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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 single-site monohydride silica-supported zirconium from azazirconacyclopropane

    KAUST Repository

    Hamzaoui, Bilel; El Eter, Mohamad; Abou-Hamad, Edy; Chen, Yin; Pelletier, Jeremie; Basset, Jean-Marie

    2015-01-01

    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.

  4. 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.

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

    KAUST Repository

    Hamzaoui, Bilel; Pelletier, Jeremie; Abou-Hamad, Edy; Basset, Jean-Marie

    2016-01-01

    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.

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

    KAUST Repository

    Werghi, Baraa; Bendjeriou-Sedjerari, Anissa; Sofack-Kreutzer, Julien; Jedidi, Abdesslem; Abou-Hamad, Edy; Cavallo, Luigi; Basset, Jean-Marie

    2015-01-01

    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.

  7. 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.

  8. A Silica-Supported Monoalkylated Tungsten Dioxo Complex Catalyst for Olefin Metathesis

    KAUST Repository

    Maity, Niladri

    2018-02-15

    A well-defined silica-supported monoalkylated tungsten dioxo complex [(Si-O-)W(=O)(CH-Bu)] was prepared by treatment of highly dehydroxylated silica (SiO: silica treated at 700 °C under high vacuum) with an ionic precursor complex [NEt][W(=O)(CH-Bu)]. The identity of the resulting neutral monoalkylated tungsten dioxo surface complex was established by means of elemental microanalysis and spectroscopic studies (IR, solid-state NMR, Raman, and X-ray absorption spectroscopies). The supported tungsten complex was found to act as a precatalyst for the self-metathesis of 1-octene in a batch reactor. The mechanistic implications of this reaction are discussed with the support of DFT calculations highlighting the potential occurrence of thus-far unexplored mechanistic pathways.

  9. A Silica-Supported Monoalkylated Tungsten Dioxo Complex Catalyst for Olefin Metathesis

    KAUST Repository

    Maity, Niladri; Barman, Samir; Minenkov, Yury; Ould-Chikh, Samy; Abou-Hamad, Edy; Ma, Tao; Qureshi, Ziyauddin; Cavallo, Luigi; D'Elia, Valerio; Gates, Bruce C.; Basset, Jean-Marie

    2018-01-01

    A well-defined silica-supported monoalkylated tungsten dioxo complex [(Si-O-)W(=O)(CH-Bu)] was prepared by treatment of highly dehydroxylated silica (SiO: silica treated at 700 °C under high vacuum) with an ionic precursor complex [NEt][W(=O)(CH-Bu)]. The identity of the resulting neutral monoalkylated tungsten dioxo surface complex was established by means of elemental microanalysis and spectroscopic studies (IR, solid-state NMR, Raman, and X-ray absorption spectroscopies). The supported tungsten complex was found to act as a precatalyst for the self-metathesis of 1-octene in a batch reactor. The mechanistic implications of this reaction are discussed with the support of DFT calculations highlighting the potential occurrence of thus-far unexplored mechanistic pathways.

  10. 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.

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

    KAUST Repository

    Hamzaoui, Bilel; Pelletier, Jé ré mie D. A.; El Eter, Mohamad; Chen, Yin; Abou-Hamad, Edy; Basset, Jean-Marie

    2015-01-01

    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.

  12. 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.

  13. 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.

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

    KAUST Repository

    Merle, Nicolas; Le Qué mé ner, Fré dé ric; Barman, Samir; Samantaray, Manoja; Szeto, Kai C.; De Mallmann, Aimery; Taoufik, Mostafa; Basset, Jean-Marie

    2017-01-01

    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.

  15. 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; Merle, Nicolas; Mallmann, Aimery De; Basset, Jean-Marie; Berrier, Elise; Delevoye, Laurent; Paul, Jean Franois; Nicholas, Christopher P.; Gauvin, Ré gis M.; Taoufik, Mostafa

    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.

  16. 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.

  17. [(≢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; Callens, Emmanuel; Abou-Hamad, Edy; Merle, Nicolas; White, Andrew J P; Taoufik, Mostafa; Copé ret, Christophe; Le Roux, Erwan; Basset, Jean-Marie

    2012-01-01

    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.

  18. [(≢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.

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

    KAUST Repository

    Saidi, Aya; Samantaray, Manoja; Tretiakov, Mykyta; Kavitake, Santosh Giridhar; Basset, Jean-Marie

    2017-01-01

    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)(CH2

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

    KAUST Repository

    Pelletier, Jé ré mie; Espinas, Jeff; Vu, Nghiem; Norsic, Sé bastien; Baudouin, Anne; Delevoye, Laurent; Tré bosc, Julien; Le Roux, Erwan; Santini, Catherine; Basset, Jean-Marie; Gauvin, Ré gis M.; Taoufik, Mostafa

    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.

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

    KAUST Repository

    Maity, Niladri; Barman, Samir; Callens, Emmanuel; Samantaray, Manoja K.; Abou-Hamad, Edy; Minenkov, Yury; D'Elia, Valerio; Hoffman, Adam S.; Widdifield, Cory M.; Cavallo, Luigi; Gates, Bruce C.; Basset, Jean-Marie

    2015-01-01

    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.

  2. 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.

  3. 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.

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

    KAUST Repository

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

    2017-01-01

    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.

  5. 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.

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

    KAUST Repository

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

    2016-01-01

    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.

  7. 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

    2016-01-01

    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

  8. 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.

  9. 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; Dey, Raju; Samantaray, Manoja; Abdel-Azeim, Safwat; Abou-Hamad, Edy; Chen, Yin; Pelletier, Jeremie; Cavallo, Luigi; Basset, Jean-Marie

    2016-01-01

    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.

  10. 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.

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

    KAUST Repository

    Merle, Nicolas; Le Qué mé ner, Fré dé ric; Bouhoute, Yassine; Szeto, Kai C.; De Mallmann, Aimery; Barman, Samir; Samantaray, Manoja; Delevoye, Laurent; Gauvin, Ré gis M.; Taoufik, Mostafa; Basset, Jean-Marie

    2016-01-01

    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.

  12. 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.

  13. 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.

  14. Tungsten

    International Nuclear Information System (INIS)

    Eschnauer, H.

    1978-01-01

    There is no substitute for tungsten in its main field of application so that the demand will not decrease, but there is a need for further important applications. If small variations are left out of account, a small but steady increase in the annual tungsten consumption can be expected. The amount of tungsten available will increase due to the exploritation of new deposits and the extension of existing mines. This tendency will probably be increased by the world-wide prospection. It is hard to make an assessment of the amount of tungsten are obtained in the People's Republic of china, the purchases of Eastern countries in the West, and the sales policy of the USA; pice forecasts are therefore hard to make. A rather interesting subject with regard to the tungsten cycle as a whole is the reprocessing of tungsten-containing wastes. (orig.) [de

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

    KAUST Repository

    Samantaray, Manoja; Dey, Raju; Kavitake, Santosh Giridhar; Abou-Hamad, Edy; Bendjeriou-Sedjerari, Anissa; Hamieh, Ali Imad Ali; Basset, Jean-Marie

    2016-01-01

    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

  16. 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.

  17. 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.

  18. 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; Chen, Yin; Abdel-Azeim, Safwat; Abou-Hamad, Edy; Goh, Li Min Serena; Samantaray, Manoja; Dey, Raju; Cavallo, Luigi; Basset, Jean-Marie

    2015-01-01

    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.

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

    KAUST Repository

    Hamzaoui, Bilel; Pelletier, Jeremie; Abou-Hamad, Edy; Chen, Yin; El Eter, Mohamad; Chermak, Edrisse; Cavallo, Luigi; Basset, Jean-Marie

    2016-01-01

    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

  20. 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...... conjugates and their use in vaccination, production of antibodies, high throughput screening, diagnostic assays and libraries....

  1. 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.

  2. 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.

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

    KAUST Repository

    Zhao, Wei; Gnanou, Yves; Hadjichristidis, Nikolaos

    2016-01-01

    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.

  4. 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.

  5. 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; Callens, Emmanuel; Abou-Hamad, Edy; Rossini, Aaron J.; Widdifield, Cory M.; Dey, Raju; Emsley, Lyndon; Basset, Jean-Marie

    2014-01-01

    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.

  6. Volumetric flame synthesis of well-defined molybdenum oxide nanocrystals.

    Science.gov (United States)

    Merchan-Merchan, Wilson; Saveliev, Alexei V; Desai, Milind

    2009-11-25

    Well-defined faceted inorganic Mo oxide nanocrystals are synthesized in the gas phase using a solid-fed-precursor flame synthesis method. The solid crystals have rectangular cross-section with characteristic size of 10-20 nm and with lengths ranging from 50 nm to a few hundred nanometres. A 1 mm diameter high purity Mo probe introduced in the oxygen-rich part of the flame serves as the material source. A combination of the strong temperature gradient and varying chemical species concentrations within the flame volume provides the ideal conditions for the rapid and direct formation of these unique nanocrystals. Oxidation and evaporation of MoO3 in the oxygen-rich zone are followed by reduction to MoO2 in the lower temperature, more fuel-rich zone. The MoO3 vapours formed are pushed in the direction of the gas flow and transformed into mature well-defined convex polyhedron nanocrystals bounded with six faces resembling rectangular parallelepipeds.

  7. Performance considerations of ultrasonic distance measurement with well defined properties

    International Nuclear Information System (INIS)

    Elmer, Hannes; Schweinzer, Herbert

    2005-01-01

    Conventional ultrasonic distance measurement systems based on narrow bandwidth ultrasonic bursts and amplitude detection are often used because of their low costs and easy implementation. However, the achievable results strongly depend on the actual environments where the system is implemented: in case of well defined objects that are always located near the measurement direction of the system, in general good results are obtained. If arbitrary objects are expected that are moreover located in arbitrary positions in front of the sensor, strongly object dependent areas where objects are detected with decreasing accuracy towards their borders must be taken into account. In previous works we developed an ultrasonic measurement system that provides accurate distance measurement values within a well defined detection area that is independent of the reflection properties of the objects. This measurement system is based on the One Bit Correlation method that is described in the following. To minimise its implementation efforts, it is necessary to examine the influence of the system parameters as e.g. the correlation length to the results that are expected in case of different signal to noise ratios of the received signal. In the following, these examinations are shown and the obtained results are discussed that allow getting a well conditioned system that makes best use of given system resources

  8. Synthesis of well-defined polystyrene macrophotoinitiators by ATRP

    International Nuclear Information System (INIS)

    Degirmenci, M.

    2004-01-01

    Macrophotointiators are polymers with a photoinitiator functionality at side chains or in the end or middle of the chain. these materials are of great scientific and technological interest because of their application in UV-curable coatings and as precursors for graft and block copolymers depending on the position of the photoinitiator moiety incorporated. Many macrophotoinitiators have been synthesized and their utilization in both applications have been studied. The major concern for their uses particulary in the latter application was related to the efficiency of functionalization, well-defined and predetermined structures, and low polydispersities. Obviously, if the all chains are not functionalized, upon irradiation non-funtionalized chains will not be activated and consequently remain as homopolymers in the system. In this study, new mono and bifunctional atom transfer radical polymerization (ATRP) initionars were synthesized by the condensation of 2-bromopropanoyl bromide with 2-hydroxy-2-methyl-1-phenyl propan-1-one (HMPP) and 2-hydroxy-1-(4-(2-hydroxyethoxy) phenyl)-2-methyl propan-1-one (HE-HMPP), respectively and characterized. The ATRP of styrene (St) in bulk at 110 degrees by means of these initiators in conjunction with a cuprous complex Cu(I) Br/bipyridine yields polystyrenes with photoactive alkoxy phenylketone groups. GPC, spectroscopic and photodegradation studies revealed that the initiation efficiency was quantitative and low-polydispersity polystyrenes with photoinitiator functionality in the end or middle of chain were obtained

  9. Silica-supported silicotungstic acid: A study by X-ray photoelectron spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Berry, Frank J.; Derrick, Glyn R. [Department of Chemistry and Analytical Sciences, Robert Hooke Building, Open University, Walton Hall, Milton Keynes, MK7 6AA (United Kingdom); Marco, Jose F. [Instituto de Quimica -Fisica ' Rocasolano' , Consejo Superior de Investigaciones Cientificas, Serrano 119, 28006 Madrid (Spain); Mortimer, Michael [Department of Chemistry and Analytical Sciences, Robert Hooke Building, Open University, Walton Hall, Milton Keynes, MK7 6AA (United Kingdom)], E-mail: m.mortimer@open.ac.uk

    2009-04-15

    W 4f and O 1s X-ray photoelectron spectra for silicotungstic acid, H{sub 4}SiW{sub 12}O{sub 40}, in pure and silica-supported form are reported. W 4f XP spectra for the supported acid are analysed in terms of contributions from two W(VI) spin-orbit doublets arising from tungsten atoms in terminal W=O bonds some of which directly interact with the silica surface. At low loading (3.2 wt.%) significant changes in the relative contributions and binding energies of the two spin-orbit doublets are taken as evidence of a strong interaction of individual [SiW{sub 12}O{sub 40}]{sup 4-} anions with highly active sites on the silica surface. It is suggested that selective ordering of silanol groups can occur on the silica surface in order to accommodate the adsorption of individual [SiW{sub 12}O{sub 40}]{sup 4-} anions.

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

    KAUST Repository

    Samantaray, Manoja; Kavitake, Santosh Giridhar; Morlanes, Natalia Sanchez; Abou-Hamad, Edy; Hamieh, Ali Imad Ali; Dey, Raju; Basset, Jean-Marie

    2017-01-01

    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.

  11. 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.

  12. 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

  13. 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.

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

    KAUST Repository

    Alyami, Mram Z.

    2016-01-01

    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

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

    KAUST Repository

    Riache, Nassima; Callens, Emmanuel; Talbi, Karima; Basset, Jean-Marie

    2015-01-01

    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

  16. 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.

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

    KAUST Repository

    Barman, Samir; Merle, Nicolas; Minenkov, Yury; De Mallmann, Aimery; Samantaray, Manoja; Le Qué mé ner, Fré dé ric; Szeto, Kai C.; Abou-Hamad, Edy; Cavallo, Luigi; Taoufik, Mostafa; Basset, Jean-Marie

    2017-01-01

    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.

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

    KAUST Repository

    Polymeropoulos, George; Bilalis, Panayiotis; Hadjichristidis, Nikolaos

    2016-01-01

    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

  19. Glycerol valorization: dehydration to acrolein over silica-supported niobia catalysts

    NARCIS (Netherlands)

    Shiju, N.R.; Brown, D.R.; Wilson, K.; Rothenberg, G.

    2010-01-01

    The catalytic dehydration of glycerol to acrolein is investigated over silica-supported niobia catalysts in a continuous fixed-bed gas-phase reactor. Various supported niobia catalysts are prepared and characterized using surface analysis and spectroscopic methods (XRD, UV-Vis, XPS, N2 adsorption),

  20. Ligand-tailored single-site silica supported titanium catalysts: Synthesis, characterization and towards cyanosilylation reaction

    International Nuclear Information System (INIS)

    Xu, Wei; Li, Yani; Yu, Bo; Yang, Jindou; Zhang, Ying; Chen, Xi; Zhang, Guofang; Gao, Ziwei

    2015-01-01

    A successive anchoring of Ti(NMe 2 ) 4 , cyclopentadiene and a O-donor ligand, 1-hydroxyethylbenzene (PEA), 1,1′-bi-2-naphthol (Binol) or 2,3-dihydroxybutanedioic acid diethyl ester (Tartrate), on silica was conducted by SOMC strategy in moderate conditions. The silica, monitored by in-situ Fourier transform infrared spectroscopy (in-situ FT-IR), was pretreated at different temperatures (200, 500 and 800 °C). The ligand tailored silica-supported titanium complexes were characterized by in-situ FT-IR, 13 C CP MAS-NMR, X-ray photoelectron spectroscopy (XPS), X-ray absorption near edge structure (XANES) and elemental analysis in detail, verifying that the surface titanium species are single sited. The catalytic activity of the ligand tailored single-site silica supported titanium complexes was evaluated by a cyanosilylation of benzaldehyde. The results showed that the catalytic activity is dependent strongly on the dehydroxylation temperatures of silica and the configuration of the ligands. - Graphical abstract: The ligand-tailored silica supported “single site” titanium complexes were synthesized by SOMC strategy and fully characterized. Their catalytic activity were evaluated by benzaldehyde silylcyanation. - Highlights: • Single-site silica supported Ti active species was prepared by SOMC technique. • O-donor ligand tailored Ti surface species was synthesized. • The surface species was characterized by XPS, 13 C CP-MAS NMR, XANES etc. • Catalytic activity of the Ti active species in silylcyanation reaction was evaluated

  1. 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) w...

  2. 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.

  3. Silica supported palladium nanoparticles for the decarboxylation of high-acid feedstocks: Design, deactivation and regeneration

    Science.gov (United States)

    Ping, Eric Wayne

    2011-12-01

    The major goals of this thesis were to (1) design and synthesize a supported catalyst with well-defined monodisperse palladium nanoparticles evenly distributed throughout an inorganic oxide substrate with tunable porosity characteristics, (2) demonstrate the catalytic activity of this material in the decarboxylation of long chain fatty acids and their derivatives to make diesel-length hydrocarbons, (3) elucidate the deactivation mechanism of supported palladium catalysts under decarboxylation conditions via post mortem catalyst characterization and develop a regeneration methodology thereupon, and (4) apply this catalytic system to a real low-value biofeedstock. Initial catalyst designs were based on the SBA-15 silica support, but in an effort to maximize loading and minimize mass transfer limitations, silica MCF was synthesized as catalyst support. Functionalization with various silane ligands yielded a surface that facilitated even distribution of palladium precursor salts throughout the catalyst particle, and, after reduction, monodisperse palladium nanoparticles approximately 2 nm in diameter. Complete characterization was performed on this Pd-MCF catalyst. The Pd-MCF catalyst showed high one-time activity in the decarboxylation of fatty acids to hydrocarbons in dodecane at 300°C. Hydrogen was found to be an unnecessary reactant in the absence of unsaturations, but was required in their presence---full hydrogenation of the double bonds occurs before any decarboxylation can take place. The Pd-MCF also exhibited good activity for alkyl esters and glycerol, providing a nice hypothetical description of a stepwise reaction pathway for catalytic decarboxylation of acids and their derivatives. As expected, the Pd-MCF catalyst experienced severe deactivation after only one use. Substantial effort was put into elucidating the nature of this deactivation via post mortem catalyst characterization. H2 chemisorption confirmed a loss of active surface area, but TEM and

  4. Advances in supramolecular polymer chemistry : well-defined terpyridine-functionalized materials

    NARCIS (Netherlands)

    Ott, C.

    2008-01-01

    Controlled/"living" polymerization techniques have attracted enormous attention in the field of polymer science since they have opened an avenue to the preparation of well-defined materials with precisely designed molecular architectures like random, block, graft and comb copolymers. These

  5. Typicality Mediates Performance during Category Verification in Both Ad-Hoc and Well-Defined Categories

    Science.gov (United States)

    Sandberg, Chaleece; Sebastian, Rajani; Kiran, Swathi

    2012-01-01

    Background: The typicality effect is present in neurologically intact populations for natural, ad-hoc, and well-defined categories. Although sparse, there is evidence of typicality effects in persons with chronic stroke aphasia for natural and ad-hoc categories. However, it is unknown exactly what influences the typicality effect in this…

  6. Well-defined single-chain polymer nanoparticles via thiol-Michael addition

    NARCIS (Netherlands)

    Kröger, A. Pia P.; Boonen, Roy J.E.A.; Paulusse, Jos M.J.

    2017-01-01

    A synthetic strategy has been developed giving facile access to well-defined single-chain polymer nanoparticles (SCNPs) from styrene-, acrylate- and methacrylate-based polymers. Random copolymers (polydispersity indices 1.10–1.15) of methyl (meth)acrylate, benzyl methacrylate or styrene containing

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

    KAUST Repository

    Ntaras, Christos; Polymeropoulos, George; Zapsas, George; Ntetsikas, Konstantinos; Liontos, George; Karanastasis, Apostolos; Moschovas, Dimitrios; Rangou, Sofia; Stewart-Sloan, Charlotte; Hadjichristidis, Nikolaos; Thomas, Edwin L.; Avgeropoulos, Apostolos

    2016-01-01

    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

  8. Predicting catalyst-support interactions between metal nanoparticles and amorphous silica supports

    Science.gov (United States)

    Ewing, Christopher S.; Veser, Götz; McCarthy, Joseph J.; Lambrecht, Daniel S.; Johnson, J. Karl

    2016-10-01

    Metal-support interactions significantly affect the stability and activity of supported catalytic nanoparticles (NPs), yet there is no simple and reliable method for estimating NP-support interactions, especially for amorphous supports. We present an approach for rapid prediction of catalyst-support interactions between Pt NPs and amorphous silica supports for NPs of various sizes and shapes. We use density functional theory calculations of 13 atom Pt clusters on model amorphous silica supports to determine linear correlations relating catalyst properties to NP-support interactions. We show that these correlations can be combined with fast discrete element method simulations to predict adhesion energy and NP net charge for NPs of larger sizes and different shapes. Furthermore, we demonstrate that this approach can be successfully transferred to Pd, Au, Ni, and Fe NPs. This approach can be used to quickly screen stability and net charge transfer and leads to a better fundamental understanding of catalyst-support interactions.

  9. Ligand-tailored single-site silica supported titanium catalysts: Synthesis, characterization and towards cyanosilylation reaction

    Energy Technology Data Exchange (ETDEWEB)

    Xu, Wei; Li, Yani; Yu, Bo; Yang, Jindou; Zhang, Ying; Chen, Xi; Zhang, Guofang, E-mail: gfzhang@snnu.edu.cn; Gao, Ziwei, E-mail: zwgao@snnu.edu.cn

    2015-01-15

    A successive anchoring of Ti(NMe{sub 2}){sub 4}, cyclopentadiene and a O-donor ligand, 1-hydroxyethylbenzene (PEA), 1,1′-bi-2-naphthol (Binol) or 2,3-dihydroxybutanedioic acid diethyl ester (Tartrate), on silica was conducted by SOMC strategy in moderate conditions. The silica, monitored by in-situ Fourier transform infrared spectroscopy (in-situ FT-IR), was pretreated at different temperatures (200, 500 and 800 °C). The ligand tailored silica-supported titanium complexes were characterized by in-situ FT-IR, {sup 13}C CP MAS-NMR, X-ray photoelectron spectroscopy (XPS), X-ray absorption near edge structure (XANES) and elemental analysis in detail, verifying that the surface titanium species are single sited. The catalytic activity of the ligand tailored single-site silica supported titanium complexes was evaluated by a cyanosilylation of benzaldehyde. The results showed that the catalytic activity is dependent strongly on the dehydroxylation temperatures of silica and the configuration of the ligands. - Graphical abstract: The ligand-tailored silica supported “single site” titanium complexes were synthesized by SOMC strategy and fully characterized. Their catalytic activity were evaluated by benzaldehyde silylcyanation. - Highlights: • Single-site silica supported Ti active species was prepared by SOMC technique. • O-donor ligand tailored Ti surface species was synthesized. • The surface species was characterized by XPS, {sup 13}C CP-MAS NMR, XANES etc. • Catalytic activity of the Ti active species in silylcyanation reaction was evaluated.

  10. Synthesis and self-assembly of well-defined block copolypeptides via controlled NCA polymerization

    OpenAIRE

    Deming, TJ

    2013-01-01

    This article summarizes advances in the synthesis of well-defined polypeptides and block copolypeptides. Traditional methods used to polymerize α-amino acid-N-carboxyanhydrides (NCAs) are described, and limitations in the utility of these systems for the preparation of polypeptides are discussed. Improved initiators and methods that allow polypeptide synthesis with good control over chain length, chain length distribution, and chain-end functionality are also discussed. Using these methods, b...

  11. Well-defined azazirconacyclopropane complexes supported on silica structurally determined by 2D NMR comparative elucidation

    KAUST Repository

    El Eter, Mohamad; Hamzaoui, Bilel; Abou-Hamad, Edy; Pelletier, Jeremie; Basset, Jean-Marie

    2013-01-01

    Grafting of Zr(NMe2)4 on mesoporous silica SBA-15 afforded selectively well-defined surface species SiOZr(NMe2) (η2NMeCH2). 2D solid-state NMR (1H- 13C HETCOR, Multiple Quantum) experiments have shown a unique structural rearrangement occurring on the immobilised zirconium bis methylamido ligand. © The Royal Society of Chemistry 2013.

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

    KAUST Repository

    Zhang, Hefeng; Gnanou, Yves; Hadjichristidis, Nikolaos

    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.

  13. 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.

  14. 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.

  15. 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.

  16. 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; Abou-Hamad, Edy; Hamieh, Ali Imad Ali; Hamzaoui, Bilel; Emsley, Lyndon; Basset, Jean-Marie

    2015-01-01

    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.

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

    KAUST Repository

    Saggio, Guillaume; Taoufik, Mostafa; Basset, Jean-Marie; Thivolle-Cazat, Jean

    2010-01-01

    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

  19. D’Andrea’s disease (angiomegaly): a currently well-defined nosological entitys.

    Science.gov (United States)

    Taurone, S; Spoletini, M; Di Matteo, F M; Mele, R; Tromba, L; Grippaudo, F R; Minni, A; Artico, M

    2017-01-01

    In 1997 D’Andrea et al. described a new nosological entity the characteristics of which consisted of lengthening, dilation and tortuosity of blood vessels, arteries or veins, less prominent, but also less circumscribed than an aneurysm. This condition does not necessarily imply specific aneurysm formation although aneurysms at multiple sites are a frequent observation. The term used by authors for angiomegaly of the venous system was venomegaly and the analogous condition of the arterial system was termed arteriomegaly. Although tortuosity and dilation of arteries and veins have been widely reported, suggesting a systemic disorder which affects the structural integrity of all vessels, most papers dealing with this intriguing condition did not describe any alterations in the components of vessel walls. In the present paper, the authors describe a well-defined condition, D’Andrea’s Disease (or DD, in this article), analyzing its salient morphological and clinical features and clarifying this pathological condition as a distinct and now well-defined nosological entity.

  20. Small angle neutron scattering study of polyelectrolyte brushes grafted to well-defined gold nanoparticle interfaces.

    Science.gov (United States)

    Jia, Haidong; Grillo, Isabelle; Titmuss, Simon

    2010-05-18

    Small angle neutron scattering (SANS) has been used to study the conformations, and response to added salt, of a polyelectrolyte layer grafted to the interfaces of well-defined gold nanoparticles. The polyelectrolyte layer is prepared at a constant coverage by grafting thiol-functionalized polystyrene (M(w) = 53k) to gold nanoparticles of well-defined interfacial curvature (R(c) = 26.5 nm) followed by a soft-sulfonation of 38% of the segments to sodium polystyrene sulfonate (NaPSS). The SANS profiles can be fit by Fermi-Dirac distributions that are consistent with a Gaussian distribution but are better described by a parabolic distribution plus an exponential tail, particularly in the high salt regime. These distributions are consistent with the predictions and measurements for osmotic and salted brushes at interfaces of low curvature. When the concentration of added salt exceeds the concentration of counterions inside the brush, there is a salt-induced deswelling, but even at the highest salt concentration the brush remains significantly swollen due to a short-ranged excluded volume interaction. This is responsible for the observed resistance to aggregation of these comparatively high concentration polyelectrolyte stabilized gold nanoparticle dispersions even in the presence of a high concentration of added salt.

  1. 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.

  2. Synthesis of an oxo trialkyl tungsten fluoride complex and its dual reactivity with silica dehydroxylated at high temperature

    KAUST Repository

    Merle, Nicolas

    2018-05-22

    The novel complex W (=O)Np3F has been prepared by fluorination of the corresponding chloride counterpart with AgBF4. The reactivity of this complex with silica dehydroxylated at 700 °C afforded a well-defined silica supported monopodal tungsten oxo trialkyl surface species (≡SiO)W (=O)Np3. The reaction proceeds both through silanolysis of the W-F bond and opening of a siloxane bridge, with formation of a Si-F fragment, thanks to the affinity of silicon for fluoride. The resulting surface species was characterized by elemental analysis, DRIFT, solid state NMR and EXAFS spectroscopy. This material presenting fluorine on its surface shows an enhanced catalytic activity in propylene self-metathesis compared to its monopodal counterpart (≡SiO)W (=O)Np3 (prepared from W (=O)Np3Cl) suggesting that the Si-F in a close vicinity to the W decreases the electron density of the W and thus increases its reactivity towards the olefinic substrate.

  3. Synthesis of an oxo trialkyl tungsten fluoride complex and its dual reactivity with silica dehydroxylated at high temperature

    KAUST Repository

    Merle, Nicolas; Mazoyer, Etienne; Szeto, Kai C.; Rouge, Pascal; de Mallmann, Aimery; Berrier, Elise; Delevoye, Laurent; Gauvin, Ré gis M.; Nicholas, Christopher P.; Basset, Jean-Marie; Taoufik, Mostafa

    2018-01-01

    The novel complex W (=O)Np3F has been prepared by fluorination of the corresponding chloride counterpart with AgBF4. The reactivity of this complex with silica dehydroxylated at 700 °C afforded a well-defined silica supported monopodal tungsten oxo trialkyl surface species (≡SiO)W (=O)Np3. The reaction proceeds both through silanolysis of the W-F bond and opening of a siloxane bridge, with formation of a Si-F fragment, thanks to the affinity of silicon for fluoride. The resulting surface species was characterized by elemental analysis, DRIFT, solid state NMR and EXAFS spectroscopy. This material presenting fluorine on its surface shows an enhanced catalytic activity in propylene self-metathesis compared to its monopodal counterpart (≡SiO)W (=O)Np3 (prepared from W (=O)Np3Cl) suggesting that the Si-F in a close vicinity to the W decreases the electron density of the W and thus increases its reactivity towards the olefinic substrate.

  4. Silica-Supported Catalyst for Enantioselective Arylation of Aldehydes under Batch and Continuous-Flow Conditions.

    Science.gov (United States)

    Watanabe, Satoshi; Nakaya, Naoyuki; Akai, Junichiro; Kanaori, Kenji; Harada, Toshiro

    2018-05-04

    A silica-supported 3-aryl H 8 -BINOL-derived titanium catalyst exhibited high performance in the enantioselective arylation of aromatic aldehydes using Grignard and organolithium reagents not only under batch conditions but also under continuous-flow conditions. Even with a simple pipet reactor packed with the heterogeneous catalyst, the enantioselective production of chiral diarylmethanols could be achieved through a continuous introduction of aldehydes and mixed titanium reagents generated from the organometallic precursors. The pipet reactor could be used repeatedly in different reactions without appreciable deterioration of the activity.

  5. 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.

  6. Self-Assembly of Hierarchical DNA Nanotube Architectures with Well-Defined Geometries.

    Science.gov (United States)

    Jorgenson, Tyler D; Mohammed, Abdul M; Agrawal, Deepak K; Schulman, Rebecca

    2017-02-28

    An essential motif for the assembly of biological materials such as actin at the scale of hundreds of nanometers and beyond is a network of one-dimensional fibers with well-defined geometry. Here, we demonstrate the programmed organization of DNA filaments into micron-scale architectures where component filaments are oriented at preprogrammed angles. We assemble L-, T-, and Y-shaped DNA origami junctions that nucleate two or three micron length DNA nanotubes at high yields. The angles between the nanotubes mirror the angles between the templates on the junctions, demonstrating that nanoscale structures can control precisely how micron-scale architectures form. The ability to precisely program filament orientation could allow the assembly of complex filament architectures in two and three dimensions, including circuit structures, bundles, and extended materials.

  7. Bottom-Up Engineering of Well-Defined 3D Microtissues Using Microplatforms and Biomedical Applications.

    Science.gov (United States)

    Lee, Geon Hui; Lee, Jae Seo; Wang, Xiaohong; Lee, Sang Hoon

    2016-01-07

    During the last decades, the engineering of well-defined 3D tissues has attracted great attention because it provides in vivo mimicking environment and can be a building block for the engineering of bioartificial organs. In this Review, diverse engineering methods of 3D tissues using microscale devices are introduced. Recent progress of microtechnologies has enabled the development of microplatforms for bottom-up assembly of diverse shaped 3D tissues consisting of various cells. Micro hanging-drop plates, microfluidic chips, and arrayed microwells are the typical examples. The encapsulation of cells in hydrogel microspheres and microfibers allows the engineering of 3D microtissues with diverse shapes. Applications of 3D microtissues in biomedical fields are described, and the future direction of microplatform-based engineering of 3D micro-tissues is discussed. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Negative magnetoresistance without well-defined chirality in the Weyl semimetal TaP.

    Science.gov (United States)

    Arnold, Frank; Shekhar, Chandra; Wu, Shu-Chun; Sun, Yan; Dos Reis, Ricardo Donizeth; Kumar, Nitesh; Naumann, Marcel; Ajeesh, Mukkattu O; Schmidt, Marcus; Grushin, Adolfo G; Bardarson, Jens H; Baenitz, Michael; Sokolov, Dmitry; Borrmann, Horst; Nicklas, Michael; Felser, Claudia; Hassinger, Elena; Yan, Binghai

    2016-05-17

    Weyl semimetals (WSMs) are topological quantum states wherein the electronic bands disperse linearly around pairs of nodes with fixed chirality, the Weyl points. In WSMs, nonorthogonal electric and magnetic fields induce an exotic phenomenon known as the chiral anomaly, resulting in an unconventional negative longitudinal magnetoresistance, the chiral-magnetic effect. However, it remains an open question to which extent this effect survives when chirality is not well-defined. Here, we establish the detailed Fermi-surface topology of the recently identified WSM TaP via combined angle-resolved quantum-oscillation spectra and band-structure calculations. The Fermi surface forms banana-shaped electron and hole pockets surrounding pairs of Weyl points. Although this means that chirality is ill-defined in TaP, we observe a large negative longitudinal magnetoresistance. We show that the magnetoresistance can be affected by a magnetic field-induced inhomogeneous current distribution inside the sample.

  9. Ligand-tailored single-site silica supported titanium catalysts: Synthesis, characterization and towards cyanosilylation reaction

    Science.gov (United States)

    Xu, Wei; Li, Yani; Yu, Bo; Yang, Jindou; Zhang, Ying; Chen, Xi; Zhang, Guofang; Gao, Ziwei

    2015-01-01

    A successive anchoring of Ti(NMe2)4, cyclopentadiene and a O-donor ligand, 1-hydroxyethylbenzene (PEA), 1,1‧-bi-2-naphthol (Binol) or 2,3-dihydroxybutanedioic acid diethyl ester (Tartrate), on silica was conducted by SOMC strategy in moderate conditions. The silica, monitored by in-situ Fourier transform infrared spectroscopy (in-situ FT-IR), was pretreated at different temperatures (200, 500 and 800 °C). The ligand tailored silica-supported titanium complexes were characterized by in-situ FT-IR, 13C CP MAS-NMR, X-ray photoelectron spectroscopy (XPS), X-ray absorption near edge structure (XANES) and elemental analysis in detail, verifying that the surface titanium species are single sited. The catalytic activity of the ligand tailored single-site silica supported titanium complexes was evaluated by a cyanosilylation of benzaldehyde. The results showed that the catalytic activity is dependent strongly on the dehydroxylation temperatures of silica and the configuration of the ligands.

  10. 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.

  11. Correlation of Theory and Function in Well-Defined Bimetallic Electrocatalysts - Final Report

    Energy Technology Data Exchange (ETDEWEB)

    Crooks, Richard M.

    2014-06-05

    The objective of this research proposal was to correlate the structure of nanoparticles that are comprised of ~100-200 atoms to their electrocatalytic function. This objective was based on the growing body of evidence suggesting that catalytic properties can be tailored through controlled synthesis of nanoparticles. What has been missing from many of these studies, and what we are contributing, is a model catalyst that is sufficiently small, structurally well-defined, and well-characterized that its function can be directly predicted by theory. Specifically, our work seeks to develop a fundamental and detailed understanding of the relationship between the structure of nanoscopic oxygen-reduction catalysts and their function. We assembled a team with expertise in theory, synthesis, and advanced characterization methods to address the primary objective of this project. We anticipated the outcomes of the study to be: (1) a better theoretical understanding of how nanoparticle structure affects catalytic properties; (2) the development of advanced, in-situ and ex-situ, atomic-scale characterization methods that are appropriate for particles containing about 100 atoms; and (3) improved synthetic methods that produce unique nanoparticle structures that can be used to test theoretical predictions. During the project period, we have made excellent progress on all three fronts.

  12. 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.

  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. Monodisperse measurement of the biotin-streptavidin interaction strength in a well-defined pulling geometry.

    Directory of Open Access Journals (Sweden)

    Steffen M Sedlak

    Full Text Available The widely used interaction of the homotetramer streptavidin with the small molecule biotin has been intensively studied by force spectroscopy and has become a model system for receptor ligand interaction. However, streptavidin's tetravalency results in diverse force propagation pathways through the different binding interfaces. This multiplicity gives rise to polydisperse force spectroscopy data. Here, we present an engineered monovalent streptavidin tetramer with a single cysteine in its functional subunit that allows for site-specific immobilization of the molecule, orthogonal to biotin binding. Functionality of streptavidin and its binding properties for biotin remain unaffected. We thus created a stable and reliable molecular anchor with a unique high-affinity binding site for biotinylated molecules or nanoparticles, which we expect to be useful for many single-molecule applications. To characterize the mechanical properties of the bond between biotin and our monovalent streptavidin, we performed force spectroscopy experiments using an atomic force microscope. We were able to conduct measurements at the single-molecule level with 1:1-stoichiometry and a well-defined geometry, in which force exclusively propagates through a single subunit of the streptavidin tetramer. For different force loading rates, we obtained narrow force distributions of the bond rupture forces ranging from 200 pN at 1,500 pN/s to 230 pN at 110,000 pN/s. The data are in very good agreement with the standard Bell-Evans model with a single potential barrier at Δx0 = 0.38 nm and a zero-force off-rate koff,0 in the 10-6 s-1 range.

  15. Monodisperse measurement of the biotin-streptavidin interaction strength in a well-defined pulling geometry.

    Science.gov (United States)

    Sedlak, Steffen M; Bauer, Magnus S; Kluger, Carleen; Schendel, Leonard C; Milles, Lukas F; Pippig, Diana A; Gaub, Hermann E

    2017-01-01

    The widely used interaction of the homotetramer streptavidin with the small molecule biotin has been intensively studied by force spectroscopy and has become a model system for receptor ligand interaction. However, streptavidin's tetravalency results in diverse force propagation pathways through the different binding interfaces. This multiplicity gives rise to polydisperse force spectroscopy data. Here, we present an engineered monovalent streptavidin tetramer with a single cysteine in its functional subunit that allows for site-specific immobilization of the molecule, orthogonal to biotin binding. Functionality of streptavidin and its binding properties for biotin remain unaffected. We thus created a stable and reliable molecular anchor with a unique high-affinity binding site for biotinylated molecules or nanoparticles, which we expect to be useful for many single-molecule applications. To characterize the mechanical properties of the bond between biotin and our monovalent streptavidin, we performed force spectroscopy experiments using an atomic force microscope. We were able to conduct measurements at the single-molecule level with 1:1-stoichiometry and a well-defined geometry, in which force exclusively propagates through a single subunit of the streptavidin tetramer. For different force loading rates, we obtained narrow force distributions of the bond rupture forces ranging from 200 pN at 1,500 pN/s to 230 pN at 110,000 pN/s. The data are in very good agreement with the standard Bell-Evans model with a single potential barrier at Δx0 = 0.38 nm and a zero-force off-rate koff,0 in the 10-6 s-1 range.

  16. Osteogenic response of human mesenchymal stem cells to well-defined nanoscale topography in vitro

    Directory of Open Access Journals (Sweden)

    de Peppo GM

    2014-05-01

    Full Text Available Giuseppe Maria de Peppo,1–3 Hossein Agheli,2,3 Camilla Karlsson,2,3 Karin Ekström,2,3 Helena Brisby,3,4 Maria Lennerås,2,3 Stefan Gustafsson,3,5 Peter Sjövall,3,5,6 Anna Johansson,2,3 Eva Olsson,3,5 Jukka Lausmaa,3,6 Peter Thomsen,2,3 Sarunas Petronis3,6 1The New York Stem Cell Foundation Research Institute, New York, NY, USA; 2Department of Biomaterials, Sahlgrenska Academy, University of Gothenburg, 3BIOMATCELL VINN Excellence Center of Biomaterials and Cell Therapy, 4Department of Orthopaedics, Sahlgrenska Academy, University of Gothenburg, 5Applied Physics, Chalmers University of Technology, Göteborg, Sweden; 6Chemistry, Materials and Surfaces, SP Technical Research Institute of Sweden, Borås, Sweden Background: Patterning medical devices at the nanoscale level enables the manipulation of cell behavior and tissue regeneration, with topographic features recognized as playing a significant role in the osseointegration of implantable devices. Methods: In this study, we assessed the ability of titanium-coated hemisphere-like topographic nanostructures of different sizes (approximately 50, 100, and 200 nm to influence the morphology, proliferation, and osteogenic differentiation of human mesenchymal stem cells (hMSCs. Results: We found that the proliferation and osteogenic differentiation of hMSCs was influenced by the size of the underlying structures, suggesting that size variations in topographic features at the nanoscale level, independently of chemistry, can be exploited to control hMSC behavior in a size-dependent fashion. Conclusion: Our studies demonstrate that colloidal lithography, in combination with coating technologies, can be exploited to investigate the cell response to well defined nanoscale topography and to develop next-generation surfaces that guide tissue regeneration and promote implant integration. Keywords: colloidal lithography, nanotopography, human mesenchymal stem cells, cell proliferation, osteogenic

  17. 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.

  18. Influence of multiple well defined conformations on small-angle scattering of proteins in solution.

    Science.gov (United States)

    Heller, William T

    2005-01-01

    A common structural motif for many proteins comprises rigid domains connected by a flexible hinge or linker. The flexibility afforded by these domains is important for proper function and such proteins may be able to adopt more than one conformation in solution under equilibrium conditions. Small-angle scattering of proteins in solution samples all conformations that exist in the sampled volume during the time of the measurement, providing an ensemble-averaged intensity. In this paper, the influence of sampling an ensemble of well defined protein structures on the small-angle solution scattering intensity profile is examined through common analysis methods. Two tests were performed using simulated data: one with the extended and collapsed states of the bilobal calcium-binding protein calmodulin and the second with the catalytic subunit of protein kinase A, which has two globular domains connected by a glycine hinge. In addition to analyzing the simulated data for the radii of gyration Rg, distance distribution function P(r) and particle volume, shape restoration was applied to the simulated data. Rg and P(r) of the ensemble profiles could be easily mistaken for a single intermediate state. The particle volumes and models of the ensemble intensity profiles show that some indication of multiple conformations exists in the case of calmodulin, which manifests an enlarged volume and shapes that are clear superpositions of the conformations used. The effect on the structural parameters and models is much more subtle in the case of the catalytic subunit of protein kinase A. Examples of how noise influences the data and analyses are also presented. These examples demonstrate the loss of the indications of multiple conformations in cases where even broad distributions of structures exist. While the tests using calmodulin show that the ensemble states remain discernible from the other ensembles tested or a single partially collapsed state, the tests performed using the

  19. Well-defined EUV wave associated with a CME-driven shock

    Science.gov (United States)

    Cunha-Silva, R. D.; Selhorst, C. L.; Fernandes, F. C. R.; Oliveira e Silva, A. J.

    2018-05-01

    Aims: We report on a well-defined EUV wave observed by the Extreme Ultraviolet Imager (EUVI) on board the Solar Terrestrial Relations Observatory (STEREO) and the Atmospheric Imaging Assembly (AIA) on board the Solar Dynamics Observatory (SDO). The event was accompanied by a shock wave driven by a halo CME observed by the Large Angle and Spectrometric Coronagraph (LASCO-C2/C3) on board the Solar and Heliospheric Observatory (SOHO), as evidenced by the occurrence of type II bursts in the metric and dekameter-hectometric wavelength ranges. We investigated the kinematics of the EUV wave front and the radio source with the purpose of verifying the association between the EUV wave and the shock wave. Methods: The EUV wave fronts were determined from the SDO/AIA images by means of two appropriate directions (slices). The heights (radial propagation) of the EUV wave observed by STEREO/EUVI and of the radio source associated with the shock wave were compared considering the whole bandwidth of the harmonic lane of the radio emission, whereas the speed of the shock was estimated using the lowest frequencies of the harmonic lane associated with the undisturbed corona, using an appropriate multiple of the Newkirk (1961, ApJ, 133, 983) density model and taking into account the H/F frequency ratio fH/fF = 2. The speed of the radio source associated with the interplanetary shock was determined using the Mann et al. (1999, A&A, 348, 614) density model. Results: The EUV wave fronts determined from the SDO/AIA images revealed the coexistence of two types of EUV waves, a fast one with a speed of 560 km s-1, and a slower one with a speed of 250 km s-1, which corresponds approximately to one-third of the average speed of the radio source ( 680 km s-1). The radio signature of the interplanetary shock revealed an almost constant speed of 930 km s-1, consistent with the linear speed of the halo CME (950 km s-1) and with the values found for the accelerating coronal shock ( 535-823 km s-1

  20. Physics and Chemistry on Well-Defined Semiconductor and Oxide Surfaces

    Science.gov (United States)

    Chen, Peijun

    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_3, PH_3 and B_ {10}H_{14} on Si(111)-(7 x 7); NH_3 on Si(100) -(2 x 1); atomic H on Si(111)-(7 x 7) and boron-modified Si(111); Al on Al_2O_3 and Sn on SiO_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 allows the elementary steps involved in these surface chemical processes to be followed on a molecular level. For adsorbate molecules such as NH_3 and PH_3, the nature of the initial low temperature (100 -300 K) adsorption is found to be dissociative, while that for B_{10}H_ {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_3 on Si(111)-(7 x 7) and Si(100)-(2 x 1), a detailed understanding on the role of substrate surface structure in 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. This discovery is potentially meaningful to the technology of gas-phase silicon etching. The

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

    KAUST Repository

    Hadjichristidis, Nikolaos; Alkayal, Nazeeha

    2015-01-01

    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

  2. Preparation of ethylene/1-hexene copolymers from ethylene using a fully silica-supported tandem catalyst system

    NARCIS (Netherlands)

    Karbach, Fabian F.; Macko, Tibor; Duchateau, Robbert

    2016-01-01

    A silica-supported tandem catalyst system, capable of producing ethylene/1-hexene copolymers from ethylene being the single monomer, has been investigated. As tandem couple a phenoxyimine titanium catalyst for ethylene trimerization was combined with a metallocene catalyst for α-olefin

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

    KAUST Repository

    Solá ns, Xavier Luis; Chow, Catherine; Gouré , Eric; Kaya, Yasemin; Basset, Jean-Marie; Taoufik, Mostafa; Quadrelli, Elsje Alessandra; Eisenstein, Odile

    2012-01-01

    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

  4. 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

  5. HDO of Methyl Palmitate over Silica-Supported Ni Phosphides: Insight into Ni/P Effect

    Directory of Open Access Journals (Sweden)

    Irina V. Deliy

    2017-10-01

    Full Text Available Two sets of silica-supported nickel phosphide catalysts with a nickel content of about 2.5 and 10 wt % and Ni/P molar ratio 2/1, 1/1 and 1/2 in each set, were prepared by way of a temperature-programmed reduction method using (Ni(CH3COO2 and ((NH42HPO4 as a precursor. The NixPy/SiO2 catalysts were characterized using chemical analysis N2 physisorption, XRD, TEM, 31P MAS NMR. Methyl palmitate hydrodeoxygenation (HDO was performed in a trickle-bed reactor at 3 MPa and 290 °C with LHSV ranging from 0.3 to 16 h−1. The Ni/P ratio was found to affect the nickel phosphide phase composition, POx groups content and catalytic properties in methyl palmitate HDO with the TOF increased along with a decline of Ni/P ratio and a growth of POx groups’ content. Taking into account the possible routes of methyl palmitate conversion (metal-catalyzed hydrogenolysis or acid-catalyzed hydrolysis, we proposed that the enhancement of acid POx groups’ content with the Ni/P ratio decrease provides an enhancement of the rate of methyl palmitate conversion through the acceleration of acid-catalyzed hydrolysis.

  6. Study of tungsten based positron moderators

    Energy Technology Data Exchange (ETDEWEB)

    Lucio, O.G. de; Pérez, M.; Mendoza, U.; Morales, J.G.; Cruz, J.C. [Instituto de Física, Universidad Nacional Autónoma de México, Apartado Postal 20-364, 01000 México DF (Mexico); DuBois, R.D. [Missouri University of Science and Technology, Rolla, MO 65409 (United States)

    2015-07-01

    Positrons and how they interact with matter has a growing interest in many fields. Most of their uses require the production of slow positron beams with a well-defined energy, but since these particles are usually generated by means of a radioactive source, they are fast and with a broad distribution of energies. For this reason it is necessary to moderate them to lower energies via inelastic collisions. Then, they can be accelerated to the desired energies. This requires the use of a moderator. Tungsten is one of the most commonly used moderator materials because of its reasonable efficiency and relatively low cost. In this work we present different methods of producing transmission tungsten-based moderators, with particular interest in a combination of tungsten thin foils and grids. We also show results about the characterization of these moderators by ion beam analysis and microscopy techniques along with their relative moderation efficiencies.

  7. Study of tungsten based positron moderators

    International Nuclear Information System (INIS)

    Lucio, O.G. de; Pérez, M.; Mendoza, U.; Morales, J.G.; Cruz, J.C.; DuBois, R.D.

    2015-01-01

    Positrons and how they interact with matter has a growing interest in many fields. Most of their uses require the production of slow positron beams with a well-defined energy, but since these particles are usually generated by means of a radioactive source, they are fast and with a broad distribution of energies. For this reason it is necessary to moderate them to lower energies via inelastic collisions. Then, they can be accelerated to the desired energies. This requires the use of a moderator. Tungsten is one of the most commonly used moderator materials because of its reasonable efficiency and relatively low cost. In this work we present different methods of producing transmission tungsten-based moderators, with particular interest in a combination of tungsten thin foils and grids. We also show results about the characterization of these moderators by ion beam analysis and microscopy techniques along with their relative moderation efficiencies

  8. Tungsten and tungsten alloys by powder metallurgy

    International Nuclear Information System (INIS)

    Belhadjhamida, A.; German, R.M.

    1991-01-01

    Tungsten has a historical link with powder metallurgy and there is continued progress in expanding the available compositions and processing options. This paper starts with an introduction to the history of tungsten powder metallurgy and use this as a basis for analyzing some of the current trends. The literature base in tungsten processing is expanding and includes new alloys, microstructures, and processing routes. A few examples will be emphasize here to produce a frame work for this program, including description of sintering mechanisms for tungsten, liquid phase sintering advances, hot consolidation fundamentals, and options for complex shaping using powder injection modeling. For this base, subsequent presentations will expand on these fundamental advances

  9. Self-standing nanoribbons of antimony selenide and antimony sulfide with well-defined size and band gap

    International Nuclear Information System (INIS)

    Vadapoo, Rajasekarakumar; Krishnan, Sridevi; Yilmaz, Hulusi; Marin, Carlos

    2011-01-01

    Sub-10 nm semiconducting nanostructures are crucial for the realization of nanoscale devices. Fabrication of nanostructures at this scale with homogeneous properties is challenging. Using ab initio calculations, we show that self-standing ribbons of antimony selenide and antimony sulfide of width 1.1 nm exhibit well-defined bandgaps of 1.66 and 2.16 eV, respectively. Molecular dynamics studies show that these ribbons are stable at 500 K. The one-dimensional (1D) heterostructure of these nanoribbons (Sb 2 Se 3 /Sb 2 S 3 ) along the [001] direction shows a straddling type behavior.

  10. 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.

  11. An Efficient Solvent-Free Protocol for the Synthesis of 1-Amidoalkyl-2-naphthols using Silica-Supported Molybdatophosphoric Acid

    Directory of Open Access Journals (Sweden)

    Abdolkarim Zare

    2010-01-01

    Full Text Available A highly efficient, green and simple solvent-free method for the synthesis of 1-amidoalkyl-2-naphthols via one-pot multi-components condensation of 2-naphthol, aromatic aldehydes and amides in the presence of catalytic amount of silica-supported molybdatophosphoric acid (H3PMo12O40.xH2O/SiO2, 3.17 mol% is described. The reactions proceed rapidly and the title compounds are produced in high to excellent yields.

  12. Moessbauer spectroscopic characterisation of catalysts obtained by interaction between tetra-n-butyl-tin and silica or silica supported rhodium

    International Nuclear Information System (INIS)

    Millet, J.M.M.; Toyir, J.; Didillon, B.; Candy, J.P.; Nedez, C.; Basset, J.M.

    1997-01-01

    Moessbauer spectroscopy at 78 K was used to study the interaction between tetra-n-butyl-tin and the surfaces of silica or silica supported rhodium. At room temperature, the tetra-n-butyl-tin was physically adsorbed on the surfaces. After reaction under hydrogen at 373 K, the formation of grafted organometallic fragments on the Rh surface was confirmed whereas with pure silica, ≡SiO-Sn(n-C 4 H 9 ) 3 moieties were observed. After treatment at 523 K, the rhodium grafted organometallic species was completely decomposed and there was formation of a defined bimetallic RhSn compound

  13. 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.

  14. 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.

  15. 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

  16. Tungsten Alloy Outgassing Measurements

    CERN Document Server

    Rutherfoord, John P; Shaver, L

    1999-01-01

    Tungsten alloys have not seen extensive use in liquid argon calorimeters so far. Because the manufacturing process for tungsten is different from the more common metals used in liquid argon there is concern that tungsten could poison the argon thereby creating difficulties for precision calorimetry. In this paper we report measurements of outgassing from the tungsten alloy slugs proposed for use in the ATLAS FCal module and estimate limits on potential poisoning with reasonable assumptions. This estimate gives an upper limit poisoning rate of tungsten slugs.

  17. Molecular characterization of apocrine carcinoma of the breast: validation of an apocrine protein signature in a well-defined cohort

    DEFF Research Database (Denmark)

    Celis, J.E.; Cabezon, T.; Moreira, José

    2009-01-01

    Invasive apocrine carcinomas (IACs), as defined by morphological features, correspond to 0.3-4% of all invasive ductal carcinomas (IDC), and despite the fact that they are histologically distinct from other breast lesions there are currently no standard molecular criteria available...... characterize these lesions as well as to dissect some of the steps in the processes underlying breast apocrine metaplasia and development of precancerous apocrine lesions. Establishing these apocrine-specific markers as best practice for the routine pathology evaluation of breast cancer, however, will require......1), in addition to a set of categorizing markers that are consistently expressed (AR, CD24) or not expressed (ERalpha, PgR, Bcl-2, and GATA-3) by apocrine metaplasia in benign breast lesions and apocrine sweat glands. This panel was used to analyze a well-defined cohort consisting of 14 apocrine...

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

    KAUST Repository

    Ratkanthwar, Kedar R.; Hadjichristidis, Nikolaos; Pudukulathan, Zubaidha

    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.

  19. 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.

  20. 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.

  1. 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.

  2. 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.

  3. Well-defined flake-like polypyrrole grafted graphene nanosheets composites as electrode materials for supercapacitors with enhanced cycling stability

    Science.gov (United States)

    Wang, Xue; Wang, Tingmei; Yang, Chao; Li, Haidong; Liu, Peng

    2013-12-01

    Well-defined flake-like polypyrrole grafted graphene nanosheets composites (PPy-g-GNS) were fabricated by the in-situ chemical oxidative grafting polymerization of pyrrole in the presence of the 4-aminophenyl modified graphene nanosheets (AP-GNS), which were prepared via the coupling reaction of the graphene nanosheets (GNS) with diazonium salt. The flake-like PPy-g-GNS composite showed the high conductivity at room temperature. A maximum discharge capacitance of 191.2 F/g at the scan rate of 10 mV/s could be achieved in the three-electrode cell electrochemical testing in 1.0 mol/L NaNO3 electrolyte solution. It is higher than those of the AP-GNS, pure PPy, and the GNS/PPy composite prepared with the unmodified graphene nanosheets (GNS). The flake-like PPy-g-GNS composites also exhibited the excellent electrochemical stability even after 1000 cycles. It revealed the synergistic effect between the conducting polymer and the carbon-based support.

  4. 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.

  5. Fabricating hierarchically porous carbon with well-defined open pores via polymer dehalogenation for high-performance supercapacitor

    Science.gov (United States)

    Guo, Mei; Li, Yu; Du, Kewen; Qiu, Chaochao; Dou, Gang; Zhang, Guoxin

    2018-05-01

    Improving specific energy of supercapacitors (SCs) at high power has been intensively investigated as a hot and challengeable topic. In this work, hierarchically porous carbon (HPC) materials with well-defined meso-/macro-pores are reported via the dehalogenation reaction of polyvinyl fluoride (PVDF) by NaNH2. The pore hierarchy is achievable mainly because of the coupled effects of NaNH2 activation and the template/bubbling effects of byproducts of NaF and NH3. Electron microscopy studies and Brunauer-Emmett-Teller (BET) measurements confirm that the structures of HPC samples contain multiple-scale pores assembled in a hierarchical pattern, and most of their volumes are contributed by mesopores. Aqueous symmetric supercapacitors (ASSCs) were fabricated using HPC-M7 materials, achieving an ultrahigh specific energy of 18.8 Wh kg-1 at specific power of 986.8 W kg-1. Remarkably, at the ultrahigh power of 14.3 kW kg-1, the HPC-ASSCs still output a very high specific energy of 16.7 Wh kg-1, which means the ASSCs can be charged or discharged within 4 s. The outstanding rate capacitive performance is mainly benefited from the hierarchical porous structure that allows highly efficient ion diffusion.

  6. Design and synthesis of structurally well-defined functional polypropylenes via transition metal-mediated olefin polymerization chemistry

    Institute of Scientific and Technical Information of China (English)

    Dong Jinyong

    2006-01-01

    Functionalization of polyolefins is an industrially important yet scientifically challenging research subject.This paper summarizes our recent effort to access structurally well-defined functional polypropylenes via transition metal-mediated olefin polymerization.In one approach,polypropylenes containing side chain functional groups of controlled concentrations were obtained by Ziegler-Natta-catalyzed copolymerization of propylene in combination with either living anionic or controlled radical polymerization of polar monomers.The copolymerization of propylene with 1,4-divinylbenzene using an isospecific MgC12-supported TIC14 catalyst yielded potypropylenes containing pendant styrene moieties.Both metalation reaction with n-butyllithium and hydrochlorination reaction with dry hydrogen chloride selectively and quantitatively occurred at the pendant reactive sites,generating polymeric benzyllithium and 1-chloroethylbenzene species.These species initiated living anionic polymerization of styrene(S)and atom transfer radical polymerization(in the presence of CuC1 and pentamethyldiethylenetriamine) of methyl methacrylate(MMA),respectively,resulting in functional polypropylene graft copolymers(PP-g-PS and PP-g-PMMA)with controllable graft lengths.In another approach,chain end-functionalized polypropylenes containing a terminal OH-group with controlled molecular weights were directly prepared by propylene polymerization with a metaUocene catalyst through a selective aluminum chain transfer reaction.Both approaches proved to be desirable polyolefin functionalization routes in terms of efficiency and polymer structure controllability.

  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. 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

  9. 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.

  10. 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

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

    International Nuclear Information System (INIS)

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

    2017-01-01

    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

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

    KAUST Repository

    Zhang, Hefeng; Hadjichristidis, Nikolaos

    2016-01-01

    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.

  13. Correlating the Impact of Well-Defined Oligosaccharide Structures on Physical Stability Profiles of IgG1-Fc Glycoforms.

    Science.gov (United States)

    More, Apurva S; Toprani, Vishal M; Okbazghi, Solomon Z; Kim, Jae H; Joshi, Sangeeta B; Middaugh, C Russell; Tolbert, Thomas J; Volkin, David B

    2016-02-01

    As part of a series of articles in this special issue describing 4 well-defined IgG1-Fc glycoforms as a model system for biosimilarity analysis (high mannose-Fc, Man5-Fc, GlcNAc-Fc and N297Q-Fc aglycosylated), the focus of this work is comparisons of their physical properties. A trend of decreasing apparent solubility (thermodynamic activity) by polyethylene glycol precipitation (pH 4.5, 6.0) and lower conformational stability by differential scanning calorimetry (pH 4.5) was observed with reducing size of the N297-linked oligosaccharide structures. Using multiple high-throughput biophysical techniques, the physical stability of the Fc glycoproteins was then measured in 2 formulations (NaCl and sucrose) across a wide range of temperatures (10°C-90°C) and pH (4.0-7.5) conditions. The data sets were used to construct 3-index empirical phase diagrams and radar charts to visualize the regions of protein structural stability. Each glycoform showed improved stability in the sucrose (vs. salt) formulation. The HM-Fc and Man5-Fc displayed the highest relative stability, followed by GlcNAc-Fc, with N297Q-Fc being the least stable. Thus, the overall physical stability profiles of the 4 IgG1-Fc glycoforms also show a correlation with oligosaccharide structure. These data sets are used to develop a mathematical model for biosimilarity analysis (as described in a companion article by Kim et al. in this issue). Copyright © 2016 American Pharmacists Association®. Published by Elsevier Inc. All rights reserved.

  14. 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.

  15. 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

  16. Experimental and statistical requirements for developing a well-defined K/sub IR/ curve. Final report

    International Nuclear Information System (INIS)

    Server, W.L.; Oldfield, W.; Wullaert, R.A.

    1977-05-01

    Further development of a statistically well-defined reference fracture toughness curve to verify and compliment the K/sub IR/ curve presently specified in Appendix G, Section III of the ASME Code was accomplished by performing critical experiments in small specimen fracture mechanics and improving techniques for statistical analysis of the data. Except for cleavage-initiated fracture, crack initiation was observed to occur prior to maximum load for all of the materials investigated. Initiation fracture toughness values (K/sub Jc/) based on R-curve heat-tinting studies were up to 50 percent less than the previously reported equivalent energy values (K*/sub d/). At upper shelf temperatures, the initiation fracture toughness (K/sub Jc/) generally increased with stress intensification rate. Both K/sub Jc/--Charpy V-notch and K/sub Ic/--specimen strength ratio correlations are promising methods for predicting thick-section behavior from small specimens. The previously developed tanh curve fitting procedure was improved to permit estimates of the variances and covariances of the regression coefficients to be computed. The distribution of the fracture toughness data was determined as a function of temperature. Instrumented precracked Charpy results were used to normalize the larger specimen fracture toughness data. The transformed large specimen fracture toughness data are used to generate statistically based lower-bound fracture toughness curves for either static or dynamic test results. A comparison of these lower bound curves with the K/sub IR/ curve shows that the K/sub IR/ curve is more conservative over most of its range. 143 figures, 26 tables

  17. Production And Characterization Of Tungsten-Based Positron Moderators

    International Nuclear Information System (INIS)

    Lucio, O. G. de; Morales, J. G.; Cruz-Manjarrez, H.

    2011-01-01

    Experiments of interest in Atomic Physics require production of well-defined low-energy positron beams through a moderation process of high-energy positrons, which can be produced by either the use of a radioactive source or by accelerator based pair production process. Tungsten is one of the most commonly used moderator materials because of its reasonable efficiency, high work function and relatively low cost. In this work we present different methods to produce tungsten-based candidate moderators in a variety of shapes. We also present results from characterizing these candidate moderators by ion beam analysis and microscopy techniques.

  18. Trends in colorectal cancer incidence: a period and birth-cohort analysis in a well-defined French population.

    Science.gov (United States)

    Chauvenet, Marion; Cottet, Vanessa; Lepage, Côme; Jooste, Valérie; Faivre, Jean; Bouvier, Anne-Marie

    2011-06-30

    France stands among high-risk areas for colorectal cancer. Different trends in CRC incidence are reported around the world. The aim of this study was to provide temporal trends in CRC incidence over a 30-year period in a French well-defined population. Between 1976 and 2005, 17,028 new cases were registered by the Burgundy digestive cancer registry. The mean variations in age-standardized incidence rates were estimated using a Poisson regression adjusted for age for each gender and location. The cumulative risk by birth cohort of developing a cancer over the age range 0-74 years was estimated using an age-cohort model. Incidence rates for right and left colon cancers increased more rapidly in males (respectively +11.7% and +10.3% on average by 5-year period) than in females (respectively +5.9% and +6.1%). It remained stable for sigmoid cancers in males (-0.1%) and decreased in females (-5.2%). It also decreased for rectal cancers both in males (-2.7%) and in females (-2.0%). The cumulative risk increased from 3.9% for males born around 1900 to 4.9% for those born around 1930 and then slightly decreased (4.5% among those born around 1950). It remained at the same level for females born around 1900 (2.7%) as for those born around 1930 (2.7%) and then slightly increased (2.9%) for those born around 1950. For right colon cancers, the cumulative risk increased strikingly in successive birth cohorts from 0.53% to 1.2% in males and 0.55% to 0.77% in females. The corresponding cumulative risks for the left colon were 0.24% and 0.42% in males and 0.14% and 0.29% in females. For sigmoid cancer, they decreased from 1.59% to 1.08% in males, and 0.88% to 0.80% in females. Temporal variations in incidence rates of colorectal cancers differed according to subsite, suggesting different aetiological factors and implications for diagnosis and screening strategies. Total colonoscopy must be the preferred strategy in high-risk groups or after a positive faecal occult blood test.

  19. Trends in colorectal cancer incidence: a period and birth-cohort analysis in a well-defined French population

    Directory of Open Access Journals (Sweden)

    Faivre Jean

    2011-06-01

    Full Text Available Abstract Background France stands among high-risk areas for colorectal cancer. Different trends in CRC incidence are reported around the world. The aim of this study was to provide temporal trends in CRC incidence over a 30-year period in a French well-defined population. Methods Between 1976 and 2005, 17,028 new cases were registered by the Burgundy digestive cancer registry. The mean variations in age-standardized incidence rates were estimated using a Poisson regression adjusted for age for each gender and location. The cumulative risk by birth cohort of developing a cancer over the age range 0-74 years was estimated using an age-cohort model. Results Incidence rates for right and left colon cancers increased more rapidly in males (respectively +11.7% and +10.3% on average by 5-year period than in females (respectively +5.9% and +6.1%. It remained stable for sigmoid cancers in males (-0.1% and decreased in females (-5.2%. It also decreased for rectal cancers both in males (-2.7% and in females (-2.0%. The cumulative risk increased from 3.9% for males born around 1900 to 4.9% for those born around 1930 and then slightly decreased (4.5% among those born around 1950. It remained at the same level for females born around 1900 (2.7% as for those born around 1930 (2.7% and then slightly increased (2.9% for those born around 1950. For right colon cancers, the cumulative risk increased strikingly in successive birth cohorts from 0.53% to 1.2% in males and 0.55% to 0.77% in females. The corresponding cumulative risks for the left colon were 0.24% and 0.42% in males and 0.14% and 0.29% in females. For sigmoid cancer, they decreased from 1.59% to 1.08% in males, and 0.88% to 0.80% in females. Conclusion Temporal variations in incidence rates of colorectal cancers differed according to subsite, suggesting different aetiological factors and implications for diagnosis and screening strategies. Total colonoscopy must be the preferred strategy in high

  20. 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.; 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,

  1. 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…

  2. Deuterium trapping in tungsten

    Science.gov (United States)

    Poon, Michael

    Tungsten is one of the primary material candidates being investigated for use in the first-wall of a magnetic confinement fusion reactor. An ion accelerator was used to simulate the type of ion interaction that may occur at a plasma-facing material. Thermal desorption spectroscopy (TDS) was the primary tool used to analyze the effects of the irradiation. Secondary ion mass spectroscopy (SIMS) was used to determine the distribution of trapped D in the tungsten specimen. The tritium migration analysis program (TMAP) was used to simulate thermal desorption profiles from the D depth distributions. Fitting of the simulated thermal desorption profiles with the measured TDS results provided values of the D trap energies. Deuterium trapping in single crystal tungsten was studied as a function of the incident ion fluence, ion flux, irradiation temperature, irradiation history, and surface impurity levels during irradiation. The results show that deuterium was trapped at vacancies and voids. Two deuterium atoms could be trapped at a tungsten vacancy, with trapping energies of 1.4 eV and 1.2 eV for the first and second D atoms, respectively. In a tungsten void, D is trapped as atoms adsorbed on the inner walls of the void with a trap energy of 2.1 eV, or as D2 molecules inside the void with a trap energy of 1.2 eV. Deuterium trapping in polycrystalline tungsten was also studied as a function of the incident fluence, irradiation temperature, and irradiation history. Deuterium trapping in polycrystalline tungsten also occurs primarily at vacancies and voids with the same trap energies as in single crystal tungsten; however, the presence of grain boundaries promotes the formation of large surface blisters with high fluence irradiations at 500 K. In general, D trapping is greater in polycrystalline tungsten than in single crystal tungsten. To simulate mixed materials comprising of carbon (C) and tungsten, tungsten specimens were pre-irradiated with carbon ions prior to D

  3. Deuterium trapping in tungsten

    International Nuclear Information System (INIS)

    Poon, M.

    2004-01-01

    Tungsten is one of the primary material candidates being investigated for use in the first-wall of a magnetic confinement fusion reactor. An ion accelerator was used to simulate the type of ion interaction that may occur at a plasma-facing material. Thermal desorption spectroscopy (TDS) was the primary tool used to analyze the effects of the irradiation Secondary ion mass spectroscopy (SIMS) was used to determine the distribution of trapped D in the tungsten specimen. The tritium migration analysis program (TMAP) was used to simulate thermal desorption profiles from the D depth distributions. Fitting of the simulated thermal desorption profiles with the measured TDS results provided values of the D trap energies. . Deuterium trapping in single crystal tungsten was studied as a function of the incident ion fluence, ion flux, irradiation temperature, irradiation history, and surface impurity levels during irradiation The results show that deuterium was trapped at vacancies and voids. Two deuterium atoms could be trapped at a tungsten vacancy, with trapping energies of 1.4 eV and 1.2 eV for the first and second D atoms, respectively. In a tungsten void, D is trapped as atoms adsorbed on the inner walls of the void with a trap energy of 2.1 eV, or as D 2 molecules inside the void with a trap energy of 1.2 eV. . Deuterium trapping in polycrystalline tungsten was also studied as a function of the incident fluence, irradiation temperature, and irradiation history. Deuterium trapping in polycrystalline tungsten also occurs primarily at vacancies and voids with the same trap energies as in single crystal tungsten; however, the presence of grain boundaries promotes the formation of large surface blisters with high fluence irradiations at 500 K. In general, D trapping is greater in polycrystalline tungsten than in single crystal tungsten. To simulate mixed materials comprising of carbon (C) and tungsten, tungsten specimens were pre-irradiated with carbon ions prior to D

  4. Deuterium trapping in tungsten

    Energy Technology Data Exchange (ETDEWEB)

    Poon, M

    2004-07-01

    Tungsten is one of the primary material candidates being investigated for use in the first-wall of a magnetic confinement fusion reactor. An ion accelerator was used to simulate the type of ion interaction that may occur at a plasma-facing material. Thermal desorption spectroscopy (TDS) was the primary tool used to analyze the effects of the irradiation Secondary ion mass spectroscopy (SIMS) was used to determine the distribution of trapped D in the tungsten specimen. The tritium migration analysis program (TMAP) was used to simulate thermal desorption profiles from the D depth distributions. Fitting of the simulated thermal desorption profiles with the measured TDS results provided values of the D trap energies. . Deuterium trapping in single crystal tungsten was studied as a function of the incident ion fluence, ion flux, irradiation temperature, irradiation history, and surface impurity levels during irradiation The results show that deuterium was trapped at vacancies and voids. Two deuterium atoms could be trapped at a tungsten vacancy, with trapping energies of 1.4 eV and 1.2 eV for the first and second D atoms, respectively. In a tungsten void, D is trapped as atoms adsorbed on the inner walls of the void with a trap energy of 2.1 eV, or as D{sub 2} molecules inside the void with a trap energy of 1.2 eV. . Deuterium trapping in polycrystalline tungsten was also studied as a function of the incident fluence, irradiation temperature, and irradiation history. Deuterium trapping in polycrystalline tungsten also occurs primarily at vacancies and voids with the same trap energies as in single crystal tungsten; however, the presence of grain boundaries promotes the formation of large surface blisters with high fluence irradiations at 500 K. In general, D trapping is greater in polycrystalline tungsten than in single crystal tungsten. To simulate mixed materials comprising of carbon (C) and tungsten, tungsten specimens were pre-irradiated with carbon ions prior to D

  5. 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 ...

  6. 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

  7. A density functional theory study of a silica-supported zirconium monohydride catalyst for depolymerization of polyethylene

    Energy Technology Data Exchange (ETDEWEB)

    Mortensen, J.J.; Parrinello, M.

    2000-04-06

    A silica-supported zirconium hydride catalyst for depolymerization of polyethylene is studied using density functional theory (DFT) together with a generalized gradient approximation (GGA) for the exchange and correlation energy. The (100) and (111) surfaces of {beta}-cristobalite are used as two possible models of a silica surface. Based on the experimental surface structure determined by J. Corker et al., they propose a detailed atomic model of the zirconium monohydride that is believed to be the active site for depolymerization of polyolefins. The model of the zirconium monohydride on the (100) surface is found to be very stable and the structure is in good agreement with extended X-ray absorption fine structure (EXAFS) measurements. Depolymerization of a small polyolefin chain (C{sub 3}H{sub 8}) was carried out to give CH{sub 4} and C{sub 2}H{sub 6} by addition of H{sub 2}. The rate-limiting step is a {beta}-methyl transfer to the zirconium atom, and the activation energy is 29 kcal/mol on the (100) surface.

  8. Plasma etching of patterned tungsten

    International Nuclear Information System (INIS)

    Franssila, S.

    1993-01-01

    Plasma etching of tungsten is discussed from the viewpoint of thin film structure and integrated circuit process engineering. The emphasis is on patterned tungsten etching for silicon device and X-ray mask fabrication. After introducing tungsten etch chemistries and mechanisms, microstructural aspects of tungsten films (crystal structure, grain size, film density, defects, impurities) in relation to etching are discussed. Approaches to etch process optimization are presented, and the current state-of-the-art of patterned tungsten etching is reviewed. (orig.)

  9. Hydrogen sulfide removal from hot coal gas by various mesoporous silica supported Mn2O3 sorbents

    International Nuclear Information System (INIS)

    Zhang, Z.F.; Liu, B.S.; Wang, F.; Wang, W.S.; Xia, C.; Zheng, S.; Amin, R.

    2014-01-01

    Graphical abstract: - Highlights: • Mn 2 O 3 /KIT-1 presented the best desulfurization performance at 600–850 °C. • High sulfur capacity of Mn 2 O 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 2 O 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 2 O 3 sorbents was investigated at 600–850 °C using hot coal gas containing 0.33 vol.% H 2 S. The fresh and used sorbents were characterized by means of N 2 -adsorption, x-ray diffraction (XRD), high resolution transmission microscopy (HRTEM) and H 2 temperature- programmed reduction (H 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 2 O 3 /diatomite, all mesoporous silica supported Mn 2 O 3 sorbents exhibited high breakthrough sulfur capacity and a sharp deactivation rate after the breakthrough point. Compared to Mn 2 O 3 /MCM-41 and Mn 2 O 3 /HMS sorbent, the Mn 2 O 3 /KIT-1 showed better desulfurization performance because of the 3D wormhole-like channel. The high sulfur capacity of the Mn 2 O 3 /KIT-1 sorbent was maintained during the eight consecutive desulfurization-regeneration cycles. The Mn 2 O 3 /KIT-1 still presented high desulfurization activity when hot coal gas contained low steam (<5%)

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

    KAUST Repository

    D'Elia, Valerio; Dong, Hailin; Rossini, Aaron J; Widdifield, Cory M.; Vummaleti, Sai V. C.; Minenkov, Yury; Poater, Albert; Abou-Hamad, Edy; Pelletier, Jeremie D. A.; Cavallo, Luigi; Emsley, Lyndon; Basset, Jean-Marie

    2015-01-01

    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.

  13. Tungsten behaviour under anodic polarization

    International Nuclear Information System (INIS)

    Vas'ko, A.T.; Patsyuk, F.N.

    1980-01-01

    Electrochemical investigations have been carried out to identify the state of elements of the tungsten galvanic coating. Active zones on anode polarization curves in the hydrogen region of galvanic tungsten are established. The difference in the behaviour of monocrystal and galvanic tungsten electrodes is shown to be connected with the oxidation of hydrogen in the galvanic sediment

  14. Electrocatalysis on tungsten carbide

    International Nuclear Information System (INIS)

    Fleischmann, R.

    1975-01-01

    General concepts of electrocatalysis, the importance of the equilibrium rest potential and its standardization on polished WC-electrodes, the influence of oxygen in the catalysts upon the oxidation of hydrogen, and the attained results of the hydrogen oxidation on tungsten carbide are treated. (HK) [de

  15. 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.

  16. 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.

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

    KAUST Repository

    Dey, Raju; Samantaray, Manoja; Callens, Emmanuel; Hamieh, Ali Imad Ali; Emwas, Abdul-Hamid M.; Abou-Hamad, Edy; Kavitake, Santosh Giridhar; 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 self-metathesis of 1-octene.

  18. The structure of well defined SiO2 supported MoO3 clusters during sulfidation : an in situ EXAFS-study

    NARCIS (Netherlands)

    Boer, de M.; Dillen, van A.J.; Koningsberger, D.C.; Geus, J.W.; Kuroda, H.; Ohta, T.

    1993-01-01

    The sulfidation of a well defined MoO3/SiO2 catalyst has been examd. by means of TPS, EXAFS, and TEM. The oxidic clusters in a 5.6 wt% MoO3/SiO2 catalyst are transformed into almost completely sulfided particles (MoOxSy) by O-S exchange at RT. A molybdenum-sulfido particle that resembles the MoS3

  19. Molecular and Silica-Supported Molybdenum Alkyne Metathesis Catalysts: Influence of Electronics and Dynamics on Activity Revealed by Kinetics, Solid-State NMR, and Chemical Shift Analysis.

    Science.gov (United States)

    Estes, Deven P; Gordon, Christopher P; Fedorov, Alexey; Liao, Wei-Chih; Ehrhorn, Henrike; Bittner, Celine; Zier, Manuel Luca; Bockfeld, Dirk; Chan, Ka Wing; Eisenstein, Odile; Raynaud, Christophe; Tamm, Matthias; Copéret, Christophe

    2017-12-06

    Molybdenum-based molecular alkylidyne complexes of the type [MesC≡Mo{OC(CH 3 ) 3-x (CF 3 ) x } 3 ] (MoF 0 , x = 0; MoF 3 , x = 1; MoF 6 , x = 2; MoF 9 , x = 3; Mes = 2,4,6-trimethylphenyl) and their silica-supported analogues are prepared and characterized at the molecular level, in particular by solid-state NMR, and their alkyne metathesis catalytic activity is evaluated. The 13 C NMR chemical shift of the alkylidyne carbon increases with increasing number of fluorine atoms on the alkoxide ligands for both molecular and supported catalysts but with more shielded values for the supported complexes. The activity of these catalysts increases in the order MoF 0 molecular and supported species. Detailed solid-state NMR analysis of molecular and silica-supported metal alkylidyne catalysts coupled with DFT/ZORA calculations rationalize the NMR spectroscopic signatures and discernible activity trends at the frontier orbital level: (1) increasing the number of fluorine atoms lowers the energy of the π*(M≡C) orbital, explaining the more deshielded chemical shift values; it also leads to an increased electrophilicity and higher reactivity for catalysts up to MoF 6 , prior to a sharp decrease in reactivity for MoF 9 due to the formation of stable metallacyclobutadiene intermediates; (2) the silica-supported catalysts are less active than their molecular analogues because they are less electrophilic and dynamic, as revealed by their 13 C NMR chemical shift tensors.

  20. Application of a Heterogeneous Chiral Titanium Catalyst Derived from Silica-Supported 3-Aryl H8-BINOL to Enantioselective Alkylation and Arylation of Aldehydes.

    Science.gov (United States)

    Akai, Junichiro; Watanabe, Satoshi; Michikawa, Kumiko; Harada, Toshiro

    2017-07-07

    A 3-aryl H 8 -BINOL was grafted on the surface of silica gel using a hydrosilane derivative as a precursor, and the resulting silica-supported ligand (6 mol %) was employed in the enantioselective alkylation and arylation of aldehydes in the presence of Ti(O i Pr) 4 . The reactions using Et 2 Zn, Et 3 B, and aryl Grignard reagents all afforded the corresponding adducts in high enantioselectivities and yields. The silica-immobilized titanium catalyst could be reused up to 14 times without appreciable deterioration of the activity.

  1. Propene and l-octene hydroformylation with silica-supported, ionic liquid-phase (SILP) Rh-phosphine catalysts in continuous fixed-bed mode

    DEFF Research Database (Denmark)

    Riisager, Anders; Eriksen, Kim Michael; Wasserscheid, Peter

    2003-01-01

    - and liquid-phase hydroformylation of propene and 1-octene, exhibiting TOFs up to 88 h(-1) for SILP Rh-2 catalysts, while only low selectivities up to 74% n-aldehyde (n/iso ratio of 2.8) were obtained. This is the first example of continuous fixed-bed liquid-phase hydroformylation using SILP catalysts.......Supported ionic liquid-phase (SILP) catalysts were made by immobilizing Rh-monophosphine complexes of bis(m-phenylguanidinium) phenylphosphine 1 and NORBOS 2 ligands in 1-n-butyl-3-methylimidazolium hexafluorophosphate, [BMIM] [PF6], on a silica support. The catalysts were active in continuous gas...

  2. Synthesis of Well-Defined Three-Arm Star-Branched Polystyrene through Arm-First Coupling Approach by Atom Transfer Radical Polymerization

    Directory of Open Access Journals (Sweden)

    Syed Shahabuddin

    2015-01-01

    Full Text Available Here we describe a simple route to synthesize three-arm star-branched polystyrene. Atom transfer radical polymerization technique has been utilized to yield branched polystyrene involving Williamson coupling strategy. Initially a linear polymeric chain of predetermined molecular weight has been synthesized which is further end-functionalized into a primary alkyl bromide moiety, a prime requisition for Williamson reaction. The end-functionalized polymer is then coupled using 1,1,1-tris(4-hydroxyphenylethane, a trifunctional core molecule, to give well-defined triple-arm star-branched polystyrene.

  3. Materials Survey: Tungsten

    Science.gov (United States)

    1956-12-01

    Columbia, from which tungsten production is planned approximately 60 miles east fromSkagway, were estimated at the end of 1951 to be Alaska. Reserves...of the principal mines inimportant producers. 1952 halted expansion programs planned by Production in Argentina reached a maxi- Patiffo Mines and...government.Concentrates International Mining Co. (W. R. Grace & from small producers are collected and Co.), La Paz; Chojlla Mine; type ore-- marketed by Banco Minero

  4. Helium bubble bursting in tungsten

    International Nuclear Information System (INIS)

    Sefta, Faiza; Juslin, Niklas; Wirth, Brian D.

    2013-01-01

    Molecular dynamics simulations have been used to systematically study the pressure evolution and bursting behavior of sub-surface helium bubbles and the resulting tungsten surface morphology. This study specifically investigates how bubble shape and size, temperature, tungsten surface orientation, and ligament thickness above the bubble influence bubble stability and surface evolution. The tungsten surface is roughened by a combination of adatom “islands,” craters, and pinholes. The present study provides insight into the mechanisms and conditions leading to various tungsten topology changes, which we believe are the initial stages of surface evolution leading to the formation of nanoscale fuzz

  5. 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.

  6. Zn(OAc2-Catalyzing Ring-Opening Polymerization of N-Carboxyanhydrides for the Synthesis of Well-Defined Polypeptides

    Directory of Open Access Journals (Sweden)

    Yanzhao Nie

    2018-03-01

    Full Text Available Despite notable progress, the fabrication of well-defined polypeptides via controlled ring-opening polymerization (ROP of α-amino acid N-carboxyanhydrides (NCAs using convenient catalysts under mild conditions in a relatively short polymerization time is still challenging. Herein, an easily obtained catalyst system composed of zinc acetate and aniline was explored to mediate the fast ROP of γ-benzyl-l-glutamate-N-carboxyanhydride (BLG-NCA monomer, to produce poly(γ-benzyl-l-glutamates (PBLGs with controllable molecular weights and narrow dispersity. Considering the excellent cooperative action of zinc acetate and a broad scope of aniline derivatives with different functional groups to control ROP of BLG-NCA, this method may offer a useful platform enabling the rapid generation of end-functionalized PBLG and block copolymers for numerous biomedical applications.

  7. Synthesis and functions of well-defined polymer-drug conjugates as efficient nanocarriers for intravesical chemotherapy of bladder cancer(a).

    Science.gov (United States)

    Yu, Qingsong; Zhang, Jiajing; Zhang, Guan; Gan, Zhihua

    2015-04-01

    Novel poly(ethylene glycol) and poly(N-(2-hydroxypropyl)methacrylamide) block copolymer (PEG-b-PHPMA) with well-defined composition was synthesized by RAFT polymerization. Folate and doxorubicin (DOX) were quantitatively introduced into the copolymer. The influences of folate content and pH value on folate receptor (FR) mediated cell endocytosis and pH-responsive DOX release were studied. It has been demonstrated that minimum folate content is needed for the enrichment of hydrophobic folate on the hydrophilic part of polymer conjugates. The cytotoxicity of targetable polymer drug conjugates was much higher than that of non-targetable ones and free DOX. It could be concluded that the folate plays a significant role in targeting and internalization of the conjugates against bladder cancer cells. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Self diffusion in tungsten

    International Nuclear Information System (INIS)

    Mundy, J.N.; Rothman, S.J.; Lam, N.Q.; Nowicki, L.J.; Hoff, H.A.

    1978-01-01

    The lack of understanding of self-diffusion in Group VI metals together with the wide scatter in the measured values of tungsten self-diffusion has prompted the present measurements to be made over a wide temperature range (1/2Tsub(m) to Tsub(m)). The diffusion coefficients have been measured in the temperature range 1430-2630 0 C. The present measurements show non-linear Arrhenius behavior but a reliable two-exponential fit of the data should await further measurements. (Auth.)

  9. Gas tungsten arc welder

    International Nuclear Information System (INIS)

    Christiansen, D.W.; Brown, W.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 grinder, co-axial with the electrode, is provided in the enclosure for refurbishing the used electrode between welds. The specification also discloses means for loading of the cladding with fuel pellets and for placement of reflectors, gas capsules and end caps. Gravity feed conveyor and inerting means are also described. (author)

  10. Reduction of blue tungsten oxide

    International Nuclear Information System (INIS)

    Wilken, T.; Wert, C.; Woodhouse, J.; Morcom, W.

    1975-01-01

    A significant portion of commercial tungsten is produced by hydrogen reduction of oxides. Although several modes of reduction are possible, hydrogen reduction is used where high purity tungsten is required and where the addition of other elements or compounds is desired for modification of the metal, as is done for filaments in the lamp industry. Although several investigations of the reduction of oxides have been reported (1 to 5), few principles have been developed which can aid in assessment of current commercial practice. The reduction process was examined under conditions approximating commercial practice. The specific objectives were to determine the effects of dopants, of water vapor in the reducing atmosphere, and of reduction temperature upon: (1) the rate of the reaction by which blue tungsten oxide is reduced to tungsten metal, (2) the intermediate oxides associated with reduction, and (3) the morphology of the resulting tungsten powder

  11. Structural and luminescence properties of europium(III)-doped zirconium carbonates and silica-supported Eu3+-doped zirconium carbonate nanoparticles

    International Nuclear Information System (INIS)

    Sivestrini, S.; Riello, P.; Freris, I.; Cristofori, D.; Enrichi, F.; Benedetti, A.

    2010-01-01

    The synthesis, morphology and luminescence properties of europium(III)-doped zirconium carbonates prepared as bulk materials and as silica-supported nanoparticles with differing calcination treatments are reported. Transmission electron microscopy and X-ray diffraction analyses have, respectively, been used to study the morphology and to quantify the atomic amount of europium present in the optically active phases of the variously prepared nanomaterials. Rietveld analysis was used to quantify the constituting phases and to determinate the europium content. Silica particles with an approximate size of 30 nm were coated with 2 nm carbonate nanoparticles, prepared in situ on the surface of the silica core. Luminescence measurements revealed the role of different preparation methods and of europium-doping quantities on the optical properties observed.

  12. 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.

  13. 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; Dey, Raju; Nekoueishahraki, Bijan; Samantaray, Manoja; Chen, Yin; Abou-Hamad, Edy; Basset, Jean-Marie

    2017-01-01

    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.

  14. 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.

  15. Well-Defined Poly(Ortho Ester Amides) for Potential Drug Carriers: Probing the Effect of Extra- and Intracellular Drug Release on Chemotherapeutic Efficacy.

    Science.gov (United States)

    Yan, Guoqing; Wang, Jun; Qin, Jiejie; Hu, Liefeng; Zhang, Panpan; Wang, Xin; Tang, Rupei

    2017-07-01

    To compare the chemotherapeutic efficacy determined by extra- and intracellular drug release strategies, poly(ortho ester amide)-based drug carriers (POEAd-C) with well-defined main-chain lengths, are successfully constructed by a facile method. POEAd-C3-doxorubicin (DOX) can be rapidly dissolved to release drug at tumoral extracellular pH (6.5-7.2), while POEAd-C6-DOX can rapidly release drug following gradual swelling at intracellular pH (5.0-6.0). In vitro cytotoxicity shows that POEAd-C3-DOX exhibits more toxic effect on tumor cells than POEAd-C6-DOX at extracellular pH, but POEAd-C6-DOX has stronger tumor penetration and inhibition in vitro and in vivo tumor models. So, POEAd-C6-DOX with the intracellular drug release strategy has stronger overall chemotherapeutic efficacy than POEAd-C3-DOX with extracellular drug release strategy. It is envisioned that these poly(ortho ester amides) can have great potential as drug carriers for efficient chemotherapy with further optimization. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. 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.

  17. The titration of carboxyl-terminated monolayers revisited: in situ calibrated fourier transform infrared study of well-defined monolayers on silicon.

    Science.gov (United States)

    Aureau, D; Ozanam, F; Allongue, P; Chazalviel, J-N

    2008-09-02

    The acid-base equilibrium at the surface of well-defined mixed carboxyl-terminated/methyl-terminated monolayers grafted on silicon (111) has been investigated using in situ calibrated infrared spectroscopy (attenuated total reflectance (ATR)) in the range of 900-4000 cm (-1). Spectra of surfaces in contact with electrolytes of various pH provide a direct observation of the COOH COO (-) conversion process. Quantitative analysis of the spectra shows that ionization of the carboxyl groups starts around pH 6 and extends over more than 6 pH units: approximately 85% ionization is measured at pH 11 (at higher pH, the layers become damaged). Observations are consistently accounted for by a single acid-base equilibrium and discussed in terms of change in ion solvation at the surface and electrostatic interactions between surface charges. The latter effect, which appears to be the main limitation, is qualitatively accounted for by a simple model taking into account the change in the Helmholtz potential associated with the surface charge. Furthermore, comparison of calculated curves with experimental titration curves of mixed monolayers suggests that acid and alkyl chains are segregated in the monolayer.

  18. Gold-Based Cubic Nanoboxes with Well-Defined Openings at the Corners and Ultrathin Walls Less Than Two Nanometers Thick.

    Science.gov (United States)

    Sun, Xiaojun; Kim, Junki; Gilroy, Kyle D; Liu, Jingyue; König, Tobias A F; Qin, Dong

    2016-08-23

    We report a facile synthesis of Au-based cubic nanoboxes as small as 20 nm for the outer edge length, together with well-defined openings at the corners and walls fewer than 10 atomic layers (or nanocubes, followed by the conformal deposition of Au on the side faces in a layer-by-layer fashion. When six atomic layers of Au are formed on the side faces to generate Ag@Au6L core-shell nanocubes, we can selectively remove the Ag2O patches at the corner sites using a weak acid, making it possible to further remove the Ag core by H2O2 etching without breaking the ultrathin Au shell. This synthetic approach works well for Ag nanocubes of 38 and 18 nm in edge length, and the wall thickness of the nanoboxes can be controlled down to 2 nm. The resultant Au nanoboxes exhibit strong plasmonic absorption in the near-infrared region, consistent with computational simulations.

  19. 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.

  20. 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.

  1. 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.

  2. Well-defined copolymers synthesized by RAFT polymerization as effective modifiers to enhance the photocatalytic performance of TiO_2

    International Nuclear Information System (INIS)

    Vasilaki, E.; Kaliva, M.; Katsarakis, N.; Vamvakaki, M.

    2017-01-01

    Highlights: • Well-defined, random functional copolymers were synthesized by RAFT polymerization. • Novel TiO_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_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_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.

  3. Size-dependent redox behavior of iron observed by in-situ single nanoparticle spectro-microscopy on well-defined model systems.

    Science.gov (United States)

    Karim, Waiz; Kleibert, Armin; Hartfelder, Urs; Balan, Ana; Gobrecht, Jens; van Bokhoven, Jeroen A; Ekinci, Yasin

    2016-01-06

    Understanding the chemistry of nanoparticles is crucial in many applications. Their synthesis in a controlled manner and their characterization at the single particle level is essential to gain deeper insight into chemical mechanisms. In this work, single nanoparticle spectro-microscopy with top-down nanofabrication is demonstrated to study individual iron nanoparticles of nine different lateral dimensions from 80 nm down to 6 nm. The particles are probed simultaneously, under same conditions, during in-situ redox reaction using X-ray photoemission electron microscopy elucidating the size effect during the early stage of oxidation, yielding time-dependent evolution of iron oxides and the mechanism for the inter-conversion of oxides in nanoparticles. Fabrication of well-defined system followed by visualization and investigation of singled-out particles eliminates the ambiguities emerging from dispersed nanoparticles and reveals a significant increase in the initial rate of oxidation with decreasing size, but the reactivity per active site basis and the intrinsic chemical properties in the particles remain the same in the scale of interest. This advance of nanopatterning together with spatially-resolved single nanoparticle X-ray absorption spectroscopy will guide future discourse in understanding the impact of confinement of metal nanoparticles and pave way to solve fundamental questions in material science, chemical physics, magnetism, nanomedicine and nanocatalysis.

  4. Size-dependent redox behavior of iron observed by in-situ single nanoparticle spectro-microscopy on well-defined model systems

    Science.gov (United States)

    Karim, Waiz; Kleibert, Armin; Hartfelder, Urs; Balan, Ana; Gobrecht, Jens; van Bokhoven, Jeroen A.; Ekinci, Yasin

    2016-01-01

    Understanding the chemistry of nanoparticles is crucial in many applications. Their synthesis in a controlled manner and their characterization at the single particle level is essential to gain deeper insight into chemical mechanisms. In this work, single nanoparticle spectro-microscopy with top-down nanofabrication is demonstrated to study individual iron nanoparticles of nine different lateral dimensions from 80 nm down to 6 nm. The particles are probed simultaneously, under same conditions, during in-situ redox reaction using X-ray photoemission electron microscopy elucidating the size effect during the early stage of oxidation, yielding time-dependent evolution of iron oxides and the mechanism for the inter-conversion of oxides in nanoparticles. Fabrication of well-defined system followed by visualization and investigation of singled-out particles eliminates the ambiguities emerging from dispersed nanoparticles and reveals a significant increase in the initial rate of oxidation with decreasing size, but the reactivity per active site basis and the intrinsic chemical properties in the particles remain the same in the scale of interest. This advance of nanopatterning together with spatially-resolved single nanoparticle X-ray absorption spectroscopy will guide future discourse in understanding the impact of confinement of metal nanoparticles and pave way to solve fundamental questions in material science, chemical physics, magnetism, nanomedicine and nanocatalysis.

  5. 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.

  6. Tungsten and optics

    International Nuclear Information System (INIS)

    Reglero, V.; Velasco, T.; Rodrigo, J.; Gasent, L.J.; Alamo, J.; Chato, R.; Ruiz Urien, I.; Santos, I.; Zarauz, J.

    2001-01-01

    High energy astronomy research requires accurate location to perform multiwavelength studies of the cosmic gamma-ray emitters. New technologies have been developed to achieve this goal, the use of large spatial signal multiplexing systems (Masks). The optical system based on the use of coded Masks together with solid stated pixelated planes provide a point source location capability of 1 arc min, that is 3600 times better than of the last NASA CGRO mission. Different materials were considered to modulate the high energy signals, tungsten was selected for implementing the codes due to both its high density and large atomic number that provide the required stooping power. An overview of the programme carried out to design and manufacture the coded Masks is provided. (nevyjel)

  7. 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.

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

    International Nuclear Information System (INIS)

    Cleaves, Peter A.; Gardner, Benedict M.; Liddle, Stephen T.; Kefalidis, Christos E.; Maron, Laurent; Tuna, Floriana; McInnes, Eric J.L.; Lewis, William

    2017-01-01

    The reactivity of terminal uranium(V/VI) nitrides with CE 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 TIPS )(N)][K(B15C5) 2 ] (1, Tren TIPS =N(CH 2 CH 2 NSiiPr 3 ) 3 ; B15C5=benzo-15-crown-5) reacts with CO 2 to give [U(Tren TIPS )(O)(NCO)][K(B15C5) 2 ] (3), whereas the uranium(VI) nitride [U(Tren TIPS )(N)] (2) reacts with CO 2 to give isolable [U(Tren TIPS )(O)(NCO)] (4); complex 4 rapidly decomposes to known [U(Tren TIPS )(O)] (5) with concomitant formation of N 2 and CO proposed, with the latter trapped as a vanadocene adduct. In contrast, 1 reacts with CS 2 to give [U(Tren TIPS )(κ 2 -CS 3 )][K(B15C5) 2 ] (6), 2, and [K(B15C5) 2 ][NCS] (7), whereas 2 reacts with CS 2 to give [U(Tren TIPS )(NCS)] (8) and ''S'', with the latter trapped as Ph 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 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 2 as a reactivity surrogate for CO 2 . (copyright 2017 Wiley-VCH Verlag GmbH and Co. KGaA, Weinheim)

  9. TIG (Tungsten Inert Gas) welding

    International Nuclear Information System (INIS)

    Anon.

    2010-01-01

    After having recalled the Tungsten Inert Gas process principle and the different alternative TIG processes, the author explains the advantages and limits of this process. The applications and recent developments are given. (O.M.)

  10. Tungsten--carbide critical assembly

    International Nuclear Information System (INIS)

    Hansen, G.E.; Paxton, H.C.

    1975-06-01

    The tungsten--carbide critical assembly mainly consists of three close-fitting spherical shells: a highly enriched uranium shell on the inside, a tungsten--carbide shell surrounding it, and a steel shell on the outside. Ideal critical specifications indicate a rather low computed value of k/sub eff/. Observed and calculated fission-rate distributions for 235 U, 238 U, and 237 Np are compared, and calculated leakage neutrons per fission in various energy groups are given. (U.S.)

  11. Micro creep mechanisms of tungsten

    International Nuclear Information System (INIS)

    Levoy, R.; Hugon, I.; Burlet, H.; Baillin, X.; Guetaz, L.

    2000-01-01

    Due to its high melting point (3410 deg C), tungsten offers good mechanical properties at elevated temperatures for several applications in non-oxidizing environment. The creep behavior of tungsten is well known between 1200 and 2500 deg C and 10 -3 to 10 -1 strain. However, in some applications when dimensional stability of components is required, these strains are excessive and it is necessary to know the creep behavior of the material for micro-strains (between 10 -4 and 10 -6 ). Methods and devices used to measure creep micro-strains are presented, and creep equations (Norton and Chaboche laws) were developed for wrought, annealed and recrystallized tungsten. The main results obtained on tungsten under low stresses are: stress exponent 1, symmetry of micro-strains in creep-tension and creep-compression, inverse creep (threshold stress), etc. TEM, SEM and EBSD studies allow interpretation of the micro-creep mechanism of tungsten under low stresses and low temperature (∼0.3 K) like the Harper-Dorn creep. In Harper-Dorn creep, micro-strains are associated with the density and the distribution of dislocations existing in the crystals before creep. At 975 deg C, the initial dislocation structure moves differently whether or not a stress is applied. To improve the micro-creep behavior of tungsten, a heat treatment is proposed to create the optimum dislocation structure. (authors)

  12. 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

  13. 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)

  14. 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

  15. Tungsten wire and tubing joined by nickel brazing

    Science.gov (United States)

    1965-01-01

    Thin tungsten wire and tungsten tubing are brazed together using a contacting coil of nickel wire heated to its melting point in an inert-gas atmosphere. This method is also effective for brazing tungsten to tungsten-rhenium parts.

  16. 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.

  17. Toughness enhancement of tungsten reinforced with short tungsten fibres

    Energy Technology Data Exchange (ETDEWEB)

    Jiang, Y. [Key Laboratory of Materials Physics, Institute of Solid State Physics, Chinese Academy of Sciences, Hefei 230031 (China); Zhang, L.H. [Key Laboratory of Materials Physics, Institute of Solid State Physics, Chinese Academy of Sciences, Hefei 230031 (China); University of Science and Technology of China, Hefei 230026 (China); Fang, Q.F., E-mail: qffang@issp.ac.cn [Key Laboratory of Materials Physics, Institute of Solid State Physics, Chinese Academy of Sciences, Hefei 230031 (China); University of Science and Technology of China, Hefei 230026 (China); Zhang, T.; Wang, X.P.; Hao, T.; Liu, C.S. [Key Laboratory of Materials Physics, Institute of Solid State Physics, Chinese Academy of Sciences, Hefei 230031 (China)

    2017-04-06

    The feasibility and toughening efficiency of the short tungsten fibre reinforcement on tungsten were investigated in W{sub f}/W composites fabricated by powder metallurgy method of spark plasma sintering. Fibres in the composites presented a Z-free laminar structure. Partial recrystallization of fibre grains occurred but fibre crack or damage was not detected. Fracture energy of W{sub f}/W composites was estimated in tensile tests, and the results indicated great toughness improvement over pure tungsten in virtue of frictional pullout and plastic deformation of fibres, and matrix-fibres interfacial debonding since 873 K. The specimen with mass fraction of 10% and fibre diameter of 100 µm exhibits the largest elongation of 9±1.1% and the highest ultimate strength of 482±13 MPa at 873 K.

  18. 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; Dé ry, Alexandre; Callens, Emmanuel; Poater, Albert; Samantaray, Manoja; Dey, Raju; Hong, Jinhua; Li, Kun; Cavallo, Luigi; Basset, Jean-Marie

    2015-01-01

    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

  19. Surface energy anisotropy of tungsten

    Energy Technology Data Exchange (ETDEWEB)

    Kumar, R; Grenga, H E [Georgia Inst. of Tech., Atlanta (USA). School of Chemical Engineering

    1976-10-01

    Field-ion microscopy was used to study the faceting behavior and/or surface energy anisotropy of tungsten in vacuum and in hydrogen. In vacuum below 1700 K the activation energy for (110) facet growth agreed with values previously reported for surface diffusion on tungsten. The observed anisotropy values at 0.5 Tsub(m), where Tsub(m) is the absolute melting temperature of tungsten (approximately 3680 K), were different from those previously reported at higher temperatures and more nearly agreed with broken bond calculations based on Mie potential using m=5, n=8, and a 1.5% lattice expansion. Hydrogen appeared to have a negligible effect on surface energy anisotropy, but did preferentially increase surface diffusion rates on (310) regions.

  20. Fractographic peculiarities of cermet tungsten fracture

    International Nuclear Information System (INIS)

    Stepanenko, V.A.; Babak, A.V.; Uskov, E.I.

    1982-01-01

    Effect of test temperature on fracture peculiarities of cermets tungsten with initial cellular structure of deformation is shown. Tungsten crack resistance increases at temperatures to Tsub(x) (ductile-brittle transition temperature) and decreases at temperatures above Tsub(x). The degree of ceramics tungsten plasticity realization depends on its crack resistance

  1. Recrystallization and embrittlement of sintered tungsten

    International Nuclear Information System (INIS)

    Bega, N.D.; Babak, A.V.; Uskov, E.I.

    1982-01-01

    The recrystallization of sintered tungsten with a cellular structure of deformation is studied as related to its embrittlement. It is stated that in case of preliminary recrystallization the sintered tungsten crack resistance does not depend on the testing temperature. The tungsten crack resistance is shown to lower with an increase of the structure tendency to primary recrystallization [ru

  2. 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.

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

    KAUST Repository

    Espinas, Jeff; Pelletier, Jeremie; Abou-Hamad, Edy; Emsley, Lyndon; Basset, Jean-Marie

    2012-01-01

    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.

  4. Gleeble Testing of Tungsten Samples

    Science.gov (United States)

    2013-02-01

    temperature on an Instron load frame with a 222.41 kN (50 kip) load cell . The samples were compressed at the same strain rate as on the Gleeble...ID % RE Initial Density (cm 3 ) Density after Compression (cm 3 ) % Change in Density Test Temperature NT1 0 18.08 18.27 1.06 1000 NT3 0...4.1 Nano-Tungsten The results for the compression of the nano-tungsten samples are shown in tables 2 and 3 and figure 5. During testing, sample NT1

  5. 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.

  6. Preparation of silica-supported carbon by Kraft lignin pyrolysis, and its use in solid-phase extraction of fluoroquinolones from environmental waters

    International Nuclear Information System (INIS)

    Speltini, Andrea; Sturini, Michela; Maraschi, Federica; Mandelli, Elettra; Dondi, Daniele; Profumo, Antonella; Vadivel, Dhanalakshmi

    2016-01-01

    The article describes a carbon-based material for solid-phase extraction (SPE) of fluoroquinolones from waters. It was obtained by pyrolytic deposition of Kraft lignin (LG) on silica particles. Marbofloxacin (MAR) and enrofloxacin (ENR) were chosen as model contaminants. The material was prepared by first adsorbing LG onto silica microparticles, this followed by pyrolytic treatment at 1200 °C for 2 h. Silica-supported carbon was characterized by scanning electron microscopy, surface area measurement (by BET), thermogravimetric analysis, and electron paramagnetic resonance. The carbon-coated silica particles were then tested as a column packing for SPE of MAR and ENR from spiked tap and river waters. Quantitative adsorption was observed at pH values of ∼7.5 for both drugs. They were eluted with a 70:30 mixture of aqueous tetrabutylammonium hydroxide and acetonitrile and then quantified by HPLC coupled to fluorescence detection. Samples spiked with MAR and ENR in the range from 10 to 1000 ng·L"−"1 gave recoveries ranging from 70 to 116% (for n = 3). Good inter-day precision (with RSDs between 7 and 16%) was observed for 20–1000 ng·L"−"1 spikes, also in natural river water. Sample volumes up to 500 mL provided enrichment factors up to 125, and this makes this material useful for determination of the two drugs at environmentally significant levels which are as low as a few ng·L"−"1. The batch-to-batch reproducibility was verified for 3 preparations. The sorbent was successfully applied to the determination of these drugs in environmental waters. (author)

  7. Hydrogen retention properties of polycrystalline tungsten and helium irradiated tungsten

    International Nuclear Information System (INIS)

    Hino, T.; Koyama, K.; Yamauchi, Y.; Hirohata, Y.

    1998-01-01

    The hydrogen retention properties of a polycrystalline tungsten and tungsten irradiated by helium ions with an energy of 5 keV were examined by using an ECR ion irradiation apparatus and a technique of thermal desorption spectroscopy, TDS. The polycrystalline tungsten was irradiated at RT with energetic hydrogen ions, with a flux of 10 15 H cm -2 and an energy of 1.7 keV up to a fluence of 5 x 10 18 H cm -2 . Subsequently, the amount of retained hydrogen was measured by TDS. The heating temperature was increased from RT to 1000 C, and the heating rate was 50 C min -1 . Below 1000 C, two distinct hydrogen desorption peaks were observed at 200 C and 400 C. The retained amount of hydrogen was observed to be five times smaller than that of graphite, but the concentration in the implantation layer was comparable with that of graphite. Also, the polycrystalline tungsten was irradiated with 5 keV helium ions up to a fluence of 1.4 x 10 18 He cm -2 , and then re-irradiated with 1.7 keV hydrogen ions. The amount of retained hydrogen in this later experiment was close to the value in the case without prior helium ion irradiation. However, the amount of hydrogen which desorbed around the low temperature peak, 200 C, was largely enhanced. The desorption amount at 200 C saturated for the helium fluence of more than 5 x 10 17 He cm -2 . The present data shows that the trapping state of hydrogen is largely changed by the helium ion irradiation. Additionally, 5 keV helium ion irradiation was conducted on a sample pre-implanted with hydrogen ions to simulate a helium ion impact desorption of hydrogen retained in tungsten. The amount of the hydrogen was reduced as much as 50%. (orig.)

  8. Deuterium inventory in tungsten after plasma exposure. A microstructural survey

    International Nuclear Information System (INIS)

    Manhard, Armin

    2012-09-01

    Tungsten is a promising material for armouring the plasma-facing wall of future nuclear fusion experiments and power plants. It has a very high melting point, good thermal conductivity and is highly resistant against physical sputtering by energetic particles from the plasma. It also has a very low solubility for hydrogen isotopes. This is important both for safety and also for economic reasons, in particular with regard to the radioactive fusion fuel tritium. Due to this low solubility, the retention of hydrogen isotopes in tungsten materials after exposure to a plasma is dominated by the trapping of hydrogen isotopes at tungsten lattice defects. Therefore, a strong dependence of the hydrogen isotope retention on the microstructure of the tungsten is to be expected. This work describes a survey study of tungsten with different microstructures exposed to deuterium plasmas under a wide range of different plasma exposure conditions. The isotope deuterium was used because its natural abundance is much smaller than that of hydrogen (i.e., 1 H). This allows detecting even very small amounts retained in the tungsten practically without background signal. Furthermore, the use of deuterium allows utilising the nuclear reaction 2 D( 3 He,p) 4 He for depth-resolved quantification of the deuterium inventory up to depths of several microns. In order to standardise the specimens as far as possible, they were all cut from the same initial material from a single manufacturing batch. After a chemo-mechanical polishing procedure, which produces a well-defined surface, the specimens were annealed at either of four different temperatures in order to modify the grain structure and the dislocation density. These were then characterised by scanning electron microscopy and scanning transmission electron microscopy. The specimens were subsequently exposed in a fully characterised deuterium plasma source at different specimen temperatures, ion energies and deuterium fluences. In addition

  9. Prompt ignition of a unipolar arc on helium irradiated tungsten

    International Nuclear Information System (INIS)

    Kajita, Shin; Takamura, Shuichi; Ohno, Noriyasu

    2009-01-01

    A fibreform nanostructured layer is formed on a tungsten surface by helium plasma bombardment. The helium fluence was of the order of 10 26 m -2 , and the surface temperature and incident ion energy during helium irradiation were, respectively, 1900 K and 75 eV. By irradiating a laser pulse to the surface in the plasma, a unipolar arc, which many people have tried to verify in well-defined experiments, is promptly initiated and continued for a much longer time than the laser pulse width. The laser pulse width (∼0.6 ms) and power (∼5 MJ m -2 ) are similar to the heat load accompanied by type-I edge localized modes (ELMs) in ITER. The unipolar arc is verified from an increase in the floating potential, a moving arc spot detected by a fast camera and arcing traces on the surface. This result suggests that the nanostructure on the tungsten surface formed by the bombardment of helium, which is a fusion product, could significantly change the ignition property of arcing, and ELMs become a trigger of unipolar arcing, which would be a great impurity source in fusion devices. (letter)

  10. 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

  11. Fabrication of tungsten wire needles

    International Nuclear Information System (INIS)

    Roder, A.

    1983-02-01

    Fine point needles for field emissoin are conventionally produced by electrolytically or chemically etching tungsten wire. Points formed in this manner have a typical tip radius of about 0.5 microns and a cone angle of some 30 degrees. The construction of needle matrix detector chambers has created a need for tungsten needles whose specifications are: 20 mil tungsten wire, 1.5 inch total length, 3 mm-long taper (resulting in a cone angle of about 5 degrees), and 25 micron-radius point (similar to that found on sewing needles). In the process described here for producing such needles, tungsten wire, immersed in a NaOH solution and in the presence of an electrode, is connected first to an ac voltage and then to a dc supply, to form a taper and a point on the end of the wire immersed in the solution. The process parameters described here are for needles that will meet the above specifications. Possible variations will be discussed under each approprite heading

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

    International Nuclear Information System (INIS)

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

    2017-01-01

    In tungsten fibre-reinforced tungsten composites (W f /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 W f /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 μ m as well as wire electrochemically thinned to a diameter of 5 μ m 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. (paper)

  13. 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%)

  14. Tungsten oxide nanowires grown on amorphous-like tungsten films

    International Nuclear Information System (INIS)

    Dellasega, D; Pezzoli, A; Russo, V; Passoni, M; Pietralunga, S M; Nasi, L; Conti, C; Vahid, M J; Tagliaferri, A

    2015-01-01

    Tungsten oxide nanowires have been synthesized by vacuum annealing in the range 500–710 °C from amorphous-like tungsten films, deposited on a Si(100) substrate by pulsed laser deposition (PLD) in the presence of a He background pressure. The oxygen required for the nanowires formation is already adsorbed in the W matrix before annealing, its amount depending on deposition parameters. Nanowire crystalline phase and stoichiometry depend on annealing temperature, ranging from W_1_8O_4_9-Magneli phase to monoclinic WO_3. Sufficiently long annealing induces the formation of micrometer-long nanowires, up to 3.6 μm with an aspect ratio up to 90. Oxide nanowire growth appears to be triggered by the crystallization of the underlying amorphous W film, promoting their synthesis at low temperatures. (paper)

  15. Thermodynamics of the hydrogen-carbon-oxygen-tungsten system, as applied to the manufacture of tungsten and tungsten carbide

    International Nuclear Information System (INIS)

    Schwenke, G.K.

    2001-01-01

    The thermodynamics of the quaternary hydrogen-carbon oxygen-tungsten system and its binary and ternary sub-systems are reviewed. Published thermodynamic data are evaluated, and expression for free energies of formation are chosen. These expressions are integrated with and equilibrium-calculating algorithm, producing a powerful tool for understanding and improving the manufacture of tungsten and tungsten carbide. Three examples are presented: reduction/carburization of tungstic oxide with hydrogen, carbon, and methane. (author)

  16. 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.

  17. Tungsten foil laminate for structural divertor applications - Joining of tungsten foils

    Science.gov (United States)

    Reiser, Jens; Rieth, Michael; Möslang, Anton; Dafferner, Bernhard; Hoffmann, Jan; Mrotzek, Tobias; Hoffmann, Andreas; Armstrong, D. E. J.; Yi, Xiaoou

    2013-05-01

    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.

  18. Development and characterisation of a tungsten-fibre reinforced tungsten composite

    International Nuclear Information System (INIS)

    Riesch, Johann

    2012-01-01

    In tungsten-fibre reinforced tungsten, tungsten wire is combined with a tungsten matrix. The outstanding ductility of the fibres and extrinsic mechanisms of energy dissipation lead to an intense toughening. With extensive analytical and experimental investigations a manufacturing method based on chemical vapour infiltration is developed and first material is produced. The toughening mechanisms are shown by means of sophisticated mechanical experiments i.a. X-ray microtomography.

  19. Potentiometric determination of the tungsten content of tantalum-tungsten alloys with chromium II

    International Nuclear Information System (INIS)

    Gavra, Z.; Ronen, S.; Levin, R.

    1977-05-01

    A method was developed for the potentiometric determination of the tungsten content of tantalum-tungsten alloys of different compositions. These were dissolved under conditions that enabled the tungsten content to be determined with chromium (II). Phosphoric acid was selected as a suitable complexing agent for the prevention of the precipitation of tungsten and tantalum compounds. The use of chromium (II) required an oxygen-tight system and therefore the work was carried out in suitable vessels for storage and tritation

  20. Tungsten Speciation in Firing Range Soils

    Science.gov (United States)

    2011-01-01

    satisfactorily, such as: which tungsten mineral phase is present in soil and to what extent is adsorption important in regu- lating soil solution concentrations... soil solution rather than discrete mineral phases. Information provided in this report will assist the following organizations in future decision...the soil solution ERDC TR-11-1 43 must affect tungsten speciation in other ways. The precipitation of soil minerals also would limit tungsten

  1. 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…

  2. 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.

  3. 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.

  4. Mechanism of the electrochemical hydrogen reaction on smooth tungsten carbide and tungsten electrodes

    International Nuclear Information System (INIS)

    Wiesener, K.; Winkler, E.; Schneider, W.

    1985-01-01

    The course of the electrochemical hydrogen reaction on smooth tungsten-carbide electrodes in hydrogen saturated 2.25 M H 2 SO 4 follows a electrochemical sorption-desorption mechanism in the potential range of -0.4 to +0.1 V. At potentials greater than +0.1 V the hydrogen oxidation is controlled by a preliminary chemical sorption step. Concluding from the similar behaviour of tungsten-carbide and tungsten electrodes after cathodic pretreatment, different tungsten oxides should be involved in the course of the hydrogen reaction on tungsten carbide electrodes. (author)

  5. Development of quantitative atomic modeling for tungsten transport study Using LHD plasma with tungsten pellet injection

    International Nuclear Information System (INIS)

    Murakami, I.; Sakaue, H.A.; Suzuki, C.; Kato, D.; Goto, M.; Tamura, N.; Sudo, S.; Morita, S.

    2014-10-01

    Quantitative tungsten study with reliable atomic modeling is important for successful achievement of ITER and fusion reactors. We have developed tungsten atomic modeling for understanding the tungsten behavior in fusion plasmas. The modeling is applied to the analysis of tungsten spectra observed from currentless plasmas of the Large Helical Device (LHD) with tungsten pellet injection. We found that extreme ultraviolet (EUV) lines of W 24+ to W 33+ ions are very sensitive to electron temperature (Te) and useful to examine the tungsten behavior in edge plasmas. Based on the first quantitative analysis of measured spatial profile of W 44+ ion, the tungsten concentration is determined to be n(W 44+ )/n e = 1.4x10 -4 and the total radiation loss is estimated as ∼4 MW, of which the value is roughly half the total NBI power. (author)

  6. 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.).

  7. Quenching and recovery experiments on tungsten

    International Nuclear Information System (INIS)

    Rasch, K.D.; Siegel, R.W.; Schultz, H.

    1976-01-01

    A short summary is given of new results concerning transmission electron microscopy and resistivity measurements on quenched tungsten. These results give evidence for the first time that the quenching and annealing of high purity tungsten leads to vacancy--defect clustering resulting in small voids observable in the electron microscope. 21 references

  8. Tungsten deposition by hydrogen-atom reaction with tungsten hexafluoride

    International Nuclear Information System (INIS)

    Lee, W.W.

    1991-01-01

    Using gaseous hydrogen atoms with WF 6 , tungsten atoms can be produced in a gas-phase reaction. The atoms then deposit in a near-room temperature process, which results in the formation of tungsten films. The W atoms (10 10 -10 11 /cm 3 ) were measured in situ by atomic absorption spectroscopy during the CVD process. Deposited W films were characterized by Auger electron spectroscopy, Rutherford backscattering, and X-ray diffraction. The surface morphology of the deposited films and filled holes was studied using scanning electron microscopy. The deposited films were highly adherent to different substrates, such as Si, SiO 2 , Ti/Si, TiN/Si and Teflon. The reaction mechanism and kinetics were studied. The experimental results indicated that this method has three advantages compared to conventional CVD or PECVD: (1) film growth occurs at low temperatures; (2) deposition takes place in a plasma-free environment; and (3) a low level of impurities results in high-quality adherent films

  9. 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; Callens, Emmanuel; Espinas, Jeff; Dé ry, Alexandre; Samantaray, Manoja; Dey, Raju; Basset, Jean-Marie

    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.

  10. 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...

  11. Reorientation measurements on tungsten isotopes

    Energy Technology Data Exchange (ETDEWEB)

    O' Brien, J J; Saladin, J X; Baktash, C; Alessi, J G [Pittsburgh Univ., Pa. (USA)

    1977-11-14

    In a particle-..gamma.. coincidence experiment, a thick tungsten target, of natural isotopic abundance, was bombarded with ..cap alpha.. and /sup 16/O beams. From analysis of the deexcitation ..gamma..-rays following Coulomb excitation, the spectroscopic quadrupole moment of the second 2/sup +/ state (the 2/sup +/' state) was determined for /sup 186/W and /sup 184/W. In a separate Coulomb excitation experiment a thin, isotopically enriched /sup 186/W target was bombarded with /sup 16/O ions. From analysis of projectiles scattered elastically and inelastically the quadrupole moment of the 2/sup +/' state of /sup 186/W was extracted. The results of the two experiments are in good agreement. The quadrupole moment of the 2/sup +/' state is found to be opposite in sign to that of the first 2/sup +/ state for both isotopes studied. However, its magnitude decreases rapidly in going from /sup 186/W to /sup 184/W, in contrast to the predictions of the rotation-vibration of asymmetric rotor models. The microscopic theory of Kumar and Baranger does predict the experimental trend, qualitatively. Thus the present results are interpreted as being evidence of strong coupling between ..beta.. and ..gamma.. degrees of freedom in the tungsten isotopes, which, according to the theory of Kumar and Baranger, is the source of the reduced value of the quadrupole moment.

  12. Development of tungsten fibre-reinforced tungsten composites towards their use in DEMO—potassium doped tungsten wire

    Science.gov (United States)

    Riesch, J.; Han, Y.; Almanstötter, J.; Coenen, J. W.; Höschen, T.; Jasper, B.; Zhao, P.; Linsmeier, Ch; Neu, R.

    2016-02-01

    For the next step fusion reactor the use of tungsten is inevitable to suppress erosion and allow operation at elevated temperature and high heat loads. Tungsten fibre-reinforced composites overcome the intrinsic brittleness of tungsten and its susceptibility to operation embrittlement and thus allow its use as a structural as well as an armour material. That this concept works in principle has been shown in recent years. In this contribution we present a development approach towards its use in a future fusion reactor. A multilayer approach is needed addressing all composite constituents and manufacturing steps. A huge potential lies in the optimization of the tungsten wire used as fibre. We discuss this aspect and present studies on potassium doped tungsten wire in detail. This wire, utilized in the illumination industry, could be a replacement for the so far used pure tungsten wire due to its superior high temperature properties. In tensile tests the wire showed high strength and ductility up to an annealing temperature of 2200 K. The results show that the use of doped tungsten wire could increase the allowed fabrication temperature and the overall working temperature of the composite itself.

  13. Development of tungsten fibre-reinforced tungsten composites towards their use in DEMO—potassium doped tungsten wire

    International Nuclear Information System (INIS)

    Riesch, J; Han, Y; Höschen, T; Zhao, P; Neu, R; Almanstötter, J; Coenen, J W; Jasper, B; Linsmeier, Ch

    2016-01-01

    For the next step fusion reactor the use of tungsten is inevitable to suppress erosion and allow operation at elevated temperature and high heat loads. Tungsten fibre-reinforced composites overcome the intrinsic brittleness of tungsten and its susceptibility to operation embrittlement and thus allow its use as a structural as well as an armour material. That this concept works in principle has been shown in recent years. In this contribution we present a development approach towards its use in a future fusion reactor. A multilayer approach is needed addressing all composite constituents and manufacturing steps. A huge potential lies in the optimization of the tungsten wire used as fibre. We discuss this aspect and present studies on potassium doped tungsten wire in detail. This wire, utilized in the illumination industry, could be a replacement for the so far used pure tungsten wire due to its superior high temperature properties. In tensile tests the wire showed high strength and ductility up to an annealing temperature of 2200 K. The results show that the use of doped tungsten wire could increase the allowed fabrication temperature and the overall working temperature of the composite itself. (paper)

  14. Development of quantitative atomic modeling for tungsten transport study using LHD plasma with tungsten pellet injection

    Science.gov (United States)

    Murakami, I.; Sakaue, H. A.; Suzuki, C.; Kato, D.; Goto, M.; Tamura, N.; Sudo, S.; Morita, S.

    2015-09-01

    Quantitative tungsten study with reliable atomic modeling is important for successful achievement of ITER and fusion reactors. We have developed tungsten atomic modeling for understanding the tungsten behavior in fusion plasmas. The modeling is applied to the analysis of tungsten spectra observed from plasmas of the large helical device (LHD) with tungsten pellet injection. We found that extreme ultraviolet (EUV) emission of W24+ to W33+ ions at 1.5-3.5 nm are sensitive to electron temperature and useful to examine the tungsten behavior in edge plasmas. We can reproduce measured EUV spectra at 1.5-3.5 nm by calculated spectra with the tungsten atomic model and obtain charge state distributions of tungsten ions in LHD plasmas at different temperatures around 1 keV. Our model is applied to calculate the unresolved transition array (UTA) seen at 4.5-7 nm tungsten spectra. We analyze the effect of configuration interaction on population kinetics related to the UTA structure in detail and find the importance of two-electron-one-photon transitions between 4p54dn+1- 4p64dn-14f. Radiation power rate of tungsten due to line emissions is also estimated with the model and is consistent with other models within factor 2.

  15. Micro-powder injection moulding of tungsten

    International Nuclear Information System (INIS)

    Zeep, B.

    2007-12-01

    For He-cooled Divertors as integral components of future fusion power plants, about 300000 complex shaped tungsten components are to be fabricated. Tungsten is the favoured material because of its excellent properties (high melting point, high hardness, high sputtering resistance, high thermal conductivity). However, the material's properties cause major problems for large scale production of complex shaped components. Due to the resistance of tungsten to mechanical machining, new fabrication technologies have to be developed. Powder injection moulding as a well established shaping technology for a large scale production of complex or even micro structured parts might be a suitable method to produce tungsten components for fusion applications but is not yet commercially available. The present thesis is dealing with the development of a powder injection moulding process for micro structured tungsten components. To develop a suitable feedstock, the powder particle properties, the binder formulation and the solid load were optimised. To meet the requirements for a replication of micro patterned cavities, a special target was to define the smallest powder particle size applicable for micro-powder injection moulding. To investigate the injection moulding performance of the developed feedstocks, experiments were successfully carried out applying diverse cavities with structural details in micro dimension. For debinding of the green bodies, a combination of solvent debinding and thermal debinding has been adopted for injection moulded tungsten components. To develop a suitable debinding strategy, a variation of the solvent debinding time, the heating rate and the binder formulation was performed. For investigating the thermal consolidation behaviour of tungsten components, sinter experiments were carried out applying tungsten powders suitable for micro-powder injection moulding. First mechanical tests of the sintered samples showed promising material properties such as a

  16. An investigation of tungsten by neutron activation techniques

    International Nuclear Information System (INIS)

    Svetsreni, R.

    1978-01-01

    This investigation used neutron from Plutonium-Beryllium source (5 curie) to analyse the amount of tungsten in tungsten oxide which was extracted from tungsten ores, slag and tungsten alloy of tungsten iron and carbon. The technique of neutron activation analysis with NaI(Tl) gamma detector 3'' x 3'' and 1024 multichannel analyzer. The dilution technique was used by mixing Fe 2 O 3 or pure sand into the sample before irradiation. In this study self shielding effect in the analysis of tungsten was solved and the detection limit of the tungsten in the sample was about 0.5%

  17. Environmental fate of tungsten from military use

    International Nuclear Information System (INIS)

    Clausen, Jay L.; Korte, Nic

    2009-01-01

    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

  18. 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.

  19. 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)

  20. Combustion of powdery tungsten in pyrotechnic mixtures

    International Nuclear Information System (INIS)

    Ivanov, G.V.; Reshetov, A.A.; Viktorenko, A.M.; Surkov, V.G.; Karmadonov, L.N.

    1982-01-01

    The basic regularities of tungsten burning (powder 2-5 μm) with oxidizers most typical for pyrotechnics: nitrates, lead and barium peroxides (powder, 2-8 μm) and potassium perchlorate (powder, 2-8 μm) are studied. Dependences of burning rate as a function of pressure and ratio of components are established. It is supposed that tungsten burning in mixtures with the mentioned nitrates is a complex and multistage process the rate of which is determined by tungsten dissolution in nitrate melts. Analysis of burning products using available methods is complex

  1. Characterization of porous tungsten by microhardness

    International Nuclear Information System (INIS)

    Selcuk, C.; Wood, J.V.; Morley, N.; Bentham, R.

    2001-01-01

    One of the applications of tungsten is as high current density dispenser cathode in the form of porous tungsten. It is used as a cathode after being impregnated with an electron emissive material so pore distribution in the part is the most important parameter for its function as a uniform and controlled porosity will lead to a better performance. In this study, application of microhardness as a characterization method for uniformity of the pore distribution and homogeneity of the structure is introduced. Optical microscopy and SEM is used to relate the results and porous tungsten structure for a better understanding of the method applied. (author)

  2. The electrodeposition of niobium on tungsten

    International Nuclear Information System (INIS)

    Taylor, R.G.

    1977-03-01

    The electrodeposition of niobium on a tungsten substrate has been demonstrated by electrolysis of an alkali metal fluoride melt. The deposit produced was non-porous, coherent and formed a good bond to the substrate. (author)

  3. Modeling of hydrogen desorption from tungsten surface

    Energy Technology Data Exchange (ETDEWEB)

    Guterl, J., E-mail: jguterl@ucsd.edu [University of California, San Diego, La Jolla, CA 92093 (United States); Smirnov, R.D. [University of California, San Diego, La Jolla, CA 92093 (United States); Krasheninnikov, S.I. [University of California, San Diego, La Jolla, CA 92093 (United States); Nuclear Research National University MEPhI, Moscow 115409 (Russian Federation); Uberuaga, B.; Voter, A.F.; Perez, D. [Los Alamos National Laboratory, Los Alamos, NM 8754 (United States)

    2015-08-15

    Hydrogen retention in metallic plasma-facing components is among key-issues for future fusion devices. For tungsten, which has been chosen as divertor material in ITER, hydrogen desorption parameters experimentally measured for fusion-related conditions show large discrepancies. In this paper, we therefore investigate hydrogen recombination and desorption on tungsten surfaces using molecular dynamics simulations and accelerated molecular dynamics simulations to analyze adsorption states, diffusion, hydrogen recombination into molecules, and clustering of hydrogen on tungsten surfaces. The quality of tungsten hydrogen interatomic potential is discussed in the light of MD simulations results, showing that three body interactions in current interatomic potential do not allow to reproduce hydrogen molecular recombination and desorption. Effects of surface hydrogen clustering on hydrogen desorption are analyzed by introducing a kinetic model describing the competition between surface diffusion, clustering and recombination. Different desorption regimes are identified and reproduce some aspects of desorption regimes experimentally observed.

  4. SINTERED REFRACTORY TUNGSTEN ALLOYS. Gesinterte hochschmelzende wolframlegierungen

    Energy Technology Data Exchange (ETDEWEB)

    Kieffer, R.; Sedlatschek, K.; Braun, H.

    1971-12-15

    Dependence of the melting point of the refractory metals on their positions in the periodic system - alloys of tungsten with other refractory metals - sintering of the alloys - processing of the alloys - technological properties.

  5. A solid tungsten divertor for ASDEX Upgrade

    International Nuclear Information System (INIS)

    Herrmann, A; Greuner, H; Jaksic, N; Böswirth, B; Maier, H; Neu, R; Vorbrugg, S

    2011-01-01

    The conceptual design of a solid tungsten divertor for ASDEX Upgrade (AUG) is presented. The Div-III design is compatible with the existing divertor structure. It re-establishes the energy and heat receiving capability of a graphite divertor and overcomes the limitations of tungsten coatings. In addition, a solid tungsten divertor allows us to investigate erosion and bulk deuterium retention as well as test castellation and target tilting. The design criteria as well as calculations of forces due to halo and eddy currents are presented. The thermal properties of the proposed sandwich structure are calculated with finite element method models. After extensive testing of a target tile in the high heat flux test facility GLADIS, two solid tungsten tiles were installed in AUG for in-situ testing.

  6. Viscoelastic model of tungsten 'fuzz' growth

    International Nuclear Information System (INIS)

    Krasheninnikov, S I

    2011-01-01

    A viscoelastic model of fuzz growth is presented. The model describes the main features of tungsten fuzz observed in experiments. It gives estimates of fuzz growth rate and temperature range close to experimental ones.

  7. Tungsten: A Preliminary Environmental Risk Assessment

    Science.gov (United States)

    2011-05-01

    Tungsten Effects on Soil Microbial Communities BUILDING STRONG® Actinobacteria Bacteroidetes Firmicutes alpha-Proteobacteria beta-Proteobacteria gamma...Persistence of Actinobacteria & gamma- Proteobacteria • Actinobacteria – includes the actinomycetes  γ-Proteobacteria – includes a variety of microbes

  8. Tungsten metallizing alumina--yttria ceramics

    International Nuclear Information System (INIS)

    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

  9. Strain aging in tungsten heavy alloys

    International Nuclear Information System (INIS)

    Dowding, R.J.; Tauer, K.J.

    1991-01-01

    This paper reports on tungsten heavy alloys which are two-phase mixtures of body center cubic (BCC) tungsten surrounded by a face center cubic (FCC) matrix. The matrix is most often composed of nickel and iron in a ratio of 70:30 but, occasionally, the matrix may also contain cobalt or copper. Nickel, however, is always the primary matrix component. The tungsten heavy alloy is fabricated through powder metallurgy techniques. Elemental powders are blended, pressed to shape, and sintered. Depending upon the tungsten content, the sintering temperatures are usually in the range of 1450 degrees C to 1525 degrees C. These temperatures are high enough that, as a result, the matrix is at the liquid phase and the process is known as liquid phase sintering. At the liquid phase temperature, the matrix becomes saturated with tungsten, but this does not change the FCC character of the matrix. The sintering is usually done in a hydrogen atmosphere furnace in order to reduce the oxides on the tungsten powder surfaces and create clean, active surfaces which will enhance the adherence between the tungsten and the matrix. The hydrogen atmosphere also creates the presence of excess dissolved hydrogen in the alloy. It has been shown that the hydrogen degrades the toughness and ductility of the heavy alloy. A post-sintering vacuum heat treatment is generally required to insure that there is no residual hydrogen present. The as-sintered tensile strength of a 90% tungsten, 7% nickel, 3% iron alloy (90W) is in the range of 800 to 940 MPa and can be increased significantly by cold working, usually rolling or swaging. Swaging to reductions in area of 20% can result in tensile strengths of 1250 MPa or more. As the strength increases, the elongation, which may have been 30% or more, decreases to less than 5%

  10. Problems of tungsten crack resistance optimization

    International Nuclear Information System (INIS)

    Babak, A.V.; Uskov, E.I.

    1986-01-01

    Technically pure and precipitation-hardening tungsten is studied for its crack resistance in the initial and hardened states at the temperatures of 20...2000 deg C. Results of the study are presented. It is shown that hardening of tungsten base alloys in oil from the temperature corresponding to the upper boundary of the temperature region of ductile-brittle transition increases a crack propagation resistance of the studied materias at elevated and high temperatures

  11. Determination of phenolic acids and flavonoids in raw propolis by silica-supported ionic liquid-based matrix solid phase dispersion extraction high performance liquid chromatography-diode array detection.

    Science.gov (United States)

    Wang, Zhibing; Sun, Rui; Wang, Yuanpeng; Li, Na; Lei, Lei; Yang, Xiao; Yu, Aimin; Qiu, Fangping; Zhang, Hanqi

    2014-10-15

    The silica-supported ionic liquid (S-SIL) was prepared by impregnation and used as the dispersion adsorbent of matrix solid phase dispersion (MSPD) for the simultaneous extraction of eight phenolic acids and flavonoids, including caffeic acid, ferulic acid, morin, luteolin, quercetin, apigenin, chrysin, and kaempferide in raw propolis. High performance liquid chromatography with a Zorbax SB-C18 column (150mm×4.6mm, 3.5μm) was used for separation of the analytes. The mobile phase consisted of 0.2% phosphoric acid aqueous solution and acetonitrile and the flow rate of the mobile phase was 0.5mL/min. The experimental conditions for silica-supported ionic liquid-based matrix solid phase dispersion (S-SIL-based MSPD) were optimized. S-SIL containing 10% [C6MIM]Cl was used as dispersant, 20mL of n-hexane as washing solvent and 15mL of methanol as elution solvent. The ratio of S-SIL to sample was selected to be 4:1. The standard curves showed good linear relationship (r>0.9995). The limits of detection and quantification were in the range of 5.8-22.2ngmL(-1) and 19.2-74.0ngmL(-1), respectively. The relative standard deviations (RSDs) of intra-day and inter-day determination were lower than 8.80% and 11.19%, respectively. The recoveries were between 65.51% and 92.32% with RSDs lower than 8.95%. Compared with ultrasound-assisted extraction (UAE) and soxhlet extraction, the present method consumed less sample, organic solvent, and extraction time, although the extraction yields obtained by S-SIL-based MSPD are slightly lower than those obtained by UAE. Copyright © 2014 Elsevier B.V. All rights reserved.

  12. Tungsten foil laminate for structural divertor applications – Analyses and characterisation of tungsten foil

    International Nuclear Information System (INIS)

    Reiser, Jens; Rieth, Michael; Dafferner, Bernhard; Hoffmann, Andreas; Yi Xiaoou; Armstrong, David E.J.

    2012-01-01

    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 μm × 3 μm × 15 μm and a clear texture in (1 0 0) 〈0 1 1〉. 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 °C). This shows that the ductility is a thermally activated process. Recrystallised tungsten foil (annealed for 1 h/2700 °C) shows ductile material behaviour at 200 °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).

  13. Substitution of thoriated tungsten electrodes in Switzerland

    International Nuclear Information System (INIS)

    Kunz, H.; Piller, G.

    2006-01-01

    Thoriated tungsten electrodes are frequently used for inert gas welding (TIG/WIG). The use of these electrodes can lead to doses which are well above the limit for the general population (1mSv/year). This has been shown by different investigations, for example from the ''Berufsgenossenschaft''. With these findings in mind, the regulatory authorities (Swiss Federal Office of Public Health (SFOPH) and Swiss National Accident Insurance Association (Suva)) started in 1999 to examine the justification of thoriated tungsten electrodes and a possible substitution with products containing no radioactive material. Up to this time, the use of thoriated tungsten electrodes could be justified since no thorium-free products leading to comparable results were available on the market. This was also the reason why the SFOPH approved several types of these electrodes. Discussions with formation centers for welding and inquiries made at welding shops, trading companies and producers showed that in the mean-time thorium-free products with comparable welding specifications and results became available on the market. Since the 1 January 2004, thoriated tungsten electrodes can only be used if the user has obtained the corresponding license from the SFOPH. The use of thoriated tungsten electrodes is thus not completely forbidden, but very strict conditions have to be fulfilled. Up to now and due to the involvement of the relevant partners, the substitution process has not met any problem. Neither trading companies nor users made any opposition and no request for obtaining a license for thoriated tungsten electrodes was made. (orig.)

  14. Tungsten Targets the Tumor Microenvironment to Enhance Breast Cancer Metastasis

    Science.gov (United States)

    Bolt, Alicia M.; Sabourin, Valérie; Molina, Manuel Flores; Police, Alice M.; Negro Silva, Luis Fernando; Plourde, Dany; Lemaire, Maryse; Ursini-Siegel, Josie; Mann, Koren K.

    2015-01-01

    The number of individuals exposed to high levels of tungsten is increasing, yet there is limited knowledge of the potential human health risks. Recently, a cohort of breast cancer patients was left with tungsten in their breasts following testing of a tungsten-based shield during intraoperative radiotherapy. While monitoring tungsten levels in the blood and urine of these patients, we utilized the 66Cl4 cell model, in vitro and in mice to study the effects of tungsten exposure on mammary tumor growth and metastasis. We still detect tungsten in the urine of patients’ years after surgery (mean urinary tungsten concentration at least 20 months post-surgery = 1.76 ng/ml), even in those who have opted for mastectomy, indicating that tungsten does not remain in the breast. In addition, standard chelation therapy was ineffective at mobilizing tungsten. In the mouse model, tungsten slightly delayed primary tumor growth, but significantly enhanced lung metastasis. In vitro, tungsten did not enhance 66Cl4 proliferation or invasion, suggesting that tungsten was not directly acting on 66Cl4 primary tumor cells to enhance invasion. In contrast, tungsten changed the tumor microenvironment, enhancing parameters known to be important for cell invasion and metastasis including activated fibroblasts, matrix metalloproteinases, and myeloid-derived suppressor cells. We show, for the first time, that tungsten enhances metastasis in an animal model of breast cancer by targeting the microenvironment. Importantly, all these tumor microenvironmental changes are associated with a poor prognosis in humans. PMID:25324207

  15. Electronic Transitions of Tungsten Monosulfide

    Science.gov (United States)

    Tsang, L. F.; Chan, Man-Chor; Zou, Wenli; Cheung, Allan S. C.

    2017-06-01

    Electronic transition spectrum of the tungsten monosulfide (WS) molecule in the near infrared region between 725 nm and 885 nm has been recorded using laser ablation/reaction free-jet expansion and laser induced fluorescence spectroscopy. The WS molecule was produced by reacting laser - ablated tungsten atoms with 1% CS_{2} seeded in argon. Fifteen vibrational bands with resolved rotational structure have been recorded and analyzed, which were organized into seven electronic transition systems. The ground state has been identified to be the X^{3}Σ^{-}(0^{+}) state, and the determined vibrational frequency, ΔG_{1/2} and bond length, r_{0}, are respectively 556.7 cm^{-1} and 2.0676 Å. In addition, vibrational bands belong to another transition system involving lower state with Ω = 1 component have also been analyzed. Least-squares fit of the measured line positions yielded molecular constants for the electronic states involved. The low-lying Λ-S states and Ω sub-states of WS have been calculated using state-averaged complete active space self-consistent field (SA-CASSCF) and followed by MRCISD+Q (internally contracted multi-reference configuration interaction with singles and doubles plus Davidson's cluster correction). The active space consists of 10 electrons in 9 orbitals corresponding to the W 5d6s and S 3p shells. The lower molecular orbitals from W 5s5p and S 3s are inactive but are also correlated, and relativistic effective core potential (RECPs) are adopted to replace the core orbitals with 60 (W) and 10 (S) core electrons, respectively. Spin-orbit coupling (SOC) is calculated via the state-interaction (SI) approach with RECP spin-orbit operators using SA-CASSCF wavefunctions, where the diagonal elements in the SOC matrix are replaced by the corresponding MRCISD+Q energies calculated above. Spectroscopic constants and potential energy curves of the ground and many low-lying Λ-S states and Ω sub-states of the WS molecule are obtained. The calculated

  16. Spin-polarized scanning tunneling microscopy experiments on the rough surface of a polycrystalline NiFe film with a fine magnetic tip sensitive to a well-defined magnetization component

    Energy Technology Data Exchange (ETDEWEB)

    Matsuyama, H., E-mail: matsu@phys.sci.hokudai.ac.jp [Department of Physics, Faculty of Science, Hokkaido University, Sapporo, Hokkaido 060-0810 (Japan); Nara, D.; Kageyama, R.; Honda, K.; Sato, T.; Kusanagi, K. [Department of Condensed Matter Physics, Graduate School of Science, Hokkaido University, Sapporo, Hokkaido 060-0810 (Japan); Srinivasan, E. [Creative Research Institution (CRIS), Hokkaido University, Sapporo, Hokkaido 001-0021 (Japan); Koike, K. [Department of Physics, Faculty of Science, Hokkaido University, Sapporo, Hokkaido 060-0810 (Japan); Creative Research Institution (CRIS), Hokkaido University, Sapporo, Hokkaido 001-0021 (Japan)

    2016-03-15

    We developed a micrometer-sized magnetic tip integrated onto the write head of a hard disk drive for spin-polarized scanning tunneling microscopy (SP-STM) in the modulated tip magnetization mode. Using SP-STM, we measured a well-defined in-plane spin-component of the tunneling current of the rough surface of a polycrystalline NiFe film. The spin asymmetry of the NiFe film was about 1.3% within the bias voltage range of -3 to 1 V. We obtained the local spin component image of the sample surface, switching the magnetic field of the sample to reverse the sample magnetization during scanning. We also obtained a spin image of the rough surface of a polycrystalline NiFe film evaporated on the recording medium of a hard disk drive.

  17. Spin-polarized scanning tunneling microscopy experiments on the rough surface of a polycrystalline NiFe film with a fine magnetic tip sensitive to a well-defined magnetization component

    Directory of Open Access Journals (Sweden)

    H. Matsuyama

    2016-03-01

    Full Text Available We developed a micrometer-sized magnetic tip integrated onto the write head of a hard disk drive for spin-polarized scanning tunneling microscopy (SP-STM in the modulated tip magnetization mode. Using SP-STM, we measured a well-defined in-plane spin-component of the tunneling current of the rough surface of a polycrystalline NiFe film. The spin asymmetry of the NiFe film was about 1.3% within the bias voltage range of -3 to 1 V. We obtained the local spin component image of the sample surface, switching the magnetic field of the sample to reverse the sample magnetization during scanning. We also obtained a spin image of the rough surface of a polycrystalline NiFe film evaporated on the recording medium of a hard disk drive.

  18. In-situ tomographic observation of crack formation and propagation in tungsten materials in the framework of FEMaS-CA

    International Nuclear Information System (INIS)

    Riesch, J.; Linsmeier, C.; Nielsen, S.F.

    2010-01-01

    The EU has funded the Fusion Energy Materials Science project Coordination Action (FEMaSCA) with the intension to utilize the know-how in the materials community to help overcome the material science problems with fusion related materials. In this framework three different material concepts, tungsten-copper-composite (W/Cu), vacuum plasma sprayed tungsten (VPSW), and tungsten-fiber/tungsten-matrix-composite (W f /W m ) were investigated by means of insitu tomography during mechanical testing. The measuring campaign was conducted at the high energy beamtine ID ISA at the European Synchrotron Radiation Facility (ESRF) in Grenoble. A tensile testing machine was used to perform displacement controlled tension tests. At the end of each well defined displacement step a tomogram was taken. Tomographic reconstructions were successfully produced of samples with high tungsten content and sample diameters up to 1 mm. Force-displacement curves were measured during loading to complete fracture. Crack propagation could he observed in the tomographic reconstructions. This paper describes the first results with special focus on the experimental work and the role of FEMaS-CA. (Author)

  19. High temperature diffusion of hafnium in tungsten and a tungsten-hafnium carbide alloy

    International Nuclear Information System (INIS)

    Ozaki, Y.; Zee, R.H.

    1994-01-01

    Refractory metals and ceramics are used extensively in energy systems due to their high temperature properties. This is particularly important in direct conversion systems where thermal to electric conversion efficiency is a direct function of temperature. Tungsten, which has the highest melting temperature among elemental metals, does not possess sufficient creep resistance at temperature above 1,600 K. Different dispersion strengthened tungsten alloys have been developed to extend the usefulness of tungsten to higher temperatures. One of these alloys, tungsten with 0.4 mole percent of finely dispersed HfC particles (W-HfC), has the optimum properties for high temperature applications. Hafnium carbide is used as the strengthening agent due to its high chemical stability and its compatibility with tungsten. The presence of HfC particles retards the rate of grain growth as well as restricting dislocation motion. Both of which are beneficial for creep resistance. The long term behavior of this alloy depends largely on the evolution of its microstructure which is governed by the diffusion of its constituents. Data on the diffusion of carbon in tungsten and tungsten self-diffusion are available, but no direct measurements have been made on the diffusion of hafnium in tungsten. The only diffusion data available are estimated from a coarsening study and these data are highly unreliable. In this study, the diffusion behavior of hafnium in pure tungsten and in a W-HfC alloy was directly measured by means of Secondary Ion Mass Spectroscopy (SIMS). The selection of the W-HfC alloy is due to its importance in high temperature engineering applications, and its higher recrystallization temperature. The presence of HfC particles in tungsten restricts grain growth resulting in better high temperature creep resistance. The higher recrystallization temperature allows measurements to be made over a wider range of temperatures at a relatively constant grain size

  20. Tungsten or Wolfram: Friend or Foe?

    Science.gov (United States)

    Zoroddu, Maria A; Medici, Serenella; Peana, Massimiliano; Nurchi, Valeria M; Lachowicz, Joanna I; Laulicht-Glickc, Freda; Costa, Max

    2018-01-01

    Tungsten or wolfram was regarded for many years as an enemy within the tin smelting and mining industry, because it conferred impurity or dirtiness in tin mining. However, later it was considered an amazing metal for its strength and flexibility, together with its diamond like hardness and its melting point which is the highest of any metal. It was first believed to be relatively inert and an only slightly toxic metal. Since early 2000, the risk exerted by tungsten alloys, its dusts and particulates to induce cancer and several other adverse effects in animals as well as humans has been highlighted from in vitro and in vivo experiments. Thus, it becomes necessary to take a careful look at all the most recent data reported in the scientific literature, covering the years 2001-2016. In fact, the findings indicate that much more attention should be devoted to thoroughly investigate the toxic effects of tungsten and the involved mechanisms of tungsten metal or tungsten metal ions. Copyright© Bentham Science Publishers; For any queries, please email at epub@benthamscience.org.

  1. Surface morphologies of He-implanted tungsten

    Energy Technology Data Exchange (ETDEWEB)

    Bannister, M.E., E-mail: bannisterme@ornl.gov [Physics Division, Oak Ridge National Laboratory, Oak Ridge, TN 37831-6371 (United States); Meyer, F.W.; Hijazi, H. [Physics Division, Oak Ridge National Laboratory, Oak Ridge, TN 37831-6371 (United States); Unocic, K.A.; Garrison, L.M.; Parish, C.M. [Materials Science and Technology Division, Oak Ridge National Laboratory, Oak Ridge, TN (United States)

    2016-09-01

    Surface morphologies of tungsten surfaces, both polycrystalline and single-crystal [1 1 0], were investigated using SEM and FIB/SEM techniques after implantations at elevated surfaces temperatures (1200–1300 K) using well-characterized, mono-energetic He ion beams with a wide range of ion energies (218 eV–250 keV). Nanofuzz was observed on polycrystalline tungsten (PCW) following implantation of 100-keV He ions at a flux threshold of 0.9 × 10{sup 16} cm{sup −2} s{sup −1}, but not following 200-keV implantations with similar fluxes. No nanofuzz formation was observed on single-crystal [1 1 0] tungsten (SCW), despite fluxes exceeding those demonstrated previously to produce nanofuzz on polycrystalline tungsten. Pre-damaging the single-crystal tungsten with implanted C impurity interstitials did not significantly affect the surface morphologies resulting from the high-flux He ion implantations. The main factor leading to the different observed surface structures for the pristine and C-implanted single-crystal W samples appeared to be the peak He ion flux characterizing the different exposures. It was speculated that nanofuzz formation was not observed for any SCW target exposures because of increased incubation fluences required for such targets.

  2. Loss of shear strength in polycrystalline tungsten under shock compression

    International Nuclear Information System (INIS)

    Dandekar, D.P.

    1976-01-01

    A reexamination of existing data on shock compression of polycrystalline tungsten at room temperature indicates that tungsten may be an exception to the common belief that metals do not behave like elastic-isotropic solids under shock compression

  3. Fabrication and evaluation of chemically vapor deposited tungsten heat pipe.

    Science.gov (United States)

    Bacigalupi, R. J.

    1972-01-01

    A network of lithium-filled tungsten heat pipes is being considered as a method of heat extraction from high temperature nuclear reactors. The need for material purity and shape versatility in these applications dictates the use of chemically vapor deposited (CVD) tungsten. Adaptability of CVD tungsten to complex heat pipe designs is shown. Deposition and welding techniques are described. Operation of two lithium-filled CVD tungsten heat pipes above 1800 K is discussed.

  4. 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.

  5. Electron work function of stepped tungsten surfaces

    International Nuclear Information System (INIS)

    Krahl-Urban, B.

    1976-03-01

    The electron work function of tungsten (110) vicinal faces was measured with the aid of thermionic emission, and its dependence on the crystallographic orientation and the surface structure was investigated. The thermionic measurements were evaluated with the aid of the Richardson plot. The real temperature of the emitting tungsten faces was determined with an accuracy of +- 0.5% in the range between 2,200 and 2,800 K. The vicinal faces under investigation have been prepared with an orientation exactness of +- 15'. In the tungsten (110) vicinal faces under investigation, a strong dependence of the temperature coefficient d PHI/dT of the work function on the crystallographic orientation was found. A strong influence of the edge structure as well as of the step density on the temperature coefficient was observed. (orig./HPOE) [de

  6. Characterization of plasma coated tungsten heavy alloy

    International Nuclear Information System (INIS)

    Bose, A.; Kapoor, D.; Lankford, J. Jr.; Nicholls, A.E.

    1996-01-01

    The detrimental environmental impact of Depleted Uranium-based penetrators have led to tremendous development efforts in the area of tungsten heavy alloy based penetrators. One line of investigation involves the coating of tungsten heavy alloys with materials that are prone to shear localization. Plasma spraying of Inconel 718 and 4340 steel have been used to deposit dense coatings on tungsten heavy alloy substrates. The aim of the investigation was to characterize the coating primarily in terms of its microstructure and a special push-out test. The paper describes the results of the push-out tests and analyzes some of the possible failure mechanisms by carrying out microstructural characterization of the failed rings obtained from the push out tests

  7. RF induction plasma spheroidization of tungsten powders

    International Nuclear Information System (INIS)

    Gu Zhogntao; Ye Gaoying; Liu Chuandong; Tong Honghui

    2009-01-01

    Irregularly-shaped tungsten powders (average granular sizes of 512 μm) have been spheroidized by radio frequency (RF)induction plasma. The effects of feed rate, mode of material dispersion, particle size on spheroidization efficiency are investigated. Experimental results show that the spheroidization efficiency decreases rapidly when the feed rate increases to more than 95 g/min. Only 30% spheroidization efficiency is gained at the feed rate of 135.75 g/min. The spheroidization efficiency is also affected by the flow rate of carrier gas. When the flow rate of carrier gas is 0.12 m 3 /h, the dispersion effect is the best, and the spheroidization efficiency is almost 100%. The apparent density of tungsten powders increases a bit with the increase of spheroidization efficiency. And the particle size uniformity of spheroidized tungsten powders is in accordance with that of original powders. (authors)

  8. 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...

  9. Process for recovering tungsten from alkaline leaching solution of tungsten ores

    International Nuclear Information System (INIS)

    Onozaki, S.; Nemoto, S.; Hazeyama, T.

    1976-01-01

    This invention relates to a process for recovering tungsten from an alkaline leaching solution of tungsten ores. This invention comprises adjusting the pH of an alkaline leaching solution which is obtained by lixiviating ore containing tungsten with an alkaline solution to 7--8 with acid to oxidize molybdic acid ions in the solution, adding a sulfide donor, then precipitating molybdenum sulfide compounds by adjusting the pH value of the solution to 2--3. Tungstic acid ions are recovered as calcium tungstate by the addition of a calcium ion donor after the molybdenum sulfide compounds are separated

  10. High resolution electron microscopy study of as-prepared and annealed tungsten-carbon multilayers

    International Nuclear Information System (INIS)

    Nguyen, T.D.; Gronsky, R.; Kortright, J.B.

    1988-12-01

    A series of sputtered tungsten-carbon multilayer structures with periods ranging from 2 to 12 nm in the as-prepared state and after annealing at 500/degree/C for 4 hours has been studied with high resolution transmission electron microscopy. The evolution with annealing of the microstructure of these multilayers depends on their period. As-prepared structures appear predominantly amorphous from TEM imaging and diffraction. Annealing results in crystallization of the W-rich layers into WC in the larger period samples, and less complete or no crystallization in the smaller period samples. X-ray scattering reveals that annealing expands the period in a systematic way. The layers remain remarkably well-defined after annealing under these conditions. 12 refs., 4 figs., 1 tab

  11. Color in 'tungsten trioxide' thin films

    International Nuclear Information System (INIS)

    Gerard, P.; Deneuville, A.; Hollinger, G.; Duc, Tran Minh

    1977-01-01

    We show that evaporated tungsten trioxide amorphous layers commonly used in electrochromic displays actually have the composition WO_2_._7H_y (0.2< y<0.5). We emphasize that coloration of virgin transparent films can be obtained without injection of any external ion into the layer, and further that around a critical substoichiometry by sputtering, namely, WO_2_._5, one can prepare blue virgin layers without any hydrogen. The effect of substoichiometry on the valence of tungsten atoms has been followed by XPS measurements of sputtered layers.

  12. Color in ''tungsten trioxide'' thin films

    International Nuclear Information System (INIS)

    Gerard, P.; Deneuville, A.; Hollinger, G.; Tran Minh Duc

    1977-01-01

    We show that evaporated tungsten trioxide amorphous layers commonly used in electrochromic displays actually have the composition WO/sub 2.7/H/sub y/ (0.2< y<0.5). We emphasize that coloration of virgin transparent films can be obtained without injection of any external ion into the layer, and further that around a critical substoichiometry by sputtering, namely, WO/sub 2.5/, one can prepare blue virgin layers without any hydrogen. The effect of substoichiometry on the valence of tungsten atoms has been followed by XPS measurements of sputtered layers

  13. 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.

  14. Room temperature one-step synthesis of microarrays of N-doped flower-like anatase TiO{sub 2} composed of well-defined multilayer nanoflakes by Ti anodization

    Energy Technology Data Exchange (ETDEWEB)

    Wang Chenglin; Wang Mengye; Xie Kunpeng; Wu Qi; Sun Lan; Lin Changjian [Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005 (China); Lin Zhiqun, E-mail: sunlan@xmu.edu.cn, E-mail: cjlin@xmu.edu.cn [Department of Materials Science and Engineering, Iowa State University, Ames, IA 50011 (United States)

    2011-07-29

    Microarrays of N-doped flower-like TiO{sub 2} composed of well-defined multilayer nanoflakes were synthesized at room temperature by electrochemical anodization of Ti in NH{sub 4}F aqueous solution. The TiO{sub 2} flowers were of good anatase crystallinity. The effects of anodizing time, applied voltage and NH{sub 4}F 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 NH{sub 4}F concentration. The size and density of the TiO{sub 2} flowers could be tuned by changing the applied voltage. The obtained N-doped flower-like TiO{sub 2} 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 TiO{sub 2} microarrays in the oxidation of methyl orange showed a significant increase compared with that of commercial P25 TiO{sub 2} film.

  15. Tritium Decay Helium-3 Effects in Tungsten

    Energy Technology Data Exchange (ETDEWEB)

    Shimada, M. [Idaho National Lab. (INL), Idaho Falls, ID (United States); Merrill, B. J. [Idaho National Lab. (INL), Idaho Falls, ID (United States)

    2016-06-01

    A critical challenge for long-term operation of ITER and beyond to a Demonstration reactor (DEMO) and future fusion reactor will be the development of plasma-facing components (PFCs) that demonstrate erosion resistance to steady-state/transient heat fluxes and intense neutral/ion particle fluxes under the extreme fusion nuclear environment, while at the same time minimizing in-vessel tritium inventories and permeation fluxes into the PFC’s coolant. Tritium will diffuse in bulk tungsten at elevated temperatures, and can be trapped in radiation-induced trap site (up to 1 at. % T/W) in tungsten [1,2]. Tritium decay into helium-3 may also play a major role in microstructural evolution (e.g. helium embrittlement) in tungsten due to relatively low helium-4 production (e.g. He/dpa ratio of 0.4-0.7 appm [3]) in tungsten. Tritium-decay helium-3 effect on tungsten is hardly understood, and its database is very limited. Two tungsten samples (99.99 at. % purity from A.L.M.T. Co., Japan) were exposed to high flux (ion flux of 1.0x1022 m-2s-1 and ion fluence of 1.0x1026 m-2) 0.5%T2/D2 plasma at two different temperatures (200, and 500°C) in Tritium Plasma Experiment (TPE) at Idaho National Laboratory. Tritium implanted samples were stored at ambient temperature in air for more than 3 years to investigate tritium decay helium-3 effect in tungsten. The tritium distributions on plasma-exposed was monitored by a tritium imaging plate technique during storage period [4]. Thermal desorption spectroscopy was performed with a ramp rate of 10°C/min up to 900°C to outgas residual deuterium and tritium but keep helium-3 in tungsten. These helium-3 implanted samples were exposed to deuterium plasma in TPE to investigate helium-3 effect on deuterium behavior in tungsten. The results show that tritium surface concentration in 200°C sample decreased to 30 %, but tritium surface concentration in 500°C sample did not alter over the 3 years storage period, indicating possible tritium

  16. Ab initio and DFT benchmarking of tungsten nanoclusters and tungsten hydrides

    International Nuclear Information System (INIS)

    Skoviera, J.; Novotny, M.; Cernusak, I.; Oda, T.; Louis, F.

    2015-01-01

    We present several benchmark calculations comparing wave-function based methods and density functional theory for model systems containing tungsten. They include W 4 cluster as well as W 2 , WH and WH 2 molecules. (authors)

  17. Substructure and electrical resistivity analyses of pure tungsten sheet

    International Nuclear Information System (INIS)

    Trybus, C.L.; Sellers, C.H.; Anderl, R.A.

    1991-01-01

    The substructure of pure tungsten sheet (0.025 mm thick) is examined and quantified by transmission electron microscopy (TEM). Dislocation populations and arrangements are evaluated for as-worked and various annealed conditions of the tungsten sheet. The worked (rolled) tungsten substructure was nonhomogeneous, consisting of areas of very high and low dislocation densities. These results are correlated to resistivity measurements of the tungsten sheet following thermal cycling to 1200 degrees C to determine the substructural changes as a function of temperature. The comparison between the two characterization techniques is used to examine the relationship between structural and electronic properties in tungsten. 15 refs., 6 figs., 2 tabs

  18. Effective Liquid-phase Nitration of Benzene Catalyzed by a Stable Solid Acid Catalyst: Silica Supported Cs{sub 2.5}H{sub 0.5}PMo{sub 12}O{sub 40}

    Energy Technology Data Exchange (ETDEWEB)

    Gong, Shu-wen; Liu, Li-jun; Zhang, Qian; Wang, Liang-yin [Liaocheng University, Liaocheng (China)

    2012-04-15

    Silica supported Cs{sub 2.5}H{sub 0.5}PMo{sub 12}O{sub 40} catalyst was prepared through sol-gel method with ethyl silicate-40 as silicon resource and characterized by X-ray diffraction, infrared spectroscopy, scanning electron microscopy, nitrogen adsorption-desorption and potentiometric titration methods. The Cs{sub 2.5}H{sub 0.5}PMo{sub 12}O{sub 40} particles with Keggin-type structure well dispersed on the surface of silica, and the catalyst exhibited high surface area and acidity. The catalytic performance of the catalysts for benzene liquid-phase nitration was examined with 65% nitric acid as nitrating agent, and the effects of various parameters were tested, which including temperature, time and amount of catalyst, reactants ratio, especially the recycle of catalyst was emphasized. Benzene was effectively nitrated to mononitro-benzene with high conversion (95%) in optimized conditions. Most importantly, the supported catalyst was proved has excellent stability in the nitration progress, and there were no any other organic solvent and sulfuric acid were used in the reaction system, so the liquid-phase nitration of benzene that we developed was an eco-friendly and attractive alternative for the commercial technology

  19. Investigation of hydrogen bubbles behavior in tungsten by high-flux hydrogen implantation

    Science.gov (United States)

    Zhao, Jiangtao; Meng, Xuan; Guan, Xingcai; Wang, Qiang; Fang, Kaihong; Xu, Xiaohui; Lu, Yongkai; Gao, Jun; Liu, Zhenlin; Wang, Tieshan

    2018-05-01

    Hydrogen isotopes retention and bubbles formation are critical issues for tungsten as plasma-facing material in future fusion reactors. In this work, the formation and growing up behavior of hydrogen bubbles in tungsten were investigated experimentally. The planar TEM samples were implanted by 6.0keV hydrogens to a fluence of 3.38 ×1018 H ṡ cm-2 at room temperature, and well-defined hydrogen bubbles were observed by TEM. It was demonstrated that hydrogen bubbles formed when exposed to a fluence of 1.5 ×1018 H ṡ cm-2 , and the hydrogen bubbles grew up with the implantation fluence. In addition, the bubbles' size appeared larger with higher beam flux until saturated at a certain flux, even though the total fluence was kept the same. Finally, in order to understand the thermal annealing effect on the bubbles behavior, hydrogen-implanted samples were annealed at 400, 600, 800, and 1000 °C for 3 h. It was obvious that hydrogen bubbles' morphology changed at temperatures higher than 800 °C.

  20. Tungsten particle reinforced Al 5083 composite with high strength and ductility

    Energy Technology Data Exchange (ETDEWEB)

    Bauri, Ranjit, E-mail: rbauri@iitm.acin; Yadav, Devinder; Shyam Kumar, C.N.; Balaji, B.

    2015-01-03

    Tungsten particles were incorporated into an Al 5083 matrix by friction stir processing (FSP). FSP resulted in uniform dispersion of the tungsten particles with excellent interfacial bonding and more importantly without the formation of any harmful intermetallics. For the first time, the particles penetrated to a depth equal to the full pin length of the tool. A novel aspect of the 5083 Al–W composite is that it showed an improvement of more than 100 MPa in the UTS and at the same time exhibited a high ductility (30%). The ductility was also evident from the well defined dimples in the fracture surface which also revealed the superior bonding between the particles and the matrix. FSP also resulted in substantial grain refinement of the Al matrix. Electron backscatter diffraction (EBSD) and transmission electron microscopy analysis revealed that the fine grains formed by dynamic recrystallization. A gradual transformation from sub-grain to high-angle grain boundaries was observed from EBSD analysis pointing towards the occurrence of a continuous type of dynamic recrystallization process.

  1. The incidence and survival of acute de novo leukaemias in Estonia and in a well-defined region of western Sweden during 1982-1996: a survey of patients aged > or =65 years.

    Science.gov (United States)

    Luik, E; Palk, K; Everaus, H; Varik, M; Aareleid, T; Wennström, L; Juntikka, E-L; Safai-Kutti, S; Stockelberg, D; Holmberg, E; Kutti, J

    2004-07-01

    To compare the incidence and survival of acute de novo leukaemias with particular reference to political/socio-economic and environmental factors in two neighbouring countries over the three 5-year periods (1982-1996). The present report covers only patients diagnosed when aged > or =65 years. A well-defined area of Sweden, the so-called Western Swedish Health Care Region and Estonia. Population-wise, the western Swedish Region and Estonia are very similar; area-wise they are also well comparable. The number of acute de novo leukaemias was quite dissimilar in the two countries (Estonia, n = 137, Sweden, n = 354). The age standardized incidence rates regarding the total number of acute de novo leukaemias was 5.31 per 100,000 inhabitants/year for Estonia and 7.99 for Sweden, this difference being statistically significant. However, the difference was merely attributable to incidence rates as regards acute myeloblastic leukaemias (AML); on the contrary, differences as regards acute lymphoblastic leukaemias (ALL) and non-classifiable, undifferentiated or biphenotypic acute leukaemias (uAL) were negligible. The relative survival for the total material of patients was significantly higher for Swedish when compared with Estonian patients (P or =65 years in Estonia at 1 year was 8.5% and at 3 years 3.5% respectively. The corresponding figures for the Swedish patients were considerably higher, 22.7 and 7.7% respectively. This difference, however, applied only for patients with AML (P acute leukemia patients in two neighbouring countries.

  2. SU-E-J-115: Correlation of Displacement Vector Fields Calculated by Deformable Image Registration Algorithms with Motion Parameters of CT Images with Well-Defined Targets and Controlled-Motion

    Energy Technology Data Exchange (ETDEWEB)

    Jaskowiak, J; Ahmad, S; Ali, I [University of Oklahoma Health Sciences Center, Oklahoma City, OK (United States); Alsbou, N [Ohio Northern University, Ada, OH (United States)

    2015-06-15

    Purpose: To investigate correlation of displacement vector fields (DVF) calculated by deformable image registration algorithms with motion parameters in helical axial and cone-beam CT images with motion artifacts. Methods: A mobile thorax phantom with well-known targets with different sizes that were made from water-equivalent material and inserted in foam to simulate lung lesions. The thorax phantom was imaged with helical, axial and cone-beam CT. The phantom was moved with a cyclic motion with different motion amplitudes and frequencies along the superior-inferior direction. Different deformable image registration algorithms including demons, fast demons, Horn-Shunck and iterative-optical-flow from the DIRART software were used to deform CT images for the phantom with different motion patterns. The CT images of the mobile phantom were deformed to CT images of the stationary phantom. Results: The values of displacement vectors calculated by deformable image registration algorithm correlated strongly with motion amplitude where large displacement vectors were calculated for CT images with large motion amplitudes. For example, the maximal displacement vectors were nearly equal to the motion amplitudes (5mm, 10mm or 20mm) at interfaces between the mobile targets lung tissue, while the minimal displacement vectors were nearly equal to negative the motion amplitudes. The maximal and minimal displacement vectors matched with edges of the blurred targets along the Z-axis (motion-direction), while DVF’s were small in the other directions. This indicates that the blurred edges by phantom motion were shifted largely to match with the actual target edge. These shifts were nearly equal to the motion amplitude. Conclusions: The DVF from deformable-image registration algorithms correlated well with motion amplitude of well-defined mobile targets. This can be used to extract motion parameters such as amplitude. However, as motion amplitudes increased, image artifacts increased

  3. Molecular complexes of tungsten oxotetrachloride with azomethins

    International Nuclear Information System (INIS)

    Abramenko, Yu.V.; Garnovskij, A.D.; Abramenko, V.A.; Medvedeva, T.E.

    1992-01-01

    Series of new molecular complexes of tungsten oxotetrachloride with benza- and salicylalimines of equimolar compositions obtained. Substances are studied using element analysis, IR spectroscopy and conductometry. Octahedral structure of complexes with central atom coordination of benzalaniline molecules via azomethin nitrogen atom, and salicylalimines - via carbonyl oxygen atom of quinoid tantometric form of ligand is assumed

  4. Deuterium transport and trapping in polycrystalline tungsten

    International Nuclear Information System (INIS)

    Anderl, R.A.; Holland, D.F.; Longhurst, G.R.; Pawelko, R.J.; Trybus, C.L.; Sellers, C.H.

    1992-01-01

    This paper reports that deuterium permeation studies for polycrystalline tungsten foil have been conducted to provide data for estimating tritium transport and trapping in tungsten-clad divertors proposed for advanced fusion-reactor concepts. Based on a detailed transmission electron microscopy (TEM) microstructural characterization of the specimen material and on analyses of permeation data measured at temperatures ranging form 610 to 823 K for unannealed and annealed tungsten foil (25 μm thick), the authors note the following key results: deuterium transport in tungsten foil is dominated by extensive trapping that varies inversely with prior anneal temperatures of the foil material, the reduction in the trapped fraction correlates with a corresponding elimination of a high density of dislocations in cell-wall structures introduced during the foil fabrication process, trapping behavior in these foils can be modelled using trap energies between 1.3 eV and 1.5 eV and trap densities ranging from 1 x 10 -5 atom fraction

  5. Analytical methods for the determination of tungsten

    International Nuclear Information System (INIS)

    Topping, J.J.

    1978-01-01

    Methods developed and employed in the recent literature (1969 to 1975) for the detection and determination of tungsten in a wide variety of matrices are reviewed. This paper is a supplement to the books, monographs and review papers which deal with the earlier literature. (author)

  6. Distribution of induced activity in tungsten targets

    International Nuclear Information System (INIS)

    Donahue, R.J.; Nelson, W.R.

    1988-09-01

    Estimates are made of the induced activity created during high-energy electron showers in tungsten, using the EGS4 code. Photon track lengths, neutron yields and spatial profiles of the induced activity are presented. 8 refs., 9 figs., 1 tab

  7. Development of tungsten collimators for industrial radiography

    International Nuclear Information System (INIS)

    Varkey, P.A.; Verma, P.B.; Jayakumar, T.K.; Mammachan, M.K.

    2001-01-01

    Collimators are essential components of industrial radiography set up as it provides radiation safety to persons involved in the radiography work. A collimator with optimum design features also helps in reducing the scattered radiation which in turn results in radiographs having better sensitivity. This papers describes the salient design features of the tungsten collimators developed by the BRIT, for industrial radiography. (author)

  8. 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.

  9. Joining of Tungsten Armor Using Functional Gradients

    International Nuclear Information System (INIS)

    John Scott O'Dell

    2006-01-01

    The joining of low thermal expansion armor materials such as tungsten to high thermal expansion heat sink materials has been a major problem in plasma facing component (PFC) development. Conventional planar bonding techniques have been unable to withstand the high thermal induced stresses resulting from fabrication and high heat flux testing. During this investigation, innovative functional gradient joints produced using vacuum plasma spray forming techniques have been developed for joining tungsten armor to copper alloy heat sinks. A model was developed to select the optimum gradient architecture. Based on the modeling effort, a 2mm copper rich gradient was selected. Vacuum plasma pray parameters and procedures were then developed to produce the functional gradient joint. Using these techniques, dual cooling channel, medium scale mockups (32mm wide x 400mm length) were produced with vacuum plasma spray formed tungsten armor. The thickness of the tungsten armor was up to 5mm thick. No evidence of debonding at the interface between the heat sink and the vacuum plasma sprayed material was observed.

  10. Tungsten and refractory metals 3, proceedings

    International Nuclear Information System (INIS)

    Bose, A.; Dowding, R.J.

    1996-01-01

    The Third International Conference on Tungsten and Refractory Metals was held in Greater Washington DC at the McLean Hilton, McLean Virginia, on November 15--16, 1995. This meeting was the third in a series of conferences held in the Washington DC area. The first meeting was in 1992 and was entitled ''International Conference on Tungsten and Tungsten Alloys.'' In 1994, the scope of the meeting was expanded to include other refractory metals such as molybdenum, iridium, rhenium, tantalum and niobium. The tremendous success of that meeting was the primary motivation for this Conference. The broader scope (the inclusion of other refractory metals and alloys) of the Conference was kept intact for this meeting. In fact, it was felt that the developments in the technology of these materials required a common forum for the interchange of current research information. The papers presented in this meeting examined the rapid advancements in the technology of refractory metals, with special emphasis on the processing, structure, and properties. Among the properties there was emphasis on both quasi-static and dynamic rates. Another topic that received considerable interest was the area of refractory carbides and tungsten-copper composites. One day of concurrent session was necessary to accommodate all of the presentations

  11. CALICE silicon-tungsten electromagnetic calorimeter

    Indian Academy of Sciences (India)

    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. A first module consisting of 14 ...

  12. Consolidation of tungsten disilicide by plasma spraying

    Czech Academy of Sciences Publication Activity Database

    Brožek, Vlastimil; Ctibor, Pavel; Matějíček, Jiří; Rohan, Pavel; Janča, J.

    2007-01-01

    Roč. 52, č. 3 (2007), s. 311-320 ISSN 0001-7043 R&D Projects: GA ČR(CZ) GA104/05/0540 Institutional research plan: CEZ:AV0Z20430508 Keywords : Water stabilized plasma * tungsten disilicide * plasma deposition * thermal spray coatings Subject RIV: JJ - Other Materials

  13. Electrospark doping of steel with tungsten

    Energy Technology Data Exchange (ETDEWEB)

    Denisova, Yulia, E-mail: yukolubaeva@mail.ru; Shugurov, Vladimir, E-mail: shugurov@opee.hcei.tsc.ru [Institute of High-Current Electronics of the Siberian Branch of the Russian Academy of Sciences, 634055, Russia, Tomsk, 2/3 Akademicheskiy Ave (Russian Federation); Petrikova, Elizaveta, E-mail: elizmarkova@yahoo.com [Institute of High-Current Electronics of the Siberian Branch of the Russian Academy of Sciences, 634055, Russia, Tomsk, 2/3 Akademicheskiy Ave (Russian Federation); National Research Tomsk State University, 36 Lenin Str. Tomsk, 634050 (Russian Federation); Seksenalina, Malika, E-mail: sportmiss@bk.ru [National Research Tomsk Polytechnic University, 30 Lenin Str. Tomsk, 634050 (Russian Federation); Ivanova, Olga, E-mail: ivaov@mail.ru; Ikonnikova, Irina, E-mail: irinaikonnikova@yandex.ru [Tomsk State University of Architecture and Building, 2 Solyanaya Sq. Tomsk, 634003 (Russian Federation); Kunitsyna, Tatyana, E-mail: kma11061990@mail.ru; Vlasov, Victor, E-mail: rector@tsuab.ru [National Research Tomsk Polytechnic University, 30 Lenin Str. Tomsk, 634050 (Russian Federation); Tomsk State University of Architecture and Building, 2 Solyanaya Sq. Tomsk, 634003 (Russian Federation); Klopotov, Anatoliy, E-mail: klopotovaa@tsuab.ru [National Research Tomsk State University, 36 Lenin Str. Tomsk, 634050 (Russian Federation); Tomsk State University of Architecture and Building, 2 Solyanaya Sq. Tomsk, 634003 (Russian Federation); Ivanov, Yuriy, E-mail: yufi55@mail.ru [Institute of High-Current Electronics of the Siberian Branch of the Russian Academy of Sciences, 634055, Russia, Tomsk, 2/3 Akademicheskiy Ave (Russian Federation); National Research Tomsk State University, 36 Lenin Str. Tomsk, 634050 (Russian Federation); National Research Tomsk Polytechnic University, 30 Lenin Str. Tomsk, 634050 (Russian Federation)

    2016-01-15

    The paper is devoted to the numerical modeling of thermal processes and the analysis of the structure and properties of the surface layer of carbon steel subjected to electrospark doping with tungsten. The problem of finding the temperature field in the system film (tungsten) / substrate (iron) is reduced to the solution of the heat conductivity equation. A one-dimensional case of heating and cooling of a plate with the thickness d has been considered. Calculations of temperature fields formed in the system film / substrate synthesized using methods of electrospark doping have been carried out as a part of one-dimensional approximation. Calculations have been performed to select the mode of the subsequent treatment of the system film / substrate with a high-intensity pulsed electron beam. Authors revealed the conditions of irradiation allowing implementing processes of steel doping with tungsten. A thermodynamic analysis of phase transformations taking place during doping of iron with tungsten in equilibrium conditions has been performed. The studies have been carried out on the surface layer of the substrate modified using the method of electrospark doping. The results showed the formation in the surface layer of a structure with a highly developed relief and increased strength properties.

  14. Technique for investigation on tungsten crack resistance

    International Nuclear Information System (INIS)

    Uskov, E.I.; Babak, A.V.

    1983-01-01

    The possibility of using the linear destruction mechanic for the estimation of tungsten crack resistance in a wide range of temperatures has been studied and grounded. Values critical of stress intensity factors in the 20-2000 deg C temperature range are given

  15. Electrospark doping of steel with tungsten

    International Nuclear Information System (INIS)

    Denisova, Yulia; Shugurov, Vladimir; Petrikova, Elizaveta; Seksenalina, Malika; Ivanova, Olga; Ikonnikova, Irina; Kunitsyna, Tatyana; Vlasov, Victor; Klopotov, Anatoliy; Ivanov, Yuriy

    2016-01-01

    The paper is devoted to the numerical modeling of thermal processes and the analysis of the structure and properties of the surface layer of carbon steel subjected to electrospark doping with tungsten. The problem of finding the temperature field in the system film (tungsten) / substrate (iron) is reduced to the solution of the heat conductivity equation. A one-dimensional case of heating and cooling of a plate with the thickness d has been considered. Calculations of temperature fields formed in the system film / substrate synthesized using methods of electrospark doping have been carried out as a part of one-dimensional approximation. Calculations have been performed to select the mode of the subsequent treatment of the system film / substrate with a high-intensity pulsed electron beam. Authors revealed the conditions of irradiation allowing implementing processes of steel doping with tungsten. A thermodynamic analysis of phase transformations taking place during doping of iron with tungsten in equilibrium conditions has been performed. The studies have been carried out on the surface layer of the substrate modified using the method of electrospark doping. The results showed the formation in the surface layer of a structure with a highly developed relief and increased strength properties

  16. 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.

  17. Kinetics of low pressure chemical vapor deposition of tungsten silicide from dichlorocilane reduction of tungsten hexafluoride

    International Nuclear Information System (INIS)

    Srinivas, D.; Raupp, G.B.; Hillman, J.

    1990-01-01

    The authors report on experiments to determine the intrinsic surface reaction rate dependences and film properties' dependence on local reactant partial pressures and wafer temperature in low pressure chemical vapor deposition (LPCVD) of tungsten silicide from dichlorosilane reduction of tungsten hexafluoride. Films were deposited in a commercial-scale Spectrum CVD cold wall single wafer reactor under near differential, gradientless conditions. Over the range of process conditions investigated, deposition rate was found to be first order in dichlorosillane and negative second order in tungsten hexafluoride partial pressure. The apparent activation energy in the surface reaction limited regime was found to be 70-120 kcal/mol. The silicon to tungsten ratio of as deposited silicide films ranged from 1.1 to 2.4, and increased with increasing temperature and dichlorosillane partial pressure, and decreased with increasing tungsten hexafluoride pressure. These results suggest that the apparent silicide deposition rate and composition are controlled by the relative rates of at least two competing reactions which deposit stoichiometric tungsten silicides and/or silicon

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

    International Nuclear Information System (INIS)

    Braida, Washington; Christodoulatos, Christos; Ogundipe, Adebayo; Dermatas, Dimitris; O'Connor, Gregory

    2007-01-01

    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

  19. ITER tungsten divertor design development and qualification program

    Energy Technology Data Exchange (ETDEWEB)

    Hirai, T., E-mail: takeshi.hirai@iter.org [ITER Organization, Route de Vinon sur Verdon, F-13115 Saint Paul lez Durance (France); Escourbiac, F.; Carpentier-Chouchana, S.; Fedosov, A.; Ferrand, L.; Jokinen, T.; Komarov, V.; Kukushkin, A.; Merola, M.; Mitteau, R.; Pitts, R.A.; Shu, W.; Sugihara, M. [ITER Organization, Route de Vinon sur Verdon, F-13115 Saint Paul lez Durance (France); Riccardi, B. [F4E, c/ Josep Pla, n.2, Torres Diagonal Litoral, Edificio B3, E-08019 Barcelona (Spain); Suzuki, S. [JAEA, Fusion Research and Development Directorate JAEA, 801-1 Mukouyama, Naka, Ibaragi 311-0193 (Japan); Villari, R. [Associazione EURATOM-ENEA sulla Fusione, Via Enrico Fermi 45, I-00044 Frascati, Rome (Italy)

    2013-10-15

    Highlights: • Detailed design development plan for the ITER tungsten divertor. • Latest status of the ITER tungsten divertor design. • Brief overview of qualification program for the ITER tungsten divertor and status of R and D activity. -- Abstract: In November 2011, the ITER Council has endorsed the recommendation that a period of up to 2 years be set to develop a full-tungsten divertor design and accelerate technology qualification in view of a possible decision to start operation with a divertor having a full-tungsten plasma-facing surface. To ensure a solid foundation for such a decision, a full tungsten divertor design, together with a demonstration of the necessary high performance tungsten monoblock technology should be completed within the required timescale. The status of both the design and technology R and D activity is summarized in this paper.

  20. 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

  1. Computer simulations for thorium doped tungsten crystals

    International Nuclear Information System (INIS)

    Eberhard, Bernd

    2009-01-01

    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 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 set of Langevin equations, i.e. stochastic

  2. Scanning tunneling microscopy measurements of the spin Hall effect in tungsten films by using iron-coated tungsten tips

    Directory of Open Access Journals (Sweden)

    Ting Xie

    2018-05-01

    Full Text Available Scanning tunneling microscopy experiments using iron-coated tungsten tips and current-carrying tungsten films have been conducted. An asymmetry of the tunneling current with respect to the change of the direction of the bias current through a tungsten film has been observed. It is argued that this asymmetry is a manifestation of the spin Hall effect in the current-carrying tungsten film. Nanoscale variations of this asymmetry across the tungsten film have been studied by using the scanning tunneling microscopy technique.

  3. Scanning tunneling microscopy measurements of the spin Hall effect in tungsten films by using iron-coated tungsten tips

    Science.gov (United States)

    Xie, Ting; Dreyer, Michael; Bowen, David; Hinkel, Dan; Butera, R. E.; Krafft, Charles; Mayergoyz, Isaak

    2018-05-01

    Scanning tunneling microscopy experiments using iron-coated tungsten tips and current-carrying tungsten films have been conducted. An asymmetry of the tunneling current with respect to the change of the direction of the bias current through a tungsten film has been observed. It is argued that this asymmetry is a manifestation of the spin Hall effect in the current-carrying tungsten film. Nanoscale variations of this asymmetry across the tungsten film have been studied by using the scanning tunneling microscopy technique.

  4. Trends in tungsten coil atomic spectrometry

    Science.gov (United States)

    Donati, George L.

    Renewed interest in electrothermal atomic spectrometric methods based on tungsten coil atomizers is a consequence of a world wide increasing demand for fast, inexpensive, sensitive, and portable analytical methods for trace analysis. In this work, tungsten coil atomic absorption spectrometry (WCAAS) and tungsten coil atomic emission spectrometry (WCAES) are used to determine several different metals and even a non-metal at low levels in different samples. Improvements in instrumentation and new strategies to reduce matrix effects and background signals are presented. Investigation of the main factors affecting both WCAAS and WCAES analytical signals points to the importance of a reducing, high temperature gas phase in the processes leading to atomic cloud generation. Some more refractory elements such as V and Ti were determined for the first time by double tungsten coil atomic emission spectrometry (DWCAES). The higher temperatures provided by two atomizers in DWCAES also allowed the detection of Ag, Cu and Sn emission signals for the first time. Simultaneous determination of several elements by WCAES in relatively complex sample matrices was possible after a simple acid extraction. The results show the potential of this method as an alternative to more traditional, expensive methods for fast, more effective analyses and applications in the field. The development of a new metallic atomization cell is also presented. Lower limits of detection in both WCAAS and WCAES determinations were obtained due to factors such as better control of background signal, smaller, more isothermal system, with atomic cloud concentration at the optical path for a longer period of time. Tungsten coil-based methods are especially well suited to applications requiring low sample volume, low cost, sensitivity and portability. Both WCAAS and WCAES have great commercial potential in fields as diverse as archeology and industrial quality control. They are simple, inexpensive, effective

  5. 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

  6. 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

  7. Irradiation effects in tungsten-copper laminate composite

    Energy Technology Data Exchange (ETDEWEB)

    Garrison, L.M., E-mail: garrisonlm@ornl.gov [Oak Ridge National Laboratory, Oak Ridge, TN 37831 (United States); Katoh, Y. [Oak Ridge National Laboratory, Oak Ridge, TN 37831 (United States); Snead, L.L. [Oak Ridge National Laboratory, Oak Ridge, TN 37831 (United States); Massachusetts Institute of Technology, Cambridge, MA 02139 (United States); Byun, T.S. [Oak Ridge National Laboratory, Oak Ridge, TN 37831 (United States); Pacific Northwest National Laboratory, Richland, WA 99352 (United States); Reiser, J.; Rieth, M. [Karlsruhe Institute of Technology, Karlsruhe (Germany)

    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 × 10{sup 25} n/m{sup 2}, 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. - Highlights: • Fusion reactors need a tough, ductile tungsten plasma-facing material. • The unirradiated tungsten-copper laminate is more ductile than tungsten alone. • After neutron irradiation, the composite has significantly less ductility. • The tungsten behavior appears to dominate the overall composite behavior.

  8. Structure of tungsten electrodeposited from oxide chloride-fluoride molten salts

    International Nuclear Information System (INIS)

    Pavlovskij, V.A.; Reznichenko, V.A.

    1998-01-01

    Investigation results on the influence of electrolysis parameters and electrolyte composition on tungsten cathode deposit structure are presented. The electrolysis was performed in NaCl-NaF-WO 3 molten salts using tungsten and tungsten coated molybdenum cathodes. Morphological and metallographic studies of tungsten crystals were carrier out. Tungsten deposits were obtained in the form of crystalline conglomerates, sponge and high dispersity powder

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

    International Nuclear Information System (INIS)

    Polignano, M.L.; Galbiati, A.; Grasso, S.; Mica, I.; Barbarossa, F.; Magni, D.

    2016-01-01

    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 10 cm -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)

  10. 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)

  11. The influence of Fe content on spreading ability of tungsten heavy alloys matrix on tungsten surface

    Directory of Open Access Journals (Sweden)

    A. Krzyńska

    2011-07-01

    Full Text Available The results of experimental study of tungsten spreading ability with W-Ni-Co-Fe matrix are presented. The aim of these investigations was to see how Fe concentration in W – Ni – Co matrix influences the wettability of tungsten grains during liquid phase sintering. Four green compact specimens containing 50%W, 10%Co and Ni + Fe = 40% but with different Ni to Fe ratio were prepared. The cylindrical specimen 5mm diameter and 5mm height were put on clean pure tungsten substrate and then 20 minutes heated at 1520oC in hydrogen atmosphere. After heating the specimens were carefully measured and then the specimens for structure observations were prepared. It was concluded, that increase of Fe content decrease the melting temperature of W – Ni – Co alloy. The melting point decrease caused by Fe content increase substantially the spreading ability of tungsten substrate with W – Ni – Co alloy. Metallography investigations showed some microstructure changes in “reaction zone” identified in tungsten substrate – (WNi40-xCo10Fex interface. The results of the study confirmed our earlier observations that even relative small Fe addition promotes Weight Heavy Alloys (WHA liquid phase sintering.

  12. Characterization of a Cobalt-Tungsten Interconnect

    DEFF Research Database (Denmark)

    Harthøj, Anders; Holt, Tobias; Caspersen, Michael

    2012-01-01

    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......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...... for 300 h at 800 °C. The coating was characterized with Glow Discharge Optical Spectroscopy (GDOES), Scanning Electron Microscopy (SEM) and X-Ray Diffraction (XRD). The oxidation properties were evaluated by measuring weight change of coated samples of Crofer 22 H and Crofer 22 APU as a function...

  13. Laser induced white lighting of tungsten filament

    Science.gov (United States)

    Strek, W.; Tomala, R.; Lukaszewicz, M.

    2018-04-01

    The sustained bright white light emission of thin tungsten filament was induced under irradiation with focused beam of CW infrared laser diode. The broadband emission centered at 600 nm has demonstrated the threshold behavior on excitation power. Its intensity increased non-linearly with excitation power. The emission occurred only from the spot of focused beam of excitation laser diode. The white lighting was accompanied by efficient photocurrent flow and photoelectron emission which both increased non-linearly with laser irradiation power.

  14. Spectroscopic modeling for tungsten EUV spectra

    International Nuclear Information System (INIS)

    Murakami, Izumi; Kato, Daiji; Sakaue, Hiroyuki A.; Suzuki, Chihiro; Morita, Shigeru; Goto, Motoshi; Sasaki, Akira; Nakamura, Nobuyuki; Yamamoto, Norimasa; Koike, Fumihiro

    2014-01-01

    We have constructed an atomic model for tungsten extreme ultraviolet (EUV) spectra to reconstruct characteristic spectral feature of unresolved transition array (UTA) observed at 4-7 nm for tungsten ions. In the tungsten atomic modeling, we considered fine-structure levels with the quantum principal number n up to 6 as the atomic structure and calculated the electron-impact collision cross sections by relativistic distorted-wave method, using HULLAC atomic code. We measured tungsten EUV spectra in Large Helical Device (LHD) and Compact Electron Beam Ion Trap device (CoBIT) and compared them with the model calculation. The model successfully explain series of emission peaks at 1.5-3.5 nm as n=5-4 and 6-4 transitions of W"2"4"+ - W"3"2"+ measured in CoBIT and LHD and the charge state distributions were estimated for LHD plasma. The UTA feature observed at 4-7 nm was also successfully reconstructed with our model. The peak at ∼5 nm is produced mainly by many 4f-4d transition of W"2"2"+ - W"3"5"+ ions, and the second peak at ∼6 nm is produced by 4f-4d transition of W"2"5"+ - W"2"8"+ ions, and 4d-4p inner-shell transitions, 4p"54d"n"+"1 - 4p"64d"n, of W"2"9"+ - W"3"5"+ ions. These 4d-4p inner-shell transitions become strong since we included higher excited states such as 4p"54d"n4f state, which ADAS atomic data set does not include for spectroscopic modeling with fine structure levels. (author)

  15. EBIT spectroscopy of Pm-like tungsten

    International Nuclear Information System (INIS)

    Hutton, R.; Zou, Y.; Reyna Almandos, J.; Biedermann, C.; Radtke, R.; Greier, A.; Neu, R.

    2003-01-01

    Methods of VUV electron beam ion trap (EBIT) spectroscopy are applied to the study of Pm-like tungsten (W 13+ ). These data show that theory appears well capable of dealing with these multi-electron (61) ions, at least for high ionization stages. A comparison of other spectroscopic methods applied to the study of other ions of the Pm I sequence is also given, and finally a search for the Pm-like W lines at the ASDEX Upgrade Tokamak is mentioned

  16. The tungsten powder study of the dispenser cathode

    International Nuclear Information System (INIS)

    Bao Jixiu; Wan Baofei

    2006-01-01

    The intercorrelation of tungsten powder properties, such as grain size, distribution and morphology, and porous matrix parameters with electron emission capability and longevity of Ba dispenser cathodes has been investigated for the different grain morphologies. It is shown that a fully cleaning step of the tungsten powder is so necessary that the tungsten powder will be reduction of oxide in hydrogen atmosphere above 700 deg. C. The porosity of the tungsten matrix distributes more even and the closed pore is fewer, the average granule size of the tungsten powder distributes more convergent. The porosity of the tungsten matrix and the evaporation of the activator are bigger and the pulse of the cathode is smaller when the granularity is bigger by the analysis of the electronic microscope and diode experiment

  17. The tungsten powder study of the dispenser cathode

    Science.gov (United States)

    Bao, Ji-xiu; Wan, Bao-fei

    2006-06-01

    The intercorrelation of tungsten powder properties, such as grain size, distribution and morphology, and porous matrix parameters with electron emission capability and longevity of Ba dispenser cathodes has been investigated for the different grain morphologies. It is shown that a fully cleaning step of the tungsten powder is so necessary that the tungsten powder will be reduction of oxide in hydrogen atmosphere above 700 °C. The porosity of the tungsten matrix distributes more even and the closed pore is fewer, the average granule size of the tungsten powder distributes more convergent. The porosity of the tungsten matrix and the evaporation of the activator are bigger and the pulse of the cathode is smaller when the granularity is bigger by the analysis of the electronic microscope and diode experiment.

  18. Synthesis and electrical characterization of tungsten oxide nanowires

    Institute of Scientific and Technical Information of China (English)

    Huang Rui; Zhu Jing; Yu Rong

    2009-01-01

    Tungsten oxide nanowires of diameters ranging from 7 to 200 nm are prepared on a tungsten rod substrate by using the chemical vapour deposition (CVD) method with vapour-solid (VS) mechanism. Tin powders are used to control oxygen concentration in the furnace, thereby assisting the growth of the tungsten oxide nanowires. The grown tungsten oxide nanowires are determined to be of crystalline W18O49. Ⅰ-Ⅴ curves are measured by an in situ transmission electron microscope (TEM) to investigate the electrical properties of the nanowires. All of the Ⅰ-Ⅴ curves observed are symmetric, which reveals that the tungsten oxide nanowires are semiconducting. Quantitative analyses of the experimental I V curves by using a metal-semiconductor-metal (MSM) model give some intrinsic parameters of the tungsten oxide nanowires, such as the carrier concentration, the carrier mobility and the conductivity.

  19. Process for separation of tungsten and molybdenum by extraction

    International Nuclear Information System (INIS)

    Zelikman, A.N.; Voldman, G.M.; Rumyantsev, V.K.; Ziberov, G.N.; Kagermanian, V.S.

    1976-01-01

    A process for the separation of tungsten and molybdenum by extraction involves the addition of HCl or HNO 3 to an aqueous solution containing tungsten and molybdenum to obtain a pH from 0.5 to 4.3, and introduction of a stabilizer comprising water-soluble phosphorus salts and a complexing agent, hydrogen peroxide, in an amount from 1.5 to 2 mole per 1 g-atom of the total content of tungsten and molybdenum. Then molybdenum is selectively extracted from the resulting aqueous solution with tri-n-butylphosphate with equal volumetric proportioning of the aqueous and organic solutions. Re-extraction of molybdenum and partially tungsten is carried out from the organic extracting agent with an alkali or soda solution. The process makes possible the preparation of tungsten solution containing no more than 0.001 g/l of molybdenum, and an increase in the degree of extraction of tungsten and molybdenum

  20. Separation of tungsten and rhenium on alumina

    Directory of Open Access Journals (Sweden)

    MILOVAN SM. STOILJKOVIC

    2004-09-01

    Full Text Available The conditions for the efficient separation of tungsten(VI and rhenium (VII on alumina were established. The distribution coefficients Kd for tungstate and perrhenate anions, as well as the separation factors a (a = KdWO42-/Kd ReO4- were determined using hydrochloric or nitric acid as the aqueous media. A solution of sodium chloride in the pH range 2–6 was also examined. Under all the tested experimental conditions, alumina is a much better adsorbent for tungsten than for rhenium. The obtained results indicated that the best separation of these two elements is achieved when 0.01– 0.1 mol dm-3 HCl or 1.0 mol dm-3 HNO3 are used as the aqueous media. If NaCl is used as the aqueous phase, the best separation is achieved with 0.20 mol dm-3 NaCl, pH 4–6. Under these experimental conditions, the breakthrough and saturation capacities of alumina for tungsten at pH 4 are 17 and 26 mg W/g Al2O3, respectively. With increasing pH, these values decrease. Thus, at pH 6 they are only 4 and 13 mg W/g Al2O3, respectively.

  1. Controlled nanostructuration of polycrystalline tungsten thin films

    Energy Technology Data Exchange (ETDEWEB)

    Girault, B. [Institut P' (UPR 3346 CNRS), Universite de Poitiers, ENSMA, Bd Pierre et Marie Curie, 86962 Futuroscope Cedex (France); Institut de Recherche en Genie Civil et Mecanique (UMR CNRS 6183), LUNAM Universite, Universite de Nantes, Centrale Nantes, CRTT, 37 Bd de l' Universite, BP 406, 44602 Saint-Nazaire Cedex (France); Eyidi, D.; Goudeau, P.; Guerin, P.; Bourhis, E. Le; Renault, P.-O. [Institut P' (UPR 3346 CNRS), Universite de Poitiers, ENSMA, Bd Pierre et Marie Curie, 86962 Futuroscope Cedex (France); Sauvage, T. [CEMHTI/CNRS (UPR 3079 CNRS), Universite d' Orleans, 3A rue de la Ferollerie, 45071 Orleans Cedex 2 (France)

    2013-05-07

    Nanostructured tungsten thin films have been obtained by ion beam sputtering technique stopping periodically the growing. The total thickness was maintained constant while nanostructure control was obtained using different stopping periods in order to induce film stratification. The effect of tungsten sublayers' thicknesses on film composition, residual stresses, and crystalline texture evolution has been established. Our study reveals that tungsten crystallizes in both stable {alpha}- and metastable {beta}-phases and that volume proportions evolve with deposited sublayers' thicknesses. {alpha}-W phase shows original fiber texture development with two major preferential crystallographic orientations, namely, {alpha}-W<110> and unexpectedly {alpha}-W<111> texture components. The partial pressure of oxygen and presence of carbon have been identified as critical parameters for the growth of metastable {beta}-W phase. Moreover, the texture development of {alpha}-W phase with two texture components is shown to be the result of a competition between crystallographic planes energy minimization and crystallographic orientation channeling effect maximization. Controlled grain size can be achieved for the {alpha}-W phase structure over 3 nm stratification step. Below, the {beta}-W phase structure becomes predominant.

  2. Separation of Rhenium (VII) from Tungsten (VI)

    International Nuclear Information System (INIS)

    Vucina, J.; Lukic, D.; Stoiljkovic, M.; Milosevic, M.; Orlic, M.

    2004-01-01

    Examined were the conditions for an effective separation of tungsten (VI) and rhenium (VII) on alumina if the solution of 0.20 mol dm -3 NaCl, ph=2.6 is used as the aqueous phase. Under the given experimental conditions alumina was found to be much better adsorbent for tungsten than for rhenium. The breakthrough and saturation capacities of alumina at pH=2 are 24 and 78 mg W/g Al 2 O 3 , respectively. With the increase of pH these values decrease. So, at pH=6 they are only 4 and 13 mg W/g Al 2 O 3 respectively. The elution volume for rhenium for the given column dimensions and quantity of the adsorbent is about 16 ml. These results were confirmed by the experiments of the radiological separations. Tungsten-187 remains firmly bound to the alumina. The radionuclide purity of the eluted 186'188 Re at pH=2 is very high. (authors)

  3. Concentration dependent hydrogen diffusion in tungsten

    Energy Technology Data Exchange (ETDEWEB)

    Ahlgren, T., E-mail: tommy.ahlgren@helsinki.fi; Bukonte, L.

    2016-10-15

    The diffusion of hydrogen in tungsten is studied as a function of temperature, hydrogen concentration and pressure using Molecular Dynamics technique. A new analysis method to determine diffusion coefficients that accounts for the random oscillation of atoms around the equilibrium position is presented. The results indicate that the hydrogen migration barrier of 0.25 eV should be used instead of the presently recommended value of 0.39 eV. This conclusion is supported by both experiments and density functional theory calculations. Moreover, the migration volume at the saddle point for H in W is found to be positive: ΔV{sub m} ≈ 0.488 Å{sup 3}, leading to a decrease in the diffusivity at high pressures. At high H concentrations, a dramatic reduction in the diffusion coefficient is observed, due to site blocking and the repulsive H-H interaction. The results of this study indicates that high flux hydrogen irradiation leads to much higher H concentrations in tungsten than expected. - Highlights: • The recommended value of 0.39 eV for the H in W migration barrier should be changed to 0.25 eV. • The random oscillation of atoms around the equilibrium position can be dealt with in diffusion simulations. • Hydrogen diffusion in tungsten is highly concentration dependent.

  4. Tungsten/copper composite deposits produced by a cold spray

    International Nuclear Information System (INIS)

    Kang, Hyun-Ki; Kang, Suk Bong

    2003-01-01

    An agglomerated tungsten/copper composite powder was both cold sprayed and plasma sprayed onto a mild steel substrate for electronic package applications. Most pores resulting from the spraying were found in the vicinity of the tungsten-rich regions of the final product. The levels of porosity varied with the amount of tungsten present. No copper oxidation was found at the cold-sprayed deposit, but relatively high copper oxidation was observed at the plasma-sprayed deposit

  5. Tungsten-induced carcinogenesis in human bronchial epithelial cells

    Energy Technology Data Exchange (ETDEWEB)

    Laulicht, Freda; Brocato, Jason; Cartularo, Laura; Vaughan, Joshua; Wu, Feng; Kluz, Thomas; Sun, Hong [Department of Environmental Medicine, New York University Langone Medical Center, Tuxedo, NY 10987 (United States); Oksuz, Betul Akgol [Genome Technology Center, New York University Langone Medical Center, New York, NY 10016 (United States); Shen, Steven [Center for Health Informatics and Bioinformatics, New York University Langone Medical Center, New York, NY 10016 (United States); Peana, Massimiliano; Medici, Serenella; Zoroddu, Maria Antonietta [Department of Chemistry and Pharmacy, University of Sassari, Sassari (Italy); Costa, Max, E-mail: Max.Costa@nyumc.org [Department of Environmental Medicine, New York University Langone Medical Center, Tuxedo, NY 10987 (United States)

    2015-10-01

    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 migration, xenograft growth in nude mice, and the activation of multiple cancer-related pathways in transformed clones as determined by RNA sequencing. Human bronchial epithelial cell line (Beas-2B) exposed to tungsten developed carcinogenic properties. In a soft agar assay, tungsten-treated cells formed more colonies than controls and the tungsten-transformed clones formed tumors in nude mice. RNA-sequencing data revealed that the tungsten-transformed clones altered the expression of many cancer-associated genes when compared to control clones. Genes involved in lung cancer, leukemia, and general cancer genes were deregulated by tungsten. Taken together, our data show the carcinogenic potential of tungsten. Further tests are needed, including in vivo and human studies, in order to validate tungsten as a carcinogen to humans. - Highlights: • Tungsten (W) induces cell transformation and increases migration in vitro. • W increases xenograft growth in nude mice. • W altered the expression of cancer-related genes such as those involved in leukemia. • Some of the dysregulated leukemia genes include, CD74, CTGF, MST4, and HOXB5. • For the first time, data is presented that demonstrates tungsten's carcinogenic potential.

  6. Surface composition of carburized tungsten trioxide and its catalytic activity

    International Nuclear Information System (INIS)

    Nakazawa, M.; Okamoto, H.

    1985-01-01

    The surface composition and electronic structure of carburized tungsten trioxide are investigated using x-ray photoelectron spectroscopy (XPS). The relationship between the surface composition and the catalytic activity for methanol electro-oxidation is clarified. The tungsten carbide concentration in the surface layer increases with the carburization time. The formation of tungsten carbide enhances the catalytic activity. On the other hand, the presence of free carbon or tungsten trioxide in the surface layer reduces the activity remarkably. It is also shown that, the higher the electronic density of states near the Fermi level, the higher the catalytic activity

  7. Radiative capture of slow electrons by tungsten surface

    International Nuclear Information System (INIS)

    Artamonov, O.M.; Belkina, G.M.; Samarin, S.N.; Yakovlev, I.I.

    1987-01-01

    Isochromatic spectra of radiation capture of slow electrons by the surface of mono- and polycrystal tungsten recorded on 322 and 405 nm wave lengths are presented. The effect of oxygen adsorption on isochromates of the (110) face of tungsten monocrystal is investigated. The obtained isochromatic spectra are compared with energy band structure of tungsten. Based on the analysis of the obtained experimental results it is assumed that optical transition to the final state at the energy of 7.3 eV relatively to Fermi level is conditioned by surface states of the tungsten face (110)

  8. On tungsten technologies and qualification for DEMO

    International Nuclear Information System (INIS)

    Laan, J. van der; Hegeman, H.; Wouters, O.; Luzginova, N.; Jonker, B.; Van der Marck, S.; Opschoor, J.; Wang, J.; Dowling, G.; Stuivenga, M.; Carton, E.

    2009-01-01

    Tungsten alloys are considered prime candidates for the in-vessel components directly facing the plasma. For example, in the HEMJ helium cooled divertor design tiles may be operated at temperatures up to 1700 deg. C, supported by a structure partially consisting of tungsten at temperatures from 600 to 1000 deg. C, and connected to a HT steel structure. The tungsten armoured primary wall is operated at 500-900 deg. C. Irradiation doses will be few tens dpa at minimum, but FPR requirements for plants availability will stretch these targets. Recently injection moulding technology was developed for pure tungsten and representative parts were manufactured for ITER monobloc divertors and DEMO HEMJ thimbles. The major advantages for this technology are the efficient use of material feedstock/resources and the intrinsic possibility to produce near-finished product, avoiding machining processes that are costly and may introduce surface defects deteriorating the component in service performance. It is well suited for mass-manufacturing of components as well known in e.g. lighting industries. To further qualify this material technology various specimen types were produced with processing parameters identical to the components, and tested successfully, showing the high potential for implementation in (fusion) devices. Furthermore, the engineering approach can clearly be tailored away from conventional design and manufacturing technologies based on bulk materials. The technology is suitable for shaping of new W-alloys and W-ODS variants as well. Basically this technology allows a particular qualification trajectory. There is no need to produce large batches of material during the material development and optimization stage. For the verification of irradiation behaviour in the specific neutron spectra, there is a further attractive feature to use e.g. isotope tailored powders to adjust to available irradiation facilities like MTR's. In addition the ingrowth of transmutation

  9. Fracture and Residual Characterization of Tungsten Carbide Cobalt Coatings on High Strength Steel

    National Research Council Canada - National Science Library

    Parker, Donald S

    2003-01-01

    Tungsten carbide cobalt coatings applied via high velocity oxygen fuel thermal spray deposition are essentially anisotropic composite structures with aggregates of tungsten carbide particles bonded...

  10. Comparative Investigation of Tungsten Fibre Nets Reinforced Tungsten Composite Fabricated by Three Different Methods

    Directory of Open Access Journals (Sweden)

    Linhui Zhang

    2017-07-01

    Full Text Available Tungsten fibre nets reinforced tungsten composites (Wf/W containing four net layers were fabricated by spark plasma sintering (SPS, hot pressing (HP and cold rolling after HP (HPCR, with the weight fraction of fibres being 17.4%, 10.5% and 10.5%, respectively. The relative density of the HPCRed samples is the highest (99.8% while that of the HPed composites is the lowest (95.1%. Optical and scanning electron microscopy and electron back scattering diffraction were exploited to characterize the microstructure, while tensile and hardness tests were used to evaluate the mechanical properties of the samples. It was found that partial recrystallization of fibres occurred after the sintering at 1800 °C. The SPSed and HPed Wf/W composites begin to exhibit plastic deformation at 600 °C with tensile strength (TS of 536 and 425 MPa and total elongation at break (TE of 11.6% and 23.0%, respectively, while the HPCRed Wf/W composites exhibit plastic deformation at around 400 °C. The TS and TE of the HPCRed Wf/W composites at 400 °C are 784 MPa and 8.4%, respectively. The enhanced mechanical performance of the Wf/W composites over the pure tungsten can be attributed to the necking, cracking, and debonding of the tungsten fibres.

  11. 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.

  12. Behavior of tungsten carbide in water stabilized plasma

    Czech Academy of Sciences Publication Activity Database

    Brožek, Vlastimil; Matějíček, Jiří; Neufuss, Karel

    2007-01-01

    Roč. 7, č. 4 (2007), s. 213-220 ISSN 1335-8987 R&D Projects: GA ČR(CZ) GA104/05/0540 Institutional research plan: CEZ:AV0Z20430508 Keywords : water stabilized plasma * tungsten carbide * tungsten hemicarbide * decarburization Subject RIV: BL - Plasma and Gas Discharge Physics

  13. Hydrogen permeation properties of plasma-sprayed tungsten

    International Nuclear Information System (INIS)

    Anderl, R.A.; Pawelko, R.J.; Hankins, M.R.; Longhurst, G.R.; Neiser, R.A.

    1994-01-01

    Tungsten has been proposed as a plasma-facing component material for advanced fusion facilities. This paper reports on laboratory-scale studies that were done to assess the hydrogen permeation properties of plasma-sprayed tungsten for such applications. The work entailed deuterium permeation measurements for plasma-sprayed (PS) tungsten coatings, sputter-deposited (SP) tungsten coatings, and steel substrate material using a mass-analyzed, 3 keV D + 3 ion beam with fluxes of similar 6.5x10 19 D/m 2 s. Extensive characterization analyses for the plasma-sprayed tungsten coatings were made using Auger spectrometry and scanning electron microscopy (SEM). Observed permeation rates through composite PS-tungsten/steel specimens were several orders of magnitude below the permeation levels observed for SP-tungsten/steel composite specimens and pure steel specimens. Characterization analyses indicated that the plasma-sprayed tungsten coating had a nonhomogeneous microstructure that consisted of splats with columnar solidification, partially-melted particles with grain boundaries, and void regions. Reduced permeation levels can be attributed to the complex microstructure and a substantial surface-connected porosity. ((orig.))

  14. Hydrogen permeation properties of plasma-sprayed tungsten

    Energy Technology Data Exchange (ETDEWEB)

    Anderl, R.A. (Idaho National Engineering Lab., EG and G Idaho Inc., Idaho Falls, ID (United States)); Pawelko, R.J. (Idaho National Engineering Lab., EG and G Idaho Inc., Idaho Falls, ID (United States)); Hankins, M.R. (Idaho National Engineering Lab., EG and G Idaho Inc., Idaho Falls, ID (United States)); Longhurst, G.R. (Idaho National Engineering Lab., EG and G Idaho Inc., Idaho Falls, ID (United States)); Neiser, R.A. (Sandia National Laboratories, Albuquerque, NM 87185 (United States))

    1994-09-01

    Tungsten has been proposed as a plasma-facing component material for advanced fusion facilities. This paper reports on laboratory-scale studies that were done to assess the hydrogen permeation properties of plasma-sprayed tungsten for such applications. The work entailed deuterium permeation measurements for plasma-sprayed (PS) tungsten coatings, sputter-deposited (SP) tungsten coatings, and steel substrate material using a mass-analyzed, 3 keV D[sup +][sub 3] ion beam with fluxes of similar 6.5x10[sup 19] D/m[sup 2] s. Extensive characterization analyses for the plasma-sprayed tungsten coatings were made using Auger spectrometry and scanning electron microscopy (SEM). Observed permeation rates through composite PS-tungsten/steel specimens were several orders of magnitude below the permeation levels observed for SP-tungsten/steel composite specimens and pure steel specimens. Characterization analyses indicated that the plasma-sprayed tungsten coating had a nonhomogeneous microstructure that consisted of splats with columnar solidification, partially-melted particles with grain boundaries, and void regions. Reduced permeation levels can be attributed to the complex microstructure and a substantial surface-connected porosity. ((orig.))

  15. Hydrogen permeation properties of plasma-sprayed tungsten*1

    Science.gov (United States)

    Anderl, R. A.; Pawelko, R. J.; Hankins, M. R.; Longhurst, G. R.; Neiser, R. A.

    1994-09-01

    Tungsten has been proposed as a plasma-facing component material for advanced fusion facilities. This paper reports on laboratory-scale studies that were done to assess the hydrogen permeation properties of plasma-sprayed tungsten for such applications. The work entailed deuterium permeation measurements for plasma-sprayed (PS) tungsten coatings, sputter-deposited (SP) tungsten coatings, and steel substrate material using a mass-analyzed, 3 keV D 3+ ion beam with fluxes of ˜6.5 × 10 19 D/m 2 s. Extensive characterization analyses for the plasma-sprayed tungsten coatings were made using Auger spectrometry and scanning electron microscopy (SEM). Observed permeation rates through composite PS-tungsten/steel specimens were several orders of magnitude below the permeation levels observed for SP-tungsten/steel composite specimens and pure steel specimens. Characterization analyses indicated that the plasma-sprayed tungsten coating had a nonhomogeneous microstructure that consisted of splats with columnar solidification, partially-melted particles with grain boundaries, and void regions. Reduced permeation levels can be attributed to the complex microstructure and a substantial surface-connected porosity.

  16. Charge-density-wave instabilities expected in monophosphate tungsten bronzes

    International Nuclear Information System (INIS)

    Canadell, E.; Whangbo, M.

    1991-01-01

    On the basis of tight-binding band calculations, we examined the electronic structures of the tungsten oxide layers found in the monophosphate tungsten bronze (MPTB) phases. The Fermi surfaces of these MPTB phases consist of five well-nested one- and two-dimensional pieces. We calculated the nesting vectors of these Fermi surfaces and discussed the expected charge-density-wave instabilities

  17. Vapor-transport of tungsten and its geologic application

    Energy Technology Data Exchange (ETDEWEB)

    Shibue, Y [Hyogo Univ. of Teacher Education, Hyogo (Japan)

    1988-11-10

    The volatility of tungsten in a hydrous system at elevated temperatures and pressures was examined, and a tentative model for the enrichment of tungsten in hydrothermal solutions for the deposits related to granitic activities was proposed. To produce vapor-saturated solution, 17 or 15ml of 20wt% NaCl solution was introduced into an autoclave. Ca(OH){sub 2} for tungsten and H{sub 2}WO{sub 4} for base metals were used as vapor-captures, and run products were identified by X-ray powder diffractometry. The results suggested that the ratio of tungsten to base metals was higher in a vapor phase than in a liquid phase, and more enrichment of tungsten in the vapor phase occurred at higher temperature and pressure under the coexistence of the vapor and liquid phase. The tentative model emphasizing the vapor-transport of tungsten could explain the presence of tungsten deposits without large mineralization of base metals. Geological schematic model for the generation of the hydrothermal solution enriched in tungsten compared with base metals was illustrated based on above mentioned results. 21 refs., 3 figs.

  18. Chromium and molybdenum diffusion in tungsten single crystals

    International Nuclear Information System (INIS)

    Klotsman, S.M.; Koloskov, V.M.; Osetrov, S.V.; Polikarpova, I.P.; Tatarinova, G.N.; Timofeev, A.N.

    1989-01-01

    Consideration is given to results of measuring temperature dependences of diffusion coefficients of homovalent impurities of chromium and molybdenum in tungsten single crystals. It is concluded that the difference of activation energies of selfdiffusion and impurity diffusion in the system 'tungsten-homovalent impurity' is conditioned by interaction of screened potentials of impurity and vacancy with Lazarus-Le Claire model

  19. 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.

  20. Processing of tungsten scrap into powders by electroerosion disintegration

    International Nuclear Information System (INIS)

    Fominskii, L.P.; Leuchuk, M.V.; Myuller, A.S.; Tarabrina, V.P.

    1985-01-01

    Utilization of tungsten and tungsten alloy swarf and other waste and also of rejected and worn parts is a matter of great importance in view of the shortage of this metal. The authors examine the electroerosion (EE) disintegration of tungsten in water as a means of utilizing swarf and other loose waste. Unlike chemical methods, EE disintegration ensures ecological purity since there are no effluent waters or toxic discharges. Swarf and trimmings of rods of diameters up to 20 mm obtained after the lathe-turning of tungsten bars sintered from PVN and PVV tungsten powders were disintegrated in water at room temperature between tungsten electrodes. The phase composition of the powder was studied using FeK /SUB alpha/ radiation, by x-ray diffraction methods in a DRON-2 diffractometer with a graphite monochromator on the secondary beam. When tungsten is heated to boiling during EE disintegration, the impurities present in it can evaporate and burn out. Thus, tungsten powder produced by EE disintegration can be purer than the starting metal

  1. Thermal Spray Coating of Tungsten for Tokamak Device

    International Nuclear Information System (INIS)

    Jiang Xianliang; Gitzhofer, F; Boulos, M I

    2006-01-01

    Thermal spray, such as direct current (d.c.) plasma spray or radio frequency induced plasma spray, was used to deposit tungsten coatings on the copper electrodes of a tokamak device. The tungsten coating on the outer surface of one copper electrode was formed directly through d.c. plasma spraying of fine tungsten powder. The tungsten coating/lining on the inner surface of another copper electrode could be formed indirectly through induced plasma spraying of coarse tungsten powder. Scanning electron microscopy (SEM) was used to examine the cross section and the interface of the tungsten coating. Energy Dispersive Analysis of X-ray (EDAX) was used to analyze the metallic elements attached to a separated interface. The influence of the particle size of the tungsten powder on the density, cracking behavior and adhesion of the coating is discussed. It is found that the coarse tungsten powder with the particle size of 45 ∼ 75 μm can be melted and the coating can be formed only by using induced plasma. The coating deposited from the coarse powder has much higher cohesive strength, adhesive strength and crack resistance than the coating made from the fine powder with a particle size of 5 μm

  2. Tungsten Deposition on Graphite using Plasma Enhanced Chemical Vapour Deposition

    International Nuclear Information System (INIS)

    Sharma, Uttam; Chauhan, Sachin S; Sharma, Jayshree; Sanyasi, A K; Ghosh, J; Choudhary, K K; Ghosh, S K

    2016-01-01

    The tokamak concept is the frontrunner for achieving controlled thermonuclear reaction on earth, an environment friendly way to solve future energy crisis. Although much progress has been made in controlling the heated fusion plasmas (temperature ∼ 150 million degrees) in tokamaks, technological issues related to plasma wall interaction topic still need focused attention. In future, reactor grade tokamak operational scenarios, the reactor wall and target plates are expected to experience a heat load of 10 MW/m 2 and even more during the unfortunate events of ELM's and disruptions. Tungsten remains a suitable choice for the wall and target plates. It can withstand high temperatures, its ductile to brittle temperature is fairly low and it has low sputtering yield and low fuel retention capabilities. However, it is difficult to machine tungsten and hence usages of tungsten coated surfaces are mostly desirable. To produce tungsten coated graphite tiles for the above-mentioned purpose, a coating reactor has been designed, developed and made operational at the SVITS, Indore. Tungsten coating on graphite has been attempted and successfully carried out by using radio frequency induced plasma enhanced chemical vapour deposition (rf -PECVD) for the first time in India. Tungsten hexa-fluoride has been used as a pre-cursor gas. Energy Dispersive X-ray spectroscopy (EDS) clearly showed the presence of tungsten coating on the graphite samples. This paper presents the details of successful operation and achievement of tungsten coating in the reactor at SVITS. (paper)

  3. Fracture peculiarities in ceramic tungsten at different temperatures in vacuum

    International Nuclear Information System (INIS)

    Uskov, E.I.; Babak, A.V.

    1981-01-01

    Stress-strain diagrams and results of metallographic analyses are presented for the ceramic tungsten samples tested for fracture toughness under conditions of eccentric tension at different temperatures (20...1600 deg C) in vacuum. The tungsten fracture is shown to be of brittle nature within the whole temperature range studied, but the fracture process has its own peculiarities at different test temperatures

  4. Low temperature photoresponse of monolayer tungsten disulphide

    Directory of Open Access Journals (Sweden)

    Bingchen Cao

    2014-11-01

    Full Text Available High photoresponse can be achieved in monolayers of transition metal dichalcogenides. However, the response times are inconveniently limited by defects. Here, we report low temperature photoresponse of monolayer tungsten disulphide prepared by exfoliation and chemical vapour deposition (CVD method. The exfoliated device exhibits n-type behaviour; while the CVD device exhibits intrinsic behaviour. In off state, the CVD device has four times larger ratio of photoresponse for laser on/off and photoresponse decay–rise times are 0.1 s (limited by our setup, while the exfoliated device has few seconds. These findings are discussed in terms of charge trapping and localization.

  5. Spectrophotometric determination of tungsten with salicylic acid

    International Nuclear Information System (INIS)

    Goncalves, Z.C.

    1976-10-01

    The method comprises the complexation of tungsten with salicylic acid in concentrated sulphuric acid yielding a reddish color. The maximum absorbance of the complex lies within 410-420 nm, 420 nm being the chosen wavelenght. The final concentration of salicylic acid is 0,080 g/ml. The sensitivity is 0,13 μg W(%T) -1 ml -1 . Titanium, vanadium, rhenium, niobium and molybdenum interferes and must be separated, titanium being the strongest interferent. The separation procedures, advantages of the process, stoichiometric relations and equilibrium constant are discussed. (Author) [pt

  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......, applicability to plasma-enhanced chemical vapor deposition (PECVD) of aligned CNT forests, and electrochemical performance are investigated. Experiments include culturing of NIH3T3 mouse embryonic fibroblast cells on TiW coated silicon scaffolds, CNT growth on TiW substrates with nickel catalyst, and cyclic...

  7. High Heat Load Properties of Ultra Fine Grain Tungsten

    International Nuclear Information System (INIS)

    Zhou, Z.; Du, J.; Ge, C.; Linke, J.; Pintsuk, G.; Song, S.X.

    2007-01-01

    Full text of publication follows: Tungsten is increasingly considered as a promising candidate armour materials facing the plasma in tokamaks for medium to high heat flux components (EAST, ASDEX, ITER). Fabrication tungsten with ultra fine grain size is considered as an effective way to ameliorate some disadvantages of tungsten, such as its brittleness at room temperature. But the research data on the performance of ultra fine grain tungsten is still very limit. In this work, high heat load properties of pure ultra-fine grain tungsten have been studied. The ultra fine grain tungsten samples with average grain size of 0.2 μm, 1 μm and 3 μm were fabricated by resistance sintering under ultra high pressure. The annealing experiments for the investigation of the material resistance against grain growth have been done by annealing samples in a vacuum furnace at different temperature holding for 2 hours respectively. It is found that recrystallization and grain growth occur at heating temperature of 1250 deg. c. The finer the initial grain sizes of tungsten, the smaller its grain growth grain. The effects of transient high thermal loads (off normal events like disruptions) on tungsten surface morphology have been performed in electron beam test facility JUDITH. The thermal loads tests have been carried out with 4 ms pulses at different power density of 0.22, 0.33, 0.44, 0.55 and 0.88 GW/m 2 respectively. Horizontal cracks formed for all tungsten samples at 0.44 GW/m 2 . Particle erosions occurred for tungsten with 3 μm size at 0.33 GW/m 2 and for tungsten with 0.2 and 1 μm size at 0.55 GW/m 2 . The weight loss of tungsten with 0.2, 1 and 3 μm size are 2,0.1,0.6 mg respectively at 0.88 GW/m 2 . The effects of a large number of very short transient repetitive thermal loads (ELM-like) on tungsten surface morphology also have been performed by using a fundamental wave of a YAG laser. It is found that tungsten with 0.2 μm size has the best performance. (authors)

  8. High Heat Load Properties of Ultra Fine Grain Tungsten

    Energy Technology Data Exchange (ETDEWEB)

    Zhou, Z.; Du, J.; Ge, C. [Lab. of Special Ceramic and P/M, University of Science and Technology, 100083 Beijing (China); Linke, J.; Pintsuk, G. [FZJ-Forschungszentrum Juelich GmbH, Association Euratom-FZJ, Institut fur Plasmaphysik, Postfach 1913, D-52425 Juelich (Germany); Song, S.X. [Research Center on Fusion Materials (RCFM), University of Science and Technology Beijing (USTB), 100083 Beijing (China)

    2007-07-01

    Full text of publication follows: Tungsten is increasingly considered as a promising candidate armour materials facing the plasma in tokamaks for medium to high heat flux components (EAST, ASDEX, ITER). Fabrication tungsten with ultra fine grain size is considered as an effective way to ameliorate some disadvantages of tungsten, such as its brittleness at room temperature. But the research data on the performance of ultra fine grain tungsten is still very limit. In this work, high heat load properties of pure ultra-fine grain tungsten have been studied. The ultra fine grain tungsten samples with average grain size of 0.2 {mu}m, 1 {mu}m and 3 {mu}m were fabricated by resistance sintering under ultra high pressure. The annealing experiments for the investigation of the material resistance against grain growth have been done by annealing samples in a vacuum furnace at different temperature holding for 2 hours respectively. It is found that recrystallization and grain growth occur at heating temperature of 1250 deg. c. The finer the initial grain sizes of tungsten, the smaller its grain growth grain. The effects of transient high thermal loads (off normal events like disruptions) on tungsten surface morphology have been performed in electron beam test facility JUDITH. The thermal loads tests have been carried out with 4 ms pulses at different power density of 0.22, 0.33, 0.44, 0.55 and 0.88 GW/m{sup 2} respectively. Horizontal cracks formed for all tungsten samples at 0.44 GW/m{sup 2}. Particle erosions occurred for tungsten with 3 {mu}m size at 0.33 GW/m{sup 2} and for tungsten with 0.2 and 1 {mu}m size at 0.55 GW/m{sup 2}. The weight loss of tungsten with 0.2, 1 and 3 {mu}m size are 2,0.1,0.6 mg respectively at 0.88 GW/m{sup 2}. The effects of a large number of very short transient repetitive thermal loads (ELM-like) on tungsten surface morphology also have been performed by using a fundamental wave of a YAG laser. It is found that tungsten with 0.2 {mu}m size has

  9. Adhesion of non-selective CVD tungsten to silicon dioxide

    International Nuclear Information System (INIS)

    Woodruff, D.W.; Wilson, R.H.; Sanchez-Martinez, R.A.

    1986-01-01

    Adhesion of non-selective, CVD tungsten to silicon dioxide is a critical issue in the development of tungsten as a metalization for VLSI circuitry. Without special adhesion promoters, tungsten deposited from WF/sub 6/ and H/sub 2/ has typically failed a standard tape test over all types of silicon oxides and nitrides. The reasons for failure of thin films, and CVD tungsten in particular are explored along with standard techniques for improving adhesion of thin films. Experiments are reported which include a number of sputtered metals as adhesion promoters, as well as chemical and plasma treatment of the oxide surface. Sputtered molybdenum is clearly the superior adhesion promoting layer from these tests. Traditional adhesion layers such as chromium or titanium failed as adhesion layers for CVD tungsten possibly due to chemical reactions between the WF/sub 6/ and Cr or Ti

  10. Corrosion of high-density sintered tungsten alloys. Part 2

    International Nuclear Information System (INIS)

    Batten, J.J.; Moore, B.T.

    1988-12-01

    The behaviour of four high-density sintered tungsten alloys has been evluated and compared with that of pure tungsten. Rates of corrosion during the cyclic humidity and the salt mist tests were ascertained from weight loss measurements. Insight into the corrosion mechanism was gained from the nature of the corrosion products and an examination of the corroded surfaces. In the tests, the alloy 95% W, 2.5% Ni, 1.5% Fe was the most corrosion resistant. The data showed that copper as an alloying element accelerates corrosion of tungsten alloys. Both attack on the tungsten particles and the binder phase were observed together with tungsten grain loss. 6 refs., 3 tabs.,

  11. New doped tungsten cathodes. Applications to power grid tubes

    International Nuclear Information System (INIS)

    Cachard, J. de; Cadoret, K; Martinez, L.; Veillet, D.; Millot, F.

    2001-01-01

    Thermionic emission behavior of tungsten/tungsten carbide modified with rare earth (La, Ce, Y) oxides is examined on account of suitability to deliver important current densities in a thermo-emissive set up and for long lifetime. Work functions of potential cathodes have been determined from Richardson plots for La 2 O 3 doped tungsten and for tungsten covered with variable compositions rare earth tungstates. The role of platinum layers covering the cathode was also examined. Given all cathodes containing mainly lanthanum oxides were good emitters, emphasis was put on service lifetime. Comparisons of lifetime in tungsten doped with rare earth oxides and with rare earth tungstates show that microstructure of the operating cathodes may play the major role in the research of very long lifetime cathodes. Based on these results, tests still running show lifetime compatible with power grid tubes applications. (author)

  12. Formation of carbon containing layers on tungsten test limiters

    International Nuclear Information System (INIS)

    Rubel, M.; Philipps, V.; Huber, A.; Tanabe, T.

    1999-01-01

    Tungsten test limiters of mushroom shape and a plasma facing area of approximately 100 cm 2 were exposed at the TEXTOR-94 tokamak to a number of deuterium fuelled discharges performed under various operation conditions. Two types of limiters were tested: a sole tungsten limiter and a twin limiter consisting of two halves, one made of tungsten and another of graphite. The exposed surfaces were examined with ion beam analysis methods and laser profilometry. The formation of some deposition zones was observed near the edges of the limiters. The deuterium-to-carbon concentration ratio was in the range from 0.04 to 0.11 and around 0.2 for the sole tungsten and the twin limiter, respectively. Significant amounts of the co-deposited tungsten and silicon atoms were found on the graphite part of the twin limiter indicating the formation of mixed W-C-Si compounds. (orig.)

  13. The gate oxide integrity of CVD tungsten polycide

    International Nuclear Information System (INIS)

    Wu, N.W.; Su, W.D.; Chang, S.W.; Tseng, M.F.

    1988-01-01

    CVD tungsten polycide has been demonstrated as a good gate material in recent very large scale integration (VLSI) technology. CVD tungsten silicide offers advantages of low resistivity, high temperature stability and good step coverage. On the other hand, the polysilicon underlayer preserves most characteristics of the polysilicon gate and acts as a stress buffer layer to absorb part of the thermal stress origin from the large thermal expansion coefficient of tungsten silicide. Nevertheless, the gate oxide of CVD tungsten polycide is less stable or reliable than that of polysilicon gate. In this paper, the gate oxide integrity of CVD tungsten polycide with various thickness combinations and different thermal processes have been analyzed by several electrical measurements including breakdown yield, breakdown fluence, room temperature TDDB, I-V characteristics, electron traps and interface state density

  14. Solvent extraction in analytical chemistry of tungsten (Review)

    International Nuclear Information System (INIS)

    Ivanov, V.M.; Busev, A.I.; Sokolova, T.A.

    1975-01-01

    The use of extraction for isolating and concentrating tungsten with subsequent determination by various methods is considered. For tungsten extractants of all types are employed: neutral, basic and acidic. Neutral extractants are used for isolating and concentrating tungsten, basic and acidic ones are employed, as a rule, for the isolation and subsequent determination of tungsten. This type of extractants is highly promising, since, selectively extracting tungsten, they allow its simultaneous determination. Neutral extractants are oxygen-containing solvents, TBP; basic extractants are aniline, pyridine, 1-naphthylamine, trialkylbenzylammoniumanitrate. As acidic reagents use is made of 8-oxyquinoline and its derivatives, oximes and hydroxamic acids, β-diketones, carbaminates. In the extraction radioactive isotope 185 W is employed

  15. Structure and phase transformation behavior of electroless Ni-P alloys containing tin and tungsten

    International Nuclear Information System (INIS)

    Balaraju, J.N.; Jahan, S. Millath; Jain, Anjana; Rajam, K.S.

    2007-01-01

    Autocatalytic ternary Ni-Sn-P, Ni-W-P and quaternary Ni-W-Sn-P films were prepared using alkaline citrate-based baths and compared with binary Ni-P coatings. Energy dispersive analysis of X-ray (EDAX) showed that binary Ni-P deposit contained 11.3 wt.% of phosphorus. Codeposition of tungsten in Ni-P matrix resulted in ternary Ni-W-P with 5 wt.% P and 7.8 wt.% of tungsten. Incorporation of tin led to ternary Ni-Sn-P deposit containing 0.4 wt.% Sn and 10.3 wt.% P. Presence of both sodium tungstate and sodium stannate in the basic bath had resulted in quaternary coating with 6.9 wt.% W, traces of Sn and 6.4 wt.% P. X-ray diffraction patterns of all the deposits revealed a single, broad peak which showed the nanocrystalline nature of the deposits. For the first time in related literature, the presence of a metastable phase Ni 12 P 5 in ternary deposits is reported in the present study. Metallographic cross-sections of all the deposits revealed the banded/lamellar structure. Scanning electron microscopy (SEM) studies of the deposits showed smooth nodules for ternary deposits, but coarse and well-defined nodules for quaternary deposits. DSC studies of phase transformation behavior of the ternary Ni-Sn-P deposit revealed a single sharp exothermic peak at 365 o C. However, ternary Ni-W-P and quaternary Ni-W-Sn-P deposits exhibited a low temperature peak at 300 o C, a split type high temperature peak at 405 and 440 o C and a very high temperature peak at 550 o C. Higher activation energy values were obtained for W-based alloy deposits. Presence of W and Sn has helped to retain high microhardness values even at higher temperatures indicating an improved thermal stability

  16. Polaron interaction energies in reduced tungsten trioxide

    International Nuclear Information System (INIS)

    Iguchi, E.; Salje, E.; Tilley, R.J.D.

    1981-01-01

    Consideration of the properties of reduced tungsten trioxide suggest that the mobile charge carriers are polarons. As it is uncertain how the presence of polarons will influence the microstructures of the crystallographic shear (CS) planes present in reduced tungsten trioxide we have calculated both the polaron-CS plane and polaron-polaron interaction energy for a variety of circumstances. Three CS plane geometries were considered, (102), (103), and (001) CS plane arrays, and the nominal compositions of the crystals ranged from WO 2 70 to WO 3 0 . The polarons were assumed to have radii from 0.6 to 1.0 nm and the polaron-CS plane electrostatic interaction was assumed to be screened. The results suggest that for the most part the total interaction energy is small and is unlikely to be of major importance in controlling the microstructures found in CS planes. However, at very high polaron densities the interaction energy could be appreciable and may have some influence on the existence range of CS phases

  17. Proton beam induced dynamics of tungsten granules

    Science.gov (United States)

    Caretta, O.; Loveridge, P.; O'Dell, J.; Davenne, T.; Fitton, M.; Atherton, A.; Densham, C.; Charitonidis, N.; Efthymiopoulos, I.; Fabich, A.; Guinchard, M.; Lacny, L. J.; Lindstrom, B.

    2018-03-01

    This paper reports the results from single-pulse experiments of a 440 GeV /c proton beam interacting with granular tungsten samples in both vacuum and helium environments. Remote high-speed photography and laser Doppler vibrometry were used to observe the effect of the beam on the sample grains. The majority of the results were derived from a trough containing ˜45 μ m diameter spheres (not compacted) reset between experiments to maintain the same initial conditions. Experiments were also carried out on other open and contained samples for the purposes of comparison both with the 45 μ m grain results and with a previous experiment carried out with sub-250 μ m mixed crystalline tungsten powder in helium [Phys. Rev. ST Accel. Beams 17, 101005 (2014), 10.1103/PhysRevSTAB.17.101005]. The experiments demonstrate that a greater dynamic response is produced in a vacuum than in a helium environment and in smaller grains compared with larger grains. The examination of the dynamics of the grains after a beam impact leads to the hypothesis that the grain response is primarily the result of a charge interaction of the proton beam with the granular medium.

  18. Tungsten - Yttrium Based Nuclear Structural Materials

    Science.gov (United States)

    Ramana, Chintalapalle; Chessa, Jack; Martinenz, Gustavo

    2013-04-01

    The challenging problem currently facing the nuclear science community in this 21st century is design and development of novel structural materials, which will have an impact on the next-generation nuclear reactors. The materials available at present include reduced activation ferritic/martensitic steels, dispersion strengthened reduced activation ferritic steels, and vanadium- or tungsten-based alloys. These materials exhibit one or more specific problems, which are either intrinsic or caused by reactors. This work is focussed towards tungsten-yttrium (W-Y) based alloys and oxide ceramics, which can be utilized in nuclear applications. The goal is to derive a fundamental scientific understanding of W-Y-based materials. In collaboration with University of Califonia -- Davis, the project is designated to demonstrate the W-Y based alloys, ceramics and composites with enhanced physical, mechanical, thermo-chemical properties and higher radiation resistance. Efforts are focussed on understanding the microstructure, manipulating materials behavior under charged-particle and neutron irradiation, and create a knowledge database of defects, elemental diffusion/segregation, and defect trapping along grain boundaries and interfaces. Preliminary results will be discussed.

  19. Serrated flow behavior in tungsten heavy alloy

    Energy Technology Data Exchange (ETDEWEB)

    Das, Jiten, E-mail: das.jiten@gmail.com; Sankaranarayana, M.; Nandy, T.K.

    2015-10-14

    Flow behavior of a tungsten heavy alloy of composition, 90.5 wt% W–7.1 wt% Ni–1.65 wt% Fe–0.5 wt% Co–0.25 wt% Mo was investigated in a temperature range of 223–973 K and strain rate range of 10{sup −5}–10{sup −2} s{sup −1}. In the temperature range of 773–873 K, the stress strain curves were characterized by jerky flow pointing towards Dynamic Strain Ageing (DSA)/Portevin Le-Chatelier's (PLC) effect. Characteristics of DSA were analyzed in detail. Based on the value of activation energy determined from the critical strain method, diffusion of interstitials (carbon, oxygen, nitrogen and hydrogen) were thought to be responsible for the DSA effect. The results were discussed in relation to information existing in this area in tungsten heavy alloys. The study of fracture surface of tensile tested samples (in the range of 823–973 K) showed that the fractographic features, mostly intergranular, predominantly govern the overall ductility of the alloy and do not change except for surface oxidation at relatively higher temperatures.

  20. Proton beam induced dynamics of tungsten granules

    Directory of Open Access Journals (Sweden)

    O. Caretta

    2018-03-01

    Full Text Available This paper reports the results from single-pulse experiments of a 440  GeV/c proton beam interacting with granular tungsten samples in both vacuum and helium environments. Remote high-speed photography and laser Doppler vibrometry were used to observe the effect of the beam on the sample grains. The majority of the results were derived from a trough containing ∼45  μm diameter spheres (not compacted reset between experiments to maintain the same initial conditions. Experiments were also carried out on other open and contained samples for the purposes of comparison both with the 45  μm grain results and with a previous experiment carried out with sub-250  μm mixed crystalline tungsten powder in helium [Phys. Rev. ST Accel. Beams 17, 101005 (2014PRABFM1098-440210.1103/PhysRevSTAB.17.101005]. The experiments demonstrate that a greater dynamic response is produced in a vacuum than in a helium environment and in smaller grains compared with larger grains. The examination of the dynamics of the grains after a beam impact leads to the hypothesis that the grain response is primarily the result of a charge interaction of the proton beam with the granular medium.

  1. Tensile properties of irradiated TZM and tungsten

    International Nuclear Information System (INIS)

    Steichen, J.M.

    1975-04-01

    The effect of neutron irradiation on the elevated temperature tensile properties of TZM and tungsten has been experimentally determined. Specimens were irradiated at a temperature of approximately 720 0 F to fluences of 0.4 and 0.9 x 10 22 n/cm 2 (E greater than 0.1 MeV). Test parameters for both control and irradiated specimens included strain rates from 3 x 10 -4 to 1 s -1 and temperatures from 72 to 1700 0 F. The results of these tests were correlated with a rate-temperature parameter (T ln A/epsilon) to provide a concise description of material behavior over the range of deformation conditions of this study. The yield strength of the subject materials was significantly increased by decreasing temperature, increasing strain rate, and increasing fluence. Ductility was significantly reduced at any temperature or strain rate by increasing fluence. Cleavage fractures occurred in both unirradiated and irradiated specimens when the yield strength was elevated to the effective cleavage stress by temperature and/or strain rate. Neutron irradiation for the conditions of this study increased the ductile-to-brittle transition temperature of tungsten by approximately 300 0 F and TZM by approximately 420 0 F. (U.S.)

  2. 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.

  3. Tungsten tetraboride, an inexpensive superhard material

    Science.gov (United States)

    Mohammadi, Reza; Lech, Andrew T.; Xie, Miao; Weaver, Beth E.; Yeung, Michael T.; Tolbert, Sarah H.; Kaner, Richard B.

    2011-01-01

    Tungsten tetraboride (WB4) is an interesting candidate as a less expensive member of the growing group of superhard transition metal borides. WB4 was successfully synthesized by arc melting from the elements. Characterization using powder X-ray diffraction (XRD) and energy-dispersive X-ray spectroscopy (EDX) indicates that the as-synthesized material is phase pure. The zero-pressure bulk modulus, as measured by high-pressure X-ray diffraction for WB4, is 339 GPa. Mechanical testing using microindentation gives a Vickers hardness of 43.3 ± 2.9 GPa under an applied load of 0.49 N. Various ratios of rhenium were added to WB4 in an attempt to increase hardness. With the addition of 1 at.% Re, the Vickers hardness increased to approximately 50 GPa at 0.49 N. Powders of tungsten tetraboride with and without 1 at.% Re addition are thermally stable up to approximately 400 °C in air as measured by thermal gravimetric analysis. PMID:21690363

  4. 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

  5. Operation of ASDEX Upgrade with tungsten coated walls

    International Nuclear Information System (INIS)

    Rohde, V.

    2002-01-01

    An alternative for low-Z materials in the main chamber of a future fusion device are high-Z materials, but the maximal tolerable concentration in the plasma core is restricted. A step by step approach to employ tungsten at the central column of ASDEX Upgrade was started in 1999. Meanwhile almost the whole central column is covered with tiles, which were coated by PVD with tungsten. Up to now 9000 s of plasma discharge covering all relevant scenarios were performed. Routine operation of ASDEX Upgrade was not affected by the tungsten. Typical concentrations below 10 -5 were found. The tungsten concentration is mostly connected to the transport into the core plasma, not to the tungsten erosion. It can be demonstrated, that additional central heating can eliminate the tungsten accumulation. These experiments demonstrate the compatibility of fusion plasmas with W plasma facing components under reactor relevant conditions. The erosion pattern found by post mortem analysis indicates that the main effect is ion sputtering. The main erosion of tungsten seems to occur during plasma ramp-up and ramp-down. (author)

  6. 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.

  7. 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.

  8. Tungsten carbide and tungsten-molybdenum carbides as automobile exhaust catalysts

    International Nuclear Information System (INIS)

    Leclercq, L.; Daubrege, F.; Gengembre, L.; Leclercq, G.; Prigent, M.

    1987-01-01

    Several catalyst samples of tungsten carbide and W, Mo mixed carbides with different Mo/W atom ratios, have been prepared to test their ability to remove carbon monoxide, nitric oxide and propane from a synthetic exhaust gas simulating automobile emissions. Surface characterization of the catalysts has been performed by X-ray photoelectron spectroscopy (XPS) and selective chemisorption of hydrogen and carbon monoxide. Tungsten carbide exhibits good activity for CO and NO conversion, compared to a standard three-way catalyst based on Pt and Rh. However, this W carbide is ineffective in the oxidation of propane. The Mo,W mixed carbides are markedly different having only a very low activity. 9 refs.; 10 figs.; 5 tabs

  9. Microstructural study of tungsten influence on Co-Cr alloys

    International Nuclear Information System (INIS)

    Karaali, A.; Mirouh, K.; Hamamda, S.; Guiraldenq, P.

    2005-01-01

    Alloying elements, such as W, Mo, Mn,..., are of a great importance in the preoxidation of dental alloys and, consequently, on the ceramic/metal bond quality. This study deals with the effect of tungsten addition on the microstructural state of Co-Cr dental alloys, before the ceramisation process. These materials were prepared by unidirectional solidification. Their characterization has been carried out, using transmission electron microscopy (TEM) and X-ray diffraction. It shows that the addition of tungsten up to 8 wt.% induces structural transformations, which are believed to be linked to the added amount of tungsten

  10. Tungsten as First Wall Material in Fusion Devices

    International Nuclear Information System (INIS)

    Kaufmann, M.

    2006-01-01

    In the PLT tokamak with a tungsten limiter strong cooling of the central plasma was observed. Since then mostly graphite has been used as limiter or target plate material. Only a few tokamaks (limiter: FTU, TEXTOR; divertor: Alcator C-Mod, ASDEX Upgrade) gained experience with high-Z-materials. With the observed strong co- deposition of tritium together with carbon in JET and as a result of design studies of fusion reactors, it became clear that in the long run tungsten is the favourite for the first-wall material. Tungsten as a plasma facing material requires intensive research in all areas, i.e. in plasma physics, plasma wall-interaction and material development. Tungsten as an impurity in the confined plasma reveals considerable differences to carbon. Strong radiation at high temperatures, in connection with mostly a pronounced inward drift forms a particular challenge. Turbulent transport plays a beneficial role in this regard. The inward drift is an additional problem in the pedestal region of H-mode plasmas in ITER-like configurations. The erosion by low energy hydrogen atoms is in contrast to carbon small. However, erosion by fast particles from heating measures and impurity ions, accelerated in the sheath potential, play an important role in the case of tungsten. Radiation by carbon in the plasma boundary reduces the load to the target plates. Neon or Argon as substitutes will increase the erosion of tungsten. So far experiments have demonstrated that in most scenarios the tungsten content in the central plasma can be kept sufficiently small. The material development is directed to the specific needs of existing or future devices. In ASDEX Upgrade, which will soon be a divertor experiment with a complete tungsten first-wall, graphite tiles are coated with tungsten layers. In ITER, the solid tungsten armour of the target plates has to be castellated because of its difference in thermal expansion compared to the cooling structure. In a reactor the technical

  11. 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.

  12. Crack resistance of tungsten strengthened by dispersed refractory oxides

    International Nuclear Information System (INIS)

    Babak, A.V.; Uskov, E.I.

    1984-01-01

    Investigation results are presented for crack resistance of commercial tungsten, obtained during specimen testing at temperatures of 20 deg C to Tsub(cr) (upper boundary of temperature range of ductile-brittle transition). Comparison of s-n diagrams and temperature dependences of crack resistance are conducted for commercial tungsten and tungsten strengthened by refractory oxides. It is shown that dispersion hardening increases crack resistance in the temperature range of 20 to 2000 deg C but the upper boundary of ductile-brittle shifts to the side of higher temperatures

  13. An effective approach to synthesize monolayer tungsten disulphide crystals using tungsten halide precursor

    Energy Technology Data Exchange (ETDEWEB)

    Thangaraja, Amutha; Shinde, Sachin M.; Kalita, Golap, E-mail: kalita.golap@nitech.ac.jp; Tanemura, Masaki [Department of Frontier Materials, Nagoya Institute of Technology, Gokiso-cho, Showa-ku, Nagoya 466-8555 (Japan)

    2016-02-01

    The synthesis of large-area monolayer tungsten disulphide (WS{sub 2}) single crystal is critical for realistic application in electronic and optical devices. Here, we demonstrate an effective approach to synthesize monolayer WS{sub 2} crystals using tungsten hexachloride (WCl{sub 6}) as a solid precursor in atmospheric chemical vapor deposition process. In this technique, 0.05M solution of WCl{sub 6} in ethanol was drop-casted on SiO{sub 2}/Si substrate to create an even distribution of the precursor, which was reduced and sulfurized at 750 °C in Ar atmosphere. We observed growth of triangular, star-shaped, as well as dendritic WS{sub 2} crystals on the substrate. The crystal geometry evolves with the shape and size of the nuclei as observed from the dendritic structures. These results show that controlling the initial nucleation and growth process, large WS{sub 2} single crystalline monolayer can be grown using the WCl{sub 6} precursor. Our finding shows an easier and effective approach to grow WS{sub 2} monolayer using tungsten halide solution-casting, rather than evaporating the precursor for gas phase reaction.

  14. An effective approach to synthesize monolayer tungsten disulphide crystals using tungsten halide precursor

    International Nuclear Information System (INIS)

    Thangaraja, Amutha; Shinde, Sachin M.; Kalita, Golap; Tanemura, Masaki

    2016-01-01

    The synthesis of large-area monolayer tungsten disulphide (WS 2 ) single crystal is critical for realistic application in electronic and optical devices. Here, we demonstrate an effective approach to synthesize monolayer WS 2 crystals using tungsten hexachloride (WCl 6 ) as a solid precursor in atmospheric chemical vapor deposition process. In this technique, 0.05M solution of WCl 6 in ethanol was drop-casted on SiO 2 /Si substrate to create an even distribution of the precursor, which was reduced and sulfurized at 750 °C in Ar atmosphere. We observed growth of triangular, star-shaped, as well as dendritic WS 2 crystals on the substrate. The crystal geometry evolves with the shape and size of the nuclei as observed from the dendritic structures. These results show that controlling the initial nucleation and growth process, large WS 2 single crystalline monolayer can be grown using the WCl 6 precursor. Our finding shows an easier and effective approach to grow WS 2 monolayer using tungsten halide solution-casting, rather than evaporating the precursor for gas phase reaction

  15. Laser irradiation of carbon–tungsten materials

    International Nuclear Information System (INIS)

    Marcu, A; Lungu, C P; Ursescu, D; Porosnicu, C; Grigoriu, C; Avotina, L; Kizane, G; Marin, A; Osiceanu, P; Grigorescu, C E A; Demitri, N

    2014-01-01

    Carbon–tungsten layers deposited on graphite by thermionic vacuum arc (TVA) were directly irradiated with a femtosecond terawatt laser. The morphological and structural changes produced in the irradiated area by different numbers of pulses were systematically explored, both along the spots and in their depths. Although micro-Raman and Synchrotron-x-ray diffraction investigations have shown no carbide formation, they have shown the unexpected presence of embedded nano-diamonds in the areas irradiated with high fluencies. Scanning electron microscopy images show a cumulative effect of the laser pulses on the morphology through the ablation process. The micro-Raman spatial mapping signalled an increased percentage of sp 3 carbon bonding in the areas irradiated with laser fluencies around the ablation threshold. In-depth x-ray photoelectron spectroscopy investigations suggested a weak cumulative effect on the percentage increase of the sp 2 -sp 3 transitions with the number of laser pulses just for nanometric layer thicknesses. (paper)

  16. High precision tungsten cutting for optics

    International Nuclear Information System (INIS)

    Reglero, V.; Velasco, T.; Rodrigo, J.; Gasent, L.J.; Alamo, J.; Chato, R.; Ruiz Urien, I.; Santos, I.; Zarauz, J.; Clemente, G.; Sanz-Tudanca, C.; Lopez, J.L.

    2001-01-01

    The results obtained during the INTEGRAL masks development program an implementing the HURA and MURA codes on tungsten plates of different thickness are presented. Hard scientific requirements on pixels size and location tolerances (tenths of microns over large areas -1 m 2 - and thickness from 0.5 mm to 60 mm) required the set up of a dedicated program for testing cutting technologies: laser, photochemical milling, spark machining and electro discharge wire cutting. After a very intensive test campaign the wire cutting process was selected as the optimum technology for code manufacturing . Accuracies achieved an the code cutting fulfill scientific requirements. In fact, they are 5 times better than required. Pixel size and centroids location accuracies of 0.01 mm over a 1 m 2 area have been obtained for the 10,000 pixels on IBIS, 100 pixels on SPI and 24000 pixels on JEM-X masks. Comparative results among different cutting technologies are also discussed. (author)

  17. The movement of screw dislocations in tungsten

    International Nuclear Information System (INIS)

    Tian Xiaogeng; Woo Chungho

    2004-01-01

    Using Acland potential for tungsten, the movement of 1/2a screw dislocation under shear stress was investigated by molecular dynamics simulation. Equilibrated core structure was obtained by relaxation of screw dislocation with proper boundary conditions. We found that the equilibrium dislocation core has three-fold symmetry and spread out in three direction on {1 1 0} planes. The screw dislocation core could not keep the original shape when the shear stress applied. The dislocation could not move until the shear stress became large enough. The dislocation moved in zigzag when the shear stress neared the Peierls stress. When the shear stress became larger, the dislocation moved in zigzag at the beginning and than moved almost in straight line in [2-bar11] direction. The large shear stress applied, the long distance moved before the dislocation stilled in z-direction and the large velocity in y-direction

  18. Dithiolato complexes of molybdenum and tungsten

    International Nuclear Information System (INIS)

    Nieuwpoort, A.

    1975-01-01

    The synthesis of eight-coordinated and six-coordinated tungsten and molybdenum complexes with dithioligands is described. Molecular and crystal structures are determined and bond angles, bond lengths and structural parameters tabulated. Infrared spectra of dithiocarbamato complexes are discussed more extensively. Redox reactions are studied by voltammetry and electron transfer properties derived. Properties of the d electrons of the metal ion are interpreted in the ligand field model with data from electronic and e.s.r. spectra and magnetic susceptibilities. The result of molecular orbital calculations with the extended Hueckel-LCAO method are presented for eight-coordinated d 1 and d 2 systems, the six-coordinated complexes, and the free ligands

  19. Thermal stability of warm-rolled tungsten

    DEFF Research Database (Denmark)

    Alfonso Lopez, Angel

    to assess the effect of the processing parameters. Characterization of theannealed state reveals the effect of the degree of deformation on the recovery and recrystallizationannealing phenomena. This allowed comparing recrystallization kinetics (in terms of nucleation andgrowth) in dependence on initial......Pure tungsten is considered as armor material for the most critical parts of fusion reactors (thedivertor and the blanket first wall), mainly due to its high melting point (3422 °C). This is becauseboth the divertor and the first wall have to withstand high temperatures during service which...... mayalter the microstructure of the material by recovery, recrystallization and grain growth, and maycause degradation in material properties as a loss in mechanical strength and embrittlement.For this reason, this project aims towards establishing the temperature and time regime under whichrecovery...

  20. Tungsten thick coatings for plasma facing components

    International Nuclear Information System (INIS)

    Riccardi, B.; Pizzuto, A.; Orsini, A.; Libera, S.; Visca, E.; Bertamini, L.; Casadei, F.; Severini, E.; Montanari, R.; Litunovsky, N.

    1998-01-01

    The aim of the R and D activity was to realize thick W coatings on CuCrZr hollow bars and to test the mock ups with respect to thermal fatigue. Eight mock ups provided of 4 mm thick W coating were finally manufactured. The bonding integrity between coating and substrate was checked by means of an Ultrasonic apparatus. Characterisation of coatings was performed in order to assess microstructure, impurity content, density, tensile strength, adhesion strength, thermal conductivity and thermal expansion coefficient. Macroscopic residual strain measurements were performed by means of 'hole drilling' technique. The activities performed demonstrated the feasibility of thick Tungsten coatings on geometries with more complex residual strain distribution. These coatings are reliable armour of medium heat flux plasma facing component. (author)

  1. Preparation and Photoluminescence of Tungsten Disulfide Monolayer

    Directory of Open Access Journals (Sweden)

    Yanfei Lv

    2018-05-01

    Full Text Available Tungsten disulfide (WS2 monolayer is a direct band gap semiconductor. The growth of WS2 monolayer hinders the progress of its investigation. In this paper, we prepared the WS2 monolayer through chemical vapor transport deposition. This method makes it easier for the growth of WS2 monolayer through the heterogeneous nucleation-and-growth process. The crystal defects introduced by the heterogeneous nucleation could promote the photoluminescence (PL emission. We observed the strong photoluminescence emission in the WS2 monolayer, as well as thermal quenching, and the PL energy redshift as the temperature increases. We attribute the thermal quenching to the energy or charge transfer of the excitons. The redshift is related to the dipole moment of WS2.

  2. Electrical properties of tungsten trioxide films

    International Nuclear Information System (INIS)

    Xu, Z.; Vetelino, J.F.; Lec, R.; Parker, D.C.

    1990-01-01

    Selectively doped semiconducting metal oxide (SMO) films have been shown to have applications as the sensing element in gas microsensors. Critical to the design and operation of these sensors is the SMO film. In the present work, the electrical properties of both intrinsic and extrinsic (doped with gold) tungsten trioxide (WO 3 ) films, which selectively sorb hydrogen sulfide (H 2 S), are investigated. Hall effect measurements are performed as a function of film thickness, temperature, gold-doping concentration, and H 2 S gas concentration. The conductivity was found to be n type and strongly dependent on temperature, gold doping concentration, and H 2 S gas concentration and less dependent on film thickness. The mobility was relatively high while the intrinsic carrier concentration was low when compared to typical semiconductor materials. The conductivity was shown to exhibit anomalous behavior at certain temperatures and H 2 S gas concentrations

  3. 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.

  4. Tungsten atomic layer deposition on polymers

    Energy Technology Data Exchange (ETDEWEB)

    Wilson, C.A. [Department of Chemistry and Biochemistry, University of Colorado, Boulder, Colorado 80309-0215 (United States); McCormick, J.A. [Department of Chemical and Biological Engineering, University of Colorado, Boulder, Colorado 80309-0424 (United States); Cavanagh, A.S. [Department of Physics, University of Colorado, Boulder, Colorado 80309-0390 (United States); Goldstein, D.N. [Department of Chemistry and Biochemistry, University of Colorado, Boulder, Colorado 80309-0215 (United States); Weimer, A.W. [Department of Chemical and Biological Engineering, University of Colorado, Boulder, Colorado 80309-0424 (United States); George, S.M. [Department of Chemistry and Biochemistry, University of Colorado, Boulder, Colorado 80309-0215 (United States); Department of Chemical and Biological Engineering, University of Colorado, Boulder, Colorado 80309-0424 (United States)], E-mail: Steven.George@Colorado.Edu

    2008-07-31

    Tungsten (W) atomic layer deposition (ALD) was investigated on a variety of polymer films and polymer particles. These polymers included polyethylene, polyvinyl chloride, polystyrene, polycarbonate, polypropylene and polymethylmethacrylate. The W ALD was performed at 80 {sup o}C using WF{sub 6} and Si{sub 2}H{sub 6} as the gas phase reactants. W ALD on flat polymer films can eventually nucleate and grow after more than 60 AB cycles. X-ray photoelectron spectroscopy studies of W ALD on polystyrene after 50 AB cycles suggested that tungsten nanoclusters are present in the W ALD nucleation regime. The W ALD nucleation is greatly facilitated by a few cycles of Al{sub 2}O{sub 3} ALD. W ALD films were grown at 80 {sup o}C on spin-coated polymers on silicon wafers after 10 AB cycles of Al{sub 2}O{sub 3} ALD. The W ALD film was observed to grow linearly with a growth rate of 3.9 A per AB cycle on the polymer films treated with the Al{sub 2}O{sub 3} ALD seed layer. The W ALD films displayed an excellent, mirror-like optical reflectivity. The resistivity was 100-400 {mu}{omega} cm for W ALD films with thicknesses from 95-845 A. W ALD was also observed on polymer particles after W ALD in a rotary reactor. Without the Al{sub 2}O{sub 3} ALD seed layer, the nucleation of W ALD directly on the polymer particles at 80 {sup o}C required > 50 AB cycles. In contrast, the polymer particles treated with only 5 AB cycles of Al{sub 2}O{sub 3} ALD were observed to blacken after 25 AB cycles of W ALD. W ALD on polymers may have applications for flexible optical mirrors, electromagnetic interference shielding and gas diffusion barriers.

  5. Fuzzy tungsten in a magnetron sputtering device

    International Nuclear Information System (INIS)

    Petty, T.J.; Khan, A.; Heil, T.; Bradley, J.W.

    2016-01-01

    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 23 –3.0 × 10 24  m −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 24  m −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 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.

  6. Chemical processes induced radiolytically in well defined aqueous systems

    International Nuclear Information System (INIS)

    Thomas, J.K.

    1979-01-01

    The radiation chemistry of dilute aqueous systems is discussed in terms of the simple primary radicals and ions produced, and also in terms of reactions of secondary radicals produced via attack of the primary species on organic solutes. These simple systems are extended to 3 more complex systems: (a) solutions of polymers, (b) micelles and vesicles, and (c) inverted micelles containing water bubbles. These latter systems all contain new and interesting features not exhibited by dilute solutions of simple molecules, and are of particular importance with respect to bio-systems

  7. 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.

  8. 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...... in the stratum corneum and stratum granulosum. Diagnosing this syndrome is important to reassure parents, obstetricians, and pediatricians about its benign course after complications in the perinatal period....

  9. Sorption behaviour of well-defined oxidation states

    International Nuclear Information System (INIS)

    Allard, B.; Olofsson, U.; Torstenfelt, B.; Kipatsi, H.

    1983-05-01

    The sorption of the actinides Am(III), Th(IV), Np(V), Pa(V), U(VI) and Pu has been studied as a function of pH (2-12) for two nuclide concentrations (10 -7 -10 -9 M) (only one for Pa and U) in the systems Al 2 0 3 - 0.01 M NaCl0 4 and Si0 2 - 0.01 M NaCl0 4 . Distribution coefficients have been determined by a batch technique after various contact times (6h - 6w) at constant temperature (25degreeC) in systems equilibrated with air. The observed sorption behaviour indicates a predominantly physical adsorption mechanism, where pH of the aqueous phase is the principal chemical parameter of influence. The sorption is highly related to the degree of hydrolysis, with a maximum in the pH-region where neutral species dominate and with a reduction of the sorption under conditions when anionic species (hydroxides or carbonates) would exist in solution. This is particularly the case for U(VI) at pH above 7-8 when anionic carbonate complexes would be formed. Plutonium is predominantly tetravalent under the present conditions, as indicated by the sorption behaviour. (authors)

  10. Well-defined power policy needed to augment power capacity

    International Nuclear Information System (INIS)

    Gupta, K.

    1997-01-01

    This paper outlines the importance of energy policy and energy development in both energy production and energy needs. A summary of key points related to energy accounting, energy consumption, energy resources, public utilities and government plans are elaborated

  11. 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

  12. Method of preparing well-defined polypeptides via rop

    KAUST Repository

    Hadjichristidis, Nikolaos; Zhao, Wei; Gnanou, Yves

    2015-01-01

    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

  13. Physical metallurgy of tungsten. Metallovedenie vol'frama

    Energy Technology Data Exchange (ETDEWEB)

    Savitskii, E M; Povarova, K B; Makarov, P V

    1978-01-01

    The physico-chemical principles of the interaction between tungsten and the elements of the periodic chart are systematized and summarized, and a description is given of the physical and mechanical properties of tungsten and its alloys. An examination is made of the nature of cold brittleness and methods of increasing the plasticity of alloys, means of producing tungsten, methods of purification, alloying, thermal and mechanical processing, and a survey is made of the contemporary use of tungsten and its alloys in advanced sectors of modern technology. The book is designed for personnel at scientific-research institutes, design bureaus and plants, engaged in the development, technology, and use of alloys of refractory metals as well as for instructors, graduate students and senior students taking metal studies and machine building courses, and aeronautical institutions of higher learning. 431 references, 11 tables.

  14. TIG (Tungsten Inert Gas) welding; Le soudage TIG

    Energy Technology Data Exchange (ETDEWEB)

    Anon.

    2010-09-15

    After having recalled the Tungsten Inert Gas process principle and the different alternative TIG processes, the author explains the advantages and limits of this process. The applications and recent developments are given. (O.M.)

  15. Corrosion of high-density sintered tungsten alloys

    International Nuclear Information System (INIS)

    Batten, J.J.; Moore, B.T.

    1989-01-01

    In comparative corrosion tests, the corrosion resistance of an Australian tungsten alloy (95% W, 3.5% Ni, 1.5% Fe) was found to be superior to three other tungsten alloys and, under certain conditions, even more corrosion-resistant than pure tungsten. Corrosion resistance was evaluated after immersion in both distilled water and 5% sodium chloride solutions, and in cyclic humidity and salt mist environments. For all but the Australian alloy, the rate of corrosion in sodium chloride solution was markedly less than that in distilated water. In all cases, alloys containing copper had the greatest corrosion rates. Corrosion mechanisms were investigated using a scanning electron microscope, analysis of corrosion products and galvanic corrosion studies. For the alloys, corrosion was attributed primarily to a galvanic reaction. Whether the tungsten or binder phase of the alloy became anodic, and thus was attacked preferentially, depended upon alloy composition and corrosion environment. 16 refs., 4 tabs., 4 figs

  16. Tungsten alloy research at the US Army Materials Technology Laboratory

    International Nuclear Information System (INIS)

    Dowding, R.J.

    1991-01-01

    This paper reports that recent research into tungsten heavy alloys at the U. S. Army Materials Technology Laboratory (MTL) has explored many areas of processing and process development. The recrystallization and respheroidization of tungsten grains in a heavily cold worked heavy alloy has been examined and resulted in the identification of a method of grain refinement. Another area of investigation has been lightly cold worked. It was determined that it was possible to increase the strength and hardness of the tungsten grains by proper hat treatment. MTL has been involved in the Army's small business innovative research (SBIR) program and several programs have been funded. Included among these are a method of coating the tungsten powders with the alloying elements and the development of techniques of powder injection molding of heavy alloys

  17. Liquid-solid surface phase transformation of fluorinated fullerene on monolayer tungsten diselenide

    KAUST Repository

    Song, Zhibo

    2018-04-04

    Hybrid van der Waals heterostructures constructed by the integration of organic molecules and two-dimensional (2D) transition metal dichalcogenide (TMD) materials have useful tunable properties for flexible electronic devices. Due to the chemically inert and atomically smooth nature of the TMD surface, well-defined crystalline organic films form atomically sharp interfaces facilitating optimal device performance. Here, the surface phase transformation of the supramolecular packing structure of fluorinated fullerene (C60F48) on single-layer tungsten diselenide (WSe2) is revealed by low-temperature scanning tunneling microscopy, from thermally stable liquid to solid phases as the coverage increases. Statistical analysis of the intermolecular interaction potential reveals that the repulsive dipole-dipole interaction induced by interfacial charge transfer and substrate-mediated interactions play important roles in stabilizing the liquid C60F48 phases. Theoretical calculations further suggest that the dipole moment per C60F48 molecule varies with the surface molecule density, and the liquid-solid transformation could be understood from the perspective of the thermodynamic free energy for open systems. This study offers insights into the growth behavior at 2D organic/TMD hybrid heterointerfaces.

  18. Liquid-solid surface phase transformation of fluorinated fullerene on monolayer tungsten diselenide

    Science.gov (United States)

    Song, Zhibo; Wang, Qixing; Li, Ming-Yang; Li, Lain-Jong; Zheng, Yu Jie; Wang, Zhuo; Lin, Tingting; Chi, Dongzhi; Ding, Zijing; Huang, Yu Li; Thye Shen Wee, Andrew

    2018-04-01

    Hybrid van der Waals heterostructures constructed by the integration of organic molecules and two-dimensional (2D) transition metal dichalcogenide (TMD) materials have useful tunable properties for flexible electronic devices. Due to the chemically inert and atomically smooth nature of the TMD surface, well-defined crystalline organic films form atomically sharp interfaces facilitating optimal device performance. Here, the surface phase transformation of the supramolecular packing structure of fluorinated fullerene (C60F48 ) on single-layer tungsten diselenide (WSe2) is revealed by low-temperature scanning tunneling microscopy, from thermally stable liquid to solid phases as the coverage increases. Statistical analysis of the intermolecular interaction potential reveals that the repulsive dipole-dipole interaction induced by interfacial charge transfer and substrate-mediated interactions play important roles in stabilizing the liquid C60F48 phases. Theoretical calculations further suggest that the dipole moment per C60F48 molecule varies with the surface molecule density, and the liquid-solid transformation could be understood from the perspective of the thermodynamic free energy for open systems. This study offers insights into the growth behavior at 2D organic/TMD hybrid heterointerfaces.

  19. Microstructure and tensile properties of tungsten at elevated temperatures

    Energy Technology Data Exchange (ETDEWEB)

    Shen, Tielong [Laboratory for Nuclear Materials, Paul Scherrer Institut, 5232 Villigen PSI (Switzerland); Institute of Modern Physics, Chinese Academy of Sciences, Lanzhou 730000 (China); Dai, Yong, E-mail: yong.dai@psi.ch [Laboratory for Nuclear Materials, Paul Scherrer Institut, 5232 Villigen PSI (Switzerland); Lee, Yongjoong [European Spallation Source, Tunavägen 24, 223 63 Lund (Sweden)

    2016-01-15

    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. - Highlights: • This work was conducted 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 and tensile behaviour was studied with hot-rolled and hot-forged tungsten. • The tungsten materials were characterized with metallography analysis, hardness measurement and tensile test in a temperature range of 25–500 °C. • The results indicate that the HR tungsten has better mechanical properties in terms of greater ductility and lower ductile-to-brittle transition temperature.

  20. Factors affecting the deformation of tungsten (a literature survey)

    International Nuclear Information System (INIS)

    Ludwig, R.L.

    1978-01-01

    Background information relative to wrought tungsten forming was required in support of development studies. Seven principal areas of tungsten metallurgy were of interest: fabrication methods, delamination, recrystallization, heat treatment, fracture characteristics, impurity effects, and surface treatments. Pertinent information in Metal Abstracts from 1967 to mid 1977 was summarized for each area. Only a few papers were reviewed in their entirety; the great majority of information was derived from abstracts of the papers. 61 references

  1. Ductile tungsten-nickel-alloy and method for manufacturing same

    Science.gov (United States)

    Ludwig, Robert L.

    1978-01-01

    The tensile elongation of a tungsten-nickel-iron alloy containing essentially 95 weight percent reprocessed tungsten, 3.5 weight percent nickel, and 1.5 weight percent iron is increased from a value of less than about 1 percent up to about 23 percent by the addition of less than 0.5 weight percent of a reactive metal consisting of niobium and zirconium.

  2. Phase equilibrium study on system uranium-plutonium-tungsten-carbon

    International Nuclear Information System (INIS)

    Ugajin, Mitsuhiro

    1976-11-01

    Metallurgical properties of the U-Pu-W-C system have been studied with emphasis on phases and reactions. Free energy of compound formation, carbon activity and U/Pu segregation in the W-doped carbide fuel are estimated using phase diagram data. The results indicate that tungsten metal is useful as a thermochemical stabilizer of the carbide fuel. Tungsten has high temperature stability in contact with uranium carbide and mixed uranium-plutonium carbide. (auth.)

  3. Hydrothermal synthesis of electrode materials pyrochlore tungsten trioxide film

    Science.gov (United States)

    Guo, Jingdong; Li, Yingjeng James; Stanley Whittingham, M.

    Hydrothermal synthesis methods have been successfully used to prepare new transition-metal oxides for cathodes in electrochemical devices such as lithium batteries and electrochromic windows. The tungsten oxides were the first studied, but the method has been extended to the oxides of molybdenum, vanadium and manganese. Sodium tungsten oxide films with the pyrochlore structure have been prepared on gold/alumina and indium-doped tin oxide substrates. These films reversibly and rapidly intercalate lithium and hydrogen ions.

  4. On the problem of high temperature embrittlement of tungsten

    International Nuclear Information System (INIS)

    Babak, A.V.; Uskov, E.I.

    1983-01-01

    The paper presents results of a complex physicomechanical study of tungsten crack resistance. The presence of a descending portion of curve in a temperature range from Tsub(x)sup(b) to 2 000 deg C is a characteristic feature of Ksub(Ic) temperature dependence. Changes in the tungsten physical state under isotherma heating were analysed on the basis of the results of metallographic, X-ray and electron fractographic studies. Certain results obtained are shown to be contradicting

  5. Study on the high temperature crack resistance of tungsten

    International Nuclear Information System (INIS)

    Uskov, E.I.; Babak, A.V.

    1983-01-01

    The possibility of a multiple use of tungsten specimens in crack resistance tests in the temperature range of 600-2000 deg C is studied. It is established experimentally that the minimum length of growth of a main crack is 1x10 -4 m for the most effective repeated use of specimens. A flow diagram of mechanical tests is suggested for investigating high temperature tungsten crack resistance and estimating the degree of weakening the grain-boundary bond

  6. Effect of neutron irradiation on the microstructure of tungsten

    Directory of Open Access Journals (Sweden)

    M. Klimenkov

    2016-12-01

    Full Text Available Two grades of pure tungsten, single and polycrystalline, were irradiated for 282 days in the HFR reactor, Petten, at 900 °C to an average damage level of 1.6dpa. Each grade of tungsten was investigated using the transmission electron microscope (TEM to assess the effect of neutron irradiation on tungsten microstructure. Investigations revealed the formation of faceted cavities, whose diameter varies from 4 to 14nm in both materials. The cavities are homogeneously distributed only inside single crystalline tungsten. The local distribution of cavities in polycrystalline tungsten is strongly influenced by grain boundaries. The number densities of cavities were measured to be 4×1021 m−3 for polycrystalline and 2.5×1021 m−3 for single crystalline tungsten. This corresponds to volumetric densities of 0.45% and 0.33% respectively. High-resolution transmission electron microscopy (HRTEM revealed that faces of cavities are oriented in (110 plane. Analytical investigations showed precipitation of rhenium and osmium produced by a transmutation reaction around cavities and at grain boundaries.

  7. Behavior of porous tungsten under shock compression at room temperature

    International Nuclear Information System (INIS)

    Dandekar, D.P.; Lamothe, R.M.

    1977-01-01

    This work reports the results of room-temperature shock-compression experiments on porous tungsten. The porous tungsten was fabricated by sintering 1-μm tungsten particles. The initial density of the material was 15290 kg/m 3 . Around 97% of the pores in the material were interconnected. The main features of the results are as follows: (1) porous tungsten behaves as a linear elastic material to 1.43 GPa; (2) the shock wave following the elastic precursor is unstable in the material in the stress range 1.43--2.7 GPa; (3) a stable two-wave structure is established at and above 6.4 GPa; (4) the response of porous tungsten is accurately described by the Mie-Grueneisen equation of state at stresses above 4.9 GPa, the stress at which the voids suffer a complete extinction in the material; (5) the deformations induced in the material due to shock compression are irreversible; (6) the recentered Hugoniot of porous tungsten becomes stiffer with the increasing magnitude of initial compressive stress

  8. Simulations of tungsten, tungsten-coated and tungsten-doped targets at low KrF laser intensities

    Science.gov (United States)

    Colombant, D.; Klapisch, M.; Lehecka, T.; Seely, J.; Schmitt, A.; Obenschain, S.

    1998-11-01

    High-Z coatings can be used to create X-rays to preheat the ablator, thus reducing the laser imprint and the R-T instability. Targets with tungsten coated on the surface or mixed with CH have recently been irradiated using Nike at intensities of a few 10^12W/cm^2, typical of the foot of a laser fusion pulse. The present simulations in 1D have been carried out to provide an interpretation of these experiments and to validate the code for radiation-preheated target designs(S. E. Bodner et al., Phys. Plasmas, 5, 1901 (1998).). All computations were performed in non-LTE(M. Busquet, Phys. Fluids B, 5, 4191 (1993); M. Klapisch, A. Bar-Shalom, J. Oreg and D. Colombant, Phys. Plasmas, 5, 1919 (1998).). Low resolution X-ray spectra obtained from on-line computations are compared to time-integrated experimental spectra between 100 eV and 500 eV. Agreements and differences between computations and experiments will be discussed.

  9. Characterization and performances of cobalt-tungsten and molybdenum-tungsten carbides as anode catalyst for PEFC

    International Nuclear Information System (INIS)

    Izhar, Shamsul; Yoshida, Michiko; Nagai, Masatoshi

    2009-01-01

    The preparation of carbon-supported cobalt-tungsten and molybdenum-tungsten carbides and their activity as an anode catalyst for a polymer electrolyte fuel cell were investigated. The electrocatalytic activity for the hydrogen oxidation reaction over the catalysts was evaluated using a single-stack fuel cell and a rotating disk electrode. The characterization of the catalysts was performed by XRD, temperature-programmed carburization, temperature-programmed reduction and X-ray photoelectron spectroscopy. The maximum power densities of the 30 wt% 873 K-carburized cobalt-tungsten and molybdenum-tungsten mixed with Ketjen carbon (cobalt-tungsten carbide (CoWC)/Ketjen black (KB) and molybdenum-tungsten carbide (MoWC)/KB) were 15.7 and 12.0 mW cm -2 , respectively, which were 14 and 11%, compared to the in-house membrane electrode assembly (MEA) prepared from a 20 wt% Pt/C catalyst. The CoWC/KB catalyst exhibited the highest maximum power density compared to the MoWC/KB and WC/KB catalysts. The 873 K-carburized CoW/KB catalyst formed the oxycarbided and/or carbided CoW that are responsible for the excellent hydrogen oxygen reaction

  10. Mechanistic, kinetic, and processing aspects of tungsten chemical mechanical polishing

    Science.gov (United States)

    Stein, David

    This dissertation presents an investigation into tungsten chemical mechanical polishing (CMP). CMP is the industrially predominant unit operation that removes excess tungsten after non-selective chemical vapor deposition (CVD) during sub-micron integrated circuit (IC) manufacture. This work explores the CMP process from process engineering and fundamental mechanistic perspectives. The process engineering study optimized an existing CMP process to address issues of polish pad and wafer carrier life. Polish rates, post-CMP metrology of patterned wafers, electrical test data, and synergy with a thermal endpoint technique were used to determine the optimal process. The oxidation rate of tungsten during CMP is significantly lower than the removal rate under identical conditions. Tungsten polished without inhibition during cathodic potentiostatic control. Hertzian indenter model calculations preclude colloids of the size used in tungsten CMP slurries from indenting the tungsten surface. AFM surface topography maps and TEM images of post-CMP tungsten do not show evidence of plow marks or intergranular fracture. Polish rate is dependent on potassium iodate concentration; process temperature is not. The colloid species significantly affects the polish rate and process temperature. Process temperature is not a predictor of polish rate. A process energy balance indicates that the process temperature is predominantly due to shaft work, and that any heat of reaction evolved during the CMP process is negligible. Friction and adhesion between alumina and tungsten were studied using modified AFM techniques. Friction was constant with potassium iodate concentration, but varied with applied pressure. This corroborates the results from the energy balance. Adhesion between the alumina and the tungsten was proportional to the potassium iodate concentration. A heuristic mechanism, which captures the relationship between polish rate, pressure, velocity, and slurry chemistry, is presented

  11. Morphology of Si/tungsten-silicides/Si interlayers

    International Nuclear Information System (INIS)

    Theodore, N.; Secco d'Aragona, F.; Blackstone, S.

    1992-01-01

    Tungsten and tungsten-silicides are of interest for semiconductor technology because of their refractory nature, low electrical-resistivity and high electromigration-resistance. This paper presents the first formation of buried tungsten-silicide layers in silicon, by proximity adhesion. The interlayers, created by a combination of chemical vapor-deposition (CVD) and proximity-adhesion were studied using transmission electron-microscopy (TEM). The behavior of the layers in the presence and absence of an adjacent silicon-dioxide interlayer was also investigated. Buried silicide layers were successfully formed with or without the adjacent silicon-dioxide. The silicide formed continuous layers with single grains encompassing the width of the interlayer. Individual grains were globular, with cusps at grain boundaries. This caused interlayer-thicknesses to be non-uniform, with lower thickness values being present at the cusps. Occasional voids were observed at grain-boundary cusps. The voids were smaller and less frequent in the presence of an adjacent oxide-layer, due to flow of the oxide during proximity adhesion. Electron-diffraction revealed a predominance of tungsten-disilicide in the interlayers, with some free tungsten being present. Stresses in the silicide layers caused occasional glide dislocations to propagate into the silicon substrate beneath the interlayers. The dislocations propagate only ∼100 nm into the substrate and therefore should not be detrimental to use of the buried layers. Occasional precipitates were observed at the end of glide-loops. These possibly arise due to excess tungsten from the interlayer diffusion down the glide dislocation to finally precipitate out as tungsten-silicide

  12. Discontinuous precipitation in cobalt-tungsten alloys

    International Nuclear Information System (INIS)

    Zieba, P.; Cliff, G.; Lorimer, G.W.

    1997-01-01

    Discontinuous precipitation in a Co32 wt% W alloy aged in the temperature range from 875 K to 1025 K has been investigated. Philips EM 430 STEM has been used to characterize the microstructure and to measure the composition profiles across individual lamellae of ε Co and Co 3 W phases in partially transformed specimens. Two kinds of cellular precipitates have been found in the alloy. The initial transformation product, identified as primary lamellae with spacing of a few nanometers is replaced during prolonged ageing by secondary lamellae with a much larger interlamellar spacing, typically a few tens of nm. Line scans across cell boundaries of the primary lamellae revealed that, just behind the advancing cell boundary, the solute content is far from the equilibrium state. This solute excess within the cells is quickly removed at the ageing temperature. Calculations show that the diffusion process was too rapid to be identified as ordinary volume diffusion. Investigation of the kinetics showed that discontinuous precipitation is controlled by diffusion processes at the advancing cell boundary. This proposal has been confirmed by STEM analysis of tungsten profiles in the depleted ε Co lamellae

  13. Deuterium accumulation in tungsten at high fluences

    Energy Technology Data Exchange (ETDEWEB)

    Zibrov, Mikhail [Max-Planck-Institut fuer Plasmaphysik, Boltzmannstrasse 2, D-85748 Garching (Germany); FOM Institute DIFFER, De Zaale 20, 5612 AJ Eindhoven (Netherlands); Balden, Martin; Matej, Matej [Max-Planck-Institut fuer Plasmaphysik, Boltzmannstrasse 2, D-85748 Garching (Germany); Bystrov, Kirill; Morgan, Thomas [FOM Institute DIFFER, De Zaale 20, 5612 AJ Eindhoven (Netherlands)

    2016-07-01

    The data on the deuterium (D) retention in tungsten (W) at high fluences (≥ 10{sup 27} D/m{sup 2}) are scarce and the existing results are contradictory. Since retention in W is known to be flux-dependent, the laboratory experiments addressing this issue should be carried out in reactor-relevant conditions (high fluxes of low-energy ions). In this work the samples made of polycrystalline W were exposed to D plasmas in the linear plasma generator Pilot-PSI at temperatures ranging from 360 K to 1140 K to fluences in the range of 0.3-8.7 x 10{sup 27} D/m{sup 2}. It was observed that at exposure temperatures of 360 K and 580 K the D retention was only slightly dependent on the ion fluence. In addition, the presence of blister-like structures was found after the exposures, and their density and size distributions were also only weakly dependent on the fluence. In the case of exposure at 1140 K no surface modifications of the samples after plasma exposure were detected and the concentrations of retained D were very small. At all temperatures used the total amounts of retained D were smaller compared to those obtained by other researchers at lower ion flux densities, which indicates that the incident ion flux may play an important role in the total D retention in W.

  14. 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.

  15. Kinetics of the tungsten hexafluoride-silane reaction for the chemical vapor deposition of tungsten

    International Nuclear Information System (INIS)

    Gokce, Huseyin.

    1991-01-01

    In this study, the kinetics of the low-pressure chemical vapor deposition (LPCVD) of tungsten by silane reduction of tungsten hexafluoride on Si(100) surfaces was studied. A single-wafer, cold-wall reactor was sued for the experiments. The SiH 4 /WF 6 ratio was 1.0. The pressure and temperature range were 1-10 torr and 137-385 degree C, respectively. Kinetic data were obtained in the absence of mass-transfer effects. The film thicknesses were measured by gravimetry. Scanning electron microscopy (SEM), Auger electron spectroscopy (AES), x-ray diffraction (XRD), and resistivity measurements were used to analyze the W films. For the horizontal substrate position and 4-minute reaction times, the apparent activation energies were determined to be 0.35 eV/atom for 10 torr, 0.17 eV/atom for 3 torr, and 0.08 eV/atom for 1 torr. Lower temperatures and higher pressures produced porous films, while higher temperatures and lower pressures resulted in continuous films with smoother surfaces. As the Si-W interface, a W(110) preferential orientation was observed. As the W films grew thicker, W orientation switched from (110) to (100). Apparent activation energy seems to change with thickness

  16. Vaporization of tungsten-metal in steam at high temperatures

    International Nuclear Information System (INIS)

    Greene, G.A.; Finfrock, C.C.

    2000-01-01

    The vaporization of tungsten from the APT spallation target dominates the radiological source term for unmitigated target overheating accidents. Chemical reactions of tungsten with steam which persist to tungsten temperatures as low as 800 C result in the formation of a hydrated tungsten-oxide which has a high vapor pressure and is readily convected in a flowing atmosphere. This low-temperature vaporization reaction essentially removes the oxide film that forms on the tungsten-metal surface as soon as it forms, leaving behind a fresh metallic surface for continued oxidation and vaporization. Experiments were conducted to measure the oxidative vaporization rates of tungsten in steam as part of the effort to quantify the MT radiological source term for severe target accidents. Tests were conducted with tungsten rods (1/8 inch diameter, six inches long) heated to temperatures from approximately 700 C to 1350 C in flowing steam which was superheated to 140 C. A total of 19 experiments was conducted. Fifteen tests were conducted by RF induction heating of single tungsten rods held vertical in a quartz glass retort. Four tests were conducted in a vertically-mounted tube furnace for the low temperature range of the test series. The aerosol which was generated and transported downstream from the tungsten rods was collected by passing the discharged steam through a condenser. This procedure insured total collection of the steam along with the aerosol from the vaporization of the rods. The results of these experiments revealed a threshold temperature for tungsten vaporization in steam. For the two tests at the lowest temperatures which were tested, approximately 700 C, the tungsten rods were observed to oxidize without vaporization. The remainder of the tests was conducted over the temperature range of 800 C to 1350 C. In these tests, the rods were found to have lost weight due to vaporization of the tungsten and the missing weight was collected in the downstream condensate

  17. 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.

  18. Development and optimisation of tungsten armour geometry for ITER divertor

    International Nuclear Information System (INIS)

    Makhankov, A.; Mazul, I.; Safronov, V.; Yablokov, N.

    1998-01-01

    The plasma facing components (PFC) of the future thermonuclear reactor in great extend determine the time of non-stop operation of the reactor. In current ITER project the most of the divertor PFC surfaces are covered by tungsten armour. Therefore selection of tungsten grade and attachment scheme for joining the tungsten armour to heat sink is a matter of great importance. Two attachment schemes for highly loaded components (up to 20 MW/m 2 ) are described in this paper. The small size mock-ups were manufactured and successfully tested at heat fluxes up to 30 MW/m 2 in screening test and up to 20 MW/m 2 at thermal fatigue test. One mock-up with four different tungsten grades was tested by consequent thermal shock (15 MJ/m 2 at 50 μs) and thermal cycling loading (15 MW/m 2 ). The damages that could lead to mock-up failure were not found but the behaviour of tungsten grades was quite different. (author)

  19. Experimental study of tungsten transport properties in T-10 plasma

    Science.gov (United States)

    Krupin, V. A.; Nurgaliev, M. R.; Klyuchnikov, L. A.; Nemets, A. R.; Zemtsov, I. A.; Dnestrovskij, A. Yu.; Sarychev, D. V.; Lisitsa, V. S.; Shurygin, V. A.; Leontiev, D. S.; Borschegovskij, A. A.; Grashin, S. A.; Ryjakov, D. V.; Sergeev, D. S.; Mustafin, N. A.; Trukhin, V. M.; Solomatin, R. Yu.; Tugarinov, S. N.; Naumenko, N. N.

    2017-06-01

    First experimental results of tungsten transport investigation in OH and ECRH plasmas in the T-10 tokamak with W-limiter and movable Li-limiter are presented. It is shown that tungsten tends to accumulate (a joint process of cumulation and peaking) near the plasma axis in ohmic regimes. The cumulation of W is enhanced in discharges with high values of the parameter γ ={{\\bar{n}}\\text{e}}\\centerdot {{\\bar{Z}}\\text{eff}}\\centerdot I\\text{pl}-1.5 that coincides with accumulation conditions of light and medium impurities in T-10 plasmas. Experiments with Li-limiter show the immeasurable level of Li3+ (0.3-0.5% of n e) of T-10 CXRS diagnostics because of the low inflow of Li with respect to other light impurities. Nevertheless, the strong influence of lithium on inflow of light and tungsten impurities is observed. In discharges with lithized walls, vanishing of light impurities occurs and values of {{Z}\\text{eff}}≈ 1 are obtained. It is also shown that the tungsten density in the plasma center decreases by 15 to 20 times while the W inflow reduces only by 2 to 4 times. In lithized discharges with high γ, the flattening of the tungsten density profile occurs and its central concentration decreases up to 10 times during the on-axis ECRH. This effect is observed together with the increase of the W inflow by 3 to 4 times at the ECRH stage.

  20. 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.

  1. Tungsten-based composite materials for fusion reactor shields

    International Nuclear Information System (INIS)

    Greenspan, E.; Karni, Y.

    1985-01-01

    Composite tungsten-based materials were recently proposed for the heavy constituent of compact fusion reactor shields. These composite materials will enable the incorporation of tungsten - the most efficient nonfissionable inelastic scattering (as well as good neutron absorbing and very good photon attenuating) material - in the shield in a relatively cheap way and without introducing voids (so as to enable minimizing the shield thickness). It is proposed that these goals be achieved by bonding tungsten powder, which is significantly cheaper than high-density tungsten, with a material having the following properties: good shielding ability and relatively low cost and ease of fabrication. The purpose of this work is to study the effectiveness of the composite materials as a function of their composition, and to estimate the economic benefit that might be gained by the use of these materials. Two materials are being considered for the binder: copper, second to tungsten in its shielding ability, and iron (or stainless steel), the common fusion reactor shield heavy constituent

  2. Tungsten anode tubes with K-edge filters for mammography

    Energy Technology Data Exchange (ETDEWEB)

    Beaman, S.; Lillicrap, S.C. (Wessex Regional Medical Physics Service, Bath (UK)); Price, J.L. (Jarvis Screening Centre, Guildford (UK))

    1983-10-01

    Optimum X-ray energies for mammography have previously been calculated using the maximum signal to noise ratio (SNR) per unit dose to the breast, or the minimum exposure for constant SNR. Filters having absorption edges at appropriate energy positions have been used to modify the shape of tungsten anode spectra towards the calculated optimum. The suitability of such spectra for practical use has been assessed by comparing the film image quality and the incident breast dose obtained using a K-edge filtered tungsten anode tube with that obtained using a molybdenum anode. Image quality has been assessed by using a 'random' phantom and by comparing mammograms where one breast was radiographed using a filtered tungsten anode tube and the other using a standard molybdenum anode unit. Relative breast doses were estimated from both ionisation chamber measurements with a phantom and thermoluminescent dosimetry measurements on the breast. Film image quality assessment indicated that the filtered tungsten anode tube gave results not significantly different from those obtained with a molybdenum anode tube for a tissue thickness of about 4 cm and which were better for larger breast thicknesses. Doses could be reduced to between one-half and one-third with the filtered tungsten anode tube.

  3. Tungsten anode tubes with K-edge filters for mammography

    International Nuclear Information System (INIS)

    Beaman, S.; Lillicrap, S.C.; Price, J.L.

    1983-01-01

    Optimum X-ray energies for mammography have previously been calculated using the maximum signal to noise ratio (SNR) per unit dose to the breast, or the minimum exposure for constant SNR. Filters having absorption edges at appropriate energy positions have been used to modify the shape of tungsten anode spectra towards the calculated optimum. The suitability of such spectra for practical use has been assessed by comparing the film image quality and the incident breast dose obtained using a K-edge filtered tungsten anode tube with that obtained using a molybdenum anode. Image quality has been assessed by using a 'random' phantom and by comparing mammograms where one breast was radiographed using a filtered tungsten anode tube and the other using a standard molybdenum anode unit. Relative breast doses were estimated from both ionisation chamber measurements with a phantom and thermoluminescent dosimetry measurements on the breast. Film image quality assessment indicated that the filtered tungsten anode tube gave results not significantly different from those obtained with a molybdenum anode tube for a tissue thickness of abut 4 cm and which were better for larger breast thicknesses. Doses could be reduced to between one-half and one-third with the filtered tungsten anode tube. (U.K.)

  4. Surface studies of tungsten erosion and deposition in JT-60U

    International Nuclear Information System (INIS)

    Ueda, Y.; Fukumoto, M.; Nishikawa, M.; Tanabe, T.; Miya, N.; Arai, T.; Masaki, K.; Ishimoto, Y.; Tsuzuki, K.; Asakura, N.

    2007-01-01

    In order to study tungsten erosion and migration in JT-60U, 13 W tiles have been installed in the outer divertor region and tungsten deposition on graphite tiles was measured. Dense local tungsten deposition was observed on a CFC tile toroidally adjacent to the W tiles, which resulted from prompt ionization and short range migration of tungsten along field lines. Tungsten deposition with relatively high surface density was found on an inner divertor tile around standard inner strike positions and on an outer wing tile of a dome. On the outer wing tile, tungsten deposition was relatively high compared with carbon deposition. In addition, roughly uniform tungsten depth distribution near the upper edge of the inner divertor tile was observed. This could be due to lift-up of strike point positions in selected 25 shots and tungsten flow in the SOL plasma

  5. 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).

  6. Simulating evaporation of surface atoms of thorium-alloyed tungsten in strong electronic fields

    International Nuclear Information System (INIS)

    Bochkanov, P.V.; Mordyuk, V.S.; Ivanov, Yu.I.

    1984-01-01

    By the Monte Carlo method simulating evaporation of surface atoms of thorium - alloyed tungsten in strong electric fields is realized. The strongest evaporation of surface atoms of pure tungsten as compared with thorium-alloyed tungsten in the contentration range of thorium atoms in tungsten matrix (1.5-15%) is shown. The evaporation rate increases with thorium atoms concentration. Determined is in relative units the surface atoms evaporation rate depending on surface temperature and electric field stront

  7. Evaporation of tungsten in vacuum at low hydrogen and water vapor pressures

    International Nuclear Information System (INIS)

    Andrievskij, R.A.; Galkin, E.A.; Khromonozhkin, V.V.

    1981-01-01

    The results of experimental investigations of tungsten evaporation rates in the temperature range 1650-2500 K, partial hydrogen and water vapours pressures 1x10 -5 -10 Pa are presented. Experi-- mental plant, equipment employed and radiometric technique of tungsten evaporation study are described. The dependences of evaporation rate and probabilities of tungsten oxidation by residual vacuum water vapours and dependences of tungsten evaporation rate on partial hydrogen and water vapours pressures are determined [ru

  8. Volatility from copper and tungsten alloys for fusion reactor applications

    International Nuclear Information System (INIS)

    Smolik, G.R.; Neilson, R.M. Jr.; Piet, S.J.

    1989-01-01

    Accident scenarios for fusion power plants present the potential for release and transport of activated constituents volatilized from first wall and structural materials. The extent of possible mobilization and transport of these activated species, many of which are ''oxidation driven'', is being addressed by the Fusion Safety Program at the Idaho National Engineering Laboratory (INEL). This report presents experimental measurements of volatilization from a copper alloy in air and steam and from a tungsten alloy in air. The major elements released included zinc from the copper alloy and rhenium and tungsten from the tungsten alloy. Volatilization rates of several constituents of these alloys over temperatures ranging from 400 to 1200 degree C are presented. These values represent release rates recommended for use in accident assessment calculations. 8 refs., 3 figs., 5 tabs

  9. Sequential and simultaneous thermal and particle exposure of tungsten

    International Nuclear Information System (INIS)

    Steudel, I; Huber, A; Kreter, A; Linke, J; Sergienko, G; Unterberg, B; Wirtz, M

    2016-01-01

    The broad array of expected loading conditions in a fusion reactor such as ITER necessitates high requirements on the plasma facing materials (PFMs). Tungsten, the PFM for the divertor region, the most affected part of the in-vessel components, must thus sustain severe, distinct exposure conditions. Accordingly, comprehensive experiments investigating sequential and simultaneous thermal and particle loads were performed on double forged pure tungsten, not only to investigate whether the thermal and particle loads cause damage but also if the sequence of exposure maintains an influence. The exposed specimens showed various kinds of damage such as roughening, blistering, and cracking at a base temperature where tungsten could be ductile enough to compensate the induced stresses exclusively by plastic deformation (Pintsuk et al 2011 J. Nucl. Mater. 417 481–6). It was found out that hydrogen has an adverse effect on the material performance and the loading sequence on the surface modification. (paper)

  10. A molecular dynamics study of helium bombardments on tungsten nanoparticles

    Science.gov (United States)

    Li, Min; Hou, Qing; Cui, Jiechao; Wang, Jun

    2018-06-01

    Molecular dynamics simulations were conducted to study the bombardment process of a single helium atom on a tungsten nanoparticle. Helium atoms ranging from 50 eV to 50 keV were injected into tungsten nanoparticles with a diameter in the range of 2-12 nm. The retention and reflection of projectiles and sputtering of nanoparticles were calculated at various times. The results were found to be relative to the nanoparticle size and projectile energy. The projectile energy of 100 eV contributes to the largest retention of helium atoms in tungsten nanoparticles. The most obvious difference in reflection exists in the range of 3-10 keV. Around 66% of sputtering atoms is in forward direction for projectiles with incident energy higher than 10 keV. Moreover, the axial direction of the nanoparticles was demonstrated to influence the bombardment to some degree.

  11. Process for reclaiming tungsten from a hazardous waste

    International Nuclear Information System (INIS)

    Scheithauer, R.A.; MacInnis, M.B.; Miller, M.J.; Vanderpool, C.D.

    1984-01-01

    A process is disclosed wherein tungsten is recovered from hazardous waste material containing said tungsten, arsenic, and other impurities which can consist of magnesium, phosphorus, and silicon and the resulting waste is treated to render it nonhazardous according to EPA standards for arsenic. Said process involves digesting said hazardous waste material in an aqueous solution of an alkali metal hydroxide, adjusting the pH of the resulting solution to about 11.0 to about 13.0 with NaOH to precipitate essentially all of the magnesium and silicon species, filtering the digestion mix to remove the solids from said resulting solution which contains about 80 to about 100% of said tungsten and essentially none of said magnesium and said silicon, slurrying the hazardous solids in hot water, and adding to the slurry a ferric salt solution to precipitate ferric hydroxide, filtering this mixture to give a solid which passes the EPA standard test for solids with respect to arsenic

  12. Titrimetric determination of tungsten in its alloys with tantalum

    International Nuclear Information System (INIS)

    Elinson, S.V.; Nezhnova, T.I.

    1982-01-01

    Titrimetric method of tungsten determination in tantalum base alloys has been developed. The method permits to determine 5-10% tungsten in the alloys with relative standard deviation of 0.013. The conditions are created by application of precipitation from homogeieous solutions or by the method of appearing reagents at pH values, which condition gradual hydrolytic precipitation of tantalum, and sodium tungstate remains in the solution and is not sorbed on tantalum hydroxide. After separation of tantalum oxide tungsten is precipitated in the form of lead tungstate by the excess of ti trated solution of lead salt during boiling and then at the background of lead tungstate precipitate without its separation lead excess is titrated by EDTA in the presence of mixed indicator-4-(2-pyridylazo)resocinol and xylenole orange in acetate buffer solution

  13. Corrosion of high-density sintered tungsten alloys. Part 1

    International Nuclear Information System (INIS)

    Batten, J.J.; McDonald, I.G.; Moore, B.T.; Silva, V.M.

    1988-10-01

    The corrosion behaviour of four tungsten alloys has been evaluated through weight loss measurements after total immersion in both distilled water insight into the mechanism of corrosion was afforded by an examination of the and 5% sodium chloride solutions. Some insight the mechanism of corrosion was afforded by using the Scanning Electron Microscopy and through an analysis of the corrosion products. Pure tungsten and all the alloys studied underwent corrosion during the tests, and in each case the rare of corrosion in sodium chloride solution was markedly less than that in distilled water. A 95% W, 3.5% Ni, 1.5% Fe alloy was found to be the most corrosion resistant of the alloys under the experimental conditions. Examination of the data shows that for each of the tests, copper as an alloying element accelerates corrosion of tungsten alloys. 9 refs., 7 tabs., 12 figs

  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. Ductile tungsten-nickel alloy and method for making same

    Science.gov (United States)

    Snyder, Jr., William B.

    1976-01-01

    The present invention is directed to a ductile, high-density tungsten-nickel alloy which possesses a tensile strength in the range of 100,000 to 140,000 psi and a tensile elongation of 3.1 to 16.5 percent in 1 inch at 25.degree.C. This alloy is prepared by the steps of liquid phase sintering a mixture of tungsten-0.5 to 10.0 weight percent nickel, heat treating the alloy at a temperature above the ordering temperature of approximately 970.degree.C. to stabilize the matrix phase, and thereafter rapidly quenching the alloy in a suitable liquid to maintain the matrix phase in a metastable, face-centered cubic, solid- solution of tungsten in nickel.

  16. Mechanical properties and structural of metal-ceramic tungsten heterogeneity

    International Nuclear Information System (INIS)

    Gnuchev, V.S.; Zasimchuk, E.Eh.; Kas'yan, K.N.; Kravchenko, V.S.; Rabinovich, E.M.; Kharchenko, V.K.; Sheina, I.V.

    1978-01-01

    The influence of the grain size and the structure nonuniformity of cermet tungsten has been studied on its stre--ngth properties at temperatures of 500, 1000, and 1500 deg C. It has been shown that at a high temperature, the samples having a coarse-grained structure (about 50/m) preserve a high level of strength with an elevated plasticity. In the samples having the fine-grained (about 16/m) and the coarse-grained (about 114/m) structure, an abrupt decrease in the plasticity is observed along with a decrease in the strength. By investigating the influence of the annealing conditions on the structure of tungsten, the temperature range of the secondary recrystallization (about 2000 to 2200 deg C) has been established. The rolling temperature of sintered tungsten does not exceed 1700 deg C; thus a supposition is made that the structural nonuniformity of the material is attributable to the process of primary recrystallization and the amount of admixtures present

  17. Mechanism of vacancy formation induced by hydrogen in tungsten

    Directory of Open Access Journals (Sweden)

    Yi-Nan Liu

    2013-12-01

    Full Text Available We report a hydrogen induced vacancy formation mechanism in tungsten based on classical molecular dynamics simulations. We demonstrate the vacancy formation in tungsten due to the presence of hydrogen associated directly with a stable hexagonal self-interstitial cluster as well as a linear crowdion. The stability of different self-interstitial structures has been further studied and it is particularly shown that hydrogen plays a crucial role in determining the configuration of SIAs, in which the hexagonal cluster structure is preferred. Energetic analysis has been carried out to prove that the formation of SIA clusters facilitates the formation of vacancies. Such a mechanism contributes to the understanding of the early stage of the hydrogen blistering in tungsten under a fusion reactor environment.

  18. Displacement disorder and reconstruction of the (001) face of tungsten

    International Nuclear Information System (INIS)

    Egorushkin, V.E.; Kul'ment'ev, A.I.; Savushkin, E.V.

    1992-01-01

    The reconstruction of the (001) border of tungsten is examined taking into consideration random static displacements of surface atoms in the high-temperature (1 x 1) phase. A microscopic model is proposed, in which the creation of c(2 x 2) phase is described as a transition of the Jahn-Teller type and an ordering of static displacements. It is shown that displacement disorder induces instability of (001) tungsten with respect to reconstruction. The effect of a uniform electric field on a disordered reconstructing surface is examined. A possible reason is given for pronounced differences in the results of investigations of the structural conversion of the (001) face in tungsten when different experimental methods are used

  19. Tungsten-microdiamond composites for plasma facing components

    International Nuclear Information System (INIS)

    Livramento, V.; Nunes, D.; Correia, J.B.; Carvalho, P.A.; Mardolcar, U.; Mateus, R.; Hanada, K.; Shohoji, N.; Fernandes, H.; Silva, C.; Alves, E.

    2011-01-01

    Tungsten is considered as one of promising candidate materials for plasma facing component in nuclear fusion reactors due to its resistance to sputtering and high melting point. High thermal conductivity is also a prerequisite for plasma facing components under the unique service environment of fusion reactor characterised by the massive heat load, especially in the divertor area. The feasibility of mechanical alloying of nanodiamond and tungsten, and the consolidation of the composite powders with Spark Plasma Sintering (SPS) was previously demonstrated. In the present research we report on the use of microdiamond instead of nanodiamond in such composites. Microdiamond is more favourable than nanodiamond in view of phonon transport performance leading to better thermal conductivity. However, there is a trade off between densification and thermal conductivity as the SPS temperature increases tungsten carbide formation from microdiamond is accelerated inevitably while the consolidation density would rise.

  20. Development of tungsten coatings for the corrosion protection of alumina-based ceramics

    International Nuclear Information System (INIS)

    Arons, R.M.; Dusek, J.T.; Hafstrom, J.W.

    1979-01-01

    A means of applying tungsten coatings to an alumina based ceramic is described. A slurry of pure tungsten was prepared and applied by brush coating or slip casting on the alumina-3 wt % Yt small crucible. The composite was fired and a very dense ceramic crucible with a crack free tungsten coating was produced

  1. Controlled tungsten melting and droplet ejection studies in ASDEX Upgrade

    International Nuclear Information System (INIS)

    Krieger, K; Lunt, T; Dux, R; Janzer, A; Müller, H W; Potzel, S; Pütterich, T; Yang, Z

    2011-01-01

    Tungsten rods of 1×1×3 mm 3 were exposed in single H-mode discharges at the outer divertor target plate of ASDEX Upgrade using the divertor manipulator system. Melting of the W rod at a pre-defined time was induced by moving the initially far away outer strike point close to the W-rod position. Visible light emissions of both the W pin and consecutively ejected W droplets were recorded by two fast cameras with crossed viewing cones. The time evolution of the local W source at the pin location was measured by spectroscopic observation of the WI line emission at 400.9 nm and compared to the subsequent increase of tungsten concentration in the confined plasma derived from tungsten vacuum UV line emission. Combining these measurements with the total amount of released tungsten due to the pin melt events and ejected droplets allowed us to derive an estimate of the screening factor for this type of tungsten source. The resulting values of the tungsten divertor retention in the range 10-20 agree with those found in previous studies using a W source of sublimated W(CO) 6 vapour at the same exposure location. Ejected droplets were found to be always accelerated in the general direction of the plasma flow, attributed to friction forces and to rocket forces. Furthermore, the vertically inclined target plates cause the droplets, which are repelled by the target plate surface potential due to their electric charge, to move upwards against gravity due to the centrifugal force component parallel to the target plate.

  2. Engineered Surface Properties of Porous Tungsten from Cryogenic Machining

    Science.gov (United States)

    Schoop, Julius Malte

    Porous tungsten is used to manufacture dispenser cathodes due to it refractory properties. Surface porosity is critical to functional performance of dispenser cathodes because it allows for an impregnated ceramic compound to migrate to the emitting surface, lowering its work function. Likewise, surface roughness is important because it is necessary to ensure uniform wetting of the molten impregnate during high temperature service. Current industry practice to achieve surface roughness and surface porosity requirements involves the use of a plastic infiltrant during machining. After machining, the infiltrant is baked and the cathode pellet is impregnated. In this context, cryogenic machining is investigated as a substitutionary process for the current plastic infiltration process. Along with significant reductions in cycle time and resource use, surface quality of cryogenically machined un-infiltrated (as-sintered) porous tungsten has been shown to significantly outperform dry machining. The present study is focused on examining the relationship between machining parameters and cooling condition on the as-machined surface integrity of porous tungsten. The effects of cryogenic pre-cooling, rake angle, cutting speed, depth of cut and feed are all taken into consideration with respect to machining-induced surface morphology. Cermet and Polycrystalline diamond (PCD) cutting tools are used to develop high performance cryogenic machining of porous tungsten. Dry and pre-heated machining were investigated as a means to allow for ductile mode machining, yet severe tool-wear and undesirable smearing limited the feasibility of these approaches. By using modified PCD cutting tools, high speed machining of porous tungsten at cutting speeds up to 400 m/min is achieved for the first time. Beyond a critical speed, brittle fracture and built-up edge are eliminated as the result of a brittle to ductile transition. A model of critical chip thickness ( hc ) effects based on cutting

  3. 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.

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

    International Nuclear Information System (INIS)

    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

  5. A study of uranium adsorption to single-crystal tungsten

    Energy Technology Data Exchange (ETDEWEB)

    Samin, Adib; Hastings, Aaron; Zhang, Jinsuo, E-mail: jzhang@osu.edu

    2015-12-15

    In this study we explore the adsorption of uranium to the (110) plane of tungsten. Potential functions were constructed to describe the interaction of adsorbed uranium atoms with the tungsten surface and the lateral interaction between adsorbed uranium atoms. Next, the behavior of the uranium adlayer under different conditions was studied through a Monte Carlo simulation of the grand canonical Hamiltonian in an off-lattice model. Our results are consistent with available studies in the literature. The simulation results indicate that the temperature and dipole–dipole interactions play an important role in governing the adsorption process.

  6. A study of uranium adsorption to single-crystal tungsten

    International Nuclear Information System (INIS)

    Samin, Adib; Hastings, Aaron; Zhang, Jinsuo

    2015-01-01

    In this study we explore the adsorption of uranium to the (110) plane of tungsten. Potential functions were constructed to describe the interaction of adsorbed uranium atoms with the tungsten surface and the lateral interaction between adsorbed uranium atoms. Next, the behavior of the uranium adlayer under different conditions was studied through a Monte Carlo simulation of the grand canonical Hamiltonian in an off-lattice model. Our results are consistent with available studies in the literature. The simulation results indicate that the temperature and dipole–dipole interactions play an important role in governing the adsorption process.

  7. 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.

  8. Characterization of molecular and elemental impurities in tungsten hexafluoride

    International Nuclear Information System (INIS)

    Streusand, B.J.; Yost, V.E.; Govorchin, S.W.; Fry, R.C.; Padula, F.J.; Hughes, S.K.

    1990-01-01

    Analysis of WF 6 is a very difficult process because of the reactivity of the compound, the low detection limits required by its use in semiconductor processing, and by the presence of large amounts of tungsten in the analyte. It is not possible to perform elemental analysis with low detection limits directly on WF 6 or on hydrolyzed WF 6 . However, it is possible to remove the interfering tungsten by physical and chemical separation techniques. This paper discusses how the analysis of molecular impurities in WF 6 may be accomplished directly in the gas phase by infrared spectroscopy and by gas chromatography

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

    International Nuclear Information System (INIS)

    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 0.4-0.8 Tsub(m) 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. (Auth.)

  10. Helium effects on tungsten surface morphology and deuterium retention

    International Nuclear Information System (INIS)

    Ueda, Y.; Peng, H.Y.; Lee, H.T.; Ohno, N.; Kajita, S.; Yoshida, N.; Doerner, R.; De Temmerman, G.; Alimov, V.; Wright, G.

    2013-01-01

    Recent experimental results on tungsten surface morphology, especially nano-structure (fuzz), induced by helium plasma exposure at temperatures between 1000 K and 2000 K are reviewed. This structure was firstly reported in 2006. In this review, most of experimental results reported so far including characteristics and formation conditions of the nano-structure in both linear plasma devices and magnetic confinement devices, erosion and arcing by steady-state plasma exposure and ELM-like pulsed heat or pulsed plasma exposure by a laser and a plasma gun are summarized. In addition, He effects on D retention under simultaneous D/He irradiation on tungsten are presented

  11. Tungsten versus depleted uranium for armour-piercing penetrators

    International Nuclear Information System (INIS)

    Johnson, P.K.

    1983-01-01

    Tungsten alloys have been widely used in the production of armour-piercing (AP) penetrators for defense purposes for the past 40 years. In recent years, however, depleted uranium (DU) has also been utilised for this application. Both materials exhibit high density and strength, two properties necessary for kinetic-energy projectiles to penetrate armour on tanks and other vehicles. The facts, however, support the view that tungsten can and should be utilised as the primary material for most armour-defeating ordnance applications. (author)

  12. Tungsten erosion and redeposition in the all-tungsten divertor of ASDEX Upgrade

    Energy Technology Data Exchange (ETDEWEB)

    Mayer, M; Krieger, K; Matern, G; Neu, R; Rasinski, M; Rohde, V; Sugiyama, K; Wiltner, A [Max-Planck-Institut fuer Plasmaphysik, EURATOM Association, Boltzmannstrasse 2, 85748 Garching (Germany); Andrzejczuk, M; Fortuna-Zalesna, E; Kurzydlowski, K J; Zielinski, W [Faculty of Materials Science and Engineering, Warsaw University of Technology, Association EURATOM-IPPLM, 02-507 Warsaw (Poland); Hakola, A; Koivuranta, S; Likonen, J [VTT Materials for Power Engineering, EURATOM Association, PO Box 1000, FI-02044 VTT (Finland); Ramos, G [CICATA-Qro, Instituto Politecnico Nacional, Queretaro (Mexico); Dux, R, E-mail: matej.mayer@ipp.mpg.de

    2009-12-15

    Net erosion and deposition of tungsten (W) in the ASDEX Upgrade divertor were determined after the 2007 campaign by using thin W marker stripes. ASDEX Upgrade had full-W plasma-facing components during this campaign. The inner divertor and the roof baffle were net W deposition areas with a maximum deposition of about 1x10{sup 18} W-atoms cm{sup -2} in the private flux region below the inner strike point. Net erosion of W was observed in the whole outer divertor, with the largest erosion close to the outer strike point. Only a small fraction of the W eroded in the main chamber and in the outer divertor was found in redeposits in the inner divertor, while a large fraction was either redeposited at unidentified places in the main chamber or has formed dust.

  13. Electronic transport in tungsten and iron-doped tungsten below 1 K

    International Nuclear Information System (INIS)

    Uher, C.; Khoshnevisan, M.; Pratt, W.P. Jr.; Bass, J.

    1979-01-01

    The electric resistivity rho and the thermoelectric ratio G have been measured for zone-refined single crystals of both tungsten and iron-doped tungsten from 5 K down to 40 mK. The samples had residual resistance ratios RRR ranging from 1750 to 90,000. The observed behavior is conveniently divided into two classes, ''normal'' and ''anomalous.'' Completely normal behavior was displayed by only three W samples with high RRRs. The Fe-doped W and the remaining W samples contained one or more anomalies. Normal behavior is that which would be expected for W containing impurities with no internal degrees of freedom. In normal behavior rho decreased monotonically with decreasing temperature and was consistent with the equation rho=rho 0 +AT 2 below about 1.5K. In normal behavior, G was positive and constant below about 0.5 K, increased in magnitude as T rose to 4 or 5 K, and then began to decrease, becoming negative above about 7 K. The anomalous class displayed at least one of three anomalies: (1) a minimum in the electrical resistivity, with an approximately logarithmic variation with T at temperatures below the minimum; (2) a positive contribution to G which increased in magnitude with decreasing temperature approximately at T/sup -1/2/ from about 4 K down to at least 0.5 K; and (3) a negative contribution to G which set in at about 0.5 K, varied approximately as log T, and dominated G at the lowest temperatures

  14. Simulation of cracks in tungsten under ITER specific heat loads

    International Nuclear Information System (INIS)

    Peschany, S.

    2006-01-01

    The problem of high tritium retention in co-deposited carbon layers on the walls of ITER vacuum chamber motivates investigation of materials for the divertor armour others than carbon fibre composite (CFC). Tungsten is most probable material for CFC replacement as the divertor armour because of high vaporisation temperature and heat conductivity. In the modern ITER design tungsten is a reference material for the divertor cover, except for the separatrix strike point armoured with CFC. As divertor armour, tungsten should withstand severe heat loads at off-normal ITER events like disruptions, ELMs and vertical displacement events. Experiments on tungsten heating with plasma streams and e-beams have shown an intense crack formation at the surface of irradiated sample [ V.I. Tereshin, A.N. Bandura, O.V. Byrka et al. Repetitive plasma loads typical for ITER type-I ELMs: Simulation at QSPA Kh-50.PLASMA 2005. ed. By Sadowski M.J., AIP Conference Proceedings, American Institute of Physics, 2006, V 812, p. 128-135., J. Linke. Private communications.]. The reason for tungsten cracking under severe heat loads is thermo stress. It appears as due to temperature gradient in solid tungsten as in resolidified layer after cooling down. Both thermo stresses are of the same value, but the gradiental stress is compressive and the stress in the resolidified layer is tensile. The last one is most dangerous for crack formation and it was investigated in this work. The thermo stress in tungsten that develops during cooling from the melting temperature down to room temperature is ∼ 8-16 GPa. Tensile strength of tungsten is much lower, < 1 GPa at room temperature, and at high temperatures it drops at least for one order of magnitude. As a consequence, various cracks of different characteristic scales appear at the heated surface of the resolidified layer. For simulation of the cracks in tungsten the numeric code PEGASUS-3D [Pestchanyi and I. Landman. Improvement of the CFC structure to

  15. Physical mechanisms related to the degradation of LPCVD tungsten contacts at elevated temperatures

    International Nuclear Information System (INIS)

    Shenai, K.; Lewis, N.; Smith, G.A.; McConnell, M.D.; Burrell, M.

    1990-01-01

    The thermal stability of LPCVD (low pressure chemical vapor deposition) tungsten contacts to n-type silicon is studied at elevated temperatures in excess of 650 degrees C. The process variants studied include silicon doping, tungsten thickness, and post tungsten deposition dielectric stress temperatures. Detailed measurements of Kelvin contact resistance were made at room temperature as well as at elevated temperatures up to 165 degrees C. The tungsten contact resistance degradation at elevated stress temperatures is correlated with worm hole formation in silicon and the formation and diffusion of tungsten silicide. Extensive analytical measurements were used to characterize the material transformation at elevated stress temperatures to understand the physical mechanisms causing contact degradation

  16. Microstructure, mechanical behaviour and fracture of pure tungsten wire after different heat treatments

    DEFF Research Database (Denmark)

    Zhao, P.; Riesch, J.; Höschen, T.

    2017-01-01

    Plastic deformation of tungsten wire is an effective source of toughening tungsten fibre-reinforced tungsten composites (Wf/W) and other tungsten fibre-reinforced composites. To provide a reference for optimization of those composites, unconstrained pure tungsten wire is studied after various hea...... a rather different microstructure. As-fabricated wire and wire recrystallized at 1273 K for 3 h show fine grains with a high aspect ratio and a substantial plastic deformability: a clearly defined tensile strength, high plastic work, similar necking shape, and the characteristic knife...

  17. Molecular dynamics study of grain boundary diffusion of hydrogen in tungsten

    International Nuclear Information System (INIS)

    Von Toussaint, U; Gori, S; Manhard, A; Höschen, T; Höschen, C

    2011-01-01

    Understanding the influence of the microstructure of tungsten on hydrogen transport is crucial for the use of tungsten as first-wall material in fusion reactors. Here, we report the results of molecular dynamics and transition state studies on the influence of grain boundaries in tungsten on the transport of hydrogen. An exhaustive mapping of possible minimum activation energy migration trajectories for hydrogen as the trace impurity reveals a strongly modified activation energy distribution in the neighborhood of grain boundaries together with an altered connectivity matrix. The results indicate that grain boundaries in polycrystalline tungsten may provide an important transport channel, especially for neutron-damaged tungsten.

  18. Incorporation of tungsten metal fibers in a metal and ceramic matrix

    Directory of Open Access Journals (Sweden)

    V. Brozek

    2017-01-01

    Full Text Available Tungsten fibers have high tensile strength but a poor oxidation resistance at elevated temperatures. Using this first characteristic and to prevent oxidation of tungsten coated composite materials in which the primary requirement: reinforcement against destruction or deformation, was studied on tungsten fibers and tungsten wires which were coated by applying the metal and ceramic powders via plasma spraying device in plasma generator WSP®. Deposition took place in an atmosphere of Ar + 7 % H2, sufficient to reduce the oxidized trace amounts of tungsten.

  19. Comparison of four tungsten alloys for use as ultrasonic thermometer sensors

    International Nuclear Information System (INIS)

    Arave, A.E.

    1975-06-01

    Four tungsten alloy materials were evaluated for use as ultrasonic sensors: (a) tungsten, (b) tungsten-1 percent thoria, (c) tungsten-2 percent thoria, and (d) tungsten-26 percent rhenium. Four parameters were checked: (1) temperature sensitivity, (2) signal attenuation as a function of temperature, (3) temperature sensitivity as a function of frequency, and (4) relative signal attenuation as a function of frequency. The temperature sensors were designed for the Loss-of-Fluid Test (LOFT) and Power Burst Facility (PBF) reactors. (U.S.)

  20. 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.

  1. 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; Sofack-Kreutzer, Julien; Minenkov, Yury; Abou-Hamad, Edy; Hamzaoui, Bilel; Werghi, Baraa; Anjum, Dalaver H.; Cavallo, Luigi; Huang, Kuo-Wei; Basset, Jean-Marie

    2016-01-01

    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.

  2. Pulse current electrodeposition of tungsten coatings on V–4Cr–4Ti alloy

    International Nuclear Information System (INIS)

    Jiang, Fan; Zhang, Yingchun; Li, Xuliang

    2015-01-01

    Highlights: • Tungsten coatings were successfully electroplated on vanadium alloy substrate. • Tungsten coatings consisted of two sub-layers. • Tungsten coatings plated at lower duty cycle has a better surface quality. • High heat flux property of tungsten coatings was investigated. • Helium ion irradiation property of tungsten coatings was investigated. - Abstract: Tungsten coatings with high (2 2 0)-orientation were formed on V alloy substrate by pulse current electrodeposition in air atmosphere. The coatings’ microstructure, crystal structure and adhesive strength between coatings and substrates were investigated. It could be observed the tungsten coatings consisted of two sub-layers with the inner tooth-like layer, and the outer columnar layer. The tungsten coatings deposited at lower duty cycle have a better surface quality with a little change in the adhesive strength. The tungsten coating was exposed to electron beam with power density of 200 MW/m 2 in the thermal shock test, the tungsten crystal grain surface melt, the microcracks are found among the crystal grains. Exfoliation, flaking and dense needle-like holes were observed on the tungsten coating after irradiation with helium ions at an energy of 65 keV and an implanted dose of 22.67 × 10 18 cm −2

  3. Understanding metal–insulator transition in sodium tungsten bronze

    Indian Academy of Sciences (India)

    2015-05-20

    May 20, 2015 ... We have carried out angle-resolved photoemission spectroscopy (ARPES) and spectromicroscopy studies to understand the metal–insulator transition (MIT) observed in sodium tungsten bronzes, NaWO3. The experimentally determined band structure is compared with the theoretical calculation based ...

  4. Helium effects on tungsten surface morphology and deuterium retention

    NARCIS (Netherlands)

    Ueda, Y.; H. Y. Peng,; H. T. Lee,; N. Ohno,; S. Kajita,; Yoshida, N.; Doerner, R.; De Temmerman, G.; V. Alimov,; G. Wright,

    2013-01-01

    Recent experimental results on tungsten surface morphology, especially nano-structure (fuzz), induced by helium plasma exposure at temperatures between 1000 K and 2000 K are reviewed. This structure was firstly reported in 2006. In this review, most of experimental results reported

  5. Radiation damage in molybdenum and tungsten in high neutron fluxes

    Energy Technology Data Exchange (ETDEWEB)

    Veljkovic, S; Milasin, N [Institute of Nuclear Sciences Boris Kidric, Department of Reactor Materials, Vinca, Beograd (Serbia and Montenegro)

    1964-04-15

    The effects of radiation on molybdenum and tungsten in high neutron fluxes are presented. The changes induced, particularly defects with a high migration activation energy, are analyzed. The correlation of these changes with the basic concepts of radiation damage in solids is considered. An attempt is made to relate the defects studied with the changes in macroscopic properties (author)

  6. Electronic structure of nanoparticles of substoichometric hexagonal tungsten oxides

    International Nuclear Information System (INIS)

    Khyzhun, O Y; Solonin, Y M

    2007-01-01

    X-ray photoelectron spectroscopy (XPS), X-ray emission spectroscopy (XES) and X-ray absorption spectroscopy (XAS) methods were used to study the electronic structure of hexagonal h-WO 3 and h-WO 2.8 nanoparticles. For comparison, nanopowder substoichiometric monoclinic tungsten oxides with close content of oxygen atoms, namely m-WO 3 and m-WO 2.77 compounds, were also investigated. For the mentioned oxides, XPS valence-band and corelevel spectra, XES O Kα bands and XAS W L III and O 1s edges were derived. The XPS valence-band spectra and O Kα emission bands in the mentioned hexagonal and monoclinic tungsten oxides were compared on a common energy scale. Both the O Kα bands and XPS valence-band spectra broaden somewhat in the sequences h-WO 3 → h-WO 2.8 and m-WO 3 → m-WO 2.77 , with the half-widths of the spectra being somewhat higher for the hexagonal oxides as compared with those for the monoclinic compounds. The effective positive charge state of tungsten atoms in h-WO 2.8 is very close to that in m-WO 2.77 , but the negative charge states of oxygen atoms are close to each other for all the tungsten oxides under consideration

  7. Tungsten migration studies by controlled injection of volatile compounds

    Energy Technology Data Exchange (ETDEWEB)

    Rubel, M., E-mail: rubel@kth.se [Royal Institute of Technology (KTH), Association EURATOM-VR, Stockholm (Sweden); Coenen, J. [IEK-4, Plasma Physics, Forschungszentrum Jülich, Association EURATOM-FZJ, Jülich (Germany); Ivanova, D. [Royal Institute of Technology (KTH), Association EURATOM-VR, Stockholm (Sweden); Möller, S. [IEK-4, Plasma Physics, Forschungszentrum Jülich, Association EURATOM-FZJ, Jülich (Germany); Petersson, P. [Royal Institute of Technology (KTH), Association EURATOM-VR, Stockholm (Sweden); Brezinsek, S.; Kreter, A.; Philipps, V.; Pospieszczyk, A.; Schweer, B. [IEK-4, Plasma Physics, Forschungszentrum Jülich, Association EURATOM-FZJ, Jülich (Germany)

    2013-07-15

    Volatile tungsten hexa-fluoride was locally injected into the TEXTOR tokamak as a marker for material migration studies. The injection was accompanied by puffing N-15 rare isotope as a nitrogen tracer in discharges with edge cooling by impurity seeding. The objective was to assess material balance by qualitative and quantitative determination of a global and local deposition pattern, material mixing effects and fluorine residence in plasma-facing components. Spectroscopy and ex situ ion beam analysis techniques were used. Tungsten was detected on all types of limiter tiles and short-term probes retrieved from the vessel. Over 80% of the injected W was identified. The largest tungsten concentration, 1 × 10{sup 18} cm{sup −2}, was in the vicinity of the gas inlet. Co-deposits contained tungsten and a mix of light isotopes: H, D, He-4, B-10, B-11, C-12, C-13, N-14, N-15, O-16 and small quantities of F-19 thus showing that both He and nitrogen are trapped following wall conditioning (He glow) and edge cooling.

  8. FABRICATION OF GAS-FILLED TUNGSTEN-COATED GLASS SHELLS

    International Nuclear Information System (INIS)

    NIKROO, A; BAUGH, W; STEINMAN, D.A.

    2003-09-01

    OAK-B135 Deuterium (D 2 ) filled glass shells coated with a high Z element are needed for high energy density (HED) experiments by researchers at Los Alamos National Laboratory. They report here on our initial attempt to produce such shells. Glass shells made using the drop tower technique were coated with gold, palladium or tungsten, or a mixture of two of these elements. It was found that gold and palladium coatings did not stick well to the glass and resulted in poor or delaminated films. Tungsten coatings resulted in films suitable for these targets. Bouncing of shells during coating resulted in uniform tungsten coatings, but the surface of such coatings were filled with small nodules. Proper agitation of shells using a tapping technique resulted in smooth films with minimal particulate contamination. For coating rates of ∼ 0.15 (micro)m/hr coatings with ∼ 2 nm RMS surface finish could be deposited. The surface roughness of coatings at higher rates, 0.7 (micro)m/hr, was considerably worse (∼ 100 nm RMS). The columnar structure of the coatings allowed permeation filling of the tungsten coated glass shells with deuterium at 300 C

  9. Conceptual design for a bulk tungsten divertor tile in JET

    International Nuclear Information System (INIS)

    Mertens, Ph.; Hirai, T.; Linke, J.; Neubauer, O.; Pintsuk, G.; Philipps, V.; Sadakov, S.; Samm, U.; Schweer, B.

    2007-01-01

    The ITER-like Wall project (ILW) for JET aims at providing the plasma chamber of the tokamak with an environment of mixed materials which will be relevant for the actual first wall construction on ITER. Tungsten plays a key role in the divertor cladding. For the central tile, also called LB-SRP for 'load-bearing septum replacement plate', bulk tungsten is envisaged in order to cope with the high heat loads expected (up to 10 MW/m 2 for 10 s). The outer strike-point in the divertor will be positioned on this tile for the most relevant configurations. Forschungszentrum Juelich (FZJ) has developed a conceptual design based on an assembly of tungsten blades or lamellae. An appropriate interface with the base carrier of JET, on which modules of two tiles are positioned and fixed by remote handling procedures, is a substantial part of the integral design. Important issues are the electromagnetic forces and expected temperature distributions. Material choices combine tungsten, TZM TM , Inconel and ceramic parts. The completed design has been finalised in a proposal to the ILW project, with utmost ITER-relevance

  10. Hollow microspheres with a tungsten carbide kernel for PEMFC application.

    Science.gov (United States)

    d'Arbigny, Julien Bernard; Taillades, Gilles; Marrony, Mathieu; Jones, Deborah J; Rozière, Jacques

    2011-07-28

    Tungsten carbide microspheres comprising an outer shell and a compact kernel prepared by a simple hydrothermal method exhibit very high surface area promoting a high dispersion of platinum nanoparticles, and an exceptionally high electrochemically active surface area (EAS) stability compared to the usual Pt/C electrocatalysts used for PEMFC application.

  11. Radiation damage in molybdenum and tungsten in high neutron fluxes

    International Nuclear Information System (INIS)

    Veljkovic, S.; Milasin, N.

    1964-01-01

    The effects of radiation on molybdenum and tungsten in high neutron fluxes are presented. The changes induced, particularly defects with a high migration activation energy, are analyzed. The correlation of these changes with the basic concepts of radiation damage in solids is considered. An attempt is made to relate the defects studied with the changes in macroscopic properties (author)

  12. Tasmanian tin and tungsten granites - their radiometric characteristics

    International Nuclear Information System (INIS)

    Yeates, A.N.

    1982-01-01

    A radiometric survey of Tasmanian granites has shown, with one exception, that tin and tungsten-bearing granites have high radioactivity, largely owing to increased uranium. Many have a high uranium/thorium ratio as well. Radiometric measurements can also delineate different granite types within composite bodies

  13. Determination of tungsten and tin ions after preconcentration by flotation

    International Nuclear Information System (INIS)

    Dietze, U.; Kunze, S.

    1990-01-01

    A highly sensitive and selective combined method of flotation followed by spectrophotometry/d.c. polarography for the determination of tungsten and tin ions in acid and alkaline waste waters and hydrometallurgical solutions is presented here. Both kinds of ions are coprecipitated in the analyte solution with zirconium hydroxide after addition of ZrOCl 2 solution and ammonia. Afterwards, the collector precipitate is separated from the aqueous phase and preconcentrated by flotation for which sodium oleate and a frother are added. The precipitate is dissolved in a small amount of acid, with the organic reagents being destroyed by oxidation. The enrichment factor of the proposed technique is 100, with variations possible. Recovery is 94 % for tungsten and 99 % for tin. Spectrophotometry of the thiocyanate complex and d.c. polarography are applied as determination techniques for tungsten and tin, respectively. Detection limits attainable by this technique are 6 ng.ml -1 for tungsten and 5 ng.ml -1 for tin for the initial sample. (Authors)

  14. 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.

  15. Thermal Cycling of Uranium Dioxide - Tungsten Cermet Fuel Specimens

    Energy Technology Data Exchange (ETDEWEB)

    Gripshover, P.J.; Peterson, J.H.

    1969-12-08

    In phase I tungsten clad cermet fuel specimens were thermal cycled, to study the effects of fuel loading, fuel particle size, stablized fuel, duplex coatings, and fabrication techniques on dimensional stability during thermal cycling. In phase II the best combination of the factors studies in phase I were combined in one specimen for evaluation.

  16. Microscopic investigations of chemo-mechanical polishing of tungsten

    International Nuclear Information System (INIS)

    Lim, Min Soo; Heide, Paul A.W. van der; Perry, Scott S.; Galloway, Heather C.; Koeck, Deborah C.

    2004-01-01

    The influence of aqueous solutions of KNO 3 , KClO 3 , and KIO 3 on tungsten surfaces has been investigated in terms of the degree of surface oxidation, metal dissolution and interfacial friction. The surface properties of tungsten films have been measured ex-situ with X-ray photoelectron spectroscopy and in situ with atomic force microscopy. Measurements of the surface composition reveal a greater degree of oxidation for surfaces treated in solutions of KIO 3 in comparison to the other solutions. This increase in surface oxidation is correlated to a greater rate of localized film dissolution that occurs under the action of the scanning probe tip. In turn, the process of material removal is the predominant origin of the higher interfacial friction measured at tungsten surfaces immersed in KIO 3 solutions, as compared to KClO 3 and KNO 3 solutions. Collectively, these measurements portray a fundamental pathway of material removal at tungsten surfaces in the presence of oxidizing species and highlight complementary roles of chemical and mechanical action

  17. Microscopic investigations of chemo-mechanical polishing of tungsten

    Energy Technology Data Exchange (ETDEWEB)

    Lim, Min Soo; Heide, Paul A.W. van der; Perry, Scott S.; Galloway, Heather C.; Koeck, Deborah C

    2004-06-15

    The influence of aqueous solutions of KNO{sub 3}, KClO{sub 3}, and KIO{sub 3} on tungsten surfaces has been investigated in terms of the degree of surface oxidation, metal dissolution and interfacial friction. The surface properties of tungsten films have been measured ex-situ with X-ray photoelectron spectroscopy and in situ with atomic force microscopy. Measurements of the surface composition reveal a greater degree of oxidation for surfaces treated in solutions of KIO{sub 3} in comparison to the other solutions. This increase in surface oxidation is correlated to a greater rate of localized film dissolution that occurs under the action of the scanning probe tip. In turn, the process of material removal is the predominant origin of the higher interfacial friction measured at tungsten surfaces immersed in KIO{sub 3} solutions, as compared to KClO{sub 3} and KNO{sub 3} solutions. Collectively, these measurements portray a fundamental pathway of material removal at tungsten surfaces in the presence of oxidizing species and highlight complementary roles of chemical and mechanical action.

  18. Inhomogeneous strain states in sputter deposited tungsten thin films

    International Nuclear Information System (INIS)

    Noyan, I.C.; Shaw, T.M.; Goldsmith, C.C.

    1997-01-01

    The results of an x-ray diffraction study of dc-magnetron sputtered tungsten thin films are reported. It is shown that the phase transformation from the β to α W can cause multilayered single-phase films where the layers have very different stress states even if the films are in the 500 nm thickness range. copyright 1997 American Institute of Physics

  19. High strength tungsten heavy alloys with molybdenum additions

    International Nuclear Information System (INIS)

    Bose, A.; Sims, D.M.; German, R.M.

    1987-01-01

    Tungsten heavy alloys are candidates for numerous applications based on the unique combination of high density, high strength, and high ductility coupled with excellent machinability. Though there has been considerable research on heavy alloys, the primary focus has been on the ductility. These alloys are well suited for ballistic uses due to their high densities and it is expected that for superior ballistic performance, a high hardness, high strength and moderate ductility alloy would be ideal. The major goal of this investigation was to obtain heavy alloys with hardness greater than HRA 72. It is evident from the phase diagrams that molybdenum, which goes into solution in tungsten, nickel and iron, could act as a potential strengthening addition. With this in view, tungsten heavy alloys with molybdenum additions were fabricated from mixed elemental powders. A baseline composition of 90W-7Ni-3Fe was chosen to its good elongation and moderate strength. The molybdenum additions were made by replacing the tungsten. Compared to the baseline properties with no molybdenum addition, the strength and hardness showed a continuous increase with molybdenum addition. The ductility of the alloy continued to decrease with increasing molybdenum content, but even with 16% wt. % molybdenum of the elongation was still around 6%. An interesting facet of these alloying additions is the grain refinement that is brought about by adding to molybdenum to the system. The grain refinement is related to the lower solubility of tunbsten in the matrix due to partial displacement by molybdenum

  20. Compressive yielding of tungsten fiber reinforced bulk metallic glass composites

    Energy Technology Data Exchange (ETDEWEB)

    Clausen, B.; Lee, S.-Y.; Uestuendag, E.; Aydiner, C.C.; Conner, R.D.; Bourke, M.A.M

    2003-07-15

    In-situ uniaxial compression tests were conducted on four tungsten fiber reinforced bulk metallic glass matrix composites using neutron diffraction. The results were interpreted with a finite element model. Both phases were seen to approximately obey the von Mises yield criterion. The fibers were observed to yield first and then transfer load to the matrix.

  1. Compressive yielding of tungsten fiber reinforced bulk metallic glass composites

    International Nuclear Information System (INIS)

    Clausen, B.; Lee, S.-Y.; Uestuendag, E.; Aydiner, C.C.; Conner, R.D.; Bourke, M.A.M.

    2003-01-01

    In-situ uniaxial compression tests were conducted on four tungsten fiber reinforced bulk metallic glass matrix composites using neutron diffraction. The results were interpreted with a finite element model. Both phases were seen to approximately obey the von Mises yield criterion. The fibers were observed to yield first and then transfer load to the matrix

  2. New developments in damage dosimetry using the tungsten dosimeter

    International Nuclear Information System (INIS)

    Alberman, A.; Genthon, J.P.; Nolthenius, H.J.; Zijp, W.L.

    1982-03-01

    Good consistency between GAMIN and tungsten damage monitors (based upon electrical resistivity change) and corresponding theoretical damage models was given at the 3rd ASTM-EURATOM Symposium (Ispra, 1979). Results obtained since then in pressure vessel mock-ups show enhanced contribution of low energy neutrons ( [fr

  3. Tungsten and carbon surface change under high dose plasma exposure

    International Nuclear Information System (INIS)

    Martynenko, Y.V.; Khripunov, B.I.; Petrov, V.B.

    2009-01-01

    Study of surface composition dynamics has been made on the LENTA linear plasma simulator. Experiments have been made on tungsten and carbon materials subjected to steady-state plasma exposure. The achieved ion doses on the surface were 10 21 ion cm -2 . WL 10 tungsten containing 1% of La2O3 oxide and titanium-doped graphite RG-T were studied. The following experimental conditions were varied in these experiments: energy of ions, surface temperature, working gas. Irradiations of tungsten WL 10 were executed in deuterium plasma at low ion energies (about 20 eV) and at 200 eV for temperatures below 340 K. Graphite RG-T was exposed at 1300 K. Elevated surface temperature (about 1050K) was also characteristic of experiments on tungsten sample under nitrogen plasma impact (simulated inter-ELMs condition). Surface microstructure modification has been observed and surface composition changes were found on the materials showing influence of high dose plasma irradiations on element redistribution in the near surface layers. (author)

  4. Helium-induced hardening effect in polycrystalline tungsten

    Science.gov (United States)

    Kong, Fanhang; Qu, Miao; Yan, Sha; Zhang, Ailin; Peng, Shixiang; Xue, Jianming; Wang, Yugang

    2017-09-01

    In this paper, helium induced hardening effect of tungsten was investigated. 50 keV He2+ ions at fluences vary from 5 × 1015 cm-2 to 5 × 1017 cm-2 were implanted into polycrystalline tungsten at RT to create helium bubble-rich layers near the surface. The microstructure and mechanical properties of the irradiated specimens were studied by TEM and nano-indentor. Helium bubble rich layers are formed in near surface region, and the layers become thicker with the rise of fluences. Helium bubbles in the area of helium concentration peak are found to grow up, while the bubble density is almost unchanged. Obvious hardening effect is induced by helium implantation in tungsten. Micro hardness increases rapidly with the fluence firstly, and more slowly when the fluence is above 5 × 1016 cm-2. The hardening effect of tungsten can be attributed to helium bubbles, which is found to be in agreement with the Bacon-Orowan stress formula. The growing diameter is the major factor rather than helium bubbles density (voids distance) in the process of helium implantation at fluences below 5 × 1017 cm-2.

  5. Selective CVD tungsten on silicon implanted SiO/sub 2/

    International Nuclear Information System (INIS)

    Hennessy, W.A.; Ghezzo, M.; Wilson, R.H.; Bakhru, H.

    1988-01-01

    The application range of selective CVD tungsten is extended by its coupling to the ion implantation of insulating materials. This article documents the results of selective CVD tungsten using silicon implanted into SiO/sub 2/ to nucleate the tungsten growth. The role of implant does, energy, and surface preparation in achieving nucleation are described. SEM micrographs are presented to demonstrate the selectivity of this process. Measurements of the tungsten film thickness and sheet resistance are provided for each of the experimental variants corresponding to successful deposition. RBS and XPS analysis are discussed in terms of characterizing the tungsten/oxide interface and to evaluate the role of the silicon implant in the CVD tungsten mechanism. Utilizing this method a desired metallization pattern can be readily defined with lithography and ion implantation, and accurately replicated with a layer of CVD tungsten. This approach avoids problems usually associated with blanket deposition and pattern transfer, which are particularly troublesome for submicron VLSI technology

  6. Low temperature processing of tungsten-fibre high-strength composite

    International Nuclear Information System (INIS)

    Semrau, W.M.

    2001-01-01

    A tungsten nickel/iron compound with a high tungsten content up to over 90 percent by volume of tungsten and an ideal distribution of the nickel-iron multilayer-matrix avoiding tungsten - tungsten interfaces, has been processed without the use of any sintering process and thus resulted in avoiding temperatures of above 700 o C during the entire manufacturing process. An electrochemical coating of coarse tungsten powder with alternating layers of nickel and iron and a forging process at temperatures not exceeding 650 o C resulted in a high strength compound, which easily could be altered into a tungsten fiber compound with a fiber-length to fiber-diameter ratio of more than 10 3 . From the viewpoint of the metallurgist, easier handling systems are obtained when both a liquid phase and high temperatures with their risks for grain structures and grain boundaries are lacking. (author)

  7. Erosion and migration of tungsten employed at the central column heat shield of ASDEX Upgrade

    International Nuclear Information System (INIS)

    Krieger, K.; Gong, X.; Balden, M.; Hildebrandt, D.; Maier, H.; Rohde, V.; Roth, J.; Schneider, W.

    2002-01-01

    In ASDEX Upgrade, tungsten was employed as plasma facing material at the central column heat shield in the plasma main chamber. The campaign averaged tungsten erosion flux was determined by measuring the difference of the W-layer thickness before and after the experimental campaign using ion beam analysis methods. The observed lateral variation and the total amount of eroded tungsten are attributed to erosion by impact of ions from the scrape-off layer plasma. Migration and redeposition of eroded tungsten were investigated by quantitative analysis of deposited tungsten on collector probes and wall samples. The obtained results, as well as the spectroscopically observed low tungsten plasma penetration probability, indicate that a major fraction of the eroded tungsten migrates predominantly through direct transport channels in the outer plasma scrape-off layer without entering the confined plasma

  8. Information extraction from FN plots of tungsten microemitters

    Energy Technology Data Exchange (ETDEWEB)

    Mussa, Khalil O. [Department of Physics, Mu' tah University, Al-Karak (Jordan); Mousa, Marwan S., E-mail: mmousa@mutah.edu.jo [Department of Physics, Mu' tah University, Al-Karak (Jordan); Fischer, Andreas, E-mail: andreas.fischer@physik.tu-chemnitz.de [Institut für Physik, Technische Universität Chemnitz, Chemnitz (Germany)

    2013-09-15

    Tungsten based microemitter tips have been prepared both clean and coated with dielectric materials. For clean tungsten tips, apex radii have been varied ranging from 25 to 500 nm. These tips were manufactured by electrochemical etching a 0.1 mm diameter high purity (99.95%) tungsten wire at the meniscus of two molar NaOH solution. Composite micro-emitters considered here are consisting of a tungsten core coated with different dielectric materials—such as magnesium oxide (MgO), sodium hydroxide (NaOH), tetracyanoethylene (TCNE), and zinc oxide (ZnO). It is worthwhile noting here, that the rather unconventional NaOH coating has shown several interesting properties. Various properties of these emitters were measured including current–voltage (IV) characteristics and the physical shape of the tips. A conventional field emission microscope (FEM) with a tip (cathode)–screen (anode) separation standardized at 10 mm was used to electrically characterize the electron emitters. The system was evacuated down to a base pressure of ∼10{sup −8}mbar when baked at up to ∼180°C overnight. This allowed measurements of typical field electron emission (FE) characteristics, namely the IV characteristics and the emission images on a conductive phosphorus screen (the anode). Mechanical characterization has been performed through a FEI scanning electron microscope (SEM). Within this work, the mentioned experimental results are connected to the theory for analyzing Fowler–Nordheim (FN) plots. We compared and evaluated the data extracted from clean tungsten tips of different radii and determined deviations between the results of different extraction methods applied. In particular, we derived the apex radii of several clean and coated tungsten tips by both SEM imaging and analyzing FN plots. The aim of this analysis is to support the ongoing discussion on recently developed improvements of the theory for analyzing FN plots related to metal field electron emitters, which in

  9. Information extraction from FN plots of tungsten microemitters

    International Nuclear Information System (INIS)

    Mussa, Khalil O.; Mousa, Marwan S.; Fischer, Andreas

    2013-01-01

    Tungsten based microemitter tips have been prepared both clean and coated with dielectric materials. For clean tungsten tips, apex radii have been varied ranging from 25 to 500 nm. These tips were manufactured by electrochemical etching a 0.1 mm diameter high purity (99.95%) tungsten wire at the meniscus of two molar NaOH solution. Composite micro-emitters considered here are consisting of a tungsten core coated with different dielectric materials—such as magnesium oxide (MgO), sodium hydroxide (NaOH), tetracyanoethylene (TCNE), and zinc oxide (ZnO). It is worthwhile noting here, that the rather unconventional NaOH coating has shown several interesting properties. Various properties of these emitters were measured including current–voltage (IV) characteristics and the physical shape of the tips. A conventional field emission microscope (FEM) with a tip (cathode)–screen (anode) separation standardized at 10 mm was used to electrically characterize the electron emitters. The system was evacuated down to a base pressure of ∼10 −8 mbar when baked at up to ∼180°C overnight. This allowed measurements of typical field electron emission (FE) characteristics, namely the IV characteristics and the emission images on a conductive phosphorus screen (the anode). Mechanical characterization has been performed through a FEI scanning electron microscope (SEM). Within this work, the mentioned experimental results are connected to the theory for analyzing Fowler–Nordheim (FN) plots. We compared and evaluated the data extracted from clean tungsten tips of different radii and determined deviations between the results of different extraction methods applied. In particular, we derived the apex radii of several clean and coated tungsten tips by both SEM imaging and analyzing FN plots. The aim of this analysis is to support the ongoing discussion on recently developed improvements of the theory for analyzing FN plots related to metal field electron emitters, which in

  10. Corrosion of tungsten microelectrodes used in neural recording applications.

    Science.gov (United States)

    Patrick, Erin; Orazem, Mark E; Sanchez, Justin C; Nishida, Toshikazu

    2011-06-15

    In neuroprosthetic applications, long-term electrode viability is necessary for robust recording of the activity of neural populations used for generating communication and control signals. The corrosion of tungsten microwire electrodes used for intracortical recording applications was analyzed in a controlled bench-top study and compared to the corrosion of tungsten microwires used in an in vivo study. Two electrolytes were investigated for the bench-top electrochemical analysis: 0.9% phosphate buffered saline (PBS) and 0.9% PBS containing 30 mM of hydrogen peroxide. The oxidation and reduction reactions responsible for corrosion were found by measurement of the open circuit potential and analysis of Pourbaix diagrams. Dissolution of tungsten to form the tungstic ion was found to be the corrosion mechanism. The corrosion rate was estimated from the polarization resistance, which was extrapolated from the electrochemical impedance spectroscopy data. The results show that tungsten microwires in an electrolyte of PBS have a corrosion rate of 300-700 μm/yr. The corrosion rate for tungsten microwires in an electrolyte containing PBS and 30 mM H₂O₂ is accelerated to 10,000-20,000 μm/yr. The corrosion rate was found to be controlled by the concentration of the reacting species in the cathodic reaction (e.g. O₂ and H₂O₂). The in vivo corrosion rate, averaged over the duration of implantation, was estimated to be 100 μm/yr. The reduced in vivo corrosion rate as compared to the bench-top rate is attributed to decreased rate of oxygen diffusion caused by the presence of a biological film and a reduced concentration of available oxygen in the brain. Copyright © 2011 Elsevier B.V. All rights reserved.

  11. The high temperature impact response of tungsten and chromium

    Science.gov (United States)

    Zaretsky, E. B.; Kanel, G. I.

    2017-09-01

    The evolution of elastic-plastic shock waves has been studied in pure polycrystalline tungsten and chromium at room and elevated temperatures over propagation distances ranging from 0.05 to 3 mm (tungsten) and from 0.1 to 2 mm (chromium). The use of fused silica windows in all but one experiment with chromium and in several high temperature experiments with tungsten led to the need for performing shock and optic characterization of these windows over the 300-1200 K temperature interval. Experiments with tungsten and chromium samples showed that annealing of the metals transforms the initial ramping elastic wave into a jump-like wave, substantially increasing the Hugoniot elastic limits of the metals. With increased annealing time, the spall strength of the two metals slightly increases. Both at room and at high temperatures, the elastic precursor in the two metals decays in two distinct regimes. At propagation distances smaller than ˜1 mm (tungsten) or ˜0.5 mm (chromium), decay is fast, with the dislocation motion and multiplication being controlled by phonon viscous drag. At greater distances, the rate of decay becomes much lower, with control of the plastic deformation being passed to the thermally activated generation and motion of dislocation double-kinks. The stress at which this transition takes place virtually coincides with the Peierls stress τP of the active glide system. Analysis of the annealing effects in both presently and previously studied BCC metals (i.e., Ta, V, Nb, Mo, W, and Cr) and of the dependencies of their normalized Peierls stresses τP(θ) /τP(0 ) on the normalized temperature θ=T /Tm allows one to conclude that the non-planar, split into several glide planes, structure of the dislocation core in these metals is mainly responsible for their plastic deformation features.

  12. Synthesis of high purity tungsten nanoparticles from tungsten heavy alloy scrap by selective precipitation and reduction route

    International Nuclear Information System (INIS)

    Kamal, S.S. Kalyan; Sahoo, P.K.; Vimala, J.; Shanker, B.; Ghosal, P.; Durai, L.

    2016-01-01

    In this paper we report synthesis of tungsten nanoparticles of high purity >99.7 wt% from heavy alloy scrap using a novel chemical route of selective precipitation and reduction. The effect of Poly(vinylpyrrolidone) polymer on controlling the particle size is established through FTIR spectra and corroborated with TEM images, wherein the average size decreased form 210 to 45 nm with increasing PVP content from zero to 2 g under different experimental conditions. This process is economical as raw material is a scrap and the efficiency of the reaction is >95%. - Highlights: • Tungsten nanoparticles were synthesized from tungsten heavy alloy scrap. • A novel chemical route of precipitation and reduction with Poly(vinylpyrrolidone) polymer as stabilizer is reported. • The average size decreased form 210 to 45 nm with increasing PVP content from zero to 2 g. • High pure tungsten nanoparticles of >99.7% purity could be synthesized using this route. • Efficiency of the reaction is >95%.

  13. Pitfalls of tungsten multileaf collimator in proton beam therapy

    Energy Technology Data Exchange (ETDEWEB)

    Moskvin, Vadim; Cheng, Chee-Wai; Das, Indra J. [Department of Radiation Oncology, Indiana University School of Medicine, Indianapolis, Indiana 46202 (United States) and Indiana University Health Proton Therapy Center (Formerly Midwest Proton Radiotherapy Institute), Bloomington, Indiana 47408 (United States)

    2011-12-15

    Purpose: Particle beam therapy is associated with significant startup and operational cost. Multileaf collimator (MLC) provides an attractive option to improve the efficiency and reduce the treatment cost. A direct transfer of the MLC technology from external beam radiation therapy is intuitively straightforward to proton therapy. However, activation, neutron production, and the associated secondary cancer risk in proton beam should be an important consideration which is evaluated. Methods: Monte Carlo simulation with FLUKA particle transport code was applied in this study for a number of treatment models. The authors have performed a detailed study of the neutron generation, ambient dose equivalent [H*(10)], and activation of a typical tungsten MLC and compared with those obtained from a brass aperture used in a typical proton therapy system. Brass aperture and tungsten MLC were modeled by absorber blocks in this study, representing worst-case scenario of a fully closed collimator. Results: With a tungsten MLC, the secondary neutron dose to the patient is at least 1.5 times higher than that from a brass aperture. The H*(10) from a tungsten MLC at 10 cm downstream is about 22.3 mSv/Gy delivered to water phantom by noncollimated 200 MeV beam of 20 cm diameter compared to 14 mSv/Gy for the brass aperture. For a 30-fraction treatment course, the activity per unit volume in brass aperture reaches 5.3 x 10{sup 4} Bq cm{sup -3} at the end of the last treatment. The activity in brass decreases by a factor of 380 after 24 h, additional 6.2 times after 40 days of cooling, and is reduced to background level after 1 yr. Initial activity in tungsten after 30 days of treating 30 patients per day is about 3.4 times higher than in brass that decreases only by a factor of 2 after 40 days and accumulates to 1.2 x 10{sup 6} Bq cm{sup -3} after a full year of operation. The daily utilization of the MLC leads to buildup of activity with time. The overall activity continues to increase

  14. 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

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

    International Nuclear Information System (INIS)

    Wirtz, Oliver Marius

    2012-01-01

    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 -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 damages

  16. Information extraction from FN plots of tungsten microemitters.

    Science.gov (United States)

    Mussa, Khalil O; Mousa, Marwan S; Fischer, Andreas

    2013-09-01

    Tungsten based microemitter tips have been prepared both clean and coated with dielectric materials. For clean tungsten tips, apex radii have been varied ranging from 25 to 500 nm. These tips were manufactured by electrochemical etching a 0.1 mm diameter high purity (99.95%) tungsten wire at the meniscus of two molar NaOH solution. Composite micro-emitters considered here are consisting of a tungsten core coated with different dielectric materials-such as magnesium oxide (MgO), sodium hydroxide (NaOH), tetracyanoethylene (TCNE), and zinc oxide (ZnO). It is worthwhile noting here, that the rather unconventional NaOH coating has shown several interesting properties. Various properties of these emitters were measured including current-voltage (IV) characteristics and the physical shape of the tips. A conventional field emission microscope (FEM) with a tip (cathode)-screen (anode) separation standardized at 10 mm was used to electrically characterize the electron emitters. The system was evacuated down to a base pressure of ∼10(-8) mbar when baked at up to ∼180 °C overnight. This allowed measurements of typical field electron emission (FE) characteristics, namely the IV characteristics and the emission images on a conductive phosphorus screen (the anode). Mechanical characterization has been performed through a FEI scanning electron microscope (SEM). Within this work, the mentioned experimental results are connected to the theory for analyzing Fowler-Nordheim (FN) plots. We compared and evaluated the data extracted from clean tungsten tips of different radii and determined deviations between the results of different extraction methods applied. In particular, we derived the apex radii of several clean and coated tungsten tips by both SEM imaging and analyzing FN plots. The aim of this analysis is to support the ongoing discussion on recently developed improvements of the theory for analyzing FN plots related to metal field electron emitters, which in particular

  17. Conceptual Design for a Bulk Tungsten Divertor Tile in JET

    International Nuclear Information System (INIS)

    Mertens, P.; Neubauer, O.; Philipps, V.; Schweer, B.; Samm, U.; Hirai, T.; Sadakov, S.

    2006-01-01

    With ITER on the verge of being build, the ITER-like Wall project (ILW) for JET aims at providing the plasma chamber of the tokamak with an environment of mixed materials which will be relevant to the support of decisions to the first wall construction and, from the point of view of plasma physics, to the corresponding investigations of possible plasma configuration and plasma-wall interaction. In both respects, tungsten plays a key role in the divertor cladding whereas beryllium will be used for the vessel's first wall. For the central tile, also called LB-SRP for '' Load-Bearing Septum Replacement Plate '', resort to bulk tungsten is envisaged in order to cope with the high loads expected (up to 10 MW/m 2 for about 10 s). This is indeed the preferred plasma-facing component for positioning the outer strike-point in the divertor. Forschungszentrum Juelich has developed a conceptual design for this tile, based on an assembly of tungsten blades or lamellae. It was selected in the frame of an extensive R-and-D study in search of a suitable, inertially cooled component(T. Hirai et al., R-and-D on full tungsten divertor and beryllium wall for JET ITER-like Wall Project: this conference). As reported elsewhere, the design is actually driven by electromagnetic considerations in the first place(S. Sadakov et al., Detailed electromagnetic analysis for optimisation of a tungsten divertor plate for JET: this conference). The lamellae are grouped in four stacks per tile which are independently attached to an equally re-designed supporting structure. A so-called adapter plate, also a new design, takes care of an appropriate interface to the base carrier of JET, onto which modules of two tiles are positioned and screwed by remote handling (RH) procedures. The compatibility of the design on the whole with RH requirements is another essential ingredient which was duly taken into account throughout. The concept and the underlying philosophy will be presented along with important

  18. High-temperature brazing for reliable tungsten-CFC joints

    International Nuclear Information System (INIS)

    Koppitz, Th; Pintsuk, G; Reisgen, U; Remmel, J; Hirai, T; Sievering, R; Rojas, Y; Casalegno, V

    2007-01-01

    The joining of tungsten and carbon-based materials is demanding due to the incompatibility of their chemical and thermophysical properties. Direct joining is unfeasible by the reason of brittle tungsten carbide formation. High-temperature brazing has been investigated in order to find a suitable brazing filler metal (BFM) which successfully acts as an intermediary between the incompatible properties of the base materials. So far only low Cr-alloyed Cu-based BFMs provide the preferential combination of good wetting action on both materials, tolerable interface reactions, and a precipitation free braze joint. Attempts to implement a higher melting metal (e.g. Pd, Ti, Zr) as a BFM have failed up to now, because the formation of brittle precipitations and pores in the seam were inevitable. But the wide metallurgical complexity of this issue is regarded to offer further joining potential

  19. Efficacy of Tantalum Tungsten Alloys for Diffusion Barrier Applications

    Science.gov (United States)

    Smathers, D. B.; Aimone, P. R.

    2017-12-01

    Traditionally either Niobium, Tantalum or a combination of both have been used as diffusion barriers in Nb3Sn Multi-filament wire. Vanadium has also been used successfully but the ultimate RRR of the copper is limited unless an external shell of Niobium is included. Niobium is preferred over Tantalum when alternating current losses are not an issue as the Niobium will react to form Nb3Sn. Pure Tantalum tends to deform irregularly requiring extra starting thickness to ensure good barrier qualities. Our evaluations showed Tantalum lightly alloyed with 3 wt% Tungsten is compatible with the wire drawing process while deforming as well as or better than pure Niobium. Ta3wt%W has been processed as a single barrier and as a distributed barrier to fine dimensions. In addition, the higher modulus and strength of the Tantalum Tungsten alloy improves the overall tensile properties of the wire.

  20. Electron field emission characteristics of carbon nanotube on tungsten tip

    International Nuclear Information System (INIS)

    Phan Ngoc Hong; Bui Hung Thang; Nguyen Tuan Hong; Phan Ngoc Minh; Lee, Soonil

    2009-01-01

    Electron field emission characteristic of carbon nanotubes on tungsten tip was investigated in 2x10 -6 Torr vacuum. The measurement results showed that the CNTs/W tip could emit electron at 0.7 V/μm (nearly 10 times lower than that of the W tip itself) and reach up to 26 μA at the electric field of 1 V/μm. The emission characteristic follows the Fowler-Nordheim mechanism. Analysis of the emission characteristic showed that the CNTs/W tip has a very high value of field enhancement factor (β = 4.1 x 10 4 cm -1 ) that is much higher than that of the tungsten tip itself. The results confirmed the excellent field emission behavior of the CNTs materials and the CNTs/W tip is a prospective candidate for advanced electron field emitter.