatment is a recent advancement in the field of machining to improve the properties of cutting tool materials. Tungsten carbide is the most commonly used cutting tool material in the industry and the technique can also be extended to it. Although the importance of tempering after cryogenic treatment has been ...

  9. Development of Bulk Nanocrystalline Cemented Tungsten Carbide for Industrial Applicaitons

    Energy Technology Data Exchange (ETDEWEB)

    Z. Zak Fang, H. Y. Sohn

    2009-03-10

    This report contains detailed information of the research program entitled "Development of Bulk Nanocrystalline Cemented Tungsten Carbide Materials for Industrial Applications". The report include the processes that were developed for producing nanosized WC/Co composite powders, and an ultrahigh pressure rapid hot consolidation process for sintering of nanosized powders. The mechanical properties of consolidated materials using the nanosized powders are also reported.

  10. Ion beam analysis of tungsten layers in EUROFER model systems and carbon plasma facing components

    Energy Technology Data Exchange (ETDEWEB)

    Ström, Petter, E-mail: pestro@kth.se [Department of Fusion Plasma Physics, School of Electrical Engineering, KTH Royal Institute of Technology, SE-10044 Stockholm (Sweden); Petersson, Per; Rubel, Marek [Department of Fusion Plasma Physics, School of Electrical Engineering, KTH Royal Institute of Technology, SE-10044 Stockholm (Sweden); Primetzhofer, Daniel [Department of Physics and Astronomy, Ion Physics, Uppsala University, P.O. Box 516, SE-75120 Uppsala (Sweden); Brezinsek, Sebastijan; Kreter, Arkadi; Unterberg, Bernhard; Sergienko, Gennady [Forschungszentrum Jülich GmbH, Institut für Energie- und Klimaforschung – Plasmaphysik, D-52425 Jülich (Germany); Sugiyama, Kazuyoshi [Max-Planck-Institut für Plasmaphysik, D-85748 Garching (Germany)

    2016-03-15

    Highlights: • Deuterium sputtered model samples for EUROFER studied by ToF-MEIS. • Tungsten enrichment by preferential sputtering quantified and depth profiled. • Iodine and chlorine beams compared for tungsten analysis. - Abstract: The tungsten enriched surface layers in two fusion-relevant EUROFER steel model samples, consisting of an iron–tungsten mixture exposed to sputtering by deuterium ions, were studied by Rutherford backscattering spectrometry and medium energy ion scattering. Exposure conditions were the same for the two samples and the total amount of tungsten atoms per unit area in the enriched layers were similar (2 · 10{sup 15} and 2.4 · 10{sup 15} atoms/cm{sup 2} respectively), despite slightly different initial atomic compositions. A depth profile featuring exponential decrease in tungsten content towards higher depths with 10–20 at.% of tungsten at the surface and a decay constant between 0.05 and 0.08 Å{sup −1} was indicated in one sample, whereas only the total areal density of tungsten atoms was measured in the other. In addition, two different beams, iodine and chlorine, were employed for elastic recoil detection analysis of the deposited layer on a polished graphite plate from a test limiter in the TEXTOR tokamak following experiments with tungsten hexafluoride injection. The chlorine beam was preferred for tungsten analysis, mainly because it (as opposed to the iodine beam) does not give rise to problems with overlap of forward scattered beam particles and recoiled tungsten in the spectrum.

  11. High temperature heterogeneous reaction kinetics and mechanisms of tungsten oxidation

    Science.gov (United States)

    Sabourin, Justin L.

    Tungsten, which is a material used in many high temperature applications, is limited by its susceptibility to oxidation at elevated temperatures. Although tungsten has the highest melting temperature of any metal, at much lower temperatures volatile oxides are formed during oxidation with oxygen containing species. This differs from many heterogeneous oxidation reactions involving metals since most reactions form very stable oxides that have higher melting or boiling points than the pure metal (e.g., aluminum, iron). Understanding heterogeneous oxidation and vaporization processes may allow for the expansion and improvement of high temperature tungsten applications. In order to increase understanding of the oxidation processes of tungsten, there is a need to develop reaction mechanisms and kinetics for oxidation processes involving oxidizers and environmental conditions of interest. Tungsten oxidation was thoroughly studied in the past, and today there is a good phenomenological understanding of these processes. However, as the design of large scale systems increasingly relies on computer modeling there becomes a need for improved descriptions of chemical reactions. With the increase in computing power over the last several decades, and the development of quantum chemistry and physics theories, heterogeneous systems can be modeled in detail at the molecular level. Thermochemical parameters that may not be measured experimentally may now be determined theoretically, a tool that was previously unavailable to scientists and engineers. Additionally, chemical kinetic modeling software is now available for both homogeneous and heterogeneous reactions. This study takes advantage of these new theoretical tools, as well as a thermogravimetric (TG) flow reactor developed as part of this study to learn about mechanisms and kinetics of tungsten oxidation. Oxidizers of interest are oxygen (O2), carbon dioxide (CO 2), water (H2O), and other oxidizers present in combustion and

  12. Tungsten(VI) Carbyne/Bis(carbene) Tautomerization Enabled by N-Donor SBA15 Surface Ligands: A Solid-State NMR and DFT Study

    KAUST Repository

    Bendjeriou-Sedjerari, Anissa

    2016-08-11

    Designing supported well-defined bis(carbene) complexes remains a key challenge in heterogeneous catalysis. The reaction of W(CtBu)(CH(2)tBu)(3) with amine-modified mesoporous SBA15 silica, which has vicinal silanol/silylamine pairs [(SiOH)(SiNH2)], leads to [(SiNH2-)(SiO-)W(CHtBu)(CH(2)tBu)(2)] and [(SiNH2-)(SiO-)W(=CHtBu)(2)(CH(2)tBu). Variable temperature, H-1-H-1 2D double-quantum, H-1-C-13 HETCOR, and HETCOR with spin diffusion solid-state NMR spectroscopy demonstrate tautomerization between the alkyl alkylidyne and the bis(alkylidene) on the SBA15 surface. Such equilibrium is possible through the coordination of W to the surface [(Si-OH)(Si-NH2)] groups, which act as a [N,O] pincer ligand. DFT calculations provide a rationalization for the surface-complex tautomerization and support the experimental results. This direct observation of such a process shows the strong similarity between molecular mechanisms in homogeneous and heterogeneous catalysis. In propane metathesis (at 150 degrees C), the tungsten bis(carbene) tautomer is favorable, with a turnover number (TON) of 262. It is the highest TON among all the tungsten alkyl-supported catalysts.

  13. Thermal shock behaviour of different tungsten grades under varying conditions

    Energy Technology Data Exchange (ETDEWEB)

    Wirtz, Oliver Marius

    2012-07-19

    Thermonuclear fusion power plants are a promising option to ensure the energy supply for future generations, but in many fields of research enormous challenges have to be faced. A major step on the way to the prototype fusion reactor DEMO will be ITER which is build in Cadarache, southern France. One of the most critical issues is the field of in-vessel materials and components, in particular the plasma facing materials (PFM). PFMs that will be used in a device like ITER have to withstand severe environmental conditions in terms of steady state and transient thermal loads as well as high particle fluxes such as hydrogen, helium and neutrons. Candidate wall materials are beryllium, tungsten and carbon based materials like CFC (carbon fibre composite). Tungsten is the most promising material for an application in the divertor region with very severe loading conditions and it will most probably also be used as PFM for DEMO. Hence, this work focuses on the investigation of the thermal shock response of different tungsten grades in order to understand the damage mechanisms and to identify material parameters which influence this behaviour under ITER and DEMO relevant operation conditions. Therefore the microstructure and the mechanical and thermal properties of five industrially manufactured tungsten grades were characterised. All five tungsten grades were exposed to transient thermal events with very high power densities of up to 1.27 GWm{sup -2} at varying base temperatures between RT and 600 C in the electron beam device JUDITH 1. The pulse numbers were limited to a maximum of 1000 in order to avoid immoderate workload on the test facility and to have enough time to cover a wide range of loading conditions. The results of this damage mapping enable to define different damage and cracking thresholds for the investigated tungsten grades and to identify certain material parameters which influence the location of these thresholds and the distinction of the induced

  14. Dendrite growth within supercooled liquid tungsten and tungsten-tantalum isomorphous alloys

    Science.gov (United States)

    Hu, L.; Wang, W. L.; Yang, S. J.; Li, L. H.; Geng, D. L.; Wang, L.; Wei, B.

    2017-02-01

    The dendrite growth in both supercooled liquid pure W and binary W-Ta isomorphous alloys has been observed and measured by an electrostatic levitation technique. The liquid W and W-x%Ta (x = 25, 50, 75) alloys were substantially supercooled by up to 733 K (0.2 Tm) and 773 K (0.23TL), respectively. The measured density and the ratio of specific heat to emissivity displayed a linearly increasing tendency versus supercooling. The thermal dendrites in supercooled liquid tungsten achieved a maximum growing velocity of 41.3 m.s-1, and the concurrent recalescence process exhibited Johnson-Mehl-Avrami type kinetics. Liquid W-Ta alloys showed stronger supercoolability but a lower maximum dendrite growth velocity of only 35.2 m.s-1. The dendritic growth kinetics was always characterized by a power function relation to liquid supercooling. The microstructure of equiaxed grains transforms to the well-developed dendrites with the increase of supercooling. The grain refinement effect resulting from dendrite fragmentation took place in a moderate supercooling regime in rapidly solidified W-Ta alloys.

  15. Surface modification of tungsten and tungsten-tantalum alloys exposed to high-flux deuterium plasma and its impact on deuterium retention

    NARCIS (Netherlands)

    Zayachuk, Y.; Hoen, M. H. J. 't; van Emmichoven, P. A. Zeijlma; Terentyev, D.; Uytdenhouwen, I.; Van Oost, G.

    2013-01-01

    Samples of tungsten and tungsten-tantalum alloy (with 5 mass per cent of Ta) were exposed to high-flux deuterium plasma at different fluences. The surface modification was studied with scanning electron microscopy, and deuterium retention was measured by thermal desorption spectroscopy (TDS). In the

  16. Gas-tungsten arc welding of aluminum alloys

    Science.gov (United States)

    Frye, L.D.

    1982-03-25

    The present invention is directed to a gas-tungsten arc welding method for joining together structures formed of aluminum alloy with these structures disposed contiguously to a heat-damagable substrate of a metal dissimilar to the aluminum alloy. The method of the present invention is practiced by diamond machining the fay surfaces of the aluminum alloy structures to profice a mirror finish thereon having a surface roughness in the order of about one microinch. The fay surface are aligned and heated sufficiently by the tungsten electrode to fuse the aluminum alloy continguous to the fay surfaces to effect the weld joint. The heat input used to provide an oxide-free weld is significantly less than that required if the fay surfaces were prepared by using conventional chemical and mechanical practices.

  17. Development of positron annihilation spectroscopy for characterizing neutron irradiated tungsten

    Energy Technology Data Exchange (ETDEWEB)

    C.N. Taylor; M. Shimada; D.W. Akers; M.W. Drigert; B.J. Merrill; Y. Hatano

    2013-05-01

    Tungsten samples (6 mm diameter, 0.2 mm thick) were irradiated to 0.025 and 0.3 dpa with neutrons in the High Flux Isotope Reactor (HFIR) at Oak Ridge National Laboratory. Samples were then exposed to deuterium plasma in the tritium plasma experiment (TPE) at 100, 200 and 500ºC to a total fluence of 1 x 1026 m-2. Nuclear reaction analysis (NRA) and Doppler broadening positron annihilation spectroscopy (DB-PAS) were performed at various stages to characterize damage and retention. We present the first known results of neutron damaged tungsten characterized by DB-PAS in order to study defect concentration. Two positron sources, 22Na and 68Ge, probe ~58 µm and through the entire 200 µm thick samples, respectively. DB-PAS results reveal clear differences between the various irradiated samples. These results, and the calibration of DB-PAS to NRA data are presented.

  18. A comparison of interatomic potentials for modeling tungsten nanocluster structures

    Energy Technology Data Exchange (ETDEWEB)

    Hao, Jiannan; Shu, Xiaolin, E-mail: shuxlin@buaa.edu.cn; Jin, Shuo; Zhang, Xuesong; Zhang, Ying; Lu, Guang-Hong

    2017-02-15

    Molecular dynamic simulation is utilized to study the nanocluster and the fuzz structure on the PFM surface of tungsten. The polyhedral and linear cluster structures based on the icosahedron, cuboctahedron and rhombic dodecahedron are built up. Three interatomic potentials are used in calculating the relationship between the cluster energy and the number of atoms. The results are compared with first-principles calculation to show each potential’s best application scale. Furthermore, the transition between the icosahedral and the cuboctahedral clusters is observed in molecular dynamic simulation at different temperatures, which follows a critical curve for different numbers of atoms. The linear structures are proved to be stable at experimental temperatures by thermodynamics. The work presents a selection of interatomic potentials in simulating tungsten cluster systems and helps researchers understand the growth and evolution laws of clusters and the fuzz-like structure formation process in fusion devices.

  19. Terminal tungsten pnictide complex formation through pnictaethynolate decarbonylation.

    Science.gov (United States)

    Joost, Maximilian; Transue, Wesley J; Cummins, Christopher C

    2017-09-26

    Tungsten(iv) tetrakis(2,6-diisopropylphenoxide) (1) has been demonstrated to be a competent platform for decarbonylative formation of anionic terminal pnictide complexes upon treatment with pnictaethynolate anions: cyanate, 2-phosphaethynolate, and 2-arsaethynolate. These transformations constitute the first examples of terminal phosphide and arsenide complex formation at a transition metal center from OCP- and OCAs-, respectively. The phosphide and arsenide complexes are also the first to be isolated in a tetragonal, all-oxygen ligand environment. The scalar NMR coupling constants between tungsten-183 and nitrogen-15 or phosphorus-31 have been measured and contextualized using natural bond orbital (NBO) methods in terms of s orbital character in the σ bonding orbital and pnictide lone pair.

  20. Field electron emission from dense array of microneedles of tungsten

    Energy Technology Data Exchange (ETDEWEB)

    Okuyama, F.; Aoyagi, M.; Kitai, T.; Ishikawa, K.

    1978-01-01

    Characteristics of field electron emission from the dense array of microneedles of tungsten prepared on a 10-..mu..m tungsten filament were measured at an environmental pressure of approx.1 x 10/sup -8/ Torr (1.33 x 10/sup -6/ Pa). Electron emission was not uniform over the filament surface, but the variation of emission current with applied voltage explicitly obeyed the Fowler-Nordheim relationship. At an emission current of approx.10/sup -4/ A, a vacuum arc was induced that led to a permanent change in current-voltage characteristic. Current fluctuation was dependent on emitter temperature and applied voltage, and the lowest fluctuation of about 4% was routinely obtained at approx.550 K and at applied voltages several percent lower than the arc-inducing voltage. Macroscopic current density amounted to approx.20-80 mA/cm/sup 2/ at the best stability.

  1. Interaction of hydrogen plasma with carbon-tungsten composite layer

    Energy Technology Data Exchange (ETDEWEB)

    Vesel, Alenka, E-mail: alenka.vesel@guest.arnes.s [Jozef Stefan Institute, Jamova 39, 1000 Ljubljana (Slovenia); Mozetic, Miran; Panjan, Peter [Jozef Stefan Institute, Jamova 39, 1000 Ljubljana (Slovenia); Hauptman,; Klanjsek-Gunde, M. [National Institute of Chemistry, Hajdrihova 19, 1000 Ljubljana (Slovenia); Balat-Pichelin, Marianne [CNRS-PROMES, Laboratoire Procedes, Materiaux and Energie Solaire, UPR 8521, 7 rue du four solaire, F-66120 Font Romeu, Odeillo (France)

    2011-04-15

    Interaction of neutral hydrogen atoms with the layer of hydrogenated carbon-tungsten composite was studied. A 1 {mu}m thick layer was prepared by sputter deposition from C and WC-targets in Ar/C{sub 2}-H{sub 2} gas mixture. After deposition the samples were treated in weakly ionized highly dissociated hydrogen plasma created in a microwave discharge at a power of 1 kW. The gas flow was 13 l/h and pressure was 90 Pa. Temperature of the samples during treatment was about 850 K. After plasma treatment the samples were analyzed by AES (Auger electron spectroscopy) depth profiling, XPS (X-ray photoelectron spectroscopy) and SEM (scanning electron microscopy). It was found that during hydrogen plasma treatment selective etching of the C-W layer occurred. Carbon was preferentially removed from the C-W layer, and after about 10 min of treatment practically only tungsten with a huge porosity was detected.

  2. Refining waste hardmetals into tungsten oxide nanosheets via facile method

    Energy Technology Data Exchange (ETDEWEB)

    Li, Zhifei; Zheng, Guangwei; Wang, Jinshu, E-mail: wangjsh@bjut.edu.cn; Li, Hongyi, E-mail: lhy06@bjut.edu.cn; Wu, Junshu; Du, Yucheng [Beijing University of Technology, Key Laboratory of Advanced Functional Materials, School of Materials Science and Engineering (China)

    2016-04-15

    A new hydrothermal system has been designed to recycle waste WC–Co hardmetal with low cobalt (Co) content (3 %). In the solution system, nitric acid was designed to dissolve Co, H{sub 2}O{sub 2} served as oxidant to accelerate the oxidation of the WC–Co hardmetals, and fluorine (F{sup −}) was designed to dissolve and recrystallize generated tungsten oxides, which were found to possess a layered structure using scanning electron microscopy and transmission electron microscopy. The obtained tungsten oxides were identified as WO{sub 3}·0.33H{sub 2}O by X-ray diffraction and their specific surface area was measured as 89.2 m{sup 2} g{sup −1} via N{sub 2} adsorption–desorption techniques. The present layered structure tungsten oxides exhibited a promising capability for removing lead ion (Pb{sup 2+}) and organic species, such as methyl blue. The adsorption model was found to be in agreement with Langmuir isotherm model. Given the facile synthesis procedure and promising properties of final products, this new approach should have great potential for refining some other waste hardmetals or tungsten products.Graphical AbstractA new hydrothermal system was designed to recycle waste hardmetal with low cobalt content. Through this method, waste hardmetal was refined into WO{sub 3}·0.33H{sub 2}O nanosheets which shows excellent adsorption capacities toward methylene blue and lead ion (Pb{sup 2+}).

  3. Erosion of nanostructured tungsten by laser ablation, sputtering and arcing

    Directory of Open Access Journals (Sweden)

    Dogyun Hwangbo

    2017-08-01

    Full Text Available Mass loss of nanostructured tungsten, which was formed by helium plasma irradiation, due to laser ablation, sputtering, and arcing was investigated. Below the helium sputtering energy threshold (200eV. Reduction in sputtering on nanostructured surface was observed. Arcing was initiated using laser pulses, and the erosion rate by arcing was measured. The erosion rate increased with arc current, while the erosion per Coulomb was not affected by arc current.

  4. Rhenium, Molybdenum, Tungsten - Prospects for Production and Industrial Applications

    Science.gov (United States)

    1998-06-18

    production E .A .Pirm atov ..................................................... 93 Use of surface-active agents in hydrometallurgy of tungsen E.A.Pirmatov...products to be ensured by using state-of- the-art technologies, such as ion-exchange processes in hydrometallurgy , plasma chemical processes in powder...the use as complex fertilizer enriched in microelements. USE OF SURFACE-ACTIVE AGENTS IN HYDROMETALLURGY OF TUNGSTEN E.A. Pirmatov, B.D.Dyusebekov

  5. Tungsten quasispherical wire loads with a profiled mass

    Energy Technology Data Exchange (ETDEWEB)

    Grabovskii, E. V.; Dzhangobegov, V. V., E-mail: jvv88@triniti.ru; Oleinik, G. M.; Rodionov, R. N. [State Research Center of the Russian Federation Troitsk Institute for Innovation and Fusion Research (TRINITI) (Russian Federation)

    2015-12-15

    Wire arrays made from micrometer tungsten wires with linear mass profiled along their height are developed for experiments on the generation of X-ray radiation upon pinch compression with a current of ∼3 MA at a pulse duration of ∼100 ns. Wires are imaged with a scanning electron microscope, and their diameter is determined. It is shown that the arrays have such a profile of height distribution of linear mass that allows for compact spherical compression upon current implosion.

  6. Mechanical recrystallization of ultra-strength tungsten nanoneedles

    Science.gov (United States)

    Mazilova, T. I.; Ksenofontov, V. A.; Voyevodin, V. N.; Sadanov, E. V.; Mikhailovskij, I. M.

    2011-04-01

    We present field-ion microscopy observation and crystallographic analysis which shows that plastic deformation mode in the tungsten nanotip in the field of high mechanical stresses occur by combining formations of strain localization bands and crystal lattice reorientations. Nanomechanical tensile tests in situ at about 15 GPa have revealed the large-angle reorientations of grains corresponding to the coincident site lattice with Σ = 33, which can be regarded as a result of reactions between lattice dislocations.

  7. Microstructure and Impurity Effects on Tungsten Heavy Alloys

    Science.gov (United States)

    1990-07-12

    UNCJ.AWSSIFIED MASTER COPY & - FOR REPRODUCTION PURPOSES SECURITY CLASSIFICATION OF THIS PAGE REPORT DOCUMENTATION PAGE garn CoPY la. REPORT SECURITY...7b. ADDRESS (City, State, and ZIP Code) Troy , NY 12180-3590 P. 0. Box 12211 -- Research Triangle Park, NC 27709-2211 Ba. NAME OF FUNDING/SPONSORING... Troy , New York 12180-3590 APPROVED FOR PUBLIC RELEASE; DISTRIBUTION UNLIMITED R. M. German 2 Microstructure and Impurity Effects on Tungsten Heavy Alloys

  8. Analysis of surface morphological change in PET films induced by tungsten ion implantation

    Energy Technology Data Exchange (ETDEWEB)

    Zhou, G., E-mail: guzhou@bnu.edu.c [Analysis and Testing Center, Beijing Normal University, Beijing 100875 (China); Wang, R.; Zhang, T.H. [Key Laboratory of Beam Technology and Materials Modification of Ministry of Education, College of Nuclear Sciences and Technology, Beijing Normal University, Beijing 100875 (China); Beijing Radiation Center, Beijing 100875 (China)

    2010-09-15

    Surface morphological changes and metal nanograin formation of polyethylene terephthalate films with tungsten ion implantation were studied. Tungsten ions were accelerated with a voltage of 40 kV and implanted at fluences from 5 x 10{sup 16} to 2 x 10{sup 17} cm{sup -2} using a metal vapor vacuum arc implanter. Scanning electron micrographs at the highest fluence show semi-spherical hills, indicating formation of tungsten nanograins on the polymer. The tungsten nanograin formation in the polymer film is confirmed by cross-sectional observation using transmission electron microscopy. Depth profiles of tungsten atoms obtained from energy dispersive X-ray spectra indicate densification and sputtering of the polymer surface layer during implantation. These results indicate that surface morphological change is related with the effects of a critical fluence and tungsten nanograin formation.

  9. Synthesis, characterization, and structure of reduced tungsten chalcogenide cluster complexes

    Energy Technology Data Exchange (ETDEWEB)

    Xiaobing, Xie [Iowa State Univ., Ames, IA (United States)

    1997-10-17

    Over the previous twenty years, ternary molybdenum chalcogenides of the general formula MxMo6Y8 (M = ternary metal cation; Y = chalcogenide), known as Chevrel phases, have been extensively studied. Many of these compounds have been found to have superconductivity, catalytic activity and ionic conductivity. The rich chemistry of the Chevrel phases raises considerable interest in finding the tungsten analogues of these phases. However, no such analogue has ever been synthesized, although the Chevrel phases are usually prepared directly from elements at high temperatures above 1000{degrees}C. The absence of the tungsten analogues may be caused by their thermodynamic instability at such high temperatures. Thus it might be necessary to avoid high-temperature synthetic procedures in order to establish the ternary and binary tungsten chalcogenides. A major focus of the McCarley research group has been on the preparation of M6Y8L6 (M = Mo, W; Y = S, Se, Te) cluster complexes as low temperature pathways to the Chevrel phases.

  10. Experimental study of cyclic action of plasma on tungsten

    Science.gov (United States)

    Voronin, A. V.; Aleksandrov, A. E.; Ber, B. Ya.; Brunkov, P. N.; Bormatov, A. A.; Gusev, V. K.; Demina, E. V.; Novokhatskii, A. N.; Pavlov, S. I.; Prusakova, M. D.; Sotnikova, G. Yu.; Yagovkina, M. A.

    2016-03-01

    We report on experimental results on multiple action of hydrogen, deuterium, and helium plasmas produced by a plasma gun and the Globus-M tokamak on tungsten. The surface temperature in the course of irradiation is measured with a bichromatic pyrometer with a time resolution of ⩾1 μs. The morphology of the surface layer is investigated and X-ray structure analysis of tungsten exposed to multiple radiations by the plasma under various conditions is carried out. A slight decrease in the lattice parameter in the sample subjected to the maximal number of irradiation cycles is detected. It is shown that the morphology of the tungsten surface irradiated by the hydrogen plasma from the gun and by the deuterium plasma from the Globus-M tokamak changes (the structure becomes smoother). The characteristic depth of the layer in which impurities have been accumulated exceeds 0.5 μm. This depth was the largest for the sample exposed to 1000 shots from the gun and 2370 shots from the tokamak. It is shown that the helium jet from the plasma gun makes it possible to simulate the action of helium ions on the International Thermonuclear Experimental Reactor (ITER) diverter, producing a layer of submicrometer particles (bubbles).

  11. Photoionization of the valence shells of the neutral tungsten atom

    CERN Document Server

    Ballance, Connor P

    2015-01-01

    Results from large-scale theoretical cross section calculations for the total photoionization of the 4f, 5s, 5p and 6s orbitals of the neutral tungsten atom using the Dirac Coulomb R-matrix approximation (DARC: Dirac-Atomic R-matrix codes) are presented. Comparisons are made with previous theoretical methods and prior experimental measurements. In previous experiments a time-resolved dual laser approach was employed for the photo-absorption of metal vapours and photo-absorption measurements on tungsten in a solid, using synchrotron radiation. The lowest ground state level of neutral tungsten is $\\rm 5p^6 5d^4 6s^2 \\; {^5}D_{\\it J}$, with $\\it J$=0, and requires only a single dipole matrix for photoionization. To make a meaningful comparison with existing experimental measurements, we statistically average the large-scale theoretical PI cross sections from the levels associated with the ground state $\\rm 5p^6 5d^4 6s^2 \\; {^5}D_{\\it J}[{\\it J}=0,1,2,3,4]$ levels and the $\\rm 5d^56s \\; ^7S_3$ excited metastable...

  12. Extraction Factor Of Pure Ammonium Paratungstate From Tungsten Scraps

    Directory of Open Access Journals (Sweden)

    Pee J.-H.

    2015-06-01

    Full Text Available Typical oxidation process of tungsten scraps was modified by the rotary kiln with oxygen burner to increase the oxidation rate of tungsten scraps. Also to accelerate the solubility of solid oxidized products, the hydrothermal reflux method was adapted. By heating tungsten scraps in rotary kiln with oxygen burner at around 900° for 2hrs, the scraps was oxidized completely. Then oxidized products (WO3 and CoWO4 was fully dissolved in the solution of NaOH by hydrothermal reflux method at 150° for 2hrs. The dissolution rate of oxidized products was increased with increasing the reaction temperature and concentration of NaOH. And then CaWO4 and H2WO4 could be generated from the aqueous sodium tungstate solution. Ammonium paratungstate (APT also could be produced from tungstic acid using by aqueous ammonium solution. The morphologies (cubic and plate types of APT was controlled by the stirring process of purified solution of ammonium paratungstate.

  13. Gas-driven hydrogen permeation through tungsten-coated graphite

    Energy Technology Data Exchange (ETDEWEB)

    Golubeva, A.V., E-mail: anna-golubeva@yandex.ru [RRC ' Kurchatov Institute' , Ac. Kurchatov sq., 1/1, Moscow RU-123182 (Russian Federation); Spitsyn, A.V., E-mail: spitsyn@nfi.kiae.ru [RRC ' Kurchatov Institute' , Ac. Kurchatov sq., 1/1, Moscow RU-123182 (Russian Federation); Mayer, M. [Max-Planck-Institut fuer Plasmaphysik, EURATOM Association, Boltzmannstrasse 2, D-85748 Garching (Germany); Cherkez, D.I. [RRC ' Kurchatov Institute' , Ac. Kurchatov sq., 1/1, Moscow RU-123182 (Russian Federation); Schwarz-Selinger, T.; Koch, F.; Lindig, S. [Max-Planck-Institut fuer Plasmaphysik, EURATOM Association, Boltzmannstrasse 2, D-85748 Garching (Germany); Skovoroda, A.A. [RRC ' Kurchatov Institute' , Ac. Kurchatov sq., 1/1, Moscow RU-123182 (Russian Federation)

    2011-08-01

    Hydrogen gas-driven permeation through graphite coated with different types of tungsten coatings with thicknesses up to 200 {mu}m has been investigated. The substrate material was fine-grain graphite R5710 and R6710, which properties with respect to hydrogen transport are well known . Magnetron-sputtered W coatings of thicknesses 1 and 3 {mu}m and two coatings of ASDEX Upgrade were investigated: A 3 {mu}m thick layer of tungsten deposited by physical vapor deposition (PVD-W) and 200 {mu}m thick layers of tungsten deposited by plasma-spaying in vacuum (VPS-W). The gas-driven permeation was investigated at a pressure gradient of 10{sup -2}-150 Pa. The gas-driven permeation occurs through the carbon base-materials by hydrogen molecular gas flow through the internal porosity network rather than hydrogen atom diffusion through the graphite lattice. It was found that W coatings with thicknesses up to 3 {mu}m are transparent for hydrogen gas penetration and do not influence the permeability of coated fine-grain graphite, because the open porosity system of graphite remains open. Even a 200 {mu}m thick layer of VPS-W has an open system of connected pores, which connects the front and rear surfaces of the deposited layer.

  14. An update to the toxicological profile for water-soluble and sparingly soluble tungsten substances

    OpenAIRE

    Lemus, Ranulfo; Carmen F. Venezia

    2015-01-01

    Abstract Tungsten is a relatively rare metal with numerous applications, most notably in machine tools, catalysts, and superalloys. In 2003, tungsten was nominated for study under the National Toxicology Program, and in 2011, it was nominated for human health assessment under the US Environmental Protection Agency's (EPA) Integrated Risk Information System. In 2005, the Agency for Toxic Substances and Disease Registry (ATSDR) issued a toxicological profile for tungsten, identifying several da...

  15. Mapping the Global Flow of Tungsten to Identify Key Material Efficiency and Supply Security Opportunities

    OpenAIRE

    Leal-Ayala, David R.; Allwood, Julian M.; Petavratzi, Evi; Brown, Teresa J; Gunn, Gus

    2015-01-01

    Tungsten is an economically important metal with diverse applications ranging from wear resistant cutting tools to its use in specialized steels and alloys. Concerns about its supply security have been raised by various studies in literature, mostly due to trade disputes arising from supply concentration and exports restrictions in China and its lack of viable substitutes. Although tungsten material flows have been analysed for specific regions, a global mass flow analysis of tungsten is stil...

  16. Predicting the performance of tungsten in a fusion environment: a literature review

    OpenAIRE

    Abernethy, RG

    2016-01-01

    Tungsten has been proposed for use in the divertor of future fusion devices. In this environment, it will be exposed to high heat fluxes, neutron damage and hydrogen and helium implantation. This review covers previous experimental and modelling work to establish our ability to predict the performance of tungsten in a fusion environment. Surrogates for high-energy neutrons have been used to predict the change in mechanical properties of tungsten, including fission neutron and self-ion exposur...

  17. Chitosan: a green carbon source for the synthesis of graphitic nanocarbon, tungsten carbide and graphitic nanocarbon/tungsten carbide composites

    Energy Technology Data Exchange (ETDEWEB)

    Wang Baoli; Tian Chuigui; Wang Lei; Wang Ruihong; Fu Honggang, E-mail: fuhg@vip.sina.com [Key Laboratory of Functional Inorganic Material Chemistry, Ministry of Education, Heilongjiang University, Harbin 150080 (China)

    2010-01-15

    In this paper, a simple approach was proposed to fabricate graphitic carbon nanocapsules, tungsten carbide and tungsten carbides/graphitic carbon composites by using chitosan, a green and renewable biopolymer, as a carbon source. The route includes, first, fabrication of the precursors that consist of chitosan coordinated with a certain metal ion (or metal complex anion) followed by carbonizing the precursors under N{sub 2} atmosphere. The composition of the final products could be regulated by changing the type and ratio of the metal source (cations or complex anions) combined with the chitosan in the precursors. The experimental results showed that uniform carbon nanocapsules could be obtained when Ni{sup 2+} was introducing in the precursors, while incorporating [PW{sub 12}O{sub 40}]{sup 3-} (PW{sub 12}) with chitosan led to the formation of WC nanoparticles. As the Ni{sup 2+} and PW{sub 12} are simultaneously coordinated with chitosan, the composites of tungsten carbide/graphitic carbon were successfully produced. Transmission electron microscopy (TEM) analysis revealed that the graphitic carbon nanocapsules are about 45 nm in diameter; uniform WC nanoparticles with a average size of 40 nm are observed. Moreover, the particle size of WC in the tungsten carbide/graphitic carbon composite is about 10 nm, which is smaller than that of the pure WC particles. Furthermore, the performance of the sample-loaded Pt nanoparticles for methanol electro-oxidation was studied in detail. The results indicated that the samples could act as good carriers for Pt in the methanol electro-oxidation reaction with high effectivity and improved stability.

  18. Molecular basis of carcinogenicity of tungsten alloy particles

    Energy Technology Data Exchange (ETDEWEB)

    Harris, Robert M.; Williams, Tim D.; Waring, Rosemary H.; Hodges, Nikolas J., E-mail: n.hodges@bham.ac.uk

    2015-03-15

    The tungsten alloy of 91% tungsten, 6% nickel and 3% cobalt (WNC 91–6–3) induces rhabdomyosarcoma when implanted into a rat thigh muscle. To investigate whether this effect is species-specific human HSkMc primary muscle cells were exposed to WNC 91–6–3 particles and responses were compared with those from a rat skeletal muscle cell line (L6-C11). Toxicity was assessed by the adenylate kinase assay and microscopy, DNA damage by the Comet assay. Caspase 3 enzyme activity was measured and oligonucleotide microarrays were used for transcriptional profiling. WNC 91–6–3 particles caused toxicity in cells adjacent to the particles and also increased DNA strand breaks. Inhibition of caspase 3 by WNC 91–6–3 occurred in rat but not in human cells. In both rat and human cells, the transcriptional response to WNC 91–6–3 showed repression of transcripts encoding muscle-specific proteins with induction of glycolysis, hypoxia, stress responses and transcripts associated with DNA damage and cell death. In human cells, genes encoding metallothioneins were also induced, together with genes related to angiogenesis, dysregulation of apoptosis and proliferation consistent with pre-neoplastic changes. An alloy containing iron, WNF 97–2–1, which is non-carcinogenic in vivo in rats, did not show these transcriptional changes in vitro in either species while the corresponding cobalt-containing alloy, WNC 97–2–1 elicited similar responses to WNC 91–6–3. Tungsten alloys containing both nickel and cobalt therefore have the potential to be carcinogenic in man and in vitro assays coupled with transcriptomics can be used to identify alloys, which may lead to tumour formation, by dysregulation of biochemical processes. - Highlights: • Use of transcriptomics to identify likely carcinogenic tungsten alloys in vitro • Cobalt containing alloys cause oxidative stress, DNA-damage and perturb apoptosis. • Presence of cobalt causes changes in gene expression

  19. Electrodeposition mechanism and corrosion behavior of multilayer nanocrystalline nickel-tungsten alloy

    DEFF Research Database (Denmark)

    Allahyarzadeh, M.H.; Aliofkhazraei, M.; Rouhaghdam, A. Sabour

    2017-01-01

    Multilayer nickel-tungsten coatings were deposited on carbon steel using the pulse reverse current technique. Nickel-tungsten layered structure coatings were developed using the continuous and alternative variation of pulse duty cycle at two specific and fixed values. In these coatings, the multi......Multilayer nickel-tungsten coatings were deposited on carbon steel using the pulse reverse current technique. Nickel-tungsten layered structure coatings were developed using the continuous and alternative variation of pulse duty cycle at two specific and fixed values. In these coatings...

  20. Direct Growth of Crystalline Tungsten Oxide Nanorod Arrays by a Hydrothermal Process and Their Electrochromic Properties

    Science.gov (United States)

    Lu, Chih-Hao; Hon, Min Hsiung; Leu, Ing-Chi

    2017-04-01

    Transparent crystalline tungsten oxide nanorod arrays for use as an electrochromic layer have been directly prepared on fluorine-doped tin oxide-coated glass via a facile tungsten film-assisted hydrothermal process using aqueous tungsten hexachloride solution. X-ray diffraction analysis and field-emission scanning electron microscopy were used to characterize the phase and morphology of the grown nanostructures. Arrays of tungsten oxide nanorods with diameter of ˜22 nm and length of ˜240 nm were obtained at 200°C after 8 h of hydrothermal reaction. We propose a growth mechanism for the deposition of the monoclinic tungsten oxide phase in the hydrothermal environment. The tungsten film was first oxidized to tungsten oxide to provide seed sites for crystal growth and address the poor connection between the growing tungsten oxide and substrate. Aligned tungsten oxide nanorod arrays can be grown by a W thin film-assisted heterogeneous nucleation process with NaCl as a structure-directing agent. The fabricated electrochromic device demonstrated optical modulation (coloration/bleaching) at 632.8 nm of ˜41.2% after applying a low voltage of 0.1 V for 10 s, indicating the potential of such nanorod array films for use in energy-saving smart windows.

  1. Preparation of size-controlled tungsten oxide nanoparticles and evaluation of their adsorption performance

    Energy Technology Data Exchange (ETDEWEB)

    Hidayat, Darmawan [Department of Chemical Engineering, Graduate School of Engineering, Hiroshima University, Higashi-Hiroshima 739-8527 (Japan); Purwanto, Agus [Department of Chemical Engineering, Faculty of Engineering, Sebelas Maret University, Jl. Ir. Sutami 36 A, Surakarta, Central Java 57126 (Indonesia); Wang, Wei-Ning [Department of Energy, Environmental and Chemical Engineering, School of Engineering and Applied Science, Washington University in St. Louis, St. Louis, MO 63130 (United States); Okuyama, Kikuo, E-mail: okuyama@hiroshima-u.ac.jp [Department of Chemical Engineering, Graduate School of Engineering, Hiroshima University, Higashi-Hiroshima 739-8527 (Japan)

    2010-02-15

    The present study investigated the effects of particle size on the adsorption performance of tungsten oxide nanoparticles. Nanoparticles 18-73 nm in diameter were prepared by evaporation of bulk tungsten oxide particles using a flame spray process. Annealing plasma-made tungsten oxide nanoparticles produced particles with diameters of 7-19 nm. The mechanism of nanoparticle formation for each synthetic route was examined. The low-cost, solid-fed flame process readily produced highly crystalline tungsten oxide nanoparticles with controllable size and a remarkably high adsorption capability. These nanoparticles are comparable to those prepared using the more expensive plasma process.

  2. Ion beam analysis of tungsten layers in EUROFER model systems and carbon plasma facing components

    Science.gov (United States)

    Ström, Petter; Petersson, Per; Rubel, Marek; Primetzhofer, Daniel; Brezinsek, Sebastijan; Kreter, Arkadi; Unterberg, Bernhard; Sergienko, Gennady; Sugiyama, Kazuyoshi

    2016-03-01

    The tungsten enriched surface layers in two fusion-relevant EUROFER steel model samples, consisting of an iron-tungsten mixture exposed to sputtering by deuterium ions, were studied by Rutherford backscattering spectrometry and medium energy ion scattering. Exposure conditions were the same for the two samples and the total amount of tungsten atoms per unit area in the enriched layers were similar (2 · 1015 and 2.4 · 1015 atoms/cm2 respectively), despite slightly different initial atomic compositions. A depth profile featuring exponential decrease in tungsten content towards higher depths with 10-20 at.% of tungsten at the surface and a decay constant between 0.05 and 0.08 Å-1 was indicated in one sample, whereas only the total areal density of tungsten atoms was measured in the other. In addition, two different beams, iodine and chlorine, were employed for elastic recoil detection analysis of the deposited layer on a polished graphite plate from a test limiter in the TEXTOR tokamak following experiments with tungsten hexafluoride injection. The chlorine beam was preferred for tungsten analysis, mainly because it (as opposed to the iodine beam) does not give rise to problems with overlap of forward scattered beam particles and recoiled tungsten in the spectrum.

  3. Solution and diffusion of hydrogen isotopes in tungsten-rhenium alloy

    Science.gov (United States)

    Ren, Fei; Yin, Wen; Yu, Quanzhi; Jia, Xuejun; Zhao, Zongfang; Wang, Baotian

    2017-08-01

    Rhenium is one of the main transmutation elements forming in tungsten under neutron irradiation. Therefore, it is essential to understand the influence of rhenium impurity on hydrogen isotopes retention in tungsten. First-principle calculations were used to study the properties of hydrogen solution and diffusion in perfect tungsten-rhenium lattice. The interstitial hydrogen still prefers the tetrahedral site in presence of rhenium, and rhenium atom cannot act directly as a trapping site of hydrogen. The presence of rhenium in tungsten raises the solution energy and the real normal modes of vibration on the ground state and the transition state, compared to hydrogen in pure tungsten. Without zero point energy corrections, the presence of rhenium decreases slightly the migration barrier. It is found that although the solution energy would tend to increase slightly with the rising of the concentration of rhenium, but which does not influence noticeably the solution energy of hydrogen in tungsten-rhenium alloy. The solubility and diffusion coefficient of hydrogen in perfect tungsten and tungsten-rhenium alloy have been estimated, according to Sievert's law and harmonic transition state theory. The results show the solubility of hydrogen in tungsten agrees well the experimental data, and the presence of Re would decrease the solubility and increase the diffusivity for the perfect crystals.

  4. Exposure assessment in the hard metal manufacturing industry with special regard to tungsten and its compounds.

    Science.gov (United States)

    Kraus, T; Schramel, P; Schaller, K H; Zöbelein, P; Weber, A; Angerer, J

    2001-10-01

    To assess the exposure to tungsten, cobalt, and nickel in a plant producing hard metals. The main components of hard metals are tungsten carbide and cobalt metal. According to recent studies, these two components may be responsible for both fibrogenic and carcinogenic effects. 87 workers were investigated (86 male, one female) with a median age of 42 (range 22-58) and a mean duration of exposure of 13 years (range 1-27 years). Stationary and personal air sampling, and biological monitoring were carried out. Ambient monitoring yielded maximum tungsten concentrations of 417 microg/m3 in the production of heavy alloys. A maximum cobalt concentration of 343 microg/m3 and a maximum nickel concentration of 30 microg/m3 were found at the sintering workshop. The highest urinary cobalt concentrations were found in the powder processing department. The mean concentration was 28.5 microg/g creatinine and the maximum value was 228 microg/g creatinine. The maximum nickel concentration in urine of 6.3 microg/g creatinine was detected in the department producing heavy alloys. The highest tungsten concentrations excreted in urine were found in grinders and had a mean value of 94.4 microg/g creatinine and a maximum of 169 microg/g creatinine. Due to the different solubility and bioavailability of the substance, there was no correlation between the tungsten concentrations in air and urine on a group basis. Despite its low solubility, tungsten carbide is bioavailable. The different bioavailability of tungsten metal and tungsten compounds has to be considered in the interpretation of ambient and biological monitoring data in the hard metal producing industry. The bioavailability increases in the order: tungsten metal, tungsten carbide, tungstenate. Only if both monitoring strategies are considered in combination can a valid and effective definition of high risk groups be derived.

  5. Systematic studies of the nucleation and growth of ultrananocrystalline diamond films on silicon substrates coated with a tungsten layer

    Energy Technology Data Exchange (ETDEWEB)

    Chu, Yueh-Chieh; Jiang, Gerald [Institute of Microelectronics, No.1, University Road, Tainan 701, Taiwan (China); Tu, Chia-Hao [Institute of Nanotechnology and Microsystems Engineering, No.1, University Road, Tainan 701, Taiwan (China); Department of Materials Science and Engineering, National Cheng Kung University, No.1, University Road, Tainan 701, Taiwan (China); Chang Chi [Institute of Nanotechnology and Microsystems Engineering, No.1, University Road, Tainan 701, Taiwan (China); Liu, Chuan-pu; Ting, Jyh-Ming [Department of Materials Science and Engineering, National Cheng Kung University, No.1, University Road, Tainan 701, Taiwan (China); Lee, Hsin-Li [Industrial Technology Research Institute - South, Tainan 701, Taiwan (China); Tzeng, Yonhua [Institute of Microelectronics, No.1, University Road, Tainan 701, Taiwan (China); Advanced Optoelectronics Technology Center, No.1, University Road, Tainan 701, Taiwan (China); Auciello, Orlando [Argonne National Laboratory, Materials Science Division, 9700 S. Cass Avenue, Argonne, Illinois 60439 (United States)

    2012-06-15

    We report on effects of a tungsten layer deposited on silicon surface on the effectiveness for diamond nanoparticles to be seeded for the deposition of ultrananocrystalline diamond (UNCD). Rough tungsten surface and electrostatic forces between nanodiamond seeds and the tungsten surface layer help to improve the adhesion of nanodiamond seeds on the tungsten surface. The seeding density on tungsten coated silicon thus increases. Tungsten carbide is formed by reactions of the tungsten layer with carbon containing plasma species. It provides favorable (001) crystal planes for the nucleation of (111) crystal planes by Microwave Plasma Enhanced Chemical Vapor Deposition (MPECVD) in argon diluted methane plasma and further improves the density of diamond seeds/nuclei. UNCD films grown at different gas pressures on tungsten coated silicon which is pre-seeded by nanodiamond along with heteroepitaxially nucleated diamond nuclei were characterized by Raman scattering, field emission-scanning electron microscopy, and high resolution-transmission electron microscopy.

  6. Potential irradiation of Cu alloys and tungsten samples in DONES

    Science.gov (United States)

    Mota, F.; Palermo, I.; Laces, S.; Molla, J.; Ibarra, A.

    2017-12-01

    Tungsten and Cu alloys are currently proposed as reference candidate material for ITER and DEMO first wall and divertor. Tungsten is proposed for its high fusion temperature and CuCrZr alloys for their high thermal conductivity together with good mechanical properties. However its behaviour under the extreme irradiation conditions as expected in ITER or DEMO fusion reactors is still unknown. Due to the determinant role of H and He played in the material behaviour any irradiation experiment must take into account the amount of these gases produced during the irradiation in Fusion reactors with high-energy neutrons. DONES (DEMO oriented neutron source) has been conceived as a simplified IFMIF (International Fusion Material Irradiation Facility) like plant to provide in a reduced time scale and with a reduced budget—both compared to IFMIF—the basic information on materials damage. The objective of DONES-IFMIF in its first stage will be to test structural materials under similar neutron irradiation nuclear fusion conditions as expected in fusion reactors. These tests will be carried out with specimens irradiated in the so called high flux test module (HFTM). The objective of this paper is to assess on the potential use of DONES to irradiate copper (Cu) alloys and tungsten (W) in the HFTM together with reduced activation ferritic martensitic steel like for example EUROFER (9%-Cr-steel). The presence of Cu alloys or W specimens may have an effect in the irradiation parameters of the EUROFER samples placed also in the HFTM and in the samples of the creep fatigue test module (CFTM). McDeLicious code is used for neutron transport calculations. Damage dose rate and H and He production are analysed in the different locations and compared with the irradiation conditions in first wall and divertor in fusion machines.

  7. Mathematical Modelling of the Process of Tungsten Fluorides Reduction by Hydrogen

    Directory of Open Access Journals (Sweden)

    Brendakov Roman

    2016-01-01

    Full Text Available The process of tungsten fluorides reduction by hydrogen is a component part of Fluoride technology of tungsten conversion. Nowadays the researchers are definitely interested in studying this process. It is connected with common use of metal tungsten products in different sectors of the economy, which is the result of unique qualities of this metal. With the help of physical and mathematical modelling of the process of tungsten hexafluoride reduction by hydrogen, it becomes possible to create an import substitution technology of metal tungsten conversion. Fluoride technology of tungsten conversion allows putting different coverings and make tungsten products of different shapes, which is impossible to get traditionally. The process of tungsten fluorides reduction by hydrogen can be referred to CVD processes (Chemical Vapor Deposition. Common use of CVD technologies for getting metal products and coverings is limited by definite problems, connected with access difficulties to initial components of research and the lack of information about their basic thermal characteristics. Therefore, mathematical description of the initial components mass-moving process, which provides with optimal value of their concentration in gas flow and in precipitation zone, is a question of current importance.

  8. On-chip microplasma reactors using carbon nanofibres and tungsten oxide nanowires as electrodes

    NARCIS (Netherlands)

    Agiral, A.; Groenland, A.W.; Chinthaginjala, J.K.; Kumar Chinthaginjala, J.; Seshan, Kulathuiyer; Lefferts, Leonardus; Gardeniers, Johannes G.E.

    2008-01-01

    Carbon nanofibres (CNFs) and tungsten oxide (W18O49) nanowires have been incorporated into a continuous flow type microplasma reactor to increase the reactivity and efficiency of the barrier discharge at atmospheric pressure. CNFs and tungsten oxide nanowires were characterized by high-resolution

  9. Growth Process Conditions of Tungsten Oxide Thin Films Using Hot-Wire Chemical Vapor Deposition

    NARCIS (Netherlands)

    Houweling, Z.S.|info:eu-repo/dai/nl/251874486; Geus, J.W.; de Jong, M.; Harks, P.P.R.M.L.; van der Werf, C.H.M.; Schropp, R.E.I.|info:eu-repo/dai/nl/072502584

    2011-01-01

    We report the growth conditions of nanostructured tungsten oxide (WO3−x) thin films using hot-wire chemical vapor deposition (HWCVD). Two tungsten filaments were resistively heated to various temperatures and exposed to an air flow at various subatmospheric pressures. The oxygen partial pressure was

  10. pH-controllable synthesis of unique nanostructured tungsten oxide aerogel and its sensitive glucose biosensor

    Science.gov (United States)

    Sun, Qiang-Qiang; Xu, Maowen; Bao, Shu-Juan; Li, Chang Ming

    2015-03-01

    This work presents a controllable synthesis of nanowire-networked tungsten oxide aerogels, which was performed by varying the pH in a polyethyleneimine (PEI)-assisted hydrothermal process. An enzyme-tungsten oxide aerogel co-modified electrode shows high activity and selectivity toward glucose oxidation, thus holding great promise for applications in bioelectronics.

  11. Thermal shock behaviour of tungsten after high flux H-plasma loading

    NARCIS (Netherlands)

    Wirtz, M.; Linke, J.; Pintsuk, G.; De Temmerman, G.; Wright, G. M.

    2013-01-01

    Previous studies have shown that transient thermal shock loads induce crack networks on tungsten samples especially at low base temperatures. To achieve test conditions which are more relevant for the performance of tungsten-armoured plasma facing components in next step thermonuclear fusion devices

  12. The influence of high grain boundary density on helium retention in tungsten

    Energy Technology Data Exchange (ETDEWEB)

    Valles, G., E-mail: gonzalovallesalberdi@hotmail.es [Instituto de Fusión Nuclear UPM, José Gutiérrez Abascal 2, 28006 Madrid (Spain); González, C. [Departamento de Física, Universidad de Oviedo, C/ Calvo Sotelo, s/n, Oviedo (Spain); Martin-Bragado, I. [IMDEA Materials Institute, C/ Enric Kandel 2, 28906 Getafe, Madrid (Spain); Iglesias, R. [Departamento de Física, Universidad de Oviedo, C/ Calvo Sotelo, s/n, Oviedo (Spain); Perlado, J.M.; Rivera, A. [Instituto de Fusión Nuclear UPM, José Gutiérrez Abascal 2, 28006 Madrid (Spain)

    2015-02-15

    Highlights: • Comparison between monocrystalline and nanostructured irradiated tungsten. • OKMC parameterization published and new DFT data. • Important role of grain boundary density on defect evolution. • Cluster pressurization much lower in nanostructured tungsten. • Promising expectations on nanocrystalline tungsten in view of results. - Abstract: In order to study the influence of a high grain boundary density on the amount, size and distribution of defects produced by pulsed helium (625 keV) irradiation in tungsten, we have carried out Object Kinetic Monte Carlo (OKMC) simulations in both monocrystalline and nanocrystalline tungsten. The parameterization of the OKMC code (MMonCa) includes binding energies obtained with our in-house Density Functional Theory (DFT) calculations. In the interior of a grain in nanocrystalline tungsten the mixed He{sub n}V{sub m} clusters are larger and have a lower He/V ratio. Thus, they are less pressurized clusters. The total elastic strain energy remains almost constant with the increasing number of pulses, contrary to its increase in monocrystalline tungsten. A better response to helium irradiation is therefore expected in nanocrystalline tungsten, opening a new path to investigate these nanostructured materials for fusion purposes.

  13. Deciphering surface behavior and deuterium retention in tin-lithium-coated fuzzy tungsten substrates

    Directory of Open Access Journals (Sweden)

    Eric Lang

    2017-08-01

    Full Text Available Tungsten will be used as plasma-facing material in the divertor in ITER, but it undergoes detrimental surface-subsurface morphological changes under irradiation. One type of tungsten that may mitigate such morphologies is porous tungsten due to higher defect sink areal density. While surface nanostructures such as fuzz may compromise plasma performance, their intrinsic porosity offers a proxy for a porous material and strategies to prevent high-Z impurity emission. Liquid metal coatings have been proposed as plasma facing materials to counteract the erosion issues faced by tungsten. Tin-lithium eutectics are an understudied class of potential liquid metal coatings for their low melting points and reduced erosion and fuel retention compared to pure lithium coatings. A 95 at.% tin-lithium eutectic was deposited on fuzzy tungsten samples and exposed to 250 eV deuterium ions at 250 °C and varying fluences. Mitigation of fuzz erosion and deuterium retention were examined post-mortem with SEM and secondary mass ion spectroscopy (SIMS of tungsten samples and witness samples used to collect eroded material. The SnLi film persisted after irradiation and protected underlying fuzz. SIMS results demonstrate surface mixing of the liquid metal and tungsten substrate and increased lithium erosion at high fluence and non-structured surfaces. The highest concentration and deepest penetration of retained deuterium was observed in the sample exposed to the lowest fluence. Results may indicate intercalation of liquid metal with tungsten tendrils at elevated temperatures.

  14. Optically Polarized Conduction-Band Electrons in Tungsten Observed by Spin-Polarized Photoemission

    DEFF Research Database (Denmark)

    Zürcher, P.; Meier, F.; Christensen, N. E.

    1979-01-01

    Along the (100) direction of tungsten, interband transitions induced by circularly polarized light of energy 1.5 eV......Along the (100) direction of tungsten, interband transitions induced by circularly polarized light of energy 1.5 eV...

  15. Efficient emission of positronium atoms from an Na-coated polycrystalline tungsten surface

    Science.gov (United States)

    Terabe, H.; Iida, S.; Wada, K.; Hyodo, T.; Yagishita, A.; Nagashima, Y.

    2013-06-01

    Time-of-flight spectra for the ortho-positronium emitted from clean and Na-coated tungsten surfaces have been measured using the pulsed slow positron beam at KEK-IMSS slow positron facility. Emission efficiency of positronium from the Na-coated sample was found to be several times greater than that from uncoated tungsten surfaces.

  16. Influence of particle flux density and temperature on surface modifications of tungsten and deuterium retention

    NARCIS (Netherlands)

    Buzi, L.; De Temmerman, G.; Unterberg, B.; M. Reinhart,; Litnovsky, A.; Philipps, V.; Van Oost, G.; Möller, S.

    2014-01-01

    Systematic study of deuterium irradiation effects on tungsten was done under ITER - relevant high particle flux density, scanning a broad surface temperature range. Polycrystalline ITER - like grade tungsten samples were exposed in linear plasma devices to two different ranges of deuterium ion flux

  17. pH-controllable synthesis of unique nanostructured tungsten oxide aerogel and its sensitive glucose biosensor.

    Science.gov (United States)

    Sun, Qiang-Qiang; Xu, Maowen; Bao, Shu-Juan; Li, Chang Ming

    2015-03-20

    This work presents a controllable synthesis of nanowire-networked tungsten oxide aerogels, which was performed by varying the pH in a polyethyleneimine (PEI)-assisted hydrothermal process. An enzyme-tungsten oxide aerogel co-modified electrode shows high activity and selectivity toward glucose oxidation, thus holding great promise for applications in bioelectronics.

  18. Vanadium Doped Tungsten Oxide Material - Electrical Physical and Sensing Properties

    Directory of Open Access Journals (Sweden)

    Shishkin N. Y.

    2008-05-01

    Full Text Available The electrical physical and sensing (to VOCs and inorganic gases properties of vanadium doped tungsten oxide in the regions of phase transition temperature were investigated. Vanadium oxide (II dimerization was observed in the doped material, corresponding to new phase transition. The extreme sensitivity and selectivity to chemically active gases and vapors in small concentrations: CO, NOx, NH3 acetone, ethanol near phase transitions temperature was found. Sensor elements were manufactured for the quantitative detection (close to 1 ppm of alcohol and ammonia.

  19. High temperature indentation of helium-implanted tungsten

    Energy Technology Data Exchange (ETDEWEB)

    Gibson, James S.K.-L., E-mail: james.gibson@materials.ox.ac.uk [Oxford University, Department of Materials, Parks Road, Oxford OX1 3PH (United Kingdom); Roberts, Steve G. [Oxford University, Department of Materials, Parks Road, Oxford OX1 3PH (United Kingdom); Culham Centre for Fusion Energy, Culham Science Centre, Abingdon OX14 3DB (United Kingdom); Armstrong, David E.J. [Oxford University, Department of Materials, Parks Road, Oxford OX1 3PH (United Kingdom)

    2015-02-11

    Nanoindentation has been performed on tungsten, unimplanted and helium-implanted to ~600 appm, at temperatures up to 750 °C. The hardening effect of the damage was 0.90 GPa at 50 °C, but is negligible above 450 °C. The hardness value at a given temperature did not change on re-testing after heating to 750 °C. This suggests that the helium is trapped in small vacancy complexes that are stable to at least 750 °C, but which can be bypassed due to increased dislocation mobility (cross slip or climb) above 450 °C.

  20. First-principles study of Frenkel pair recombination in tungsten

    Energy Technology Data Exchange (ETDEWEB)

    Qin, Shi-Yao; Jin, Shuo, E-mail: jinshuo@buaa.edu.cn; Li, Yu-Hao; Zhou, Hong-Bo; Zhang, Ying; Lu, Guang-Hong

    2017-02-15

    The recombination of one Frenkel pair in tungsten has been investigated through first-principles simulation. Two different recombination types have been identified: instantaneous and thermally activated. The small recombination barriers for thermally activated recombination cases indicate that recombination can occur easily with a slightly increased temperature. For both of the two recombination types, recombination occurs through the self-interstitial atom moving towards the vacancy. The recombination process can be direct or through replacement sequences, depending on the vertical distance between the vacancy and the 〈1 1 1〉 line of self-interstitial atom pair.

  1. In situ monitoring of the electrochemical dissolution of tungsten

    Energy Technology Data Exchange (ETDEWEB)

    Krebsz, Melinda [Christian Doppler Laboratory for Combinatorial Oxide Chemistry at ICTAS, Johannes Kepler University Linz (Austria); Kollender, Jan Philipp [Institute for Chemical Technology of Inorganic Materials (ICTAS), Johannes Kepler University Linz (Austria); Hassel, Achim Walter [Christian Doppler Laboratory for Combinatorial Oxide Chemistry at ICTAS, Johannes Kepler University Linz (Austria); Institute for Chemical Technology of Inorganic Materials (ICTAS), Johannes Kepler University Linz (Austria)

    2017-09-15

    In the present work, which is aimed to monitor in situ the electrochemical dissolution of tungsten by using a Flow-Type Scanning Droplet Cell Microscope (FT-SDCM) and Inductively Coupled Plasma Mass Spectrometry (ICP-MS), novel results are reported. The anodic oxide growth and its dissolution on the surface of W have been monitored in situ. The results of this current study show the importance of coupling electrochemical experiments to ICP-MS. (copyright 2017 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  2. First-principles study of Frenkel pair recombination in tungsten

    Science.gov (United States)

    Qin, Shi-Yao; Jin, Shuo; Li, Yu-Hao; Zhou, Hong-Bo; Zhang, Ying; Lu, Guang-Hong

    2017-02-01

    The recombination of one Frenkel pair in tungsten has been investigated through first-principles simulation. Two different recombination types have been identified: instantaneous and thermally activated. The small recombination barriers for thermally activated recombination cases indicate that recombination can occur easily with a slightly increased temperature. For both of the two recombination types, recombination occurs through the self-interstitial atom moving towards the vacancy. The recombination process can be direct or through replacement sequences, depending on the vertical distance between the vacancy and the line of self-interstitial atom pair.

  3. Evaluation of stable tungsten isotopes in the resolved resonance region

    Directory of Open Access Journals (Sweden)

    Schillebeeckx P.

    2013-03-01

    Full Text Available In the last decade benchmark experiments and simulations, together with newly obtained neutron cross section data, have pointed out deficiencies in evaluated data files of W isotopes. The role of W as a fundamental structural material in different nuclear applications fully justifies a new evaluation of 182, 183, 184, 186W neutron resonance parameters. In this regard transmission and capture cross section measurements on natural and enriched tungsten samples were performed at the GELINA facility of the EC-JRC-IRMM. A resonance parameter file used as input in the resonance shape analysis was prepared based on the available literature and adjusted in first instance to transmission data.

  4. Transient induced tungsten melting at the Joint European Torus (JET).

    Czech Academy of Sciences Publication Activity Database

    Coenen, J.W.; Matthews, G.F.; Krieger, K.; Iglesias, D.; Bunting, P.; Corre, Y.; Silburn, S.; Balboa, I.; Bazylev, B.; Conway, N.; Coffey, I.; Dejarnac, Renaud; Gauthier, E.; Gaspar, J.; Jachmich, S.; Jepu, I.; Makepeace, C.; Scannell, R.; Stamp, M.; Petersson, P.; Pitts, R.A.; Wiesen, S.; Widdowson, A.; Heinola, K.; Baron-Wiechec, A.

    T170, December (2017), č. článku 014013. ISSN 0031-8949. [PFMC 2017: 16th International Conference on Plasma-Facing Materials and Components for Fusion Applications. Düsseldorf, 16.05.2017-19.05.2017] EU Projects: European Commission(XE) 633053 - EUROfusion Institutional support: RVO:61389021 Keywords : fusion * melting * plasma wall interaction * tungsten * plasma facing components Subject RIV: BL - Plasma and Gas Discharge Physics Impact factor: 1.280, year: 2016 http://iopscience.iop.org/article/10.1088/1402-4896/aa8789/meta

  5. Surface studies of barium and barium oxide on tungsten and its application to understanding the mechanism of operation of an impregnated tungsten cathode

    Science.gov (United States)

    Forman, R.

    1976-01-01

    Surface studies have been made of multilayer and monolayer films of barium and barium oxide on a tungsten substrate. The purpose of the investigation was to synthesize the surface conditions that exist on an activated impregnated tungsten cathode and obtain a better understanding of the mechanism of operation of such cathodes. The techniques employed in these measurements were Auger spectroscopy and work-function measurements. The results of this study show that the surface of an impregnated cathode is identical to that observed for a synthesized monolayer or partial monolayer of barium on oxidized tungsten by evaluating Auger spectra and work-function measurements. Data obtained from desorption studies of barium monolayers on a tungsten substrate in conjunction with Auger and work-function results have been interpreted to show that throughout most of its life an impreganated cathode has a partial monolayer, rather than a monolayer, of barium on its surface.

  6. Effects of carbon impurity on deuterium retention in VPS-tungsten coatings exposed to JT-60U divertor plasmas

    Science.gov (United States)

    Fukumoto, M.; Nakano, T.; Itami, K.; Wada, T.; Ueda, Y.; Tanabe, T.

    2011-08-01

    Carbon eroded from carbon armor tiles during plasma discharge was implanted into and accumulated in tungsten coating exposed to JT-60U divertor plasmas. The D/C ratio of 0.06 ± 0.02 evaluated in the tungsten coating was half to one-quarter that in carbon codeposits formed at similar temperature of the tungsten coating. These results suggest that simultaneous use of carbon and tungsten coating would enhance tritium retention in the tungsten coating in future deuterium-tritium fusion devices. To investigate the carbon diffusion mechanism in the tungsten coating exposed to JT-60U divertor plasmas, the carbon diffusion coefficient in tungsten coating was measured by tracer methods. Using the apparent carbon diffusion coefficient obtained in this study (˜8 × 10-19 m2/s), the carbon diffusion length in the tungsten coating exposed to JT-60U divertor plasmas was evaluated to ˜100 nm. This diffusion length was quite shorter than that observed in the tungsten coating exposed to JT-60U divertor plasmas. Therefore, it remains possible that diffusion of implanted carbon in tungsten coating would be enhanced by other diffusion mechanisms which did not arise in the diffusion experiments or heat loads to the tungsten coating during transient events and plasma discharges with a strike point positioned on the tungsten-coated tiles.

  7. A molecular dynamics study of melting and dissociation of tungsten nanoparticles

    Directory of Open Access Journals (Sweden)

    Min Li

    2015-12-01

    Full Text Available Molecular dynamics simulations were conducted to study the melting and dissociation of free tungsten nanoparticles. For the various interatomic potentials applied, the melting points of the tungsten nanoparticles increased with increasing nanoparticle diameter. Combining these results with the melting point of bulk tungsten in the experiment, the melting point of nanoparticles with diameters ranging from 4 to 12 nm could be determined. As the temperature increases, free nanoparticles are subject to dissociation phenomena. The dissociation rate was observed to follow Arrhenius behavior, and the Meyer–Neldel rule was obeyed. These results are useful in understanding the behavior of tungsten dust generated in nuclear fusion devices as well as for the preparation, formation, and application of tungsten powders.

  8. Self-castellation of tungsten monoblock under high heat flux loading and impact of material properties

    Directory of Open Access Journals (Sweden)

    S. Panayotis

    2017-08-01

    Full Text Available In the full-tungsten divertor qualification program at ITER Organization, macro-cracks, so called self-castellation were found in a fraction of tungsten monoblocks during cyclic high heat flux loading at 20MW/m2. The number of monoblocks with macro-cracks varied with the tungsten products used as armour material. In order to understand correlation between the macro-crack appearance and W properties, an activity to characterize W monoblock materials was launched at the IO. The outcome highlighted that the higher the recrystallization resistance, the lower the number of cracks detected during high heat flux tests. Thermo-mechanical finite element modelling demonstrated that the maximum surface temperature ranges from 1800 °C to 2200 °C and in this range recrystallization of tungsten occurred. Furthermore, it indicated that loss of strength due to recrystallization is responsible for the development of macro-cracks in the tungsten monoblock.

  9. Recent developments toward the use of tungsten as armour material in plasma facing components

    Energy Technology Data Exchange (ETDEWEB)

    Mitteau, R. [Euratom-CEA, Direction des sciences de matiere, departement de recherches sur la fusion controlee, CEA Cadarache, Saint Paul les Durances (France)], E-mail: Raphael.mitteau@cea.fr; Missiaen, J.M. [LTPCM, UMR CNRS 5614, Universite Joseph Fourier, Grenoble (France); Brustolin, P. [Institut de Soudure, YUTZ (France); Ozer, O. [LTPCM, UMR CNRS 5614, Universite Joseph Fourier, Grenoble (France); Durocher, A. [Euratom-CEA, Direction des sciences de matiere, departement de recherches sur la fusion controlee, CEA Cadarache, Saint Paul les Durances (France); Ruset, C.; Lungu, C.P. [NILPRP, Magurele-Bucharest (Romania); Courtois, X. [Euratom-CEA, Direction des sciences de matiere, departement de recherches sur la fusion controlee, CEA Cadarache, Saint Paul les Durances (France); Dominicy, C. [CP2M, Universite d' Aix Marseille III, Marseille (France); Maier, H. [Max-Planck-Institut fuer Plasmaphysik, Euratom Association, Garching (Germany); Grisolia, C. [Euratom-CEA, Direction des sciences de matiere, departement de recherches sur la fusion controlee, CEA Cadarache, Saint Paul les Durances (France); Piazza, G. [EFDA JET, Close Support Unit, Culham Science Centre (United Kingdom); Chappuis, P. [Euratom-CEA, Direction des sciences de matiere, departement de recherches sur la fusion controlee, CEA Cadarache, Saint Paul les Durances (France)

    2007-10-15

    Future fusion experiments will rely on tungsten armour tile for their plasma facing components. In order to sustain steady state operation, the components need to be cooled through an attachment to a heat sink. All current reference concepts rely on contact bonds, unfavourable for long-term application (high temperature service, cycle fatigue, thermal shocks). Three routes toward the development of thick tungsten bonds are presented here, namely functionally graded tungsten copper assembly, electron beam welding of tungsten, and coating processes. All present favourable prospects, and tend to indicate that a thick bond is possible with tungsten. Dedicated programs as well as industrial implication are however required if such concepts are to be used actually for the fabrication of large components series.

  10. Microstructure analysis and comparison of tungsten alloy rod and [001] oriented columnar-grained tungsten rod ballistic penetrators

    Energy Technology Data Exchange (ETDEWEB)

    Pappu, S.; Kennedy, C.; Murr, L.E. [Texas Univ., El Paso, TX (United States). Dept. of Metallurgical and Materials Engineering; Magness, L.S. [US Army Research Lab., Aberdeen Proving Ground, MD (United States); Kapoor, D. [US Army Armament, Research, Development, and Engineering Center (ARDEC), Picatinny Arsenal, NJ (United States)

    1999-04-01

    Tungsten heavy alloy (WHA) penetrator rods (93% W particles in a matrix of 4.9% Ni and 2.1% Fe) were compared with [001] columnar-grained W penetrator rods in the as-fabricated condition, and after penetration into thick targets at impact velocities of 1 and 1.5 km s{sup -1}, respectively. Light metallography and transmission electron microscopy revealed the initial W microstructures to be similar arrangements of predominantly a left angle 111 right angle /2 screw dislocations. The in-target (deformed) microstructures were characterized by recovered and elongated sub-grains having misorientations ranging from 1 to 5 . (orig.) 22 refs.

  11. Terawatt laser system irradiation of carbon/tungsten bilayers

    Energy Technology Data Exchange (ETDEWEB)

    Lungu, C.P.; Marcu, A.; Porosnicu, C.; Jepu, I.; Lungu, A.M.; Chiru, P.; Luculescu, C.; Banici, R.; Ursescu, D.; Dabu, R. [National Institute for Laser, Plasma and Radiation Physics, 077125 Bucharest (Romania); Feraru, I.D.; Grigorescu, C.E.A. [National Institute R and D for Optoelectronics, INOE 2000, 077125 Bucharest (Romania); Iacobescu, G.; Osiac, M. [University of Craiova, Faculty of Physics, Craiova 200585 (Romania); Kovac, J. [Institute (JSI), Jamova 39, 1000 Ljubljana (Slovenia); Center of Excellence for Polymer Materials and Technologies, 1000 Ljubljana (Slovenia); Nemanic, V. [Institute (JSI), Jamova 39, 1000 Ljubljana (Slovenia); Hinkov, I. [Center of Excellence for Polymer Materials and Technologies, 1000 Ljubljana (Slovenia); Farhat, S.; Gicquel, A.; Brinza, O. [Laboratoire des Sciences des Materiaux et des Procedes, LSPM, Universite Paris 13, 93430 Villetaneuse (France)

    2012-09-15

    Using the original thermionic vacuum arc method (TVA), carbon films with the thickness of about 2500 nm were coated on top of 200 nm tungsten films deposited on fine grain graphite substrates. The carbon/tungsten bilayers were irradiated using a terawatt laser system (TEWALAS), 360 ps and 100 fs pulse duration, 110-150 mJ pulse energy. The analysis of the selected area electron diffraction (SAED) pattern allowed the identification of rhomboedral structures corresponding to diamond. The Raman scattering measurements were also performed on the produced craters and the specific peak at 1330 cm{sup -1} corresponding to diamond was observed. The C-C sp{sup 3} bonding content increased to 39.4% in the irradiated region compared to 30.8% in the ''as deposited'' zone, as shown by XPS. The craters produced by the laser irradiation were morphologically studied using optical imaging and scanning electron microscopy. (Copyright copyright 2012 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  12. Tungsten based Anisotropic Metamaterial as an Ultra-broadband Absorber

    CERN Document Server

    Lin, Yinyue; Ding, Fei; Fung, Kin Hung; Ji, Ting; Li, Dongdong; Hao, Yuying

    2016-01-01

    The trapped rainbow effect has been mostly found on tapered anisotropic metamaterials (MMs) made of low loss noble metals, such as gold, silver, etc. In this work, we demonstrate that an anisotropic MM waveguide made of high loss metal tungsten can also support the trapped rainbow effect similar to the noble metal based structure. We show theoretically that an array of tungsten/germanium anisotropic nano-cones placed on top of a reflective substrate can absorb light at the wavelength range from 0.3 micrometer to 9 micrometer with an average absorption efficiency approaching 98%. It is found that the excitation of multiple orders of slow-light resonant modes is responsible for the efficient absorption at wavelengths longer than 2 micrometer, and the anti-reflection effect of tapered lossy material gives rise to the near perfect absorption at shorter wavelengths. The absorption spectrum suffers a small dip at around 4.2 micrometer where the first order and second order slow-light modes get overlapped, but we ca...

  13. Photocatalysis and Photoelectrochemical Properties of Tungsten Trioxide Nanostructured Films

    Directory of Open Access Journals (Sweden)

    Chin Wei Lai

    2014-01-01

    Full Text Available Tungsten trioxide (WO3 possesses a small band gap energy of 2.4–2.8 eV and is responsive to both ultraviolet and visible light irradiation including strong absorption of the solar spectrum and stable physicochemical properties. Thus, controlled growth of one-dimensional (1D WO3 nanotubular structures with desired length, diameter, and wall thickness has gained significant interest. In the present study, 1D WO3 nanotubes were successfully synthesized via electrochemical anodization of tungsten (W foil in an electrolyte composed of 1 M of sodium sulphate (Na2SO4 and ammonium fluoride (NH4F. The influence of NH4F content on the formation mechanism of anodic WO3 nanotubular structure was investigated in detail. An optimization of fluoride ions played a critical role in controlling the chemical dissolution reaction in the interface of W/WO3. Based on the results obtained, a minimum of 0.7 wt% of NH4F content was required for completing transformation from W foil to WO3 nanotubular structure with an average diameter of 85 nm and length of 250 nm within 15 min of anodization time. In this case, high aspect ratio of WO3 nanotubular structure is preferred because larger active surface area will be provided for better photocatalytic and photoelectrochemical (PEC reactions.

  14. Simulations of thermionic suppression during tungsten transient melting experiments

    Science.gov (United States)

    Komm, M.; Tolias, P.; Ratynskaia, S.; Dejarnac, R.; Gunn, J. P.; Krieger, K.; Podolnik, A.; Pitts, R. A.; Panek, R.

    2017-12-01

    Plasma-facing components receive enormous heat fluxes under steady state and especially during transient conditions that can even lead to tungsten (W) melting. Under these conditions, the unimpeded thermionic current density emitted from the W surfaces can exceed the incident plasma current densities by several orders of magnitude triggering a replacement current which drives melt layer motion via the {\\boldsymbol{J}}× {\\boldsymbol{B}} force. However, in tokamaks, the thermionic current is suppressed by space-charge effects and prompt re-deposition due to gyro-rotation. We present comprehensive results of particle-in-cell modelling using the 2D3V code SPICE2 for the thermionic emissive sheath of tungsten. Simulations have been performed for various surface temperatures and selected inclinations of the magnetic field corresponding to the leading edge and sloped exposures. The surface temperature dependence of the escaping thermionic current and its limiting value are determined for various plasma parameters; for the leading edge geometry, the results agree remarkably well with the Takamura analytical model. For the sloped geometry, the limiting value is observed to be proportional to the thermal electron current and a simple analytical expression is proposed that accurately reproduces the numerical results.

  15. Electrochromic study on amorphous tungsten oxide films by sputtering

    Energy Technology Data Exchange (ETDEWEB)

    Li, Chuan, E-mail: cli10@yahoo.com [Department of Biomedical Engineering, National Yang Ming University, Taipei 11221, Taiwan (China); Department of Mechanical Engineering, National Central University, Jhongli, Taoyuan 32001, Taiwan (China); Hsieh, J.H. [Department of Materials Engineering, Ming Chi University of Technology, Taishan, Taipei 24301, Taiwan (China); Hung, Ming-Tsung [Department of Mechanical Engineering, National Central University, Jhongli, Taoyuan 32001, Taiwan (China); Huang, B.Q. [Department of Biomedical Engineering, National Yang Ming University, Taipei 11221, Taiwan (China)

    2015-07-31

    Tungsten oxide films under different oxygen flow rates are deposited by DC sputtering. The voltage change at target and analyses for the deposited films by X-ray diffraction, scanning electronic microscope, X-ray photoelectron spectroscopy and ultraviolet–visible-near infrared spectroscopy consistently indicate that low oxygen flow rate (5 sccm) only creates metal-rich tungsten oxide films, while higher oxygen flow rate (10–20 sccm) assures the deposition of amorphous WO{sub 3} films. To explore the electrochromic function of deposited WO{sub 3} films, we use electrochemical tests to perform the insertion of lithium ions and electrons into films. The WO{sub 3} films switch between color and bleach states effectively by both potentiostat and cyclic voltammetry. Quantitative evaluation on electrochemical tests indicates that WO{sub 3} film with composition close to its stoichiometry is an optimal choice for electrochromic function. - Highlights: • Amorphous WO{sub 3} films are deposited by DC sputtering under different O{sub 2} flow rates. • Higher oxygen flow rate (> 10 sccm) assures the deposition of amorphous WO{sub 3} films. • Both potentiostat and cyclic voltammetry make WO{sub 3} films switch its color. • An optimal electrochromic WO{sub 3} is to make films close to its stoichiometry.

  16. A review of the deformation behavior of tungsten at temperatures less than 0.2 of the melting point /K/

    Science.gov (United States)

    Stephens, J. R.

    1974-01-01

    The deformation behavior of tungsten at temperatures below 0.2 times the absolute melting temperature is reviewed with primary emphasis on the temperature dependence of the yield stress and the ductile-brittle transition. It is concluded that a model based on the high Peierls stress of tungsten best accounts for the observed mechanical behavior at low temperatures. Recent research suggests an important role of electron concentration and bonding on the mechanical behavior of tungsten. Future research on tungsten should include studies to define more clearly the correlation between electron concentration and mechanical behavior of alloys of tungsten and other transition metal alloys.

  17. Microstructures and Wear Performance of PTAW Deposited Ni-Based Coatings with Spherical Tungsten Carbide

    Directory of Open Access Journals (Sweden)

    Dewei Deng

    2015-10-01

    Full Text Available The Ni-based coatings with different content of spherical tungsten carbide were deposited by plasma transfer arc welding (PTAW method on 304 austenitic stainless steel sheets in this study. The microstructure and wear property of spherical tungsten carbide particle reinforced composite coatings were investigated by means of optical microscope, scanning electron microscope (SEM, X-ray diffraction (XRD, electron probe microanalysis (EPMA and sliding wear test. It is shown that the fraction of spherical tungsten carbides has an important influence on microstructure of Ni-based overlay. The Ni40 overlay consists of γ-Ni dendrites with interdendritic Ni-based eutectics, borides and carbides improving the wear resistance. In the case of composite coatings with different content of tungsten carbide, many new phases are observed, such as Ni2W4C and NiW. In addition, there are a large number of irregular structures in composite coatings, such as acicular structure and irregular stripe organization. The results of sliding wear test indicate that the mass loss of coatings is influenced by the content of tungsten carbide. The mass loss decreases with the increase of tungsten carbide fraction. At high load, the abrasive resistance of composite coating with 60 wt. % tungsten carbide is improved about 50-fold compared to that of Ni40 overlay.

  18. Simple preparation of tungsten supported carbon nanoreactors for specific applications: Adsorption, catalysis and electrochemical activity

    Energy Technology Data Exchange (ETDEWEB)

    Mayani, Vishal J.; Mayani, Suranjana V.; Kim, Sang Wook, E-mail: swkim@dongguk.ac.kr

    2015-08-01

    Graphical abstract: - Highlights: • Tungsten carbon composites have shown great recognition in catalysis and electrochemistry. • W-carbon composites are prepared by template replication and W-doping on carbon cage. • Nanocomposites offer enormous assurance as adsorbent, electrode and heterogeneous catalyst. - Abstract: Porous carbon supported tungsten carbide nanoreactors, two sizes (∼25 and 170 nm), were designed using economical petroleum pitch residue followed by tungsten (W) doping. X-ray diffractions showed both carbon tungsten composites (CTC-25 and CTC-170) contained tungsten subcarbide (W{sub 2}C) and monocarbide (WC) as the major and minor crystalline phases, respectively. The present study provides a multiple perspective of carbon tungsten composites (CTCs) for methanol oxidation (as an electrode), adsorption (as an adsorbent) and degradation (as a solid catalyst) of methylene blue (MB). The operational electrodes were designed from both CTCs and used as a catalyst in an electrocatalysis process. The electrocatalysts exhibited high and stable catalytic performance (CTCE-25 > CTCE-170) in methanol electro-oxidation. The newly synthesized W-doped carbon nanoreactors were used successfully as an adsorbent for MB and a heterogeneous catalyst for MB oxidation. Ordered CTC-25 and CTC-170 exhibited dynamic MB adsorption within 15 min and complete oxidation of MB in 25–40 min. A synergetic effect between tungsten carbide and the carbon cage framework was noted.

  19. A modified acid digestion procedure for extraction of tungsten from soil.

    Science.gov (United States)

    Bednar, A J; Jones, W T; Chappell, M A; Johnson, D R; Ringelberg, D B

    2010-01-15

    Interest in tungsten occurrence and geochemistry is increasing due to increased use of tungsten compounds and its unknown biochemical effects. Tungsten has a complex geochemistry, existing in most environmental matrices as the soluble and mobile tungstate anion, as well as poly- and heteropolytungstates. Because the geochemistry of tungsten is substantially different than most trace metals, including the formation of insoluble species under acidic conditions, it is not extracted from soil matrices using standard acid digestion procedures. Therefore, the current work describes a modification to a commonly used acid digestion procedure to facilitate quantification of tungsten in soil matrices. Traditional soil digestion procedures, using nitric and hydrochloric acids with hydrogen peroxide yield soil matrix spike samples, whereas the modified method reported here, which includes the addition of phosphoric acid, yields spike recoveries in the 76-98% range. Comparison of the standard and modified digestion procedures on National Institute of Standards and Technology Standard Reference Materials yielded significantly improved tungsten recoveries for the phosphoric acid modified method. The modified method also produces comparable results for other acid extractable metals as the standard methods, and therefore can be used simultaneously for tungsten and other metals of interest.

  20. Coupled interactions between tungsten surfaces and transient high-heat-flux deuterium plasmas

    Science.gov (United States)

    Takamura, S.; Uesugi, Y.

    2015-03-01

    Fundamental studies on the interactions between transient deuterium-plasma heat pulses and tungsten surfaces were carried out in terms of electrical, mechanical and thermal response in a compact plasma device AIT-PID (Aichi Institute of Technology-Plasma Irradiation Device). Firstly, electron-emission-induced surface-temperature increase is discussed in the surface-temperature range near tungsten's melting point, which is accomplished by controlling the sheath voltage and power transmission factor. Secondly, anomalous penetration of tungsten atomic efflux into the surrounding plasma was observed in addition to a normal layered population; it is discussed in terms of the effect of substantial tungsten influx into the deuterium plasma, which causes dissipation of plasma electron energy. Thirdly, a momentum input from pulsed plasma onto a tungsten target was observed visually. The force is estimated numerically by the accelerated ion flow to the target as well as the reaction of tungsten-vapour efflux. Finally, a discussion follows on the effects of the plasma heat pulses on the morphology of tungsten surface (originally a helium-induced ‘fuzzy’ nanostructure). A kind of bifurcated effect is obtained: melting and annealing. Open questions remain for all the phenomena observed, although sheath-voltage-dependent plasma-heat input may be a key parameter. Discussions on all these phenomena are provided by considering their implications to tokamak fusion devices.

  1. Spinodal decomposition of tungsten-containing phases in functional coatings obtained via high-energy implantation processes

    Science.gov (United States)

    Davydov, S. V.; Petrov, E. V.

    2017-08-01

    We have studied structural and phase transformations in tungsten-containing functional coatings of carbon steels obtained during the high-energy processes of implanting tungsten carbide micropowders by the method of complex pulse electromechanical processing and micropowders of tungsten by technology of directed energy of explosion based on the effect of superdeep penetration of solid particles (Usherenko effect). It has been shown that, during thermomechanical action, intensive steel austenization occurs in the deformation zone with the dissolution of tungsten carbide powder, the carbidization of tungsten powder, and the subsequent formation of composite gradient structures as a result of the decay of supercooled austenite supersaturated by tungsten according to the diffusion mechanism and the mechanism of spinodal decomposition. Separate zones of tungsten-containing phases of the alloy are in the liquid-phase state, as well as undergo spinodal decomposition with the formation of highly disperse carbide phases of globular morphology.

  2. Complexity of Products of Tungsten Corrosion: Comparison of the 3D Pourbaix Diagrams with the Experimental Data

    Science.gov (United States)

    Nave, Maryana I.; Kornev, Konstantin G.

    2017-03-01

    Tungsten is one of the most attractive metals in applications where materials are subject to high temperature and strong fields. However, in harsh aqueous environment, tungsten is prone to corrosion. Control of tungsten corrosion in aqueous solutions is a challenging task: as a transition metal, tungsten is able to produce a vast variety of oxides and hydrates. To reveal the thermodynamic pathway of corrosion at different conditions, the 3D Pourbaix diagrams relating the reduction potential, pH, and concentration of different tungsten-based compounds were constructed. These diagrams allow one to identify the most thermodynamically stable tungsten-based compounds. The 3D Pourbaix diagrams were used to explain different regimes of anodic dissolution of tungsten in aqueous solutions of potassium hydroxide.

  3. Structural stability of super duplex stainless weld metals and its dependence on tungsten and copper

    Science.gov (United States)

    Nilsson, J.-O.; Huhtala, T.; Jonsson, P.; Karlsson, L.; Wilson, A.

    1996-08-01

    Three different superduplex stainless weld metals have been produced using manual metal arc welding under identical welding conditions. The concentration of the alloying elements tungsten and copper corresponded to the concentrations in commercial superduplex stainless steels (SDSS). Aging experiments in the temperature range 700 °C to 1110 °C showed that the formation of intermetallic phase was enhanced in tungsten-rich weld metal and also dissolved at higher temperatures compared with tungsten-poor and tungsten-free weld metals. It could be inferred from time-temperature-transformation (TTT) and continuous-cooling-transformation (CCT) diagrams produced in the present investigation that the critical cooling rate to avoid 1 wt pct of intermetallic phase was 2 times faster for tungsten-rich weld metal. Microanalysis in combination with thermodynamic calculations showed that tungsten was accommodated in χ phase, thereby decreasing the free energy. Experimental evidence supports the view that the formation of intermetallic phase is enhanced in tungsten-rich weld metal, owing to easier nucleation of nonequilibrium χ phase compared with σ phase. The formation of secondary austenite (γ2) during welding was modeled using the thermodynamic computer program Thermo-Calc. Satisfactory agreement between theory and practice was obtained. Thermo-Calc was capable of predicting observed lower concentrations of chromium and nitrogen in γ2 compared with primary austenite. The volume fraction of γ2 was found to be significantly higher in tungsten-rich and tungsten + copper containing weld metal. The results could be explained by a higher driving force for precipitation of γ2 in these.

  4. Smart tungsten alloys as a material for the first wall of a future fusion power plant

    Science.gov (United States)

    Litnovsky, A.; Wegener, T.; Klein, F.; Linsmeier, Ch.; Rasinski, M.; Kreter, A.; Unterberg, B.; Coenen, J. W.; Du, H.; Mayer, J.; Garcia-Rosales, C.; Calvo, A.; Ordas, N.

    2017-06-01

    Tungsten is currently deemed as a promising plasma-facing material (PFM) for the future power plant DEMO. In the case of an accident, air can get into contact with PFMs during the air ingress. The temperature of PFMs can rise up to 1200 °C due to nuclear decay heat in the case of damaged coolant supply. Heated neutron-activated tungsten forms a volatile radioactive oxide which can be mobilized into the atmosphere. New self-passivating ‘smart’ alloys can adjust their properties to the environment. During plasma operation the preferential sputtering of lighter alloying elements will leave an almost pure tungsten surface facing the plasma. During an accident the alloying elements in the bulk are forming oxides thus protecting tungsten from mobilization. Good plasma performance and the suppression of oxidation are required for smart alloys. Bulk tungsten (W)-chroimum (Cr)-titanium (Ti) alloys were exposed together with pure tungsten (W) samples to the steady-state deuterium plasma under identical conditions in the linear plasma device PSI 2. The temperature of the samples was ~576 °C-715 °C, the energy of impinging ions was 210 eV matching well the conditions expected at the first wall of DEMO. Weight loss measurements demonstrated similar mass decrease of smart alloys and pure tungsten samples. The oxidation of exposed samples has proven no effect of plasma exposure on the oxidation resistance. The W-Cr-Ti alloy demonstrated advantageous 3-fold lower mass gain due to oxidation than that of pure tungsten. New yttrium (Y)-containing thin film systems are demonstrating superior performance in comparison to that of W-Cr-Ti systems and of pure W. The oxidation rate constant of W-Cr-Y thin film is 105 times less than that of pure tungsten. However, the detected reactivity of the bulk smart alloy in humid atmosphere is calling for a further improvement.

  5. A novel composite electrode based on tungsten oxide nanoparticles and carbon nanotubes for the electrochemical determination of paracetamol

    Energy Technology Data Exchange (ETDEWEB)

    Baytak, Aysegul Kutluay; Duzmen, Sehriban; Teker, Tugce; Aslanoglu, Mehmet, E-mail: maslanoglu@harran.edu.tr

    2015-12-01

    An electrochemical sensor was prepared by the modification of a glassy carbon electrode (GCE) with a composite of nanoparticles of tungsten oxide (WO{sub 3}) and carbon nanotubes (CNTs) for the quantification of paracetamol (PR). Energy dispersive X-ray analysis (EDX) and scanning electron microscopy (SEM) were performed for the characterization of the nanocomposite layer. Compared with a bare GCE and a GCE modified with CNTs, the proposed electrode (WO{sub 3}NPs/CNTs/GCE) exhibited a well-defined redox couple for PR and a marked enhancement of the current response. The experimental results also showed that ascorbic acid (AA) did not interfere with the selective determination of PR. The proposed electrode was used for the determination of PR in 0.1 M phosphate buffer solution (PBS) at pH 7.0 using square wave voltammetry (SWV). The peak current increased linearly with the concentration of PR in the range of 1.0 × 10{sup −9}–2.0 × 10{sup −7} M. The detection limit (LOD) was 5.54 × 10{sup −11} M (based on 3 S{sub b}/m). The proposed voltammetric sensor provided long-time stability, improved voltammetric behavior and good reproducibility for PR. The selective, accurate and precise determination of PR makes the proposed electrode of great interest for monitoring its therapeutic use. - Highlights: • A voltammetric nanosensor was prepared using nanoparticles of WO{sub 3} and CNTs. • A selective quantification of paracetamol was carried out in the presence of AA. • A linear plot was obtained for current responses versus concentrations over the range from 1.0 × 10{sup −9} to 2.0 × 10{sup −7} M. • A detection limit of 554 pM was obtained for paracetamol using the proposed nanosensor. • An accurate quantification makes the proposed nanosensor of great interest for public health.

  6. Investigation on the structural and mechanical properties of anti-sticking sputtered tungsten chromium nitride films

    Energy Technology Data Exchange (ETDEWEB)

    Lin, Tai-Nan [Chemical Engineering Division, Institute of Nuclear Energy Research, Taiwan, ROC (China); Han, Sheng [Department of Leisure and Recreation Management, National Taichung University of Science and Technology, Taiwan, ROC (China); Weng, Ko-Wei, E-mail: kowei@nqu.edu.tw [Department of Electronic Engineering, National Quemoy University, Taiwan, ROC (China); Lee, Chin-Tan [Department of Electronic Engineering, National Quemoy University, Taiwan, ROC (China)

    2013-02-01

    Tungsten chromium nitride (WCrN) thin films are prepared by dual-gun co-sputter process. As the surface coatings on the molding die for glass forming, WCrN films show less deterioration at high temperature than the conventional CrN coating. WCrN thin films are deposited via the reactive co-sputtering of Cr/W targets. The working pressure is kept at 2.66 Pa and the argon/nitrogen ratio is 10. Applied power of chromium is fixed and the applied power of tungsten is varied. Experimental results indicate that the atomic ratio of tungsten in the films increases with the applied power of tungsten. The dominant crystalline phase is chromium nitride when the tungsten target power is below 100 W, while tungsten nitride dominates in the film structure when the tungsten target power is beyond 200 W. A dense structure with much finer particles is developed as the tungsten power is 200 W. As the power is increased to 300 W, the particles become coarser in size. The film roughness exhibits a decreasing trend at low tungsten power and then increases as the tungsten power increased up to 300 and 400 W, presumably due to the phase change from chromium nitrides to tungsten nitrides. Further annealing of the WCrN thin films is simulated as the glass molding condition to check the anti-sticking property which is a critical requirement in molding die surface coating application. The WCrN thin film coating shows good anti-sticking property at 400 °C annealing when the tungsten target power is 200 W. - Highlights: ► WCrN films are deposited by dual sputtering of pure Cr and W targets. ► The covalent bonding character of WCrN films explains the difference in hardness. ► WCrN (200 W W-target-power/400 °C-annealing) exhibits the best anti-sticking performance.

  7. The Tungsten Project: Dielectronic Recombination Data For Collisional-RadiativeModelling In ITER

    CERN Document Server

    Preval, S P; O'Mullane, M G

    2016-01-01

    Tungsten is an important metal in nuclear fusion reactors. It will be used in the divertor component of ITER (Latin for 'the way'). The Tungsten Project aims to calculate partial and total DR rate coefficients for the isonuclear sequence of Tungsten. The calculated data will be made available as and when they are produced via the open access database OPEN- ADAS in the standard adf09 and adf48 file formats. We present our progress thus far, detailing calculational methods, and showing comparisons with other available data. We conclude with plans for the future.

  8. Nuclear Rocket Ceramic Metal Fuel Fabrication Using Tungsten Powder Coating and Spark Plasma Sintering

    Science.gov (United States)

    Barnes, M. W.; Tucker, D. S.; Hone, L.; Cook, S.

    2017-01-01

    Nuclear thermal propulsion is an enabling technology for crewed Mars missions. An investigation was conducted to evaluate spark plasma sintering (SPS) as a method to produce tungsten-depleted uranium dioxide (W-dUO2) fuel material when employing fuel particles that were tungsten powder coated. Ceramic metal fuel wafers were produced from a blend of W-60vol% dUO2 powder that was sintered via SPS. The maximum sintering temperatures were varied from 1,600 to 1,850 C while applying a 50-MPa axial load. Wafers exhibited high density (>95% of theoretical) and a uniform microstructure (fuel particles uniformly dispersed throughout tungsten matrix).

  9. Easy growth of undoped and doped tungsten oxide nanowires with high purity and orientation

    Science.gov (United States)

    Liu, Kun; Foord, David T.; Scipioni, Lawrence

    2005-01-01

    An economic method is presented to grow undoped/doped tungsten oxide nanowires with high purity and erect orientation, simply by heating a tungsten filament in a vacuum chamber with some room air leakage. Tungsten oxide nanowires were studied using scanning electron microscopy (SEM), energy dispersion x-ray spectroscopy (EDS) and transmission electron microscopy (TEM). Wires are found standing straight and clean on the filament, {\\sim }30 nm in diameter and up to a few tens of micrometres long. The composition along the wire is uniform for all elements including dopants.

  10. Solvent Extraction of Tungsten(VI) from Moderate Hydrochloric Acid Solutions with LIX 63

    Energy Technology Data Exchange (ETDEWEB)

    Truong, Hoai Thanh; Lee, Man Seung [Mokpo National University, Jeollanamdo (Korea, Republic of); Kim, Yong Hwan [Incheon Technology Service Centre, Incheon (Korea, Republic of)

    2017-06-15

    The solvent extraction of tungsten(VI) from hydrochloric acid solutions using 5,8-diethyl-7-hydroxydodecan-6-one oxime (LIX 63) was analyzed in solutions having an initial pH range from 2 to 5, by varying the concentration of metal and extractant. In our experimental range, the cationic exchange reaction as well as the solvation reaction occurred simultaneously. The cation exchange reaction was identified by applying a slope analysis method to the extraction data. The existence of cationic tungsten(VI) species was confirmed by ion exchange experiments with Diphonix resin at pH 3. Further study is needed to identify the nature of this tungsten cationic species.

  11. Preservation of Earth-forming events in the tungsten isotopic composition of modern flood basalts

    Science.gov (United States)

    Rizo, Hanika; Walker, Richard J.; Carlson, Richard W.; Horan, Mary F.; Mukhopadhyay, Sujoy; Manthos, Vicky; Francis, Don; Jackson, Matthew G.

    2016-05-01

    How much of Earth's compositional variation dates to processes that occurred during planet formation remains an unanswered question. High-precision tungsten isotopic data from rocks from two large igneous provinces, the North Atlantic Igneous Province and the Ontong Java Plateau, reveal preservation to the Phanerozoic of tungsten isotopic heterogeneities in the mantle. These heterogeneities, caused by the decay of hafnium-182 in mantle domains with high hafnium/tungsten ratios, were created during the first ~50 million years of solar system history, indicating that portions of the mantle that formed during Earth’s primary accretionary period have survived to the present.

  12. Formation of interstitial atoms in surface layers of helium-implanted tungsten

    Science.gov (United States)

    Dudka, O. V.; Ksenofontov, V. A.; Masilov, A. A.; Sadanov, E. V.

    2013-11-01

    Using a method of field ion microscopy, the atomic structure of surface and near-surface layers of a perfect dislocation-free tungsten irradiated by helium ions with energies below the threshold of displacement was studied. We have found the output of tungsten atoms from the bulk as a result of their displacement from regular lattice positions occupied by implanted helium atoms and the formation of interstitial tungsten atoms. It is shown that high concentrations of helium and the presence of image forces have a considerable effect on the development of these processes. Depleted zones consisting of helium-vacancy complexes are revealed within the irradiated near-surface layer.

  13. Fabrication of Tungsten-UO 2 Hexagonal-Celled Fuel-Element Configurations

    Energy Technology Data Exchange (ETDEWEB)

    Goetsch, R.R.; Cover, P.W.; Gripshover, P.J.; Wilson, W.J.

    1964-12-04

    The gas-pressure-bonding process is being evaluated as a means of fabricating tungsten-UO 2 hexagonal-celled fuel geometries. A two-part study was initiated to optimize the fuel materials and to develp the required fixturing and loading techniques. Production of fueled tungsten-coated UO 2 particles in in progress so that geometries embodying coated particles or coated particles plus fine tungsten powder can be evaluated. Tests to data have shown the rquirement for a pretreatment in which a gaseous oxide phase is removed. Initial loading and fixturing procedures were proven satisfactory by the fabrication of a 19-cylindrical-hole hexagonal-type composite.

  14. Effect of tungsten doping on catalytic properties of niobium oxide

    Energy Technology Data Exchange (ETDEWEB)

    Cardoso, Franciane P.; Nogueira, Andre E. [Departamento de Quimica, Universidade Federal de Lavras, Lavras-MG (Brazil); Patricio, Patricia S.O., E-mail: patriciapatricio@cefetmg.br [Centro Federal de Educacao Tecnologica, CEFET, Belo Horizonte, MG (Brazil); Oliveira, Luiz C.A. [Departamento de Quimica, ICEx, Universidade Federal de Minas Gerais, Belo Horizonte, MG (Brazil)

    2012-04-15

    A novel material based on niobia (Nb{sub 2}O{sub 5}) was synthesized to oxidize an organic compound in aqueous medium in the presence of H{sub 2}O{sub 2} after chemical modifications. Niobia was modified by doping with tungsten and also treating with H{sub 2}O{sub 2} in order to maximize the oxidative properties of this oxide. The analysis of the products from methylene blue dye oxidation with electro spray ionization mass spectrometry (ESI-MS) showed that the dye was successively oxidized to different intermediate compounds. The successive hydroxylation during this oxidation strongly suggests that highly reactive hydroxyl radicals are generated involving H{sub 2}O{sub 2} on the W-doped niobia grain surface. These results strongly suggest that the H{sub 2}O{sub 2} can regenerate in situ the peroxo group remaining active the system. (author)

  15. Hematite modified tungsten trioxide nanoparticle photoanode for solar water oxidation

    Science.gov (United States)

    Mao, Aiming; Kim, Jung Kyu; Shin, Kahee; Wang, Dong Hwan; Yoo, Pil J.; Han, Gui Young; Park, Jong Hyeok

    2012-07-01

    Hematite (α-Fe2O3) film is electrochemically deposited onto the surface of tungsten trioxide (WO3) nanoparticulate film. The synthesis of the WO3 nanostructure is directed by surfactants for control of its morphology. The resulting composite shows visible light harvesting and is tested as photoanodes in heterojunction photoelectrochemical cells for the possibility of direct water splitting under visible illumination. The composite's structural and optical properties are characterized by FESEM, EDS, XRD, XPS, and UV-vis spectrometry; its photocurrent responses are also investigated under simulated solar illumination. Coupling WO3 with hematite results in over 9 times greater photocurrent density than that shown by pure WO3 in sodium sulfate electrolyte. This simple modification can significantly improve the performance of WO3.

  16. Deuterium retention in molten salt electrodeposition tungsten coatings

    Energy Technology Data Exchange (ETDEWEB)

    Zhou, Hai-Shan [Institute of Plasma Physics, Chinese Academy of Sciences, Hefei (China); Xu, Yu-Ping [Science Island Branch of Graduate School, University of Science and Technology of China, Hefei (China); Sun, Ning-Bo; Zhang, Ying-Chun [School of Materials Science and Engineering, University of Science and Technology Beijing, Beijing (China); Oya, Yasuhisa [Radioscience Research Laboratory, Faculty of Science, Shizuoka University, Shizuoka (Japan); Zhao, Ming-Zhong [Institute of Plasma Physics, Chinese Academy of Sciences, Hefei (China); Mao, Hong-Min [Science Island Branch of Graduate School, University of Science and Technology of China, Hefei (China); Ding, Fang; Liu, Feng [Institute of Plasma Physics, Chinese Academy of Sciences, Hefei (China); Luo, Guang-Nan, E-mail: gnluo@ipp.ac.cn [Institute of Plasma Physics, Chinese Academy of Sciences, Hefei (China); Science Island Branch of Graduate School, University of Science and Technology of China, Hefei (China); Hefei Center for Physical Science and Technology, Hefei (China); Hefei Science Center of Chinese Academy of Science, Hefei (China)

    2016-12-15

    Highlights: • We investigate D retention in electrodeposition W coatings. • W coatings are exposed to D plasmas in the EAST tokamak. • A cathodic current density dependence on D retention is found. • Electrodeposition W exhibits lower D retention than VPS-W. - Abstract: Molten salt electrodeposition is a promising technology to manufacture the first wall of a fusion reactor. Deuterium (D) retention behavior in molten salt electrodeposition tungsten (W) coatings has been investigated by D-plasma exposure in the EAST tokamak and D-ion implantation in an ion beam facility. Tokamak exposure experiments demonstrate that coatings prepared with lower current density exhibit less D retention and milder surface damage. Deuterium-ion implantation experiments indicate the D retention in the molten salt electrodeposition W is less than that in vacuum plasma spraying W and polycrystalline W.

  17. PLD Grown Polycrystalline Tungsten Disulphide (WS2 Films

    Directory of Open Access Journals (Sweden)

    Salman Alfihed

    2013-01-01

    Full Text Available Polycrystalline WS2 films were grown by pulsed laser deposition (PLD system at relatively low temperature. The main objective of this study is to optimize the growth conditions for polycrystalline WS2 films at relatively low temperature to use them for photovoltaics (PVs. Different growth conditions and substrates are used and examined systematically. It is found out that films grown on strontium titanate SrTiO3 (STO substrate have the best structural properties when compared to other substrates examined in this work. X-ray diffraction and optical characterizations of these films reveal crystallographic growth and very promising optical properties for PVs. Furthermore, it was observed that higher growth temperature (>300°C has an unfavorable effect on the layers by creating some tungsten metallic droplets.

  18. Electronic transport properties of tungsten silicide thin films

    Science.gov (United States)

    Martin, T. L.; Malhotra, V.; Mahan, J. E.

    1984-03-01

    Tungsten suicide thin films have been prepared by neutralized ion beam sputtering of the metal onto a polycrystalline silicon layer followed by furnace annealing. The films appear to be essentially sing le-phase disilicide with the possibility of a percent or so carbon and oxygen content. The material behaves as a classical metallic conductor, with a temperature-independent residual resistivity of 16 μΩ-cm and a room temperature intrinsic resistivity of 7 μΩ-cm. Hall effect measurements indicate the material is predominantly a hole conductor, with a room temperature Hall mobility of 30cm2/V-s and an apparent free carrier concentration of 8.9×1021 cm-3. The effective one-carrier mobility derived from geometrical magnetoresistance data, on the other hand, is ≈95 cm2/V-s; this difference, taken together with the effect of temperature on the transport properties, suggests there is mixed conduction.

  19. Spatial features control of self-organised tungsten nanowire arrays

    Energy Technology Data Exchange (ETDEWEB)

    Milenkovic, Srdjan; Hassel, Achim Walter [Max-Planck-Institut fuer Eisenforschung GmbH, Duesseldorf (Germany)

    2009-03-15

    Self-organised tungsten nanowire arrays were produced by a recently established templateless method. Control of spatial features such as diameter and spacing of nanowires was successfully achieved by changing the growth rate during directional solidification. An increase in the growth rate from 1.4 {mu}m s{sup -1} to 55.5 {mu}m s{sup -1} led to a decrease in the nanowire diameter from 560 to 290 nm and the spacing from 3.5 {mu}m to 1.7 {mu}m. The scaling laws of the variation in nanowire diameter and spacing with growth rate are quantitatively determined. Distribution of both, the diameter and the spacing around the average value were quite narrow. Potential applications of such self-organised W nanowire arrays in nanotechnology are discussed. (copyright 2009 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim) (orig.)

  20. Dissimilar Brazed Joints Between Steel and Tungsten Carbide

    Science.gov (United States)

    Voiculescu, I.; Geanta, V.; Binchiciu, H.; Iovanas, D.; Stefanoiu, R.

    2017-06-01

    Brazing is a joining process used to obtain heterogeneous assemblies between different materials, such as steels, irons, non-ferrous metals, ceramics etc. Some application, like asphalt cutters, require quick solutions to obtain dissimilar joints at acceptable costs, given the very short period of operation of these parts. This paper presents some results obtained during the brazing of dissimilar joints between steel and tungsten carbide by using different types of Ag-Cu system filler materials alloyed with P and Sn. The brazing techniques used were oxygen-gas flame and induction joining. The brazing behaviour was analysed in cross sections by optical and electron microscopy. The metallographic analysis enhanced the adhesion features and the length of penetration in the joining gap. The melting range of the filler materials was measured using thermal analysis.

  1. Gas tungsten arc welding of vanadium alloys with impurity control

    Science.gov (United States)

    Grossbeck, M. L.; King, J. F.; Nagasaka, T.; David, S. A.

    2002-12-01

    Gas tungsten arc welding in vanadium alloys is controlled by interstitial impurities. Techniques have been developed to weld V-4Cr-4Ti in a high-purity argon atmosphere resulting in a DBTT of -20 °C. The atmosphere was controlled by a Zr-Al getter which is activated at high temperature to obtain a clean surface then cooled and allowed to absorb hydrogen and oxygen impurities. Through the use of low-oxygen base metal and high-purity weld filler wire, a DBTT of -145 °C was obtained. Experiments using electron beam welding have shown that grain size also has an important effect on weld ductility. Introduction of nitrogen and yttrium has been used to study their effect on grain size. Using a combination of atmosphere control, alloy purity control, and grain size control, it is anticipated that V-Cr-Ti alloys will be weldable in field conditions.

  2. Low-chromium reduced-activation chromium-tungsten steels

    Energy Technology Data Exchange (ETDEWEB)

    Klueh, R.L.; Alexander, D.J.; Maziasz, P.J. [Oak Ridge National Lab., TN (United States)

    1996-10-01

    Bainitic microstructures formed during continuous cooling can differ from classical upper and lower bainite formed during isothermal transformation. Two types of non-classical bainite were observed depending on the cooling rate: carbide-free acicular bainite at rapid cooling rates and granular bainite at slower cooling rates. The Charpy impact toughness of the acicular ferrite was found to be considerably better than for the granular bainite. It was postulated that alloying to improve the hardenability of the steel would promote the formation of acicular bainite, just as increasing the cooling rate does. To test this, chromium and tungsten were added to the 2 1/4Cr-2W and 2 1/4Cr-2WV steel compositions to increase their hardenability, and the microstructures and mechanical properties were examined.

  3. Gamma Spectrum from Neutron Capture on Tungsten Isotopes

    Energy Technology Data Exchange (ETDEWEB)

    Hurst, Aaron; Summers, Neil; Sleaford, Brad; Firestone, Richard B; Belgya, T.; Revay, Z.S.

    2010-04-29

    An evaluation of thermal neutron capture on the stable tungsten isotopes is presented, with preliminary results for the compound systems 183;184;185;187W. The evaluation procedure compares the g-ray cross-section data collected at the Budapest reactor, with Monte Carlo simulations of g-ray emission following the thermal neutron-capture process. The statistical-decay code DICEBOX was used for the Monte Carlo simulations. The evaluation yields new gamma rays in 185W and the confirmation of spins in 187W, raising the number of levels below which the level schemes are considered complete, thus increasing the number of levels that can be used in neutron data libraries.

  4. Electron beam treatment of tungsten mock-ups

    Science.gov (United States)

    Zalavutdinov, R.; Novokhatsky, A.; Gusev, V.; Bukhovets, V.; Gorodetsky, A.; Kuznetsov, V.; Litunovsky, N.; Makhankov, A.; Mazul, I.; Mukhin, E.; Petrov, Yu; Rybkina, T.; Sakharov, N.; Tolstyakov, S.; Voronin, A.; Zakharov, A.

    2017-12-01

    To simulate thermal loads in ITER several tungsten (W) water cooled mock-ups were treated by a scanning electron beam (Tsefey-M) at a heat flux up to 1.68 GW m‑2 for a duration of 18 μs and a frequency about 30 kHz. Surface morphology, chemical composition, structure, and microhardness of formed W layers were analyzed by SEM, EPMA, XRD, OM, and Vickers hardness tester. The irradiation treatment resulted in W melting to a depth of 0.3 mm, increasing sub-surface grain sizes, grain ordering in the metal bulk, deep cracking, and decreasing of microhardness to a depth of 2–4 mm. Installation of the pre-damaged W samples in a tokamak Globus-M divertor did not change practically discharge conditions.

  5. Downsizing of single crystalline high aspect ratio tungsten nanowires

    Energy Technology Data Exchange (ETDEWEB)

    Milenkovic, Srdjan [IMDEA Materials Institute, Eric Kandel 2, 28906, Getafe (Spain); Drensler, Stefanie [Institute for Chemical Technology of Inorganic Materials, Johannes Kepler University, Altenberger Str. 69, 4040, Linz (Austria); Hassel, Achim Walter [Institute for Chemical Technology of Inorganic Materials, Johannes Kepler University, Altenberger Str. 69, 4040, Linz (Austria); Christian Doppler Laboratory for Combinatorial Oxide Chemistry, Institute for Chemical Technology of Inorganic Materials, Johannes Kepler University Linz, Altenberger Str. 69, 4040, Linz (Austria)

    2015-06-15

    Directional solidification of eutectic NiAl-W alloys offers an intuitive method to produce tungsten nanowires. Through the use of two different methods, the well-established Bridgman method and a newer type floating zone method, the direct influence of process parameters, like the withdrawal rate and the temperature gradient, onto the sample microstructure were studied. The sharp temperature gradient, built up using a four mirror system focusing the light emitted by halogen lamps inside the optical floating zone furnace allows producing nanowires with a diameter as small as 75 nm. Differences in the solid/liquid interface morphology depending on the solidification method used are discussed. (copyright 2015 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  6. Special Grain Boundaries in Ultrafine-Grained Tungsten

    Science.gov (United States)

    Dudka, O. V.; Ksenofontov, V. A.; Sadanov, E. V.; Starchenko, I. V.; Mazilova, T. I.; Mikhailovskij, I. M.

    2016-07-01

    Field ion microscopy and computer simulation were used for the study of an atomic structure high-angle grain boundary in hard-drawn ultrafine-grained tungsten wire. These boundaries with special misorientations are beyond the scope of the coincident site lattice model. It was demonstrated that the special non-coincident grain boundaries are the plane-matching boundaries, and rigid-body displacements of adjacent nanograins are normal to the misorientation axis. The vectors of rigid-body translations of grains are described by broad asymmetric statistical distribution. Mathematical modeling showed that special incommensurate boundaries with one grain oriented along the {211} plane have comparatively high cohesive energies. The grain-boundary dislocations ½ were revealed and studied at the line of local mismatch of {110} atomic planes of adjacent grains.

  7. Carbon adsorption on tungsten and electronic field emission

    Science.gov (United States)

    Márquez-Mijares, Maykel; Lepetit, Bruno; Lemoine, Didier

    2016-03-01

    Electronic emission taking place at the electrodes of high voltage systems and responsible for detrimental breakdown processes is known to be strongly dependent on the cathode surface state and in particular on the presence of carbon contamination. To understand better the effect of carbon adsorption on cathode electronic emission, density functional theory calculations are reported for bulk bcc tungsten as well as for clean and carbon-covered W(100) surfaces for several coverages up to 2 ML. Adsorption geometries and energies, work functions and electronic densities of states are analyzed to assess the effect of the presence of adlayers on surface electronic field emission properties. It is shown that flat carbon adlayer deposition on clean W(100) surfaces induces an increase of the surface work function and a decrease of electronic density near the Fermi level. Both factors contribute to reducing electronic field emission levels.

  8. Dynamics of femtosecond laser produced tungsten nanoparticle plumes

    Energy Technology Data Exchange (ETDEWEB)

    Harilal, S. S.; Hassanein, A. [Center for Materials Under Extreme Environment, School of Nuclear Engineering, Purdue University, West Lafayette, Indiana 47907 (United States); Farid, N. [Center for Materials Under Extreme Environment, School of Nuclear Engineering, Purdue University, West Lafayette, Indiana 47907 (United States); School of Physics and Optical Engineering, Dalian University of Technology, Dalian 116024 (China); Kozhevin, V. M. [Ioffe Physics Technical Institute, Russian Academy of Sciences, St. Petersburg 194021 (Russian Federation)

    2013-11-28

    We investigated the expansion features of femtosecond laser generated tungsten nanoparticle plumes in vacuum. Fast gated images showed distinct two components expansion features, viz., plasma and nanoparticle plumes, separated by time of appearance. The persistence of plasma and nanoparticle plumes are ∼500 ns and ∼100 μs, respectively, and propagating with velocities differed by 25 times. The estimated temperature of the nanoparticles showed a decreasing trend with increasing time and space. Compared to low-Z materials (e.g., Si), ultrafast laser ablation of high-Z materials like W provides significantly higher nanoparticle yield. A comparison between the nanoparticle plumes generated by W and Si is also discussed along with other metals.

  9. Dynamics of femtosecond laser produced tungsten nanoparticle plumes

    Science.gov (United States)

    Harilal, S. S.; Farid, N.; Hassanein, A.; Kozhevin, V. M.

    2013-11-01

    We investigated the expansion features of femtosecond laser generated tungsten nanoparticle plumes in vacuum. Fast gated images showed distinct two components expansion features, viz., plasma and nanoparticle plumes, separated by time of appearance. The persistence of plasma and nanoparticle plumes are ˜500 ns and ˜100 μs, respectively, and propagating with velocities differed by 25 times. The estimated temperature of the nanoparticles showed a decreasing trend with increasing time and space. Compared to low-Z materials (e.g., Si), ultrafast laser ablation of high-Z materials like W provides significantly higher nanoparticle yield. A comparison between the nanoparticle plumes generated by W and Si is also discussed along with other metals.

  10. Determination of tungsten by amperometric redox titration with dichromate

    Energy Technology Data Exchange (ETDEWEB)

    Wuensch, G.; Aupers, R.; Kranich, R.

    1985-11-01

    Tungsten is reduced by an excess of Cr(II) in about 10 M HCl. This is technically simpler than the use of reductor columns or liquid amalgams. Titration with Fe(III) or Cr(VI) first consumes the excess of Cr(II) and then oxidizes W(V) to W(VI). The potentiometric response of metal electrodes to W(V) is slow but biamperometric indication at Esub(pol) = 0.2 V applies well. A mixture of W, Fe and Mo can be analyzed in a consecutive titration. Only Ti interferes. As compared to the reductometric titration of W(VI) with Cr(II) the method uses a stable titrant and avoids deairating of the sample solution. Sample preparations for ferrotungsten, steel and wolframite ore are described. (orig.).

  11. Effect of rhenium irradiations on the mechanical properties of tungsten for nuclear fusion applications

    Energy Technology Data Exchange (ETDEWEB)

    Khan, Aneeqa, E-mail: aneeqa.khan-3@postgrad.manchester.ac.uk [School of Mechanical, Aerospace and Civil Engineering, The University of Manchester, M13 9PL (United Kingdom); Elliman, Robert; Corr, Cormac [Research School of Physics and Engineering, The Australian National University, Canberra, ACT 2601 (Australia); Lim, Joven J.H.; Forrest, Andrew [School of Materials, The University of Manchester, M13 9PL (United Kingdom); Mummery, Paul [School of Mechanical, Aerospace and Civil Engineering, The University of Manchester, M13 9PL (United Kingdom); Evans, Llion M. [Culham Centre for Fusion Energy, Culham Science Centre, Abingdon, Oxon, OX14 3DB (United Kingdom)

    2016-08-15

    As-received and annealed tungsten samples were irradiated at a temperature of 400 °C with Re and W ions to peak concentrations of 1600 appm (atomic parts per million) and damage levels of 40 dpa (displacements per atom). Mechanical properties were investigated using nanoindentation, and the orientation and depth dependence of irradiation damage was investigated using Electron Back Scatter Diffraction (EBSD). Following irradiation there was a 13% increase in hardness in the as received sheet and a 23% increase in the annealed material for both tungsten and rhenium irradiation. The difference between the tungsten and rhenium irradiated samples was negligible, suggesting that for the concentrations and damage levels employed, the presence of rhenium does not have a significant effect on the hardening mechanism. Energy dependent EBSD of annealed samples provided information about the depth distribution of the radiation damage in individual tungsten grains and confirmed that the radiation damage is orientation dependant.

  12. Combustion synthesis of nano-sized tungsten carbide powder and effects of sodium halides

    Science.gov (United States)

    Won, H. I.; Nersisyan, H. H.; Won, C. W.

    2010-02-01

    The synthesis of nano-size tungsten carbide powder has been investigated with a WO3 + Mg + C + carbonate system using alkali halides. The effects of different types of alkali halides on combustion temperature and tungsten carbide formation were discussed. Sodium fluoride had a notable effect on the particle size of the product and the degree of transformation from the initial mixture. A small amount of ammonium carbonate activated the carburization of tungsten carbide by the gas phase carbon transportation. X-ray diffraction data and particle analysis showed that the final product synthesized from a WO3-Mg-C-(NH4)2CO3-NaF system contains pure-phase tungsten carbide with a particle size of 50-100 nm.

  13. A supercritical carbon dioxide plasma process for preparing tungsten oxide nanowires.

    Science.gov (United States)

    Kawashima, Ayato; Nomura, Shinfuku; Toyota, Hiromichi; Takemori, Toshihiko; Mukasa, Shinobu; Maehara, Tsunehiro

    2007-12-12

    A supercritical carbon dioxide (CO(2)) plasma process for fabricating one-dimensional tungsten oxide nanowires coated with amorphous carbon is presented. High-frequency plasma was generated in supercritical carbon dioxide at 20 MPa by using tungsten electrodes mounted in a supercritical cell, and subsequently an organic solvent was introduced with supercritical carbon dioxide into the plasma. Electron microscopy and Raman spectroscopy investigations of the deposited materials showed the production of tungsten oxide nanowires with or without an outer layer. The nanowires with an outer layer exhibited a coaxial structure with an outer concentric layer of amorphous carbon and an inner layer of tungsten oxide with a thickness and diameter of 20-30 and 10-20 nm, respectively.

  14. Measurements of temperature of the tungsten hexa-ethoxide pyrolysis flame using IR camera

    CSIR Research Space (South Africa)

    Mudau, AE

    2010-09-01

    Full Text Available In laser pyrolysis, temperature measurement and control plays a vital role during the development of nanoparticles. Authors present the results of temperature measurements using infrared camera on a tungsten hexa-ethoxide pyrolysis flame used...

  15. APPLICATION OF AN EXPERIMENTAL METHODOLOGY IN THE OPTIMIZATION OF A TUNGSTEN CONCENTRATION PROCESS BY MICROEMULSIONS

    Directory of Open Access Journals (Sweden)

    A.C.S. RAMOS

    1997-06-01

    Full Text Available Abstract - In this work, we applied an experimental planning methodology in order to correlate the necessary amounts with the description of the a tungsten extraction process by microemulsions. The result is a mathematical modelling carried out using the Sheffe Net method, where the mixtures concentration values are represented inside an equilateral triangle. The tungsten concentration process occurs in two stages: extraction and reextraction. The extraction stage was determined by monitoring: phase relative volume (Vr, extraction percentage (%E and tungsten concentration in the microemulsion phase (Ctm e. The reextraction phase was determined by monitoring: reextraction percentage (%Re and tungsten concentration in the aqueous phase (Ctaq. Finally, we obtained equations that relate the extraction / reextraction properties to the composition of specific points inside the extraction region, obeying the error limits specified for the acceptance of each parameter. The results were evaluated through the construction of isoresponse diagrams and correlation graphics between experimental values and those obtained through use of equations.

  16. High Rate Plastic Deformation and Failure of Tungsten-Sintered Metals

    National Research Council Canada - National Science Library

    Bjerke, Todd

    2004-01-01

    The competition between plastic deformation and brittle fracture during high rate loading of a tungsten-sintered metal is examined through impact experiments, post-experiment microscopy, and numerical simulation...

  17. Cracking behavior of tungsten armor under ELM-like thermal shock loads: A computational study

    National Research Council Canada - National Science Library

    Li, Muyuan; Werner, Ewald; You, Jeong-Ha

    2015-01-01

    In this work, the cracking behavior of tungsten under edge-localized mode (ELM)-like thermal shock loads was investigated on the basis of a rigorous computational fracture mechanical analysis combined with the finite element method...

  18. Optimization Studies of Photocatalytic Tungsten-Doped Titania Coatings Deposited by Reactive Magnetron Co-Sputtering

    National Research Council Canada - National Science Library

    Marina Ratova; Glen T West; Peter J Kelly

    2013-01-01

    .... The methylene blue decomposition experiments showed that, at the optimum dopant concentration of tungsten, the photocatalytic activity can be improved by a factor of 6, compared to undoped titania...

  19. Synthesis, Consolidation and Characterization of Sol-gel Derived Tantalum-Tungsten Oxide Thermite Composites

    Energy Technology Data Exchange (ETDEWEB)

    Cervantes, O [Univ. of California, Davis, CA (United States)

    2010-06-01

    Energetic composite powders consisting of sol-gel (SG) derived nanostructured tungsten oxide were produced with various amounts of micrometer-scale tantalum fuel metal. Such energetic composite powders were ignition-tested and results show that the powders are not sensitive to friction, spark and/or impact ignition. Initial consolidation experiments, using the High Pressure Spark Plasma Sintering (HPSPS) technique, on the SG derived nanostructured tungsten oxide produced samples with higher relative density than can be achieved with commercially available tungsten oxide. The SG derived nanostructured tungsten oxide with immobilized tantalum fuel metal (Ta - WO3) energetic composite was consolidated to a density of 9.17 g·cm-3 or 93% relative density. In addition, those samples were consolidated without significant pre-reaction of the constituents, thus retaining their stored chemical energy.

  20. Chitosan coated tungsten trioxide nanoparticles as a contrast agent for X-ray computed tomography.

    Science.gov (United States)

    Firouzi, Mehdi; Poursalehi, Reza; Delavari H, Hamid; Saba, Fakhredin; Oghabian, Mohammad A

    2017-05-01

    Recent advances have shown that inorganic nanoparticles (NPs) based on heavy elements are highly appropriate for X-ray computed tomography (CT). In this contribution, tungsten trioxide NPs are prepared by the electrical arc discharge (EAD) method in DI water. The effect of chitosan (CTS) and glutaraldehyde (GTA) as coating and cross-linking agent, respectively, on the hydrodynamic size and zeta potential of prepared tungsten trioxide NPs is investigated. It is found that zeta potential increases by increasing the amounts of CTS. Meanwhile, by increasing the volume of glutaraldehyde (GTA), the final particle size increases whereas the zeta potential deceases. Chitosan coated tungsten trioxide demonstrated no significant cytotoxicity at concentration up to 5mg/mL after 24h. Finally, the X-ray attenuation of prepared chitosan coated tungsten trioxide NPs are higher than Iohexol as the commercially available iodinated contrasting agent at the same concentrations. Copyright © 2017 Elsevier B.V. All rights reserved.

  1. Ultraviolet radiation and blue-light emissions from spotlights incorporating tungsten halogen lamps

    CERN Document Server

    MacKinlay, Alistair F; Whillock, M J

    1989-01-01

    This report summarises measurements of the ultraviolet radiation and blue-light emissions from eleven 'desk-top' tungsten halogen (quartz) lamps and one 'floor-standing' tungsten halogen (quartz) lamp available in the UK. Values of occupational hazard weighted and erythemally weighted ultraviolet radiation irradiance and measurements and relevant calculations of blue-light hazards are presented. It is concluded that the safety design of some desk-top tungsten halogen lamps is inadequate to prevent unnecessary exposure of the skin to potentially harmful ultraviolet radiation. It is recommended that all tungsten halogen lamps should have sufficient filtration to reduce their ultraviolet emissions to an acceptably low level. As long as the comfort aversion responses of the eye are respected, direct viewing of the lamps examined should not constitute a retinal hazard.

  2. OEDGE modeling for the planned tungsten ring experiment on DIII-D

    Directory of Open Access Journals (Sweden)

    J.D. Elder

    2017-08-01

    Full Text Available The OEDGE code is used to model tungsten erosion and transport for experiments with toroidal rings of high-Z metal tiles in the DIII-D tokamak. Such modeling is needed for both experimental and diagnostic design to have estimates of the expected core and edge tungsten density and to understand the various factors contributing to the uncertainties in these calculations. OEDGE simulations are performed using the planned experimental magnetic geometries and plasma conditions typical of both L-mode and inter-ELM H-mode discharges in DIII-D. OEDGE plasma reconstruction based on specific representative discharges for similar geometries is used to determine the plasma conditions applied to tungsten plasma impurity simulations. A new model for tungsten erosion in OEDGE was developed which imports charge-state resolved carbon impurity fluxes and impact energies from a separate OEDGE run which models the carbon production, transport and deposition for the same plasma conditions as the tungsten simulations. These values are then used to calculate the gross tungsten physical sputtering due to carbon plasma impurities which is then added to any sputtering by deuterium ions; tungsten self-sputtering is also included. The code results are found to be dependent on the following factors: divertor geometry and closure, the choice of cross-field anomalous transport coefficients, divertor plasma conditions (affecting both tungsten source strength and transport, the choice of tungsten atomic physics data used in the model (in particular ionization rate for W-atoms, and the model of the carbon flux and energy used for calculating the tungsten source due to sputtering. Core tungsten density is found to be of order 1015m−3 (excluding effects of any core transport barrier and with significant variability depending on the other factors mentioned with density decaying into the scrape off layer. For the typical core density in the plasma conditions examined of 2 to 4

  3. Effect of tungsten carbide in carbon Pt catalyst support on electrochemical oxygen reduction in acid solution

    Directory of Open Access Journals (Sweden)

    Obradović Maja D.

    2013-01-01

    Full Text Available Tungsten carbide was synthesized by calcination of carbon cryogel with embedded tungsten in a form of metatungstate. This material was used as a support for Pt nanoparticles. XRD pattern of W-C support indicates the presence of WC, W2C, and unreacted W, as well as graphitized carbon. According to the previous TEM analysis of W-C support, it contains particles with core-shell structure, where W particle was covered with the shell of a mixture of WC and W2C. The average Pt grain size calculated from XRD pattern was about 6 nm. Cyclic voltammogram of W-C support was recorded within potential range relevant for its application as a catalyst support in fuel cells. Pair of anodic/cathodic peaks close to the negative potential limit could be ascribed to the intercalation of hydrogen within hydrous tungsten oxide, which is always present on the surface of WC in aqueous solutions. Cyclic voltammogram of Pt/W-C indicated that tungsten oxide species are present on tungsten carbide shell as well as on the surface of Pt nanoparticles. Pt surface is only partially covered by hydrous tungsten oxide. Hydrogen intercalation in hydrous tungsten oxide is enhanced in the presence of Pt nanoparticles. Also, the presence of hydrated tungsten oxide leads to the decrease of OH chemisorbed on Pt surface. Stripping of underpotentially deposited copper was used for the assessment of Pt surface area and the specific surface area of Pt was estimated to 41 m2 g-1. Electrochemical oxygen reduction reaction was examined on the synthesized Pt/W-C catalyst and compared with the results on the commercial Pt/C catalyst. It was found that the current densities at Pt/W-C are almost double as those on Pt/C. The Tafel plots for both catalysts are characterized with two Tafel slopes: -0.060 V dec-1 at low current densities, and -0.120 V dec-1 at high current densities. From the rotational dependence of the reaction rate, it was found that oxygen reduction on both Pt/W-C and Pt

  4. Molybdenum-copper and tungsten-copper alloys and method of making

    Science.gov (United States)

    Schmidt, Frederick A.; Verhoeven, John D.; Gibson, Edwin D.

    1989-05-23

    Molybdenum-copper and tungsten-copper alloys are prepared by a consumable electrode method in which the electrode consists of a copper matrix with embedded strips of refractory molybdenum or tungsten. The electrode is progressively melted at its lower end with a superatmospheric inert gas pressure maintained around the liquifying electrode. The inert gas pressure is sufficiently above the vapor pressure of copper at the liquidus temperature of the alloy being formed to suppress boiling of liquid copper.

  5. Effect of precursor mass on product phase composition in plasma dynamic synthesis of tungsten carbide

    Science.gov (United States)

    Shatrova, K. N.; Sivkov, A. A.; Shanenkov, I. I.; Saigash, A. S.

    2017-05-01

    An interest in WC1-x cubic tungsten carbide results from its catalytic properties similar to those of platinum group metals and the synergistic effect between WC1-x and Pt in reactions of hydrogen evolution and hydrogen oxidation. However, according to the phase diagram of the W-C system, the cubic phase WC1-x only exists in a narrow range of temperature stability (about 2798-3058 K), which makes it difficult for being obtained. To date, there are different methods for synthesizing tungsten carbide powder with a low content of cubic phase that complicates the study of WC1-x properties. A direct plasma dynamic synthesis is known as one of the promising methods to produce WC1-x. The aim of this work is to find the optimal amount of tungsten precursor to obtain cubic tungsten carbide with a high purity by plasma dynamic method. The synthesized products were examined by X-ray diffraction (XRD) and transmission electron microscopy (TEM). The XRD patterns showed that the main phase was cubic tungsten carbide with negligible content of hexagonal tungsten carbide W2C and pure tungsten W. According to a quantitative analysis of synthesized products, which were obtained using masses of initial tungsten equal to 1.0, 0.7, 0.6 and 0.5 gram, the yield of WC1-x phase was 84, 89, 95 and 92 wt%, respectively. The results of TEM displayed that the synthesized powders consist of crystallites, having the size less than 100 nm (WC1-x), and a carbon matrix. This carbon was not detected in XRD due to its presence as an amorphous phase.

  6. Demonstration of Shear Localization in Ultrafine Grained Tungsten Alloys via Powder Metallurgy Processing Route

    Science.gov (United States)

    2012-09-01

    which remained elastic during each experiment. Interfaces between the specimen and platens were lubricated with molybdenum disulfide (MoS2) grease to...of a di-tungsten boride (W2B) phase was not detected in the nW-B sample, but the low concentration of boron may have made this phase undetectable by...Further Studies on Rhenium Alloying Effects in Molybdenum , Tungsten, and Chromium, Battelle Memorial Inst., Columbus, Ohio, 1960. 20. Lassner, E

  7. The Enrichment of Stale Tailings of Bom-gorhon Tungsten Ore Deposits

    OpenAIRE

    Frolova, I.V.; Tikhonov, V V; Nalesnik, O.I.; Streltsova, A. A.

    2014-01-01

    The results of mineralogical studies of technogenic tungsten raw material (stale tailings of Bom-Gorhon deposit) are represented. Its particle size distribution as well as tungsten and accompanying element distribution among the fractions were determined. The necessity of grinding the heaps down to 0.2-0.25 mm in size was established. It allows increasing the recovery rate of two or more times in comparison with the traditional pattern of tailing processing.

  8. Influence of equation of state on interpretation of electrical conductivity measurements in strongly coupled tungsten plasma

    OpenAIRE

    Tkachenko, S. I.; Levashov, P. R.; Khishchenko, K. V.

    2006-01-01

    We study the influence of equation-of-state (EOS) model on the interpretation of electrical conductivity measurements in strongly coupled plasma of tungsten by Korobenko et al. (2002 Plasma Physics Reports 28(12) 1008--1016). Three different semiempirical EOS models for tungsten are used. Discrepancies in obtained thermodynamic parameters and specific resistivity values as compared with calculation results of Korobenko et al. are analysed.

  9. Effect of temperature and geometric parameters on elastic properties of tungsten nanowire: A molecular dynamics study

    Energy Technology Data Exchange (ETDEWEB)

    Saha, Sourav, E-mail: ssaha09@me.buet.ac.bd; Mojumder, Satyajit; Mahboob, Monon [Department of Mechanical Engineering, Bangladesh University of Engineering and Technology, Dhaka-1000 (Bangladesh); Islam, M. Zahabul [Department of Mechanical and Nuclear Engineering, The Pennsylvania State University, University Park, Pennsylvania 16802 (United States)

    2016-07-12

    Tungsten is a promising material and has potential use as battery anode. Tungsten nanowires are gaining attention from researchers all over the world for this wide field of application. In this paper, we investigated effect of temperature and geometric parameters (diameter and aspect ratio) on elastic properties of Tungsten nanowire. Aspect ratios (length to diameter ratio) considered are 8:1, 10:1, and 12:1 while diameter of the nanowire is varied from 1-4 nm. For 2 nm diameter sample (aspect ratio 10:1), temperature is varied (10 K ~ 1500 K) to observe elastic behavior of Tungsten nanowire under uniaxial tensile loading. EAM potential is used for molecular dynamic simulation. We applied constant strain rate of 10{sup 9} s{sup −1} to deform the nanowire. Elastic behavior is expressed through stress vs. strain plot. We also investigated the fracture mechanism of tungsten nanowire and radial distribution function. Investigation suggests peculiar behavior of Tungsten nanowire in nano-scale with double peaks in stress vs. strain diagram. Necking before final fracture suggests that actual elastic behavior of the material is successfully captured through atomistic modeling.

  10. High Heat Flux Testing of Tungsten PFCs for the Fusion Reactor Development

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Suk-Kwon; Park, Seong Dae; Jin, Hyung Gon; Lee, Eo Hwak; Yoon, Jae-Sung; Lee, Dong Won [Korea Atomic Energy Research Institute, Daejeon (Korea, Republic of)

    2016-10-15

    Tungsten divertor plasma facing components (PFCs) were fabricated by using hot isostatic-pressing (HIP) bonding and vacuum plasma spray method (VPS) for the fusion reactor development. Tungsten mockups were designed for the high heat flux test with the Korean high heat flux test facility - electron beam (KoHLT-EB), which was constructed for the performance qualification of various PFCs. KoHLT-EB was used to qualify the PFCs performances of each fusion research. The high heat load conditions were simulated by using a thermo-hydraulic analysis tool with the ANSYS-CFX code. A high heat flux testing was performed up to the thermal life-time of each mockup with the evaluated conditions in 1 ⁓ 5 MW/m{sup 2}. HIP-bonded testing mockups consisted of 2 mm pure tungsten PFCs and ferritic-martensitic steel (FMS) as structural materials, and VPS mockups are comprised with 1 ⁓ 2 mm coated tungsten layer and FMS. These tungsten mockups are the candidate for the blanket and divertor in DEMO or a fusion power reactor. For the thermal fatigue test, two types of tungsten mock-ups were fabricated by using HIP bonding and VPS method for the fusion reactor development. The verification of the cooling performance was tested under the operation condition of ITER and fusion reactor. After the completion of the preliminary mockup test and facility qualification, the high heat flux test facility assess the performance test for two type of plasma facing components.

  11. New oxidation-resistant tungsten alloys for use in the nuclear fusion reactors

    Science.gov (United States)

    Litnovsky, A.; Wegener, T.; Klein, F.; Linsmeier, Ch; Rasinski, M.; Kreter, A.; Tan, X.; Schmitz, J.; Coenen, J. W.; Mao, Y.; Gonzalez-Julian, J.; Bram, M.

    2017-12-01

    Smart tungsten-based alloys are under development as plasma-facing components for a future fusion power plant. Smart alloys are planned to adjust their properties depending on environmental conditions: acting as a sputter-resistant plasma-facing material during plasma operation and suppressing the sublimation of radioactive tungsten oxide in case of an accident on the power plant. New smart alloys containing yttrium are presently in the focus of research. Thin film smart alloys are featuring an remarkable 105-fold suppression of mass increase due to an oxidation as compared to that of pure tungsten at 1000 °C. Newly developed bulk smart tungsten alloys feature even better oxidation resistance compared to that of thin films. First plasma test of smart alloys under DEMO-relevant conditions revealed the same mass removal as for pure tungsten due to sputtering by plasma ions. Exposed smart alloy samples demonstrate the superior oxidation performance as compared to tungsten-chromium-titanium systems developed earlier.

  12. Simulation of residual thermostress in tungsten after repetitive ELM-like heat loads

    Energy Technology Data Exchange (ETDEWEB)

    Pestchanyi, S., E-mail: serguei.pestchanyi@kit.edu [Karlsruhe Institute of Technology, IHM (Germany); Garkusha, I. [Institute of Plasma Physics of the NSC KIPT, Kharkov (Ukraine); Landman, I. [Karlsruhe Institute of Technology, IHM (Germany)

    2011-10-15

    Brittle destruction of tungsten armour under action of edge localised modes of plasma instabilities (ELMs) in ITER is an important issue determining the lifetime of the divertor. Besides, cracking of the armour produces tungsten dust with characteristic size of 1-10 {mu}m flying from the armour surface with velocities up to 10 m/s. Influx of the tungsten dust into the ITER confinement decreases the temperature of the plasma, reduces the thermonuclear gain and even may run the confinement into disruption. This paper describes experiments in QSPA-Kh50 plasma gun and modeling, which has been performed for providing more insight into the physics of tungsten cracking under action of ELMs and for confirmation of the important result on stabilization of the crack development at the tungsten armour surface, predicted in our previous paper - the same authors, 2010. The threshold value of energy density deposition for start of tungsten cracking has been measured as 0.3 MJ/m{sup 2} after 5-10 shots. From analytical considerations three times smaller threshold value has been predicted with increasing number of shots.

  13. Enhancement of deuterium retention in damaged tungsten by plasma-induced defect clustering

    Science.gov (United States)

    Jin, Younggil; Roh, Ki-Baek; Sheen, Mi-Hyang; Kim, Nam-Kyun; Song, Jaemin; Kim, Young-Woon; Kim, Gon-Ho

    2017-12-01

    The enhancement of deuterium retention was investigated for tungsten in the presence of both 2.8 MeV self-ion induced cascade damage and fuel hydrogen isotope plasma. Vacancy clustering in cascade damaged polycrystalline tungsten occurred due to deuterium irradiation and was observed near the grain boundary by using all-step transmission electron microscopy analysis. Analysis of the highest desorption temperature peak using thermal desorption spectroscopy supports reasonable evidence of defect clustering in the damaged polycrystalline tungsten. The defect clustering was neither observed on the damaged polycrystalline tungsten without deuterium irradiation nor on the damaged single-crystalline tungsten with deuterium irradiation. This result implies the synergetic role of deuterium and grain boundary on defect clustering. This study proposes a path for the defect transform from point defect to defect cluster, by the agglomeration between irradiated deuterium and cascade damage-induced defect. This agglomeration may induce more severe damage on the tungsten divertor at which the high fuel hydrogen ions, fast neutrons, and self-ions are irradiated simultaneously and it would increase the in-vessel tritium inventory.

  14. Multi-strange baryon and antibaryon production in sulphur-tungsten and proton-tungsten interactions at 200 GeV/c per nucleon

    Energy Technology Data Exchange (ETDEWEB)

    Abatzis, S.; Stassinaki, M.; Vassiliadis, G. (Athens Univ. (Greece)); Barnes, R.P.; Bloodworth, I.J.; Carney, J.N.; Evans, D.; Kinson, J.B.; Villalobos Baillie, O.; Votruba, M.F. (Birmingham Univ. (UK)); Benayoun, M.; Kahane, J.; Leruste, P.; Lima Frances, L.; Malamant, A.; Narjoux, J.L.; Sene, M.; Sene, R.; Tamazouzt, M.; Volte, A. (College de France, 75 - Paris (France)); Beusch, W. (Istituto Nazionale di Fisica Nucleare, Trieste (Italy)); Dufey, J.P.; French, B.R.; Jacholkowski, A.; Kirk, A.; Knudson, K.; Lassalle, J.C.; Quercigh, E.; Rossi, L.; Trainor, M.T. (European Organization for Nuclear Research, Geneva (Switzerland)); Bravar, A.; Penzo, A.; Falcone, R.; Ghidini, B.; Lenti, V.; Loconsole, R.A.; Manzari, V.; Navach, F.; Palano, A. (Bari Univ. (Italy) Istituto Nazionale di Fisica Nucleare, Bari (Italy)); WA85 Collaboration

    1991-04-01

    Production of multi-strange baryons and antibaryons is expected to be a useful indicator in the search for Quark-Gluon Plasma formation. Production of {gamma}{sup -} and anti {gamma}- has been observed for the first time in ultra-relativistic heavy ion interactions by the WA85 Experiment. We describe the procedure used to select these cascade candidates and show that {gamma}{sup -} and anti {gamma}{sup -} decays can be identified. Preliminary ratios of anti {gamma}/{gamma} production in sulphur-tungsten and proton-tungsten interactions are also presented. (orig.).

  15. Reduced ternary molybdenum and tungsten sulfides and hydroprocessing catalysis therewith

    Science.gov (United States)

    Hilsenbeck, S.J.; McCarley, R.E.; Schrader, G.L.; Xie, X.B.

    1999-02-16

    New amorphous molybdenum/tungsten sulfides with the general formula M{sup n+}{sub 2x/n}(L{sub 6}S{sub 8})S{sub x}, where L is molybdenum or tungsten and M is a ternary metal, has been developed. Characterization of these amorphous materials by chemical and spectroscopic methods (IR, Raman, PES) shows that the (M{sub 6}S{sub 8}){sup 0} cluster units are present. Vacuum thermolysis of the amorphous Na{sub 2x}(Mo{sub 6}S{sub 8})S{sub x}{hor_ellipsis}yMeOH first produces poorly crystalline NaMo{sub 6}S{sub 8} by disproportionation at 800 C and well-crystallized NaMo{sub 6}S{sub 8} at {>=} 900 C. Ion-exchange of the sodium material in methanol with soluble M{sup 2+} and M{sup 3+} salts (M=Sn, Co, Ni, Pb, La, Ho) produces the M{sup n+}{sub 2x/n}(Mo{sub 6}S{sub 8})S{sub x}{hor_ellipsis}yMeOH compounds. Additionally, the new reduced ternary molybdenum sulfides with the general formula M{sup n+}{sub 2x/n}Mo{sub 6}S{sub 8+x}(MeOH){sub y}[MMOS] (M=Sn, Co, Ni) is an effective hydrodesulfurization (HDS) catalyst both as-prepared and after a variety of pretreatment conditions. Under specified pretreatment conditions with flowing hydrogen gas, the SnMoS type catalyst can be stabilized, and while still amorphous, can be considered as ``Chevrel phase-like`` in that both contain Mo{sub 6}S{sub 8} cluster units. Furthermore, the small cation NiMoS and CoMoS type pretreated catalyst is shown to be very active HDS catalysts with rates that exceeded the model unpromoted and cobalt-promoted MoS{sub 2} catalysts. 9 figs.

  16. Ductile-Phase-Toughened Tungsten for Plasma-Facing Materials

    Science.gov (United States)

    Cunningham, Kevin Hawkins

    A variety of processing approaches were employed to fabricate ductile-phase-toughened (DPT) tungsten (W) composites. Mechanical testing and analytical modeling were used to guide composite development. This work provides a basis for further development of W composites to be used in structural divertor components of future fusion reactors. W wire was tested in tension, showing significant ductility and strength. Coatings of copper (Cu) or tungsten carbide (WC) were applied to the W wire via electrodeposition and carburization, respectively. Composites were fabricated using spark plasma sintering (SPS) to consolidate W powders together with each type of coated W wire. DPT behavior, e.g. crack arrest and crack bridging, was not observed in three-point bend testing of the sintered composites. A laminate was fabricated by hot pressing W and Cu foils together with W wires, and subsequently tested in tension. This laminate was bonded via hot pressing to thick W plate as a reinforcing layer, and the composite was tested in three-point bending. Crack arrest was observed along with some fiber pullout, but significant transverse cracking in the W plate confounded further fracture toughness analysis. The fracture toughness of thin W plate was measured in three-point bending. W plates were brazed with Cu foils to form a laminate. Crack arrest and crack bridging were observed in three-point bend tests of the laminate, and fracture resistance curves were successfully calculated for this DPT composite. An analytical model of crack bridging was developed using the basis described by Chao in previous work by the group. The model uses the specimen geometry, matrix properties, and the stress-displacement function of a ductile reinforcement ("bridging law") to calculate the fracture resistance curve (R-curve) and load-displacement curve (P-D curve) for any test specimen geometry. The code was also implemented to estimate the bridging law of an arbitrary composite using R-curve data

  17. Neutronic effects on tungsten-186 double neutron capture

    Science.gov (United States)

    Garland, Marc Alan

    Rhenium-188, a daughter product of tungsten-188, is an isotope of great interest in therapeutic nuclear medicine, being used in dozens of laboratory and clinical investigations worldwide. Applications include various cancer therapy strategies, treatment of rheumatoid arthritis, prevention of restenosis following coronary artery angioplasty, and palliation of bone pain associated with cancer metastases. With its half-life of 17 hours, 2.12 MeV (maximum) beta-particle emission, chemical similarity to technetium-99m (the most widely used diagnostic radioisotope), and its availability in a convenient tungsten-188/rhenium-188 generator system, rhenium-188 is a superb candidate for a broad range of applications. Production of 188W is typically via double neutron capture by 186W in a high flux nuclear reactor, predominantly the High Flux Isotope Reactor at the Oak Ridge National Laboratory in Tennessee. Experience at HFIR has shown that production yields (measured in Ci of 188W produced per g of 186W target) decrease considerably as target size increases. While the phenomenon of neutron resonance self-shielding would be expected to produce such an effect, temperature effects on neutron flux distribution and neutron capture rates may also be involved. Experimental investigations of these phenomena have not been previously performed. The work presented in this thesis evaluates the factors that contribute to the decrease in 188W yield from both theoretical and experimental standpoints. Neutron self-shielding and temperature effects were characterized to develop a strategy for target design that would optimize production yield, an important factor in minimizing health care costs. It was determined that decrease in yield due to neutron self-shielding can be attributed to depletion of epithermal neutrons at resonant energies, most significantly within the initial 0.4 mm depth of the target. The results from these studies further show that 188W yield in the interior of the

  18. Effects of thickness reduction on recrystallization process of warm-rolled pure tungsten plates at 1350 °C

    DEFF Research Database (Denmark)

    Wang, Kang; Zan, Xiang; Yu, Ming

    2017-01-01

    Investigations are conducted of the recrystallization behavior of pure tungsten through different thickness reductions by isothermal annealing at 1350 °C. Concise description is made of the recrystallization kinetics by the Johnson-Mehl-Avrami-Kolmogorov (JMAK) model in combination with hardness ...... on the transversal section comprising the rolling direction (RD) and the normal direction (ND). The average grain size and its distribution of pure tungsten can be easily calculated, and hence the grain aspect ratios of pure tungsten....

  19. Development of ultrafine-grained tungsten-based materials for applications under conditions of high-velocity impact

    Science.gov (United States)

    Tabachenko, A. N.; Biryukov, Yu. A.; Belov, N. N.; Yugov, N. T.; Ischenko, A. N.; Burkin, V. V.; Afanasieva, S. A.; Martsunova, L. S.; Yugov, A. A.; Skosyrskii, A. B.

    2012-03-01

    The effect of green porosity of powder specimens and dispersion of nanostructured tungsten powder specimens on the density of sintered alloys of the tungsten - nickel system is investigated. It is shown that the maximum density of the alloys is achieved during liquid-phase sintering of powder compacts for one hour irrespective of their initial porosity within the range from 30 to 65 vol.%. Dispersion of the nanostructured tungsten powders also affects the final porosity. Using the calculations and experimental studies, the effective penetration of cylindrical striker bars made from the WNi-91 tungsten-nickel alloy into steel plates is investigated.

  20. Physical and Mechanical Properties of W-Ni-Fe-Co Metal Foam Modified by Titanium Tungsten Carbide Alloying

    Science.gov (United States)

    Ishchenko, A. N.; Tabachenko, A. N.; Afanas'eva, S. A.; Belov, N. N.; Biryukov, Yu. A.; Burkin, V. V.; D'yachkovskii, A. S.; Rogaev, K. S.; Skosyrskii, A. B.; Yugov, N. T.

    2018-02-01

    The paper studies physical and mechanical properties of tungsten-nickel-iron-cobalt metal foam alloyed with titanium tungsten carbide. Test specimens are obtained by the liquid phase sintering of powder materials, including those containing tungsten nanopowders. High porosity metal foams are prepared through varying the porosity of powder specimens and the content of filling material. The penetration capability of cylinder projectiles made of new alloys is explored in this paper. It is shown that their penetration depth exceeds that of the prototype with relevant weight and size, made of tungsten-nickel-iron alloy, other factors being equal.

  1. Reactions of synthesis gas on silica supported transition metal catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Niemelae, M. [VTT Chemical Technology, Espoo (Finland). Lab. of Industrial Chemistry

    1997-12-31

    The effect of catalyst precursor and composition on the activation of CO was investigated using CO hydrogenation as a test reaction. The interrelations of preparation, pretreatment, characteristics and activity were clarified. For Co/SiO{sub 2} catalyst, MgO promotion increased the CO adsorption capacity and the hydrogen uptake, although the extent of reduction for cobalt remained the same or decreased. The conversion per active metallic cobalt site consequently increased in conjunction with MgO promotion, while the effect on overall performance per 1 g of catalyst remained moderate. The precursor affected the performance of Co/SiO{sub 2} considerably. CO was more strongly adsorbed on catalysts of carbonyl origin than on those derived from cobalt nitrate, the activity thus being higher. Although the nitrate derived Co/SiO{sub 2} appeared both to retain its activity and to regain its adsorption capacity better than the catalysts of carbonyl origin, the performance of the latter was superior with time on stream. For tetranuclear cluster based Co-Ru and Co-Rh catalysts, rhodium or ruthenium was in contact with the support and cobalt was enriched on top. On Co-Ru/SiO{sub 2} ruthenium enhanced deactivation, and no benefits in activity or oxygenate selectivity were achieved relative to the monometallic catalysts of cluster origin. The Co-Rh/SiO{sub 2} catalysts were also less active than those derived from monometallic clusters, but they exhibited higher selectivities to oxygenated compounds due to the presence of active sites on the perimeter of the cobalt particles located on rhodium. The highest selectivity to oxygenates was achieved by changing the decomposition atmosphere of Rh{sub 4}(CO){sub 12}/SiO{sub 2} from hydrogen to carbon monoxide. The results also showed two types of active sites to be operative in the formation of oxygenates - one for ethanol and another for aldehydes. (orig.) 69 refs.

  2. Mesoporous silica supported Pd/Ag bimetallic nanoparticles as a ...

    Indian Academy of Sciences (India)

    ... YAMASHITA1 2. Division of Materials and Manufacturing Science, Graduate School of Engineering, Osaka University, 2-1 Yamada-oka, Suita, Japan; Unit of Elements Strategy Initiative for Catalysts and Batteries, Kyoto University, Katsura, Kyoto 615-8520, Japan; JST, PRESTO, 4-1-8 Honcho, Kawaguchi, Saitama, Japan ...

  3. Silica-Supported Yttrium Nitrate Hexahydrate as a Heterogeneous ...

    African Journals Online (AJOL)

    NICO

    Moleele and C.B. de Koning, Tetrahedron 2005, 61, 9996–10006. 10 A.F. Ward, Y. Xu and J.P. Wolfe, Chem. Commun., 2012, 48, 609–611. 11 Y.L.N. Murthy, K.P. Suhasini, A.S. Pathania, S. Bhushan and Y.N.. Sastry, Eur. J. Med. Chem., 2013, 62, 545–555. 12 M.M. Heravi, B. Baghernejad and H.A. Oskooie, J. Chin. Chem.

  4. Hydrogen and oxygen adsorption stoichiometries on silica supported ruthenium nanoparticles

    Energy Technology Data Exchange (ETDEWEB)

    Berthoud, Romain; Delichere, Pierre; Gajan, David; Lukens, Wayne; Pelzer, Katrin; Basset, Jean-Marie; Candy, Jean-Pierre; Coperet, Christophe

    2008-12-01

    Treatment under H{sub 2} at 300 C of Ru(COD)(COT) dispersed on silica yields 2 nm ruthenium nanoparticles, [Ru{sub p}/SiO{sub 2}], according to EXAFS, HRTEM and XPS. H{sub 2} adsorption measurements on [Ru{sub p}/SiO{sub 2}] in the absence of O{sub 2} show that Ru particles adsorb up to ca. 2 H per surface ruthenium atoms (2H/Ru{sub s}) on various samples; this technique can therefore be used to measure the dispersion of Ru particles. In contrast, O{sub 2} adsorption on [Ru{sub p}/SiO{sub 2}] leads to a partial oxidation of the bulk at 25 C, to RuO{sub 2} at 200 C and to sintering upon further reduction under H{sub 2}, showing that O{sub 2} adsorption cannot be used to measure the dispersion of Ru particles.

  5. Mesoporous silica supported Pd/Ag bimetallic nanoparticles as a ...

    Indian Academy of Sciences (India)

    Priyanka Verma

    2017-09-19

    Sep 19, 2017 ... The catalysts display higher selectivity under visible light irradiation which can be due to the efficient adsorption and transfer of. H. +/H. − pair to the polar bonds in the nitro group. Keywords. Ag-plasmon; visible light irradiation; chemoselective hydrogenation; bimetallic; mesoporous silica. 1. Introduction.

  6. Quantitative XPS analysis of silica-supported Cu Co oxides

    Science.gov (United States)

    Cesar, Deborah V.; Peréz, Carlos A.; Schmal, Martin; Salim, Vera Maria M.

    2000-04-01

    Copper-cobalt oxides with Cu/Co=5:5, 15:15 and 35:35 bulk ratio have been prepared by deposition-precipitation method at constant pH from copper and cobalt nitrate solutions. Different oxides were obtained by decomposition of the precursors at 673 K for 7 h in air and analyzed by X-ray diffraction (XRD), transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS). XRD data showed the formation of different oxide phases; for the bulk atomic ratio of 15Cu:15Co, a phase containing Cu and Co with spinel-like structure was observed, while the other bimetallic oxides presented CuO and Co 3O 4 as distinct phases. The XPS qualitative analysis has shown that all samples exhibited Cu 2+ and Co 3+ species at the surface. The Cu-Co spinel presented a displacement in Cu 2p binding energy value. A mathematical model was proposed from relative intensity ratios, which allowed the determination of the oxide particle thickness and the fraction of coverage at the support. This model described accurately the system and showed that cobalt improved the copper dispersion.

  7. Hydrogen diffusion in tungsten: A molecular dynamics study

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Yi-Nan [School of Physics and Nuclear Energy Engineering, Beihang University, Beijing 100191 (China); Wu, Tiefeng [Shanghai Aircraft Design and Research Institute, Shanghai 201210 (China); Yu, Yi [School of Physics and Nuclear Energy Engineering, Beihang University, Beijing 100191 (China); Li, Xiao-Chun [Institute of Plasma Physics, Chinese Academy of Sciences, Hefei, Anhui 230031 (China); Shu, Xiaolin, E-mail: shuxlin@buaa.edu.cn [School of Physics and Nuclear Energy Engineering, Beihang University, Beijing 100191 (China); Lu, Guang-Hong, E-mail: lgh@buaa.edu.cn [School of Physics and Nuclear Energy Engineering, Beihang University, Beijing 100191 (China)

    2014-12-15

    The diffusion behavior of hydrogen (H) in tungsten (W) has been studied by molecular dynamics simulations. The diffusivities from 200 K to 3000 K are calculated and the diffusion equation is fitted to D = 5.13 × 10{sup −8}exp(−0.21 eV/kT) m{sup 2}/s. The diffusion equations in different temperature ranges of 200–500 K, 500–2400 K and 2400–3000 K are also given separately and the results imply different H diffusion modes in different temperature ranges, which is proved by analyzing equilibrium H positions at low and high temperatures. The H atom jumps between different tetrahedral interstitial sites (TISs) at lower temperatures, but the transition to octahedral interstitial sites (OISs) is also observed at high temperatures. Moreover, with a vacancy present in the W system, vacancy trapping of H is observed, and it is shown that the vacancy trapping reduces with the increasing temperature. The H binding energy to monovacancy is obtained using three different methods including NEB and fitting both H diffusivity and time for H to detrap from the vacancy, which provides more information of the H behaviors with the existence of defects.

  8. Experimental investigation on laser removal of carbon and tungsten particles

    Energy Technology Data Exchange (ETDEWEB)

    Vatry, A. [Laboratoire Lasers, Plasmas et Procedes Photoniques, campus de Luminy, 163 av. de Luminy, 13009 Marseille (France); Association Euratom/CEA, DSM/IRFM, 13108 Saint Paul lez Durance (France)], E-mail: vatry@lp3.univ-mrs.fr; Habib, M. Naiim; Delaporte, Ph.; Sentis, M.; Grojo, D. [Laboratoire Lasers, Plasmas et Procedes Photoniques, campus de Luminy, 163 av. de Luminy, 13009 Marseille (France); Grisolia, C.; Rosanvallon, S. [Association Euratom/CEA, DSM/IRFM, 13108 Saint Paul lez Durance (France)

    2009-03-01

    During the operation of the ITER fusion facility, particles with size from 10 nm to 100 {mu}m, mainly composed of carbon, beryllium, and tungsten, will be produced. Since dust could lead to safety issues, it must be periodically removed from the facility in order to keep their quantity below the safety limit requirements. In this context, laser cleaning appeared as a very promising technique, and investigations have to be done to understand the physical processes and optimize the procedure. Several experiments were carried out to improve the understanding of the phenomena involved during the laser-induced removal of Carbon particles. The ejection mechanisms have been experimentally studied for different irradiation conditions with nanosecond laser pulses. The removal efficiency and the fluence threshold were determined by optical microscopy. The influence of the substrate was studied for the dry laser cleaning configuration. This study presents scanning electronic microscopy pictures which show that the particle removal leads to a damage of the substrate. These damages give evidences on the ablation mechanism. The laser shock cleaning was also studied. In this configuration, the laser-induced shock wave can be used to push the particles away from the surface. This technique appears to be very useful to clean shadowed areas.

  9. Generation of powerful tungsten reductants by visible light excitation.

    Science.gov (United States)

    Sattler, Wesley; Ener, Maraia E; Blakemore, James D; Rachford, Aaron A; LaBeaume, Paul J; Thackeray, James W; Cameron, James F; Winkler, Jay R; Gray, Harry B

    2013-07-24

    The homoleptic arylisocyanide tungsten complexes, W(CNXy)6 and W(CNIph)6 (Xy = 2,6-dimethylphenyl, Iph = 2,6-diisopropylphenyl), display intense metal to ligand charge transfer (MLCT) absorptions in the visible region (400-550 nm). MLCT emission (λ(max) ≈ 580 nm) in tetrahydrofuran (THF) solution at rt is observed for W(CNXy)6 and W(CNIph)6 with lifetimes of 17 and 73 ns, respectively. Diffusion-controlled energy transfer from electronically excited W(CNIph)6 (*W) to the lowest energy triplet excited state of anthracene (anth) is the dominant quenching pathway in THF solution. Introduction of tetrabutylammonium hexafluorophosphate, [Bu(n)4N][PF6], to the THF solution promotes formation of electron transfer (ET) quenching products, [W(CNIph)6](+) and [anth](•-). ET from *W to benzophenone and cobalticenium also is observed in [Bu(n)4N][PF6]/THF solutions. The estimated reduction potential for the [W(CNIph)6](+)/*W couple is -2.8 V vs Cp2Fe(+/0), establishing W(CNIph)6 as one of the most powerful photoreductants that has been generated with visible light.

  10. Activation Energy of Tantalum-Tungsten Oxide Thermite Reaction

    Energy Technology Data Exchange (ETDEWEB)

    Cervantes, O; Kuntz, J; Gash, A; Munir, Z

    2010-02-25

    The activation energy of a high melting temperature sol-gel (SG) derived tantalum-tungsten oxide thermite composite was determined using the Kissinger isoconversion method. The SG derived powder was consolidated using the High Pressure Spark Plasma Sintering (HPSPS) technique to 300 and 400 C to produce pellets with dimensions of 5 mm diameter by 1.5 mm height. A custom built ignition setup was developed to measure ignition temperatures at high heating rates (500-2000 C {center_dot} min{sup -1}). Such heating rates were required in order to ignite the thermite composite. Unlike the 400 C samples, results show that the samples consolidated to 300 C undergo an abrupt change in temperature response prior to ignition. This change in temperature response has been attributed to the crystallization of the amorphous WO{sub 3} in the SG derived Ta-WO{sub 3} thermite composite and not to a pre-ignition reaction between the constituents. Ignition temperatures for the Ta-WO{sub 3} thermite ranged from approximately 465-670 C. The activation energy of the SG derived Ta-WO{sup 3} thermite composite consolidated to 300 and 400 C were determined to be 37.787 {+-} 1.58 kJ {center_dot} mol{sup -1} and 57.381 {+-} 2.26 kJ {center_dot} mol{sup -1}, respectively.

  11. Iron binary and ternary coatings with molybdenum and tungsten

    Energy Technology Data Exchange (ETDEWEB)

    Yar-Mukhamedova, Gulmira, E-mail: gulmira-alma-ata@mail.ru [Institute Experimental and Theoretical Physics Al-Farabi Kazakh National University, 050038, Al-Farabi av., 71, Almaty (Kazakhstan); Ved, Maryna; Sakhnenko, Nikolay; Karakurkchi, Anna; Yermolenko, Iryna [National Technical University “Kharkov Polytechnic Institute”, Kharkov (Ukraine)

    2016-10-15

    Highlights: • High quality coatings of double Fe-Mo and ternary Fe-Mo-W electrolytic alloys can be produced both in a dc and a pulsed mode. • Application of unipolar pulsed current allows receiving an increased content of the alloying components and their more uniform distribution over the surface. • It is established that Fe-Mo and Fe-Mo-W coatings have an amorphous structure and exhibit improved corrosion resistance and microhardness as compared with the steel substrate due to the inclusion molybdenum and tungsten. - Abstract: Electrodeposition of Fe-Mo-W and Fe-Mo layers from a citrate solution containing iron(III) on steel and iron substrates is compared. The utilization of iron(III) compounds significantly improved the electrolyte stability eliminating side anodic redox reactions. The influence of concentration ratios and electrodeposition mode on quality, chemical composition, and functional properties of the alloys is determined. It has been found that alloys deposited in pulse mode have more uniform surface morphology and chemical composition and contain less impurities. Improvement in physical and mechanical properties as well as corrosion resistance of Fe-Mo and Fe-Mo-W deposits when compared with main alloy forming metals is driven by alloying components chemical passivity as well as by alloys amorphous structure. Indicated deposits can be considered promising materials in surface hardening technologies and repair of worn out items.

  12. Photoelectrocatalytic degradation of benzoic acid using immobilized tungsten trioxide photocatalyst

    Energy Technology Data Exchange (ETDEWEB)

    Mohite, S.V.; Ganbavle, V.V.; Patil, V.V.; Rajpure, K.Y., E-mail: rajpure@yahoo.com

    2016-11-01

    The thin films of WO{sub 3} were deposited with different solution quantities using chemical spray pyrolysis technique. The WO{sub 3} film thickness effect on the photoelectrochemical, structural, morphological and optical properties is studied. Polycrystalline, monoclinic WO{sub 3} films possess photoelectrochemical performance having onset potentials around +0.3 V/SCE in 0.01 M HClO{sub 4}. The maximum photocurrent density (I{sub ph} = 635 μA/cm{sup 2}) is observed for the film deposited with 75 ml solution quantity. The FE-SEM image shows compact structure with petals like morphology. The estimated indirect band gap of WO{sub 3} films lies in the range of 2.60–2.65 eV. The photoelectrocatalytic degradation of benzoic acid is studied using WO{sub 3} photoelectrode under UV light illumination and 57 ± 3% removal of benzoic acid is achieved. The mineralization of benzoic acid in aqueous solution has been studied by measuring COD values. - Highlights: • The photoactivity of sprayed tungsten trioxide (WO{sub 3}) thin film. • Structural analysis of WO{sub 3} thin films. • Photoelectrocatalytic and photocatalytic degradation of benzoic acid. • Reaction kinetics and mineralization of pollutants by COD.

  13. DISPLACEMENT CASCADE SIMULATION IN TUNGSTEN AT 1025 K

    Energy Technology Data Exchange (ETDEWEB)

    Setyawan, Wahyu; Nandipati, Giridhar; Roche, Kenneth J.; Heinisch, Howard L.; Kurtz, Richard J.; Wirth, Brian D.

    2013-09-30

    Molecular dynamics simulation was employed to investigate the irradiation damage properties of bulk tungsten at 1025 K (0.25 melting temperature). A comprehensive data set of primary cascade damage was generated up to primary knock-on atom (PKA) energies 100 keV. The dependence of the number of surviving Frenkel pairs (NFP) on the PKA energy (E) exhibits three different characteristic domains presumably related to the different cascade morphologies that form. The low-energy regime < 0.2 keV is characterized by a hit-or-miss type of Frenkel pair (FP) production near the displacement threshold energy of 128 eV. The middle regime 0.3 – 30 keV exhibits a sublinear dependence of log(NFP) vs log(E) associated with compact cascade morphology with a slope of 0.73. Above 30 keV, the cascade morphology consists of complex branches or interconnected damage regions. In this extended morphology, large interstitial clusters form from superposition of interstitials from nearby damage regions. Strong clustering above 30 keV results in a superlinear dependence of log(NFP) vs log(E) with a slope of 1.365. At 100 keV, an interstitial cluster of size 92 and a vacancy cluster of size 114 were observed.

  14. Hydrogen isotope accumulation in the helium implantation zone in tungsten

    Science.gov (United States)

    Markelj, S.; Schwarz-Selinger, T.; Založnik, A.

    2017-06-01

    The influence of helium (He) on deuterium (D) transport and retention was studied experimentally in tungsten (W). Helium was implanted 1 µm deep into W to a maximum calculated concentration of 3.4 at.%. To minimize the influence of displacement damage created during the He implantation on D retention, so-called self-damaged W was used. W was damaged by 20 MeV W ion bombardment and defects were populated by low-temperature D plasma at room temperature before He implantation. Deuterium depth profiling was performed in situ during isochronal annealing in the temperature range from 300 K to 800 K. It is shown for the first time unambiguously that He attracts D and locally increases D trapping. Deuterium retention increased by a factor of two as compared to a non-He implanted W reference after sample annealing at 450 K. Rate equation modelling can explain the measured D depth profiles quantitatively when keeping the de-trapping parameters unchanged but only increasing the number of traps in the He zone. This bolsters the confidence in the theoretical calculations predicting that more hydrogen isotopes can be stored around a He cluster zone.

  15. An atomistic study of the deformation behavior of tungsten nanowires

    Science.gov (United States)

    Xu, Shuozhi; Su, Yanqing; Chen, Dengke; Li, Longlei

    2017-12-01

    Large-scale atomistic simulations are performed to study tensile and compressive loading of single-crystalline nanowires in body-centered cubic tungsten (W). Effects of loading mode, wire cross-sectional shape, wire size, strain rate, and crystallographic orientations of the lateral surfaces are explored. Uniaxial deformation of a W bulk single crystal is also investigated for reference. Our results reveal a strong tension-compression asymmetry in both the stress-strain response and the deformation behavior due to different yielding/failure modes: while the nanowires fail by brittle fracture under tensile loading, they yield by nucleation of dislocations from the wire surface under compressive loading. It is found that (1) nanowires have a higher strength than the bulk single crystal; (2) with a cross-sectional size larger than 10 nm, there exists a weak dependence of strength on wire size; (3) when the wire size is equal to or smaller than 10 nm, nanowires buckle under compressive loading; (4) the cross-sectional shape, strain rate, and crystallographic orientations of the lateral surfaces affect the strength and the site of defect initiation but not the overall deformation behavior.

  16. Axial Instability Growth in Tungsten Wire Array Z-Pinches

    Science.gov (United States)

    Cahill, Adam; Knapp, Patrick; Greenly, John; Pikuz, Sergei; Shelkovenko, Tania; Hammer, David

    2010-11-01

    The individual exploding wires in wire array z-pinches have been shown to suffer from axially non-uniformity beginning from the moment of plasma formation. This non-uniformity grows in amplitude and wavelength until it reaches what appears to be a material dependent wavelength at the time array implosion begins. Previous work by Knapp et al. [1] studied the temporal evolution of this instability in aluminum wire arrays. We have extended that work to include the evolution of tungsten wire array instabilities. Time gated laser shadowgraphy is used to track wavelength and amplitude over a series of shots to develop a record of the instability's growth. We attempt to identify array parameters which significantly contribute to the growth of this instability. [4pt] [1] Knapp, P. F., J. B. Greenly, P. A. Gourdain, C. L. Hoyt, M. R. Martin, S. A. Pikuz, C. E. Seyler, T. A. Shelkovenko, and D. A. Hammer. ``Growth and Saturation of the Axial Instability in Low Wire Number Wire Array Z Pinches.'' Physics of Plasmas 17 (2010). Web.

  17. Photodecomposition of Molybdenum andTungsten Carbonyl Complexes

    Directory of Open Access Journals (Sweden)

    Thamer A. Alwani

    2009-01-01

    Full Text Available The photodecomposition of four different colored organometallic molybdenum and tungsten carbonyl complexes, i.e. [Mo(CO52LA] (complex I, [(Mo(CO3(bipy2LB] (complex II, [(W(CO3(tmen2LB] (complex III and [Mo(CO2LC]2 (complex I V where LA 2-phenyl-1,3-indandionebis(2-methyl anilines, LB 2-phenyl-1,3-indandione bis (4-hydroxy anilines and LCbis (2-hydroxo-benzalydine benzidine ion have been performed at 365 nm in chloroform at 25 °C under oxygen atmosphere. The absorbance spectrum of these complexes has been recorded with the time of irradiation in order to examine the kinetics of photodecomposition. The rate of the photodecomposition process was investigated and the relative values of the rate constants of dissociation (Kd for the first-order reaction are tabulated. The apparent rate constant of photodecomposition was found to be (8.33-11.50 × 10-5 s-1.

  18. A Silicon-Tungsten ECal with Integrated Electronics

    Energy Technology Data Exchange (ETDEWEB)

    Frey, R.; /Oregon U.; Brau, James E.; /Oregon U.; Breidenbach, Martin; /SLAC; Freytag, D.; /SLAC; Haller, G.; /SLAC; Herbst, R.; /SLAC; Lander, R.; /UC, Davis; Nelson, Timothy Knight; /SLAC; Radeka, V.; /Brookhaven; Tripathi, M.; /UC, Davis

    2011-11-10

    We summarize recent R&D progress for a silicon-tungsten electromagnetic calorimeter (ECal) with integrated electronics, designed to meet the ILC physics requirements. A basic physics requirement for ILC detectors is that they provide excellent reconstruction of hadronic final states. This allows access to new physics which is complementary to the LHC. One statement for a requirement on jet reconstruction is that intermediate particles which decay into jets, such as W, Z, or top, can be identified and isolated. This places unprecedented requirements on 2-jet or 3-jet mass resolution, typically at the level of 3-5% using the PFA technique, which makes challenging demands on the calorimeters. The electromagnetic energy resolution is not expected to limit jet resolution using a PFA. However, particle separation - photon-photon and charged hadron-photon - is crucial. In addition, if one provides this kind of imaging calorimeter to meet the PFA needs, these same features will also be put to good use for reconstruction of specific tau decay modes (to enable final-state polarization measurement), to 'track' photons (even if originating from a vertex displaced from the interaction point), to track MIPS, and so forth. Figure 1 and Table 1 provide some context for our ECal design within the SiD detector concept, along with some main design parameters. More detail is included in the presentation.

  19. Spatial heterogeneity of tungsten transmutation in a fusion device

    Science.gov (United States)

    Gilbert, M. R.; Sublet, J.-Ch.; Dudarev, S. L.

    2017-04-01

    Accurately quantifying the transmutation rate of tungsten (W) under neutron irradiation is a necessary requirement in the assessment of its performance as an armour material in a fusion power plant. The usual approach of calculating average responses, assuming large, homogenised material volumes, is insufficient to capture the full complexity of the transmutation picture in the context of a realistic fusion power plant design, particularly for rhenium (Re) production from W. Combined neutron transport and inventory simulations for representative spatially heterogeneous high-resolution models of a fusion power plant show that the production rate of Re is strongly influenced by the surrounding local spatial environment. Localised variation in neutron moderation (slowing down) due to structural steel and coolant, particularly water, can dramatically increase Re production because of the huge cross sections of giant resolved resonances in the neutron-capture reaction of 186W at low neutron energies. Calculations using cross section data corrected for temperature (Doppler) effects suggest that temperature may have a relatively lesser influence on transmutation rates.

  20. Sodium tungsten bronze thin films by rf sputtering

    Energy Technology Data Exchange (ETDEWEB)

    Anderegg, J.W.

    1977-03-01

    Polycrystalline Na/sub x/WO/sub 3/ films were produced by rf sputtering. Films of low x-value resulted when co-sputtering WO/sub 3/ on a Na/sub 0.83/WO/sub 3/ target, and Na/sub 0/./sub 83/ on WO/sub 3/ target. Films of high x and of mixed phase were produced by sputtering a powder mixture of Na/sub 2/WO/sub 4/ and WO/sub 3/ on a tungsten target. Of the sputtering parameters studied, the substrate temperature is the most critical with temperatures above 500/sup 0/C producing films which were cubic in structure with only a small amount of Tetragonal I. The presence of oxygen up to 3 percent by volume had minimal effect on film quality or x-value. Auger, electron microprobe, SIMS, SEM, x-ray diffraction, and sheet resistivity techniques were used in characterizing these films. Resistivity of the films was a factor of 10 higher than the bulk crystalline data for Na/sub 0/./sub 83/WO/sub 3/.

  1. Annealing effects on deuterium retention behavior in damaged tungsten

    Directory of Open Access Journals (Sweden)

    S. Sakurada

    2016-12-01

    Full Text Available Effects of annealing after/under iron (Fe ion irradiation on deuterium (D retention behavior in tungsten (W were studied. The D2 TDS spectra as a function of heating temperature for 0.1dpa damaged W showed that the D retention was clearly decreased as the annealing temperature was increased. In particular, the desorption of D trapped by voids was largely reduced by annealing at 1173K. The TEM observation indicated that the size of dislocation loops was clearly grown, and its density was decreased by the annealing above 573K. After annealing at 1173K, almost all the dislocation loops were recovered. The results of positron annihilation spectroscopy suggested that the density of vacancy-type defects such as voids, was decreased as the annealing temperature was increased, while its size was increased, indicating that the D retention was reduced by the recovery of the voids. Furthermore, it was found that the desorption temperature of D trapped by the voids for damaged W above 0.3dpa was shifted toward higher temperature side. These results lead to a conclusion that the D retention behavior is controlled by defect density. The D retention in the samples annealed during irradiation was less than that annealed after irradiation. This result shows that defects would be quickly annihilated before stabilization by annealing during irradiation.

  2. EUV nanosecond laser ablation of silicon carbide, tungsten and molybdenum

    Science.gov (United States)

    Frolov, Oleksandr; Kolacek, Karel; Schmidt, Jiri; Straus, Jaroslav; Choukourov, Andrei; Kasuya, Koichi

    2015-09-01

    In this paper we present results of study interaction of nanosecond EUV laser pulses at wavelength of 46.9 nm with silicon carbide (SiC), tungsten (W) and molybdenum (Mo). As a source of laser radiation was used discharge-plasma driver CAPEX (CAPillary EXperiment) based on high current capillary discharge in argon. The laser beam is focused with a spherical Si/Sc multilayer-coated mirror on samples. Experimental study has been performed with 1, 5, 10, 20 and 50 laser pulses ablation of SiC, W and Mo at various fluence values. Firstly, sample surface modification in the nanosecond time scale have been registered by optical microscope. And the secondly, laser beam footprints on the samples have been analyzed by atomic-force microscope (AFM). This work supported by the Czech Science Foundation under Contract GA14-29772S and by the Grant Agency of the Ministry of Education, Youth and Sports of the Czech Republic under Contract LG13029.

  3. Reduced deuterium retention in simultaneously damaged and annealed tungsten

    Science.gov (United States)

    Simmonds, M. J.; Wang, Y. Q.; Barton, J. L.; Baldwin, M. J.; Yu, J. H.; Doerner, R. P.; Tynan, G. R.

    2017-10-01

    Deuterium (D) retention in polycrystalline tungsten (W) with copper (Cu) ion damage concurrently produced at elevated surface temperature is investigated. An in situ heated stage held W samples at a controlled temperature up to 1243 K, which were subjected to displacement damage produced by 3.4 MeV Cu ions. D retention is subsequently explored by exposure of the W samples held at 383 K to a D2 plasma ion fluence of 1024 D+/m2. Nuclear reaction analysis (NRA), utilizing the D(3He,p)4He nuclear reaction, is used to probe the D concentration in the near surface up to 6 μm. Thermal desorption spectroscopy (TDS) is used to measure outgassed HD and D2 molecules to determine the bulk D concentration. Both NRA and TDS measure a significant reduction in D retention for samples damaged at elevated temperature. TDS quantitatively shows that the lowest energy trap remains largely unaffected while higher energy traps, induced by Cu ions, are annealed and approach intrinsic concentrations as the temperature during ion damage approaches 1243 K. Analysis of TDS data yields an activation energy of (0.10 ± 0.02) eV for recovery of ion-damage induced traps at elevated temperature.

  4. Construction of Tungsten Halogen, Pulsed LED, and Combined Tungsten Halogen-LED Solar Simulators for Solar Cell I-V Characterization and Electrical Parameters Determination

    Directory of Open Access Journals (Sweden)

    Anon Namin

    2012-01-01

    Full Text Available I-V characterization of solar cells is generally done under natural sunlight or solar simulators operating in either a continuous mode or a pulse mode. Simulators are classified on three features of irradiance, namely, spectral match with respect to air mass 1.5, spatial uniformity, and temporal stability. Commercial solar simulators use Xenon lamps and halogen lamps, whereas LED-based solar simulators are being developed. In this work, we build and test seven simulators for solar cell characterization, namely, one tungsten halogen simulator, four monochromatic (red, green, blue, and white LED simulators, one multicolor LED simulator, and one tungsten halogen-blue LED simulator. The seven simulators provide testing at nonstandard test condition. High irradiance from simulators is obtained by employing elevated supply voltage to tungsten halogen lamps and high pulsing voltages to LEDs. This new approach leads to higher irradiance not previously obtained from tungsten halogen lamps and LEDs. From I-V curves, electrical parameters of solar cell are made and corrected based on methods recommended in the IEC 60891 Standards. Corrected values obtained from non-STC measurements are in good agreement with those obtained from Class AAA solar simulator.

  5. Tungsten carbide nanoparticles as efficient cocatalysts for photocatalytic overall water splitting

    KAUST Repository

    Garcia Esparza, Angel T.

    2012-12-17

    Tungsten carbide exhibits platinum-like behavior, which makes it an interesting potential substitute for noble metals in catalytic applications. Tungsten carbide nanocrystals (≈5 nm) are directly synthesized through the reaction of tungsten precursors with mesoporous graphitic C3N 4 (mpg-C3N4) as the reactive template in a flow of inert gas at high temperatures. Systematic experiments that vary the precursor compositions and temperatures used in the synthesis selectively generate different compositions and structures for the final nanocarbide (W 2C or WC) products. Electrochemical measurements demonstrate that the WC phase with a high surface area exhibits both high activity and stability in hydrogen evolution over a wide pH range. The WC sample also shows excellent hydrogen oxidation activity, whereas its activity in oxygen reduction is poor. These tungsten carbides are successful cocatalysts for overall water splitting and give H2 and O2 in a stoichiometric ratio from H 2O decomposition when supported on a Na-doped SrTiO3 photocatalyst. Herein, we present tungsten carbide (on a small scale) as a promising and durable catalyst substitute for platinum and other scarce noble-metal catalysts in catalytic reaction systems used for renewable energy generation. Platinum replacement: The phase-controlled synthesis of tungsten carbide nanoparticles from the nanoconfinement of a mesoporous graphite C 3N4 (mpg-C3N4) reactive template is shown. The nanomaterials catalyze hydrogen evolution/oxidation reactions, but are inactive in the oxygen reduction reaction. Tungsten carbide is an effective cocatalyst for photocatalytic overall water splitting (see picture). Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. Tungsten and Barium Transport in the Internal Plasma of Hollow Cathodes

    Science.gov (United States)

    Polk, James E.; Mikellides, Ioannis G.; Katz, Ira; Capece, Angela M.

    2008-01-01

    The effect of tungsten erosion, transport and redeposition on the operation of dispenser hollow cathodes was investigated in detailed examinations of the discharge cathode inserts from an 8200 hour and a 30,352 hour ion engine wear test. Erosion and subsequent re-deposition of tungsten in the electron emission zone at the downstream end of the insert reduces the porosity of the tungsten matrix, preventing the flow of barium from the interior. This inhibits the interfacial reactions of the barium-calcium-aluminate impregnant with the tungsten in the pores. A numerical model of barium transport in the internal xenon discharge plasma shows that the barium required to reduce the work function in the emission zone can be supplied from upstream through the gas phase. Barium that flows out of the pores of the tungsten insert is rapidly ionized in the xenon discharge and pushedback to the emitter surface by the electric field and drag from the xenon ion flow. Thisbarium ion flux is sufficient to maintain a barium surface coverage at the downstream endgreater than 0.6, even if local barium production at that point is inhibited by tungsten deposits. The model also shows that the neutral barium pressure exceeds the equilibrium vapor pressure of the impregnant decomposition reaction over much of the insert length,so the reactions are suppressed. Only a small region upstream of the zone blocked by tungsten deposits is active and supplies the required barium. These results indicate that hollowcathode failure models based on barium depletion rates in vacuum dispenser cathodes are very conservative.

  7. In vivo corrosion, tumor outcome, and microarray gene expression for two types of muscle-implanted tungsten alloys.

    Science.gov (United States)

    Schuster, B E; Roszell, L E; Murr, L E; Ramirez, D A; Demaree, J D; Klotz, B R; Rosencrance, A B; Dennis, W E; Bao, W; Perkins, E J; Dillman, J F; Bannon, D I

    2012-11-15

    Tungsten alloys are composed of tungsten microparticles embedded in a solid matrix of transition metals such as nickel, cobalt, or iron. To understand the toxicology of these alloys, male F344 rats were intramuscularly implanted with pellets of tungsten/nickel/cobalt, tungsten/nickel/iron, or pure tungsten, with tantalum pellets as a negative control. Between 6 and 12 months, aggressive rhabdomyosarcomas formed around tungsten/nickel/cobalt pellets, while those of tungsten/nickel/iron or pure tungsten did not cause cancers. Electron microscopy showed a progressive corrosion of the matrix phase of tungsten/nickel/cobalt pellets over 6 months, accompanied by high urinary concentrations of nickel and cobalt. In contrast, non-carcinogenic tungsten/nickel/iron pellets were minimally corroded and urinary metals were low; these pellets having developed a surface oxide layer in vivo that may have restricted the mobilization of carcinogenic nickel. Microarray analysis of tumors revealed large changes in gene expression compared with normal muscle, with biological processes involving the cell cycle significantly up-regulated and those involved with muscle development and differentiation significantly down-regulated. Top KEGG pathways disrupted were adherens junction, p53 signaling, and the cell cycle. Chromosomal enrichment analysis of genes showed a highly significant impact at cytoband 7q22 (chromosome 7) which included mouse double minute (MDM2) and cyclin-dependant kinase (CDK4) as well as other genes associated with human sarcomas. In conclusion, the tumorigenic potential of implanted tungsten alloys is related to mobilization of carcinogenic metals nickel and cobalt from corroding pellets, while gene expression changes in the consequent tumors are similar to radiation induced animal sarcomas as well as sporadic human sarcomas. Published by Elsevier Inc.

  8. Extreme Ultraviolet Spectra of Few-Times Ionized Tungsten for Divertor Plasma Diagnostics

    Directory of Open Access Journals (Sweden)

    Joel Clementson

    2015-09-01

    Full Text Available The extreme ultraviolet (EUV emission from few-times ionized tungsten atoms has been experimentally studied at the Livermore electron beam ion trap facility. The ions were produced and confined during low-energy operations of the EBIT-I electron beam ion trap. By varying the electron-beam energy from around 30–300 eV, tungsten ions in charge states expected to be abundant in tokamak divertor plasmas were excited, and the resulting EUV emission was studied using a survey spectrometer covering 120–320 Å. It is found that the emission strongly depends on the excitation energy; below 150 eV, it is relatively simple, consisting of strong isolated lines from a few charge states, whereas at higher energies, it becomes very complex. For divertor plasmas with tungsten impurity ions, this emission should prove useful for diagnostics of tungsten flux rates and charge balance, as well as for radiative cooling of the divertor volume. Several lines in the 194–223 Å interval belonging to the spectra of five- and seven-times ionized tungsten (Tm-like W VI and Ho-like W VIII were also measured using a high-resolution spectrometer.

  9. ERO modelling of tungsten erosion and re-deposition in EAST L mode discharges

    Science.gov (United States)

    Xie, H.; Ding, R.; Kirschner, A.; Chen, J. L.; Ding, F.; Mao, H. M.; Feng, W.; Borodin, D.; Wang, L.

    2017-09-01

    Tungsten erosion and re-deposition at the upper outer divertor of the Experimental Advanced Superconducting Tokamak has been modelled using the 3D Monte Carlo code ERO. The measured divertor plasma condition in attached L mode discharges with upper single null configuration has been used to build the background plasma in the simulations. The tungsten gross erosion rate is mainly determined by carbon impurity in the background plasma. Increasing carbon concentration can first increase and afterwards suppress the tungsten erosion rate. Taking into account the material mixing surface model, the influence of eroded particles returning to the surface on sputtering has been studied. Sputtering by eroded particles returning to the surface can significantly enhance the gross erosion by reduction of the carbon ratio within the surface interaction layer and by increasing the erosion rate due to sputtering by both eroded tungsten and carbon particles. Modelling indicates that carbon deposition occurs on the dome plate and part of the vertical plate close to the dome plate, whereas tungsten net erosion occurs on most of the vertical plate. The modelling results are in reasonable agreement with the experimental WI spectroscopy.

  10. Tungsten carbide nanoparticles as efficient cocatalysts for photocatalytic overall water splitting.

    Science.gov (United States)

    Garcia-Esparza, Angel T; Cha, Dongkyu; Ou, Yiwei; Kubota, Jun; Domen, Kazunari; Takanabe, Kazuhiro

    2013-01-01

    Tungsten carbide exhibits platinum-like behavior, which makes it an interesting potential substitute for noble metals in catalytic applications. Tungsten carbide nanocrystals (≈5 nm) are directly synthesized through the reaction of tungsten precursors with mesoporous graphitic C(3)N(4) (mpg-C(3)N(4)) as the reactive template in a flow of inert gas at high temperatures. Systematic experiments that vary the precursor compositions and temperatures used in the synthesis selectively generate different compositions and structures for the final nanocarbide (W(2)C or WC) products. Electrochemical measurements demonstrate that the WC phase with a high surface area exhibits both high activity and stability in hydrogen evolution over a wide pH range. The WC sample also shows excellent hydrogen oxidation activity, whereas its activity in oxygen reduction is poor. These tungsten carbides are successful cocatalysts for overall water splitting and give H(2) and O(2) in a stoichiometric ratio from H(2)O decomposition when supported on a Na-doped SrTiO(3) photocatalyst. Herein, we present tungsten carbide (on a small scale) as a promising and durable catalyst substitute for platinum and other scarce noble-metal catalysts in catalytic reaction systems used for renewable energy generation. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. WS{sub 2} nanotube formation by sulphurization: Effect of precursor tungsten film thickness and stress

    Energy Technology Data Exchange (ETDEWEB)

    Ng, Sheung Mei; Wong, Hon Fai; Wong, Wang Cheung; Tan, Choon Kiat; Choi, Sin Yuk; Mak, Chee Leung; Li, Gui Jun [Department of Applied Physics, The Hong Kong Polytechnic University, Hung Hom, Kowloon (Hong Kong); Dong, Qing Chen [MOE Key Laboratory for Interface Science and Engineering in Advanced Materials and Research Center of Advanced Materials Science and Technology, Taiyuan University of Technology, 79 Yingze West Street, Taiyuan 030024 (China); Leung, Chi Wah, E-mail: dennis.leung@polyu.edu.hk [Department of Applied Physics, The Hong Kong Polytechnic University, Hung Hom, Kowloon (Hong Kong)

    2016-09-15

    Transition metal dichalcogenides can exhibit as 2-dimensional layers, 1-dimensional nanotubes or 0-dimensional quantum dot structures. In general, dichalcogenide nanotubes are grown under stringent conditions, using high growth temperatures with tedious processes. Here, we report the controlled formation of tungsten disulphide (WS{sub 2}) nanostructures by manipulating the precursor film thickness, followed by a direct sulphurization process. WS{sub 2} nanotubes were formed by ultra-thin tungsten precursor films, while particle-like WS{sub 2} were obtained from thicker tungsten films under identical sulphurization conditions. To elucidate the origin of WS{sub 2} nanostructure formation, micron-sized tungsten film tracks were prepared, and such patterned films were found to suppress the growth of WS{sub 2} nanotubes. We attribute the suppression of nanotube formation to the relieving of film stress in patterned precursor films. - Highlights: • WS{sub 2} were obtained by sulphurization of sputtered tungsten films on Si substrates. • Resultant WS{sub 2} nanostructure morphology was dependent on precursor film thickness. • Patterning into micro-size W tracks suppressed the formation of nanotubes. • Stress relaxation was attributed as controlling factor for WS{sub 2} structure formation.

  12. Toxic and transcriptional responses of PC12 cells to soluble tungsten alloy surrogates

    Directory of Open Access Journals (Sweden)

    V.H. Adams

    2015-01-01

    Full Text Available There is increasing evidence that metals have a role in the etiology of diverse neurological diseases. This study used PC12 cells as an in vitro model to examine the toxicity of tungsten alloys that have important military applications. Initially, the relative concentrations of tungsten (W, nickel (Ni, and cobalt (Co mobilized from pellets of a weapons-grade tungsten alloy incubated in physiologically relevant solutions were determined. Dosing solutions of soluble metal salts that were equivalent in ratio to those mobilized from these alloy pellets were used to treat nerve growth factor (NGF differentiated PC12 cells. Treatments consisted of single (W, Ni or Co, paired (W/Ni, W/Co or Ni/Co or complete (W/Ni/Co metal exposures for 24 h followed by measurement of cytotoxicity, viability, and microarray analysis to examine their impact on survival and viability, global gene expression, and biological processes. Gene expression changed dramatically with addition of NGF. Addition of Ni or Co either singly or in combination further impacted gene expression. An observed additive effect of Ni and Co on gene expression was unaffected by the addition of W. The work showed that tungsten, as found in this tungsten alloy, had minimal relative toxicity as compared to the other alloy components when used either alone or in combination.

  13. Recrystallization and grain growth induced by ELMs-like transient heat loads in deformed tungsten samples

    Science.gov (United States)

    Suslova, A.; El-Atwani, O.; Sagapuram, D.; Harilal, S. S.; Hassanein, A.

    2014-11-01

    Tungsten has been chosen as the main candidate for plasma facing components (PFCs) due to its superior properties under extreme operating conditions in future nuclear fusion reactors such as ITER. One of the serious issues for PFCs is the high heat load during transient events such as ELMs and disruption in the reactor. Recrystallization and grain size growth in PFC materials caused by transients are undesirable changes in the material, since the isotropic microstructure developed after recrystallization exhibits a higher ductile-to-brittle transition temperature which increases with the grain size, a lower thermal shock fatigue resistance, a lower mechanical strength, and an increased surface roughening. The current work was focused on careful determination of the threshold parameters for surface recrystallization, grain growth rate, and thermal shock fatigue resistance under ELM-like transient heat events. Transient heat loads were simulated using long pulse laser beams for two different grades of ultrafine-grained tungsten. It was observed that cold rolled tungsten demonstrated better power handling capabilities and higher thermal stress fatigue resistance compared to severely deformed tungsten. Higher recrystallization threshold, slower grain growth, and lower degree of surface roughening were observed in the cold rolled tungsten.

  14. Electrochemical Dissolution of Tungsten Carbide in NaCl-KCl-Na2WO4 Molten Salt

    Science.gov (United States)

    Zhang, Liwen; Nie, Zuoren; Xi, Xiaoli; Ma, Liwen; Xiao, Xiangjun; Li, Ming

    2017-11-01

    Tungsten carbide was utilized as anode to extract tungsten in a NaCl-KCl-Na2WO4 molten salt, and the electrochemical dissolution was investigated. Although the molten salt electrochemical method is a short process method of tungsten extraction from tungsten carbide in one step, the dissolution efficiency and current efficiency are quite low. In order to improve the dissolution rate and current efficiency, the sodium tungstate was added as the active substance. The dissolution rate, the anode current efficiency, and the cathode current efficiency were calculated with different contents of sodium tungstate addition. The anodes prior to and following the reaction, as well as the product, were analyzed through X-ray diffraction, scanning electron microscopy, and energy dispersive spectrometry. The results demonstrated that the sodium tungstate could improve the dissolution rate and the current efficiency, due to the addition of sodium tungstate decreasing the charge transfer resistance in the electrolysis system. Due to the fact that the addition of sodium tungstate could remove the carbon during electrolysis, pure tungsten powders with 100 nm diameter were obtained when the content of sodium tungstate was 1.0 pct.

  15. Tungsten oxide thin films obtained by anodisation in low electrolyte concentration

    Energy Technology Data Exchange (ETDEWEB)

    Costa, Nadja B.D. da [Centro de Ciências Químicas, Farmacêuticas e de Alimentos, Universidade Federal de Pelotas, Campus Capão do Leão, s/n, Pelotas, RS (Brazil); Pazinato, Julia C.O. [Instituto de Química, Universidade Federal do Rio Grande do Sul, Av. Bento Gonçalves, 9500 Porto Alegre, RS (Brazil); Sombrio, Guilherme; Pereira, Marcelo B.; Boudinov, Henri [Instituto de Física, Universidade Federal do Rio Grande do Sul, Av. Bento Gonçalves, 9500 Porto Alegre, RS (Brazil); Gündel, André; Moreira, Eduardo C. [Universidade Federal do Pampa, Travessa 45, 1650 Bagé, RS (Brazil); Garcia, Irene T.S., E-mail: irene.garcia@ufrgs.br [Instituto de Química, Universidade Federal do Rio Grande do Sul, Av. Bento Gonçalves, 9500 Porto Alegre, RS (Brazil)

    2015-03-02

    Tungsten oxide nanostructured films were grown on tungsten substrates by anodisation under a fixed voltage and with sodium fluoride as electrolyte. The effect of the anion chloride and the influence of the modifying agent disodium hydrogen phosphate in the tungsten oxide films were also investigated. The structural characterisation of the films was performed by scanning electron microscopy, atomic force microscopy and Raman spectroscopy. The band gap was determined through diffuse reflectance spectroscopy. The thin films were photoluminescent and emitted in the range of 300 to 630 nm when irradiated at 266 nm. The synthesised films efficiently degraded of methyl orange dye in the presence of hydrogen peroxide and 250 nm radiation. The modifying agent was responsible for the improvement of the photocatalytic activity. Films with similar photocatalytic performance were obtained when the system sodium fluoride and disodium hydrogen phosphate were replaced by sodium chloride. The porous structure and low band gap values were responsible for the photocatalytic behaviour. - Highlights: • Tungsten oxide thin films were obtained by anodisation of tungsten in aqueous media. • The performance of the NaCl, NaF and NaF/Na{sub 2}HPO{sub 4} as electrolytes was investigated. • The relation between structure and optical behaviour has been discussed. • Films obtained with NaCl and NaF/Na{sub 2}HPO{sub 4} present similar photocatalytic activity.

  16. Dual catalytic purpose of the tungsten filament during the synthesis of single-helix carbon microcoils by hot-wire CVD

    CSIR Research Space (South Africa)

    Oliphant, CJ

    2009-10-01

    Full Text Available post-deposition annealing. Tungsten, originating from the heated tungsten filament, is identified as the catalyst material responsible for the growth of the microcoils. High-resolution transmission spectroscopy, combined with Raman spectroscopy, confirm...

  17. Characterization of Tungsten Carbide coatings deposited on AISI 1020 steel

    Science.gov (United States)

    Santos, A.; Gonzalez, C.; Ramirez, Z. Y.

    2017-01-01

    In order to determine the variation in the mechanical properties of AISI 1020 standardized steel, heat treated by a quenching and tempering process and with a Tungsten Carbide coating, was performed a microstructural and chemical characterization of the coating material through electron microscopy scanning and X-ray energy dispersive spectroscopy. The steel received a heat treatment of quenching performed by heating to 850°C, followed by cooling in water and tempering at a temperature of 450°C with air cooling. Tests of a) microhardness with a Wilson-Wolpert Tukon 2100B micro durometer and b) resistance to adhesive and abrasive wear following the ASTM G99-05 “Standard test method for wear testing with a pin-on-disk machine” and ASTM G65-04 “standard test method for measuring abrasion using dry sand and rubber Wheel” standards respectively. The results show that the microhardness of the steel do not vary with the load used to perform the test; in addition, the heat treatment of quenching and tempering improves by 5.5% the property while the coating increase it by 124.2%. Regarding the abrasive wear resistance, it is observed that the amount of material lost increases linearly with the distance covered. It was determined that the heat treatment decreased on average by 17.5% the volume of released material during the tests while the coating recued it by 66.7%. The amount volume of material lost during the adhesive wear tests increases linearly with the distance covered while the heat treatment decreased on average by 10.5% the volume of released material during the trial and the coating reduced it by 66.5%.

  18. Tungsten isotope composition of the Acasta Gneiss Complex

    Science.gov (United States)

    Willbold, M.; Mojzsis, S. J.; Chen, H.-W.; Elliott, T.

    2015-06-01

    High-precision tungsten (182W/184W) isotope measurements on well-characterised mafic and felsic samples of the ca. 3960 Ma Acasta Gneiss Complex (AGC; Northwest Territories, Canada) show radiogenic ε182W values between +0.06 to +0.15. Two ca. 3600 Ma felsic samples from this terrane have ε182W ∼ 0 and are the oldest samples so far documented to have a W isotopic composition indistinguishable from that of the modern mantle. The ε182W data are correlated with ε142Nd (Roth et al., 2014) and we attribute this variability to incomplete metamorphic homogenisation of the 3960 Ma protolith with more recent material in a 3370 Ma tectono-thermal event. Notably, the value of the positive ε182W anomalies seen in the 3960 Ma AGC samples that are least affected by metamorphic homogenisation is comparable to that observed in other early Archean rocks (Isua Supracrustal Belt, Greenland; Nuvvuagittuq Supracrustal Belt, Canada) and the late Archean Kostomuksha komatiites (Karelia). This demonstrates a globally constant signature. We infer that the presence of a pre-late veneer mantle represents the most straightforward interpretation of a uniform distribution of ε182W ∼ + 0.15 value in Archean rocks of different ages. We show that such a notion is compatible with independent constraints from highly siderophile element abundances in mafic and ultra-mafic Archean mantle-derived rocks. The absence of anomalous ε182W and ε142Nd so far measured in samples younger than ca. 2800 Ma suggests progressive convective homogenisation of silicate reservoirs. The downward mixing of an upper mantle rich in late-delivered meteoritic material might account for these combined observations.

  19. Electron impact ionization cross sections of beryllium-tungsten clusters*

    Science.gov (United States)

    Sukuba, Ivan; Kaiser, Alexander; Huber, Stefan E.; Urban, Jan; Probst, Michael

    2016-01-01

    We report calculated electron impact ionization cross sections (EICSs) of beryllium-tungsten clusters, BenW with n = 1,...,12, from the ionization threshold to 10 keV using the Deutsch-Märk (DM) and the binary-encounter-Bethe (BEB) formalisms. The positions of the maxima of DM and BEB cross sections are mostly close to each other. The DM cross sections are more sensitive with respect to the cluster size. For the clusters smaller than Be4W they yield smaller cross sections than BEB and vice versa larger cross sections than BEB for clusters larger than Be6W. The maximum cross section values for the singlet-spin groundstate clusters range from 7.0 × 10-16 cm2 at 28 eV (BeW) to 54.2 × 10-16 cm2 at 43 eV (Be12W) for the DM cross sections and from 13.5 × 10-16 cm2 at 43 eV (BeW) to 38.9 × 10-16 cm2 at 43 eV (Be12W) for the BEB cross sections. Differences of the EICSs in different isomers and between singlet and triplet states are also explored. Both the DM and BEB cross sections could be fitted perfectly to a simple expression used in modeling and simulation codes in the framework of nuclear fusion research. Contribution to the Topical Issue "Atomic Cluster Collisions (7th International Symposium)", edited by Gerardo Delgado Barrio, Andrey Solov'Yov, Pablo Villarreal, Rita Prosmiti.Supplementary material in the form of one pdf file available from the Journal web page at http://dx.doi.org/10.1140/epjd/e2015-60583-7

  20. Synthesis and Ligand-Exchange Reactions of a Tri-Tungsten Cluster with Applications in Biomedical Imaging

    Science.gov (United States)

    Noey, Elizabeth; Curtis, Jeff C.; Tam, Sylvia; Pham, David M.; Jones, Ella F.

    2011-01-01

    In this experiment students are exposed to concepts in inorganic synthesis and various spectroscopies as applied to a tri-tungsten cluster with applications in biomedical imaging. The tungsten-acetate cluster, Na[W[superscript 3](mu-O)[subscript 2](CH[superscript 3]COO)[superscript 9

  1. Evaluation of health and environmental risks associated with the life-cycle of tungsten-based ammunition

    NARCIS (Netherlands)

    Langenberg, J.P.; Horst, R.M. van der; Carol-Visser, J.; Hulst, M. van; Grand, N.P. le; Elst, O.A.A.M. ter; Lander, H.J.; Brekelmans, F.J.A.M.

    2009-01-01

    Tungsten-based ammunition is generally considered to be less harmful and more environmentally friendly than ammunition based on depleted uranium. However, recent studies have shown severe health effects in rats after embedding fragments of weapons grade Tungsten/Nickel/Cobalt in their leg muscle

  2. Study of deuterium retention on lithiated tungsten exposed to high-flux deuterium plasma using laser-induced breakdown spectroscopy

    NARCIS (Netherlands)

    Li, C.; Wu, X.; Zhang, C.; Ding, H.; De Temmerman, G.; van der Meiden, H. J.

    2014-01-01

    Tungsten is under consideration for use as a plasma-facing material in the divertor region of ITER. Lithiation can significantly improve plasma performance in long-pulse tokamaks like EAST. The investigation of lithiated tungsten is important for understanding the lithium conditioning effects for

  3. Influence of high flux hydrogen-plasma exposure on the thermal shock induced crack formation in tungsten

    NARCIS (Netherlands)

    Wirtz, M.; Linke, J.; Pintsuk, G.; Rapp, J.; Wright, G. M.

    2012-01-01

    The influence of high flux hydrogen-plasma on the thermal shock behaviour of tungsten was investigated in a combined experiment using the linear plasma device Pilot-PSI and the electron beam facility JUDITH 1. Tungsten targets were exposed to high flux hydrogen plasma, cyclic thermal shock tests and

  4. Fatigue strength of tungsten-copper duplex structures for divertor plates

    Science.gov (United States)

    Seki, M.; Horie, T.; Tone, T.; Nagata, K.; Kitamura, K.; Shibutani, Y.; Shibui, M.; Araki, T.

    1988-07-01

    A tungsten-copper duplex structure is specified in a conceptual design of the Japan Fusion Experimental Reactor (FER). The evaluation of the fatigue and creep life of the interface region between tungsten and copper is essential for design of the divertor plate. Fatigue crack initiation life and crack propagation behavior at room temperature and 200°C were measured for fully-annealed OFHC copper and for tungsten-OFHC copper joints brazed with amorphous nickel-base filler metal. The debonding fatigue strength for the brazed joints was relatively high, but less than that of the copper. Fatigue crack growth rates in the braze layer was approximately similar to that of the copper. Fatigue lives were estimated for the divertor plate with small defects, and a method for analyzing the apparent K- values of interface cracks was presented.

  5. Heat load and deuterium plasma effects on SPS and WSP tungsten

    Directory of Open Access Journals (Sweden)

    Vilémová Monika

    2015-06-01

    Full Text Available Tungsten is a prime choice for armor material in future nuclear fusion devices. For the realization of fusion, it is necessary to address issues related to the plasma–armor interactions. In this work, several types of tungsten material were studied, i.e. tungsten prepared by spark plasma sintering (SPS and by water stabilized plasma spraying (WSP technique. An intended surface porosity was created in the samples to model hydrogen/helium bubbles. The samples were subjected to a laser heat loading and a radiation loading of deuterium plasma to simulate edge plasma conditions of a nuclear fusion device (power density of 108 W/cm2 and 107 W/cm2, respectively, in the pulse intervals up to 200 ns. Thermally induced changes in the morphology and the damage to the studied surfaces are described. Possible consequences for the fusion device operation are pointed out.

  6. Tungsten erosion under plasma heat loads typical for ITER type I Elms and disruptions

    Energy Technology Data Exchange (ETDEWEB)

    Garkusha, I.E. [Institute of Plasma Physics of the NSC KIPT, 61108 Kharkov (Ukraine)]. E-mail: garkusha@ipp.kharkov.ua; Bandura, A.N. [Institute of Plasma Physics of the NSC KIPT, 61108 Kharkov (Ukraine); Byrka, O.V. [Institute of Plasma Physics of the NSC KIPT, 61108 Kharkov (Ukraine); Chebotarev, V.V. [Institute of Plasma Physics of the NSC KIPT, 61108 Kharkov (Ukraine); Landman, I.S. [Forschungszentrum Karlsruhe, IHM, 76021 Karlsruhe (Germany); Makhlaj, V.A. [Institute of Plasma Physics of the NSC KIPT, 61108 Kharkov (Ukraine); Marchenko, A.K. [Institute of Plasma Physics of the NSC KIPT, 61108 Kharkov (Ukraine); Solyakov, D.G. [Institute of Plasma Physics of the NSC KIPT, 61108 Kharkov (Ukraine); Tereshin, V.I. [Institute of Plasma Physics of the NSC KIPT, 61108 Kharkov (Ukraine); Trubchaninov, S.A. [Institute of Plasma Physics of the NSC KIPT, 61108 Kharkov (Ukraine); Tsarenko, A.V. [Institute of Plasma Physics of the NSC KIPT, 61108 Kharkov (Ukraine)

    2005-03-01

    The behavior of pure sintered tungsten under repetitive plasma heat loads of {approx}1 MJ/m{sup 2} (which is relevant to ITER ELMs) and 25 MJ/m{sup 2} (ITER disruptions) is studied with the quasi-steady-state plasma accelerator QSPA Kh-50. The ELM relevant heat loads have resulted in formation of two kinds of crack networks, with typical sizes of 10-20 {mu}m and {approx}1 mm, at the surface. Tungsten preheating to 600 deg. C indicates that fine intergranular cracks are probably caused by thermal stresses during fast resolidification of the melt, whereas large cracks are the result of ductile-to-brittle transition. For several hundreds of ELM-like exposures, causing surface melting, the melt motion does not dominate the profile of the melt spot. The disruption relevant experiments demonstrated that melt motion became the main factor of tungsten damage.

  7. Tungsten erosion under plasma heat loads typical for ITER type I ELMs and disruptions

    Science.gov (United States)

    Garkusha, I. E.; Bandura, A. N.; Byrka, O. V.; Chebotarev, V. V.; Landman, I. S.; Makhlaj, V. A.; Marchenko, A. K.; Solyakov, D. G.; Tereshin, V. I.; Trubchaninov, S. A.; Tsarenko, A. V.

    2005-03-01

    The behavior of pure sintered tungsten under repetitive plasma heat loads of ˜1 MJ/m 2 (which is relevant to ITER ELMs) and 25 MJ/m 2 (ITER disruptions) is studied with the quasi-steady-state plasma accelerator QSPA Kh-50. The ELM relevant heat loads have resulted in formation of two kinds of crack networks, with typical sizes of 10-20 μm and ˜1 mm, at the surface. Tungsten preheating to 600 °C indicates that fine intergranular cracks are probably caused by thermal stresses during fast resolidification of the melt, whereas large cracks are the result of ductile-to-brittle transition. For several hundreds of ELM-like exposures, causing surface melting, the melt motion does not dominate the profile of the melt spot. The disruption relevant experiments demonstrated that melt motion became the main factor of tungsten damage.

  8. Tungsten nitride coatings obtained by HiPIMS as plasma facing materials for fusion applications

    Science.gov (United States)

    Tiron, Vasile; Velicu, Ioana-Laura; Porosnicu, Corneliu; Burducea, Ion; Dinca, Paul; Malinský, Petr

    2017-09-01

    In this work, tungsten nitride coatings with nitrogen content in the range of 19-50 at% were prepared by reactive multi-pulse high power impulse magnetron sputtering as a function of the argon and nitrogen mixture and further exposed to a deuterium plasma jet. The elemental composition, morphological properties and physical structure of the samples were investigated by Rutherford backscattering spectrometry, atomic force microscopy and X-ray diffraction. Deuterium implantation was performed using a deuterium plasma jet and its retention in nitrogen containing tungsten films was investigated using thermal desorption spectrometry. Deuterium retention and release behaviour strongly depend on the nitrogen content in the coatings and the films microstructure. All nitride coatings have a polycrystalline structure and retain a lower deuterium level than the pure tungsten sample. Nitrogen content in the films acts as a diffusion barrier for deuterium and leads to a higher desorption temperature, therefore to a higher binding energy.

  9. Microstructure and properties of surface-modified tungsten powders mechanically activated in different media

    Science.gov (United States)

    Savenko, V. I.; Toporov, Yu. P.; Chernyshev, V. V.; Malkin, A. I.

    2017-11-01

    The results of an experimental-theoretical study of the effect of thin-film coatings on residual microstrains, microstresses, and local microdistortions of the atomic structure of powder tungsten mechanically activated in the centrifugal ball mill have been presented. It has been shown that microdistortions of the crystal structure of different system-hierarchical levels arise in the surface-oxidized powders, which increase with an increase in the time of the activation process. It has been shown that this should lead to a significant increase in the reactivity of the mechanically activated powder tungsten. In contrast, the adsorption films that plasticize the near-surface layer of particles can decrease the efficiency of the mechanoactivation process of the tungsten powder.

  10. In situ chemical imaging of lithiated tungsten using laser-induced breakdown spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Li, Cong; Wu, Xingwei; Zhang, Chenfei [Key Laboratory of Materials Modification by Laser, Ion and Electron Beams, Chinese Ministry of Education, School of Physics and Optical Electronic Technology, Dalian University of Technology, Dalian 116024 (China); Ding, Hongbin, E-mail: hding@dlut.edu.cn [Key Laboratory of Materials Modification by Laser, Ion and Electron Beams, Chinese Ministry of Education, School of Physics and Optical Electronic Technology, Dalian University of Technology, Dalian 116024 (China); Hu, Jiansheng; Luo, Guang-Nan [Institute of Plasma Physics, Chinese Academy of Sciences, P.O. Box 1126, Hefei 230031 (China)

    2014-09-15

    Lithium conditioning can significantly improve the plasma confinement of EAST tokamak by reducing the amount of hydrogen and impurities recycled from the wall, but the details of this mechanism and approaches that reduce the concentrations of hydrogen and impurities recycle still remain unclear. In this paper, we studied lithiated tungsten via a cascaded-arc plasma simulator. An in situ laser-induced breakdown spectroscopy (LIBS) diagnostic system has been developed to chemically image the three-dimensional distribution of lithium and impurities on the surface of lithiated tungsten co-deposition layer for the first time. The results indicate that lithium has a strong ability to draw hydrogen and oxygen. The impurity components from the co-deposition processes present more intensity on the surface of co-deposition layer. This work improves the understanding of lithiated tungsten mechanism and is useful for using LIBS as a wall-diagnostic technique for EAST.

  11. Aging Thermal Treatment in the Inconel 725 Brazed Incorporating Tungsten Nanoparticles

    Directory of Open Access Journals (Sweden)

    H. M. Hdz-García

    2016-01-01

    Full Text Available Fractures in blade sections of Inconel 725 were impregnated with tungsten nanoparticles and jointed by the brazing process. In order to evaluate their effect over the microstructure, aging thermal treatments at 750°C for 2, 6, 10, and 14 h were done. BNi-9 was selected as brazing filler metal and was characterized by scanning electron microscopy and X-ray fluorescence. Before brazing, the fractures were impregnated with a mixture of tungsten NPs in ethanol. Measurements of Vickers microhardness showed an increase in the melting zone of samples with aging thermal treatment for 14 h, which is attributed to the precipitation of the γ′ phase with a typical size of ca. 100 nm. Likewise, the tungsten NPs modified the size and morphology of Cr-Ni eutectics into finer and uniformly distributed microstructures.

  12. Plasma effect on tungsten damaged by high-energy alpha particles: Erosion and deuterium trapping

    Energy Technology Data Exchange (ETDEWEB)

    Khripunov, B.I., E-mail: boris@nfi.kiae.ru [RRC Kurchatov Institute, Kurchatov Sq. 1, Moscow 123182 (Russian Federation); Brukhanov, A.N.; Gureev, V.M.; Koidan, V.S.; Kornienko, S.N.; Latushkin, S.T.; Petrov, V.B.; Ryazanov, A.I.; Semenov, E.V.; Stolyarova, V.G.; Unezhev, V.N.; Danelyan, L.S. [RRC Kurchatov Institute, Kurchatov Sq. 1, Moscow 123182 (Russian Federation); Kulikauskas, V.S.; Zatekin, V.V.; Vostrikov, V.G.; Romanovsky, E.A. [Institute of Nuclear Physics, Lomonosov University, Moscow 119991 (Russian Federation)

    2011-08-01

    Experimental study of tungsten at high level of displacement damage is reported. The damage of 1-80 dpa was produced by high-energy helium ions {sup 4}He{sup 2+} (3-4 MeV) from cyclotron. Properties of the irradiated tungsten were studied in deuterium plasma on the LENTA linear divertor simulator. Plasma exposures were made at 250 eV of ion energy to reach fluence 10{sup 25}-10{sup 26} ion/m{sup 2}. Erosion dynamics of the damaged layer and deuterium retention were studied. Surface modifications have been observed in the damaged material. Increased deuterium retention was detected on damaged tungsten by nuclear analysis methods; implanted helium accumulation was also measured.

  13. In situ observation of structural change of nanostructured tungsten during annealing

    Energy Technology Data Exchange (ETDEWEB)

    Yajima, Miyuki, E-mail: yajima-miyuki10@ees.nagoya-u.ac.jp [Graduate School of Eng., Nagoya Univ., Nagoya 464-8603 (Japan); Yoshida, Naoaki, E-mail: yoshida@riam.kyushu-u.ac.jp [Research Inst. for Appl. Mech., Kyushu Univ., Kasuga 816-8580 (Japan); Kajita, Shin, E-mail: kajita@ees.nagoya-u.ac.jp [EcoTopia Science Institute, Nagoya Univ., Nagoya 464-8603 (Japan); Tokitani, Masayuki, E-mail: tokitani.masayuki@LHD.nifs.ac.jp [National Institute for Fusion Science, Toki 509-5292 (Japan); Baba, Tomotsugu [Research Inst. for Appl. Mech., Kyushu Univ., Kasuga 816-8580 (Japan); Ohno, Noriyasu, E-mail: ohno@ees.nagoya-u.ac.jp [Graduate School of Eng., Nagoya Univ., Nagoya 464-8603 (Japan)

    2014-06-01

    Deformation of fiberform nanostructure and the dynamic behavior of helium (He) bubbles in fuzz tungsten (W) during annealing have been investigated by means of in situ cross-section observation using transmission electron microscopy and He desorption rate observation using thermal desorption spectroscopy (TDS). Thermal recovery of the nanostructure, such as shrinkage and coalescence of fine structure, annihilation of He bubbles, and large desorption of He gas, occurred around 1073–1173 K. The activation energy of He was estimated from a TDS peak that appeared around 300–400 K by using the Kissinger–Akahira–Sunose model-free-kinetics method. In addition, the TDS results of fiberform nanostructured tungsten were compared with those of tungsten samples irradiated with a high-energy He ion beam.

  14. In situ observation of structural change of nanostructured tungsten during annealing

    Science.gov (United States)

    Yajima, Miyuki; Yoshida, Naoaki; Kajita, Shin; Tokitani, Masayuki; Baba, Tomotsugu; Ohno, Noriyasu

    2014-06-01

    Deformation of fiberform nanostructure and the dynamic behavior of helium (He) bubbles in fuzz tungsten (W) during annealing have been investigated by means of in situ cross-section observation using transmission electron microscopy and He desorption rate observation using thermal desorption spectroscopy (TDS). Thermal recovery of the nanostructure, such as shrinkage and coalescence of fine structure, annihilation of He bubbles, and large desorption of He gas, occurred around 1073-1173 K. The activation energy of He was estimated from a TDS peak that appeared around 300-400 K by using the Kissinger-Akahira-Sunose model-free-kinetics method. In addition, the TDS results of fiberform nanostructured tungsten were compared with those of tungsten samples irradiated with a high-energy He ion beam.

  15. Transparent conductive oxide thin films of tungsten-doped indium oxide

    Energy Technology Data Exchange (ETDEWEB)

    Li Xifeng [Department of Materials Science, Fudan University, Shanghai 200433 (China); Zhang Qun [Department of Materials Science, Fudan University, Shanghai 200433 (China)]. E-mail: zhangqun@fudan.edu.cn; Miao Weina [Department of Materials Science, Fudan University, Shanghai 200433 (China); Huang Li [Department of Materials Science, Fudan University, Shanghai 200433 (China); Zhang Zhuangjian [Department of Materials Science, Fudan University, Shanghai 200433 (China)

    2006-12-05

    Transparent conductive oxide thin film of tungsten-doped In{sub 2}O{sub 3} (IWO) has been prepared by reactive direct current magnetron sputtering from the tungsten-embedded indium metal target. The effect of tungsten doping content on the optoelectrical properties of IWO films was investigated. The lowest resistivity of 2.7 x 10{sup -4} {omega}.cm was reproducibly obtained, with carrier mobility greater than 57 cm{sup 2} V{sup -1} s{sup -1} and carrier concentration of 4.0 x 10{sup 20} cm{sup -3}, as well as the transmission in visible light range exceeding 80%. X-ray diffraction measurements indicate that the as-deposited IWO films are well crystallized with a preferential orientation of (222)

  16. Advanced Electrochemical Machining (ECM) for tungsten surface micro-structuring in blanket applications

    Energy Technology Data Exchange (ETDEWEB)

    Holstein, Nils, E-mail: nils.holstein@kit.edu [Karlsruhe Institute of Technology, Hermann-von-Helmholtz-Platz 1, D-76344 Eggenstein-Leopoldshafen, Baden-Württemberg (Germany); Krauss, Wolfgang; Konys, Jürgen [Karlsruhe Institute of Technology, Hermann-von-Helmholtz-Platz 1, D-76344 Eggenstein-Leopoldshafen, Baden-Württemberg (Germany); Heuer, Simon; Weber, Thomas [Research Center Jülich, Institute of Energy- and Climate Research – Plasma Physics (IEK-4), D-52425 Jülich (Germany)

    2016-11-01

    Highlights: • Electrochemical Machining is an appropriate tool for tungsten shaping. • Progress in shaping achieved by combination of ECM with advanced micro-lithography. • Application in First Wall for connection of plasma facing material to breeder blanket. • Successful development of adhesion promotors by ECM for plasma spraying interlayers. • Microstructure electrochemical manufacturing of tungsten in sizes of 100 μm achieved. - Abstract: Plasma facing components for fusion applications must have to exhibit long-term stability under extreme physical conditions, and therefore any material imperfections caused by mechanical and/or thermal stresses in the shaping processes cannot be tolerated due to a high risk of possible technical failures under fusion conditions. To avoid such defects, the method of Electrochemical Machining (ECM) enables a complete defect-free processing of removal of tungsten material during the desired shaping, also for high penetration depths. Furthermore, supported by lithographic mask pretreatment, three-dimensional distinct geometric structures can be positive-imaged via the directional galvanic dissolution applying M-ECM process into the tungsten bulk material. New required applications for tungsten components, e.g. as adhesion promotors in W-surfaces to enable sure grip and bonding of thick plasma-spraying layers for blanket components, will define the way of further miniaturization of well-established millimeter dimensioned M-ECM shaping processes to dimensions of 100 μm and furthermore down to 50 μm. Besides current M-ECM limits the article describes inevitable needs of further developments for mask resists, mask materials and the resulting ECM parameters, to reach the needed accuracy in tungsten microstructure. The achieved progress and observed correlations of processing parameters will be manifested by produced demonstrators made by the new “μM”-ECM process.

  17. Chemical vapor deposition of amorphous tungsten nitride for applications in ultra-large scale interconnect technologies

    Science.gov (United States)

    Kelsey, Jean E.

    Increasing demands on computer chip technology require exploration of novel materials and deposition techniques. The driving need to reduce device dimensions without increasing device delay time has forced a move towards copper interconnects. Copper interconnects require an encapsulating barrier layer to prevent diffusion into the dielectric layer, as well as a passivation layer to protect against oxidation. One potential material for the barrier layer is tungsten nitride (WNx). Tungsten nitride is expected to perform well as a barrier because of its refractory nature and excellent thermal, chemical, and mechanical properties. In addition, it can be deposited in amorphous form. Amorphous materials have no grain boundaries, thereby making grain boundary diffusion, a fast path diffusion mechanism, impossible. In this work, a chemical vapor deposition (CVD) process was developed for the deposition of tungsten nitride. CVD was selected because it has the potential to deposit highly conformal film. High conformality is critical in a barrier layer in order to ensure viable coverage at the bottom and sides of device structures without sacrificing critical space that would be better used by the copper metal. In this manner, the total resistivity of the interconnect is minimized. The CVD WNx process was systematically optimized for film conformality, resistivity and growth rate. This was achieved by thoroughly examining film nucleation and growth characteristics, and analyzing resulting film properties. Adhesion of copper to the CVD films was qualified using stud pull tests, while X-ray diffraction was implemented to determine crystallization temperature of the amorphous phase. Additionally, diffusion barrier properties of the CVD tungsten nitride were assessed using sputter deposited copper, and compared to those of sputter deposited tungsten nitride. Thermally activated barrier failure was studied as a function of barrier thickness using Rutherford backscattering

  18. Deuterium Depth Profile in Neutron-Irradiated Tungsten Exposed to Plasma

    Energy Technology Data Exchange (ETDEWEB)

    Masashi Shimada; G. Cao; Y. Hatano; T. Oda; Y. Oya; M. Hara; P. Calderoni

    2011-05-01

    The effect of radiation damage has been mainly simulated using high-energy ion bombardment. The ions, however, are limited in range to only a few microns into the surface. Hence, some uncertainty remains about the increase of trapping at radiation damage produced by 14 MeV fusion neutrons, which penetrate much farther into the bulk material. With the Japan-US joint research project: Tritium, Irradiations, and Thermofluids for America and Nippon (TITAN), the tungsten samples (99.99 % pure from A.L.M.T., 6mm in diameter, 0.2mm in thickness) were irradiated to high flux neutrons at 50 C and to 0.025 dpa in the High Flux Isotope Reactor (HFIR) at the Oak Ridge National Laboratory (ORNL). Subsequently, the neutron-irradiated tungsten samples were exposed to a high-flux deuterium plasma (ion flux: 1021-1022 m-2s-1, ion fluence: 1025-1026 m-2) in the Tritium Plasma Experiment (TPE) at the Idaho National Laboratory (INL). First results of deuterium retention in neutron-irradiated tungsten exposed in TPE have been reported previously. This paper presents the latest results in our on-going work of deuterium depth profiling in neutron-irradiated tungsten via nuclear reaction analysis. The experimental data is compared with the result from non neutron-irradiated tungsten, and is analyzed with the Tritium Migration Analysis Program (TMAP) to elucidate the hydrogen isotope behavior such as retention and depth distribution in neutron-irradiated and non neutron-irradiated tungsten.

  19. Determination of absolute population densities of eroded tungsten in hollow cathode lamps and fluorescent lamps by laser-induced fluorescence

    Energy Technology Data Exchange (ETDEWEB)

    Hadrath, S [Institute of Low-Temperature Plasma Physics, Friedrich-Ludwig-Jahn-Str. 19, D-17489 Greifswald (Germany); Ehlbeck, J [Institute of Low-Temperature Plasma Physics, Friedrich-Ludwig-Jahn-Str. 19, D-17489 Greifswald (Germany); Lieder, G [Research Light Sources, Osram GmbH, Hellabrunner Str. 1, D 81536 Muenchen (Germany); Sigeneger, F [Institute of Low-Temperature Plasma Physics, Friedrich-Ludwig-Jahn-Str. 19, D-17489 Greifswald (Germany)

    2005-09-07

    The high energy ion bombardment during instant start of a fluorescent lamp (FL) leads to intense sputtering of the electrode material including tungsten and emitter. Thus, a cold started FL often suffers from early failures due to coil fracture. The main goal of this paper is to investigate tungsten erosion. We have employed the ultra-sensitive method of laser-induced fluorescence. This technique is particularly well-suited to determining absolute population densities of neutral and singly ionized atoms of liberated electrode material. In addition to FL, our investigations have been performed also on hollow cathode lamps (HCLs). These are useful because they provide a variable source of sputtered tungsten atoms and can serve as tuning tools for precise adjustment of the laser radiation. We will present absolute atomic tungsten population densities in a commercial FL and in an HCL. Furthermore, the results of a theoretical investigation of the argon plasma and the tungsten density in the HCL are represented.

  20. Spark Plasma Sintering of high-strength ultrafine-grained tungsten carbide

    Science.gov (United States)

    Nokhrin, A. V.; Chuvil'deev, V. N.; Blagoveshchenskiy, Yu V.; Boldin, M. S.; Sakharov, N. V.; Isaeva, N. V.; Popov, A. A.; Lantcev, E. A.; Belkin, O. A.; Smirnova, E. S.

    2017-07-01

    The paper dwells on the research conducted into high-rate consolidation of pure tungsten carbide nanopowders using the Spark Plasma Sintering. Studies included the effect that the original size of WC nanoparticles and their preparation modes have on density, structure parameters, and mechanical properties of tungsten carbide. It has been found that materials that show abnormal grain growth during sintering have lower values of sintering activation energy as compared to materials the structure of which is more stable during high-rate heating. A qualitative model is proposed that explains this effect through the dependence of the grain boundary diffusion coefficient on the grain boundary migration rate.