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.

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.

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.

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.

Effect of support on hydro-metathesis of propene: A comparative study of W(CH 3 ) 6 anchored to silica vs. silica-alumina

KAUST Repository

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

2018-01-01

Hydro-metathesis of propene was carried out by using well-defined W(CH3)6 supported on silica and silica-alumina. It was observed that W(CH3)6 supported silica-alumina catalyst is much better (TON 4577) than the silica supported catalyst (TON 2104

[(≢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.

[(≢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.

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.

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.

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.

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.

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.

Effect of support on hydro-metathesis of propene: A comparative study of W(CH 3 ) 6 anchored to silica vs. silica-alumina

KAUST Repository

Tretiakov, Mykyta

2018-03-27

Hydro-metathesis of propene was carried out by using well-defined W(CH3)6 supported on silica and silica-alumina. It was observed that W(CH3)6 supported silica-alumina catalyst is much better (TON 4577) than the silica supported catalyst (TON 2104). We demonstrated that the present catalysts are much better than the previously reported (tantalum hydride/KCC-1, TON 786) catalyst. For the first time, we observed the formation of n-decane from propene, which enables us to think of using cheaper raw materials and converting them to petroleum range alkanes using hydro-metathesis reaction.

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.

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.

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.

Incorporation of polyoxotungstate complexes in silica spheres and in situ formation of tungsten trioxide nanoparticles.

Science.gov (United States)

Zhao, Yuanyuan; Fan, Haimei; Li, Wen; Bi, Lihua; Wang, Dejun; Wu, Lixin

2010-09-21

In this paper, we demonstrated a new convenient route for in situ fabrication of well separated small sized WO(3) nanoparticles in silica spheres, through a predeposition of surfactant encapsulated polyoxotungates as tungsten source, and followed by a calcination process. In a typical procedure, selected polyoxotungates with different charges were enwrapped with dioctadecyldimethylammonium cations through electrostatic interaction. Elemental analysis, thermogravimetric analysis, and spectral characterization confirmed the formation of prepared complexes with the anticipated chemical structure. The complexes were then phase-transferred into aqueous solution that predissolved surfactant cetyltrimethylammonium bromide, and finally incorporated into silica spheres through a joint sol-gel reaction with tetraethyl orthosilicate in a well dispersed state under the protection of organic layer for polyoxotungates from the alkaline reaction condition. Transmission electron microscopic images illustrated the well dispersed WO(3) nanoparticles in the size range of ca. 2.2 nm in the silica spheres after the calcination at 465 °C. The sizes of both the silica spheres and WO(3) nanoparticles could be adjusted independently through changing the doping content to a large extent. Meanwhile, the doped polyoxotungate complexes acted as the template for the mesoporous structure in silica spheres after the calcination. Along with the increase of doping content and surfactant, the mesopore size changed little (2.0-2.9 nm), but the specific surface areas increased quite a lot. Importantly, the WO(3)-nanoparticle-doped silica spheres displayed an interesting photovoltaic property, which is favorable for the funtionalization of these nanomaterials.

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.

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.

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.

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.

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.

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

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.

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.

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

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.

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.

Synthesis and characterization of titanium oxide supported silica materials

Science.gov (United States)

Schrijnemakers, Koen

2002-01-01

Titania-silica materials are interesting materials for use in catalysis, both as a catalyst support as well as a catalyst itself. Titania-silica materials combine the excellent support and photocatalytic properties of titania with the high thermal and mechanical stability of silica. Moreover, the interaction of titania with silica leads to new active sites, such as acid and redox sites, that are not found on the single oxides. In this Ph.D. two recently developed deposition methods were studied and evaluated for their use to create titanium oxide supported silica materials, the Chemical Surface Coating (CSC) and the Molecular Designed Dispersion (MDD). These methods were applied to two structurally different silica supports, an amorphous silica gel and the highly ordered MCM-48. Both methods are based on the specific interaction between a titanium source and the functional groups on the silica surface. With the CSC method high amounts of titanium can be obtained. However, clustering of the titania phase is observed in most cases. The MDD method allows much lower titanium amounts to be deposited without the formation of crystallites. Only at the highest Ti loading very small crystallites are formed after calcination. MCM-48 and silica gel are both pure SiO2 materials and therefore chemically similar to each other. However, they possess a different morphology and are synthesized in a different way. As such, some authors have reported that the MCM-48 surface would be more reactive than the surface of silica gel. In our experiments however no differences could be observed that confirmed this hypothesis. In the CSC method, the same reactions were observed and similar amounts of Ti and Cl were deposited. In the case of the MDD method, no difference in the reaction mechanism was observed. However, due to the lower thermal and hydrothermal stability of the MCM-48 structure compared to silica gel, partial incorporation of Ti atoms in the pore walls of MCM-48 took place

Influence of tungsten on the carbon nanotubes growth by CVD process

Energy Technology Data Exchange (ETDEWEB)

Escobar, Mariano [Instituto de Fisicoquimica de Materiales, Ambiente y Energia, CONICET-UBA, Pabellon II, Ciudad Universitaria (1428) Bs As (Argentina); LP and MC, Dep. De Fisica, FCEyN-UBA, Pabellon 1, Ciudad Universitaria (1428) Bs As (Argentina)], E-mail: mescobar@qi.fcen.uba.ar; Rubiolo, Gerardo H. [LP and MC, Dep. De Fisica, FCEyN-UBA, Pabellon 1, Ciudad Universitaria (1428) Bs As (Argentina); Unidad de Actividad Materiales, CNEA, Av. Gral. Paz 1499, San Martin (1650), Bs As (Argentina); Moreno, M. Sergio [Centro Atomico Bariloche, (8400) S.C. de Bariloche, Rio Negro (Argentina); Goyanes, Silvia [LP and MC, Dep. De Fisica, FCEyN-UBA, Pabellon 1, Ciudad Universitaria (1428) Bs As (Argentina); Candal, Roberto [Instituto de Fisicoquimica de Materiales, Ambiente y Energia, CONICET-UBA, Pabellon II, Ciudad Universitaria (1428) Bs As (Argentina)

2009-06-24

The effect of tungsten (W) on the growth of multi-walled carbon nanotubes (MWNTs) using the chemical vapour deposition (CVD) process over a metal Fe-W catalyst incorporated into a silica matrix is reported. A W molar content in Fe/SiO{sub 2} up to 10% was studied. The incorporation of only 2% of W substantially modifies the crystalline phases and the crystalline degree of the catalyst during the MWNTs synthesis. This fact seems to have a strong influence on the type and yield of the carbonaceous species obtained by the CVD of acetylene, at 600 deg. C and 180 Torr, over each catalyst. Tungsten interacts with iron within the matrix, diminishing the catalytic activity of the metal nanoparticles, and both, carbon nanotubes and carbon nanofibers, are obtained when tungsten is present. The results obtained support the hypothesis of a base growth model for carbon nanotubes indicating a strong interaction between silica matrix and Fe/W nanoparticles, independently of the content of W.

Influence of tungsten on the carbon nanotubes growth by CVD process

International Nuclear Information System (INIS)

Escobar, Mariano; Rubiolo, Gerardo H.; Moreno, M. Sergio; Goyanes, Silvia; Candal, Roberto

2009-01-01

The effect of tungsten (W) on the growth of multi-walled carbon nanotubes (MWNTs) using the chemical vapour deposition (CVD) process over a metal Fe-W catalyst incorporated into a silica matrix is reported. A W molar content in Fe/SiO 2 up to 10% was studied. The incorporation of only 2% of W substantially modifies the crystalline phases and the crystalline degree of the catalyst during the MWNTs synthesis. This fact seems to have a strong influence on the type and yield of the carbonaceous species obtained by the CVD of acetylene, at 600 deg. C and 180 Torr, over each catalyst. Tungsten interacts with iron within the matrix, diminishing the catalytic activity of the metal nanoparticles, and both, carbon nanotubes and carbon nanofibers, are obtained when tungsten is present. The results obtained support the hypothesis of a base growth model for carbon nanotubes indicating a strong interaction between silica matrix and Fe/W nanoparticles, independently of the content of W.

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.

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

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.

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.

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.

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.

Synthesis of uniform carbon at silica nanocables and luminescent silica nanotubes with well controlled inner diameters

International Nuclear Information System (INIS)

Qian Haisheng; Yu Shuhong; Ren Lei; Yang Yipeng; Zhang Wei

2006-01-01

Uniform carbon at silica nanocables and silica nanotubes with well-controlled inner diameters can be synthesized in an easy way by a sacrificial templating method. This was performed using carbon nanofibres as hard templates that were synthesized previously by a hydrothermal carbonization process. Silica nanotubes with well-controlled inner diameters were synthesized from carbon at silica core-shell nanostructures by removal of the core carbon component. The inner diameters of the as-prepared silica nanotubes can be well controlled from several nanometres to hundreds of nanometres by adjusting the diameters of the carbon nanofibres. The silica nanotubes synthesized by this method display strong photoluminescence in ultraviolet at room temperature. Such uniform silica nanotubes might find potential applications in many fields such as encapsulation, catalysis, chemical/biological separation, and sensing

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.

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.

Aminopropyl-Silica Hybrid Particles as Supports for Humic Acids Immobilization

Directory of Open Access Journals (Sweden)

Mónika Sándor

2016-01-01

Full Text Available A series of aminopropyl-functionalized silica nanoparticles were prepared through a basic two step sol-gel process in water. Prior to being aminopropyl-functionalized, silica particles with an average diameter of 549 nm were prepared from tetraethyl orthosilicate (TEOS, using a Stöber method. In a second step, aminopropyl-silica particles were prepared by silanization with 3-aminopropyltriethoxysilane (APTES, added drop by drop to the sol-gel mixture. The synthesized amino-functionalized silica particles are intended to be used as supports for immobilization of humic acids (HA, through electrostatic bonds. Furthermore, by inserting beside APTES, unhydrolysable mono-, di- or trifunctional alkylsilanes (methyltriethoxy silane (MeTES, trimethylethoxysilane (Me3ES, diethoxydimethylsilane (Me2DES and 1,2-bis(triethoxysilylethane (BETES onto silica particles surface, the spacing of the free amino groups was intended in order to facilitate their interaction with HA large molecules. Two sorts of HA were used for evaluating the immobilization capacity of the novel aminosilane supports. The results proved the efficient functionalization of silica nanoparticles with amino groups and showed that the immobilization of the two tested types of humic acid substances was well achieved for all the TEOS/APTES = 20/1 (molar ratio silica hybrids having or not having the amino functions spaced by alkyl groups. It was shown that the density of aminopropyl functions is low enough at this low APTES fraction and do not require a further spacing by alkyl groups. Moreover, all the hybrids having negative zeta potential values exhibited low interaction with HA molecules.

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.

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

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.

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).

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.

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.

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

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

Well-Dispersed Nanoscale Zero-Valent Iron Supported in Macroporous Silica Foams: Synthesis, Characterization, and Performance in Cr(VI Removal

Directory of Open Access Journals (Sweden)

Chaoxia Zhao

2017-01-01

Full Text Available Well-dispersed nanoscale zero-valent iron (NZVI supported inside the pores of macroporous silica foams (MOSF composites (Mx-NZVI has been prepared as the Cr(VI adsorbent by simply impregnating the MOSF matrix with ferric chloride, followed by the chemical reduction with NaHB4 in aqueous solution at ambient atmosphere. Through the support of MOSF, the reactivity and stability of NZVI are greatly improved. Transmission electron microscopy (TEM results show that NZVI particles are spatially well-dispersed with a typical core-shell structure and supported inside MOSF matrix. The N2 adsorption-desorption isotherms demonstrate that the Mx-NZVI composites can maintain the macroporous structure of MOSF and exhibit a considerable high surface area (503 m2·g−1. X-ray photoelectron spectroscopy (XPS and powder X-ray diffraction (XRD measurements confirm the core-shell structure of iron nanoparticles composed of a metallic Fe0 core and an Fe(II/Fe(III species shell. Batch experiments reveal that the removal efficiency of Cr(VI can reach 100% when the solution contains 15.0 mg·L−1 of Cr(VI at room temperature. In addition, the solution pH and the composites dosage can affect the removal efficiency of Cr(VI. The Langmuir isotherm is applicable to describe the removal process. The kinetic studies demonstrate that the removal of Cr(VI is consistent with pseudo-second-order kinetic model.

Preparation of Mesoporous Silica-Supported Palladium Catalysts for Biofuel Upgrade

Directory of Open Access Journals (Sweden)

Ling Fei

2012-01-01

Full Text Available We report the preparation of two hydrocracking catalysts Pd/CoMoO4/silica and Pd/CNTs/CoMoO4/silica (CNTs, carbon nanotubes. The structure, morphologies, composition, and thermal stability of catalysts were studied by X-ray diffraction (XRD, scanning electron microscopy (SEM, Raman spectroscopy, transmission electron microscopy (TEM, energy-dispersive X-ray (EDX, and thermogravimetric analysis (TGA. The catalyst activity was measured in a Parr reactor with camelina fatty acid methyl esters (FAMEs as the feed. The analysis shows that the palladium nanoparticles have been incorporated onto mesoporous silica in Pd/CoMoO4/silica or on the CNTs surface in Pd/CNTs/CoMoO4/silica catalysts. The different combinations of metals and supports have selective control cracking on heavy hydrocarbons.

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

Simple preparation of tungsten supported carbon nanoreactors for specific applications: Adsorption, catalysis and electrochemical activity

Energy Technology Data Exchange (ETDEWEB)

Mayani, Vishal J.; Mayani, Suranjana V.; Kim, Sang Wook, E-mail: swkim@dongguk.ac.kr

2015-08-01

Graphical abstract: - Highlights: • Tungsten carbon composites have shown great recognition in catalysis and electrochemistry. • W-carbon composites are prepared by template replication and W-doping on carbon cage. • Nanocomposites offer enormous assurance as adsorbent, electrode and heterogeneous catalyst. - Abstract: Porous carbon supported tungsten carbide nanoreactors, two sizes (∼25 and 170 nm), were designed using economical petroleum pitch residue followed by tungsten (W) doping. X-ray diffractions showed both carbon tungsten composites (CTC-25 and CTC-170) contained tungsten subcarbide (W{sub 2}C) and monocarbide (WC) as the major and minor crystalline phases, respectively. The present study provides a multiple perspective of carbon tungsten composites (CTCs) for methanol oxidation (as an electrode), adsorption (as an adsorbent) and degradation (as a solid catalyst) of methylene blue (MB). The operational electrodes were designed from both CTCs and used as a catalyst in an electrocatalysis process. The electrocatalysts exhibited high and stable catalytic performance (CTCE-25 > CTCE-170) in methanol electro-oxidation. The newly synthesized W-doped carbon nanoreactors were used successfully as an adsorbent for MB and a heterogeneous catalyst for MB oxidation. Ordered CTC-25 and CTC-170 exhibited dynamic MB adsorption within 15 min and complete oxidation of MB in 25–40 min. A synergetic effect between tungsten carbide and the carbon cage framework was noted.

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

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.

Mass transport in thin supported silica membranes

NARCIS (Netherlands)

Benes, Nieck Edwin

2000-01-01

In this thesis multi-component mass transport in thin supported amorphous silica membranes is discussed. These membranes are micro-porous, with pore diameters smaller than 4Å and show high fluxes for small molecules (such as hydrogen) combined with high selectivities for these molecules with respect

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.

Sol-gel synthesis of iron catalysers supported on silica and titanium for selectively oxidising methane to formaldehyde

Directory of Open Access Journals (Sweden)

Carlos Alberto Guerrero Fajardo

2008-01-01

Full Text Available Iron materials supported on silica were prepared by the sol-gel method for evaluating catalytic activity in selective o-xidation of methane to formaldehyde. Four catalysts were prepared, one corresponding to the silica support (catalyst 1S, another to the titanium support (catalyst 1T and two more having 0.5% weight iron loads, one for the silica su-pport (catalyst 2FS and the last one the titanium support (catalyst 2FT. The higher BET areas were 659 and 850 m2/g for catalysts 1S and 2FS, respectively while catalysts 1T and 2FT displayed areas of 65 and 54 m2/g, respec-tively. Scanning and transmission electronic microscopy displayed an amorphous structure in the silica-supported materials while titanium-supported materials displayed dense materials having defined structure. X-ray diffraction confirmed the silica’s amorphous structure in 1S and 2FS catalysts and displayed the 1T and 2FT catalysts’ anatase structure. The programmed temperature reduction for the 1S and 2FS catalysts did not display reducible species, while displaying hydrogen consumption peaks related to Fe3O4 reduction to α-Fe via FexO route for 1T and 2FT ca-talysts. The electronic spectroscopy X-ray photo confirmed the Fe(III specie as having 710.6 e.V binding energy for both 2FS and 2FT catalysts. Catalytic activity was carried out at atmospheric pressure in a quartz reactor, reaction mixture as CH4/O2/N2 =7.5/1/4 at 400-800°C temperature range. The reaction products were analysed by gas chromatography on Hayesep R and T columns using 5Å molecular screening. The best response for selective oxida-tion of methane to formaldehyde was displayed by the 2FS catalyst with 3.4% mol methane conversion at 650°C, 11.9% mol formaldehyde selectivity and 0.0211 g HCHO/Kg catalyst yield.

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.

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

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.

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.

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)

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.).

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),

Thermal and electrochemical stability of tungsten carbide catalyst supports

Energy Technology Data Exchange (ETDEWEB)

Chhina, H. [Ballard Power Systems, 9000 Glenlyon Parkway, Burnaby, BC (Canada); Department of Materials Engineering, University of British Columbia, Vancouver, BC (Canada); Campbell, S. [Ballard Power Systems, 9000 Glenlyon Parkway, Burnaby, BC (Canada); Kesler, O. [Department of Mechanical Engineering, University of British Columbia, Vancouver, BC (Canada)

2007-02-10

The thermal and electrochemical stability of tungsten carbide (WC), with and without a catalyst dispersed on it, have been investigated to evaluate the potential suitability of the material as an oxidation-resistant catalyst support. Standard techniques currently used to disperse Pt on carbon could not be used to disperse Pt on WC, so an alternative method was developed and used to disperse Pt on both commercially available WC and on carbon for comparison of stability. Electrochemical testing was performed by applying oxidation cycles between +0.6 V and +1.8 V to the support-catalyst material combinations and monitoring the activity of the supported catalyst over 100 oxidation cycles. Comparisons of activity change with cumulative oxidation cycles were made between C and WC supports with comparable loadings of catalyst by weight, solid volume, and powder volume. WC was found to be more thermally and electrochemically stable than currently used carbon support material Vulcan XC-72R. However, further optimization of the particle sizes and dispersion of Pt/WC catalyst/support materials and of comparison standards between new candidate materials and existing carbon-based supports are required. (author)

Nitriles at Silica Interfaces Resemble Supported Lipid Bilayers.

Science.gov (United States)

Berne, Bruce J; Fourkas, John T; Walker, Robert A; Weeks, John D

2016-09-20

Nitriles are important solvents not just for bulk reactions but also for interfacial processes such as separations, heterogeneous catalysis, and electrochemistry. Although nitriles have a polar end and a lipophilic end, the cyano group is not hydrophilic enough for these substances to be thought of as prototypical amphiphiles. This picture is now changing, as research is revealing that at a silica surface nitriles can organize into structures that, in many ways, resemble lipid bilayers. This unexpected organization may be a key component of unique interfacial behavior of nitriles that make them the solvents of choice for so many applications. The first hints of this lipid-bilayer-like (LBL) organization of nitriles at silica interfaces came from optical Kerr effect (OKE) experiments on liquid acetonitrile confined in the pores of sol-gel glasses. The orientational dynamics revealed by OKE spectroscopy suggested that the confined liquid is composed of a relatively immobile sublayer of molecules that accept hydrogen bonds from the surface silanol groups and an interdigitated, antiparallel layer that is capable of exchanging into the centers of the pores. This picture of acetonitrile has been borne out by molecular dynamics simulations and vibrational sum-frequency generation (VSFG) experiments. Remarkably, these simulations further indicate that the LBL organization is repeated with increasing disorder at least 20 Å into the liquid from a flat silica surface. Simulations and VSFG and OKE experiments indicate that extending the alkyl chain to an ethyl group leads to the formation of even more tightly packed LBL organization featuring entangled alkyl tails. When the alkyl portion of the molecule is a bulky t-butyl group, packing constraints prevent well-ordered LBL organization of the liquid. In each case, the surface-induced organization of the liquid is reflected in its interfacial dynamics. Acetonitrile/water mixtures are favored solvent systems for separations

Advanced Electrochemical Machining (ECM) for tungsten surface micro-structuring in blanket applications

International Nuclear Information System (INIS)

Holstein, Nils; Krauss, Wolfgang; Konys, Jürgen; Heuer, Simon; Weber, Thomas

2016-01-01

Highlights: • Electrochemical Machining is an appropriate tool for tungsten shaping. • Progress in shaping achieved by combination of ECM with advanced micro-lithography. • Application in First Wall for connection of plasma facing material to breeder blanket. • Successful development of adhesion promotors by ECM for plasma spraying interlayers. • Microstructure electrochemical manufacturing of tungsten in sizes of 100 μm achieved. - Abstract: Plasma facing components for fusion applications must have to exhibit long-term stability under extreme physical conditions, and therefore any material imperfections caused by mechanical and/or thermal stresses in the shaping processes cannot be tolerated due to a high risk of possible technical failures under fusion conditions. To avoid such defects, the method of Electrochemical Machining (ECM) enables a complete defect-free processing of removal of tungsten material during the desired shaping, also for high penetration depths. Furthermore, supported by lithographic mask pretreatment, three-dimensional distinct geometric structures can be positive-imaged via the directional galvanic dissolution applying M-ECM process into the tungsten bulk material. New required applications for tungsten components, e.g. as adhesion promotors in W-surfaces to enable sure grip and bonding of thick plasma-spraying layers for blanket components, will define the way of further miniaturization of well-established millimeter dimensioned M-ECM shaping processes to dimensions of 100 μm and furthermore down to 50 μm. Besides current M-ECM limits the article describes inevitable needs of further developments for mask resists, mask materials and the resulting ECM parameters, to reach the needed accuracy in tungsten microstructure. The achieved progress and observed correlations of processing parameters will be manifested by produced demonstrators made by the new “μM”-ECM process.

Advanced Electrochemical Machining (ECM) for tungsten surface micro-structuring in blanket applications

Energy Technology Data Exchange (ETDEWEB)

Holstein, Nils, E-mail: nils.holstein@kit.edu [Karlsruhe Institute of Technology, Hermann-von-Helmholtz-Platz 1, D-76344 Eggenstein-Leopoldshafen, Baden-Württemberg (Germany); Krauss, Wolfgang; Konys, Jürgen [Karlsruhe Institute of Technology, Hermann-von-Helmholtz-Platz 1, D-76344 Eggenstein-Leopoldshafen, Baden-Württemberg (Germany); Heuer, Simon; Weber, Thomas [Research Center Jülich, Institute of Energy- and Climate Research – Plasma Physics (IEK-4), D-52425 Jülich (Germany)

2016-11-01

Highlights: • Electrochemical Machining is an appropriate tool for tungsten shaping. • Progress in shaping achieved by combination of ECM with advanced micro-lithography. • Application in First Wall for connection of plasma facing material to breeder blanket. • Successful development of adhesion promotors by ECM for plasma spraying interlayers. • Microstructure electrochemical manufacturing of tungsten in sizes of 100 μm achieved. - Abstract: Plasma facing components for fusion applications must have to exhibit long-term stability under extreme physical conditions, and therefore any material imperfections caused by mechanical and/or thermal stresses in the shaping processes cannot be tolerated due to a high risk of possible technical failures under fusion conditions. To avoid such defects, the method of Electrochemical Machining (ECM) enables a complete defect-free processing of removal of tungsten material during the desired shaping, also for high penetration depths. Furthermore, supported by lithographic mask pretreatment, three-dimensional distinct geometric structures can be positive-imaged via the directional galvanic dissolution applying M-ECM process into the tungsten bulk material. New required applications for tungsten components, e.g. as adhesion promotors in W-surfaces to enable sure grip and bonding of thick plasma-spraying layers for blanket components, will define the way of further miniaturization of well-established millimeter dimensioned M-ECM shaping processes to dimensions of 100 μm and furthermore down to 50 μm. Besides current M-ECM limits the article describes inevitable needs of further developments for mask resists, mask materials and the resulting ECM parameters, to reach the needed accuracy in tungsten microstructure. The achieved progress and observed correlations of processing parameters will be manifested by produced demonstrators made by the new “μM”-ECM process.

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.

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.

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.

Sol-gel synthesis of iron catalysers supported on silica and titanium for selectively oxidising methane to formaldehyde

OpenAIRE

Carlos Alberto Guerrero Fajardo; Francisco José Sánchez Castellanos; Anne Cécile Roger; Claire Courson

2010-01-01

Iron materials supported on silica were prepared by the sol-gel method for evaluating catalytic activity in selective o-xidation of methane to formaldehyde. Four catalysts were prepared, one corresponding to the silica support (catalyst 1S), another to the titanium support (catalyst 1T) and two more having 0.5% weight iron loads, one for the silica su-pport (catalyst 2FS) and the last one the titanium support (catalyst 2FT). The higher BET areas were 659 and 850 m2/g for catalysts 1S and 2FS,...

Effects of Cu over Pd based catalysts supported on silica or niobia

Directory of Open Access Journals (Sweden)

Roma M.N.S.C.

2000-01-01

Full Text Available Palladium and palladium-copper catalysts supported on silica and niobia were characterized by H2 chemisorption and H2-O2 titration. Systems over silica were also analyzed by transmission electron microscopy and EXAFS. The metallic dispersion decreased from 20% to 7% when the content of Pd was increased from 0.5wt.-% to 3wt.-% in monometallic catalysts. The addition of 3 wt.-% Cu to obtain Pd-Cu catalysts caused a remarkable capacity loss of hydrogen chemisorption. TPR analysis suggested an interaction between the two metals and EXAFS characterization of the catalyst supported on silica confirmed the formation of Pd-Cu alloy. Pd/Nb2O5 catalysts showed turnover numbers higher than those obtained with the Pd/SiO2 systems in the cyclohexane dehydrogenation. However, the bimetallic catalysts showed very low turnover numbers.

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)

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

Health hazards due to the inhalation of amorphous silica

Energy Technology Data Exchange (ETDEWEB)

Merget, R.; Bruening, T. [Research Institute for Occupational Medicine (BGFA), Bochum (Germany); Bauer, T. [Bergmannsheil, University Hospital, Department of Internal Medicine, Division of Pneumonology, Allergology and Sleep Medicine, Bochum (Germany); Kuepper, H.U.; Breitstadt, R. [Degussa-Huels Corp., Wesseling (Germany); Philippou, S. [Department of Pathology, Augusta Krankenanstalten, Bochum (Germany); Bauer, H.D. [Research Institute for Hazardous Substances (IGF), Bochum (Germany)

2002-01-01

Occupational exposure to crystalline silica dust is associated with an increased risk for pulmonary diseases such as silicosis, tuberculosis, chronic bronchitis, chronic obstructive pulmonary disease (COPD) and lung cancer. This review summarizes the current knowledge about the health effects of amorphous (non-crystalline) forms of silica. The major problem in the assessment of health effects of amorphous silica is its contamination with crystalline silica. This applies particularly to well-documented pneumoconiosis among diatomaceous earth workers. Intentionally manufactured synthetic amorphous silicas are without contamination of crystalline silica. These synthetic forms may be classified as (1) wet process silica, (2) pyrogenic (''thermal'' or ''fumed'') silica, and (3) chemically or physically modified silica. According to the different physico-chemical properties, the major classes of synthetic amorphous silica are used in a variety of products, e.g. as fillers in the rubber industry, in tyre compounds, as free-flow and anti-caking agents in powder materials, and as liquid carriers, particularly in the manufacture of animal feed and agrochemicals; other uses are found in toothpaste additives, paints, silicon rubber, insulation material, liquid systems in coatings, adhesives, printing inks, plastisol car undercoats, and cosmetics. Animal inhalation studies with intentionally manufactured synthetic amorphous silica showed at least partially reversible inflammation, granuloma formation and emphysema, but no progressive fibrosis of the lungs. Epidemiological studies do not support the hypothesis that amorphous silicas have any relevant potential to induce fibrosis in workers with high occupational exposure to these substances, although one study disclosed four cases with silicosis among subjects exposed to apparently non-contaminated amorphous silica. Since the data have been limited, a risk of chronic bronchitis, COPD or

Health hazards due to the inhalation of amorphous silica

International Nuclear Information System (INIS)

Merget, R.; Bruening, T.; Bauer, T.; Kuepper, H.U.; Breitstadt, R.; Philippou, S.; Bauer, H.D.

2002-01-01

Occupational exposure to crystalline silica dust is associated with an increased risk for pulmonary diseases such as silicosis, tuberculosis, chronic bronchitis, chronic obstructive pulmonary disease (COPD) and lung cancer. This review summarizes the current knowledge about the health effects of amorphous (non-crystalline) forms of silica. The major problem in the assessment of health effects of amorphous silica is its contamination with crystalline silica. This applies particularly to well-documented pneumoconiosis among diatomaceous earth workers. Intentionally manufactured synthetic amorphous silicas are without contamination of crystalline silica. These synthetic forms may be classified as (1) wet process silica, (2) pyrogenic (''thermal'' or ''fumed'') silica, and (3) chemically or physically modified silica. According to the different physico-chemical properties, the major classes of synthetic amorphous silica are used in a variety of products, e.g. as fillers in the rubber industry, in tyre compounds, as free-flow and anti-caking agents in powder materials, and as liquid carriers, particularly in the manufacture of animal feed and agrochemicals; other uses are found in toothpaste additives, paints, silicon rubber, insulation material, liquid systems in coatings, adhesives, printing inks, plastisol car undercoats, and cosmetics. Animal inhalation studies with intentionally manufactured synthetic amorphous silica showed at least partially reversible inflammation, granuloma formation and emphysema, but no progressive fibrosis of the lungs. Epidemiological studies do not support the hypothesis that amorphous silicas have any relevant potential to induce fibrosis in workers with high occupational exposure to these substances, although one study disclosed four cases with silicosis among subjects exposed to apparently non-contaminated amorphous silica. Since the data have been limited, a risk of chronic bronchitis, COPD or emphysema cannot be excluded. There is no

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

Fabrication of silica ceramic membrane via sol-gel dip-coating method at different nitric acid amount

Science.gov (United States)

Kahlib, N. A. Z.; Daud, F. D. M.; Mel, M.; Hairin, A. L. N.; Azhar, A. Z. A.; Hassan, N. A.

2018-01-01

Fabrication of silica ceramics via the sol-gel method has offered more advantages over other methods in the fabrication of ceramic membrane, such as simple operation, high purity homogeneous, well defined-structure and complex shapes of end products. This work presents the fabrication of silica ceramic membrane via sol-gel dip-coating methods by varying nitric acid amount. The nitric acid plays an important role as catalyst in fabrication reaction which involved hydrolysis and condensation process. The tubular ceramic support, used as the substrate, was dipped into the sol of Tetrethylorthosilicate (TEOS), distilled water and ethanol with the addition of nitric acid. The fabricated silica membrane was then characterized by (Field Emission Scanning Electron Microscope) FESEM and (Fourier transform infrared spectroscopy) FTIR to determine structural and chemical properties at different amount of acids. From the XRD analysis, the fabricated silica ceramic membrane showed the existence of silicate hydrate in the final product. FESEM images indicated that the silica ceramic membrane has been deposited on the tubular ceramic support as a substrate and penetrate into the pore walls. The intensity peak of FTIR decreased with increasing of amount of acids. Hence, the 8 ml of acid has demonstrated the appropriate amount of catalyst in fabricating good physical and chemical characteristic of silica ceramic membrane.

Constrained Geometry Organotitanium Catalysts Supported on Nanosized Silica for Ethylene (co)Polymerization.

Science.gov (United States)

Li, Kuo-Tseng; Wu, Ling-Huey

2017-05-05

Supported olefin polymerization catalysts can prevent reactor-fouling problems and produce uniform polymer particles. Constrained geometry complexes (CGCs) have less sterically hindered active sites than bis-cyclopentadienyl metallocene catalysts. In the literature, micrometer-sized silica particles were used for supporting CGC catalysts, which might have strong mass transfer limitations. This study aims to improve the activity of supported CGC catalysts by using nanometer-sized silica. Ti[(C₅Me₄)SiMe₂(N t Bu)]Cl₂, a "constrained-geometry" titanium catalyst, was supported on MAO-treated silicas (nano-sized and micro-sized) by an impregnation method. Ethylene homo-polymerization and co-polymerization with 1-octene were carried out in a temperature range of 80-120 °C using toluene as the solvent. Catalysts prepared and polymers produced were characterized. For both catalysts and for both reactions, the maximum activities occurred at 100 °C, which is significantly higher than that (60 °C) reported before for supported bis-cyclopentadienyl metallocene catalysts containing zirconium, and is lower than that (≥140 °C) used for unsupported Ti[(C₅Me₄)SiMe₂(N t Bu)]Me₂ catalyst. Activities of nano-sized catalyst were 2.6 and 1.6 times those of micro-sized catalyst for homopolymerization and copolymerization, respectively. The former produced polymers with higher crystallinity and melting point than the latter. In addition, copolymer produced with nanosized catalyst contained more 1-octene than that produced with microsized catalyst.

Monodisperse metal nanoparticle catalysts on silica mesoporous supports: synthesis, characterizations, and catalytic reactions

Energy Technology Data Exchange (ETDEWEB)

Somorjai, G.A.

2009-09-14

The design of high performance catalyst achieving near 100% product selectivity at maximum activity is one of the most important goals in the modern catalytic science research. To this end, the preparation of model catalysts whose catalytic performances can be predicted in a systematic and rational manner is of significant importance, which thereby allows understanding of the molecular ingredients affecting the catalytic performances. We have designed novel 3-dimensional (3D) high surface area model catalysts by the integration of colloidal metal nanoparticles and mesoporous silica supports. Monodisperse colloidal metal NPs with controllable size and shape were synthesized using dendrimers, polymers, or surfactants as the surface stabilizers. The size of Pt, and Rh nanoparticles can be varied from sub 1 nm to 15 nm, while the shape of Pt can be controlled to cube, cuboctahedron, and octahedron. The 3D model catalysts were generated by the incorporation of metal nanoparticles into the pores of mesoporous silica supports via two methods: capillary inclusion (CI) and nanoparticle encapsulation (NE). The former method relies on the sonication-induced inclusion of metal nanoparticles into the pores of mesoporous silica, whereas the latter is performed by the encapsulation of metal nanoparticles during the hydrothermal synthesis of mesoporous silica. The 3D model catalysts were comprehensively characterized by a variety of physical and chemical methods. These catalysts were found to show structure sensitivity in hydrocarbon conversion reactions. The Pt NPs supported on mesoporous SBA-15 silica (Pt/SBA-15) displayed significant particle size sensitivity in ethane hydrogenolysis over the size range of 1-7 nm. The Pt/SBA-15 catalysts also exhibited particle size dependent product selectivity in cyclohexene hydrogenation, crotonaldehyde hydrogenation, and pyrrole hydrogenation. The Rh loaded SBA-15 silica catalyst showed structure sensitivity in CO oxidation reaction. In

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

Tungsten carbide/porous carbon composite as superior support for platinum catalyst toward methanol electro-oxidation

International Nuclear Information System (INIS)

Jiang, Liming; Fu, Honggang; Wang, Lei; Mu, Guang; Jiang, Baojiang; Zhou, Wei; Wang, Ruihong

2014-01-01

Graphical abstract: The WC nanoparticles are well dispersed in the carbon matrix. The size of WC nanoparticles is about 30 nm. It can be concluded that tungsten carbide and carbon composite was successfully prepared by the present synthesis conditions. - Highlights: • The WC/PC composite with high specific surface area was prepared by a simple way. • The Pt/WC/PC catalyst has superior performance toward methanol electro-oxidation. • The current density for methanol electro-oxidation is as high as 595.93 A g −1 Pt. • The Pt/WC/PC catalyst shows better durability and stronger CO electro-oxidation. • The performance of Pt/WC/PC is superior to the commercial Pt/C (JM) catalyst. - Abstract: Tungsten carbide/porous carbon (WC/PC) composites have been successfully synthesized through a surfactant assisted evaporation-induced-assembly method, followed by a thermal treatment process. In particular, WC/PC-35-1000 composite with tungsten content of 35% synthesized at the carbonized temperature of 1000 °C, exhibited a specific surface area (S BET ) of 457.92 m 2 g −1 . After loading Pt nanoparticles (NPs), the obtained Pt/WC/PC-35-1000 catalyst exhibits the highest unit mass electroactivity (595.93 A g −1 Pt) toward methanol electro-oxidation, which is about 2.6 times as that of the commercial Pt/C (JM) catalyst. Furthermore, the Pt/WC/PC-35-1000 catalyst displays much stronger resistance to CO poisoning and better durability toward methanol electrooxidation compared with the commercial Pt/C (JM) catalyst. The high electrocatalytic activity, strong poison-resistivity and good stability of Pt/WC/PC-35-1000 catalyst are attributed to the porous structures and high specific surface area of WC/PC support could facilitate the rapid mass transportation. Moreover, synergistic effect between WC and Pt NPs is favorable to the higher catalytic performance

Wettability of modified silica layers deposited on glass support activated by plasma

Energy Technology Data Exchange (ETDEWEB)

Terpiłowski, Konrad, E-mail: terpil@umcs.pl [Department of Physical Chemistry – Interfacial Phenomena, Faculty of Chemistry, Maria Curie-Sklodowska University, Lublin (Poland); Rymuszka, Diana [Department of Physical Chemistry – Interfacial Phenomena, Faculty of Chemistry, Maria Curie-Sklodowska University, Lublin (Poland); Goncharuk, Olena V.; Sulym, Iryna Ya.; Gun’ko, Vladimir M. [Chuiko Institute of Surface Chemistry, National Academy of Science of Ukraine, Kiev (Ukraine)

2015-10-30

Highlights: • New modified silica materials synthesis. • Support surface plasma activation. • Apparent surface free energy determination. • Equilibrium contact angle calculation. - Abstract: Fumed silica modified by hexamethyldisilazane [HDMS] and polydimethylsiloxane [PDMS] was dispersed in a polystyrene/chloroform solution. To increase adhesion between deposited silica layers and a glass surface, the latter was pretreated with air plasma for 30 s. The silica/polystyrene dispersion was deposited on the glass support using a spin coater. After deposition, the plates were dried in a desiccator for 24 h. Water advancing and receding contact angles were measured using the tilted plate method. The apparent surface free energy (γ{sub S}) was evaluated using the contact angle hysteresis approach. The surface topography was determined using the optical profilometry method. Contact angles changed from 59.7° ± 4.4 (at surface coverage with trimethylsilyl groups Θ = 0.14) to 155° ± 3.1 at Θ = 1. The value of γ{sub S} decreased from 51.3 ± 2.8 mJ/m{sup 2} (for the sample at the lowest value of Θ) to 1.0 ± 0.4 mJ/m{sup 2} for the most hydrophobic sample. Thus, some systems with a high degree of modification by HDMS showed superhydrophobicity, and the sliding angle amounted to about 16° ± 2.1.

High surface area synthesis, electrochemical activity, and stability of tungsten carbide supported Pt during oxygen reduction in proton exchange membrane fuel cells

Science.gov (United States)

Chhina, H.; Campbell, S.; Kesler, O.

The oxidation of carbon catalyst supports to carbon dioxide gas leads to degradation in catalyst performance over time in proton exchange membrane fuel cells (PEMFCs). The electrochemical stability of Pt supported on tungsten carbide has been evaluated on a carbon-based gas diffusion layer (GDL) at 80 °C and compared to that of HiSpec 4000™ Pt/Vulcan XC-72R in 0.5 M H 2SO 4. Due to other electrochemical processes occurring on the GDL, detailed studies were also performed on a gold mesh substrate. The oxygen reduction reaction (ORR) activity was measured both before and after accelerated oxidation cycles between +0.6 V and +1.8 V vs. RHE. Tafel plots show that the ORR activity remained high even after accelerated oxidation tests for Pt/tungsten carbide, while the ORR activity was extremely poor after accelerated oxidation tests for HiSpec 4000™. In order to make high surface area tungsten carbide, three synthesis routes were investigated. Magnetron sputtering of tungsten on carbon was found to be the most promising route, but needs further optimization.

High surface area synthesis, electrochemical activity, and stability of tungsten carbide supported Pt during oxygen reduction in proton exchange membrane fuel cells

Energy Technology Data Exchange (ETDEWEB)

Chhina, H. [Automotive fuel cell corporation, 9000 Glenlyon Parkway, Burnaby, BC (Canada); Department of Mechanical and Industrial Engineering, 5 King' s College Road, University of Toronto, Toronto, Ontario (Canada); Campbell, S. [Automotive fuel cell corporation, 9000 Glenlyon Parkway, Burnaby, BC (Canada); Kesler, O. [Department of Mechanical and Industrial Engineering, 5 King' s College Road, University of Toronto, Toronto, Ontario (Canada)

2008-04-15

The oxidation of carbon catalyst supports to carbon dioxide gas leads to degradation in catalyst performance over time in proton exchange membrane fuel cells (PEMFCs). The electrochemical stability of Pt supported on tungsten carbide has been evaluated on a carbon-based gas diffusion layer (GDL) at 80 C and compared to that of HiSpec 4000 trademark Pt/Vulcan XC-72R in 0.5 M H{sub 2}SO{sub 4}. Due to other electrochemical processes occurring on the GDL, detailed studies were also performed on a gold mesh substrate. The oxygen reduction reaction (ORR) activity was measured both before and after accelerated oxidation cycles between +0.6 V and +1.8 V vs. RHE. Tafel plots show that the ORR activity remained high even after accelerated oxidation tests for Pt/tungsten carbide, while the ORR activity was extremely poor after accelerated oxidation tests for HiSpec 4000 trademark. In order to make high surface area tungsten carbide, three synthesis routes were investigated. Magnetron sputtering of tungsten on carbon was found to be the most promising route, but needs further optimization. (author)

Particle size effect of redox reactions for Co species supported on silica

International Nuclear Information System (INIS)

Chotiwan, Siwaruk; Tomiga, Hiroki; Katagiri, Masaki; Yamamoto, Yusaku; Yamashita, Shohei; Katayama, Misaki; Inada, Yasuhiro

2016-01-01

Conversions of chemical states during redox reactions of two silica-supported Co catalysts, which were prepared by the impregnation method, were evaluated by using an in situ XAFS technique. The addition of citric acid into the precursor solution led to the formation on silica of more homogeneous and smaller Co particles, with an average diameter of 4 nm. The supported Co 3 O 4 species were reduced to metallic Co via the divalent CoO species during a temperature-programmed reduction process. The reduced Co species were quantitatively oxidized with a temperature-programmed oxidation process. The higher observed reduction temperature of the smaller CoO particles and the lower observed oxidation temperature of the smaller metallic Co particles were induced by the higher dispersion of the Co oxide species, which apparently led to a stronger interaction with supporting silica. The redox temperature between CoO and Co 3 O 4 was found to be independent of the particle size. - Graphical abstract: Chemical state conversions of SiO 2 -supported Co species and the particle size effect have been analyzed by means of in situ XAFS technique. The small CoO particles have endurance against the reduction and exist in a wide temperature range. Display Omitted - Highlights: • The conversions of the chemical state of supported Co species during redox reaction are evaluated. • In operando XAFS technique were applied to measure redox properties of small Co particles. • A small particle size affects to the redox temperatures of cobalt catalysts.

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

Polymerization of Methyl Methacrylate with Samarocene Complex Supported on Mesoporous Silica

Institute of Scientific and Technical Information of China (English)

无

2001-01-01

Samarocene complex was supported on a series of mesoporous silica with various pore sizes. Polymerization of methyl methacrylate (MMA) by these catalysts provide highly syndiotactic PMMAs with higher molecular weights compared with those obtained by solution polymerization with homogeneous catalyst system.

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

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

Effect of Support Pretreatment Temperature on the Performance of an Iron Fischer–Tropsch Catalyst Supported on Silica-Stabilized Alumina

Directory of Open Access Journals (Sweden)

Kamyar Keyvanloo

2018-02-01

Full Text Available The effect of support material pretreatment temperature, prior to adding the active phase and promoters, on Fischer–Tropsch activity and selectivity was explored. Four iron catalysts were prepared on silica-stabilized alumina (AlSi supports pretreated at 700 °C, 900 °C, 1100 °C or 1200 °C. Addition of 5% silica to alumina made the AlSi material hydrothermally stable, which enabled the unusually high support pretreatment temperatures (>900 °C to be studied. High-temperature dehydroxylation of the AlSi before impregnation greatly reduces FeO·Al2O3 surface spinel formation by removing most of the support-surface hydroxyl groups leading to more effectively carbided catalyst. The activity increases more than four-fold for the support calcined at elevated temperatures (1100–1200 °C compared with traditional support calcination temperatures of <900 °C. This unique pretreatment also facilitates the formation of ε′-Fe2.2C rather than χ-Fe2.5C on the AlSi support, which shows an excellent correlation with catalyst productivity.

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

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...

Enhancing Pt-Ni/CeO2 performances for ethanol reforming by catalyst supporting on high surface silica

NARCIS (Netherlands)

Palma, V.; Ruocco, C; Meloni, E.; Gallucci, F.; Ricca, A.

2018-01-01

In this paper, bimetallic Pt-Ni/CeO2 catalysts supported over mesoporous silica were employed for ethanol reforming in the low-temperature range. In particular, catalyst behaviour was investigated under a H2O/C2H5OH/N2 as well as H2O/C2H5OH/AIR mixture between 300 and 600 °C at different space

Characteristics of supported nano-TiO2/ZSM-5/silica gel (SNTZS): Photocatalytic degradation of phenol

International Nuclear Information System (INIS)

Zainudin, Nor Fauziah; Abdullah, Ahmad Zuhairi; Mohamed, Abdul Rahman

2010-01-01

Photocatalytic degradation of phenol was investigated using the supported nano-TiO 2 /ZSM-5/silica gel (SNTZS) as a photocatalyst in a batch reactor. The prepared photocatalyst was characterized using XRD, TEM, FT-IR and BET surface area analysis. The synthesized photocatalyst composition was developed using nano-TiO 2 as the photoactive component and zeolite (ZSM-5) as the adsorbents, all supported on silica gel using colloidal silica gel binder. The optimum formulation of SNTZS catalyst was observed to be (nano-TiO 2 :ZSM-5:silica gel:colloidal silica gel = 1:0.6:0.6:1) which giving about 90% degradation of 50 mg/L phenol solution in 180 min. The SNTZS exhibited higher photocatalytic activity than that of the commercial Degussa P25 which only gave 67% degradation. Its high photocatalytic activity was due to its large specific surface area (275.7 m 2 /g), small particle size (8.1 nm), high crystalline quality of the synthesized catalyst and low electron-hole pairs recombination rate as ZSM-5 adsorbent was used. The SNTZS photocatalyst synthesized in this study also has been proven to have an excellent adhesion and reusability.

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.

Tungsten carbide/porous carbon composite as superior support for platinum catalyst toward methanol electro-oxidation

Energy Technology Data Exchange (ETDEWEB)

Jiang, Liming [School of Chemical Engineering and Technology, Harbin Institute of Technology, Harbin 150001 (China); Fu, Honggang, E-mail: fuhg@vip.sina.com [School of Chemical Engineering and Technology, Harbin Institute of Technology, Harbin 150001 (China); Key Laboratory of Functional Inorganic Material Chemistry, Heilongjiang University, Harbin 150080 (China); Wang, Lei; Mu, Guang; Jiang, Baojiang; Zhou, Wei; Wang, Ruihong [Key Laboratory of Functional Inorganic Material Chemistry, Heilongjiang University, Harbin 150080 (China)

2014-01-01

Graphical abstract: The WC nanoparticles are well dispersed in the carbon matrix. The size of WC nanoparticles is about 30 nm. It can be concluded that tungsten carbide and carbon composite was successfully prepared by the present synthesis conditions. - Highlights: • The WC/PC composite with high specific surface area was prepared by a simple way. • The Pt/WC/PC catalyst has superior performance toward methanol electro-oxidation. • The current density for methanol electro-oxidation is as high as 595.93 A g{sup −1} Pt. • The Pt/WC/PC catalyst shows better durability and stronger CO electro-oxidation. • The performance of Pt/WC/PC is superior to the commercial Pt/C (JM) catalyst. - Abstract: Tungsten carbide/porous carbon (WC/PC) composites have been successfully synthesized through a surfactant assisted evaporation-induced-assembly method, followed by a thermal treatment process. In particular, WC/PC-35-1000 composite with tungsten content of 35% synthesized at the carbonized temperature of 1000 °C, exhibited a specific surface area (S{sub BET}) of 457.92 m{sup 2} g{sup −1}. After loading Pt nanoparticles (NPs), the obtained Pt/WC/PC-35-1000 catalyst exhibits the highest unit mass electroactivity (595.93 A g{sup −1} Pt) toward methanol electro-oxidation, which is about 2.6 times as that of the commercial Pt/C (JM) catalyst. Furthermore, the Pt/WC/PC-35-1000 catalyst displays much stronger resistance to CO poisoning and better durability toward methanol electrooxidation compared with the commercial Pt/C (JM) catalyst. The high electrocatalytic activity, strong poison-resistivity and good stability of Pt/WC/PC-35-1000 catalyst are attributed to the porous structures and high specific surface area of WC/PC support could facilitate the rapid mass transportation. Moreover, synergistic effect between WC and Pt NPs is favorable to the higher catalytic performance.

Preparation and Properties of Nano Dy/TiO2 Films Supported on High Silica Fiber

Directory of Open Access Journals (Sweden)

HUANG Feng-ping

2017-07-01

Full Text Available In order to improve the photocatalytic degradation performance and stability of nano TiO2, Dy doped TiO2 supported on high silica glass fiber was prepared by microwave-sol method combined with dip-coating method. The samples were analyzed by XRD,SEM,PL,EDS,XPS and other equipments for phase composition of films,surface topography, surface elements and the stability of films. And the effects of pretreatment solution and coating method on the high-silica fiber film were investigated.In addition, the photocatalytic performance of the sample has been investigated by degrading methylene blue. The results show that the catalytic stability of Dy doping TiO2 nanofilms supported on high silica glass fiber can be improved and the degradation of methyl orange can reach 94% in 30min after 5 times of coating treatment.

Enhancement of Degradation and Dechlorination of Trichloroethylene via Supporting Palladium/Iron Bimetallic Nanoparticles onto Mesoporous Silica

Directory of Open Access Journals (Sweden)

Jianjun Wei

2016-07-01

Full Text Available This study is aimed to prevent the agglomeration of Pd/Fe bimetallic nanoparticles and thus improve the efficiency toward degradation and dechlorination of chlorinated organic contaminants. A mesoporous silica with a primary pore diameter of 8.3 nm and a specific surface area of 688 m2/g was prepared and used as the host of Pd/Fe nanoparticles. The Pd/Fe nanoparticles were deposited onto or into the mesoporous silica by reduction of ferrous ion and hexachloropalladate ion in aqueous phase. Batch degradation and dechlorination reactions of trichloroethylene were conducted with initial trichloroethylene concentration of 23.7 mg/L, iron loading of 203 or 1.91 × 103 mg/L and silica loading of 8.10 g/L at 25 °C. Concentration of trichloroethylene occurs on the supported Pd/Fe nanoparticles, with trichloroethylene degrading to 56% and 59% in 30 min on the supported Pd/Fe nanoparticles with weight percentage of palladium to iron at 0.075% and 0.10% respectively. The supported Pd/Fe nanoparticles exhibit better dechlorination activity. When the supported Pd/Fe nanoparticles with a weight percentage of palladium to iron of 0.10% were loaded much less than the bare counterpart, the yield of ethylene plus ethane in 10 h on them was comparable, i.e., 19% vs. 21%. This study offers a future approach to efficiently combine the reactivity of supported Pd/Fe nanoparticles and the adsorption ability of mesoporous silica.

A Robust Fiber Bragg Grating Hydrogen Gas Sensor Using Platinum-Supported Silica Catalyst Film

OpenAIRE

Marina Kurohiji; Seiji Ichiriyama; Naoki Yamasaku; Shinji Okazaki; Naoya Kasai; Yusuke Maru; Tadahito Mizutani

2018-01-01

A robust fiber Bragg grating (FBG) hydrogen gas sensor for reliable multipoint-leakage monitoring has been developed. The sensing mechanism is based on shifts of center wavelength of the reflection spectra due to temperature change caused by catalytic combustion heat. The sensitive film which consists of platinum-supported silica (Pt/SiO2) catalyst film was obtained using sol-gel method. The precursor solution was composed of hexachloroplatinic acid and commercially available silica precursor...

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.

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

SPS Fabrication of Tungsten-Rhenium Alloys in Support of NTR Fuels Development

International Nuclear Information System (INIS)

Webb, Jonathan A.; Charit, Indrajit; Sparks, Cory; Butt, Darryl P.; Frary, Megan; Carroll, Mark

2011-01-01

Tungsten metal slugs were fabricated via Spark Plasma Sintering (SPS) of powdered metals at temperatures ranging from 1575 K to 1975 K and hold times of 5 minutes to 30 minutes, using powders with an average diameter of 7.8 ?m. Sintered tungsten specimens were found to have relative densities ranging from 83 % to 94 % of the theoretical density for tungsten. Consolidated specimens were also tested for their Vickers Hardness Number (VHN), which was fitted as a function of relative density; the fully consolidated VHN was extrapolated to be 381.45 kg/mm2. Concurrently, tungsten and rhenium powders with average respective diameters of 0.5 ?m and 13.3 ?m were pre-processed either by High-Energy-Ball-Milling (HEBM) or by homogeneous mixing to yield W-25at.%Re mixtures. The powder batches were sintered at temperatures of 1975 K and 2175 K for hold times ranging from 0 minutes to 60 minutes yielding relative densities ranging from 94% to 97%. The combination of HEBM and sintering showed a significant decrease in the inter-metallic phases compared to that of the homogenous mixing and sintering.

Clean Chlorination of Silica Surfaces by a Single-site Substitution Approach

KAUST Repository

Maity, Niladri; Barman, Samir; Abou-Hamad, Edy; D'Elia, Valerio; Basset, Jean-Marie

2018-01-01

A chlorination method for the selective substitution of well-defined isolated silanol groups of the silica surface has been developed using the catalytic Appel reaction. Spectroscopic analysis, complemented by elemental microanalysis studies, reveals that a quantitative chlorination could be achieved with highly dehydroxylated silica materials that exclusively possess non-hydrogen bonded silanol groups. The employed method did not leave any carbon or phosphorous residue on the silica surface and can be regarded as a promising tool for the future functionalization of metal oxide surfaces.

Clean Chlorination of Silica Surfaces by a Single-site Substitution Approach

KAUST Repository

Maity, Niladri

2018-02-12

A chlorination method for the selective substitution of well-defined isolated silanol groups of the silica surface has been developed using the catalytic Appel reaction. Spectroscopic analysis, complemented by elemental microanalysis studies, reveals that a quantitative chlorination could be achieved with highly dehydroxylated silica materials that exclusively possess non-hydrogen bonded silanol groups. The employed method did not leave any carbon or phosphorous residue on the silica surface and can be regarded as a promising tool for the future functionalization of metal oxide surfaces.

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

Synthesis, characterization, and photocatalytic properties of core/shell mesoporous silica nanospheres supporting nanocrystalline titania

International Nuclear Information System (INIS)

Cendrowski, K.; Chen, X.; Zielinska, B.; Kalenczuk, R. J.; Rümmeli, M. H.; Büchner, B.; Klingeler, R.; Borowiak-Palen, E.

2011-01-01

The facile bulk synthesis of silica nanospheres makes them an attractive support for the transport of chemical compounds such as nanocrystalline titanium dioxide. In this contribution we present a promising route for the synthesis of mesoporous silica nanospheres (m-SiO 2 ) with diameter in range 200 nm, which are ideal supports for nanocrystalline titanium dioxide (TiO 2 ). The detailed microscopic and spectroscopic characterizations of core/shell structure (m-SiO 2 /TiO 2 ) were conducted. Moreover, the photocatalytic potential of the nanostructures was investigated via phenol decomposition and hydrogen generation. A clear enhancement of photoactivity in both reactions as compared to commercial TiO 2 -Degussa P25 catalyst is detected.

Synthesis, characterization, and photocatalytic properties of core/shell mesoporous silica nanospheres supporting nanocrystalline titania

Science.gov (United States)

Cendrowski, K.; Chen, X.; Zielinska, B.; Kalenczuk, R. J.; Rümmeli, M. H.; Büchner, B.; Klingeler, R.; Borowiak-Palen, E.

2011-11-01

The facile bulk synthesis of silica nanospheres makes them an attractive support for the transport of chemical compounds such as nanocrystalline titanium dioxide. In this contribution we present a promising route for the synthesis of mesoporous silica nanospheres (m-SiO2) with diameter in range 200 nm, which are ideal supports for nanocrystalline titanium dioxide (TiO2). The detailed microscopic and spectroscopic characterizations of core/shell structure (m-SiO2/TiO2) were conducted. Moreover, the photocatalytic potential of the nanostructures was investigated via phenol decomposition and hydrogen generation. A clear enhancement of photoactivity in both reactions as compared to commercial TiO2-Degussa P25 catalyst is detected.

Effect of Al content on the gas-phase dehydration of glycerol over silica-alumina-supported silicotungstic acid catalysts

International Nuclear Information System (INIS)

Kim, Yong Tae; You, Su Jin; Park, Eun Duck; Jung, Kwangdeog

2012-01-01

The gas-phase dehydration of glycerol to acrolein was carried out over silicotungstic acid (H 4 SiW 12 O 40 ·xH 2 O, HSiW) catalysts supported on SiO 2 , η-Al 2 O 3 , and silica-alumina with different Al contents. The HSiW catalysts supported on silica-alumina showed higher glycerol conversions and acrolein yields during the initial 2 h at 315.deg.C than did SiO 2 - and η-Al 2 O 3 -supported HSiW catalysts. Among the tested catalysts, HSiW/Si 0.9 Al 0.1Ox exhibited the highest space-time yield during the initial 2 h. The loaded HSiW species can change the acid types and suppress the formation of carbonaceous species on Al-rich silica-alumina. The deactivated HSiW supported on silica-alumina can be fully regenerated after calcination in air at 500.deg.C. As long as the molar ratio between water and glycerol was in the range of 2-11, the acrolein selectivity increased significantly with increasing water content in the feed, while the surface carbon content decreased owing to the suppression of heavy compounds

Characteristics of supported nano-TiO{sub 2}/ZSM-5/silica gel (SNTZS): Photocatalytic degradation of phenol

Energy Technology Data Exchange (ETDEWEB)

Zainudin, Nor Fauziah; Abdullah, Ahmad Zuhairi [School of Chemical Engineering, Engineering Campus, Universiti Sains Malaysia, Seri Ampangan, 14300 Nibong Tebal, Penang (Malaysia); Mohamed, Abdul Rahman, E-mail: chrahman@eng.usm.my [School of Chemical Engineering, Engineering Campus, Universiti Sains Malaysia, Seri Ampangan, 14300 Nibong Tebal, Penang (Malaysia)

2010-02-15

Photocatalytic degradation of phenol was investigated using the supported nano-TiO{sub 2}/ZSM-5/silica gel (SNTZS) as a photocatalyst in a batch reactor. The prepared photocatalyst was characterized using XRD, TEM, FT-IR and BET surface area analysis. The synthesized photocatalyst composition was developed using nano-TiO{sub 2} as the photoactive component and zeolite (ZSM-5) as the adsorbents, all supported on silica gel using colloidal silica gel binder. The optimum formulation of SNTZS catalyst was observed to be (nano-TiO{sub 2}:ZSM-5:silica gel:colloidal silica gel = 1:0.6:0.6:1) which giving about 90% degradation of 50 mg/L phenol solution in 180 min. The SNTZS exhibited higher photocatalytic activity than that of the commercial Degussa P25 which only gave 67% degradation. Its high photocatalytic activity was due to its large specific surface area (275.7 m{sup 2}/g), small particle size (8.1 nm), high crystalline quality of the synthesized catalyst and low electron-hole pairs recombination rate as ZSM-5 adsorbent was used. The SNTZS photocatalyst synthesized in this study also has been proven to have an excellent adhesion and reusability.

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.

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

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

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)

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...

Synthesis and nature of heterogeneous catalysts of low-valent tungsten supported on alumina

Energy Technology Data Exchange (ETDEWEB)

Brenner, A.; Hucul, D.A.

1980-01-01

Temperature-programed decomposition of catalysts prepared from zero-valent W(CO)/sub 6/ and alumina under rigorously air-free conditions showed a low-temperature carbon monoxide desorption peak at 110/sup 0/-172/sup 0/C, depending on alumina pretreatment, in which a relatively stable surface W(CO)/sub 3/ complex was formed; and a high-temperature carbon monoxide desorption peak at 257/sup 0/ to > 400/sup 0/C, which gave zero-valent tungsten if the ratio of hydroxyl groups of alumina to tungsten surface complexes was low, and hexavalent tungsten if the ratio was high. Up to about half the W(CO)/sub 6/ sublimated from the alumina during activation.

Ultra-large bandwidth hollow-core guiding in all-silica bragg fibers with nano-supports

DEFF Research Database (Denmark)

Vienne, Guillaume; Xu, Yong; Jakobsen, Christian

2004-01-01

We demonstrate a new class of hollow-core Bragg fibers that are composed of concentric cylindrical silica rings separated by nanoscale support bridges. We theoretically predict and experimentally observe hollow-core confinement over an octave frequency range. The bandwidth of bandgap guiding in t...... in this new class of Bragg fibers exceeds that of other hollow-core fibers reported in the literature. With only three rings of silica cladding layers, these Bragg fibers achieve propagation loss of the order of 1 dB/m....

Microporous silica membranes

DEFF Research Database (Denmark)

Boffa, Vittorio; Yue, Yuanzheng

2012-01-01

Hydrothermal stability is a crucial factor for the application of microporous silica-based membranes in industrial processes. Indeed, it is well established that steam exposure may cause densification and defect formation in microporous silica membranes, which are detrimental to both membrane...... permeability and selectivity. Numerous previous studies show that microporous transition metal doped-silica membranes are hydrothermally more stable than pure silica membranes, but less permeable. Here we present a quantitative study on the impact of type and concentration of transition metal ions...... on the microporous structure, stability and permeability of amorphous silica-based membranes, providing information on how to design chemical compositions and synthetic paths for the fabrication of silica-based membranes with a well accessible and highly stabile microporous structure....

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)

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)

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.

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.

Catalyst for disproportionation/double-bond isomerization of olefins

International Nuclear Information System (INIS)

Hughes, W.; Reusser, R.

1980-01-01

An activated calcined homogenous catalyst composition consists essentially of a support uranium and at least one of tungsten and rhenium, wherein said composition contains about 0.1 to 25 weight percent total uranium, tungsten, and rhenium, each calculated as the metal; and a weight ratio of uranium:at least one of tungsten and rhenium of about 2:1 to 1:1. The activated catalyst composition is prepared by steps which comprise forming a homogenous composite, calcining said homogenous composite in a molecular oxygen-containing atmosphere at elevated temperatures, and subsequently activating said calcined homogenous composite under reducing conditions at elevated temperatures. The catalyst composition according to claim 1 is one in which the total of uranium, tungsten, and rhenium is about 1 to 15 weight percent. The catalyst composition according to claim 2 is one in which the ratio of uranium to at least one of tungsten and rhenium is about 2:1 to 0.5:1. The catalyst composition according to claim 3 is one in which the support is alumina, silica, silica-alumina, zirconia, titania, thoria, aluminum phosphate, magnisium silicate, zinc aluminate, or mixture. The catalyst composition according to claim 4is one in which support is silica

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.

Simulation from the first principal theory on the effect of supporting silica on graphene and the new composite material

CSIR Research Space (South Africa)

Kiarii, EM

2017-07-01

Full Text Available Silica has been used as support material with many photocatalytic materials. In this study, silica polymorphs on graphene and epoxy graphene were studied using Density Functional Theory (DFT) to determine the interfacial and optical properties...

Surface morphology changes to tungsten under exposure to He ions from an electron cyclotron resonance plasma source

Science.gov (United States)

Donovan, David; Maan, Anurag; Duran, Jonah; Buchenauer, Dean; Whaley, Josh

2015-11-01

Exposure of tungsten to low energy (ALMT ITER grade tungsten samples. A similar He plasma exposure stage has now been developed at the University of Tennessee-Knoxville with an improved compact ECR plasma source. Status of the new UTK exposure stage will be discussed as well as planned experiments and new material characterization techniques (EBSD, GIXRD). Work supported by US DOE Contract DE-AC04-94AL85000 and the PSI Science Center.

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

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.

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)

Poly(2-aminothiazole)-silica nanocomposite particles: Synthesis and morphology control

Science.gov (United States)

Zou, Hua; Wu, Di; Sun, Hao; Chen, Suwu; Wang, Xia

2018-04-01

Synthesis of conducting polymer-silica colloidal nanocomposites has been recognized as an effective method to overcome the poor processability of heterocyclic conducting polymers prepared by chemical oxidative method. However, the morphology control of such conducting polymer-silica nanocomposites was seldomly reported in the literature. Novel poly(2-aminothiazole)(PAT)-silica nanocomposite particles can be conveniently prepared by chemical oxidative polymerization of 2-aminothiazole using CuCl2 oxidant in the presence of ∼20 nm silica nanoparticles. The effects of varying the oxidant/monomer ratio and silica sol concentration on the morphology and size of the resulting PAT-silica nanocmposites have been studied. Optimization of the oxidant/monomer molar ratio and initial silica sol concentration allows relatively round spherical particles of 150-350 nm in diameter to be achieved. The nanocomposite particles have a well-defined raspberry-like morphology with a silica-rich surface, but a significant fraction of PAT component still exists on the surface and, which is beneficial for its applications. Furthermore, the surface compositions of the colloidal nanocomposites could be regulated to some extent. Based on the above results, a possible formation mechanism of the spherical nanocomposite particles is proposed.

Synthesis and separation properties of an α-alumina-supported high-silica MEL membrane

NARCIS (Netherlands)

Kosinov, N.; Hensen, E.J.M.

2013-01-01

A thin high-silica MEL membrane was synthesized on a porous a-alumina hollow fiber support by a secondary growth approach. The membrane quality was evaluated by permporometry, single-gas permeation and butane isomer separation. Comparison of the pervaporation performance of MEL membranes with a MFI

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

Catalytic removal of sulfur dioxide from dibenzothiophene sulfone over Mg-Al mixed oxides supported on mesoporous silica.

Science.gov (United States)

You, Nansuk; Kim, Min Ji; Jeong, Kwang-Eun; Jeong, Soon-Yong; Park, Young-Kwon; Jeon, Jong-Ki

2010-05-01

Dibenzothiophene sulfone (DBTS), one of the products of the oxidative desulfurization of heavy oil, can be removed through extraction as well as by an adsorption process. It is necessary to utilize DBTS in conjunction with catalytic cracking. An object of the present study is to provide an Mg-Al-mesoporous silica catalyst for the removal of sulfur dioxide from DBTS. The characteristics of the Mg-Al-mesoporous silica catalyst were investigated through N2 adsorption, XRD, ICP, and XRF. An Mg-Al-mesoporous silica catalyst formulated in a direct incorporation method showed higher catalytic performance compared to pure MgO during the catalytic removal of sulfur dioxide from DBTS. The higher dispersion of Mg as well as the large surface area of the Mg-Al-mesoporous silica catalyst strongly influenced the catalyst basicity in DBTS cracking.

Design of supported bi-metallic nanoparticles based on Platinum and Palladium using Surface Organometallic Chemistry (SOMC)

KAUST Repository

Al-Shareef, Reem A.

2017-01-01

Well-defined silica supported bimetallic catalysts Pt100-x Pdx (where x is the molar ratio of Pd) are prepared by Surface Organometallic Chemistry (SOMC) via controlled decomposition of Pd2(allyl)2Cl2 on Pt/SiO2. For comparison purposes, Pt100-x Pdx

Silica gel-Supported Palladium Catalyst for the Acyl Sonogashira Reaction

Energy Technology Data Exchange (ETDEWEB)

Hossain, Shahin; Park, Jihoon; Park, Minkyu; Jin, Myungjong [Inha Univ., Incheon (Korea, Republic of)

2013-06-15

We have demonstrated an efficient and eco-friendly procedure for the synthesis of ynones using silica supported thiol-palladium complex as a recyclable catalyst under copper free mild reaction conditions. The material was synthesized by post grafting of 3-mercaptopropyltrimethoxysilane on amorphous silica and subsequently Pd(II) attached onto thiol groups. This synthetic method has notable advantages because it involves easily available, less costly and produces an easily recyclable catalyst in high yields of the products. The mild reaction conditions encouraged us to further extension for the development of novel multicomponent reactions. Thus we have explained the three component synthesis of pyrazoles in one-pot fashion with good yields. Specifically, this simple procedure for the ynone synthesis and this approach to synthesize N-containing heterocycles may be valuable tool in future. The acyl Sonogashira reaction between acyl chlorides and terminal alkynes is one of the most useful method for the preparation of ynones which are important intermediates to prepare versatile pharmaceutically and biologically active heterocyclic compounds such as pyrroles, pyrazoles, furans, furanones, isoxazoles, pyrimidines, quinolines, indolizidinones.

Silica gel-Supported Palladium Catalyst for the Acyl Sonogashira Reaction

International Nuclear Information System (INIS)

Hossain, Shahin; Park, Jihoon; Park, Minkyu; Jin, Myungjong

2013-01-01

We have demonstrated an efficient and eco-friendly procedure for the synthesis of ynones using silica supported thiol-palladium complex as a recyclable catalyst under copper free mild reaction conditions. The material was synthesized by post grafting of 3-mercaptopropyltrimethoxysilane on amorphous silica and subsequently Pd(II) attached onto thiol groups. This synthetic method has notable advantages because it involves easily available, less costly and produces an easily recyclable catalyst in high yields of the products. The mild reaction conditions encouraged us to further extension for the development of novel multicomponent reactions. Thus we have explained the three component synthesis of pyrazoles in one-pot fashion with good yields. Specifically, this simple procedure for the ynone synthesis and this approach to synthesize N-containing heterocycles may be valuable tool in future. The acyl Sonogashira reaction between acyl chlorides and terminal alkynes is one of the most useful method for the preparation of ynones which are important intermediates to prepare versatile pharmaceutically and biologically active heterocyclic compounds such as pyrroles, pyrazoles, furans, furanones, isoxazoles, pyrimidines, quinolines, indolizidinones

Stellate macroporous silica nanospheres in bio-macromolecules encapsulation and delivery

Science.gov (United States)

Chi, Hao-Hsin

This project focused on using mesoporous silica as a solid support to encapsulate enzymes for operating a highly economic, and recyclable biomass processing system. The main objective is to turn non-food biomass sources into food products. Enzymes are macromolecules with the structural backbone of proteins or ribonucleic acid sequences (RNAs) which work as catalysts in living organisms. Enzymes have the advantage of being the least contaminating catalyst due to normal catalyst might generate toxic by-product, and preferable to organic and inorganic catalysts, especially when used for product related to human used, which require biocompatibility of final product. However, there are several disadvantages in enzyme utilization. Their fabrication is time-consuming and requires elaborated molecular biology processes. Most of the enzymes need well-defined reaction conditions to be functional and operate at high yield. Unfortunately, although they are reusable as normal catalysts, it proves difficult to extract or reuse the enzymes from a reaction. Also, enzyme molecules are easily degradable and demand proper storage. To overcome some of the disadvantages, especially regarding stability to degradation, recovery, and reusability, immobilization of enzyme on solid support has become a thriving methodology. In recent years, mesoporous silica nanomaterials(MSN) have been at the forefront of enzyme immobilization given their extensive surface area, which provides capability to increase enzyme loading and for their demonstrate ability to protect enzyme from degradation, thus enabling high recyclability. Mesoporous silica is biocompatible and has already been used for several applications included. Catalysis, drug delivery, and Bio-imaging. Previously published research utilized mesoporous silica to deliver drugs, DNAs, RNAs or encapsulate single enzyme. The objective of this research is completed to develop a new porous silica platform that is unique in its porosity structure

Cooperative catalysis by silica-supported organic functional groups

OpenAIRE

Margelefsky, Eric L.; Zeidan, Ryan K.; Davis, Mark E.

2008-01-01

Hybrid inorganic–organic materials comprising organic functional groups tethered from silica surfaces are versatile, heterogeneous catalysts. Recent advances have led to the preparation of silica materials containing multiple, different functional groups that can show cooperative catalysis; that is, these functional groups can act together to provide catalytic activity and selectivity superior to what can be obtained from either monofunctional materials or homogeneous catalysts. This tutorial...

Mesoporous Silica Supported Au Nanoparticles with Controlled Size as Efficient Heterogeneous Catalyst for Aerobic Oxidation of Alcohols

Directory of Open Access Journals (Sweden)

Xuefeng Chu

2015-01-01

Full Text Available A series of Au catalysts with different sizes were synthesized and employed on amine group functionalized ordered mesoporous silica solid supports as catalyst for the aerobic oxidation of various alcohols. The mesoporous silica of MCM-41 supported Au nanoparticles (Au-1 exhibited the smallest particle size at ~1.8 nm with superior catalytic activities owing to the confinement effect of the mesoporous channels. Au-1 catalyst is also very stable and reusable under aerobic condition. Therefore, this presented work would obviously provide us a platform for synthesizing more size-controlled metal catalysts to improve the catalytic performances.

Three-dimensional structure of Au nanoparticles supported on amorphous silica and carbon substrates

International Nuclear Information System (INIS)

Bruma, A; Li, Z Y

2012-01-01

Scanning Transmission Electron Microscope (STEM) has been employed to study the three-dimensional structure of gold (Au) nanoparticles deposited by means of thermal evaporation in high vacuum on amorphous silica (a-SiO 2 ) and amorphous carbon (a-C) supports. By performing quantitative analysis on the evolution of the high angle annular dark field (HAADF) images, we studied the influence of the nature and the temperature of support on the growth mode of gold nanoparticles.

Effect of Support on Metathesis of n-Decane: Drastic Improvement in Alkane Metathesis with WMe5 Linked to Silica-Alumina

KAUST Repository

Samantaray, Manoja

2015-03-11

[WMe6] (1) supported on the surface of SiO2-Al2O3(500) (2) has been extensively characterized by solid-state NMR spectroscopy, elemental analysis, and gas quantification, which clearly reveal the formation of a mixture of monopodal and bipodal species with the migration of methyl from W to Al. The supported species SiO2-Al2O3(500) (2) transformed at 120°C into two types of carbynic centers, one of which is cationic and the other neutral. These species are very efficient for the metathesis of n-decane. Comparison with already-synthesized neutral bipodal tungsten indicates that the high increase in activity is due to the cationic character of the grafted tungsten.

Effect of Support on Metathesis of n-Decane: Drastic Improvement in Alkane Metathesis with WMe5 Linked to Silica-Alumina

KAUST Repository

Samantaray, Manoja; Dey, Raju; Abou-Hamad, Edy; Hamieh, Ali Imad Ali; Basset, Jean-Marie

2015-01-01

[WMe6] (1) supported on the surface of SiO2-Al2O3(500) (2) has been extensively characterized by solid-state NMR spectroscopy, elemental analysis, and gas quantification, which clearly reveal the formation of a mixture of monopodal and bipodal species with the migration of methyl from W to Al. The supported species SiO2-Al2O3(500) (2) transformed at 120°C into two types of carbynic centers, one of which is cationic and the other neutral. These species are very efficient for the metathesis of n-decane. Comparison with already-synthesized neutral bipodal tungsten indicates that the high increase in activity is due to the cationic character of the grafted tungsten.

Status of technology R&D for the ITER tungsten divertor monoblock

Energy Technology Data Exchange (ETDEWEB)

Hirai, T., E-mail: takeshi.hirai@iter.org [ITER Organization, Route de Vinon-sur-Verdon, CS 90 046, 13067 St. Paul Lez Durance Cedex (France); Escourbiac, F.; Barabash, V.; Durocher, A.; Fedosov, A.; Ferrand, L.; Jokinen, T.; Komarov, V.; Merola, M.; Carpentier-Chouchana, S. [ITER Organization, Route de Vinon-sur-Verdon, CS 90 046, 13067 St. Paul Lez Durance Cedex (France); Arkhipov, N. [Project Center ITER, 1, Building 3, Kurchatov Sq., 123182 Moscow (Russian Federation); Kuznetcov, V.; Volodin, A. [NIIEFA, 3 doroga na Metallostroy, Metallostroy, St. Petersburg 196641 (Russian Federation); Suzuki, S.; Ezato, K.; Seki, Y. [JAEA, Fusion Research and Development Directorate JAEA, 801-1 Mukouyama, Naka, Ibaragi 311-0193 (Japan); Riccardi, B.; Bednarek, M.; Gavila, P. [F4E, c/Josep Pla, n.2, Torres Diagonal Litoral, Edificio B3, E-08019 Barcelona (Spain)

2015-08-15

In order to develop and validate the high performance tungsten monoblock technology, the full-tungsten divertor qualification program was defined. As the first step, small-scale mock-ups were manufactured and successfully tested under the required high heat flux loads. The test results demonstrated that the technology is available in Japan and Europe. Post-tests observation of the loaded W monoblocks showed generation of self-castellation – a crack along coolant tube axis. The cause of the self-castellation was discussed and a tungsten material characterization program is being developed with the objective to understand mechanical properties that influence the occurrence of the self-castellation.

Granite-related Yangjiashan tungsten deposit, southern China

Science.gov (United States)

Xie, Guiqing; Mao, Jingwen; Li, Wei; Fu, Bin; Zhang, Zhiyuan

2018-04-01

The Yangjiashan scheelite-bearing deposit (38,663 metric tons of WO3 with an average ore grade of 0.70% WO3) is hosted in quartz veins in a biotite monzogranite intrusion and surrounding slate in the Xiangzhong Metallogenic Province of southern China. The monzogranite has a zircon SHRIMP U-Pb age of 406.6 ± 2.8 Ma (2σ, n = 20, MSWD = 1.4). Cassiterite coexisting with scheelite yields a weighted mean 206Pb/238U age of 409.8 ± 5.9 Ma (2σ, n = 30, MSWD = 0.20), and molybdenite intergrown with scheelite yields a weighted mean Re-Os age of 404.2 ± 3.2 Ma (2σ, n = 3, MSWD = 0.10). These results suggest that the Yangjiashan tungsten deposit is temporally related to the Devonian intrusion. The δD and calculated δ18OH2O values of quartz intergrown with scheelite range from - 87 to - 68‰, and - 1.2 to 3.4‰, respectively. Sulfides have a narrow range of δ34S values of - 2.9 to - 0.7‰ with an average value of - 1.6‰ (n = 16). The integration of geological, stable isotope, and geochronological data, combined with the quartz-muscovite greisen style of ore, supports a magmatic-hydrothermal origin for the tungsten mineralization. Compared to the more common tungsten skarn, quartz-wolframite vein, and porphyry tungsten deposits, as well as orogenic gold deposits worldwide, the Yangjiashan tungsten deposit is an unusual example of a granite-related, gold-poor, scheelite-bearing quartz vein type of deposit. The calcium needed for the formation of scheelite is derived from the sericitization of calcic plagioclase in the monzogranite and Ca-bearing psammitic country rocks, and the relatively high pH, reduced and Ca-rich mineralizing fluid may be the main reasons for the formation of scheelite rather than wolframite at Yangjiashan.

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

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.

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.

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.

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.

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.

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

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

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

Preparation of Mesoporous SBA-16 Silica-Supported Biscinchona Alkaloid Ligand for the Asymmetric Dihydroxylation of Olefins

Directory of Open Access Journals (Sweden)

Shaheen M. Sarkar

2014-01-01

Full Text Available Optically active cinchona alkaloid was anchored onto mesoporous SBA-16 silica and the as-prepared complex was used as a heterogeneous chiral ligand of osmium tetraoxide for the asymmetric dihydroxylation of olefins. The prepared catalytic system provided 90–93% yield of vicinal diol with 92–99% enantioselectivity. The ordered mesoporous SBA-16 silica was found to be a valuable support for the cinchona alkaloid liganded osmium catalyst system which is frequently used in chemical industries and research laboratories for olefin functionalization.

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

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

Ordered cubic nanoporous silica support MCM-48 for delivery of poorly soluble drug indomethacin

Science.gov (United States)

Zeleňák, Vladimír; Halamová, Dáša; Almáši, Miroslav; Žid, Lukáš; Zeleňáková, Adriána; Kapusta, Ondrej

2018-06-01

Ordered MCM-48 nanoporous silica (SBET = 923(3) m2·g-1, VP = 0.63(2) cm3·g-1) with cubic Ia3d symmetry was used as a support for drug delivery of anti-inflammatory poorly soluble drug indomethacin. The delivery from parent, unmodified MCM-48, and 3-aminopropyl modified silica carrier was studied into the simulated body fluids with the pH = 2 and pH = 7.4. The studied samples were characterized by thermal analysis (TG/DTG-DTA), N2 adsorption/desorption, infrared spectroscopy (FT-IR), powder XRD, SEM, HRTEM methods, measurements of zeta potential (ζ) and dynamic light scattering (DLS). The determined content of indomethacin in pure MCM-48 was 21 wt.% and in the amine-modified silica MCM-48A-I the content was 45 wt.%. The release profile of the drug, in the time period up to 72 h, was monitored by TLC chromatographic method. It as shown, that by the modification of the surface, the drug release can be controlled. The slower release of indomethacin was observed from amino modified sample MCM-48A-I in the both types of studied simulated body fluids (slightly alkaline intravenous solution with pH = 7.4 and acidic gastric fluid with pH = 2), which was supported and explained by zeta potential and DLS measurements. The amount of the released indomethacin into the fluids with various pH was different. The maximum released amount of the drug was 97% for sample containing unmodified silica, MCM-48-I at pH = 7.4 and lowest released amount, 57%, for amine modified sample MCM-48A-I at pH = 2. To compare the indomethacin release profile four kinetic models were tested. Results showed, that that the drug release based on diffusion Higuchi model, mainly governs the release.

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.

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

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.

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)

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

Structural, mechanical, and tribological characterization of sol-gel layers with inbedded anorganic fullerene-like tungsten-disulphide particles

International Nuclear Information System (INIS)

Hattermann, Hilke

2010-01-01

The preparation of composite coatings consisting of different materials with improved properties has been an intensively studied area of thin film technology in recent years. One method to prepare such composite coatings is the incorporation of nano or micro particles into a matrix of a different material. In this thesis, such composite coatings are investigated which have been prepared via a sol-gel route und contain up to about 30 wt.-% tungsten disulfide particles. These inorganic fullerenes have typical particle sizes of about 100 nm to 200 nm. Two different types of composite coatings with a thickness of up to a few micrometers and with embedded tungsten disulfide particles are prepared: First, coatings with a relatively stiff alumina matrix, and second, coatings with a matrix made of organically modified silica. Different analytical methods are used for the structural characterization of the coatings. The crystal structure and the chemical composition of the coatings are determined via X-ray diffraction and X-ray fluorescence measurements and via energy-dispersive X-ray spectroscopy. Through scanning and transmission electron microscopy the incorporation and the distribution of the tungsten disulfide particles in the respective matrix are analysed. Furthermore, the roughness and the adhesion of the coatings on the substrate are investigated. The influence of the embedded particles and of the temperature of the final heat treatment during the sample preparation on the mechanical properties, like elastic modulus and hardness, of the composite coatings are measured through nanoindentation testing. These experimental results are compared with theoretical values determined via different analytical models for effective materials. Finally, the tribological behavior of the composite coatings is investigated in comparison to pure coatings made of alumina or organically modified silica. With ball-on-disc tests the coefficient of friction of the coatings is measured

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

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.

Mesoporous silica nanotubes hybrid membranes for functional nanofiltration

International Nuclear Information System (INIS)

El-Safty, Sherif A; Shahat, Ahmed; Mekawy, Moataz; Nguyen, Hoa; Warkocki, Wojciech; Ohnuma, Masato

2010-01-01

The development of nanofiltration systems would greatly assist in the production of well-defined particles and biomolecules with unique properties. We report a direct, simple synthesis of hexagonal silica nanotubes (NTs), which vertically aligned inside anodic alumina membranes (AAM) by means of a direct templating method of microemulsion phases with cationic surfactants. The direct approach was used as soft templates for predicting ordered assemblies of surfactant/silica composites through strong interactions within AAM pockets. Thus, densely packed NTs were successfully formed in the entirety of the AAM channels. These silica NTs were coated with layers of organic moieties to create a powerful technique for the ultrafine filtration. The resulting modified-silica NTs were chemically robust and showed affinity toward the transport of small molecular particles. The rigid silica NTs inside AAM channels had a pore diameter of ≤ 4 nm and were used as ultrafine filtration systems for noble metal nanoparticles (NM NPs) and semiconductor nanocrystals (SC NCs) fabricated with a wide range of sizes (1.0-50 nm) and spherical/pyramidal morphologies. Moreover, the silica NTs hybrid membranes were also found to be suitable for separation of biomolecules such as cytochrome c (CytC). Importantly, this nanofilter design retains high nanofiltration efficiency of NM NPs, SC NCs and biomolecules after a number of reuse cycles. Such retention is crucial in industrial applications.

Mesoporous Silica-Supported Sulfonyldiamine Ligand for Microwave-Assisted Transfer Hydrogenation

Directory of Open Access Journals (Sweden)

Shaheen M. Sarkar

2015-01-01

Full Text Available N-Sulfonyl-1,2-diamine ligands, derived from 1,2-diaminocyclohexane and 1,2-diaminopropane, were immobilized onto mesoporous SBA-15 silica. The SBA-15-supported sulfonyldiamine-Ru complex was prepared in situ under microwave heating at 60 W for 3 min. The prepared sulfonyldiamine-Ru complex was used as an efficient catalyst for the transfer hydrogenation of ketones to the corresponding secondary alcohols. The heterogeneous complex showed extremely high catalytic activity with 99% conversion rate under microwave heating condition. The complexes were regenerated by simple filtration and reused two times without significant loss of activity.

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

Preparation, surface characterization and performance of a Fischer-Tropsch catalyst of cobalt supported on silica nanosprings

International Nuclear Information System (INIS)

Kengne, Blaise-Alexis Fouetio; Alayat, Abdulbaset M.; Luo, Guanqun; McDonald, Armando G.; Brown, Justin; Smotherman, Hayden; McIlroy, David N.

2015-01-01

Graphical abstract: - Highlights: • Determined that the reduction of Co nanoparticles on silica nanosprings 200 °C higher than the reduction temperature of Co in a solgel support. • The high reduction temperature of Co supported on silica nanosprings is attributed to the heat transfer properties of the nanosprings due to their high surface area. Co-silica nanospring Fischer-Tropsch catalyst can be used to produce drop in fuels such as JP-4. - Abstract: The reduction of cobalt (Co) catalyst supported on silica nanosprings for Fischer-Tropsch synthesis (FTS) has been monitored by X-ray photoelectron spectroscopy (XPS) and compared to FT catalytic activity. The cobalt is present in the starting catalyst as a Co 3 O 4 spinel phase. A two-step reduction of Co 3 O 4 to CoO and then to Co 0 is observed, which is consistent with the results of H 2 -temperature programmed reduction. During the reduction the two steps occur concurrently. The deconvolution of the Co 2p core level state for the catalyst reduced at 385 °C and 1.0 × 10 −6 Torr of H 2 revealed signatures of Co 0 , CoO, and Co 3 O 4 . The reduction saturates at a Co o concentration of approximately 41% after 20 h, which correlates with the activity and lifetime of the catalyst during FTS testing. Conversely, at 680 °C and 10 Torr of H 2 , the catalyst is completely reduced after 10 h. The evolution of the Co d-band at the Fermi level in the valence band XPS spectrum definitively verifies the metallic phase of Co. FTS evaluation of the Co/NS catalyst reduced at 609 °C showed higher production rate (3-fold) of C 6 -C 17 hydrocarbons than the catalyst reduced at 409 °C and is consistent with the XPS analysis.

Incorporation of tungsten metal fibers in a metal and ceramic matrix

Czech Academy of Sciences Publication Activity Database

Brožek, Vlastimil; Vokáč, M.; Kolísko, J.; Pokorný, P.; Kubatík, Tomáš František

2017-01-01

Roč. 56, 1-2 (2017), s. 79-82 ISSN 0543-5846 Institutional support: RVO:61389021 Keywords : tungsten wires * tungsten fibers * plasma spraying * metallic coatings * ceramic coatings Subject RIV: JI - Composite Materials OBOR OECD: Composites (including laminates, reinforced plastics, cermets, combined natural and synthetic fibre fabrics http://hrcak.srce.hr/168890

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

Effect of occupational silica exposure on pulmonary function.

Science.gov (United States)

Hertzberg, Vicki Stover; Rosenman, Kenneth D; Reilly, Mary Jo; Rice, Carol H

2002-08-01

To assess the effect of occupational silica exposure on pulmonary function. Epidemiologic evaluation based on employee interview, plant walk-through, and information abstracted from company medical records, employment records, and industrial hygiene measurements. Drawn from 1,072 current and former hourly wage workers employed before January 1, 1986. Thirty-six individuals with radiographic evidence of parenchymal changes consistent with asbestosis or silicosis were excluded. In addition, eight individuals whose race was listed as other than white or black were excluded. Analysis of spirometry data (FVC, FEV1, FEV1/FVC) only using the test results that met American Thoracic Society criteria for reproducibility and acceptability shows decreasing percent-predicted FVC and FEV1 and decreasing FEV1/FVC in relationship to increasing silica exposure among smokers. Logistic regression analyses of abnormal FVC and abnormal FEV1 values (where abnormal is defined as OSHA)-allowable level of 0.1 mg/m3. Longitudinal analyses of FVC and FEV1 measurements show a 1.6 mL/yr and 1.1 mL/yr, respectively, decline per milligram/cubic meter mean silica exposure (p = 0.011 and p = 0.001, respectively). All analyses were adjusted for weight, height, age, ethnicity, smoking status, and other silica exposures. Systematic problems leading to measurement error were possible, but would have been nondifferential in effect and not related to silica measurements. There is a consistent association between increased pulmonary function abnormalities and estimated measures of cumulative silica exposure within the current allowable OSHA regulatory level. Despite concerns about the quality control of the pulmonary function measurements use in these analyses, our results support the need to lower allowable air levels of silica and increase efforts to encourage cessation of cigarette smoking among silica-exposed workers.

Use of graphene supported on aminopropyl silica for microextraction of parabens from water samples.

Science.gov (United States)

Fumes, Bruno Henrique; Lanças, Fernando Mauro

2017-03-03

This paper describes the synthesis, characterization and use of graphene supported on aminopropyl silica through covalent bonds (Si-G) as a sorbent for microextraction by packed sorbent (MEPS). Five parabens (methyl, ethyl, propyl, butyl and benzyl) present in water matrices were used as model compounds for this evaluation. The Si-G phase was compared to other sorbents used in MEPS (C18 and Strata™-X) and also with graphene supported on primary-secondary amine (PSA) silica, where Si-G showed better results. After this, the MEPS experimental parameters were optimized using the Si-G sorbent. The following variables were optimized through univariate experiments: pH (4,7 and 10), desorption solvent (ACN:MeOH (50:50), ACN:H 2 O (40:60), MeOH and ACN) and ionic strength (0, 10 and 20% of NaCl). A factorial design 2 6-2 was then employed to evaluate other variables, such as the sample volume, desorption volume, sampling cycles, wash cycles and desorption cycles, as well as the influence of NaCl% on the extraction performance. The optimized method achieved a linear range of 0.2-20μg/L for most parabens; weighted calibration models were employed during the linearity evaluation to reduce the absolute sum of the residue values and improve R 2 , which ranged from 0.9753 to 0.9849. The method's accuracy was 82.3-119.2%; precision, evaluated as the coefficient of variance for intraday and interday analysis, ranged from 1.5 to 19.2%. After evaluation of the figures of merit, the method was applied to the determination of parabens in water samples. Copyright © 2017 Elsevier B.V. All rights reserved.

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

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

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)

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)

Origins of secondary silica within Yucca Mountain, Nye County, southwestern Nevada

International Nuclear Information System (INIS)

Moscati, R.J.; Whelan, J.F.

1996-01-01

The accuracy of predictions of the hydrologic response of Yucca Mountain to future climate depends largely on how well relations between past climate and hydrology can be resolved. To advance this reconstruction, secondary minerals in and near Yucca Mountain, deposited by ground waters that originated both as surficial recharge at Yucca Mountain and from regional aquifers, are being studied to determine past ground-water sources and chemistries. Preliminary data on stable oxygen isotopes indicate that, although silica (opal, quartz, and chalcedony) and calcite and have formed in similar settings and from somewhat similar fluids, the authors have found no compelling evidence of coprecipitation or formation from identical fluids. If verified by further analyses, this precludes the use of silica-calcite mineral pairs for precise geothermometry. The preliminary data also indicate that opal and calcite occurrences in pedogenic and unsaturated-zone settings are invariably compatible with formation under modern ambient surface or subsurface temperatures. Silica and calcite stable-isotope studies are being integrated with soil geochemical modeling. This modeling will define the soil geochemical condition (climate) leading to opal or calcite deposition and to the transfer functions that may apply at the meteorologic soil unsaturated-zone interfaces. Additional study of pedogenic and unsaturated-zone silica is needed to support these models. The hypothesis that the transformation of vapor-phase tridymite to quartz requires saturated conditions is being tested through stable oxygen-isotope studies of lithophysal tridymite/quartz mixtures. Should this hypothesis be verified, mineralogic analysis by X-ray diffraction theoretically would permit reconstruction of past maximum water-table elevations

Densification of Silica Spheres: A New Pathway to Nano-Dimensioned Zeolite-Based Catalysts.

Science.gov (United States)

Machoke, Albert Gonche Fortunatus; Apeleo Zubiri, Benjamin; Leonhardt, Rainer; Marthala, Venkata Ramana Reddy; Schmiele, Martin; Unruh, Tobias; Hartmann, Martin; Spiecker, Erdman; Schwieger, Wilhelm

2017-08-16

Nanosized materials are expected to play a unique role in the development of future catalytic processes. Herein, pre-prepared and geometrically well-defined amorphous silica spheres are densified into silica-rich zeolites with nanosized dimensions. After the densification, the obtained nanosized zeolites exhibit the same spherical morphology like the starting precursor but characterized by a drastically reduced size, higher density, and high crystallinity. The phase transformation into crystalline zeolite material and the densification effect are achieved through a well-controlled steam-assisted treatment of the larger precursor particles so that the transformation process proceeds always towards the center of the spheres, just like a shrinking process. Furthermore, this procedure is applicable also to commercially available silica particles, as well as aluminum-containing systems (precursors) leading to acidic nano-catalysts with improved catalytic performance. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Biogenic porous silica and silicon sourced from Mexican Giant Horsetail (Equisetum myriochaetum) and their application as supports for enzyme immobilization.

Science.gov (United States)

Sola-Rabada, Anna; Sahare, Padma; Hickman, Graham J; Vasquez, Marco; Canham, Leigh T; Perry, Carole C; Agarwal, Vivechana

2018-06-01

Porous silica-based materials are attractive for biomedical applications due to their biocompatibility and biodegradable character. In addition, inorganic supports such as porous silicon are being developed due to integrated circuit chip compatibility and tunable properties leading to a wide range of multidisciplinary applications. In this contribution, biosilica extracted from a rarely studied plant material (Equisetum Myriochaetum), its conversion to silicon and the potential for both materials to be used as supports for enzyme immobilization are investigated. E. myriochaetum was subject to conventional acid digestion to extract biogenic silica with a% yield remarkably higher (up to 3 times) than for other Equisetum sp. (i.e. E. Arvense). The surface area of the isolated silica was ∼400 m 2 /g, suitable for biotechnological applications. Biogenic silicon was obtained by magnesiothermic reduction. The materials were characterized by SEM-EDX, XRD, FT-IR, ICP-OES, TGA and BET analysis and did not contain significant levels of class 1 heavy elements (such as Pb, Cd, Hg and As). Two commercial peroxidases, horseradish peroxidase (HRP) and Coprinus cinereus peroxidase (CiP) were immobilized onto the biogenic materials using three different functionalization routes: (A) carbodiimide, (B) amine + glutaraldehyde and (C) amine + carbodiimide. Although both biogenic silica and porous silicon could be used as supports differences in behaviour were observed for the two enzymes. For HRP, loading onto biogenic silica via the glutaraldehyde immobilization technique (route B) was most effective. The loading of CiP showed a much higher peroxidase activity onto porous silicon than silica functionalized by the carbodiimide method (route A). From the properties of the extracted materials obtained from Equisetum Myriochaetum and the immobilization results observed, these materials appear to be promising for industrial and biomedical applications. Copyright © 2018 Elsevier

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

Evaluation of catalytic properties of tungsten carbide for the anode of microbial fuel cells

Energy Technology Data Exchange (ETDEWEB)

Rosenbaum, Miriam; Zhao, Feng; Quaas, Marion; Wulff, Harm; Schroeder, Uwe; Scholz, Fritz [Universitaet Greifswald, Institut fuer Biochemie, Felix-Hausdorff-Strasse 4, 17487 Greifswald (Germany)

2007-07-31

In this communication we discuss the properties of tungsten carbide, WC, as anodic electrocatalyst for microbial fuel cell application. The electrocatalytic activity of tungsten carbide is evaluated in the light of its preparation procedure, its structural properties as well as the pH and the composition of the anolyte solution and the catalyst load. The activity of the noble-metal-free electrocatalyst towards the oxidation of several common microbial fermentation products (hydrogen, formate, lactate, ethanol) is studied for microbial fuel cell conditions (e.g., pH 5, room temperature and ambient pressure). Current densities of up to 8.8 mA cm{sup -2} are achieved for hydrogen (hydrogen saturated electrolyte solution), and up to 2 mA cm{sup -2} for formate and lactate, respectively. No activity was observed for ethanol electrooxidation. The electrocatalytic activity and chemical stability of tungsten carbide is excellent in acidic to pH neutral potassium chloride electrolyte solutions, whereas higher phosphate concentrations at neutral pH support an oxidative degradation. (author)

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

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.)

GEMAS - Tin and Tungsten: possible sources of enriched concentrations in soils in European countries

Science.gov (United States)

João Batista, Maria; Filipe, Augusto; Reimann, Clemens

2014-05-01

southern soils and SiO2 is higher in loess sediments region, in the North German-Poland basin and in the Paris basin. Organic matter may immobilise these metals and silica content influences metallic elements concentrations in soils. Natural processes of soil development, land management of agricultural soils and population density all together may be responsible for higher concentrations of W in the soils of Netherlands Germany, Belgium, Switzerland and northeast France which seems not related with Sn-W mineral provinces. Tin and tungsten are enriched in the Precambrian shields compared to the Caledonian shields soils in the northern countries, although in northern countries climatic conditions may play the most important role in these elements concentrations. Tin and tungsten and tin or tungsten alone or in association of precious metals, copper, uranium, niobium, beryllium, titanium altogether were extracted in 650 small or median size mines in Portugal. Except tin in Neves Corvo mine of the Iberian Pyrite Belt the rest of these mines occurred in the Variscides granitic intrusions region. Tin and tungsten concentrations are therefore well reflected in the northern Portugal soils. At the GEMAS density of sampling pollution and local natural phenomena are not reflected in mapping but this important province is well delimited.

Selective and regular localization of accessible Pt nanoparticles inside the walls of an ordered silica: Application as a highly active and well-defined heterogeneous catalyst for propene and styrene hydrogenation reactions

KAUST Repository

Boualleg, Malika; Norsic, Sé bastien; Baudouin, David; Sayah, Reine; Quadrelli, Elsje Alessandra; Basset, Jean-Marie; Candy, Jean Pierre; Dé lichè re, Pierre; Pelzer, Katrin; Veyre, Laurent; Thieuleux, Chloé

2011-01-01

We describe here an original methodology related to the "build-the-bottle-around-the-ship" approach yielding a highly ordered silica matrix containing regularly distributed Pt nanoparticles (NPs) located inside the silica walls, Pt@{walls}SiO2. The starting colloidal solution of crystalline Pt nanoparticles was obtained from Pt(dba)2 (dba = dibenzylidene acetone) and 3-chloropropylsilane. The resulting nanoparticles (diameter: 2.0 ± 0.4 nm determined by HRTEM) resulted hydrophilic. The NPs present in the THF colloidal solution were incorporated inside the walls of a highly ordered 2D hexagonal mesoporous silica matrix via sol-gel process using a templating route with tetraethylorthosilicate, TEOS, as the silica source, and block copolymer (EthyleneOxide) 20(PropyleneOxide)70(EthyleneOxide)20 (Pluronic P123) as the structure-directing agent. Low-temperature calcination of the crude material at 593 K led to the final solid Pt@{walls}SiO2. Characterization by IR, HRTEM, BF-STEM and HAADF-STEM, SAXS, WAXS, XRD, XPS, H2 chemisorption, etc. of Pt@{walls}SiO2 confirmed the 2D hexagonal structuration and high mesoporosity (870 m2/g) of the material as well as the presence of stable 2-nm-sized crystalline Pt(0) NPs embedded inside the walls of the silica matrix. The material displayed no tendency to NPs sintering or leaching (Pt loading 0.3 wt.%) during its preparation. Pt@{walls}SiO2 was found to be a stable, selective and highly active hydrogenation catalyst. The catalytic performances in propene hydrogenation were tested under chemical regime conditions in a tubular flow reactor (278 K, propene/H2/He = 20/16/1.09 cm3/min, P tot = 1 bar) and were found superior to those of an homologous solid containing Pt NPs along its pore channels Pt@{pores}SiO2 and to those of a classical industrial catalysts Pt/Al2O3, (TOF = 2.3 s-1 vs. TOF = 0.90 and 0.92 s-1, respectively, calculated per surface platinum atoms). Pt@{walls}SiO2 also catalyzes fast and selective styrene

Selective and regular localization of accessible Pt nanoparticles inside the walls of an ordered silica: Application as a highly active and well-defined heterogeneous catalyst for propene and styrene hydrogenation reactions

KAUST Repository

Boualleg, Malika

2011-12-01

We describe here an original methodology related to the "build-the-bottle-around-the-ship" approach yielding a highly ordered silica matrix containing regularly distributed Pt nanoparticles (NPs) located inside the silica walls, Pt@{walls}SiO2. The starting colloidal solution of crystalline Pt nanoparticles was obtained from Pt(dba)2 (dba = dibenzylidene acetone) and 3-chloropropylsilane. The resulting nanoparticles (diameter: 2.0 ± 0.4 nm determined by HRTEM) resulted hydrophilic. The NPs present in the THF colloidal solution were incorporated inside the walls of a highly ordered 2D hexagonal mesoporous silica matrix via sol-gel process using a templating route with tetraethylorthosilicate, TEOS, as the silica source, and block copolymer (EthyleneOxide) 20(PropyleneOxide)70(EthyleneOxide)20 (Pluronic P123) as the structure-directing agent. Low-temperature calcination of the crude material at 593 K led to the final solid Pt@{walls}SiO2. Characterization by IR, HRTEM, BF-STEM and HAADF-STEM, SAXS, WAXS, XRD, XPS, H2 chemisorption, etc. of Pt@{walls}SiO2 confirmed the 2D hexagonal structuration and high mesoporosity (870 m2/g) of the material as well as the presence of stable 2-nm-sized crystalline Pt(0) NPs embedded inside the walls of the silica matrix. The material displayed no tendency to NPs sintering or leaching (Pt loading 0.3 wt.%) during its preparation. Pt@{walls}SiO2 was found to be a stable, selective and highly active hydrogenation catalyst. The catalytic performances in propene hydrogenation were tested under chemical regime conditions in a tubular flow reactor (278 K, propene/H2/He = 20/16/1.09 cm3/min, P tot = 1 bar) and were found superior to those of an homologous solid containing Pt NPs along its pore channels Pt@{pores}SiO2 and to those of a classical industrial catalysts Pt/Al2O3, (TOF = 2.3 s-1 vs. TOF = 0.90 and 0.92 s-1, respectively, calculated per surface platinum atoms). Pt@{walls}SiO2 also catalyzes fast and selective styrene

The use of a well-defined surface organometallic complex as a probe molecule: [(≡SiO)TaVCl2Me2] shows different isolated silanol sites on the silica surface

KAUST Repository

Chen, Yin

2014-01-01

TaVCl2Me3 reacts with silica(700) and produces two different [(≡SiO)TaVCl2Me2] surface organometallic species, suggesting a heterogeneity of the highly dehydroxylated silica surface, which was studied with a combined experimental and theoretical approach. This journal is © the Partner Organisations 2014.

Exploiting the interactions between the ruthenium Hoveyda–Grubbs catalyst and Al-modified mesoporous silica: the case of SBA15 vs. KCC-1

KAUST Repository

Werghi, Baraa; Pump, Eva; Tretiakov, Mykyta; Abou-Hamad, Edy; Gurinov, Andrei; Doggali, Pradeep; Anjum, Dalaver H.; Cavallo, Luigi; Bendjeriou-Sedjerari, Anissa; Basset, Jean-Marie

2018-01-01

Immobilization of the 2 generation Hoveyda-Grubbs catalyst HG-II onto well-ordered 2D hexagonal (SBA15) and 3D fibrous (KCC-1) mesostructured silica, which contained tetra-coordinated Al, has been investigated through the Surface Organometallic Chemistry (SOMC) methodology. The main interest of this study lies in the peculiarity of the silica supports, which display a well-defined tetrahedral aluminum hydride site displaying a strong Lewis acid character, [(Si-O-Si)(Si-O-)Al-H]. The resulting supported Hoveyda-Grubbs catalysts have been fully characterized by advanced solid state characterization techniques (FT-IR, H and C solid state NMR, DNP-SENS, EF-TEM...). Together with DFT calculations, the immobilization of HG-II does not occur through the formation of a covalent bond between the complex and the Al-modified mesoporous silica as expected, but through an Al⋯Cl-[Ru]-coordination. It is not surprising that in functionalized olefin metathesis of diethyldiallyl malonate, DEDAM (liquid phase), leaching of the catalyst is observed which is not the case in non-functionalized olefin metathesis of propene (gas phase). Besides, the results obtained in propene metathesis with HG-II immobilized either on SBA15 (d = 6 nm) or KCC-1 (d = 4 or 8 nm) highlight the importance of the accessibility of the catalytic site. Therefore, we demonstrate that KCC-1 is a promising and suitable 3D mesoporous support to overcome the diffusion of reactants into the porous network of heterogeneous catalysts.

Exploiting the interactions between the ruthenium Hoveyda–Grubbs catalyst and Al-modified mesoporous silica: the case of SBA15 vs. KCC-1

KAUST Repository

Werghi, Baraa

2018-03-05

Immobilization of the 2 generation Hoveyda-Grubbs catalyst HG-II onto well-ordered 2D hexagonal (SBA15) and 3D fibrous (KCC-1) mesostructured silica, which contained tetra-coordinated Al, has been investigated through the Surface Organometallic Chemistry (SOMC) methodology. The main interest of this study lies in the peculiarity of the silica supports, which display a well-defined tetrahedral aluminum hydride site displaying a strong Lewis acid character, [(Si-O-Si)(Si-O-)Al-H]. The resulting supported Hoveyda-Grubbs catalysts have been fully characterized by advanced solid state characterization techniques (FT-IR, H and C solid state NMR, DNP-SENS, EF-TEM...). Together with DFT calculations, the immobilization of HG-II does not occur through the formation of a covalent bond between the complex and the Al-modified mesoporous silica as expected, but through an Al⋯Cl-[Ru]-coordination. It is not surprising that in functionalized olefin metathesis of diethyldiallyl malonate, DEDAM (liquid phase), leaching of the catalyst is observed which is not the case in non-functionalized olefin metathesis of propene (gas phase). Besides, the results obtained in propene metathesis with HG-II immobilized either on SBA15 (d = 6 nm) or KCC-1 (d = 4 or 8 nm) highlight the importance of the accessibility of the catalytic site. Therefore, we demonstrate that KCC-1 is a promising and suitable 3D mesoporous support to overcome the diffusion of reactants into the porous network of heterogeneous catalysts.

Physical-analytical model for cesium/oxygen coadsorption on tungsten

International Nuclear Information System (INIS)

Rasor, N.S.

1992-01-01

In this paper a physical-analytical model is formulated for computing the emission and vaporization properties of a surface immersed in a multi-species vapor. The evaporation and condensation processes are assumed to be identical to those for an equilibrium adsorbed phase in equilibrium with its vapor, permitting statistical mechanical computation of the sticking coefficient for the practical non-equilibrium condensation condition. Two classes of adsorption sites are defined corresponding to superficial and interstitial coadsorption. The work function is computed by a self-consistent summation over the dipole moments of the various coadsorbed species in their mutual electric field. The model adequately describes observed emission and evaporation from tungsten surfaces immersed in pure cesium vapor and in pure oxygen vapor. Using available and estimated properties for 17 species of cesium, oxygen, tungsten and their compounds, the computed work function for tungsten immersed in Cs/O vapor is compared with limited available experimental data, and the basic phenomenology of Cs/O coadsorption electrodes is discussed

Direct hydrothermal synthesis of iron-containing mesoporous silica SBA-15 : potential as a support for gold nanoparticles

NARCIS (Netherlands)

Li, Y.; Guan, Y.; Santen, van R.A.; Kooyman, P.J.; Dugulan, A.I.; Li, C.; Hensen, E.J.M.

2009-01-01

The preparation of mesoporous silica SBA-15 with high iron loadings (14-90 wt % Fe2O3) as a suitable support for gold nanoparticles to be used in CO oxidation catalysis has been investigated. The support materials were prepared by a direct hydrothermal two-step pH adjusting method which consisted of

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

Recent progress of ordered mesoporous silica-supported chiral metallic catalysts

Directory of Open Access Journals (Sweden)

LIU Rui

2013-02-01

Full Text Available Recently,ordered silica-based mesoporous chiral organometallics-functionalized heterogeneous catalysts have attracted extensive research interest due to their excellent properties,such as easy preparation,high activity and convenient recycle.This review mainly summarizesthe generally prepared strategy and the silica-based organometallics-functionalized heterogeneous catalysts reported in the literatures.

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.

Interconnected mesopores and high accessibility in UVM-7-like silicas

Energy Technology Data Exchange (ETDEWEB)

Perez-Cabero, Monica [Universitat de Valencia, Institut de Ciencia dels Materials (Spain); Hungria, Ana B. [Universidad de Cadiz, Departamento de Ciencia de Materiales, Ingenieria Metalurgica y Quimica Inorganica (Spain); Morales, Jose Manuel [Universitat de Valencia, Institut de Ciencia dels Materials (Spain); Tortajada, Marta; Ramon, Daniel [Biopolis S. L. (Spain); Moragues, Alaina; El Haskouri, Jamal; Beltran, Aurelio; Beltran, Daniel; Amoros, Pedro, E-mail: pedro.amoros@uv.es [Universitat de Valencia, Institut de Ciencia dels Materials (Spain)

2012-08-15

Nanoparticulated bimodal mesoporous silicas (NBS) have proved to constitute adequate supports in a variety of applications requiring enhanced accessibility to the active sites. Mass-transfer kinetics seems to be highly favoured in UVM-7-derived NBS materials. To understand the mass-diffusion phenomena throughout UVM-7-like supports requires well-grounded knowledge about their pore architecture. 3-D reconstructions of the UVM-7 mesostructure carried out by electron tomography reveal the existence of a true hierarchic connectivity involving both inter- and intra-nanoparticle pores. This connectivity makes self-supported nanoparticulated mesoporous bimodal carbon replicas of the supports feasible to obtaining by nanocasting. Both the temperature-induced mobility of gold nanodomains and the fast and efficient enzyme adsorption in UVM-7-like silicas are examples of non-constrained diffusion processes happening inside such an open network.

Interconnected mesopores and high accessibility in UVM-7-like silicas

International Nuclear Information System (INIS)

Pérez-Cabero, Mónica; Hungría, Ana B.; Morales, José Manuel; Tortajada, Marta; Ramón, Daniel; Moragues, Alaina; El Haskouri, Jamal; Beltrán, Aurelio; Beltrán, Daniel; Amorós, Pedro

2012-01-01

Nanoparticulated bimodal mesoporous silicas (NBS) have proved to constitute adequate supports in a variety of applications requiring enhanced accessibility to the active sites. Mass-transfer kinetics seems to be highly favoured in UVM-7-derived NBS materials. To understand the mass-diffusion phenomena throughout UVM-7-like supports requires well-grounded knowledge about their pore architecture. 3-D reconstructions of the UVM-7 mesostructure carried out by electron tomography reveal the existence of a true hierarchic connectivity involving both inter- and intra-nanoparticle pores. This connectivity makes self-supported nanoparticulated mesoporous bimodal carbon replicas of the supports feasible to obtaining by nanocasting. Both the temperature-induced mobility of gold nanodomains and the fast and efficient enzyme adsorption in UVM-7-like silicas are examples of non-constrained diffusion processes happening inside such an open network.

Synthesis Of Silver Nanoparticles Supported On Silica Using As Antifungal Agent By Gamma Irradiation

International Nuclear Information System (INIS)

Nguyen Thi Kim Lan; Nguyen Tue Anh; Dang Van Phu; Vo Kim Lang; Nguyen Thuy Khanh; Nguyen Quoc Hien

2011-01-01

Silver nanoparticles supported on silica (Ag nano/SiO 2 ) were prepared by gamma Co-60 irradiation method. The formation of Ag nano doped on silica particles was confirmed by the UV-Vis spectroscopy. The size of silver nanoparticles was characterized by transmission electron microscopy (TEM), X-ray diffraction (XRD) which showed the particle size of Ag nano to be in range of 15-30 nm for Ag + concentration 10 mM. In addition, antifungal activity of Ag nano/SiO 2 was tested against Aspergillus niger var Tieghn by plate count method. The results indicated that the antifungal efficiency of Ag nano/SiO 2 was about 64, 71, 81, 82 and 96% at the concentrations of Ag nanoparticles of 30, 50, 70, 100 and 150 ppm respectively. (author)

Silica Nephropathy

Directory of Open Access Journals (Sweden)

N Ghahramani

2010-06-01

Full Text Available Occupational exposure to heavy metals, organic solvents and silica is associated with a variety of renal manifestations. Improved understanding of occupational renal disease provides insight into environmental renal disease, improving knowledge of disease pathogenesis. Silica (SiO2 is an abundant mineral found in sand, rock, and soil. Workers exposed to silica include sandblasters, miners, quarry workers, masons, ceramic workers and glass manufacturers. New cases of silicosis per year have been estimated in the US to be 3600–7300. Exposure to silica has been associated with tubulointerstitial disease, immune-mediated multisystem disease, chronic kidney disease and end-stage renal disease. A rare syndrome of painful, nodular skin lesions has been described in dialysis patients with excessive levels of silicon. Balkan endemic nephropathy is postulated to be due to chronic intoxication with drinking water polluted by silicates released during soil erosion. The mechanism of silica nephrotoxicity is thought to be through direct nephrotoxicity, as well as silica-induced autoimmune diseases such as scleroderma and systemic lupus erythematosus. The renal histopathology varies from focal to crescentic and necrotizing glomerulonephritis with aneurysm formation suggestive of polyarteritis nodosa. The treatment for silica nephrotoxicity is non-specific and depends on the mechanism and stage of the disease. It is quite clear that further research is needed, particularly to elucidate the pathogenesis of silica nephropathy. Considering the importance of diagnosing exposure-related renal disease at early stages, it is imperative to obtain a thorough occupational history in all patients with renal disease, with particular emphasis on exposure to silica, heavy metals, and solvents.

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.

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.

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.

Preparation, surface characterization and performance of a Fischer-Tropsch catalyst of cobalt supported on silica nanosprings

Energy Technology Data Exchange (ETDEWEB)

Kengne, Blaise-Alexis Fouetio [Department of Physics, University of Idaho, Moscow, ID 83844-0903 (United States); Alayat, Abdulbaset M. [Environmental Science Program, University of Idaho, Moscow, ID 83844-3006 (United States); Luo, Guanqun [Department of Forest, Rangeland & Fire Sciences, University of Idaho, Moscow, ID 83844-1132 (United States); McDonald, Armando G. [Environmental Science Program, University of Idaho, Moscow, ID 83844-3006 (United States); Department of Forest, Rangeland & Fire Sciences, University of Idaho, Moscow, ID 83844-1132 (United States); Brown, Justin; Smotherman, Hayden [Department of Physics, University of Idaho, Moscow, ID 83844-0903 (United States); McIlroy, David N., E-mail: dmcilroy@uidaho.edu [Department of Physics, University of Idaho, Moscow, ID 83844-0903 (United States)

2015-12-30

Graphical abstract: - Highlights: • Determined that the reduction of Co nanoparticles on silica nanosprings 200 °C higher than the reduction temperature of Co in a solgel support. • The high reduction temperature of Co supported on silica nanosprings is attributed to the heat transfer properties of the nanosprings due to their high surface area. Co-silica nanospring Fischer-Tropsch catalyst can be used to produce drop in fuels such as JP-4. - Abstract: The reduction of cobalt (Co) catalyst supported on silica nanosprings for Fischer-Tropsch synthesis (FTS) has been monitored by X-ray photoelectron spectroscopy (XPS) and compared to FT catalytic activity. The cobalt is present in the starting catalyst as a Co{sub 3}O{sub 4} spinel phase. A two-step reduction of Co{sub 3}O{sub 4} to CoO and then to Co{sup 0} is observed, which is consistent with the results of H{sub 2}-temperature programmed reduction. During the reduction the two steps occur concurrently. The deconvolution of the Co 2p core level state for the catalyst reduced at 385 °C and 1.0 × 10{sup −6} Torr of H{sub 2} revealed signatures of Co{sup 0}, CoO, and Co{sub 3}O{sub 4}. The reduction saturates at a Co{sup o} concentration of approximately 41% after 20 h, which correlates with the activity and lifetime of the catalyst during FTS testing. Conversely, at 680 °C and 10 Torr of H{sub 2}, the catalyst is completely reduced after 10 h. The evolution of the Co d-band at the Fermi level in the valence band XPS spectrum definitively verifies the metallic phase of Co. FTS evaluation of the Co/NS catalyst reduced at 609 °C showed higher production rate (3-fold) of C{sub 6}-C{sub 17} hydrocarbons than the catalyst reduced at 409 °C and is consistent with the XPS analysis.

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

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

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

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.

Assessment of concrete bridge decks with alkali silica reactions

DEFF Research Database (Denmark)

Eriksen, Kirsten; Jansson, Jacob; Geiker, Mette Rica

2008-01-01

Based on investigations of concrete from an approximately 40 years old bridge a procedure to support the management of maintenance and repair of alkali silica damaged bridges is proposed. Combined petrography and accelerated expansion testing were undertaken on cores from the Bridge at Skovdiget......, Bagsværd, Denmark to provide information on the damage condition as well as the residual reactivity of the concrete. The Danish Road Directory’s guidelines for inspection and assessment of alkali silica damaged bridges will be briefly presented, and proposed modifications will be describe...

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.)

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

Wrinkling of graphene membranes supported by silica nanoparticles on substrates

Science.gov (United States)

Yamamoto, Mahito; Cullen, William; Fuhrer, Michael; Einstein, Theodore; Department of Physics, University of Maryland Team

2011-03-01

The challenging endeavor of modulating the morphology of graphene via a patterned substrate to produce a controlled deformation has great potential importance for strain engineering the electronic properties of graphene. An essential step in this direction is to understand the response of graphene to substrate features of known geometry. Here we employ silica nanoparticles with a diameter of 10-100 nm to uniformly decorate Si O2 and mica substrates before depositing graphene, to promote nanoscale modulation of graphene geometry. The morphology of graphene on this modified substrate is then characterized by atomic force spectroscopy. We find that graphene on the substrate is locally raised by the supporting nanoparticles, and wrinkling propagates radially from the protrusions to form a ridge network which links the protrusions. We discuss the dependence of the wrinkled morphology on nanoparticle diameter and graphene thickness in terms of graphene elasticity and adhesion energy. Supported by NSF-MRSEC, Grant DMR 05-20471

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)

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)

Insights into the deactivation mechanism of supported tungsten hydride on alumina (W-H/Al2O3) catalyst for the direct conversion of ethylene to propylene

KAUST Repository

Mazoyer, Etienne; Szeto, Kaï Chung; Merle, Nicolas; Thivolle-Cazat, Jean; Boyron, Olivier; Basset, Jean-Marie; Nicholas, Christopher P.; Taoufik, Mostafa

2014-01-01

Tungsten hydride supported on alumina prepared by the surface organometallic chemistry method is an active precursor for the direct conversion of ethylene to propylene at low temperature and pressure. An extensive contact time study revealed

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 ...

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.

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

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.

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.

Silica-supported, single-site titanium catalysts for olefin epoxidation. A molecular precursor strategy for control of catalyst structure.

Science.gov (United States)

Jarupatrakorn, Jonggol; Don Tilley, T

2002-07-17

A molecular precursor approach involving simple grafting procedures was used to produce site-isolated titanium-supported epoxidation catalysts of high activity and selectivity. The tris(tert-butoxy)siloxy titanium complexes Ti[OSi(O(t)Bu)(3)](4) (TiSi4), ((i)PrO)Ti[OSi(O(t)Bu)(3)](3) (TiSi3), and ((t)BuO)(3)TiOSi(O(t)Bu)(3) (TiSi) react with the hydroxyl groups of amorphous Aerosil, mesoporous MCM-41, and SBA-15 via loss of HO(t)Bu and/or HOSi(O(t)Bu)(3) and introduction of titanium species onto the silica surface. Powder X-ray diffraction, nitrogen adsorption/desorption, infrared, and diffuse reflectance ultraviolet spectroscopies were used to investigate the structures and chemical natures of the surface-bound titanium species. The titanium species exist mainly in isolated, tetrahedral coordination environments. Increasing the number of siloxide ligands in the molecular precursor decreases the amount of titanium that can be introduced this way, but also enhances the catalytic activity and selectivity for the epoxidation of cyclohexene with cumene hydroperoxide as oxidant. In addition, the high surface area mesoporous silicas (MCM-41 and SBA-15) are more effective than amorphous silica as supports for these catalysts. Supporting TiSi3 on the SBA-15 affords highly active cyclohexene epoxidation catalysts (0.25-1.77 wt % Ti loading) that provide turnover frequencies (TOFs) of 500-1500 h(-1) after 1 h (TOFs are reduced by about half after calcination). These results demonstrate that oxygen-rich siloxide complexes of titanium are useful as precursors to supported epoxidation catalysts.

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.

Cu(II) recognition materials: Fluorophores grafted on mesoporous silica supports

International Nuclear Information System (INIS)

Kledzik, Krzysztof; Orlowska, Maja; Patralska, Dorota; Gwiazda, Marcin; Jezierska, Julia; Pikus, Stanislaw; Ostaszewski, Ryszard; Klonkowski, Andrzej M.

2007-01-01

There were designed and synthesized naphthalene and pyrene derivatives consisting of fluorophore group and of receptor fragment with donor N and O atoms. These fluorosensors were covalently attached by grafting carboxyl group to surfaces of silica xerogel or mesoporous silicas (MCM-41 and MCM-48) functionalized either with 3-aminopropyl or 3-glycidoxypropyl groups. The pyrene derivatives 2 and 3 covalently grafted on MCM-48 silica functionalized with 3-aminopropyl groups are potential recognition elements of a fluorescence chemical sensor. Fluorescence emission of the prepared recognition materials is quenched specifically owing to photoinduced electron transfer (PET) effect after coordination reactions with Cu(II) ions. Moreover, both the materials exhibit selectivity for Cu(II) ions in aqueous solutions in presence of such metal ions as: alkali, alkaline earth and transition. During UV irradiation the studied recognition elements undergo slowly photochemical degradation

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

Structural Stability of Light-harvesting Protein LH2 Adsorbed on Mesoporous Silica Supports.

Science.gov (United States)

Shibuya, Yuuta; Itoh, Tetsuji; Matsuura, Shun-ichi; Yamaguchi, Akira

2015-01-01

In the present study, we examined the reversible thermal deformation of the membrane protein light-harvesting complex LH2 adsorbed on mesoporous silica (MPS) supports. The LH2 complex from Thermochromatium tepidum cells was conjugated to MPS supports with a series of pore diameter (2.4 to 10.6 nm), and absorption spectra of the resulting LH2/MPS conjugates were observed over a temperature range of 273 - 313 K in order to examine the structure of the LH2 adsorbed on the MPS support. The experimental results confirmed that a slight ellipsoidal deformation of LH2 was induced by adsorption on the MPS supports. On the other hand, the structural stability of LH2 was not perturbed by the adsorption. Since the pore diameter of MPS support did not influence the structural stability of LH2, it could be considered that the spatial confinement of LH2 in size-matches pore did not improve the structural stability of LH2.

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…

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.

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.

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

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

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

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

Kinetic and Thermodynamics of Methylene Blue Adsorption onto Zero Valent Iron Supported on Mesoporous Silica

Directory of Open Access Journals (Sweden)

Atyaf Khalid Hameed

2016-08-01

Full Text Available Zero valent iron supported on mesoporous silicanano particles (NZVI/MSNs was prepared by the aqueous phase borohydride reduction methods. Prior to the reduction, mesoporous silica nanoparticles (MSNs were prepared through the activation of fumed silica with concentrated HCl by refluxing at 90 °C. FTIR, XRD, FESEM, EDX and BET were used to characterize theadsorbents prepared. BET surface areas of MSNs, NZVI, and NZVI/MSNs were 126, 41, and 72 m2/g for, respectively. The performance of NZVI/MSNs as adsorbent was examined by adsorption of methylene blue (MB, performed in series of batch experiments. In the kinetic studies, pseudo first order and pseudo second order kinetic models were examined. The pseudo second order equation provided the best fit with the experimental data. Thermodynamic studies indicated that the adsorption process is endothermic with ΔH° was 90.53 kJ/mol. Positive ΔS° (300 J/mol and negative ΔG° (-6.42 kJ/mol was recorded, indicating the spontaneous of the adsorption process and naturally favorable. Copyright © 2016 BCREC GROUP. All rights reserved Received: 5th March 2016; Revised: 18th March 2016; Accepted: 18th March 2016 How to Cite: Hameed, A.K., Dewayanto, N., Dongyun, D., Nordin, M.R., Mohd Hasbi Ab. Rahim, M.H.A. (2016. Kinetic and Thermodynamics of Methylene Blue Adsorption onto Zero Valent Iron Supported on Mesoporous Silica. Bulletin of Chemical Reaction Engineering & Catalysis, 11 (2: 250-261 (doi:10.9767/bcrec.11.2.443.250-261 Permalink/DOI: http://dx.doi.org/10.9767/bcrec.11.2.443.250-261

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.

Large area synthesis, characterization, and anisotropic etching of two dimensional tungsten disulfide films

International Nuclear Information System (INIS)

Mutlu, Zafer; Ozkan, Mihrimah; Ozkan, Cengiz S.

2016-01-01

Emergent properties of tungsten disulfide at the quantum confinement limit hold promise for electronic and optoelectronic applications. Here we report on the large area synthesis of atomically thin tungsten disulfide films with strong photoluminescence properties via sulfurization of the pre-deposited tungsten films. Detailed characterization of the pre-deposited tungsten films and tungsten disulfide films are performed using microscopy and spectroscopy methods. By directly heating tungsten disulfide films in air, we have shown that the films tend to be etched into a series of triangular shaped pits with the same orientations, revealing the anisotropic etching behavior of tungsten disulfide edges. Moreover, the dimensions of the triangular pits increase with the number of layers, suggesting a thickness dependent behavior of etching in tungsten disulfide films. This method offers a promising new avenue for engineering the edge structures of tungsten disulfide films. - Highlights: • Large-scale synthesis of WS_2 films is achieved via sulfurization of W films. • Annealing of W films leads to a substantial improvement in the quality of WS_2 films. • WS_2 films show laser power dependent photoluminescence characteristics. • WS_2 films are etched with well-oriented triangular pits upon annealing in air. • Anisotropic oxidative etching is greatly affected by the thickness of WS_2 films.

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.

Development and qualification of a bulk tungsten divertor row for JET

Science.gov (United States)

Mertens, Ph.; Altmann, H.; Hirai, T.; Philipps, V.; Pintsuk, G.; Rapp, J.; Riccardo, V.; Schweer, B.; Uytdenhouwen, I.; Samm, U.

2009-06-01

A bulk tungsten divertor row has been developed in the frame of the ITER-like Wall project at JET. It consists of 96 tiles grouped in 48 modules around the torus. The outer strike point is located on those tiles for most of the ITER-relevant, high triangularity plasmas. High power loads (locally up to 10-20 MW/m 2) and erosion rates are expected, even a risk of melting, especially with the transients or ELM loads. These are demanding conditions for an inertially cooled design as prescribed. A lamella design has been selected for the tungsten, arranged to control the eddy and halo current flows. The lamellae must also withstand high temperature gradients (2200 to 220 °C over 40 mm height), without overheating the supporting carrier (600-700 °C maximum). As a consequence of the tungsten emissivity, the radiative cooling drops appreciably in comparison with the current CFC tiles, calling for interleaved plasma scenarios in terms of performance. The compromise between shadowing and power handling is discussed, as well as the consequences for operation. Prototypes have been exposed in TEXTOR and in an electron beam facility (JUDITH-2) to the nominal power density of 7 MW/m 2 for 10 s and, in addition, to higher loads leading to surface temperatures above 2000 °C.

Silicosis and Silica-Induced Autoimmunity in the Diversity Outbred Mouse

Directory of Open Access Journals (Sweden)

Jessica M. Mayeux

2018-04-01

Full Text Available Epidemiological studies have confidently linked occupational crystalline silica exposure to autoimmunity, but pathogenic mechanisms and role of genetic predisposition remain poorly defined. Although studies of single inbred strains have yielded insights, understanding the relationships between lung pathology, silica-induced autoimmunity, and genetic predisposition will require examination of a broad spectrum of responses and susceptibilities. We defined the characteristics of silicosis and autoimmunity and their relationships using the genetically heterogeneous diversity outbred (DO mouse population and determined the suitability of this model for investigating silica-induced autoimmunity. Clinically relevant lung and autoimmune phenotypes were assessed 12 weeks after a transoral dose of 0, 5, or 10 mg crystalline silica in large cohorts of DO mice. Data were further analyzed for correlations, hierarchical clustering, and sex effects. DO mice exhibited a wide range of responses to silica, including mild to severe silicosis and importantly silica-induced systemic autoimmunity. Strikingly, about half of PBS controls were anti-nuclear antibodies (ANA positive, however, few had disease-associated specificities, whereas most ANAs in silica-exposed mice showed anti-ENA5 reactivity. Correlation and hierarchical clustering showed close association of silicosis, lung biomarkers, and anti-ENA5, while other autoimmune characteristics, such as ANA and glomerulonephritis, clustered separately. Silica-exposed males had more lung inflammation, bronchoalveolar lavage fluid cells, IL-6, and autoantibodies. DO mice are susceptible to both silicosis and silica-induced autoimmunity and show substantial individual variations reflecting their genetic diverseness and the importance of predisposition particularly for autoimmunity. This model provides a new tool for deciphering the relationship between silica exposure, genes, and disease.

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.

Precipitation formation in recrystallized nickel-plated non-sag tungsten wire

International Nuclear Information System (INIS)

Lai, Z.H.

1994-01-01

It is well established that some metals, such as palladium and nickel, can easily penetrate into tungsten by fast diffusion via crystal defects such as grain boundaries and dislocations. As a result of the fast penetration of these so called activators the recrystallization temperature of heavily drawn non-sag tungsten wire can be lower from about 2,000 C to about 1,000 C, thus the application of the tungsten wire, serving as reinforcement material in metal matrix composites used at high temperatures, is limited. An interesting question is in which form these activators exist in the recrystallized tungsten wire. It is generally believed that W-Ni intermediate compounds could form in the recrystallized material, presumably at grain boundaries. The free energy difference between the pure tungsten fibbers and the precipitating W(Ni) solid solution was suggested as the chemical driving force which governed the recrystallization process. The presence of nickel in small particles had also been observed in recrystallized grains of nickel plated tungsten wires using scanning electron microscopy (SEM) and secondary ion mass spectroscopy. These particles were considered to be nickel rich precipitates. However, a detailed investigation of the precipitation process has not been reported. In the present work an investigation of the structure, composition and distribution of nickel rich particles precipitated in recrystallized grains of nickel plated heavily drawn non-sage tungsten wires was carried out using analytical electron microscopy (AEM)

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.

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.

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.

W-containing oxide layers obtained on aluminum and titanium by PEO as catalysts in thiophene oxidation

Science.gov (United States)

Rudnev, V. S.; Lukiyanchuk, I. V.; Vasilyeva, M. S.; Morozova, V. P.; Zelikman, V. M.; Tarkhanova, I. G.

2017-11-01

W-containing oxide layers fabricated on titanium and aluminum alloys by Plasma electrolytic oxidation (PEO) have been tested in the reaction of the peroxide oxidation of thiophene. Samples with two types of coatings have been investigated. Coatings I contained tungsten oxide in the matrix and on the surface of amorphous silica-titania or silica-alumina layers, while coatings II comprised crystalline WO3 and/or Al2(WO4)3. Aluminum-supported catalyst containing a smallest amount of transition metals in the form of tungsten oxides and manganese oxides in low oxidation levels showed high activity and stability.

Gold Nanoparticles Supported on Fibrous Silica Nanospheres (KCC-1) as Efficient Heterogeneous Catalysts for CO Oxidation

KAUST Repository

Qureshi, Ziyauddin S.; Sarawade, Pradip B.; Hussain, Irshad; Zhu, Haibo; Al-Johani, Hind; Anjum, Dalaver H.; Hedhili, Mohamed N.; Maity, Niladri; D'Elia, Valerio; Basset, Jean-Marie

2016-01-01

Gold nanoparticles (Au NPs) of different sizes were supported on fibrous silica nanospheres (KCC-1) by various methods. The size and the location of the Au NPs on the support were found to depend on the preparation method. The KCC-1-supported Au NPs were thoroughly characterized by using HR-TEM, XRD, X-ray photoelectron spectroscopy, UV, and Brunauer-Emmett-Teller surface area measurements and were applied in catalysis for the oxidation of CO. The catalytic performance is discussed in relation to the morphological properties of KCC-1. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Gold Nanoparticles Supported on Fibrous Silica Nanospheres (KCC-1) as Efficient Heterogeneous Catalysts for CO Oxidation

KAUST Repository

Qureshi, Ziyauddin S.

2016-04-13

Gold nanoparticles (Au NPs) of different sizes were supported on fibrous silica nanospheres (KCC-1) by various methods. The size and the location of the Au NPs on the support were found to depend on the preparation method. The KCC-1-supported Au NPs were thoroughly characterized by using HR-TEM, XRD, X-ray photoelectron spectroscopy, UV, and Brunauer-Emmett-Teller surface area measurements and were applied in catalysis for the oxidation of CO. The catalytic performance is discussed in relation to the morphological properties of KCC-1. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

Morphological characterisation and spectroscopic studies of the corrosion behaviour of tungsten heavy alloys

International Nuclear Information System (INIS)

Ogundipe, A.; Greenberg, B.; Braida, W.; Christodoulatos, C.; Dermatas, D.

2006-01-01

Tungsten-based alloys have been used in a wide variety of industrial and military applications. These alloys are composed mainly of tungsten (88-95%) with various combinations of nickel, cobalt, iron and copper usually making up the remaining fraction. The corrosion behaviours of five munitions grade tungsten alloys of interest have been examined using immersion tests and wet-dry cycle tests to determine the mechanisms involved in the release of the metallic components. Analyses carried out using SEM, EDS and grazing incidence XRD techniques, show the release of tungsten as well as alloying elements due to galvanic corrosion resulting from the difference in electrode potential between the tungsten phase and the binder phase in all cases studied. The extent of corrosion was directly related with the dissolution of tungsten in the binder phase during the sintering stage of manufacture. In W-Ni-Co-Fe alloys binder phase corrosion was observed while the relatively noble tungsten phase was less affected. The reverse was observed for a W-Cu alloy

The effect of phosphorus on the formation of tungsten dioxide: A novel morphology

International Nuclear Information System (INIS)

Hegedus, E.; Neugebauer, J.

1999-01-01

The industrial production of tungsten is based on the hydrogen reduction of tungsten oxides, ammonium paratungstate (APT) or ammonium tungsten oxide bronze (ATOB). Hydrogen reduction is applied when high purity tungsten is required and when the addition of other elements or compounds (dopants) is desired for modification of the properties of the metal powder. The first stage of the reduction is finished when WO 2 is formed and it seems that the efficient incorporation of the additives starts mainly at this reduction step. The study reported here was undertaken to investigate the effect of phosphorus dope on the morphology of the intermediate tungsten dioxide and analyze its influence on the grain size of the final tungsten metal powder. The authors observed star shaped morphology of WO 2 , a structure which has not been describe in the literature. Contrary to the well-known cauliflower shaped tungsten dioxide, these starlets are not pseudomorphic to the initial ATOB particles; they grow separately and have a great influence on the grain size of the final metal powder

Iron supported on bioinspired green silica for water remediation.

Science.gov (United States)

Alotaibi, Khalid M; Shiels, Lewis; Lacaze, Laure; Peshkur, Tanya A; Anderson, Peter; Machala, Libor; Critchley, Kevin; Patwardhan, Siddharth V; Gibson, Lorraine T

2017-01-01

Iron has been used previously in water decontamination, either unsupported or supported on clays, polymers, carbons or ceramics such as silica. However, the reported synthesis procedures are tedious, lengthy (involving various steps), and either utilise or produce toxic chemicals. Herein, the use of a simple, rapid, bio-inspired green synthesis method is reported to prepare, for the first time, a family of iron supported on green nanosilica materials (Fe@GN) to create new technological solutions for water remediation. In particular, Fe@GN were employed for the removal of arsenate ions as a model for potentially toxic elements in aqueous solution. Several characterization techniques were used to study the physical, structural and chemical properties of the new Fe@GN. When evaluated as an adsorption platform for the removal of arsenate ions, Fe@GN exhibited high adsorption capacity (69 mg of As per g of Fe@GN) with superior kinetics (reaching ∼35 mg As per g sorbent per hr) - threefold higher than the highest removal rates reported to date. Moreover, a method was developed to regenerate the Fe@GN allowing for a full recovery and reuse of the adsorbent in subsequent extractions; strongly highlighting the potential technological benefits of these new green materials.

TiO2 supported over porous silica photocatalysts for pesticide degradation using solar light: Part 2. Silica prepared using acrylic acid emulsion

International Nuclear Information System (INIS)

Phanikrishna Sharma, Mangalampalli V.; Durga Kumari, Valluri; Subrahmanyam, Machiraju

2010-01-01

An acrylic acid emulsion mixture is used for synthesis of novel porous silica (E-Si) material. The photocatalytic activity of TiO 2 under solar light irradiation for isoproturon (herbicide) degradation is drastically increased when dispersed over E-Si support using solid state dispersion (SSD) technique. The composite material is characterized by XRD, nitrogen adsorption-desorption isotherms, UV-vis DRS, SEM and TEM measurements. The photocatalytic activities of the composite catalysts are evaluated for different parameters. The 5 wt% TiO 2 /E-Si is found to be highly active for isoproturon degradation.

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...

Thermally stable silica-coated hydrophobic gold nanoparticles.

Science.gov (United States)

Kanehara, Masayuki; Watanabe, Yuka; Teranishi, Toshiharu

2009-01-01

We have successfully developed a method for silica coating on hydrophobic dodecanethiol-protected Au nanoparticles with coating thickness ranging from 10 to 40 nm. The formation of silica-coated Au nanoparticles could be accomplished via the preparation of hydrophilic Au nanoparticle micelles by cationic surfactant encapsulation in aqueous phase, followed by hydrolysis of tetraethylorthosilicate on the hydrophilic surface of gold nanoparticle micelles. Silica-coated Au nanoparticles exhibited quite high thermal stability, that is, no agglomeration of the Au cores could be observed after annealing at 600 degrees C for 30 min. Silica-coated Au nanoparticles could serve as a template to derive hollow nanoparticles. An addition of NaCN solution to silica-coated Au nanoparticles led the formation of hollow silica nanoparticles, which were redispersible in deionized water. The formation of the hollow silica nanoparticles results from the mesoporous structures of the silica shell and such a mesoporous structure is applicable to both catalyst support and drug delivery.

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

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.

Research and development of tungsten electrodes added with rare earth oxides

International Nuclear Information System (INIS)

Zuoren Nie; Ying Chen; Meiling Zhou; Tieyong Zuo

2001-01-01

The recent research and development of tungsten electrodes used in TIG and Plasma technologies are introduced, and the tungsten materials as well as the effects of rare earth oxides are specially discussed. in W-La 2 O 3 , W-CeO 2 , W-Y 2 O 3 and W-ThO 2 electrode materials, the W-2.2mass%La 2 O 3 electrode exhibited the best properties when the current is of little or middle volume, and when the electrodes are used in large current, the W-Y 2 O 3 electrode is the best. By a comparative study between the tungsten electrodes activated with single metal oxides, as above-mentioned, and those containing two or three rare earth oxides, namely La 2 O 3 , CeO 2 and Y 2 O 3 , it was indicated that the welding arc properties of the tungsten electrodes activated with combined rare earth oxides additions is superior than that of the electrodes containing single oxides as above mentioned. It was also shown that the operating properties of tungsten electrodes depend intensively on the rare earth oxides contained in the electrodes, and the actions of rare earth oxides during arcing are the most important factors to the electrodes' operating properties, temperature, work function as well as the arc stability. (author)

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.

Structure–acidity correlation of supported tungsten(VI)-oxo-species: FT-IR and TPD studies of adsorbed pyridine and catalytic decomposition of 2-propanol

Energy Technology Data Exchange (ETDEWEB)

Zaki, M.I., E-mail: mizaki@mu.edu.eg; Mekhemer, G.A.H.; Fouad, N.E.; Rabee, A.I.M.

2014-07-01

The amount of 10 wt%-WO{sub 3} was supported on alumina, titania or silica by impregnation with aqueous solution of ammonium paratungstate and subsequent calcination at 500 °C for 10 h. Tungstate-related chemical and physical changes in the calcination products were resolved by ex-situ infrared (IR) spectroscopy. Nature of exposed surface acid sites were probed by in-situ IR spectroscopy of adsorbed pyridine (Py) molecules at room temperature (RT). The relative strength of the acid sites thus probed was gauged by combining results of temperature-programmed desorption (TPD) measurements of the RT-adsorbed Py with those communicated by in-situ IR spectra of residual Py on the surface after a brief thermoevacuation at high temperatures (100–300 °C). Reactivity of the surface acid sites was tested toward 2-propanal catalytic decomposition, and observed by in-situ IR gas phase spectra. Results obtained were correlated with predominant structures assumed by the supported tungstate species. Accordingly, polymerization of the supported tungstate into 2-/3-dimensional structures, was found to be relatively most advanced on favorable locations of titania surfaces as compared to the case on alumina or silica surfaces. Consequently, the Lewis acidity was strengthened, and strong Bronsted acidity was evolved, leading to a 2-propanol dehydration catalyst (tungstate/titania) of optimal activity and selectivity. Strong tungstate/support interfacial interactions were found to hamper the formation of the strongly acidic and catalytically active polymeric structures of the supported tungstate (i.e., the case on alumina or silica).

Structure–acidity correlation of supported tungsten(VI)-oxo-species: FT-IR and TPD studies of adsorbed pyridine and catalytic decomposition of 2-propanol

International Nuclear Information System (INIS)

Zaki, M.I.; Mekhemer, G.A.H.; Fouad, N.E.; Rabee, A.I.M.

2014-01-01

The amount of 10 wt%-WO 3 was supported on alumina, titania or silica by impregnation with aqueous solution of ammonium paratungstate and subsequent calcination at 500 °C for 10 h. Tungstate-related chemical and physical changes in the calcination products were resolved by ex-situ infrared (IR) spectroscopy. Nature of exposed surface acid sites were probed by in-situ IR spectroscopy of adsorbed pyridine (Py) molecules at room temperature (RT). The relative strength of the acid sites thus probed was gauged by combining results of temperature-programmed desorption (TPD) measurements of the RT-adsorbed Py with those communicated by in-situ IR spectra of residual Py on the surface after a brief thermoevacuation at high temperatures (100–300 °C). Reactivity of the surface acid sites was tested toward 2-propanal catalytic decomposition, and observed by in-situ IR gas phase spectra. Results obtained were correlated with predominant structures assumed by the supported tungstate species. Accordingly, polymerization of the supported tungstate into 2-/3-dimensional structures, was found to be relatively most advanced on favorable locations of titania surfaces as compared to the case on alumina or silica surfaces. Consequently, the Lewis acidity was strengthened, and strong Bronsted acidity was evolved, leading to a 2-propanol dehydration catalyst (tungstate/titania) of optimal activity and selectivity. Strong tungstate/support interfacial interactions were found to hamper the formation of the strongly acidic and catalytically active polymeric structures of the supported tungstate (i.e., the case on alumina or silica).

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%

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.))

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.))

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

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....

The anomalous yield behavior of fused silica glass

Science.gov (United States)

Schill, W.; Heyden, S.; Conti, S.; Ortiz, M.

2018-04-01

We develop a critical-state model of fused silica plasticity on the basis of data mined from molecular dynamics (MD) calculations. The MD data is suggestive of an irreversible densification transition in volumetric compression resulting in permanent, or plastic, densification upon unloading. The MD data also reveals an evolution towards a critical state of constant volume under pressure-shear deformation. The trend towards constant volume is from above, when the glass is overconsolidated, or from below, when it is underconsolidated. We show that these characteristic behaviors are well-captured by a critical state model of plasticity, where the densification law for glass takes the place of the classical consolidation law of granular media and the locus of constant-volume states defines the critical-state line. A salient feature of the critical-state line of fused silica, as identified from the MD data, that renders its yield behavior anomalous is that it is strongly non-convex, owing to the existence of two well-differentiated phases at low and high pressures. We argue that this strong non-convexity of yield explains the patterning that is observed in molecular dynamics calculations of amorphous solids deforming in shear. We employ an explicit and exact rank-2 envelope construction to upscale the microscopic critical-state model to the macroscale. Remarkably, owing to the equilibrium constraint the resulting effective macroscopic behavior is still characterized by a non-convex critical-state line. Despite this lack of convexity, the effective macroscopic model is stable against microstructure formation and defines well-posed boundary-value problems.

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.)

Biodiesel production from transesterification of palm oil with methanol over CaO supported on bimodal meso-macroporous silica catalyst.

Science.gov (United States)

Witoon, Thongthai; Bumrungsalee, Sittisut; Vathavanichkul, Peerawut; Palitsakun, Supaphorn; Saisriyoot, Maythee; Faungnawakij, Kajornsak

2014-03-01

Calcium oxide-loaded porous materials have shown promise as catalysts in transesterification. However, the slow diffusion of bulky triglycerides through the pores limited the activity of calcium oxide (CaO). In this work, bimodal meso-macroporous silica was used as a support to enhance the accessibility of the CaO dispersed inside the pores. Unimodal porous silica having the identical mesopore diameter was employed for the purpose of comparison. Effects of CaO content and catalyst pellet size on the yield of fatty acid methyl esters (FAME) were investigated. The basic strength was found to increase with increasing the CaO content. The CaO-loaded bimodal porous silica catalyst with the pellet size of 325μm achieved a high %FAME of 94.15 in the first cycle, and retained an excellent %FAME of 88.87 after five consecutive cycles. Copyright © 2014 Elsevier Ltd. All rights reserved.

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

Tungsten carbide nanoparticles as efficient cocatalysts for photocatalytic overall water splitting

KAUST Repository

Garcia Esparza, Angel T.

2012-12-17

Tungsten carbide exhibits platinum-like behavior, which makes it an interesting potential substitute for noble metals in catalytic applications. Tungsten carbide nanocrystals (≈5 nm) are directly synthesized through the reaction of tungsten precursors with mesoporous graphitic C3N 4 (mpg-C3N4) as the reactive template in a flow of inert gas at high temperatures. Systematic experiments that vary the precursor compositions and temperatures used in the synthesis selectively generate different compositions and structures for the final nanocarbide (W 2C or WC) products. Electrochemical measurements demonstrate that the WC phase with a high surface area exhibits both high activity and stability in hydrogen evolution over a wide pH range. The WC sample also shows excellent hydrogen oxidation activity, whereas its activity in oxygen reduction is poor. These tungsten carbides are successful cocatalysts for overall water splitting and give H2 and O2 in a stoichiometric ratio from H 2O decomposition when supported on a Na-doped SrTiO3 photocatalyst. Herein, we present tungsten carbide (on a small scale) as a promising and durable catalyst substitute for platinum and other scarce noble-metal catalysts in catalytic reaction systems used for renewable energy generation. Platinum replacement: The phase-controlled synthesis of tungsten carbide nanoparticles from the nanoconfinement of a mesoporous graphite C 3N4 (mpg-C3N4) reactive template is shown. The nanomaterials catalyze hydrogen evolution/oxidation reactions, but are inactive in the oxygen reduction reaction. Tungsten carbide is an effective cocatalyst for photocatalytic overall water splitting (see picture). Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Tungsten carbide nanoparticles as efficient cocatalysts for photocatalytic overall water splitting

KAUST Repository

Garcia Esparza, Angel T.; Cha, Dong Kyu; Ou, Yiwei; Kubota, Jun; Domen, Kazunari; Takanabe, Kazuhiro

2012-01-01

Tungsten carbide exhibits platinum-like behavior, which makes it an interesting potential substitute for noble metals in catalytic applications. Tungsten carbide nanocrystals (≈5 nm) are directly synthesized through the reaction of tungsten precursors with mesoporous graphitic C3N 4 (mpg-C3N4) as the reactive template in a flow of inert gas at high temperatures. Systematic experiments that vary the precursor compositions and temperatures used in the synthesis selectively generate different compositions and structures for the final nanocarbide (W 2C or WC) products. Electrochemical measurements demonstrate that the WC phase with a high surface area exhibits both high activity and stability in hydrogen evolution over a wide pH range. The WC sample also shows excellent hydrogen oxidation activity, whereas its activity in oxygen reduction is poor. These tungsten carbides are successful cocatalysts for overall water splitting and give H2 and O2 in a stoichiometric ratio from H 2O decomposition when supported on a Na-doped SrTiO3 photocatalyst. Herein, we present tungsten carbide (on a small scale) as a promising and durable catalyst substitute for platinum and other scarce noble-metal catalysts in catalytic reaction systems used for renewable energy generation. Platinum replacement: The phase-controlled synthesis of tungsten carbide nanoparticles from the nanoconfinement of a mesoporous graphite C 3N4 (mpg-C3N4) reactive template is shown. The nanomaterials catalyze hydrogen evolution/oxidation reactions, but are inactive in the oxygen reduction reaction. Tungsten carbide is an effective cocatalyst for photocatalytic overall water splitting (see picture). Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Effect of tungsten on tensile properties and flow behaviour of RAFM steel

Energy Technology Data Exchange (ETDEWEB)

Vanaja, J., E-mail: jvanaja@igcar.gov.in [Metallurgy and Materials Group, Indira Gandhi Centre for Atomic Research, Kalpakkam 603 102 (India); Laha, K.; Nandagopal, M. [Metallurgy and Materials Group, Indira Gandhi Centre for Atomic Research, Kalpakkam 603 102 (India); Sam, Shiju [Institute for Plasma Research, Gandhinagar 382 428, Gujarat (India); Mathew, M.D.; Jayakumar, T. [Metallurgy and Materials Group, Indira Gandhi Centre for Atomic Research, Kalpakkam 603 102 (India); Rajendra Kumar, E. [Institute for Plasma Research, Gandhinagar 382 428, Gujarat (India)

2013-02-15

Effect of tungsten in the range of 1–2 wt.% on tensile properties and flow behaviour of 9Cr–W–Ta–V Reduced Activation Ferritic–Martensitic (RAFM) steel has been investigated. The tungsten in the investigated range was found to have only minor effect on the tensile properties of the steel over the temperature range of 300–873 K and at a strain rate of 3 × 10{sup −3} s{sup −1}. The tensile flow behaviour of the RAFM steels was adequately described by the Voce’s constitutive equation. The tensile strength of the steels were predicted well from the parameters of the Voce’s constitutive equation. The Voce’s strain hardening parameter ‘n{sub v}’ was found to be quite sensitive to the tungsten content and predicted the onset of dislocation climbing process at relatively higher testing temperature with the increase in tungsten content. The equivalence between tensile and creep deformations and the influence of tungsten have been discussed.

Effect of tungsten on tensile properties and flow behaviour of RAFM steel

International Nuclear Information System (INIS)

Vanaja, J.; Laha, K.; Nandagopal, M.; Sam, Shiju; Mathew, M.D.; Jayakumar, T.; Rajendra Kumar, E.

2013-01-01

Effect of tungsten in the range of 1–2 wt.% on tensile properties and flow behaviour of 9Cr–W–Ta–V Reduced Activation Ferritic–Martensitic (RAFM) steel has been investigated. The tungsten in the investigated range was found to have only minor effect on the tensile properties of the steel over the temperature range of 300–873 K and at a strain rate of 3 × 10 −3 s −1 . The tensile flow behaviour of the RAFM steels was adequately described by the Voce’s constitutive equation. The tensile strength of the steels were predicted well from the parameters of the Voce’s constitutive equation. The Voce’s strain hardening parameter ‘n v ’ was found to be quite sensitive to the tungsten content and predicted the onset of dislocation climbing process at relatively higher testing temperature with the increase in tungsten content. The equivalence between tensile and creep deformations and the influence of tungsten have been discussed

Numerical simulation of CFC and tungsten target erosion in ITER-FEAT divertor

International Nuclear Information System (INIS)

Filatov, V.

2003-01-01

Physical, chemical and thermal surface erosion for water-cooled target armoured by CFC and tungsten is simulated by numerical code ERosion OF Immolated Layer (EROFIL-1). Some calculation results on the CFC and tungsten vertical target (VT) erosion in the ITER-FEAT divertor are presented for various operation modes (normal operations, slow transients, ELMs and disruptions). The main erosion mechanisms of CFC armour are the chemical and sublimation ones. Maximum erosion depth per 3000 cycles during normal operations and slow transients is of 2.7 mm at H phase and of 13.5 mm at DT phase. An evaluation of VT tungsten armour erosion per 3000 cycles of H and DT operations shows that no physical or chemical erosion as well as no melting are expected for tungsten armour at normal operations and slow transients. The tungsten armour melting at 2x10 6 ELMs is not allowable. The 300 disruptions are not dangerous in view of evaporation

In vivo corrosion, tumor outcome, and microarray gene expression for two types of muscle-implanted tungsten alloys

Energy Technology Data Exchange (ETDEWEB)

Schuster, B.E. [U.S. Army Research Laboratory, Weapons and Materials Research Directorate, B434 Mulberry Road, Aberdeen Proving Ground, MD 21005-5609 (United States); Roszell, L.E. [U.S. Army Institute of Public Health, 5158 Blackhawk Road, Aberdeen Proving Ground, MD 21010‐5403 (United States); Murr, L.E.; Ramirez, D.A. [Department of Metallurgical and Materials Engineering, University of Texas, El Paso, TX 79968 (United States); Demaree, J.D. [U.S. Army Research Laboratory, Weapons and Materials Research Directorate, B434 Mulberry Road, Aberdeen Proving Ground, MD 21005-5609 (United States); Klotz, B.R. [Dynamic Science Inc., Aberdeen Proving Ground, MD 21005‐5609 (United States); Rosencrance, A.B.; Dennis, W.E. [U.S. Army Center for Environmental Health Research, Department of Chemistry, Ft. Detrick, MD 21702‐5010 (United States); Bao, W. [SAS Institute, Inc. SAS Campus Drive, Cary, NC 27513 (United States); Perkins, E.J. [U.S. Army Engineer Research and Development Center, 3909 Hall Ferry Road, Vicksburg MS 39180 (United States); Dillman, J.F. [U.S. Army Medical Research Institute of Chemical Defense, 3100 Ricketts Point Road, Aberdeen Proving Ground, MD 21010‐5400 (United States); Bannon, D.I., E-mail: desmond.bannon@us.army.mil [U.S. Army Institute of Public Health, 5158 Blackhawk Road, Aberdeen Proving Ground, MD 21010‐5403 (United States)

2012-11-15

Tungsten alloys are composed of tungsten microparticles embedded in a solid matrix of transition metals such as nickel, cobalt, or iron. To understand the toxicology of these alloys, male F344 rats were intramuscularly implanted with pellets of tungsten/nickel/cobalt, tungsten/nickel/iron, or pure tungsten, with tantalum pellets as a negative control. Between 6 and 12 months, aggressive rhabdomyosarcomas formed around tungsten/nickel/cobalt pellets, while those of tungsten/nickel/iron or pure tungsten did not cause cancers. Electron microscopy showed a progressive corrosion of the matrix phase of tungsten/nickel/cobalt pellets over 6 months, accompanied by high urinary concentrations of nickel and cobalt. In contrast, non-carcinogenic tungsten/nickel/iron pellets were minimally corroded and urinary metals were low; these pellets having developed a surface oxide layer in vivo that may have restricted the mobilization of carcinogenic nickel. Microarray analysis of tumors revealed large changes in gene expression compared with normal muscle, with biological processes involving the cell cycle significantly up‐regulated and those involved with muscle development and differentiation significantly down‐regulated. Top KEGG pathways disrupted were adherens junction, p53 signaling, and the cell cycle. Chromosomal enrichment analysis of genes showed a highly significant impact at cytoband 7q22 (chromosome 7) which included mouse double minute (MDM2) and cyclin‐dependant kinase (CDK4) as well as other genes associated with human sarcomas. In conclusion, the tumorigenic potential of implanted tungsten alloys is related to mobilization of carcinogenic metals nickel and cobalt from corroding pellets, while gene expression changes in the consequent tumors are similar to radiation induced animal sarcomas as well as sporadic human sarcomas. -- Highlights: ► Tungsten/nickel/cobalt, tungsten/nickel/iron, and pure tungsten were studied. ► Male Fischer rats implanted with

In vivo corrosion, tumor outcome, and microarray gene expression for two types of muscle-implanted tungsten alloys

International Nuclear Information System (INIS)

Schuster, B.E.; Roszell, L.E.; Murr, L.E.; Ramirez, D.A.; Demaree, J.D.; Klotz, B.R.; Rosencrance, A.B.; Dennis, W.E.; Bao, W.; Perkins, E.J.; Dillman, J.F.; Bannon, D.I.

2012-01-01

Tungsten alloys are composed of tungsten microparticles embedded in a solid matrix of transition metals such as nickel, cobalt, or iron. To understand the toxicology of these alloys, male F344 rats were intramuscularly implanted with pellets of tungsten/nickel/cobalt, tungsten/nickel/iron, or pure tungsten, with tantalum pellets as a negative control. Between 6 and 12 months, aggressive rhabdomyosarcomas formed around tungsten/nickel/cobalt pellets, while those of tungsten/nickel/iron or pure tungsten did not cause cancers. Electron microscopy showed a progressive corrosion of the matrix phase of tungsten/nickel/cobalt pellets over 6 months, accompanied by high urinary concentrations of nickel and cobalt. In contrast, non-carcinogenic tungsten/nickel/iron pellets were minimally corroded and urinary metals were low; these pellets having developed a surface oxide layer in vivo that may have restricted the mobilization of carcinogenic nickel. Microarray analysis of tumors revealed large changes in gene expression compared with normal muscle, with biological processes involving the cell cycle significantly up‐regulated and those involved with muscle development and differentiation significantly down‐regulated. Top KEGG pathways disrupted were adherens junction, p53 signaling, and the cell cycle. Chromosomal enrichment analysis of genes showed a highly significant impact at cytoband 7q22 (chromosome 7) which included mouse double minute (MDM2) and cyclin‐dependant kinase (CDK4) as well as other genes associated with human sarcomas. In conclusion, the tumorigenic potential of implanted tungsten alloys is related to mobilization of carcinogenic metals nickel and cobalt from corroding pellets, while gene expression changes in the consequent tumors are similar to radiation induced animal sarcomas as well as sporadic human sarcomas. -- Highlights: ► Tungsten/nickel/cobalt, tungsten/nickel/iron, and pure tungsten were studied. ► Male Fischer rats implanted with

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%)

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.

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

Fibrous nano-silica (KCC-1)-supported palladium catalyst: Suzuki coupling reactions under sustainable conditions

KAUST Repository

Fihri, Aziz; Cha, Dong Kyu; Bouhrara, Mohamed; Al Mana, Noor; Polshettiwar, Vivek

2011-01-01

Noble amines recycled: Fibrous high-surface-area nano-silica functionalized with aminopropyl groups and loaded with well-dispersed Pd nanoparticles is evaluated for the Suzuki coupling of aromatic halides. It is active for the reaction of a range of aryl bromides and iodides as well as chlorides with aryl boronic acids in good to excellent yields. The catalyst can be recovered and reused for a number of cycles with negligible loss in activity. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Fibrous nano-silica (KCC-1)-supported palladium catalyst: Suzuki coupling reactions under sustainable conditions

KAUST Repository

Fihri, Aziz

2011-11-15

Noble amines recycled: Fibrous high-surface-area nano-silica functionalized with aminopropyl groups and loaded with well-dispersed Pd nanoparticles is evaluated for the Suzuki coupling of aromatic halides. It is active for the reaction of a range of aryl bromides and iodides as well as chlorides with aryl boronic acids in good to excellent yields. The catalyst can be recovered and reused for a number of cycles with negligible loss in activity. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Carbon monoxide adsorption studies on Ru:Mn bimetallic catalysts supported on alumina, silica and titania supported for the determination of metal surface area overview

International Nuclear Information System (INIS)

Hussain, S.T.

1992-01-01

Supported Ru: Mn bimetallic samples were studied using CO-chemisorption on alumina, silica and titania supports for the determination of active metal site/metal surface area. The data indicates the presence of Mn on the surface of Ru. With the increase of Mn loadings a decrease in the CO adsorption occurred indicating that presence of Mn masks the active sites responsible for Co-adsorption. On the titania supported system reduced at high and low temperature the CO-chemisorption data suggest the unusual behaviour. This behaviour is possibly caused due to creation of new active surface sites. (author)

Failure study of helium-cooled tungsten divertor plasma-facing units tested at DEMO relevant steady-state heat loads

International Nuclear Information System (INIS)

Ritz, G; Pintsuk, G; Linke, J; Hirai, T; Norajitra, P; Reiser, J; Giniyatulin, R; Makhankov, A; Mazul, I

2009-01-01

Tungsten was selected as armor material for the helium-cooled divertor in future DEMO-type fusion reactors and fusion power plants. After realizing the design and testing of them under cyclic thermal loads of up to ∼14 MW m -2 , the tungsten divertor plasma-facing units were examined by metallography; they revealed failures such as cracks at the thermal loaded and as-machined surfaces, as well as degradation of the brazing layers. Furthermore, in order to optimize the machining processes, the quality of tungsten surfaces prepared by turning, milling and using a diamond cutting wheel were examined. This paper presents a metallographic examination of the tungsten plasma-facing units as well as technical studies and the characterization on machining of tungsten and alternative brazing joints.

Failure study of helium-cooled tungsten divertor plasma-facing units tested at DEMO relevant steady-state heat loads

Science.gov (United States)

Ritz, G.; Hirai, T.; Norajitra, P.; Reiser, J.; Giniyatulin, R.; Makhankov, A.; Mazul, I.; Pintsuk, G.; Linke, J.

2009-12-01

Tungsten was selected as armor material for the helium-cooled divertor in future DEMO-type fusion reactors and fusion power plants. After realizing the design and testing of them under cyclic thermal loads of up to ~14 MW m-2, the tungsten divertor plasma-facing units were examined by metallography; they revealed failures such as cracks at the thermal loaded and as-machined surfaces, as well as degradation of the brazing layers. Furthermore, in order to optimize the machining processes, the quality of tungsten surfaces prepared by turning, milling and using a diamond cutting wheel were examined. This paper presents a metallographic examination of the tungsten plasma-facing units as well as technical studies and the characterization on machining of tungsten and alternative brazing joints.

Silica-supported (nBuCp)2ZrCl2: Effect of catalyst active center distribution on ethylene-1-hexene copolymerization

KAUST Repository

Atiqullah, Muhammad

2013-08-12

Metallocenes are a modern innovation in polyolefin catalysis research. Therefore, two supported metallocene catalysts-silica/MAO/(nBuCp)2ZrCl2 (Catalyst 1) and silica/nBuSnCl3/MAO/(nBuCp)2ZrCl2 (Catalyst 2), where MAO is methylaluminoxane-were synthesized, and subsequently used to prepare, without separate feeding of MAO, ethylene-1-hexene Copolymer 1 and Copolymer 2, respectively. Fouling-free copolymerization, catalyst kinetic stability and production of free-flowing polymer particles (replicating the catalyst particle size distribution) confirmed the occurrence of heterogeneous catalysis. The catalyst active center distribution was modeled by deconvoluting the measured molecular weight distribution and copolymer composition distribution. Five different active center types were predicted for each catalyst, which was corroborated by successive self-nucleation and annealing experiments, as well as by an extended X-ray absorption fine structure spectroscopy report published in the literature. Hence, metallocenes impregnated particularly on an MAO-pretreated support may be rightly envisioned to comprise an ensemble of isolated single sites that have varying coordination environments. This study shows how the active center distribution and the design of supported MAO anions affect copolymerization activity, polymerization mechanism and the resulting polymer microstructures. Catalyst 2 showed less copolymerization activity than Catalyst 1. Strong chain transfer and positive co-monomer effect-both by 1-hexene-were common. Each copolymer demonstrated vinyl, vinylidene and trans-vinylene end groups, and compositional heterogeneity. All these findings were explained, as appropriate, considering the modeled active center distribution, MAO cage structure repeat units, proposed catalyst surface chemistry, segregation effects and the literature that concerns and supports this study. While doing so, new insights were obtained. Additionally, future research, along the direction

Silica-supported (nBuCp)2ZrCl2: Effect of catalyst active center distribution on ethylene-1-hexene copolymerization

KAUST Repository

Atiqullah, Muhammad; Anantawaraskul, Siripon; Emwas, Abdul-Hamid M.; Al-Harthi, Mamdouh Ahmed; Hussain, Ikram; Ul-Hamid, Anwar; Hossaen, Anwar

2013-01-01

Metallocenes are a modern innovation in polyolefin catalysis research. Therefore, two supported metallocene catalysts-silica/MAO/(nBuCp)2ZrCl2 (Catalyst 1) and silica/nBuSnCl3/MAO/(nBuCp)2ZrCl2 (Catalyst 2), where MAO is methylaluminoxane-were synthesized, and subsequently used to prepare, without separate feeding of MAO, ethylene-1-hexene Copolymer 1 and Copolymer 2, respectively. Fouling-free copolymerization, catalyst kinetic stability and production of free-flowing polymer particles (replicating the catalyst particle size distribution) confirmed the occurrence of heterogeneous catalysis. The catalyst active center distribution was modeled by deconvoluting the measured molecular weight distribution and copolymer composition distribution. Five different active center types were predicted for each catalyst, which was corroborated by successive self-nucleation and annealing experiments, as well as by an extended X-ray absorption fine structure spectroscopy report published in the literature. Hence, metallocenes impregnated particularly on an MAO-pretreated support may be rightly envisioned to comprise an ensemble of isolated single sites that have varying coordination environments. This study shows how the active center distribution and the design of supported MAO anions affect copolymerization activity, polymerization mechanism and the resulting polymer microstructures. Catalyst 2 showed less copolymerization activity than Catalyst 1. Strong chain transfer and positive co-monomer effect-both by 1-hexene-were common. Each copolymer demonstrated vinyl, vinylidene and trans-vinylene end groups, and compositional heterogeneity. All these findings were explained, as appropriate, considering the modeled active center distribution, MAO cage structure repeat units, proposed catalyst surface chemistry, segregation effects and the literature that concerns and supports this study. While doing so, new insights were obtained. Additionally, future research, along the direction

TiO{sub 2} supported over porous silica photocatalysts for pesticide degradation using solar light: Part 2. Silica prepared using acrylic acid emulsion

Energy Technology Data Exchange (ETDEWEB)

Phanikrishna Sharma, Mangalampalli V.; Durga Kumari, Valluri [Inorganic and Physical Chemistry Division, Indian Institute of Chemical Technology, Tarnaka, Hyderabad 500607, Andhra Pradesh (India); Subrahmanyam, Machiraju, E-mail: subrahmanyam@iict.res.in [Inorganic and Physical Chemistry Division, Indian Institute of Chemical Technology, Tarnaka, Hyderabad 500607, Andhra Pradesh (India)

2010-03-15

An acrylic acid emulsion mixture is used for synthesis of novel porous silica (E-Si) material. The photocatalytic activity of TiO{sub 2} under solar light irradiation for isoproturon (herbicide) degradation is drastically increased when dispersed over E-Si support using solid state dispersion (SSD) technique. The composite material is characterized by XRD, nitrogen adsorption-desorption isotherms, UV-vis DRS, SEM and TEM measurements. The photocatalytic activities of the composite catalysts are evaluated for different parameters. The 5 wt% TiO{sub 2}/E-Si is found to be highly active for isoproturon degradation.

Preparation of resveratrol-loaded nanoporous silica materials with different structures

Science.gov (United States)

Popova, Margarita; Szegedi, Agnes; Mavrodinova, Vesselina; Novak Tušar, Natasa; Mihály, Judith; Klébert, Szilvia; Benbassat, Niko; Yoncheva, Krassimira

2014-11-01

Solid, nanoporous silica-based spherical mesoporous MCM-41 and KIL-2 with interparticle mesoporosity as well as nanosized zeolite BEA materials differing in morphology and pore size distribution, were used as carriers for the preparation of resveratrol-loaded delivery systems. Two preparation methods have been applied: (i) loading by mixing of resveratrol and mesoporous carrier in solid state and (ii) deposition in ethanol solution. The parent and the resveratrol loaded carriers were characterized by XRD, TEM, N2 physisorption, thermal analysis, and FT-IR spectroscopy. The influence of the support structure on the adsorption capacity and the release kinetics of this poorly soluble compound were investigated. Our results indicated that the chosen nanoporous silica supports are suitable for stabilization of trans-resveratrol and reveal controlled release and ability to protect the supported compound against degradation regardless of loading method. The solid-state dry mixing appears very effective for preparation of drug formulations composed of poorly soluble compound.

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...

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

Gas Separation through Bilayer Silica, the Thinnest Possible Silica Membrane.

Science.gov (United States)

Yao, Bowen; Mandrà, Salvatore; Curry, John O; Shaikhutdinov, Shamil; Freund, Hans-Joachim; Schrier, Joshua

2017-12-13

Membrane-based gas separation processes can address key challenges in energy and environment, but for many applications the permeance and selectivity of bulk membranes is insufficient for economical use. Theory and experiment indicate that permeance and selectivity can be increased by using two-dimensional materials with subnanometer pores as membranes. Motivated by experiments showing selective permeation of H 2 /CO mixtures through amorphous silica bilayers, here we perform a theoretical study of gas separation through silica bilayers. Using density functional theory calculations, we obtain geometries of crystalline free-standing silica bilayers (comprised of six-membered rings), as well as the seven-, eight-, and nine-membered rings that are observed in glassy silica bilayers, which arise due to Stone-Wales defects and vacancies. We then compute the potential energy barriers for gas passage through these various pore types for He, Ne, Ar, Kr, H 2 , N 2 , CO, and CO 2 gases, and use the data to assess their capability for selective gas separation. Our calculations indicate that crystalline bilayer silica, which is less than a nanometer thick, can be a high-selectivity and high-permeance membrane material for 3 He/ 4 He, He/natural gas, and H 2 /CO separations.

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.

Electronic Structure Control of Tungsten Oxide Activated by Ni for Ultrahigh-Performance Supercapacitors.

Science.gov (United States)

Meng, Tian; Kou, Zongkui; Amiinu, Ibrahim Saana; Hong, Xufeng; Li, Qingwei; Tang, Yongfu; Zhao, Yufeng; Liu, Shaojun; Mai, Liqiang; Mu, Shichun

2018-04-17

Tuning the electron structure is of vital importance for designing high active electrode materials. Here, for boosting the capacitive performance of tungsten oxide, an atomic scale engineering approach to optimize the electronic structure of tungsten oxide by Ni doping is reported. Density functional theory calculations disclose that through Ni doping, the density of state at Fermi level for tungsten oxide can be enhanced, thus promoting its electron transfer. When used as electrode of supercapacitors, the obtained Ni-doped tungsten oxide with 4.21 at% Ni exhibits an ultrahigh mass-specific capacitance of 557 F g -1 at the current density of 1 A g -1 and preferable durability in a long-term cycle test. To the best of knowledge, this is the highest supercapacitor performance reported so far in tungsten oxide and its composites. The present strategy demonstrates the validity of the electronic structure control in tungsten oxide via introducing Ni atoms for pseudocapacitors, which can be extended to other related fields as well. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Preparation and characterization of tungsten-loaded titanium dioxide photocatalyst for enhanced dye degradation

International Nuclear Information System (INIS)

Saepurahman; Abdullah, M.A.; Chong, F.K.

2010-01-01

Tungsten-loaded TiO 2 photocatalyst has been successfully prepared and characterized. TEM analysis showed that the photocatalysts were nanosize with the tungsten species forming layers of coverage on the surface of TiO 2 , but not in clustered form. This was confirmed by XRD and FT-Raman analyses where tungsten species were well dispersed at lower loading ( 3 at higher loadings (>12 mol%). In addition, loading with tungsten could stabilize the anatase phase from transforming into inactive rutile phase and did not shift the optical absorption to the visible region as shown by DRUV-vis analysis. PZC value of TiO 2 was found at 6.4, but the presence of tungsten at 6.5 mol% WO 3 , decreased the PZC value to 3. Tungsten-loaded TiO 2 was superior to unmodified TiO 2 with 2-fold increase in degradation rate of methylene blue, and equally effective for the degradation of different class of dyes such as methyl violet and methyl orange at 1 mol% WO 3 loading.

Investigating unexpected magnetism of mesoporous silica-supported Pd and PdO nanoparticles

KAUST Repository

Song, Hyon Min

2015-01-13

The synthesis and magnetic behavior of matrix-supported Pd and PdO nanoparticles (NPs) are described. Mesoporous silica with hexagonal columnal packing is selected as a template, and the impregnation method with thermal annealing is used to obtain supported Pd and PdO NPs. The heating rate and the annealing conditions determine the particle size and the phase of the NPs, with a fast heating rate of 30 °C/min producing the largest supported Pd NPs. Unusual magnetic behaviors are observed. (1) Contrary to the general belief that smaller Pd NPs or cluster size particles have higher magnetization, matrix-supported Pd NPs in this study maintain the highest magnetization with room temperature ferromagnetism when the size is the largest. (2) Twin boundaries along with stacking faults are more pronounced in these large Pd NPs and are believed to be the reason for this high magnetization. Similarly, supported PdO NPs were prepared under air conditions with different heating rates. Their phase is tetragonal (P42/mmc) with cell parameters of a = 3.050 Å and c = 5.344 Å, which are slightly larger than in the bulk phase (a = 3.03 Å, c = 5.33 Å). Faster heating rate of 30 °C/min also produces larger particles and larger magnetic hysteresis loop, although magnetization is smaller and few twin boundaries are observed compared to the supported metallic Pd NPs.

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.

Facile synthesis of mesoporous silica sublayer with hierarchical pore structure on ceramic membrane using anionic polyelectrolyte.

Science.gov (United States)

Kang, Taewook; Oh, Seogil; Kim, Honggon; Yi, Jongheop

2005-06-21

A facile method for introducing mesoporous silica sublayer onto the surface of a ceramic membrane for use in liquid-phase separation is described. To reduce the electrostatic repulsion between the mesoporous silica sol and the ceramic membrane in highly acidic conditions (pH ceramic membrane, as confirmed by experimental titration data. Consistent with the titration results, the amount of mesoporous silica particles on the surface of the ceramic membrane was low, in the absence of PSS- treatment, whereas mesoporous silica sublayer with hierarchical pore structure was produced, when 1 wt % PSS- was used. The results show that mesoporous silica grows in the confined surface, eventually forming a multistacked surface architecture. The mesoporous silica sublayer contained uniform, ordered (P6 mm) mesopores of ca. 7.5 nm from mesoporous silica as well as macropores ( approximately mum) from interparticle voids, as evidenced by transmission electron microscopy and scanning electron microscopy analyses. The morphologies of the supported mesoporous silica could be manipulated, thus permitting the generation of uniform needlelike forms or uniform spheroid particles by varying the concentration of PSS-.

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

Tungsten - rhenium alloys wire: overview of thermomechanical processing and properties data

International Nuclear Information System (INIS)

Bryskin, B.

2001-01-01

The scope of this study encompasses the compositional modifications of the tungsten-rhenium dual system (W-3/5 Re up to W-27 Re) as well as some of the tungsten-molybdenum-rhenium ternary system. The alloys of interest are considered with a specific representation of powder metallurgy route based on doped or undoped tungsten vs. vacuum melted materials. This paper constitutes an in-depth review of structural and mechanical properties and systematic compilation of challenges necessary to provide the quality consistency of severely drawn filaments. The issue of thermomechanical processing trends is addressed as an important part of W-Re fabrication technology to achieve further improvement in design properties of rod and wire. (author)

Facile and tunable synthesis of hierarchical mesoporous silica materials ranging from flower structure with wrinkled edges to hollow structure with coarse surface

Energy Technology Data Exchange (ETDEWEB)

Hao, Nanjing, E-mail: nanjing.hao@dartmouth.edu [Dartmouth College, Thayer School of Engineering (United States); Li, Laifeng; Tang, Fangqiong, E-mail: tangfq@mail.ipc.ac.cn [Chinese Academy of Sciences, Technical Institute of Physics and Chemistry (China)

2016-11-15

Mesoporous silica materials have attracted great attention in many fields. However, facile and tunable synthesis of hierarchical mesoporous silica structures is still a big challenge, and thus the development of them still lags behind. Herein, well-defined mesoporous silica flower structure with wrinkled edges and mesoporous silica hollow structure with coarse surface were synthesized simply by using poly(vinylpyrrolidone) and hexadecylamine as cotemplates in different water/ethanol solvent systems. The shape evolution from flower to hollow can be easily realized by tuning the volume ratio of water to ethanol, and the yields of both materials can reach gram scale. The formation mechanisms of mesoporous silica flower and hollow structures were also experimentally investigated and discussed. These novel hierarchical structures having unique physicochemical properties may bring many interesting insights into scientific research and technological application.

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.

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.

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.

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.

Danish Investigations on Silica Fume Concretes at Elevated Temperatures

DEFF Research Database (Denmark)

Hertz, Kristian Dahl

1992-01-01

Describes fire tests in which the increased risk of explosive spalling of concrete densified by silica fume was first discovered. Further results are discussed from tests to define appropriate limits of silica fume content and to develop a new concrete for slender column units. Observations are m...... are made about circumstances under which superplasticizing additives in concrete gave rise to the development of toxic gases....

Structural stability of super duplex stainless weld metals and its dependence on tungsten and copper

International Nuclear Information System (INIS)

Nilsson, J.O.; Wilson, A.; Huhtala, T.; Karlsson, L.; Jonsson, P.

1996-01-01

Three different superduplex stainless weld metals have been produced using manual metal arc welding under identical welding conditions. The concentration of the alloying elements tungsten and copper corresponded to the concentrations in commercial superduplex stainless steels (SDSS). Aging experiments in the temperature range 700 C to 1,110 C showed that the formation of intermetallic phase was enhanced in tungsten-rich weld metal and also dissolved at higher temperatures compared with tungsten-poor and tungsten-free weld metals. It could be inferred from time-temperature-transformation (TTT) and continuous-cooling-transformation (CCT) diagrams produced in the present investigation that the critical cooling rate to avoid 1 wt pct of intermetallic phase was 2 times faster for tungsten-rich weld metal. Microanalysis in combination with thermodynamic calculations showed that tungsten was accommodated in χ phase, thereby decreasing the free energy. Experimental evidence supports the view that the formation of intermetallic phase is enhanced in tungsten-rich weld metal, owing to easier nucleation of nonequilibrium χ phase compared with σ phase. The formation of secondary austenite (γ 2 ) during welding was modeled using the thermodynamic computer program Thermo-Calc. Satisfactory agreement between theory and practice was obtained. Thermo-Calc was capable of predicting observed lower concentrations of chromium and nitrogen in γ 2 compared with primary austenite. The volume fraction of γ 2 was found to be significantly higher in tungsten-rich and tungsten + copper containing weld metal. The results could be explained by a higher driving force for precipitation of γ 2 in these

Structural stability of super duplex stainless weld metals and its dependence on tungsten and copper

Science.gov (United States)

Nilsson, J.-O.; Huhtala, T.; Jonsson, P.; Karlsson, L.; Wilson, A.

1996-08-01

Three different superduplex stainless weld metals have been produced using manual metal arc welding under identical welding conditions. The concentration of the alloying elements tungsten and copper corresponded to the concentrations in commercial superduplex stainless steels (SDSS). Aging experiments in the temperature range 700 °C to 1110 °C showed that the formation of intermetallic phase was enhanced in tungsten-rich weld metal and also dissolved at higher temperatures compared with tungsten-poor and tungsten-free weld metals. It could be inferred from time-temperature-transformation (TTT) and continuous-cooling-transformation (CCT) diagrams produced in the present investigation that the critical cooling rate to avoid 1 wt pct of intermetallic phase was 2 times faster for tungsten-rich weld metal. Microanalysis in combination with thermodynamic calculations showed that tungsten was accommodated in χ phase, thereby decreasing the free energy. Experimental evidence supports the view that the formation of intermetallic phase is enhanced in tungsten-rich weld metal, owing to easier nucleation of nonequilibrium χ phase compared with σ phase. The formation of secondary austenite (γ2) during welding was modeled using the thermodynamic computer program Thermo-Calc. Satisfactory agreement between theory and practice was obtained. Thermo-Calc was capable of predicting observed lower concentrations of chromium and nitrogen in γ2 compared with primary austenite. The volume fraction of γ2 was found to be significantly higher in tungsten-rich and tungsten + copper containing weld metal. The results could be explained by a higher driving force for precipitation of γ2 in these.

Preparation of resveratrol-loaded nanoporous silica materials with different structures

International Nuclear Information System (INIS)

Popova, Margarita; Szegedi, Agnes; Mavrodinova, Vesselina; Novak Tušar, Natasa; Mihály, Judith; Klébert, Szilvia; Benbassat, Niko; Yoncheva, Krassimira

2014-01-01

Solid, nanoporous silica-based spherical mesoporous MCM-41 and KIL-2 with interparticle mesoporosity as well as nanosized zeolite BEA materials differing in morphology and pore size distribution, were used as carriers for the preparation of resveratrol-loaded delivery systems. Two preparation methods have been applied: (i) loading by mixing of resveratrol and mesoporous carrier in solid state and (ii) deposition in ethanol solution. The parent and the resveratrol loaded carriers were characterized by XRD, TEM, N2 physisorption, thermal analysis, and FT-IR spectroscopy. The influence of the support structure on the adsorption capacity and the release kinetics of this poorly soluble compound were investigated. Our results indicated that the chosen nanoporous silica supports are suitable for stabilization of trans-resveratrol and reveal controlled release and ability to protect the supported compound against degradation regardless of loading method. The solid-state dry mixing appears very effective for preparation of drug formulations composed of poorly soluble compound. - Graphical abstract: trans-Resveratrol was stabilized in the pores of BEA zeolite, MCM-41and KIL2 mesoporous silicas. - Highlights: • BEA, KIL-2 and MCM-41 materials were used as carriers for resveratrol loading. • Resveratrol encapsulation in ethanol solution and solid state procedure were applied. • The solid-state preparation appears very effective for stabilization of trans-resveratrol

Preparation of resveratrol-loaded nanoporous silica materials with different structures

Energy Technology Data Exchange (ETDEWEB)

Popova, Margarita, E-mail: mpopova@orgchem.bas.bg [Institute of Organic Chemistry with Centre of Phytochemistry, Bulgarian Academy of Sciences, 1113 Sofia (Bulgaria); Szegedi, Agnes [Research Centre for Natural Sciences, Institute of Materials and Environmental Chemistry, Hungarian Academy of Sciences, 1117 Budapest, Magyar tudósok körútja 2. (Hungary); Mavrodinova, Vesselina [Institute of Organic Chemistry with Centre of Phytochemistry, Bulgarian Academy of Sciences, 1113 Sofia (Bulgaria); Novak Tušar, Natasa [National Institute of Chemistry, Ljubljana (Slovenia); Mihály, Judith; Klébert, Szilvia [Research Centre for Natural Sciences, Institute of Materials and Environmental Chemistry, Hungarian Academy of Sciences, 1117 Budapest, Magyar tudósok körútja 2. (Hungary); Benbassat, Niko; Yoncheva, Krassimira [Faculty of Pharmacy, 2 Dunav Str., 1000 Sofia (Bulgaria)

2014-11-15

Solid, nanoporous silica-based spherical mesoporous MCM-41 and KIL-2 with interparticle mesoporosity as well as nanosized zeolite BEA materials differing in morphology and pore size distribution, were used as carriers for the preparation of resveratrol-loaded delivery systems. Two preparation methods have been applied: (i) loading by mixing of resveratrol and mesoporous carrier in solid state and (ii) deposition in ethanol solution. The parent and the resveratrol loaded carriers were characterized by XRD, TEM, N2 physisorption, thermal analysis, and FT-IR spectroscopy. The influence of the support structure on the adsorption capacity and the release kinetics of this poorly soluble compound were investigated. Our results indicated that the chosen nanoporous silica supports are suitable for stabilization of trans-resveratrol and reveal controlled release and ability to protect the supported compound against degradation regardless of loading method. The solid-state dry mixing appears very effective for preparation of drug formulations composed of poorly soluble compound. - Graphical abstract: trans-Resveratrol was stabilized in the pores of BEA zeolite, MCM-41and KIL2 mesoporous silicas. - Highlights: • BEA, KIL-2 and MCM-41 materials were used as carriers for resveratrol loading. • Resveratrol encapsulation in ethanol solution and solid state procedure were applied. • The solid-state preparation appears very effective for stabilization of trans-resveratrol.

Tetragonal zirconia quantum dots in silica matrix prepared by a modified sol-gel protocol

Science.gov (United States)

Verma, Surbhi; Rani, Saruchi; Kumar, Sushil

2018-05-01

Tetragonal zirconia quantum dots (t-ZrO2 QDs) in silica matrix with different compositions ( x)ZrO2-(100 - x)SiO2 were fabricated by a modified sol-gel protocol. Acetylacetone was added as a chelating agent to zirconium propoxide to avoid precipitation. The powders as well as thin films were given thermal treatment at 650, 875 and 1100 °C for 4 h. The silica matrix remained amorphous after thermal treatment and acted as an inert support for zirconia quantum dots. The tetragonal zirconia embedded in silica matrix transformed into monoclinic form due to thermal treatment ≥ 1100 °C. The stability of tetragonal phase of zirconia is found to enhance with increase in silica content. A homogenous dispersion of t-ZrO2 QDs in silica matrix was indicated by the mapping of Zr, Si and O elements obtained from scanning electron microscope with energy dispersive X-ray analyser. The transmission electron images confirmed the formation of tetragonal zirconia quantum dots embedded in silica. The optical band gap of zirconia QDs (3.65-5.58 eV) was found to increase with increase in zirconia content in silica. The red shift of PL emission has been exhibited with increase in zirconia content in silica.

Au and AuCu Nanoparticles Supported on SBA-15 Ordered Mesoporous Titania-Silica as Catalysts for Methylene Blue Photodegradation

Directory of Open Access Journals (Sweden)

Isabel Barroso-Martín

2018-05-01

Full Text Available The photocatalytic degradation of methylene blue (MB dye has been performed under UV irradiation in aqueous suspension, employing photocatalysts based on Au (1.5 wt % and AuCu (Au/Cu = 1, 2.0 wt %, and supported on SBA-15-ordered mesoporous silica, with and without titania (Si/Ti = 3, in order to evaluate the versatility of this mesoporous support in this type of reaction of great impact from the environmental point of view. Samples were characterized by X-ray diffraction (XRD, transmission electron microscopy (TEM, N2 adsorption-desorption at −196 °C, and X-ray photoelectron spectroscopy (XPS, so as to study their structural, optical, and chemical properties. All the prepared catalysts were found to be active in the test reaction. The bimetallic AuCu-based catalysts attained very high MB degradation values, in particular AuCu/SBA-15 titania-silica sample reached 100% of dye oxidation after the monitored reaction period (120 min.

Impact of microstructure on the plasma performance of industrial and high-end tungsten grades

Energy Technology Data Exchange (ETDEWEB)

Pintsuk, G., E-mail: g.pintsuk@fz-juelich.de [Forschungszentrum Jülich, EURATOM Association, 52428 Jülich (Germany); Loewenhoff, Th. [Forschungszentrum Jülich, EURATOM Association, 52428 Jülich (Germany)

2013-07-15

Tungsten and tungsten alloys are actually the primary choice as plasma facing materials for future fusion reactors. Thereby, the material’s response to the different loading conditions occurring in a tokamak is strongly depending on the material properties and therefore the material’s microstructure. This is on the one hand controlled via the manufacturing process and/or the material’s composition and on the other hand by the operational conditions causing recrystallization and melting, and subsequently not only a modified microstructure but also locally a modified composition. The influence of the variation in microstructure is addressed and the pros and cons for using the respective materials and tungsten in general in a fusion environment with steady state and transient thermal loads are outlined. While roughening and the related cracking can hardly be avoided, melting will thwart all efforts to establish a high end microstructure with defined directional properties.

Impact of microstructure on the plasma performance of industrial and high-end tungsten grades

International Nuclear Information System (INIS)

Pintsuk, G.; Loewenhoff, Th.

2013-01-01

Tungsten and tungsten alloys are actually the primary choice as plasma facing materials for future fusion reactors. Thereby, the material’s response to the different loading conditions occurring in a tokamak is strongly depending on the material properties and therefore the material’s microstructure. This is on the one hand controlled via the manufacturing process and/or the material’s composition and on the other hand by the operational conditions causing recrystallization and melting, and subsequently not only a modified microstructure but also locally a modified composition. The influence of the variation in microstructure is addressed and the pros and cons for using the respective materials and tungsten in general in a fusion environment with steady state and transient thermal loads are outlined. While roughening and the related cracking can hardly be avoided, melting will thwart all efforts to establish a high end microstructure with defined directional properties

A polyacrylonitrile copolymer-silica template for three-dimensional hierarchical porous carbon as a Pt catalyst support for the oxygen reduction reaction.

Science.gov (United States)

Liu, Minmin; Li, Jian; Cai, Chao; Zhou, Ziwei; Ling, Yun; Liu, Rui

2017-08-01

Herein, we report a novel route to construct a hierarchical three-dimensional porous carbon (3DC) through a copolymer-silica assembly. In the synthesis, silica acts as a hard template and leads to the formation of an interconnected 3D macropore, whereas styrene-co-acrylonitrile polymer has been used as both a carbon source and a soft template for micro- and meso-pores. The obtained 3DC materials possess a large surface area (∼550.5 m 2 g -1 ), which facilitates high dispersion of Pt nanoparticles on the carbon support. The 3DC-supported Pt electrocatalyst shows excellent performance in the oxygen reduction reaction (ORR). The easy processing ability along with the characteristics of hierarchical porosity offers a new strategy for the preparation of carbon nanomaterials for energy application.

Palladium nanoparticles supported on fibrous-structured silica nanospheres (KCC-1): An efficient and selective catalyst for the transfer hydrogenation of alkenes

KAUST Repository

Qureshi, Ziyauddin; Sarawade, Pradip; Albert, Matthias; D'Elia, Valerio; Hedhili, Mohamed Nejib; Kö hler, Klaus; Basset, Jean-Marie

2015-01-01

An efficient palladium catalyst supported on fibrous silica nanospheres (KCC-1) has been developed for the hydrogenation of alkenes and α,β-unsaturated carbonyl compounds, providing excellent yields of the corresponding products with remarkable chemoselectivity. Comparison (high-resolution TEM, chemisorption) with analogous mesoporous (MCM-41, SBA-15) silica-supported Pd nanocatalysts prepared under identical conditions, demonstrates the advantage of employing the fibrous KCC-1 morphology versus traditional supports because it ensures superior accessibility of the catalytically active cores along with excellent Pd dispersion at high metal loading. This morphology ultimately leads to higher catalytic activity for the KCC-1-supported nanoparticles. The protocol developed for hydrogenation is advantageous and environmentally benign owing to the use of HCOOH as a source of hydrogen, water as a solvent, and because of efficient catalyst recyclability and durability. The recycled catalyst has been analyzed by XPS spectroscopy and TEM showing only minor changes in the oxidation state of Pd and in the morphology after the reaction, thus confirming the robustness of the catalyst.

Palladium nanoparticles supported on fibrous-structured silica nanospheres (KCC-1): An efficient and selective catalyst for the transfer hydrogenation of alkenes

KAUST Repository

Qureshi, Ziyauddin

2015-01-09

An efficient palladium catalyst supported on fibrous silica nanospheres (KCC-1) has been developed for the hydrogenation of alkenes and α,β-unsaturated carbonyl compounds, providing excellent yields of the corresponding products with remarkable chemoselectivity. Comparison (high-resolution TEM, chemisorption) with analogous mesoporous (MCM-41, SBA-15) silica-supported Pd nanocatalysts prepared under identical conditions, demonstrates the advantage of employing the fibrous KCC-1 morphology versus traditional supports because it ensures superior accessibility of the catalytically active cores along with excellent Pd dispersion at high metal loading. This morphology ultimately leads to higher catalytic activity for the KCC-1-supported nanoparticles. The protocol developed for hydrogenation is advantageous and environmentally benign owing to the use of HCOOH as a source of hydrogen, water as a solvent, and because of efficient catalyst recyclability and durability. The recycled catalyst has been analyzed by XPS spectroscopy and TEM showing only minor changes in the oxidation state of Pd and in the morphology after the reaction, thus confirming the robustness of the catalyst.

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

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%

Detailed electromagnetic analysis for optimization of a tungsten divertor plate for JET

International Nuclear Information System (INIS)

Sadakov, S.; Bondarchuk, E.; Doinikov, N.; Kitaev, B.; Kozhukhovskaya, N.; Maximiva, I.; Hirai, T.; Mertens, P.; Neubauer, O.; Obidenko, T.

2006-01-01

. Each stack consists of 22 or 24 tungsten lamellae interleaved with insulated and non-insulated spacers. The insulated spacers cut the largest loops of eddy currents. Non-insulated spacers have extrusions used for the tile attachment. The tree-shaped design compensates the drawback of high electrical conductivity and becomes Halo-defined. This means that eddy-current related loads become smaller than Halo-current related loads, which depend mostly on divertor height and thus cannot be reduced much. Further main design features justified by this study are: (1) equal widths of all tiles; (2) fifth pair of wings; (3) multiple elastic attachment links; (4) avoidance of thick outer lamellae; (5) location of all feet on a span of ∼ 58% of a gross toroidal size. (author)

Polyoxotungstate nanoclusters supported on silica as an efficient solid-phase microextraction fiber of polycyclic aromatic hydrocarbons

International Nuclear Information System (INIS)

Abolghasemi, Mir Mahdi; Yousefi, Vahid; Rafiee, Ezzat

2014-01-01

A highly porous silica-supported tungstophosphoric acid (PW) nanocluster was prepared for use in solid-phase microextraction (SPME) of polycyclic aromatic hydrocarbons (PAHs). The PWs represent a class of discrete transition metal-oxide nanoclusters and their structures resemble discrete fragments of metal-oxide structures of definite size and shape. Transition metal-oxide nanoclusters display large structural diversity, and their monodisperse sizes can be tuned from several Ångstroms up to 10 nm. The highly porous silica-supported tungstophosphoric acid nanocluster material is found to be capable of efficiently extracting PAHs from aqueous sample solutions. The nanomaterial was immobilized on a stainless steel wire for fabrication of the SPME fiber. Following thermal desorption, the PAHs were quantified by GC-MS. Analytical merits include limits of detection that range from 0.02 to 0.1 pg mL −1 and a dynamic range as wide as from 0.001 to 100 ng mL −1 . Under optimum conditions, the repeatability for one fiber (n = 3), expressed as the relative standard deviation, is between 4.3 % and 8.6 %. The method is simple, rapid, and inexpensive. The thermal stability of the fiber and the high relative recovery make this method superior to conventional methods of extraction. (author)

Hydrothermal stability of silica, hybrid silica and Zr-doped hybrid silica membranes

NARCIS (Netherlands)

ten Hove, Marcel; Luiten-Olieman, Mieke W.J.; Huiskes, Cindy; Nijmeijer, Arian; Winnubst, Louis

2017-01-01

Hybrid silica membranes have demonstrated to possess a remarkable hydrothermal stability in pervaporation and gas separation processes allowing them to be used in industrial applications. In several publications the hydrothermal stability of pure silica or that of hybrid silica membranes are

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.

Quantum efficiency of silica-coated rare-earth doped yttrium silicate

International Nuclear Information System (INIS)

Cervantes-Vásquez, D.; Contreras, O.E.; Hirata, G.A.

2013-01-01

The photoluminescent properties of rare earth-activated white-emitting Y 2 SiO 5 :Ce,Tb nanocrystalline phosphor prepared by two different methods, pressure-assisted combustion synthesis and sol–gel, were studied. The synthesized phosphor samples were post-annealed at 1373 K and 1623 K in order to obtain the X1-Y 2 SiO 5 and X2-Y 2 SiO 5 phases, respectively, which were confirmed by X-ray diffraction measurements. Photoluminescence analysis showed the contribution of two blue-emission bands within the 380–450 nm region originating from 5d–4f transitions in Ce 3+ ions and a well-defined green emission of Tb 3+ ions located at 545 nm corresponding to 5 D 4 → 7 F 5 electronic transitions. Thereafter, Y 2 SiO 5 :Ce,Tb powders were coated with colloidal silica in order to investigate the effect of silica coatings on their luminescent properties. Absolute fluorescence quantum efficiency measurements were carefully performed, which revealed an increase of 12% of efficiency in coated compared with bare-Y 2 SiO 5 :Ce,Tb phosphor. -- Highlights: • Y 2 SiO 5 :Ce,Tb phosphor powders were successfully coated with colloidal silica. • Post-annealing treatments improved the quantum efficiency of silica-coated Y 2 SiO 5 :Ce,Tb phosphors. • Absolute fluorescence quantum efficiency measurements showed an increase of 12%

Production of propylene from 1-butene on highly active "bi-functional single active site" catalyst: Tungsten carbene-hydride supported on alumina

KAUST Repository

Mazoyer, Etienne; Szeto, Kaï Chung; Norsic, Sé bastien; Garron, Anthony; Basset, Jean-Marie; Nicholas, Christopher P.; Taoufik, Mostafa

2011-01-01

1-Butene is transformed in a continuous flow reactor over tungsten hydrides precursor W-H/Al2O3, 1, giving a promising yield into propylene at 150 °C and different pressures. Tungsten carbene-hydride single active site operates as a "bi

Selective conversion of butane into liquid hydrocarbon fuels on alkane metathesis catalysts

KAUST Repository

Szeto, Kaï Chung; Hardou, Lucie; Merle, Nicolas; Basset, Jean-Marie; Thivolle-Cazat, Jean; Papaioannou, Charalambos; Taoufik, Mostafa

2012-01-01

We report a selective direct conversion of n-butane into higher molecular weight alkanes (C 5+) by alkane metathesis reaction catalysed by silica-alumina supported tungsten or tantalum hydrides at moderate temperature and pressure. The product

Fumed silica. Fumed silica

Energy Technology Data Exchange (ETDEWEB)

Sukawa, T.; Shirono, H. (Nippon Aerosil Co. Ltd., Tokyo (Japan))

1991-10-18

The fumed silica is explained in particulate superfineness, high purity, high dispersiveness and other remarkable characteristics, and wide application. The fumed silica, being presently produced, is 7 to 40nm in average primary particulate diameter and 50 to 380m{sup 2}/g in specific surface area. On the surface, there coexist hydrophilic silanol group (Si-OH) and hydrophobic siloxane group (Si-O-Si). There are many characteristics, mutually different between the fumed silica, made hydrophobic by the surface treatment, and untreated hydrophilic silica. The treated silica, if added to the liquid product, serves as agent to heighten the viscosity, prevent the sedimentation and disperse the particles. The highest effect is given to heighten the viscosity in a region of 4 to 9 in pH in water and alcohol. As filling agent to strengthen the elastomer and polymer, and powder product, it gives an effect to prevent the consolidation and improve the fluidity. As for its other applications, utilization is made of particulate superfineness, high purity, thermal insulation properties and adsorption characteristics. 2 to 3 patents are published for it as raw material of quartz glass. 38 refs., 16 figs., 4 tabs.

Supporting wellness in adult online education

Directory of Open Access Journals (Sweden)

Jacklyn J. Thompson

2014-02-01

Full Text Available Online education cannot continue to grow at the current pace while ignoring a crucial component of campus support, wellness for adult online learners. This paper brings awareness to the concept of wellness as an important student support service in adult online education. It includes a summarized review of relevant literature and identifies specific wellness concerns of adult online learners. The paper also provides examples of how three American higher education institutions are addressing the issue of wellness promotion in online learning. It identifies areas for improvement in current wellness initiatives and offers recommended strategies for supporting adult online learner wellness to professional organizations, institutions, instructors, and distance learners.http://dx.doi.org/10.5944/openpraxis.6.1.100

Production of propylene from 1-butene on highly active "bi-functional single active site" catalyst: Tungsten carbene-hydride supported on alumina

KAUST Repository

Mazoyer, Etienne

2011-12-02

1-Butene is transformed in a continuous flow reactor over tungsten hydrides precursor W-H/Al2O3, 1, giving a promising yield into propylene at 150 °C and different pressures. Tungsten carbene-hydride single active site operates as a "bi-functional catalyst" through 1-butene isomerization on W-hydride and 1-butene/2-butenes cross-metathesis on W-carbene. This active moiety is generated in situ at the initiation steps by insertion of 1-butene on tungsten hydrides precursor W-H/Al2O3, 1 followed by α-H and β-H abstraction. © 2011 American Chemical Society.

Polyethyleneimine-loaded bimodal porous silica as low-cost and high-capacity sorbent for CO{sub 2} capture

Energy Technology Data Exchange (ETDEWEB)

Witoon, Thongthai, E-mail: fengttwi@ku.ac.th [National Center of Excellence for Petroleum, Petrochemicals and Advance Material, Department of Chemical Engineering, Faculty of Engineering, Kasetsart University, Bangkok 10900 (Thailand); Center for Advanced Studies in Nanotechnology and Its Applications in Chemical Food and Agricultural Industries, Kasetsart University, Bangkok 10900 (Thailand)

2012-11-15

In this work, bimodal (meso-macro) porous silicas with different mesopore diameters synthesized by using rice husk ash as a low-cost silica source and chitosan as a natural template were used as a polyethyleneimine (PEI) support for CO{sub 2} capture. Unimodal porous silica supports with equivalent mesopore diameters to bimodal porous silica supports have been prepared for purpose of comparison. Effects of different PEI contents (10, 20, 30, 40 and 50 wt%) on CO{sub 2} sorption capacity have been systematically investigated. The porous silica supports and the PEI-loaded porous silica supports were characterized by N{sub 2}-sorption analysis, scanning electron microscopy, Fourier transform infrared spectroscopy and thermal gravimetric analysis. CO{sub 2} sorption measurements of all PEI-loaded porous silica supports were performed at different adsorption temperatures (60, 75, 85, 90, 95 and 105 Degree-Sign C). At low PEI contents (10-20 wt%), the CO{sub 2} sorption of all adsorbents was found to decrease as a function of adsorption temperature, which was a characteristic of a thermodynamically-controlled regime. A transition from the thermodynamically-controlled regime to a kinetically-controlled regime was found when the PEI content was increased up to 30 wt% for PEI-loaded unimodal porous silicas and 40 wt% for PEI-loaded bimodal porous silicas. At high PEI contents (40-50 wt%), the CO{sub 2} capturing efficiency of the PEI-loaded bimodal porous silicas was found to be considerably greater than that of the PEI-loaded unimodal porous silicas, indicating that most of the amine groups of PEI molecules loaded on the unimodal porous silica supports was useless, and thus the appeared macroporosity of the bimodal porous silica supports could provide a higher effective amine density to adsorb CO{sub 2}. Highlights: Black-Right-Pointing-Pointer PEI-impregnated bimodal porous silica as low-cost sorbent for CO{sub 2} capture. Black-Right-Pointing-Pointer Macropores enhances

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

Conflict minerals from the Democratic Republic of the Congo: global tungsten processing plants, a critical part of the tungsten supply chain

Science.gov (United States)

Bermúdez-Lugo, Omayra

2014-01-01

The U.S. Geological Survey (USGS) analyzes supply chains to identify and define major components of mineral and material flows from ore extraction, through intermediate forms, to a final product. Two major reasons necessitate these analyses: (1) to identify risks associated with the supply of critical and strategic minerals to the United States and (2) to provide greater supply chain transparency so that policymakers have the information necessary to ensure domestic legislation compliance. This fact sheet focuses on the latter. The USGS National Minerals Information Center has been asked by governmental and non-governmental organizations to provide information on tin, tantalum, tungsten, and gold (collectively known as “3TG minerals”) processing facilities worldwide in response to U.S. legislation aimed at removing the link between the trade in these minerals and civil unrest in the Democratic Republic of the Congo. Post beneficiation processing plants (smelters and refineries) of 3TG mineral ores and concentrates were identified by company and industry association representatives as being the link in the 3TG mineral supply chain through which these minerals can be traced to their source of origin (mine); determining the point of origin is critical to establishing a transparent conflict mineral supply chain. This fact sheet, the first in a series of 3TG mineral fact sheets, focuses on the tungsten supply chain by listing plants that consume tungsten concentrates to produce ammonium paratungstate and ferrotungsten worldwide.

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

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.

Tungsten recrystallization and cracking under ITER-relevant heat loads

Energy Technology Data Exchange (ETDEWEB)

Budaev, V.P., E-mail: Budaev@mail.ru [NRC «Kurchatov Institute», Akademika Kurchatova pl., Moscow (Russian Federation); Martynenko, Yu.V. [NRC «Kurchatov Institute», Akademika Kurchatova pl., Moscow (Russian Federation); National Research Nuclear University MEPhI, Kashirskoe sh. 31, Moscow (Russian Federation); Karpov, A.V.; Belova, N.E. [NRC «Kurchatov Institute», Akademika Kurchatova pl., Moscow (Russian Federation); Zhitlukhin, A.M. [SRC RF TRINITI, Moscow Region (Russian Federation); Klimov, N.S., E-mail: klimov@triniti.ru [SRC RF TRINITI, Moscow Region (Russian Federation); National Research Nuclear University MEPhI, Kashirskoe sh. 31, Moscow (Russian Federation); Podkovyrov, V.L.; Barsuk, V.A.; Putrik, A.B.; Yaroshevskaya, A.D. [SRC RF TRINITI, Moscow Region (Russian Federation); Giniyatulin, R.N. [Efremov Institute, St. Petersburg (Russian Federation); Safronov, V.M. [Institution «Project Center ITER», Moscow (Russian Federation); SRC RF TRINITI, Moscow Region (Russian Federation); Khimchenko, L.N. [Institution «Project Center ITER», Moscow (Russian Federation)

2015-08-15

The tungsten surface structure was analyzed after the test in the QSPA-T under heat loads relevant to those expected in the ITER during disruptions. Repeated pulses lead to the melting and the resolidification of the tungsten surface layer of ∼50 μm thickness. There is ∼50 μm thickness intermediate layer between the original structure and the resolidified layer. The intermediate layer is recrystallized and has a random grains’ orientation whereas the resolidified layer and basic structure have texture with preferable orientation 〈1 0 0〉 normal to the surface. The cracks which were normal to the surface were observed in the resolidified layer as well as the cracks which were parallel to the surface at the depth up to 300 μm. Such cracks can result in the brittle destruction which is a hazard for the full tungsten divertor of the ITER. The theoretical analysis of the crack formation reasons and a possible consequence for the ITER are given.

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

Extrudate versus Powder Silica Alumina as Support for Re2O7 Catalyst in the Metathesis of Seed Oil-Derivatives – A Comparison

Directory of Open Access Journals (Sweden)

Bassie B. Marvey

2009-01-01

Full Text Available Self- and cross-metathesis of fatty acid methyl esters (FAMEs was investigated using a silica alumina supported Re2O7 catalyst. Although a 3 wt% Re2O7/SiO2-Al2O3/SnBu4 is already active for the metathesis of unsaturated FAMEs, the results have shown that particle size of silica alumina support has a profound influence on its activity and selectivity. Consequently, high substrate conversions coupled with improved product yields (for mono- and diesters and reaction rates were obtained upon using powder, as opposed to extrudate silica alumina as the support material. Diesters are platform compounds for the synthesis of polymers and fragrances. In this paper a comparative outline of the influence of particle size of silica alumina (extrudate versus powder on catalytic performance of a 3 wt% Re2O7/SiO2-Al2O3/SnBu4 for self- and cross-metathesis of FAMEs is made. Low surface area and diffusion constraints associated with extrudates were identified as some of the factors leading to low catalytic activity and selectivity.

Laser-assisted nanostructuring of Tungsten in liquid environment

Energy Technology Data Exchange (ETDEWEB)

Barmina, E.V., E-mail: barminaev@gmail.com [Wave Research Center of A.M. Prokhorov General Physics Institute of the Russian Academy of Sciences, 38, Vavilov Street, 119991 Moscow (Russian Federation); Stratakis, E. [Institute of Electronic Structure and Laser, Foundation for Research and Technology, Hellas (IESL-FORTH), P.O. Box 1527, Heraklion 711 10 (Greece); Materials Science and Technology Department, University of Crete, Heraklion 710 03 (Greece); Barberoglou, M. [Institute of Electronic Structure and Laser, Foundation for Research and Technology, Hellas (IESL-FORTH), P.O. Box 1527, Heraklion 711 10 (Greece); Physics Department, University of Crete, Heraklion 714 09 (Greece); Stolyarov, V.N.; Stolyarov, I.N. [Roentgenprom, 35 Lenin str., Protvino, 1442281 Moscow region (Russian Federation); Fotakis, C. [Institute of Electronic Structure and Laser, Foundation for Research and Technology, Hellas (IESL-FORTH), P.O. Box 1527, Heraklion 711 10 (Greece); Physics Department, University of Crete, Heraklion 714 09 (Greece); Shafeev, G.A. [Wave Research Center of A.M. Prokhorov General Physics Institute of the Russian Academy of Sciences, 38, Vavilov Street, 119991 Moscow (Russian Federation)

2012-05-15

Formation of surface nanostructures on Tungsten target immersed into liquids is experimentally studied under its exposure to femtosecond laser pulses with different durations. In particular, nanotexturing of Tungsten upon its exposure to delayed femtosecond pulses is investigated. Two different types of morphological features are observed, namely periodic ripples and nanostructures. Field emission scanning electron microscopy shows that the density of nanostructures as well as their morphology depends on the time delay between pulses and reaches its maximum at 1 ps delay. Thermionic emission of nano-structured W cathode is investigated. The work function of nanostructured W surface is measured to be 0.3 eV lower than that of the pristine surface.

Grafting of polymer onto silica surface in the presence of γ-ray irradiated silica

International Nuclear Information System (INIS)

Tsuchida, A.; Yokoyama, R.; Takami, M.; Chen, J.; Ohta, M.; Tsubokawa, N.

2002-01-01

Complete text of publication follows. We have reported the graft polymerization of vinyl monomers initiated by surface radicals formed by the decomposition of azo and peroxide groups previously introduced onto the surface. In addition, the grafting of polymers onto carbon black has been reported by the reaction of polymer radicals with the surface. On the other hand, it is well known that the relatively stable radicals are generated on the surface by the γ-ray irradiation. In this paper, the grafting of polystyrene onto silica surface during the thermal polymerization of styrene in the presence of γ-ray irradiated silica, grafting mechanism and thermal stability of grafted polymer will be discussed. The grafting of polymers onto silica surface by irradiation of polymer-adsorbed silica was also investigated. Silica obtained from Mitsubishi Chemical Co., Japan was used after pulverization: the particle size was 0.037-0.088 mm. Irradiation was performed in Cs-137 source at room temperature. The silica was irradiated at 50 Gy with dose rate of 3.463 Gy/min. Into a polymerization tube, styrene and irradiated silica was charged and the polymerization was carried out under argon under stirring. The percentage of polystyrene grafting was determined from weight loss when polystyrene-grafted silica was heated at 600 deg C by a thermal analyzer. Untreated silica did not affect the thermal polymerization of styrene. On the contrary, the thermal polymerization of styrene was remarkably retarded in the presence of the irradiated silica at 60 deg C. Similar tendency was reported during the polymerization of vinyl monomers in the presence of carbon black. In the initial stage of the polymerization in the presence of the irradiated silica below 50 deg C, the polymerization was accelerated. During the polymerization in the presence of irradiated silica, polystyrene was grafted onto the surface: the percentage of grafting was 5-11%. The amount of polystyrene grafted onto silica

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

Cellular membrane trafficking of mesoporous silica nanoparticles

Energy Technology Data Exchange (ETDEWEB)

Fang, I-Ju [Iowa State Univ., Ames, IA (United States)

2012-01-01

This dissertation mainly focuses on the investigation of the cellular membrane trafficking of mesoporous silica nanoparticles. We are interested in the study of endocytosis and exocytosis behaviors of mesoporous silica nanoparticles with desired surface functionality. The relationship between mesoporous silica nanoparticles and membrane trafficking of cells, either cancerous cells or normal cells was examined. Since mesoporous silica nanoparticles were applied in many drug delivery cases, the endocytotic efficiency of mesoporous silica nanoparticles needs to be investigated in more details in order to design the cellular drug delivery system in the controlled way. It is well known that cells can engulf some molecules outside of the cells through a receptor-ligand associated endocytosis. We are interested to determine if those biomolecules binding to cell surface receptors can be utilized on mesoporous silica nanoparticle materials to improve the uptake efficiency or govern the mechanism of endocytosis of mesoporous silica nanoparticles. Arginine-glycine-aspartate (RGD) is a small peptide recognized by cell integrin receptors and it was reported that avidin internalization was highly promoted by tumor lectin. Both RGD and avidin were linked to the surface of mesoporous silica nanoparticle materials to investigate the effect of receptor-associated biomolecule on cellular endocytosis efficiency. The effect of ligand types, ligand conformation and ligand density were discussed in Chapter 2 and 3. Furthermore, the exocytosis of mesoporous silica nanoparticles is very attractive for biological applications. The cellular protein sequestration study of mesoporous silica nanoparticles was examined for further information of the intracellular pathway of endocytosed mesoporous silica nanoparticle materials. The surface functionality of mesoporous silica nanoparticle materials demonstrated selectivity among the materials and cancer and normal cell lines. We aimed to determine

Genotoxic Changes to Rodent Cells Exposed in Vitro to Tungsten, Nickel, Cobalt and Iron

Directory of Open Access Journals (Sweden)

Stephanie Bardack

2014-03-01

Full Text Available Tungsten-based materials have been proposed as replacements for depleted uranium in armor-penetrating munitions and for lead in small-arms ammunition. A recent report demonstrated that a military-grade composition of tungsten, nickel, and cobalt induced a highly-aggressive, metastatic rhabdomyosarcoma when implanted into the leg muscle of laboratory rats to simulate a shrapnel wound. The early genetic changes occurring in response to embedded metal fragments are not known. In this study, we utilized two cultured rodent myoblast cell lines, exposed to soluble tungsten alloys and the individual metals comprising the alloys, to study the genotoxic effects. By profiling cell transcriptomes using microarray, we found slight, yet distinct and unique, gene expression changes in rat myoblast cells after 24 h metal exposure, and several genes were identified that correlate with impending adverse consequences of ongoing exposure to weapons-grade tungsten alloy. These changes were not as apparent in the mouse myoblast cell line. This indicates a potential species difference in the cellular response to tungsten alloy, a hypothesis supported by current findings with in vivo model systems. Studies examining genotoxic-associated gene expression changes in cells from longer exposure times are warranted.

On the kinetics of high-temperature interaction of tungsten with light hydrocarbons

International Nuclear Information System (INIS)

Kharatyan, S.L.; Chatilyan, A.A.; Merzhanov, A.G.

1989-01-01

Comparative investigation of tungsten carbidizing treatment in ethylene, acetylene and methane media at T=1750-2500 deg C and p=2-10 Torr is carried out by the electrothermographical method. In all cases interaction is shown to proceed in stages due to step-by-step formation of carbide phases of tungsten W 2 C and WC as well as pyrocarbon. It is established that efficiency of carbidizing treatment is turned out to be maximum in methane medium in spite of great absolute values of ethylene and acetylene pyrolysis velocities on the surface of tungsten carbides in comparison with methane. Criterion of carburizing capability of hydrocarbous relatively to a metal is given on the basis of the results obtained

Multifunctional nanomedicine with silica: Role of silica in nanoparticles for theranostic, imaging, and drug monitoring.

Science.gov (United States)

Chen, Fang; Hableel, Ghanim; Zhao, Eric Ruike; Jokerst, Jesse V

2018-07-01

The idea of multifunctional nanomedicine that enters the human body to diagnose and treat disease without major surgery is a long-standing dream of nanomaterials scientists. Nanomaterials show incredible properties that are not found in bulk materials, but achieving multi-functionality on a single material remains challenging. Integrating several types of materials at the nano-scale is critical to the success of multifunctional nanomedicine device. Here, we describe the advantages of silica nanoparticles as a tool for multifunctional nano-devices. Silica nanoparticles have been intensively studied in drug delivery due to their biocompatibility, degradability, tunable morphology, and ease of modification. Moreover, silica nanoparticles can be integrated with other materials to obtain more features and achieve theranostic capabilities and multimodality for imaging applications. In this review, we will first compare the properties of silica nanoparticles with other well-known nanomaterials for bio-applications and describe typical routes to synthesize and integrate silica nanoparticles. We will then highlight theranostic and multimodal imaging application that use silica-based nanoparticles with a particular interest in real-time monitoring of therapeutic molecules. Finally, we will present the challenges and perspective on future work with silica-based nanoparticles in medicine. Copyright © 2018 Elsevier Inc. All rights reserved.

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

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)

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.

Synthesis of Macroporous Silica Particles by Continuous Generation of Droplets for Insulating Materials.

Science.gov (United States)

Cho, Young-Sang; Lee, Dokyoung

2018-09-01

We report on the synthesis of porous silica particles by self-assembly routes in a continuous manner for application to thermal insulators. A continuous process was employed to produce tiny droplets containing precursor materials such as silica and organic templates for self-organization to fabricate particles with well defined pores. A rotating cylinder system or a spray drying process was adopted to form emulsions or aerosol droplets as micro-reactors for self-assembly, and the physical properties including the thermal conductivity of the resulting porous particles were compared between the two methods. The porous particles could be coated as a thick film by solution dripping, and the fluorination treatment using a silane coupling agent was performed to produce superhydrophobic surfaces of insulating layers by a lotus effect.

Electrodeposition of zinc–silica composite coatings: challenges in incorporating functionalized silica particles into a zinc matrix

Directory of Open Access Journals (Sweden)

Tabrisur Rahman Khan, Andreas Erbe, Michael Auinger, Frank Marlow and Michael Rohwerder

2011-01-01

Full Text Available Zinc is a well-known sacrificial coating material for iron and co-deposition of suitable particles is of interest for further improving its corrosion protection performance. However, incorporation of particles that are well dispersible in aqueous electrolytes, such as silica particles, is extremely difficult. Here, we report a detailed study of Zn–SiO2 nanocomposite coatings deposited from a zinc sulfate solution at pH 3. The effect of functionalization of the silica particles on the electro-codeposition was investigated. The best incorporation was achieved for particles modified with SiO2–SH, dithiooxamide or cysteamine; these particles have functional groups that can strongly interact with zinc and therefore incorporate well into the metal matrix. Other modifications (SiO2–NH3+, SiO2–Cl and N,N-dimethyldodecylamine of the silica particles lead to adsorption and entrapment only.

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

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

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

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

Influence of structures on fracture and fracture toughness of cemented tungsten carbides

International Nuclear Information System (INIS)

Zhao, W.; Zhang, X.

1987-01-01

A study was made of the influence of structures on fracture and fracture toughness of cemented tungsten carbides with different compositions and grain sizes. The measurement of the fracture toughness of cemented tungsten carbide was carried out using single edge notched beam. The microstructural parameters and the proportion for each fracture mode on the fracture surface were obtained. The brittle fracture of the alloy is mainly due to the interfacial decohesion fracture following the interface of the carbide crystals. It has been observed that there are localized fractures region ahead of the crack tip. The morphology of the crack propagation path as well as the slip structure in the cobalt phase of the deformed region have been investigated. In addition, a study of the correlation between the plane strain fracture toughness and microstructural parameters, such as mean free path of the cobalt phase, tungsten carbide grain size and the contiguity of tungsten carbide crystals was also made

Photometric investigation of tungsten (6) reaction with monoazo compound based on pyrogallol

International Nuclear Information System (INIS)

Gambarov, D.G.; Gusejnov, A.G.

1980-01-01

The possibility has been studied to use a new monoazo compound 2,3,4-trihydroxy-4'-sulfoazobenzene (TSAB) for the photometric determination of tungsten in steels. The maximum yield of W(6) complex is observed in the interval from 0.3 NHCl to pH2. The maximum absorption of the complex is observed at 460 nm and that of reagent - at 380 nm. The complex coloring immediately develops and in stable for more than one day. Molar coefficient of complex extinctior equals 43000+-300. Tungsten concentration interval being determined in 0.3 N HCl is 10-140 μg/25 ml. Tungsten determination technique in chromium-nickel-tungsten and chromium-silicon-nickel steels is given. If steel samples contain Mo > 0.1 mg, Y > 0.2 mg, Zr > 1.0 mg, Fe > 0.03 mg and Si > 0.3 mg then it is necessary to separate Mo, Y and Zr beforehand. Fe and Si are respectively well camouflaged by ascorbic acid and EDTA

Chemoselective Hydrogenation with Supported Organoplatinum(IV) Catalyst on Zn(II)-Modified Silica

Energy Technology Data Exchange (ETDEWEB)

Camacho-Bunquin, Jeffrey [Chemical Sciences and Engineering Division, Argonne National Laboratory, 9700 S Cass Avenue, Lemont, Illinois 60439, United States; Ferrandon, Magali [Chemical Sciences and Engineering Division, Argonne National Laboratory, 9700 S Cass Avenue, Lemont, Illinois 60439, United States; Sohn, Hyuntae [Chemical Sciences and Engineering Division, Argonne National Laboratory, 9700 S Cass Avenue, Lemont, Illinois 60439, United States; Yang, Dali [Chemical Sciences and Engineering Division, Argonne National Laboratory, 9700 S Cass Avenue, Lemont, Illinois 60439, United States; Liu, Cong [Chemical Sciences and Engineering Division, Argonne National Laboratory, 9700 S Cass Avenue, Lemont, Illinois 60439, United States; Ignacio-de Leon, Patricia Anne [Energy Sciences Division, Argonne National Laboratory, 9700 S Cass Avenue, Lemont, Illinois 60439, United States; Perras, Frédéric A. [Ames Laboratory, U.S. Department of Energy, Ames, Iowa 50010, United States; Pruski, Marek [Ames Laboratory, U.S. Department of Energy, Ames, Iowa 50010, United States; Department of Chemistry, Iowa State University, 2416 Pammel Drive, Ames, Iowa 50011, United States; Stair, Peter C. [Chemical Sciences and Engineering Division, Argonne National Laboratory, 9700 S Cass Avenue, Lemont, Illinois 60439, United States; Department of Chemistry, Northwestern University, 2145 Sheridan Road, Evanston, Illinois 60208, United States; Delferro, Massimiliano [Chemical Sciences and Engineering Division, Argonne National Laboratory, 9700 S Cass Avenue, Lemont, Illinois 60439, United States

2018-02-22

Well-defined organoplatinum(IV) sites were grafted on a Zn(II)-modified SiO2 support via surface organometallic chemistry in toluene at room temperature. Solid-state spectroscopies including XAS, DRIFTS, DRUV-Vis, and solid-state (SS)NMR enhanced by dynamic nuclear polarization (DNP), as well as TPR-H2 and TEM techniques revealed highly dispersed (methylcyclopentadi-enyl)methylplatinum(IV) sites on the surface ((MeCp)PtMe/Zn/SiO2, 1). In addition, computational modelling suggests that the surface reaction of (MeCp)PtMe3 with Zn(II)-modified SiO2 support is thermodynamically favorable (ΔG = -12.4 kcal/mol), likely due to the increased acidity of the hydroxyl group, as confirmed by NH3-TPD and DNP-enhanced 17O{1H} SSNMR. In situ DRIFTS and XAS hydrogenation experiments reveal the formation of a surface Pt(IV)-H upon hydrogenolysis of Pt-Me groups. The heterogenized organoplatinum(IV)-H sites catalyze the selective partial hydrogenation of 1,3-butadiene to butenes (up to 95%) and the reduction of nitrobenzene derivatives to anilines (up to 100%) with excellent tolerance of reduction-sensitive func-tional groups (olefin, carbonyl, nitrile, halogens) under mild reaction conditions.

Hydration kinetics study of class G oil-well cement and olivine nano-silica mixtures at 20–60 °C

NARCIS (Netherlands)

Quercia Bianchi, G.; Brouwers, H.J.H.; Sobolev, K.; Shah, S.P.

2015-01-01

In this study the heat evolution of standard density slurries (1.89 g/cm3) of Class G oil-well cement and olivine nano-silica additions (0.5–2.0 % bwoc), cured under different temperatures (20–60 °C) and atmospheric pressure, were examined by isothermal calorimetry. Under isothermal and isobaric

Solvent Extraction of Tungsten(VI) from Moderate Hydrochloric Acid Solutions with LIX 63

Energy Technology Data Exchange (ETDEWEB)

Truong, Hoai Thanh; Lee, Man Seung [Mokpo National University, Jeollanamdo (Korea, Republic of); Kim, Yong Hwan [Incheon Technology Service Centre, Incheon (Korea, Republic of)

2017-06-15

The solvent extraction of tungsten(VI) from hydrochloric acid solutions using 5,8-diethyl-7-hydroxydodecan-6-one oxime (LIX 63) was analyzed in solutions having an initial pH range from 2 to 5, by varying the concentration of metal and extractant. In our experimental range, the cationic exchange reaction as well as the solvation reaction occurred simultaneously. The cation exchange reaction was identified by applying a slope analysis method to the extraction data. The existence of cationic tungsten(VI) species was confirmed by ion exchange experiments with Diphonix resin at pH 3. Further study is needed to identify the nature of this tungsten cationic species.

Enhanced accumulation and visible light-assisted degradation of azo dyes in poly(allylamine hydrochloride)-modified mesoporous silica spheres

International Nuclear Information System (INIS)

Tao Xia; Liu Bing; Hou Qian; Xu Hui; Chen Jianfeng

2009-01-01

A new route for the economic and efficient treatment of azo dye pollutants is reported, in which surface-modified organic-inorganic hybrid mesoporous silica (MS) spheres were chosen as microreactors for the accumulation and subsequent photodegradation of pollutants in defined regions. The surface-modified silica materials were prepared by anchoring the polycationic species such as poly(allylamine hydrochloride) on MS spheres via a simple wet impregnation method. The as-synthesized spheres with well-defined porous structures exhibited 15 times of accumulating capacity for orange II and Congo red compared to that of the pure MS spheres. Diffuse reflectance UV-vis spectroscopy and confocal laser scanning microscopy demonstrated that the accumulated orange II and CR in defined MS spheres were rapidly degraded in the presence of Fenton reagent under visible radiation. Kinetics analysis in recycling degradation showed that the as-synthesized materials might be utilized as environment-friendly preconcentrators/microreactors for the remediation of dye wastewater

Measurement and modelization of silica opal optical properties

OpenAIRE

Avoine , Amaury; Ngoc Hong , Phan; Frederich , Hugo; Aregahegn , Kifle; Bénalloul , Paul; Coolen , Laurent; Schwob , Catherine; Thu Nga , Pham; Gallas , Bruno; Maître , Agnès

2014-01-01

International audience; We present the synthesis process and optical characterization of artificial silica opals. The specular reflection spectra are analyzed and compared to band structure calculations and finite difference time domain (FDTD) simulations. The silica optical index is a key parameter to correctly describe an opal and is usually not known and treated as a free parameter. Here we propose a method to infer the silica index, as well as the silica spheres diameter, from the reflect...

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.

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.

Investigation of dielectric breakdown in silica-epoxy nanocomposites using designed interfaces.

Science.gov (United States)

Bell, Michael; Krentz, Timothy; Keith Nelson, J; Schadler, Linda; Wu, Ke; Breneman, Curt; Zhao, Su; Hillborg, Henrik; Benicewicz, Brian

2017-06-01

Adding nano-sized fillers to epoxy has proven to be an effective method for improving dielectric breakdown strength (DBS). Evidence suggests that dispersion state, as well as chemistry at the filler-matrix interface can play a crucial role in property enhancement. Herein we investigate the contribution of both filler dispersion and surface chemistry on the AC dielectric breakdown strength of silica-epoxy nanocomposites. Ligand engineering was used to synthesize bimodal ligands onto 15nm silica nanoparticles consisting of long epoxy compatible, poly(glycidyl methacrylate) (PGMA) chains, and short, π-conjugated, electroactive surface ligands. Surface initiated RAFT polymerization was used to synthesize multiple graft densities of PGMA chains, ultimately controlling the dispersion of the filler. Thiophene, anthracene, and terthiophene were employed as π-conjugated surface ligands that act as electron traps to mitigate avalanche breakdown. Investigation of the synthesized multifunctional nanoparticles was effective in defining the maximum particle spacing or free space length (L f ) that still leads to property enhancement, as well as giving insight into the effects of varying the electronic nature of the molecules at the interface on breakdown strength. Optimization of the investigated variables was shown to increase the AC dielectric breakdown strength of epoxy composites as much as 34% with only 2wt% silica loading. Copyright © 2017 Elsevier Inc. All rights reserved.

Synthesis of Reusable Silica Nanosphere-Supported Pt(IV Complex for Formation of Disulfide Bonds in Peptides

Directory of Open Access Journals (Sweden)

Xiaonan Hou

2017-02-01

Full Text Available Some peptide-based drugs, including oxytocin, vasopressin, ziconotide, pramlintide, nesiritide, and octreotide, contain one intramolecular disulfide bond. A novel and reusable monodispersed silica nanosphere-supported Pt(IV complex (SiO2@TPEA@Pt(IV; TPEA: N-[3-(trimethoxysilylpropyl]ethylenediamine was synthesized via a four-step procedure and was used for the formation of intramolecular disulfide bonds in peptides. Transmission electron microscopy (TEM and chemical mapping results for the Pt(II intermediates and for SiO2@TPEA@Pt(IV show that the silica nanospheres possess a monodisperse spherical structure and contain uniformly-distributed Si, O, C, N, Cl, and Pt. The valence state of Pt on the silica nanospheres was characterized by X-ray photoelectron spectroscopy (XPS. The Pt(IV loaded on SiO2@TPEA@Pt(IV was 0.15 mmol/g, as determined by UV-VIS spectrometry. The formation of intramolecular disulfides in six dithiol-containing peptides of variable lengths by the use of SiO2@TPEA@Pt(IV was investigated, and the relative oxidation yields were determined by high-performance liquid chromatography (HPLC. In addition, peptide 1 (Ac-CPFC-NH2 was utilized to study the reusability of SiO2@TPEA@Pt(IV. No significant decrease in the relative oxidation yield was observed after ten reaction cycles. Moreover, the structure of SiO2@TPEA@Pt(IV after being used for ten cycles was determined to be similar to its initial one, demonstrating the cycling stability of the complex.

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

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

Corrugation of Phase-Separated Lipid Bilayers Supported by Nanoporous Silica Xerogel Surfaces

Energy Technology Data Exchange (ETDEWEB)

Goksu, E I; Nellis, B A; Lin, W; Satcher Jr., J H; Groves, J T; Risbud, S H; Longo, M L

2008-10-30

Lipid bilayers supported by substrates with nanometer-scale surface corrugations holds interest in understanding both nanoparticle-membrane interactions and the challenges of constructing models of cell membranes on surfaces with desirable properties, e.g. porosity. Here, we successfully form a two-phase (gel-fluid) lipid bilayer supported by nanoporous silica xerogel. Surface topology, diffusion, and lipid density in comparison to mica-supported lipid bilayers were characterized by AFM, FRAP, FCS, and quantitative fluorescence microscopy, respectively. We found that the two-phase lipid bilayer follows the xerogel surface contours. The corrugation imparted on the lipid bilayer results in a lipid density that is twice that on a flat mica surface. In direct agreement with the doubling of actual bilayer area in a projected area, we find that the lateral diffusion coefficient (D) of lipids on xerogel ({approx}1.7 {micro}m{sup 2}/s) is predictably lower than on mica ({approx}4.1 {micro}m{sup 2}/s) by both FRAP and FCS techniques. Furthermore, the gel-phase domains on xerogel compared to mica were larger and less numerous. Overall, our results suggest the presence of a relatively defect-free continuous two-phase bilayer that penetrates approximately midway into the first layer of {approx}50 nm xerogel beads.

Direct esterification of olive-pomace oil using mesoporous silica supported sulfonic acids

Directory of Open Access Journals (Sweden)

F. Alrouh

2017-02-01

Full Text Available Mesoporous silica MCM-41 and SBA-15 containing propyl sulfonic acid groups were synthesized according to the literature and were characterized by X-ray diffraction, N2 adsorption and the H+ exchange capacities of the sulfonic acid groups were titrated. The esterification reaction of glycerol with olive-pomace oil has been carried out by using prepared functionalized mesoporous silica (MCM-41 and SBA-15 as catalysts. It has been monitored by GC two fatty acids (palmitic and oleic acids as reactants in olive-pomace oil and their related monoacylglycerols (Glycerol monopalmitate GMP and monooleate GMO as reaction product. The catalytic activities of the functionalized mesoporous silica were compared with commercial catalysts, these included homogeneous catalysts (p-toluenesulfonic acid and heterogeneous catalysts (Amberlyst-15. The total yield of monoacylglycerols (GMO + GMP was nearly 40%. Remarkably, we found that MCM-41-SO3H was recycled at least 3 times without any loss of activity.

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.

Separation of tungsten and rhenium on alumina

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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.

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)

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

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.

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.)

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.

Synthesis of AL-MCM-41 using gravel drilling the source of silica from wells drilling

International Nuclear Information System (INIS)

Fontes, M.S.B.; Costa, C.C.; Melo, D.M.A.; Viana, L.M.; Viana, S.O.; Santos, L.M.

2016-01-01

The aim of this study was to synthesize Al-MCM-41 using gravel drilling as alternative source of silica, aiming at sustainable production and low cost. For hydrothermal synthesis of Al-MCM-41 was used gravel and sodium silicate as source of silica and sodium, respectively. The structural driver used was cetyltrimethylammonium bromide (CTMABr) and solvent distilled water. The hydrothermal synthesis was conducted at 100 ° C in a Teflon autoclave 45 ml jacketed stainless steel for a period of 120 hours with daily correcting pH (range 9-10) using 30% acetic acid. The material obtained was filtered, washed, dried at 100 ° C for 3 hours and then calcined at 550 ° C for 2 hours. Then it was characterized by XRD, FTIR and TG. For the results of characterization has been observed that the use of the gravel drilling as a source of silica was promising alternative for producing a mesoporous material with a high degree of hexagonal ordering. (author)

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

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)

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

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

Ferrocenyl-doped silica nanoparticles as an immobilized affinity support for electrochemical immunoassay of cancer antigen 15-3

International Nuclear Information System (INIS)

Hong Chenglin; Yuan Ruo; Chai Yaqin; Zhuo Ying

2009-01-01

The aim of this study is to elaborate a simple and sensitive electrochemical immunoassay using ferrocenecarboxylic (Fc-COOH)-doped silica nanoparticles (SNPs) as an immobilized affinity support for cancer antigen 15-3 (CA 15-3) detection. The Fc-COOH-doped SNPs with redox-active were prepared by using a water-in-oil microemulsion method. The use of colloidal silica could prevent the leakage of Fc-COOH and were easily modified with trialkoxysilane reagents for covalent conjugation of CA 15-3 antibodies (anti-CA 15-3). The Fc-COOH-doped SNPs were characterized by X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM). The fabrication process of the electrochemical immunosensor was demonstrated by using cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) techniques. Under optimal conditions, the developed immunosensor showed good linearity at the studied concentration range of 2.0-240 U mL -1 with a coefficient 0.9986 and a detection limit of 0.64 U mL -1 at S/N = 3

Ferrocenyl-doped silica nanoparticles as an immobilized affinity support for electrochemical immunoassay of cancer antigen 15-3.

Science.gov (United States)

Hong, Chenglin; Yuan, Ruo; Chai, Yaqin; Zhuo, Ying

2009-02-09

The aim of this study is to elaborate a simple and sensitive electrochemical immunoassay using ferrocenecarboxylic (Fc-COOH)-doped silica nanoparticles (SNPs) as an immobilized affinity support for cancer antigen 15-3 (CA 15-3) detection. The Fc-COOH-doped SNPs with redox-active were prepared by using a water-in-oil microemulsion method. The use of colloidal silica could prevent the leakage of Fc-COOH and were easily modified with trialkoxysilane reagents for covalent conjugation of CA 15-3 antibodies (anti-CA 15-3). The Fc-COOH-doped SNPs were characterized by X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM). The fabrication process of the electrochemical immunosensor was demonstrated by using cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) techniques. Under optimal conditions, the developed immunosensor showed good linearity at the studied concentration range of 2.0-240 UmL(-1) with a coefficient 0.9986 and a detection limit of 0.64 UmL(-1) at S/N=3.

In situ synthesis of copper nanoparticles on SBA-16 silica spheres

Directory of Open Access Journals (Sweden)

Asma Tufail Shah

2016-07-01

Full Text Available A chemical method for in situ synthesis of copper nanoparticles on SBA-16 silica spheres under ambient conditions has been reported. The silica support has been introduced into copper precursor solution before chemical reduction. Metal ions diffuse into mesopores (pore diameter 5–7 nm of silica where in situ reduction by hydrazine leads to formation of nanoparticles. These mesopores act as nanoreactor and their walls prevent metal particle’s agglomeration by providing a physical barrier. The obtained copper nanoparticles have been investigated by electron microscopy, X-ray diffraction, UV–Visible spectroscopy, Fourier transform Infra-red spectroscopy and thermogravimetric analyzer. SEM, TEM and UV–Visible spectroscopic images revealed that nanosized particles have been successfully synthesized by this method. Thermogravimetric investigations revealed that copper nanoparticles impregnated on silica were thermally more stable compared to unsupported nanoparticles. Silica not only helps in maintaining the particle size but also makes nanoparticles stable at high temperatures due to its thick pore walls. Macro sized silica support also makes separation/handling of nanoparticles easy and simple.

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)

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)

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)

Hydrogen Release From 800-MeV Proton-Irradiated Tungsten

International Nuclear Information System (INIS)

Oliver, Brian M.; Venhaus, Thomas J.; Causey, Rion A.; Garner, Francis A.; Maloy, Stuart A.

2002-01-01

Tungsten irradiated in spallation neutron sources such as those proposed for the Accelerator Production of Tritium (APT) project, or in proposed fusion reactors, will contain large quantities of generated helium and hydrogen gas. In the APT, spallation neutrons would be generated by the interaction of high energy (∼1 GeV) protons with solid tungsten rods or cylinders. In fusion reactors, tungsten used in a tokamak diverter will contain hydrogen, as well as deuterium and tritium diffusing in from the plasma-facing surface. The release kinetics of these gases during various off-normal scenarios involving loss of coolant and afterheat-induced rises in temperature is of particular interest for both applications. To determine the release kinetics of hydrogen from tungsten, tungsten rods irradiated with 800 MeV protons in the Los Alamos Neutron Science Center (LANCE) to high exposures as part of the APT project have been examined. Hydrogen evolution from the tungsten was measured using a dedicated mass spectrometer system by subjecting the specimens to an essentially linear temperature ramp from ∼323 K to ∼1473 K. Release profiles are compared with predictions obtained using the Tritium Migration Analysis Program (TMAP4). Input parameters for the modeling, consisting of diffusivity, recombination rate coefficient, and trapping, are discussed. The measurements show that for high proton doses, the majority of the hydrogen is released gradually, starting at about 900 K and reaching a maximum at about 1400 K, where it drops fairly rapidly. Comparisons with TMAP show reasonable agreement at high proton dose using a trap value of 1.4 eV and a trap density of 3%. There is also a small release fraction occurring at ∼600 K which predominates at lower proton doses, and which is relatively independent of dose. This lower-temperature release is predicted by TMAP if no traps are assumed, suggesting that this release may represent an adsorbed surface component

Supporting Wellness in Adult Online Education

Science.gov (United States)

Thompson, Jacklyn J.; Porto, Stella C. S.

2014-01-01

Online education cannot continue to grow at the current pace while ignoring a crucial component of campus support, wellness for adult online learners. This paper brings awareness to the concept of wellness as an important student support service in adult online education. It includes a summarized review of relevant literature and identifies…

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.

Validation of tungsten cross sections in the neutron energy region up to 100 keV

Science.gov (United States)

Pigni, Marco T.; Žerovnik, Gašper; Leal, Luiz. C.; Trkov, Andrej

2017-09-01

Following a series of recent cross section evaluations on tungsten isotopes performed at Oak Ridge National Laboratory (ORNL), this paper presents the validation work carried out to test the performance of the evaluated cross sections based on lead-slowing-down (LSD) benchmarks conducted in Grenoble. ORNL completed the resonance parameter evaluation of four tungsten isotopes - 182,183,184,186W - in August 2014 and submitted it as an ENDF-compatible file to be part of the next release of the ENDF/B-VIII.0 nuclear data library. The evaluations were performed with support from the US Nuclear Criticality Safety Program in an effort to provide improved tungsten cross section and covariance data for criticality safety sensitivity analyses. The validation analysis based on the LSD benchmarks showed an improved agreement with the experimental response when the ORNL tungsten evaluations were included in the ENDF/B-VII.1 library. Comparison with the results obtained with the JEFF-3.2 nuclear data library are also discussed.

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

Palladium nanoparticles encapsulated in core-shell silica: A structured hydrogenation catalyst with enhanced activity for reduction of oxyanion water pollutants

KAUST Repository

Wang, Yin; Liu, Jinyong; Wang, Peng; Werth, Charles; Strathmann, Timothy J.

2014-01-01

Noble metal nanoparticles have been applied to mediate catalytic removal of toxic oxyanions and halogenated hydrocarbons in contaminated water using H2 as a clean and sustainable reductant. However, activity loss by nanoparticle aggregation and difficulty of nanoparticle recovery are two major challenges to widespread technology adoption. Herein, we report the synthesis of a core-shell-structured catalyst with encapsulated Pd nanoparticles and its enhanced catalytic activity in reduction of bromate (BrO3-), a regulated carcinogenic oxyanion produced during drinking water disinfection process, using 1 atm H2 at room temperature. The catalyst material consists of a nonporous silica core decorated with preformed octahedral Pd nanoparticles that were further encapsulated within an ordered mesoporous silica shell (i.e., SiO2@Pd@mSiO2). Well-defined mesopores (2.3 nm) provide a physical barrier to prevent Pd nanoparticle (6 nm) movement, aggregation, and detachment from the support into water. Compared to freely suspended Pd nanoparticles and SiO2@Pd, encapsulation in the mesoporous silica shell significantly enhanced Pd catalytic activity (by a factor of 10) under circumneutral pH conditions that are most relevant to water purification applications. Mechanistic investigation of material surface properties combined with Langmuir-Hinshelwood modeling of kinetic data suggest that mesoporous silica shell enhances activity by promoting BrO3- adsorption near the Pd active sites. The dual function of the mesoporous shell, enhancing Pd catalyst activity and preventing aggregation of active nanoparticles, suggests a promising general strategy of using metal nanoparticle catalysts for water purification and related aqueous-phase applications.

Palladium nanoparticles encapsulated in core-shell silica: A structured hydrogenation catalyst with enhanced activity for reduction of oxyanion water pollutants

KAUST Repository

Wang, Yin

2014-10-03

Noble metal nanoparticles have been applied to mediate catalytic removal of toxic oxyanions and halogenated hydrocarbons in contaminated water using H2 as a clean and sustainable reductant. However, activity loss by nanoparticle aggregation and difficulty of nanoparticle recovery are two major challenges to widespread technology adoption. Herein, we report the synthesis of a core-shell-structured catalyst with encapsulated Pd nanoparticles and its enhanced catalytic activity in reduction of bromate (BrO3-), a regulated carcinogenic oxyanion produced during drinking water disinfection process, using 1 atm H2 at room temperature. The catalyst material consists of a nonporous silica core decorated with preformed octahedral Pd nanoparticles that were further encapsulated within an ordered mesoporous silica shell (i.e., SiO2@Pd@mSiO2). Well-defined mesopores (2.3 nm) provide a physical barrier to prevent Pd nanoparticle (6 nm) movement, aggregation, and detachment from the support into water. Compared to freely suspended Pd nanoparticles and SiO2@Pd, encapsulation in the mesoporous silica shell significantly enhanced Pd catalytic activity (by a factor of 10) under circumneutral pH conditions that are most relevant to water purification applications. Mechanistic investigation of material surface properties combined with Langmuir-Hinshelwood modeling of kinetic data suggest that mesoporous silica shell enhances activity by promoting BrO3- adsorption near the Pd active sites. The dual function of the mesoporous shell, enhancing Pd catalyst activity and preventing aggregation of active nanoparticles, suggests a promising general strategy of using metal nanoparticle catalysts for water purification and related aqueous-phase applications.

FEM investigation and thermo-mechanic tests of the new solid tungsten divertor tile for ASDEX Upgrade

International Nuclear Information System (INIS)

Jaksic, Nikola; Greuner, Henri; Herrmann, Albrecht

2013-01-01

Highlights: • New solid tungsten divertor for fusion experiment ASDEX Upgrade. • Design validation in the high heat flux (HHF) test facility GLADIS (Garching Large Divertor Sample Test Facility). • FEA simulation. -- Abstract: A new solid tungsten divertor for the fusion experiment ASDEX Upgrade is under construction at present. A new divertor tile design has been developed to improve the thermal performance of the current divertor made of tungsten coated fine grain graphite. Compared to thin tungsten coatings, divertor tiles made of massive tungsten allow to extend the operational range and to study the plasma material interaction of tungsten in more detail. The improved design for the solid tungsten divertor was tested on different full scale prototypes with a hydrogen ion beam. The influence of a possible material degradation due to thermal cracking or recrystallization can be studied. Furthermore, intensive Finite Element Method (FEM) numerical analysis with the respective test parameters has been performed. The elastic–plastic calculation was applied to analyze thermal stress and the observed elastic and plastic deformation during the heat loading. Additionally, the knowledge gained by the tests and especially by the numerical analysis has been used to optimize the shape of the divertor tiles and the accompanying divertor support structure. This paper discusses the main results of the high heat flux tests and their numerical simulations. In addition, results from some special structural mechanic analysis by means of FEM tools are presented. Finally, first results from the numerical lifecycle analysis of the current tungsten tiles will be reported

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

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)

Alcohols react with MCM-41 at room temperature and chemically modify mesoporous silica.

Science.gov (United States)

Björklund, Sebastian; Kocherbitov, Vitaly

2017-08-30

Mesoporous silica has received much attention due to its well-defined structural order, high surface area, and tunable pore diameter. To successfully employ mesoporous silica for nanotechnology applications it is important to consider how it is influenced by solvent molecules due to the fact that most preparation procedures involve treatment in various solvents. In the present work we contribute to this important topic with new results on how MCM-41 is affected by a simple treatment in alcohol at room temperature. The effects of alcohol treatment are characterized by TGA, FTIR, and sorption calorimetry. The results are clear and show that treatment of MCM-41 in methanol, ethanol, propanol, butanol, pentanol, or octanol at room temperature introduces alkoxy groups that are covalently bound to the silica surface. It is shown that alcohol treated MCM-41 becomes more hydrophobic and that this effect is sequentially more prominent going from methanol to octanol. Chemical formation of alkoxy groups onto MCM-41 occurs both for calcined and hydroxylated MCM-41 and the alkoxy groups are hydrolytically unstable and can be replaced by silanol groups after exposure to water. The results are highly relevant for mesoporous silica applications that involve contact or treatment in protic solvents, which is very common.

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.

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

Synthesis and carbon dioxide sorption of layered double hydroxide/silica foam nanocomposites with hierarchical mesostructure

KAUST Repository

Fu, Liling; Qi, Genggeng; Shekhah, Osama; Belmabkhout, Youssef; Esté vez, Luis Antonio; Eddaoudi, Mohamed; Giannelis, Emmanuel P.

2014-01-01

Layered double hydroxides (LDHs) with a hierarchical mesostructure are successfully synthesized on mesoporous silica foams by simple impregnation and hydrothermal treatment. The as-synthesized LDH/silica foam nanocomposites show well-defined mesostructures with high surface areas, large pore volumes, and mesopores of 6-7 nm. The nanocomposites act as carbon dioxide (CO2) sorbents under simulated flue gas conditions. They also exhibit significantly enhanced CO2 capacities under high-pressure conditions and high CO2/N2 and CO2/CH4 selectivities. Respect the hierarchy: Hierarchical mesoporous layered double hydroxide (LDH) nanocomposites with high surface areas and large pore volumes are synthesized by controlled hydrothermal growth of LDH precursors on a mesoporous silica foam. The as-synthesized nanocomposites exhibit a significantly enhanced capacity and selectivity towards carbon dioxide, making them very promising candidates for carbon dioxide (CO2) separation applications. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Synthesis and carbon dioxide sorption of layered double hydroxide/silica foam nanocomposites with hierarchical mesostructure

KAUST Repository

Fu, Liling

2014-03-05

Layered double hydroxides (LDHs) with a hierarchical mesostructure are successfully synthesized on mesoporous silica foams by simple impregnation and hydrothermal treatment. The as-synthesized LDH/silica foam nanocomposites show well-defined mesostructures with high surface areas, large pore volumes, and mesopores of 6-7 nm. The nanocomposites act as carbon dioxide (CO2) sorbents under simulated flue gas conditions. They also exhibit significantly enhanced CO2 capacities under high-pressure conditions and high CO2/N2 and CO2/CH4 selectivities. Respect the hierarchy: Hierarchical mesoporous layered double hydroxide (LDH) nanocomposites with high surface areas and large pore volumes are synthesized by controlled hydrothermal growth of LDH precursors on a mesoporous silica foam. The as-synthesized nanocomposites exhibit a significantly enhanced capacity and selectivity towards carbon dioxide, making them very promising candidates for carbon dioxide (CO2) separation applications. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Analysis of the retention of water vapor on silica gel; Analisis de la retencion del vapor de agua en silica gel

Energy Technology Data Exchange (ETDEWEB)

Herranz, M.; Pinilla, J. L.; Alegria, N.; Idoeta, R.; Legarda, F.

2011-07-01

Among the various sampling systems tritium content in the atmosphere as water vapor, one of the most basic and, therefore, of widespread use in the environmental field, is the retention on silica gel. However, the behavior of the collection efficiency of silica gel under varying conditions of air temperature and relative humidity makes it difficult to define the amount of this necessary for proper completion of sampling, especially in situations of prolonged sampling. This paper presents partial results obtained in a study on the analysis of these efficiencies under normal conditions of sampling. (Author)

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

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

Synthesis of internally functionalized silica nanoparticles for theranostic applications

Science.gov (United States)

Walton, Nathan Isaac

This thesis addresses the synthesis and characterization of novel inorganic silica nanoparticle hybrids. It focuses in large part on their potential applications in the medical field. Silica acts as a useful carrier for a variety of compounds and this thesis silica will demonstrate its use as a carrier for boron or gadolinium. Boron-10 and gadolinium-157 have been suggested for the radiological treatment of tumor cells through the process called neutron capture therapy (NCT). Gadolinium is also commonly used as a Magnetic Resonance Imaging (MRI) contrast agent. Particles that carry it have potential theranostic applications of both imaging and treating tumors. Chapter 1 presents a background on synthetic strategies and usages of silica nanoparticles, and NCT theory. Chapter 2 describes a procedure to create mesoporous metal chelating silica nanoparticles, mDTTA. This is achieved via a co-condensation of tetraethoxysilane (TEOS) and 3-trimethoxysilyl-propyl diethylenetriamine (SiDETA) followed by a post-synthesis modification step with bromoacetic acid (BrAA). These particles have a large surface area and well-defined pores of ~2 nm. The mDTTA nanoparticles were used to chelate the copper(II), cobalt(II) and gadolinium(III). The chelating of gadolinium is the most interesting since it can be used as a MRI contrast agent and a neutron capture therapeutic. The synthetic procedure developed also allows for the attachment of a fluorophore that gives the gadolinium chelating mDTTA nanoparticles a dual imaging modality. Chapter 3 presents the synthetic method used to produce two classes of large surface area organically modified silica (ORMOSIL) nanoparticles. Condensating the organosilane vinyltrimethoxysilane in a micellar solution results in nanoparticles that are either surface rough (raspberry-like) or mesoporous nanoparticles, which prior to this thesis has not been demonstrated in ORMOSIL chemistry. Furthermore, the vinyl functionalities are modified, using

Software-Defined Ground Stations - Enhancing Multi-Mission Support, Phase I

Data.gov (United States)

National Aeronautics and Space Administration — This SBIR Phase 1 proposal to NASA requests $99,055.69 to enhance multiple mission support in ground stations through the use of software defined radios and virtual...

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

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.

The use of a well-defined surface organometallic complex as a probe molecule: [(≡SiO)Ta^VCl₂Me₂] shows different isolated silanol sites on the silica surface

KAUST Repository

Chen, Yin; Zheng, Bin; Abou-Hamad, Edy; Hamieh, Ali Imad Ali; Hamzaoui, Bilel; Huang, Kuo-Wei; Basset, Jean-Marie

2014-01-01

TaVCl2Me3 reacts with silica(700) and produces two different [(≡SiO)TaVCl2Me2] surface organometallic species, suggesting a heterogeneity of the highly dehydroxylated silica surface, which was studied with a combined experimental and theoretical approach. This journal is © the Partner Organisations 2014.

Structure-performance relations of molybdenum- and tungsten carbide catalysts for deoxygenation

NARCIS (Netherlands)

Stellwagen, D.R.; Bitter, J.H.

2015-01-01

This work demonstrates for the first time that carbide particle size is a critical factor for the activity and stability of carbon supported tungsten- and molybdenum carbide catalysts in (hydro-)deoxygenation reactions. The stability of the catalyst was shown to increase for larger particles due to

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.

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.

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.,

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

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,

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

Bio-inspired synthesis of hybrid silica nanoparticles templated from elastin-like polypeptide micelles

Science.gov (United States)

Han, Wei; MacEwan, Sarah R.; Chilkoti, Ashutosh; López, Gabriel P.

2015-07-01

The programmed self-assembly of block copolymers into higher order nanoscale structures offers many attractive attributes for the development of new nanomaterials for numerous applications including drug delivery and biosensing. The incorporation of biomimetic silaffin peptides in these block copolymers enables the formation of hybrid organic-inorganic materials, which can potentially enhance the utility and stability of self-assembled nanostructures. We demonstrate the design, synthesis and characterization of amphiphilic elastin-like polypeptide (ELP) diblock copolymers that undergo temperature-triggered self-assembly into well-defined spherical micelles. Genetically encoded incorporation of the silaffin R5 peptide at the hydrophilic terminus of the diblock ELP leads to presentation of the silaffin R5 peptide on the coronae of the micelles, which results in localized condensation of silica and the formation of near-monodisperse, discrete, sub-100 nm diameter hybrid ELP-silica particles. This synthesis method, can be carried out under mild reaction conditions suitable for bioactive materials, and will serve as the basis for the development and application of functional nanomaterials. Beyond silicification, the general strategies described herein may also be adapted for the synthesis of other biohybrid nanomaterials as well.The programmed self-assembly of block copolymers into higher order nanoscale structures offers many attractive attributes for the development of new nanomaterials for numerous applications including drug delivery and biosensing. The incorporation of biomimetic silaffin peptides in these block copolymers enables the formation of hybrid organic-inorganic materials, which can potentially enhance the utility and stability of self-assembled nanostructures. We demonstrate the design, synthesis and characterization of amphiphilic elastin-like polypeptide (ELP) diblock copolymers that undergo temperature-triggered self-assembly into well-defined

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%.

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)

A Robust Fiber Bragg Grating Hydrogen Gas Sensor Using Platinum-Supported Silica Catalyst Film

Directory of Open Access Journals (Sweden)

Marina Kurohiji

2018-01-01

Full Text Available A robust fiber Bragg grating (FBG hydrogen gas sensor for reliable multipoint-leakage monitoring has been developed. The sensing mechanism is based on shifts of center wavelength of the reflection spectra due to temperature change caused by catalytic combustion heat. The sensitive film which consists of platinum-supported silica (Pt/SiO2 catalyst film was obtained using sol-gel method. The precursor solution was composed of hexachloroplatinic acid and commercially available silica precursor solution. The atom ratio of Si : Pt was fixed at 13 : 1. A small amount of this solution was dropped on the substrate and dried at room temperature. After that, the film was calcined at 500°C in air. These procedures were repeated and therefore thick hydrogen-sensitive films were obtained. The catalytic film obtained by 20-time coating on quartz glass substrate showed a temperature change 75 K upon exposure to 3 vol.% H2. For realizing robust sensor device, this catalytic film was deposited and FBG portion was directly fixed on titanium substrate. The sensor device showed good performances enough to detect hydrogen gas in the concentration range below lower explosion limit at room temperature. The enhancement of the sensitivity was attributed to not only catalytic combustion heat but also related thermal strain.

Pretreatments of porous silica for improving the activity of a nickel-loaded catalyst

Energy Technology Data Exchange (ETDEWEB)

Arai, M.; Ikushima, Y.; Nishiyama, Y.

1986-02-01

Nickel catalysts supported on porous silicas treated with water, ethanol, and 1-butanol were found to be more active than that supported on untreated silica for ethane hydrogenolysis and furan hydrogenation. To elucidate the reason for the activation, some surface properties of the treated silicas were examined. The treatments decreased the surface area and increased the volume of the macropores, the surface density of hydroxyl groups, and the heat of immersion in water per unit surface area. The state of nickel on the support was examined by temperature programed desorption (TPD) of hydrogen, X-ray diffraction (XRD), and scanning electron microscopy/X-ray microanalysis. The dispersion measured by XRD was not appreciably altered by the treatments, but the TPD showed more hydrogen desorbed above 150/sup 0/C from nickel on the treated supports. The activation of nickel by pretreatment of the support was ascribed to the increase of those nickel atoms which dispersed finely over the support by the increased number of surface hydroxyl groups. This was based on the number of hydroxyl groups per unit surface area. The nickel catalyst supported on the pretreated silicas showed greater thermal stability. 16 references, 5 figures, 1 table.

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

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