Electrical and band structural analyses of Ti1-x Al x O y films grown by atomic layer deposition on p-type GaAs

NASA Astrophysics Data System (ADS)

An, Youngseo; Mahata, Chandreswar; Lee, Changmin; Choi, Sungho; Byun, Young-Chul; Kang, Yu-Seon; Lee, Taeyoon; Kim, Jiyoung; Cho, Mann-Ho; Kim, Hyoungsub

2015-10-01

Amorphous Ti1-x Al x O y films in the Ti-oxide-rich regime (x  <  0.5) were deposited on p-type GaAs via atomic layer deposition with titanium isopropoxide, trimethylaluminum, and H2O precursor chemistry. The electrical properties and energy band alignments were examined for the resulting materials with their underlying substrates, and significant frequency dispersion was observed in the accumulation region of the Ti-oxide-rich Ti1-x Al x O y films. Although a further reduction in the frequency dispersion and leakage current (under gate electron injection) could be somewhat achieved through a greater addition of Al-oxide in the Ti1-x Al x O y film, the simultaneous decrease in the dielectric constant proved problematic in finding an optimal composition for application as a gate dielectric on GaAs. The spectroscopic band alignment measurements of the Ti-oxide-rich Ti1-x Al x O y films indicated that the band gaps had a rather slow increase with the addition of Al-oxide, which was primarily compensated for by an increase in the valance band offset, while a nearly-constant conduction band offset with a negative electron barrier height was maintained.

Complexes with Tunable Intramolecular Ferrocene to Ti(IV) Electronic Transitions: Models for Solid State Fe(II) to Ti(IV) Charge Transfer.

PubMed

Turlington, Michael D; Pienkos, Jared A; Carlton, Elizabeth S; Wroblewski, Karlee N; Myers, Alexis R; Trindle, Carl O; Altun, Zikri; Rack, Jeffrey J; Wagenknecht, Paul S

2016-03-07

Iron(II)-to-titanium(IV) metal-to-metal-charge transfer (MMCT) is important in the photosensitization of TiO2 by ferrocyanide, charge transfer in solid-state metal-oxide photocatalysts, and has been invoked to explain the blue color of sapphire, blue kyanite, and some lunar material. Herein, a series of complexes with alkynyl linkages between ferrocene (Fc) and Ti(IV) has been prepared and characterized by UV-vis spectroscopy and electrochemistry. Complexes with two ferrocene substituents include Cp2Ti(C2Fc)2, Cp*2Ti(C2Fc)2, and Cp2Ti(C4Fc)2. Complexes with a single ferrocene utilize a titanocene with a trimethylsilyl derivatized Cp ring, (TMS)Cp, and comprise the complexes (TMS)Cp2Ti(C2Fc)(C2R), where R = C6H5, p-C6H4CF3, and CF3. The complexes are compared to Cp2Ti(C2Ph)2, which lacks the second metal. Cyclic voltammetry for all complexes reveals a reversible Ti(IV/III) reduction wave and an Fe(II/III) oxidation that is irreversible for all complexes except (TMS)Cp2Ti(C2Fc)(C2CF3). All of the complexes with both Fc and Ti show an intense absorption (4000 M(-1)cm(-1) < ε < 8000 M(-1)cm(-1)) between 540 and 630 nm that is absent in complexes lacking a ferrocene donor. The energy of the absorption tracks with the difference between the Ti(IV/III) and Fe(III/II) reduction potentials, shifting to lower energy as the difference in potentials decreases. Reorganization energies, λ, have been determined using band shape analysis (2600 cm(-1) < λ < 5300 cm(-1)) and are in the range observed for other donor-acceptor complexes that have a ferrocene donor. Marcus-Hush-type analysis of the electrochemical and spectroscopic data are consistent with the assignment of the low-energy absorption as a MMCT band. TD-DFT analysis also supports this assignment. Solvatochromism is apparent for the MMCT band of all complexes, there being a bathochromic shift upon increasing polarizability of the solvent. The magnitude of the shift is dependent on both the electron density at Ti

Oxidation of Ti silicide surfaces

NASA Astrophysics Data System (ADS)

Cros, A.; Pirri, C.; Derrien, J.

1985-04-01

The oxidation of clean Ti suicide surface prepared under ultra high vacuum conditions, has been studied by ultraviolet and X-ray photo-emission spectroscopy techniques. At room temperature, the oxide overlayer is composed of both TiO 2 and SiO 2. An annealing at 400-600°C provokes the reduction of TiO 2 in the form of Ti suboxide while the liberated oxygen atoms bond to Si. This is not due to the presence of Si atoms and is rather an intrinsic property of native TiO 2. The simultaneous presence at high temperature of both SiO 2 and Ti suboxide is attributed to the existence of a rate limiting process due to diffusion barriers.

Hydride oxidation from a titanium–aluminum bimetallic complex: insertion, thermal and electrochemical reactivity

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

Brown, Alexandra C.; Altman, Alison B.; Lohrey, Trevor D.

We report the synthesis and reactivity of paramagnetic heterometallic complexes containing a Ti(III)-μ-H-Al(III) moiety. Combining different stoichiometries amounts of Cp 2TiCl and KH 3AlC(TMS) 3 (Cp = cyclopentadienyl, TMS = trimethylsilyl) resulted in the formation of either bimetallic Cp 2Ti(μ-H) 2(H)AlC(TMS) 3 (2) or trimetallic (Cp 2Ti) 2(μ-H) 3(H)AlC(TMS) 3 (3) via salt metathesis pathways. While these complexes were indefinitely stable at room temperature, the bridging hydrides were readily activated upon exposure to heteroallenes, heating, or electrochemical oxidation. In each case, formal hydride oxidation occurred, but the isolated product maintained the +3 oxidation state at both metal centers. The naturemore » of this reactivity was explored using deuterium labelling experiments and Density Functional Theory (DFT) calculations. It was found that while C–H activation from the Ti(III) bimetallic may occur through a σ-bond metathesis pathway, chemical oxidation to Ti(IV) promotes bimolecular reductive elimination of dihydrogen to form a Ti(III) product.« less

Hydride oxidation from a titanium–aluminum bimetallic complex: insertion, thermal and electrochemical reactivity

DOE PAGES

Brown, Alexandra C.; Altman, Alison B.; Lohrey, Trevor D.; ...

2017-05-31

We report the synthesis and reactivity of paramagnetic heterometallic complexes containing a Ti(III)-μ-H-Al(III) moiety. Combining different stoichiometries amounts of Cp 2TiCl and KH 3AlC(TMS) 3 (Cp = cyclopentadienyl, TMS = trimethylsilyl) resulted in the formation of either bimetallic Cp 2Ti(μ-H) 2(H)AlC(TMS) 3 (2) or trimetallic (Cp 2Ti) 2(μ-H) 3(H)AlC(TMS) 3 (3) via salt metathesis pathways. While these complexes were indefinitely stable at room temperature, the bridging hydrides were readily activated upon exposure to heteroallenes, heating, or electrochemical oxidation. In each case, formal hydride oxidation occurred, but the isolated product maintained the +3 oxidation state at both metal centers. The naturemore » of this reactivity was explored using deuterium labelling experiments and Density Functional Theory (DFT) calculations. It was found that while C–H activation from the Ti(III) bimetallic may occur through a σ-bond metathesis pathway, chemical oxidation to Ti(IV) promotes bimolecular reductive elimination of dihydrogen to form a Ti(III) product.« less

Electrically coupling complex oxides to semiconductors: A route to novel material functionalities

DOE PAGES

Ngai, J. H.; Ahmadi-Majlan, K.; Moghadam, J.; ...

2017-01-12

Complex oxides and semiconductors exhibit distinct yet complementary properties owing to their respective ionic and covalent natures. By electrically coupling complex oxides to traditional semiconductors within epitaxial heterostructures, enhanced or novel functionalities beyond those of the constituent materials can potentially be realized. Essential to electrically coupling complex oxides to semiconductors is control of the physical structure of the epitaxially grown oxide, as well as the electronic structure of the interface. In this paper, we discuss how composition of the perovskite A- and B-site cations can be manipulated to control the physical and electronic structure of semiconductor—complex oxide heterostructures. Two prototypicalmore » heterostructures, Ba 1-xSr xTiO 3/Ge and SrZr xTi 1-xO 3/Ge, will be discussed. In the case of Ba 1-xSr xTiO 3/Ge, we discuss how strain can be engineered through A-site composition to enable the re-orientable ferroelectric polarization of the former to be coupled to carriers in the semiconductor. In the case of SrZr xTi 1-xO 3/Ge we discuss how B-site composition can be exploited to control the band offset at the interface. Finally, analogous to heterojunctions between compound semiconducting materials, control of band offsets, i.e., band-gap engineering, provides a pathway to electrically couple complex oxides to semiconductors to realize a host of functionalities.« less

Electrically coupling complex oxides to semiconductors: A route to novel material functionalities

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

Ngai, J. H.; Ahmadi-Majlan, K.; Moghadam, J.

Complex oxides and semiconductors exhibit distinct yet complementary properties owing to their respective ionic and covalent natures. By electrically coupling complex oxides to traditional semiconductors within epitaxial heterostructures, enhanced or novel functionalities beyond those of the constituent materials can potentially be realized. Essential to electrically coupling complex oxides to semiconductors is control of the physical structure of the epitaxially grown oxide, as well as the electronic structure of the interface. In this paper, we discuss how composition of the perovskite A- and B-site cations can be manipulated to control the physical and electronic structure of semiconductor—complex oxide heterostructures. Two prototypicalmore » heterostructures, Ba 1-xSr xTiO 3/Ge and SrZr xTi 1-xO 3/Ge, will be discussed. In the case of Ba 1-xSr xTiO 3/Ge, we discuss how strain can be engineered through A-site composition to enable the re-orientable ferroelectric polarization of the former to be coupled to carriers in the semiconductor. In the case of SrZr xTi 1-xO 3/Ge we discuss how B-site composition can be exploited to control the band offset at the interface. Finally, analogous to heterojunctions between compound semiconducting materials, control of band offsets, i.e., band-gap engineering, provides a pathway to electrically couple complex oxides to semiconductors to realize a host of functionalities.« less

Enhanced magnetism of perovskite oxides, Sr(Sn,Fe)O3- δ , by substitution of nonmagnetic Ca and Ti ions

NASA Astrophysics Data System (ADS)

Nomura, Kiyoshi; Suzuki, Shigeyo; Mizunuma, Tomoya; Koike, Yuya; Okazawa, Atsushi

2017-11-01

Magnetic properties of perovskite oxides, SrSn1- x Fe x O3- δ ( x ≤ 0.15), substituted with nonmagnetic Ca and Ti ions were studied. XRD patterns showed the orthorhombic structure (close to tetragonal) of (Sr1- y Ca y )(Sn1- x Fe x )O3- δ and Sr(Sn1- x- y Fe x Ti y )O3- δ . The cell volumes decreased with the increase of Ca and Ti doping rates. Although Ti-substituted Sr(Sn, Fe)O3- δ showed small saturation magnetizations as compared with non-Ti substituted one, the magnetization increased a little with Ti doping rates up to 15%. On the other hand, all Ca-substituted Sr(Sn, Fe)O3- δ showed larger saturation magnetization than non-Ca substituted one. Two doublets of Fe3+ and a doublet of Fe4+ were observed in Mössbauer spectra of Ca-substituted Sr(Sn, Fe)O3- δ with weak ferromagnetism, and two sextets of high spin Fe3+ were additionally observed in Mössbauer spectra of Ca-doped Sr(Sn, Fe)O3- δ with relatively strong ferromagnetism. When Sr(Sn, Fe)O3- δ were further codoped with Ca and Ti ions, they showed the stable and enhanced ferromagnetic properties. It is considered that magnetic polarons among high spin Fe3+ species are overlapped by shrinking or deforming the crystal structure of perovskite oxides. That is the magnetism induced by a chemical pressure of perovskite oxides.

Oxidation characteristics of Ti-25Al-10Nb-3V-1Mo intermetallic alloy

NASA Technical Reports Server (NTRS)

Wallace, Terryl A.; Clark, Ronald K.; Sankaran, Sankara N.; Wiedemann, Karl E.

1990-01-01

Static oxidation kinetics of the super-alpha 2 titanium-aluminide alloy Ti-25Al-10Nb-3V-1Mo (at. percent) were investigated in air over the temperature range of 650 to 1000 C using thermogravimetric analysis. The oxidation kinetics were complex at all exposure temperatures and displayed up to three distinct oxidation rates. Breakaway oxidation occurred after long exposure times at high temperatures. Oxidation products were determined using x ray diffraction techniques, electron microprobe analysis, and energy dispersive x ray analysis. Oxide scale morphology was examined by scanning electron microscopy of the surfaces and cross sections of oxidized specimens. The oxides during the parabolic stages were compact and multilayered, consisting primarily of TiO2 doped with Nb, a top layer of Al2O3, and a thin bottom layer of TiN. The transition between the second and third parabolic stage was found to be linked to the formation of a TiAl layer at the oxide-metal interface. Porosity was formed during the third stage, causing degradation of the oxide and the beginning of breakaway oxidation.

Oxidation Resistant Ti-Al-Fe Diffusion Barrier for FeCrAlY Coatings on Titanium Aluminides

NASA Technical Reports Server (NTRS)

Brady, Michael P. (Inventor); Smialke, James L. (Inventor); Brindley, William J. (Inventor)

1996-01-01

A diffusion barrier to help protect titanium aluminide alloys, including the coated alloys of the TiAl gamma + Ti3Al (alpha2) class, from oxidative attack and interstitial embrittlement at temperatures up to at least 1000 C is disclosed. The coating may comprise FeCrAlX alloys. The diffusion barrier comprises titanium, aluminum, and iron in the following approximate atomic percent: Ti-(50-55)Al-(9-20)Fe. This alloy is also suitable as an oxidative or structural coating for such substrates.

Opportunities for functional oxides in yttrium oxide-titanium oxide-zirconium oxide system: Applications for novel thermal barrier coatings

NASA Astrophysics Data System (ADS)

Francillon, Wesley

a single tetragonal phase. Thus, compositions are of single phase tetragonal phase, theoretically, should not undergo high temperature partitioning. Single Tetragonal phase oxides of Ti-YSZ also offer the possibility of enhanced toughness and higher temperature stability akin to those observed in yttria partially stabilized zirconia. Many pyrochlore oxides are under review because they have shown to have lower thermal conductivity than YSZ oxides. This study focused on chemically synthesizing homogeneous starting material compositions in a metastable state (preferably amorphous), following its evolution according to the phase hierarchy under conditions of kinetic constraints. The current equilibrium diagram of YO1.5-TiO2-ZrO 2 is based on theoretical calculations. One of the contributions of this work is the redefined phase fields in YO1.5-TiO2-ZrO 2 based on our experimental results. Investigated compositions were based on tie lines of Y2-xTi2ZrxO7+x/2 and Y2Ti2-yZryO7 representing substitution of Zr4+ for Y3+ and Zr4+ for Ti4+ respectively. More notably, we observed extended metastable phases in pyrochlore and fluorite oxides at low temperature. The significance of this result is that it offers a larger compositional range for investing pyrochlore oxides with associated high temperature phase stability for TBC applications. In tetragonal oxides, our results showed that Ti-YSZ results have slower partitioning kinetics in comparison to YSZ at high temperature. This study also emphasized the deposition of advanced ceramic coatings by plasma spray for tetragonal and pyrochlore systems, compositionally complex functional oxides that may potentially have lower thermal conductivity values compared to current YSZ oxides. Next generation thermal barrier coatings require powders with high chemical purity, chemical homogeneity, controlled particle size/shape and pertinent phase state. Thermal spray offers an avenue to create novel materials and deposits directly from the

Structure of metal-oxide Ti-Ta-(Ti,Ta)xOy coatings during spark alloying and induction-thermal oxidation

NASA Astrophysics Data System (ADS)

Koshuro, V.; Fomin, A.; Fomina, M.; Rodionov, I.; Brzhozovskii, B.; Martynov, V.; Zakharevich, A.; Aman, A.; Oseev, A.; Majcherek, S.; Hirsch, S.

2016-08-01

The study focuses on combined spark alloying of titanium and titanium alloy surface and porous matrix structure oxidation. The metal-oxide coatings morphology is the result of melt drop transfer, heat treatment, and oxidation. The study establishes the influence of technological regimes of alloying and oxidation on morphological heterogeneity of metal- oxide system Ti-Ta-(Ti,Ta)xOy.

Strain-induced phenomenon in complex oxide thin films

NASA Astrophysics Data System (ADS)

Haislmaier, Ryan

Complex oxide materials wield an immense spectrum of functional properties such as ferroelectricity, ferromagnetism, magnetoelectricity, optoelectricity, optomechanical, magnetoresistance, superconductivity, etc. The rich coupling between charge, spin, strain, and orbital degrees of freedom makes this material class extremely desirable and relevant for next generation electronic devices and technologies which are trending towards nanoscale dimensions. Development of complex oxide thin film materials is essential for realizing their integration into nanoscale electronic devices, where theoretically predicted multifunctional capabilities of oxides could add tremendous value. Employing thin film growth strategies such as epitaxial strain and heterostructure interface engineering can greatly enhance and even unlock novel material properties in complex oxides, which will be the main focus of this work. However, physically incorporating oxide materials into devices remains a challenge. While advancements in molecular beam epitaxy (MBE) of thin film oxide materials has led to the ability to grow oxide materials with atomic layer precision, there are still major limitations such as controlling stoichiometric compositions during growth as well as creating abrupt interfaces in multi-component layered oxide structures. The work done in this thesis addresses ways to overcome these limitations in order to harness intrinsic material phenomena. The development of adsorption-controlled stoichiometric growth windows of CaTiO3 and SrTiO3 thin film materials grown by hybrid MBE where Ti is supplied using metal-organic titanium tetraisopropoxide material is thoroughly outlined. These growth windows enable superior epitaxial strain-induced ferroelectric and dielectric properties to be accessed as demonstrated by chemical, structural, electrical, and optical characterization techniques. For tensile strained CaTiO3 and compressive strained SrTiO 3 films, the critical effects of

Reaction products and oxide thickness formed by Ti out-diffusion and oxidization in poly-Pt/Ti/SiO 2/Si with oxide films deposited

NASA Astrophysics Data System (ADS)

Chen, Changhong; Huang, Dexiu; Zhu, Weiguang; Feng, Yi; Wu, Xigang

2006-08-01

In the paper, we present experimental results to enhance the understanding of Ti out-diffusion and oxidization in commercial poly-Pt/Ti/SiO 2/Si wafers with perovskite oxide films deposited when heat-treated in flowing oxygen ambient. It indicates that when heat-treated at 550 and 600 °C, PtTi 3+PtTi and PtTi are the reaction products from interfacial interaction, respectively; while heat-treated at 650 °C and above, the products become three layers of titanium oxides instead of the alloys. Confirmed to be rutile TiO 2, the first two layers spaced by 65 nm encapsulate the Pt surface by the first layer with 60 nm thick forming at its surface and by the next layer with 35 nm thick inserting its original layer. In addition, the next layer is formed as a barrier to block up continuous diffusion paths of Ti, and thus results in the last layer of TiO 2- x formed by the residual Ti oxidizing.

Dye sensitized solar cell applications of CdTiO{sub 3}–TiO{sub 2} composite thin films deposited from single molecular complex

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

Ehsan, Muhammad Ali; Khaledi, Hamid; Pandikumar, Alagarsamy

2015-10-15

A heterobimetallic complex [Cd{sub 2}Ti{sub 4}(μ-O){sub 6}(TFA){sub 8}(THF){sub 6}]·1.5THF (1) (TFA=trifluoroacetato, THF=tetrahydrofuran) comprising of Cd:Ti (1:2) ratio was synthesized by a chemical reaction of cadmium (II) acetate with titanium (IV) isopropoxide and triflouroacetic acid in THF. The stoichiometry of (1) was recognized by single crystal X-ray diffraction, spectroscopic and elemental analyses. Thermal studies revealed that (1) neatly decomposes at 450 °C to furnish 1:1 ratio of cadmium titanate:titania composite oxides material. The thin films of CdTiO{sub 3}–TiO{sub 2} composite oxides were deposited at 550 °C on fluorine doped tin oxide coated conducting glass substrate in air ambient. The micro-structure, crystallinity,more » phase identification and chemical composition of microspherical architectured CdTiO{sub 3}–TiO{sub 2} composite thin film have been determined by scanning electron microscopy, X-ray diffraction, Raman spectroscopy and energy dispersive X-ray analysis. The scope of composite thin film having band gap of 3.1 eV was explored as photoanode for dye-sensitized solar cell application. - Graphical abstarct: Microspherical designed CdTiO{sub 3}–TiO{sub 2} composite oxides photoanode film has been fabricated from single source precursor [Cd{sub 2}Ti{sub 4}(μ-O){sub 6}(TFA){sub 8}(THF){sub 6}]·1.5THF via aerosol assisted chemical vapor deposition technique for dye sensitized solar cell application. - Highlights: • Synthesis and characterization of a heterobimetallic Cd–Ti complex. • Fabrication of CdTiO{sub 3}–TiO{sub 2} thin film photoelectrode. • Application as dye sensitized photoanode for solar application.« less

Dye sensitized solar cell applications of CdTiO3-TiO2 composite thin films deposited from single molecular complex

NASA Astrophysics Data System (ADS)

Ehsan, Muhammad Ali; Khaledi, Hamid; Pandikumar, Alagarsamy; Huang, Nay Ming; Arifin, Zainudin; Mazhar, Muhammad

2015-10-01

A heterobimetallic complex [Cd2Ti4(μ-O)6(TFA)8(THF)6]·1.5THF (1) (TFA=trifluoroacetato, THF=tetrahydrofuran) comprising of Cd:Ti (1:2) ratio was synthesized by a chemical reaction of cadmium (II) acetate with titanium (IV) isopropoxide and triflouroacetic acid in THF. The stoichiometry of (1) was recognized by single crystal X-ray diffraction, spectroscopic and elemental analyses. Thermal studies revealed that (1) neatly decomposes at 450 °C to furnish 1:1 ratio of cadmium titanate:titania composite oxides material. The thin films of CdTiO3-TiO2 composite oxides were deposited at 550 °C on fluorine doped tin oxide coated conducting glass substrate in air ambient. The micro-structure, crystallinity, phase identification and chemical composition of microspherical architectured CdTiO3-TiO2 composite thin film have been determined by scanning electron microscopy, X-ray diffraction, Raman spectroscopy and energy dispersive X-ray analysis. The scope of composite thin film having band gap of 3.1 eV was explored as photoanode for dye-sensitized solar cell application.

Biocompatilibity-related surface characteristics of oxidized NiTi.

PubMed

Danilov, Anatoli; Tuukkanen, Tuomas; Tuukkanen, Juha; Jämsä, Timo

2007-09-15

In the present study, we examined the effect of NiTi oxidation on material surface characteristics related to biocompatibility. Correspondence between electron work function (EWF) and adhesive force predicted by electron theory of adsorption as well as the effect of surface mechanical stress on the adhesive force were studied on the nonoxidized and oxidized at 350, 450, and 600 degrees C NiTi alloy for medical application. The adhesive force generated by the material surface towards the drops of alpha-minimal essential medium (alpha-MEM) was used as a characteristic of NiTi adsorption properties. The study showed that variations in EWF and mechanical stress caused by surface treatment were accompanied by variations in adhesive force. NiTi oxidation at all temperatures used gave rise to decrease in adhesive force and surface stress values in comparison to the nonoxidized state. In contrary, the EWF value revealed increase under the same condition. Variations in surface oxide layer thickness and its phase composition were also followed. The important role of oxide crystallite size in EWF values within the range of crystallite dimensions typical for NiTi surface oxide as an instrument for the fine regulation of NiTi adsorption properties was demonstrated. The comparative oxidation of pure titanium and NiTi showed that the effect of Ni on the EWF value of NiTi surface oxide is negligible. Copyright 2007 Wiley Periodicals, Inc.

Low temperature oxidative desulfurization with hierarchically mesoporous titaniumsilicate Ti-SBA-2 single crystals.

PubMed

Shi, Chengxiang; Wang, Wenxuan; Liu, Ni; Xu, Xueyan; Wang, Danhong; Zhang, Minghui; Sun, Pingchuan; Chen, Tiehong

2015-07-21

Hierarchically porous Ti-SBA-2 with high framework Ti content (up to 5 wt%) was firstly synthesized by employing organic mesomorphous complexes of a cationic surfactant (CTAB) and an anionic polyelectrolyte (PAA) as templates. The material exhibited excellent performance in oxidative desulfurization of diesel fuel at low temperature (40 °C or 25 °C) due to the unique hierarchically porous structure and high framework Ti content.

Influence of Ti content on synthesis and characteristics of W-Ti ODS alloy

NASA Astrophysics Data System (ADS)

Chen, Chun-Liang; Zeng, Yong

2016-02-01

Tungsten-titanium alloys are considered as promising materials for the future fusion devices, in particular for the divertor and other first wall components. The microstructure and the mechanical properties of the material are dependent on the amount of Ti present in the alloy. In this study, W-Ti-Y2O3 alloys with varied Ti contents between 1 wt.% and 10 wt.% fabricated by mechanical alloying were investigated. The effect of Ti on the phase formation and mechanical properties of W-Ti-Y2O3 alloys has been examined. The results suggest that the alloys containing low Ti content exhibit homogeneous microstructure with a uniform distribution of fine titanium oxide particles and tungsten carbides, leading to a significant increase in hardness and elastic modulus of alloys. In addition, high-energy ball milling can facilitate a solid-state reaction between Y2O3 particles and the tungsten-titanium matrix and the subsequent sintering processing promotes the formation of stable nano Ti2Y2O7 oxide particles, which greatly increase the mechanical properties at elevated temperature and enhance irradiation resistance.

Characterisation of a complex thin walled structure fabricated by selective laser melting using a ferritic oxide dispersion strengthened steel

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

Boegelein, Thomas, E-mail: t.boegelein@liv.ac.uk; Louvis, Eleftherios; Dawson, Karl

2016-02-15

Oxide dispersion strengthened (ODS) alloys exhibit superior mechanical and physical properties due to the presence of nanoscopic Y(Al, Ti) oxide precipitates, but their manufacturing process is complex. The present study is aimed at further investigation of the application of an alternative, Additive Manufacturing (AM) technique, Selective Laser Melting (SLM), to the production of consolidated ODS alloy components. Mechanically alloyed PM2000 (ODS-FeCrAl) powders have been consolidated and a fine dispersion of Y-containing precipitates were observed in an as built thin-walled component, but these particles were typically poly-crystalline and contained a variety of elements including O, Al, Ti, Cr and Fe. Applicationmore » of post-build heat treatments resulted in the modification of particle structures and compositions; in the annealed condition most precipitates were transformed to single crystal yttrium aluminium oxides. During the annealing treatment, precipitate distributions homogenised and localised variations in number density were diminished. The resulting volume fractions of those precipitates were 25–40% lower than have been reported in conventionally processed PM2000, which was attributed to Y-rich slag-like surface features and inclusions formed during SLM. - Highlights: • A wall structure was grown from ODS steel powder using selective laser melting. • A fine dispersion of nano-precipitates was apparent in as-build material. • Precipitates were multi-phased containing several elements, e.g. O, Ti, Al, Fe, Cr, Y. • Post-build annealing changed those into typically single-crystalline Y–Al–O. • The anneal also reduced and stabilised the volume fraction of precipitates to ~ 0.006.« less

Investigation on Tribological Properties of the Pre-oxidized Ti2AlN/TiAl Composite

NASA Astrophysics Data System (ADS)

Wang, Daqun; Sun, Dongli; Han, Xiuli; Wang, Qing; Wang, Guangwei

2018-03-01

Different oxidation layers on the Ti2AlN/TiAl substrate which was fabricated by in situ synthesis were prepared through thermal oxidation process. The microstructure, phase identification and elements distribution of the oxidation layers were analyzed. The tribological performance of pre-oxidized composites against Si3N4 ball at 25 and 600 °C, as well as the effect of pre-oxidation layers on tribological performance was systematically investigated. The results show that, compared to Ti2AlN/TiAl, the pre-oxidized composites present more excellent tribological properties, especially the wear resistance at 600 °C. It is a significant finding that, different from severe abrasive wear and plastic deformation of Ti2AlN/TiAl, the tribo-films formed by the pre-oxidation layers on the worn surface of pre-oxidized composites weaken abrasive wear and suppress the development of plastic deformation to protect the underlying composite substrate from wear. Moreover, the stable cooperation on the interface between tribo-films and Si3N4 ball results in the relatively steady friction coefficient.

Calculation of the Ti(C y N1- y )-Ti4C2S2-MnS-austenite equilibrium in Ti-bearing steels

NASA Astrophysics Data System (ADS)

Liu, W. J.; Jonas, J. J.

1989-08-01

A thermodynamic model is presented for the equilibria among various precipitates (Ti(C y N1- y ), Ti4C2S2, and MnS) and austenite containing six alloying elements (C, Mn, N, S, Si, and Ti). This model is applied to four microalloyed steels with Ti levels of 0.05, 0.11, 0.18, and 0.25 pct. The calculations show that the Ti in these steels cannot be completely dissolved over the austenite temperature range. However, the compositions of the undissolved Ti carbonitrides differ significantly from pure TiN, as 10 to 40 pct of the nitrogen is replaced by carbon. An expression for the Gibbs energy for the formation of Ti4C2S2 in austenite is estimated. The present predictions are compared with those of the Hudd, Jones, and Kale (HJK) model; considerable differences are observed at temperatures below 1250°C.

Preparation and Properties of (YCa)(TiMn)O3−δ Ceramics Interconnect of Solid Oxide Fuel Cells

PubMed Central

Liou, Yi-Cheng; Tsai, Wen-Chou; Yen, Hao-Hsuan; Chang, Yung-Chia

2015-01-01

(YCa)(TiMn)O3–δ ceramics prepared using a reaction-sintering process were investigated. Without any calcination involved, the mixture of raw materials was pressed and sintered directly. Y2Ti2O7 instead of YTiO3 formed when a mixture of Y2O3 and TiO2 with Y/Ti ratio 1/1 were sintered in air. Y2Ti2O7, YTiO2.085 and some unknown phases were detected in Y0.6Ca0.4Ti0.6Mn0.4O3–δ. Monophasic Y0.6Ca0.4Ti0.4Mn0.6O3–δ ceramics were obtained after 1400–1500 °C sintering. Dense Y0.6Ca0.4Ti0.4Mn0.6O3–δ with a density 4.69 g/cm3 was observed after 1500 °C/4 h sintering. Log σ for Y0.6Ca0.4Ti0.6Mn0.4O3–δ increased from –3.73 Scm–1 at 350 °C to –2.14 Scm–1 at 700 °C. Log σ for Y0.6Ca0.4Ti0.4Mn0.6O3–δ increased from –2.1 Scm–1 at 350 °C to –1.36 Scm–1 at 700 °C. Increasing Mn content decreased activation energy Ea and increased electrical conductivity. Reaction-sintering process is proved to be a simple and effective method to obtain (YCa)(TiMn)O3–δ ceramics for interconnects in solid oxide fuel cells. PMID:28793436

Osteoconductivity and Hydrophilicity of TiO2 Coatings on Ti Substrates Prepared by Different Oxidizing Processes

PubMed Central

Yamamoto, Dai; Kawai, Ikki; Kuroda, Kensuke; Ichino, Ryoichi; Okido, Masazumi; Seki, Azusa

2012-01-01

Various techniques for forming TiO2 coatings on Ti have been investigated for the improvement of the osteoconductivity of Ti implants. However, it is not clear how the oxidizing process affects this osteoconductivity. In this study, TiO2 coatings were prepared using the following three processes: anodizing in 0.1 M H3PO4 or 0.1 M NaOH aqueous solution; thermal oxidation at 673 K for 2 h in air; and a two-step process of anodizing followed by thermal oxidation. The oxide coatings were evaluated using SEM, XRD, and XPS. The water contact angle on the TiO2 coatings was measured as a surface property. The osteoconductivity of these samples was evaluated by measuring the contact ratio of formed hard tissue on the implanted samples (defined as the R B-I value) after 14 d implantation in rats' tibias. Anatase was formed by anodizing and rutile by thermal oxidation, but the difference in the TiO2 crystal structure did not influence the osteoconductivity. Anodized TiO2 coatings were hydrophilic, but thermally oxidized TiO2 coatings were less hydrophilic than anodized TiO2 coatings because they lacked in surface OH groups. The TiO2 coating process using anodizing without thermal oxidation gave effective improvement of the osteoconductivity of Ti samples. PMID:23316128

Oxidation Kinetics of Cast TiAl3

NASA Technical Reports Server (NTRS)

Smialek, J. L.; Humphrey, D. L.

1992-01-01

The isothermal oxidation kinetics of the TiAl3 compound over a wide temperature range is documented, and these rates are related to exclusive alpha-Al2O3 scale growth. The specific weight change vs time curves are shown. Two abnormalities are immediately apparent. One is that a rapid initial uptake of oxygen occurs at times less than 5 h, followed by a lower oxidation rate at longer times, for tests at 900 C and below. The other is that the final weight changes for the 700, 800, and 900 C tests are not in the sequence expected with respect to temperature. Isothermal oxidation of drop cast TiAl above 1000 C was found to exhibit parabolic oxidation controlled by protective alpha-Al2O3 scale formation. TiAl is the only phase in the binary Ti-Al system that forms exclusive scales of alpha-Al2O3 in isothermal oxidation. High anomalous rates at short times and at temperatures below 1000 C resulted from the internal oxidation of a second phase of aluminum.

Surface oxidation of NiTi shape memory alloy.

PubMed

Firstov, G S; Vitchev, R G; Kumar, H; Blanpain, B; Van Humbeeck, J

2002-12-01

Mechanically polished NiTi alloy (50 at% Ni) was subjected to heat treatment in air in the temperature range 300-800 degrees C and characterised by scanning electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy and Raman spectroscopy. Thermogravimetry measurements were carried out to investigate the kinetics of oxidation. The results of thermodynamic calculations were compared to the experimental observations. It was found that NiTi alloy exhibits different oxidation behaviour at temperatures below and above 500 degrees C. A Ni-free zone was found in the oxide layer for oxidation temperatures of 500 degrees C and 600 degrees C. The oxidation at 500 degrees C produces a smooth protective nickel-free oxide layer with a relatively small amount of Ni species at the air/oxide interface, which is in favour of good biocompatibility of NiTi implants. The oxidation mechanism for the NiTi shape memory alloy is discussed. Copyright 2002 Elsevier Science Ltd.

A metallic metal oxide (Ti5O9)-metal oxide (TiO2) nanocomposite as the heterojunction to enhance visible-light photocatalytic activity

NASA Astrophysics Data System (ADS)

Li, L. H.; Deng, Z. X.; Xiao, J. X.; Yang, G. W.

2015-06-01

Coupling titanium dioxide (TiO2) with other semiconductors is a popular method to extend the optical response range of TiO2 and improve its photon quantum efficiency, as coupled semiconductors can increase the separation rate of photoinduced charge carriers in photocatalysts. Differing from normal semiconductors, metallic oxides have no energy gap separating occupied and unoccupied levels, but they can excite electrons between bands to create a high carrier mobility to facilitate kinetic charge separation. Here, we propose the first metallic metal oxide-metal oxide (Ti5O9-TiO2) nanocomposite as a heterojunction for enhancing the visible-light photocatalytic activity of TiO2 nanoparticles and we demonstrate that this hybridized TiO2-Ti5O9 nanostructure possesses an excellent visible-light photocatalytic performance in the process of photodegrading dyes. The TiO2-Ti5O9 nanocomposites are synthesized in one step using laser ablation in liquid under ambient conditions. The as-synthesized nanocomposites show strong visible-light absorption in the range of 300-800 nm and high visible-light photocatalytic activity in the oxidation of rhodamine B. They also exhibit excellent cycling stability in the photodegrading process. A working mechanism for the metallic metal oxide-metal oxide nanocomposite in the visible-light photocatalytic process is proposed based on first-principle calculations of Ti5O9. This study suggests that metallic metal oxides can be regarded as partners for metal oxide photocatalysts in the construction of heterojunctions to improve photocatalytic activity.

A metallic metal oxide (Ti5O9)-metal oxide (TiO2) nanocomposite as the heterojunction to enhance visible-light photocatalytic activity.

PubMed

Li, L H; Deng, Z X; Xiao, J X; Yang, G W

2015-01-26

Coupling titanium dioxide (TiO2) with other semiconductors is a popular method to extend the optical response range of TiO2 and improve its photon quantum efficiency, as coupled semiconductors can increase the separation rate of photoinduced charge carriers in photocatalysts. Differing from normal semiconductors, metallic oxides have no energy gap separating occupied and unoccupied levels, but they can excite electrons between bands to create a high carrier mobility to facilitate kinetic charge separation. Here, we propose the first metallic metal oxide-metal oxide (Ti5O9-TiO2) nanocomposite as a heterojunction for enhancing the visible-light photocatalytic activity of TiO2 nanoparticles and we demonstrate that this hybridized TiO2-Ti5O9 nanostructure possesses an excellent visible-light photocatalytic performance in the process of photodegrading dyes. The TiO2-Ti5O9 nanocomposites are synthesized in one step using laser ablation in liquid under ambient conditions. The as-synthesized nanocomposites show strong visible-light absorption in the range of 300-800 nm and high visible-light photocatalytic activity in the oxidation of rhodamine B. They also exhibit excellent cycling stability in the photodegrading process. A working mechanism for the metallic metal oxide-metal oxide nanocomposite in the visible-light photocatalytic process is proposed based on first-principle calculations of Ti5O9. This study suggests that metallic metal oxides can be regarded as partners for metal oxide photocatalysts in the construction of heterojunctions to improve photocatalytic activity.

Scavenging of oxygen from SrTiO3 by metals and its implications for oxide thin film deposition

NASA Astrophysics Data System (ADS)

Posadas, Agham; Kormondy, Kristy; Guo, Wei; Ponath, Patrick; Kremer, Jacqueline; Hadamek, Tobias; Demkov, Alexander

SrTiO3 is a widely used substrate for the growth of other functional oxide thin films. However, SrTiO3 loses oxygen very easily during oxide thin film deposition even under relatively high oxygen pressures. In some cases, there will be an interfacial layer of oxygen-deficient SrTiO3 formed at the interface with the deposited oxide film, depending on the metals present in the film. By depositing a variety of metals layer by layer and measuring the evolution of the core level spectra of both the deposited metal and SrTiO3 using x-ray photoelectron spectroscopy, we show that there are three distinct types of behavior that occur for thin metal films on SrTiO3. We discuss the implications of these types of behavior for the growth of complex oxide thin films on SrTiO3, and which oxide thin films are expected to produce an interfacial oxygen-deficient layer depending on their elemental constituents.

Cycle oxidation behavior and anti-oxidation mechanism of hot-dipped aluminum coating on TiBw/Ti6Al4V composites with network microstructure.

PubMed

Li, X T; Huang, L J; Wei, S L; An, Q; Cui, X P; Geng, L

2018-04-10

Controlled and compacted TiAl 3 coating was successfully fabricated on the network structured TiBw/Ti6Al4V composites by hot-dipping aluminum and subsequent interdiffusion treatment. The network structure of the composites was inherited to the TiAl 3 coating, which effectively reduces the thermal stress and avoids the cracks appeared in the coating. Moreover, TiB reinforcements could pin the TiAl 3 coating which can effectively improve the bonding strength between the coating and composite substrate. The cycle oxidation behavior of the network structured coating on 873 K, 973 K and 1073 K for 100 h were investigated. The results showed the coating can remarkably improve the high temperature oxidation resistance of the TiBw/Ti6Al4V composites. The network structure was also inherited to the Al 2 O 3 oxide scale, which effectively decreases the tendency of cracking even spalling about the oxide scale. Certainly, no crack was observed in the coating after long-term oxidation due to the division effect of network structured coating and pinning effect of TiB reinforcements. Interfacial reaction between the coating and the composite substrate occurred and a bilayer structure of TiAl/TiAl 2 formed next to the substrate after oxidation at 973 K and 1073 K. The anti-oxidation mechanism of the network structured coating was also discussed.

Corrosion of NiTi Wires with Cracked Oxide Layer

NASA Astrophysics Data System (ADS)

Racek, Jan; Šittner, Petr; Heller, Luděk; Pilch, Jan; Petrenec, Martin; Sedlák, Petr

2014-07-01

Corrosion behavior of superelastic NiTi shape memory alloy wires with cracked TiO2 surface oxide layers was investigated by electrochemical corrosion tests (Electrochemical Impedance Spectroscopy, Open Circuit Potential, and Potentiodynamic Polarization) on wires bent into U-shapes of various bending radii. Cracks within the oxide on the surface of the bent wires were observed by FIB-SEM and TEM methods. The density and width of the surface oxide cracks dramatically increase with decreasing bending radius. The results of electrochemical experiments consistently show that corrosion properties of NiTi wires with cracked oxide layers (static load keeps the cracks opened) are inferior compared to the corrosion properties of the straight NiTi wires covered by virgin uncracked oxides. Out of the three methods employed, the Electrochemical Impedance Spectroscopy seems to be the most appropriate test for the electrochemical characterization of the cracked oxide layers, since the impedance curves (Nyquist plot) of differently bent NiTi wires can be associated with increasing state of the surface cracking and since the NiTi wires are exposed to similar conditions as the surfaces of NiTi implants in human body. On the other hand, the potentiodynamic polarization test accelerates the corrosion processes and provides clear evidence that the corrosion resistance of bent superelastic NiTi wires degrades with oxide cracking.

Oxide Scales Formed on NiTi and NiPtTi Shape Memory Alloys

NASA Technical Reports Server (NTRS)

Smialek, James L.; Garg, Anita; Rogers, Richard B.; Noebe, Ronald D.

2011-01-01

Ni-49Ti and Ni-30Pt-50Ti (at.%) shape memory alloys were oxidized isothermally in air over the temperature range of 500 to 900 C. The microstructure, composition, and phase content of the scales were studied by SEM, EDS, XRD, and metallography. Extensive plan view SEM/EDS identified various features of intact or spalled scale surfaces. The outer surface of the scale was a relatively pure TiO2 rutile structure, typified by a distinct highly striated and faceted crystal morphology. Crystal size increased significantly with temperature. Spalled regions exhibited some porosity and less distinct features. More detailed information was obtained by correlation of SEM/EDS studies of 700 C/100 hr cross-sections with XRD analyses of serial or taper-polishing of plan surfaces. Overall, multiple layers exhibited graded mixtures of NiO, TiO2, NiTiO3, Ni(Ti) or Pt(Ni,Ti) metal dispersoids, Ni3Ti or Pt3Ti depletion zones, and substrate, in that order. The NiTi alloy contained a 3 at.% Fe impurity that appeared in embedded localized Fe-Ti-rich oxides, while the NiPtTi alloy contained a 2 v/o dispersion of TiC that appeared in lower layers. The oxidation kinetics of both alloys (in a previous report) indicated parabolic growth and an activation energy (250 kJ/mole) near those reported in other Ti and NiTi studies. This is generally consistent with TiO2 existing as the primary scale constituent, as described here.

Complete titanium substitution by boron in a tetragonal prism: exploring the complex boride series Ti(3-x)Ru(5-y)Ir(y)B(2+x) (0 ≤ x ≤ 1 and 1 < y < 3) by experiment and theory.

PubMed

Fokwa, Boniface P T; Hermus, Martin

2011-04-18

Polycrystalline samples and single crystals of four members of the new complex boride series Ti(3-x)Ru(5-y)Ir(y)B(2+x) (0 ≤ x ≤ 1 and 1 < y < 3) were synthesized by arc-melting the elements in a water-cooled copper crucible under an argon atmosphere. The new silvery phases were structurally characterized by powder and single-crystal X-ray diffraction as well as energy- and wavelength-dispersive X-ray spectroscopy analyses. They crystallize with the tetragonal Ti(3)Co(5)B(2) structure type in space group P4/mbm (No. 127). Tetragonal prisms of Ru/Ir atoms are filled with titanium in the boron-poorest phase (Ti(3)Ru(2.9)Ir(2.1)B(2)). Gradual substitution of titanium by boron then results in the successive filling of this site by a Ti/B mixture en route to the complete boron occupation, leading to the boron-richest phase (Ti(2)Ru(2.8)Ir(2.2)B(3)). Furthermore, both ruthenium and iridium share two sites in these structures, but a clear Ru/Ir site preference is found. First-principles density functional theory calculations (Vienna ab initio simulation package) on appropriate structural models (using a supercell approach) have provided more evidence on the stability of the boron-richest and -poorest phases, and the calculated lattice parameters corroborate very well with the experimentally found ones. Linear muffin-tin orbital atomic sphere approximation calculations further supported these findings through crystal orbital Hamilton population bonding analyses, which also show that the Ru/Ir-B and Ru/Ir-Ti heteroatomic interactions are mainly responsible for the structural stability of these compounds. Furthermore, some stable and unstable phases of this complex series could be predicted using the rigid-band model. According to the density of states analyses, all phases should be metallic conductors, as was expected from these metal-rich borides.

Characteristics of growth of complex ferroelectric oxide films by plasma-ion sputtering

NASA Astrophysics Data System (ADS)

Mukhortov, V. M.; Golovko, Yu. I.; Mukhortov, Vl. M.; Dudkevich, V. P.

1981-02-01

An experimental investigation was made of the process of growth of a complex oxide film, such as BaTiO3 or (Ba, Sr)TiO3, by plasma-ion sputtering. It was found that ion bombardment of a ceramic target knocked out neutral excited atoms. These atoms lost energy away from the target by collisions and at a certain critical distance hcr they were capable of oxidation to produce BaO, TiO, TiO2, and SrO. Therefore, depending on the distance between the cathode and the substrate, the “construction” material arrived in the form of atoms or molecules of simple oxides. These two (atomic and molecular) deposition mechanisms corresponded to two mechanisms of synthesis and crystallization differing in respect of the dependences of the growth rate, unit cell parameters, and other structural properties on the deposition temperature. The role of re-evaporation and of oxidation-reduction processes was analyzed.

Structural & oxidation behavior of TiN & AlxTi1-xN coatings deposited by CA-PVD technique

NASA Astrophysics Data System (ADS)

Thorat, Nirmala; Mundotia, Rajesh; Varma, Ranjana; Kale, Ashwin; Mhatre, Umesh; Patel, Nainesh

2018-04-01

Coatings with thermal stability at elevated temperatures are prerequisite for various high speed machining and high temperature applications. The present work compares the oxidation behavior of the AlxTi1-xN coating prepared with different Al composition. Coated samples were tested at different temperatures in the range of 400 - 800 C to study their oxidation behavior. Percentage weight gain of all the samples were evaluated using high accuracy weighing balance. The depth of oxide layers were studied using Calo-test instrument. The XRD analysis was carried out to specify the phase structure. Higher oxidation rate was observed for TiN coating at all the oxidation temperatures. Oxidation rate was higher for Al13Ti87N and Al70Ti30N coatings compared to Al60Ti40N and Al50Ti50N coatings which exhibits better oxygen diffusion barrier at all the temperature.

Color tone and interfacial microstructure of white oxide layer on commercially pure Ti and Ti-Nb-Ta-Zr alloys

NASA Astrophysics Data System (ADS)

Miura-Fujiwara, Eri; Mizushima, Keisuke; Watanabe, Yoshimi; Kasuga, Toshihiro; Niinomi, Mitsuo

2014-11-01

In this study, the relationships among oxidation condition, color tone, and the cross-sectional microstructure of the oxide layer on commercially pure (CP) Ti and Ti-36Nb-2Ta-3Zr-0.3O were investigated. “White metals” are ideal metallic materials having a white color with sufficient strength and ductility like a metal. Such materials have long been sought for in dentistry. We have found that the specific biomedical Ti alloys, such as CP Ti, Ti-36Nb-2Ta-3Zr-0.3O, and Ti-29Nb-13Ta-4.6Zr, form a bright yellowish-white oxide layer after a particular oxidation heat treatment. The brightness L* and yellowness +b* of the oxide layer on CP Ti and Ti-36Nb-2Ta-3Zr-0.3O increased with heating time and temperature. Microstructural observations indicated that the oxide layer on Ti-29Nb-13Ta-4.6Zr and Ti-36Nb-2Ta-3Zr-0.3O was dense and firm, whereas a piecrust-like layer was formed on CP Ti. The results obtained in this study suggest that oxide layer coating on Ti-36Nb-2Ta-3Zr-0.3O is an excellent technique for dental applications.

Relationship between crystallographic structure of the Ti{sub 2}O{sub 3}/MnS complex inclusion and microstructure in the heat-affected zone (HAZ) in steel processed by oxide metallurgy route and impact toughness

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

Xiong, Zhihui; Liu, Shilong; Wang, Xuemin, E-mail: wxm@mater.ustb.edu.cn

2015-08-15

A new method based on electron back scattered diffraction (EBSD) is proposed to determine the structure of titanium oxide/MnS complex inclusion which induced the formation of intragranular acicular ferrite (IAF) in heat-affected zone (HAZ) in steel processed by oxide metallurgy route. It was found that the complex inclusion was Ti{sub 2}O{sub 3}/MnS, the orientation relationship between Ti{sub 2}O{sub 3} and MnS was also examined, and the crystallographic orientation relationship among IAF, Ti{sub 2}O{sub 3}/MnS complex inclusion, austenite, bainite formed at lower temperature is researched systematically. It was observed that MnS precipitated on Ti{sub 2}O{sub 3} at specific habit plane andmore » direction and MnS had a specific orientation relationship ((0001) Ti{sub 2}O{sub 3}//(111) MnS), <10–10> Ti{sub 2}O{sub 3}//<110> MnS) with respect to Ti{sub 2}O{sub 3}. Intragranular acicular ferrite (IAF) nucleated on MnS part of the Ti{sub 2}O{sub 3}/MnS complex inclusion had no specific orientation relationship with MnS. IAF and the surrounding bainite had different Bain groups, so that there was an increase in high angle boundaries, which was beneficial for the toughness of HAZ. - Highlights: • The inclusion of TiO{sub x}/MnS that induced IAF formation is identified to be Ti{sub 2}O{sub 3}/MnS. • The inclusion is identified based on electron back scattered diffraction (EBSD). • MnS and Ti{sub 2}O{sub 3} had specific orientation relationship of Ti{sub 2}O{sub 3}/MnS complex inclusion. • The IAFs formed on the same inclusion tend to be in one Bain group. • IAF and the surrounding bainite tend to be in different Bain groups.« less

Photocatalytic activity of low temperature oxidized Ti-6Al-4V.

PubMed

Unosson, Erik; Persson, Cecilia; Welch, Ken; Engqvist, Håkan

2012-05-01

Numerous advanced surface modification techniques exist to improve bone integration and antibacterial properties of titanium based implants and prostheses. A simple and straightforward method of obtaining uniform and controlled TiO(2) coatings of devices with complex shapes is H(2)O(2)-oxidation and hot water aging. Based on the photoactivated bactericidal properties of TiO(2), this study was aimed at optimizing the treatment to achieve high photocatalytic activity. Ti-6Al-4V samples were H(2)O(2)-oxidized and hot water aged for up to 24 and 72 h, respectively. Degradation measurements of rhodamine B during UV-A illumination of samples showed a near linear relationship between photocatalytic activity and total treatment time, and a nanoporous coating was observed by scanning electron microscopy. Grazing incidence X-ray diffraction showed a gradual decrease in crystallinity of the surface layer, suggesting that the increase in surface area rather than anatase formation was responsible for the increase in photocatalytic activity.

Growth of aluminum-free porous oxide layers on titanium and its alloys Ti-6Al-4V and Ti-6Al-7Nb by micro-arc oxidation.

PubMed

Duarte, Laís T; Bolfarini, Claudemiro; Biaggio, Sonia R; Rocha-Filho, Romeu C; Nascente, Pedro A P

2014-08-01

The growth of oxides on the surfaces of pure Ti and two of its ternary alloys, Ti-6Al-4V and Ti-6Al-7Nb, by micro-arc oxidation (MAO) in a pH 5 phosphate buffer was investigated. The primary aim was to form thick, porous, and aluminum-free oxide layers, because these characteristics favor bonding between bone and metal when the latter is implanted in the human body. On Ti, Ti-6Al-4 V, and Ti-6Al-7Nb, the oxides exhibited breakdown potentials of about 200 V, 130 V, and 140 V, respectively, indicating that the oxide formed on the pure metal is the most stable. The use of the MAO procedure led to the formation of highly porous oxides, with a uniform distribution of pores; the pores varied in size, depending on the anodizing applied voltage and time. Irrespective of the material being anodized, Raman analyses allowed us to determine that the oxide films consisted mainly of the anatase phase of TiO2, and XPS results indicated that this oxide is free of Al and any other alloying element. Copyright © 2014 Elsevier B.V. All rights reserved.

Thermoelectric Properties of Complex Oxide Heterostructures

NASA Astrophysics Data System (ADS)

Cain, Tyler Andrew

Thermoelectrics are a promising energy conversion technology for power generation and cooling systems. The thermal and electrical properties of the materials at the heart of thermoelectric devices dictate conversion efficiency and technological viability. Studying the fundamental properties of potentially new thermoelectric materials is of great importance for improving device performance and understanding the electronic structure of materials systems. In this dissertation, investigations on the thermoelectric properties of a prototypical complex oxide, SrTiO3, are discussed. Hybrid molecular beam epitaxy (MBE) is used to synthesize La-doped SrTiO3 thin films, which exhibit high electron mobilities and large Seebeck coefficients resulting in large thermoelectric power factors at low temperatures. Large interfacial electron densities have been observed in SrTiO3/RTiO 3 (R=Gd,Sm) heterostructures. The thermoelectric properties of such heterostructures are investigated, including the use of a modulation doping approach to control interfacial electron densities. Low-temperature Seebeck coefficients of extreme electron-density SrTiO3 quantum wells are shown to provide insight into their electronic structure.

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

PubMed Central

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

2017-01-01

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

Ordered Fe(II)Ti(IV)O3 Mixed Monolayer Oxide on Rutile TiO2(011).

PubMed

Halpegamage, Sandamali; Ding, Pan; Gong, Xue-Qing; Batzill, Matthias

2015-08-25

Oxide monolayers supported or intermixed with an oxide support are potential nanocatalysts whose properties are determined by the interplay with the support. For fundamental studies of monolayer oxides on metal oxide supports, well-defined systems are needed, but so far, the synthesis of monolayer oxides with long-range order on single-crystal oxide surfaces is rare. Here, we show by a combination of scanning tunneling microscopy, photoemission spectroscopy, and density functional theory (DFT)-based computational analysis that the rutile TiO2(011) surface supports the formation of an ordered mixed FeTiO3 monolayer. Deposition of iron in a slightly oxidizing atmosphere (10(-8) Torr O2) and annealing to 300 °C results in a well-ordered surface structure with Fe in a 2+ charge state and Ti in a 4+ charge states. Low-energy ion scattering suggests that the cation surface composition is close to half Fe and half Ti. This surface is stable in ultrahigh vacuum to annealing temperatures of 300 °C before the iron is reduced. DFT simulations confirm that a surface structure with coverage of 50% FeO units is stable and forms an ordered structure. Although distinct from known bulk phases of the iron-titanium oxide systems, the FeTiO3 monolayer exhibits some resemblance to the ilmenite structure, which may suggest that a variety of different mixed oxide phases (of systems that exist in a bulk ilmenite phase) may be synthesized in this way on the rutile TiO2(011) substrate.

Thermoelectric properties of the yttrium-doped ceramic oxide SrTiO3

NASA Astrophysics Data System (ADS)

Khan, Tamal Tahsin; Ur, Soon-Chul

2017-01-01

The doping dependence of the thermoelectric figure of merit, ZT, of the ceramic oxide SrTiO3 at high temperature has been studied. In this study, yttrium was used as the doping element. A conventional solid-state reaction method was used for the preparation of Y-doped SrTiO3. The doping level in SrTiO3 was controlled to be in the doping range of 2 - 10 mole%. Almost all the yttrium atoms incorporated into the SrTiO3 provided charge carriers, as was observed by using X-ray diffraction pattern. The relative densities of all the samples varied from 98.53% to 99.45%. The thermoelectric properties, including the electrical conductivity σ, Seebeck coefficient S, thermal conductivity k, and the figure of merit, ZT, were investigated at medium temperatures. The ZT value showed an obvious doping level dependence, in which a value as high as 0.18 is realized at 773 K for a doping of 8 mole%.

Ferromagnetism and spin-dependent transport at a complex oxide interface

NASA Astrophysics Data System (ADS)

Ayino, Yilikal; Xu, Peng; Tigre-Lazo, Juan; Yue, Jin; Jalan, Bharat; Pribiag, Vlad S.

2018-03-01

Complex oxide interfaces are a promising platform for studying a wide array of correlated electron phenomena in low dimensions, including magnetism and superconductivity. The microscopic origin of these phenomena in complex oxide interfaces remains an open question. Here we investigate the magnetic properties of semi-insulating NdTi O3/SrTi O3 (NTO/STO) interfaces and present the first millikelvin study of NTO/STO. The magnetoresistance (MR) reveals signatures of local ferromagnetic order and of spin-dependent thermally activated transport, which are described quantitatively by a simple phenomenological model. We discuss possible origins of the interfacial ferromagnetism. In addition, the MR also shows transient hysteretic features on a time scale of ˜10 -100 s . We demonstrate that these are consistent with an extrinsic magnetothermal origin, which may have been misinterpreted in previous reports of magnetism in STO-based oxide interfaces. The existence of these two MR regimes (steady-state and transient) highlights the importance of time-dependent measurements for distinguishing signatures of ferromagnetism from other effects that can produce hysteresis at low temperatures.

The complex behavior of the Pd 7 cluster supported on TiO 2 (110) during CO oxidation: adsorbate-driven promoting effect

DOE PAGES

An, Wei; Liu, Ping

2016-09-07

When using the TiO 2(110)-supported Pd7 cluster as a model catalyst, we identified the dynamics of supported metal nanoparticles using density functional theory calculations, at the sub-nanometer scale and under reactive environments. Increasing the CO coverage can induce a structural transformation from Pd 7-3D/TiO 2(110) at low coverage to Pd 7-2D/TiO 2(110) at the saturation coverage wherein CO saturation-driven Pd7-2D/TiO 2(110) structure displays superior CO oxidation activity at the interfacial sites, which are highly active for catalyzing O 2 dissociation and CO oxidation via bifunctional synergy.

Microstructure and high-temperature oxidation resistance of TiN/Ti3Al intermetallic matrix composite coatings on Ti6Al4V alloy surface by laser cladding

NASA Astrophysics Data System (ADS)

Zhang, Xiaowei; Liu, Hongxi; Wang, Chuanqi; Zeng, Weihua; Jiang, Yehua

2010-11-01

A high-temperature oxidation resistant TiN embedded in Ti3Al intermetallic matrix composite coating was fabricated on titanium alloy Ti6Al4V surface by 6kW transverse-flow CO2 laser apparatus. The composition, morphology and microstructure of the laser clad TiN/Ti3Al intermetallic matrix composite coating were characterized by optical microscopy (OM), scanning electron microscopy (SEM), X-ray diffraction (XRD) and energy dispersive spectrometer (EDS). In order to evaluate the high-temperature oxidation resistance of the composite coatings and the titanium alloy substrate, isothermal oxidation test was performed in a conventional high-temperature resistance furnace at 600°C and 800°C respectively. The result shows that the laser clad intermetallic composite coating has a rapidly solidified fine microstructure consisting of TiN primary phase (granular-like, flake-like, and dendrites), and uniformly distributed in the Ti3Al matrix. It indicates that a physical and chemical reaction between the Ti powder and AlN powder occurred completely under the laser irradiation. In addition, the microhardness of the TiN/Ti3Al intermetallic matrix composite coating is 844HV0.2, 3.4 times higher than that of the titanium alloy substrate. The high-temperature oxidation resistance test reveals that TiN/Ti3Al intermetallic matrix composite coating results in the better modification of high-temperature oxidation behavior than the titanium substrate. The excellent high-temperature oxidation resistance of the laser cladding layer is attributed to the formation of the reinforced phase TiN and Al2O3, TiO2 hybrid oxide. Therefore, the laser cladding TiN/Ti3Al intermetallic matrix composite coating is anticipated to be a promising oxidation resistance surface modification technique for Ti6Al4V alloy.

Al-to-oxide and Ti-to-organic linkages in biogenic sediment: relationships to paleo-export production and bulk Al/Ti

NASA Astrophysics Data System (ADS)

Kryc, K. A.; Murray, R. W.; Murray, D. W.

2003-06-01

To increase our understanding of the mechanisms that control the distribution of Al and Ti within marine sediment, we performed sequential extractions targeting the chemical signatures of the loosely bound, exchangeable, carbonate, oxide, organic, opal, and residual fraction of sediment from a carbonate-dominated regime (equatorial Pacific) and from a mixed opal-terrigenous regime (West Antarctic Peninsula). We observe a systematic partitioning of Al and Ti between sediment phases that is related to bulk Al/Ti. We show that, where we can quantify an Alexcess component, the dissolved Al is preferentially affiliated with the oxide fraction, resulting in Al/Ti molar ratios of 500-3000. This is interpreted as the result of surface complexation in the water column of dissolved Al onto oxyhydroxides. We also observe a previously undetected Tiexcess with as much as 80% of the total Ti in the organic fraction, which is most likely a function of metal-organic colloidal removal from the water column. In samples where the excess metals are obscured by the detrital load, the Al and Ti are almost exclusively found in the residual phase. This argues for the paired removal of Al (preferentially by the oxide component) and Ti (preferentially by the organic component) from the water column by settling particulate matter. This research builds upon earlier work that shows changes in the bulk ratio of Al to Ti in carbonate sediment from the central-equatorial Pacific that coincide with changes in the sedimentary bulk accumulation rate (BAR). The ratios that are observed are as much as three times higher than typical shale values, and were interpreted as the result of scavenging of dissolved Al onto particles settling in the water column. Because this non-terrigenous Alexcess accounts for up to 50% of the total sedimentary Al inventory and correlates best with BAR, the bulk Al/Ti may be a sensitive tracer of particle flux and, therefore, export production. Because we show that the

Microstructure, Wear Resistance and Oxidation Behavior of Ni-Ti-Si Coatings Fabricated on Ti6Al4V by Laser Cladding

PubMed Central

Zhuang, Qiaoqiao; Zhang, Peilei; Li, Mingchuan; Yan, Hua; Yu, Zhishui; Lu, Qinghua

2017-01-01

The Ni-Ti-Si composite coatings were successfully fabricated on Ti6Al4V by laser cladding. The microstructure were studied by SEM (scanning electron microscopy) and EDS (energy dispersive spectrometer). It has been found that Ti2Ni and Ti5Si3 phases exist in all coatings, and some samples have TiSi2 phases. Moreover, due to the existence of these phases, coatings presented relatively higher microhardness than that of the substrate (826 HV (Vickers hardness)) and the microhardness value of coating 3 is about twice larger than that of the substrate. During the dry sliding friction and wear test, due to the distribution of the relatively ductile phase of Ti2Ni and reinforcement phases of Ti5Si3 and TiSi2, the coatings performed good wear resistance. The oxidation process contains two stages: the rapid oxidation and slow oxidation by high temperature oxidation test at 800 °C for 50 h. Meanwhile, the value of the oxidation weight gain of the substrate is approximately three times larger than that of the coating 4. During the oxidation process, the oxidation film formed on the coating is mainly consisted of TiO2, Al2O3 and SiO2. Phases Ti2Ni, Ti5Si3, TiSi2 and TiSi were still found and it could be responsible for the improvement in oxidation resistance of the coatings by laser cladding. PMID:29084174

Crystal structure and electrical conductivity of lanthanum-calcium chromites-titanates La 1-xCa xCr 1-yTi yO 3-δ ( x=0-1, y=0-1)

NASA Astrophysics Data System (ADS)

Vashook, V.; Vasylechko, L.; Zosel, J.; Gruner, W.; Ullmann, H.; Guth, U.

2004-10-01

Five series of perovskite-type compounds in the system La1-xCaxCr1-yTiyO3 with the nominal compositions y = 0 , x = 0 - 0.5 ; y = 0.2 , x = 0.2 - 0.8 ; y = 0.5 , x = 0.5 - 1.0 ; y = 0.8 , x = 0.6 - 1.0 and y = 1 , x = 0.8 - 1 were synthesized by a ceramic technique in air (final heating 1350 °C). On the basis of the X-ray analysis of the samples with (Ca/Ti)⩾1, the phase diagram of the CaTiO3-LaCrIIIO3-CaCrIVO3 quasi-ternary system was constructed. Extended solid solution with a wide homogeneity range is formed in the quasi-ternary system CaCrIVO3-CaTiO3-LaCrIIIO3. The solid solution La(1-x‧-y)Ca(x‧+y)CrIVx‧CrIII(1-x‧-y)TiyO3 exists by up to 0.6-0.7 mol fractions of CaCrIVO3 (x‧ < 0.6 - 0.7) at the experimental conditions. The crystal structure of the compounds is orthorhombic in the space group Pbnm at room temperature. The lattice parameters and the average interatomic distances of the samples within the solid solution ranges decrease uniformly with increasing Ca content. Outside the quasi-ternary system, the nominal compositions La0.1Ca0.9TiO3, La0.2Ca0.8TiO3, La0.4Ca0.6Cr0.2Ti0.8O3 and La0.3Ca0.7Cr0.2Ti0.8O3 in the system La1-xCaxCr1-yTiyO3 were found as single phases with an orthorhombic structure. In the temperature range between 850 and 1000 °C, the synthesized single-phase compositions are stable at pO2=6×10-16-0.21×105 Pa. Oxygen stoichiometry and electrical conductivity of the separate compounds were investigated as functions of temperature and oxygen partial pressure. The chemical stability of these oxides with respect to oxygen release during thermal dissociation decreases with increasing Ca-content. At 900 °C and oxygen partial pressure 1×10-15-0.21×105 Pa, the compounds with x > y (acceptor doped) are p-type semiconductors and those with x < y (donor doped) and x = y are n-type semiconductors. The type and level of electrical conductivity are functions of the concentration ratios of cations occupying the B-sites of the perovskite

Thermally oxidized titania nanotubes enhance the corrosion resistance of Ti6Al4V.

PubMed

Grotberg, John; Hamlekhan, Azhang; Butt, Arman; Patel, Sweetu; Royhman, Dmitry; Shokuhfar, Tolou; Sukotjo, Cortino; Takoudis, Christos; Mathew, Mathew T

2016-02-01

The negative impact of in vivo corrosion of metallic biomedical implants remains a complex problem in the medical field. We aimed to determine the effects of electrochemical anodization (60V, 2h) and thermal oxidation (600°C) on the corrosive behavior of Ti-6Al-4V, with serum proteins, at physiological temperature. Anodization produced a mixture of anatase and amorphous TiO2 nanopores and nanotubes, while the annealing process yielded an anatase/rutile mixture of TiO2 nanopores and nanotubes. The surface area was analyzed by the Brunauer-Emmett-Teller method and was estimated to be 3 orders of magnitude higher than that of polished control samples. Corrosion resistance was evaluated on the parameters of open circuit potential, corrosion potential, corrosion current density, passivation current density, polarization resistance and equivalent circuit modeling. Samples both anodized and thermally oxidized exhibited shifts of open circuit potential and corrosion potential in the noble direction, indicating a more stable nanoporous/nanotube layer, as well as lower corrosion current densities and passivation current densities than the smooth control. They also showed increased polarization resistance and diffusion limited charge transfer within the bulk oxide layer. The treatment groups studied can be ordered from greatest corrosion resistance to least as Anodized+Thermally Oxidized > Anodized > Smooth > Thermally Oxidized for the conditions investigated. This study concludes that anodized surface has a potential to prevent long term implant failure due to corrosion in a complex in-vivo environment. Copyright © 2015 Elsevier B.V. All rights reserved.

Theory and Application of Photoelectron Diffraction for Complex Oxide Systems

NASA Astrophysics Data System (ADS)

Chassé, Angelika; Chassé, Thomas

2018-06-01

X-ray photoelectron diffraction (XPD) has been used to investigate film structures and local sites of surface and dopant atoms in complex oxide materials. We have performed angular-resolved measurements of intensity distribution curves (ADCs) and patterns (ADPs) of elemental core level intensities from binary to quaternary mixed oxide samples and compared them to multiple-scattering cluster (MSC) calculations in order to derive information on structural models and related parameters. MSC calculations permitted to describe both bulk diffraction features of binary oxide MnO(001) and the thickness-dependence of the tetragonal distortion of epitaxial MnO films on Ag(001). XPD was further used to investigate the surface termination of perovskite SrTiO3 and BaTiO3 substrates in order to evaluate influence of different ex situ and in situ preparation procedures on the surface layers, which are crucial for quality of following film growth. Despite the similarity of local environments of Sr (Ba) and Ti atoms in the perovskite film structure an angular region in the ADCs was identified as a fingerprint with the help of MSC simulations which provided clear conclusions on the perovskite oxide surfaces. Dopant sites in quaternary perovskite manganites La1-xCaxMnO3, La1-xSrxMnO3, and La1-xCexMnO3 were studied with polar angle scans of the photoemission intensities of host and dopant atoms. Both direct comparison of experimental ADCs and to the simulations within MSC models confirm the occupation of A sites by the dopants and the structural quality of the complex oxide films.

High strength, light weight Ti-Y composites and method of making same

DOEpatents

Verhoeven, John D.; Ellis, Timothy W.; Russell, Alan M.; Jones, Lawrence L.

1993-04-06

A high strength, light weight "in-situ" Ti-Y composite is produced by deformation processing a cast body having Ti and Y phase components distributed therein. The composite comprises elongated, ribbon-shaped Ti and Y phase components aligned along an axis of the deformed body.

High strength, light weight Ti-Y composites and method of making same

DOEpatents

Verhoeven, J.D.; Ellis, T.W.; Russell, A.M.; Jones, L.L.

1993-04-06

A high strength, light weight in-situ'' Ti-Y composite is produced by deformation processing a cast body having Ti and Y phase components distributed therein. The composite comprises elongated, ribbon-shaped Ti and Y phase components aligned along an axis of the deformed body.

Initial oxidation of pure and K doped NiTi shape memory alloys

NASA Astrophysics Data System (ADS)

Tollefsen, H.; Raaen, S.

2009-06-01

Initial oxidation of pure and K doped nitinol has been studied by photoelectron spectroscopy. The composition of the TiOx layer that forms on the surface is found to depend on the temperature during oxidation. The oxidation at high temperatures results in enhanced formation of lower oxides, whereas TiO2 predominates for oxidation at lower temperatures, e.g., 70 °C. Submonolayer coverage of K on NiTi enhances the formation of TiO2 on the expense of lower oxides, which is of consequence for formation of a protective oxide layer and biocompatibility. Oxidation in the martensitic phase was found to be independent of temperature for temperatures between -40 and 10 °C, whereas in the austenitic phase the oxide growth is thermally activated.

Low modulus and bioactive Ti/α-TCP/Ti-mesh composite prepared by spark plasma sintering.

PubMed

Guo, Yu; Tan, Yanni; Liu, Yong; Liu, Shifeng; Zhou, Rui; Tang, Hanchun

2017-11-01

A titanium mesh scaffold composite filled with Ti/α-TCP particles was prepared by spark plasma sintering (SPS). The microstructures and interfacial reactions of the composites were investigated by scanning electron microscopy (SEM), Energy Dispersive Spectroscopy (EDS) and X-ray diffraction (XRD) analyses. The compressive strength and elastic modulus were also measured. In vitro bioactivity and biocompatibility was evaluated by using simulated body fluid and cells culture, respectively. After high temperature sintering, Ti oxides, Ti x P y and CaTiO 3 were formed. The formation of Ti oxides and Ti x P y were resulted from the diffusion of O and P elements from α-TCP to Ti. CaTiO 3 was the reaction product of Ti and α-TCP. The composite of 70Ti/α-TCP incorporated with Ti mesh showed a high compressive strength of 589MPa and a low compressive modulus of 30GPa. The bioactivity test showed the formation of a thick apatite layer on the composite and well-spread cells attachment. A good combination of mechanical properties and bioactivity indicated a high potential application of Ti/α-TCP/Ti-mesh composite for orthopedic implants. Copyright © 2017. Published by Elsevier B.V.

Impact of ultra-thin Al2O3-y layers on TiO2-x ReRAM switching characteristics

NASA Astrophysics Data System (ADS)

Trapatseli, Maria; Cortese, Simone; Serb, Alexander; Khiat, Ali; Prodromakis, Themistoklis

2017-05-01

Transition metal-oxide resistive random access memory devices have demonstrated excellent performance in switching speed, versatility of switching and low-power operation. However, this technology still faces challenges like poor cycling endurance, degradation due to high electroforming (EF) switching voltages and low yields. Approaches such as engineering of the active layer by doping or addition of thin oxide buffer layers have been often adopted to tackle these problems. Here, we have followed a strategy that combines the two; we have used ultra-thin Al2O3-y buffer layers incorporated between TiO2-x thin films taking into account both 3+/4+ oxidation states of Al/Ti cations. Our devices were tested by DC and pulsed voltage sweeping and in both cases demonstrated improved switching voltages. We believe that the Al2O3-y layers act as reservoirs of oxygen vacancies which are injected during EF, facilitate a filamentary switching mechanism and provide enhanced filament stability, as shown by the cycling endurance measurements.

Y-doping TiO2 nanorod arrays for efficient perovskite solar cells

NASA Astrophysics Data System (ADS)

Deng, Xinlian; Wang, Yanqing; Cui, Zhendong; Li, Long; Shi, Chengwu

2018-05-01

To improve the electron transportation in TiO2 nanorod arrays and charge separation in the interface of TiO2/perovskite, Y-doping TiO2 nanorod arrays with the length of 200 nm, diameter of 11 nm and areal density of 1050 μm-2 were successfully prepared by the hydrothermal method and the influence of Y/Ti molar ratios of 0%, 3%, 5% in the hydrothermal grown solutions on the growth of TiO2 nanorod arrays was investigated. The results revealed that the appropriate Y/Ti molar ratios can increase the areal density of the corresponding TiO2 nanorod arrays and improve the charge separation in the interface of the TiO2/perovskite. The Y-doping TiO2 nanorod array perovskite solar cells with the Y/Ti molar ratio of 3% exhibited a photoelectric conversion efficiency (PCE) of 18.11% along with an open-circuit voltage (Voc) of 1.06 V, short-circuit photocurrent density (Jsc) of 22.50 mA cm-2 and fill factor (FF) of 76.16%, while the un-doping TiO2 nanorod array perovskite solar cells gave a PCE of 16.42% along with Voc of 1.04 V, Jsc of 21.66 mA cm-2 and FF of 72.97%.

Issues Concerning the Oxidation of Ni(Pt)Ti Shape Memory Alloys

NASA Technical Reports Server (NTRS)

Smialek, James

2011-01-01

The oxidation behavior of the Ni-30Pt-50Ti high temperature shape memory alloy is compared to that of conventional NiTi nitinol SMAs. The oxidation rates were 1/4 those of NiTi under identical conditions. Ni-Ti-X SMAs are dominated by TiO2 scales, but, in some cases, the activation energy diverges for unexplained reasons. Typically, islands of metallic Ni or Pt(Ni) particles are embedded in lower scale layers due to rapid selective growth of TiO2 and low oxygen potential within the scale. The blocking effect of Pt-rich particles and lower diffusivity of Pt-rich depletion zones are proposed to account for the reduction in oxidation rates.

The Impact of Fe-Ti Oxide Concentration on the Structural Rigidity of the Lower Oceanic Crust, Atlantis Bank, Southwest Indian Ridge

NASA Astrophysics Data System (ADS)

Deans, J. R.; Winkler, D. A.

2017-12-01

Fe-Ti oxides are important components of oceanic core complexes (OCC) formed at slow-spreading ridges, since Fe-Ti oxide phases form throughout the crustal column and are weaker than silicate phases. This study investigated the predicted relationship between the presence and concentration of Fe-Ti oxides and the presence/intensity of crystal-plastic deformation in samples from Atlantis Bank, Southwest Indian Ridge (SWIR). Atlantis Bank is an OCC that formed through the exhumation of lower oceanic crust along a detachment shear zone/fault. OCCs form along slow-spreading ridges and are characterized by the complex interactions between magmatism and crustal extension, thus, making them more susceptible to crystal-plastic deformation at higher temperatures and for weaker phases like Fe-Ti oxides to preferentially partition strain. Atlantis Bank has been the focus of many scientific expeditions to various sites including; Ocean Drilling Program (ODP) Holes 735B and 1105A, and the International Oceanic Discovery Program (IODP) Hole U1473A. A total of 589 thin sections from all three holes were analyzed using the software package Fiji to calculate the Fe-Ti oxide concentration within the thin sections. The Fe-Ti oxide percentage was correlated with the crystal-plastic fabric (CPF) intensity, from 0-5 (no foliation - ultramylonite), for each thin section using the statistical software R. All three holes show a positive correlation between the abundance of Fe-Ti oxides and the CPF intensity. Specifically, 76.3% of samples with a concentration of 5% or more Fe-Ti oxides have a corresponding CPF intensity value of 2 or more (porphyroclastic foliation - ultramylonitic). The positive correlation may be explained by the Fe-Ti oxides preferentially partitioning strain, especially at temperatures below where dry plagioclase can recrystallize. This allows for a mechanism of continued slip along the shear zone or form new shear zones at amphibolite grade conditions while the lower

X-ray absorption spectroscopy characterization of embedded and extracted nano-oxides

DOE PAGES

Stan, Tiberiu; Sprouster, David J.; Ofan, Avishai; ...

2016-12-29

Here, the chemistries and structures of both embedded and extracted Ysingle bondTisingle bondO nanometer-scale oxides in a nanostructured ferritic alloy (NFA) were probed by x-ray absorption spectroscopy (XAS). Y 2Ti 2O 7 is the primary embedded phase, while the slightly larger extracted oxides are primarily Y 2TiO 5. Analysis of the embedded nano-oxides is difficult partly due to the multiple Ti environments associated with different oxides and those still residing in matrix lattice sites. Thus, bulk extraction followed by selective filtration was used to isolate the larger Y 2TiO 5 oxides for XAS, while the smaller predominant embedded phase Ymore » 2Ti 2O 7 oxides passed through the filters and were analyzed using the log-ratio method.« less

Quasi 2D Ultrahigh Carrier Density in a Complex Oxide Broken Gap Heterojunction

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

Xu, Peng; Droubay, Timothy C.; Jeong, Jong S.

2016-01-21

Two-dimensional (2D) ultra-high carrier densities at complex oxide interfaces are of considerable current research interest for novel plasmonic and high charge-gain devices. However, the highest 2D electron density obtained in oxide heterostructures is thus far limited to 3×1014 cm-2 (½ electron/unit cell/interface) at GdTiO3/SrTiO3 interfaces, and is typically an order of magnitude lower at LaAlO3/SrTiO3 interfaces. Here we show that carrier densities much higher than 3×1014 cm-2 can be achieved via band engineering. Transport measurements for 3 nm SrTiO3/t u.c. NdTiO3/3 nm SrTiO3/LSAT (001) show that charge transfer significantly in excess of the value expected from the polar discontinuity modelmore » occurs for higher t values. The carrier density remains unchanged, and equivalent to ½ electron/unit cell/interface for t < 6 unit cells. However, above a critical NdTiO3 thickness of 6 u.c., electrons from the valence band of NdTiO3 spill over into the SrTiO3 conduction band as a natural consequence of the band alignment. An atomistic model consistent with first-principle calculations and experimental results is proposed for the charge transfer mechanisms. These results may provide an exceptional route to the realization of the room-temperature oxide electronics.« less

Oxidation of S(IV) in Seawater by Pulsed High Voltage Discharge Plasma with TiO2/Ti Electrode as Catalyst

NASA Astrophysics Data System (ADS)

Gong, Jianying; Zhang, Xingwang; Wang, Xiaoping; Lei, Lecheng

2013-12-01

Oxidation of S(IV) to S(VI) in the effluent of a flue gas desulfurization(FGD) system is very critical for industrial applications of seawater FGD. This paper reports a pulsed corona discharge oxidation process combined with a TiO2 photocatalyst to convert S(IV) to S(VI) in artificial seawater. Experimental results show that the oxidation of S(IV) in artificial seawater is enhanced in the pulsed discharge plasma process through the application of TiO2 coating electrodes. The oxidation rate of S(IV) using Ti metal as a ground electrode is about 2.0×10-4 mol · L-1 · min-1, the oxidation rate using TiO2/Ti electrode prepared by annealing at 500°C in air is 4.5×10-4 mol · L-1 · min-1, an increase with a factor 2.25. The annealing temperature for preparing TiO2/Ti electrode has a strong effect on the oxidation of S(IV) in artificial seawater. The results of in-situ emission spectroscopic analysis show that chemically active species (i.e. hydroxyl radicals and oxygen radicals) are produced in the pulsed discharge plasma process. Compared with the traditional air oxidation process and the sole plasma-induced oxidation process, the combined application of TiO2 photocatalysts and a pulsed high-voltage electrical discharge process is useful in enhancing the energy and conversion efficiency of S(IV) for the seawater FGD system.

Synthesis of visible-light responsive graphene oxide/TiO(2) composites with p/n heterojunction.

PubMed

Chen, Chao; Cai, Weimin; Long, Mingce; Zhou, Baoxue; Wu, Yahui; Wu, Deyong; Feng, Yujie

2010-11-23

Graphene oxide/TiO(2) composites were prepared by using TiCl(3) and graphene oxide as reactants. The concentration of graphene oxide in starting solution played an important role in photoelectronic and photocatalytic performance of graphene oxide/TiO(2) composites. Either a p-type or n-type semiconductor was formed by graphene oxide in graphene oxide/TiO(2) composites. These semiconductors could be excited by visible light with wavelengths longer than 510 nm and acted as sensitizer in graphene oxide/TiO(2) composites. Visible-light driven photocatalytic performance of graphene oxide/TiO(2) composites in degradation of methyl orange was also studied. Crystalline quality and chemical states of carbon elements from graphene oxide in graphene oxide/TiO(2) composites depended on the concentration of graphene oxide in the starting solution. This study shows a possible way to fabricate graphene oxide/semiconductor composites with different properties by using a tunable semiconductor conductivity type of graphene oxide.

[Cr-Ti-Al-N complex coating on titanium to strengthen Ti/porcelain bonding].

PubMed

Zhang, Hui; Guo, Tian-wen; Li, Jun-ming; Pan, Jing-guang; Dang, Yong-gang; Tong, Yu

2006-02-01

To study the feasibility of magnetron sputtering Cr-Ti-Al-N complex coating as an interlayer on titanium to enhance the titanium-ceramic binding strength. With a three-point bending test according to ISO 9693, the binding strength of Duceratin (Degussa) to titanium substrate prepared with 4 different surface treatments (polishing, polishing and megnetron sputtering Cr, Ti, Al, and N complex coating, sandblasting, sandblasting and coating) was evaluated. Ti/porcelain interface and fractured Ti surface were examined using scanning electron microscopy with energy-dispersive spectrometry (EDS). The binding strength of polished and coated titanium/Duceratin was significantly higher than polished titanium group (P<0.05). The binding strength of sandblasted and coated titanium/Duceratin did not differ significantly from that of sandblasted titanium group (P>0.05), and the strength in the two sandblasted titanium groups was significantly higher than that in polished and coated titanium group (P<0.05). Megnetron sputtering Cr-Ti-Al-N complex on polished titanium can increase the titanium/porcelain binding strength. Megnetron sputtering coating is a promising Ti/porcelain interlayer.

Molecular structure of Ti8C12 and related complexes.

PubMed Central

Pauling, L

1992-01-01

Application of valence-bond theory leads to the assignment to the molecule Ti8C12 of a cubic structure, point group Ohm3m, with 8 Ti at the cube corners, +/-(x x x, x, x x [symbol, see text]) where x = 1.78 A, and with 12 C in pairs in the cube faces, +/-(0 y z, [symbol, see text], 0, y z [symbol, see text]) where y = 1.78 A and z = 0.71 A. The Ti-C and C-C bonds have bond number 4/3, corresponding to resonance of single and double bonds in 2:1 ratio. PMID:11607323

Control of cerium oxidation state through metal complex secondary structures

DOE PAGES

Levin, Jessica R.; Dorfner, Walter L.; Carroll, Patrick J.; ...

2015-08-11

A series of alkali metal cerium diphenylhydrazido complexes, M x(py) y[Ce(PhNNPh) 4], M = Li, Na, and K, x = 4 (Li and Na) or 5 (K), and y = 4 (Li), 8 (Na), or 7 (K), were synthesized to probe how a secondary coordination sphere would modulate electronic structures at a cerium cation. The resulting electronic structures of the heterobimetallic cerium diphenylhydrazido complexes were found to be strongly dependent on the identity of the alkali metal cations. When M = Li + or Na +, the cerium(III) starting material was oxidized with concomitant reduction of 1,2-diphenylhydrazine to aniline. Reductionmore » of 1,2-diphenylhydrazine was not observed when M = K +, and the complex remained in the cerium(III) oxidation state. Oxidation of the cerium(III) diphenylhydrazido complex to the Ce( IV) diphenylhydrazido one was achieved through a simple cation exchange reaction of the alkali metals. As a result, UV-Vis spectroscopy, FTIR spectroscopy, electrochemistry, magnetic susceptibility, and DFT studies were used to probe the oxidation state and the electronic changes that occurred at the metal centre.« less

XPS Spectra Analysis of Ti2+, Ti3+ Ions and Dye Photodegradation Evaluation of Titania-Silica Mixed Oxide Nanoparticles

NASA Astrophysics Data System (ADS)

Chinh, Vu Duc; Broggi, Alessandra; Di Palma, Luca; Scarsella, Marco; Speranza, Giorgio; Vilardi, Giorgio; Thang, Pham Nam

2018-04-01

TiO2-SiO2 mixed oxides have been prepared by the sol-gel technique from tetrabutyl orthotitanate and tetraethyl orthosilicate. The prepared materials were characterized by x-ray diffraction, scanning electron microscopy, energy dispersive x-ray spectroscopy, nitrogen physisorption, Fourier-transform infrared spectroscopy (FT-IR) and x-ray photoelectron spectroscopy (XPS). The results indicate that the TiO2-SiO2 mixed oxides have a large surface area and a nanoscale size. FT-IR spectra show that Ti atoms are bonded to silica by oxygen bridging atoms in Ti-O-Si bonds. The titanium valence states in TiO2-SiO2 mixed oxides were investigated by XPS, and their spectra report the presence of Ti2+ and Ti3+ cations for high silica concentration, suggesting the formation of oxygen vacancies. The photocatalytic activity of the prepared materials has been evaluated for the photodegradation of methylene blue (MB). The mixed oxides were activated by means of a UV light source, and the concentration of MB was monitored by UV-Vis spectroscopy. The synthesized TiO2-SiO2 shows significantly higher MB removal efficiency in comparison with that of the commercial TiO2 Degussa, P25.

Uranium and minor-element partitioning in Fe-Ti oxides and zircon from partially melted granodiorite, Crater Lake, Oregon

USGS Publications Warehouse

Tourrette, T.Z.L.; Burnett, D.S.; Bacon, C.R.

1991-01-01

Crystal-liquid partitioning in Fe-Ti oxides and zircon was studied in partially melted granodiorite blocks ejected during the climactic eruption of Mt. Mazama (Crater Lake), Oregon. The blocks, which contain up to 33% rhyolite glass (75 wt% SiO2), are interpreted to be portions of the magma chamber walls that were torn off during eruption. The glass is clear and well homogenized for all measured elements except Zr. Results for Fe-Ti oxides give DUoxide/liq ??? 0.1. Partitioning of Mg, Mn, Al, Si, V, and Cr in Fe-Ti oxides indicates that grains surrounded by glass are moderately well equilibrated with the melt for many of the minor elements, while those that are inclusions in relict plagioclase are not. Uranium and ytterbium inhomogeneities in zircons indicate that the zircons have only partially equilibrated with the melt and that uranium appears to have been diffusing out of the zircons faster than the zircons were dissolving. Minimum U, Y, and P concentrations in zircons give maximum DUzrc/liq = 13,DYzrc/liq = 23, and DPzrc/liq = 1, but these are considerably lower than reported by other workers for U and Y. Based on our measurements and given their low abundances in most rocks, Fe-Ti oxides probably do not play a major role in U-Th fractionation during partial melting. The partial melts were undersaturated with zircon and apatite, but both phases are present in our samples. This demonstrates an actual case of non-equilibrium source retention of accessory phases, which in general could be an important trace-element fractionation mechanism. Our results do not support the hypothesis that liquid structure is the dominant factor controlling trace-element partitioning in high-silica rhyolites. Rough calculations based on Zr gradients in the glass indicate that the samples could have been partially molten for 800 to 8000 years. ?? 1991.

Removal of emerging pollutants by Ru/TiO2-catalyzed permanganate oxidation.

PubMed

Zhang, Jing; Sun, Bo; Xiong, Xinmei; Gao, Naiyun; Song, Weihua; Du, Erdeng; Guan, Xiaohong; Zhou, Gongming

2014-10-15

TiO2 supported ruthenium nanoparticles, Ru/TiO2 (0.94‰ as Ru), was synthesized to catalyze permanganate oxidation for degrading emerging pollutants (EPs) with diverse organic moieties. The presence of 1.0 g L(-1) Ru/TiO2 increased the second order reaction rate constants of bisphenol A, diclofenac, acetaminophen, sulfamethoxazole, benzotriazole, carbamazepine, butylparaben, diclofenac, ciprofloxacin and aniline at mg L(-1) level (5.0 μM) by permanganate oxidation at pH 7.0 by 0.3-119 times. The second order reaction rate constants of EPs with permanganate or Ru/TiO2-catalyzed permanganate oxidation obtained at EPs concentration of mg L(-1) level (5.0 μM) underestimated those obtained at EPs concentration of μg L(-1) level (0.050 μM). Ru/TiO2-catalyzed permanganate could decompose a mixture of nine EPs at μg L(-1) level efficiently and the second order rate constant for each EP was not decreased due to the competition of other EPs. The toxicity tests revealed that Ru/TiO2-catalyzed permanganate oxidation was effective not only for elimination of EPs but also for detoxification. The removal rates of sulfamethoxazole by Ru/TiO2-catalyzed permanganate oxidation in ten successive cycles remained almost constant in ultrapure water and slightly decreased in Songhua river water since the sixth run, indicating the satisfactory stability of Ru/TiO2. Ru/TiO2-catalyzed permanganate oxidation was selective and could remove selected EPs spiked in real waters more efficiently than chlorination. Therefore, Ru/TiO2-catalyzed permanganate oxidation is promising for removing EPs with electron-rich moieties. Copyright © 2014 Elsevier Ltd. All rights reserved.

EUV-induced oxidation of carbon on TiO2.

PubMed

Faradzhev, Nadir S; Hill, Shannon B

2016-10-01

Previously we reported estimates of the maximum etch rates of C on TiO 2 by oxidizers including NO, O 3 and H 2 O 2 when irradiated by a spatially-non-uniform beam of extreme ultraviolet (EUV) radiation at 13.5 nm (Faradzhev et al., 2013). Here we extend that work by presenting temporally and spatially resolved measurements of the C etching by these oxidizers as a function of EUV intensity in the range (0.3 to 3) mW/mm 2 [(0.2 to 2) × 10 16 photons s -1 cm -2 ]. We find that the rates for NO scale linearly with intensity and are smaller than those for O 3 , which exhibit a weak, sub-linear intensity dependence in this range. We demonstrate that these behaviors are consistent with adsorption of the oxidizing precursor on the C surface followed by a photon-stimulated reaction resulting in volatile C-containing products. The kinetics of photon-induced C etching by hydrogen peroxide, however, appear to be more complex. The spatially resolved measurements reveal that C removal by H 2 O 2 begins at the edges of the C spot, where the light intensity is the lowest, and proceeds toward the center of the spot. This localization of the reaction may occur because hydroxyl radicals are produced efficiently on the catalytically active TiO 2 surface.

Resistive switching characteristics of thermally oxidized TiN thin films

NASA Astrophysics Data System (ADS)

Biju, K. P.

2018-04-01

Resistive switching characteristics of thermally oxidized TiN thin films and mechanisms were investigated.XPS results indicates Ti-O content decreases with sputter etching and Ti 2p peak shift towards lower binding energy due to formation of Ti-O-N and Ti-N. Pt/TiO2/TiON/TiN stack exhibits both clockwise switching (CWS) and counter clockwise switching(CCWS) characteristic depending on polarity of the applied voltage. However the transition from CCWS to CWS is irreversible. Two stable switching modes with opposite switching polarity and different electrical characteristics are found to coexist in the same memory cell. Clockwise switching shows filamentary characteristics that lead to faster switching with excellent retention at high temperature. Counter-clockwise switching exhibits homogeneous conduction with slower switching and moderate retention. The field-induced switching in both CCWS and CWS might be due to inhomogeneous defect distribution due to thermal oxidation.

Photo-oxidative degradation of TiO{sub 2}/polypropylene films

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

García-Montelongo, X.L.; Martínez-de la Cruz, A., E-mail: azael70@yahoo.com.mx; Vázquez-Rodríguez, S.

Graphical abstract: - Highlights: • Photo-oxidative degradation of polypropylene is accelerated by TiO{sub 2} incorporation. • Weight loss, FTIR, SEM and GPC shown high degree of degradation of polypropylene. • A mechanism of the photo-degradation of polypropylene by TiO{sub 2} is proposed. - Abstract: Photo-oxidative degradation of polypropylene films with TiO{sub 2} nanoparticles incorporated was studied in a chamber of weathering with Xenon lamps as irradiation source. TiO{sub 2} powder with crystalline structure of anatase was synthesized by thermal treatments at 400 and 500 °C starting from a precursor material obtained by sol–gel method. Composites of TiO{sub 2}/polypropylene were preparedmore » with 0.1, 0.5 and 1.0 wt% of TiO{sub 2}. The mixture of components was performed using a twin screw extruder, the resulting material was pelletized by mechanical fragmenting and then hot-pressed in order to form polypropylene films with TiO{sub 2} dispersed homogeneously. Photo-oxidative degradation process was followed by visual inspection, weight loss of films, scanning electron microscopy (SEM), infrared spectroscopy with Fourier transformed (FTIR), and gel permeation chromatography (GPC)« less

A comparative study of TiN and TiC: Oxidation resistance and retention of xenon at high temperature and under degraded vacuum

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

Gavarini, S.; Bes, R.; Millard-Pinard, N.

2011-01-01

Dense TiN and TiC samples were prepared by hot pressing using micrometric powders. Xenon species (simulating rare gas fission products) were then implanted into the ceramics. The samples were annealed for 1 h at 1500 deg. C under several degraded vacuums with P{sub O{sub 2}} varying from 10{sup -6} to 2x10{sup -4} mbars. The oxidation resistance of the samples and their retention properties with respect to preimplanted xenon species were analyzed using scanning electron microscopy, grazing incidence x-ray diffraction, Rutherford backscattering spectrometry, and nuclear backscattering spectrometry. Results indicate that TiC is resistant to oxidation and does not release xenon formore » P{sub O{sub 2{<=}}}6x10{sup -6} mbars. When P{sub O{sub 2}} increases, geometric oxide crystallites appear at the surface depending on the orientation and size of TiC grains. These oxide phases are Ti{sub 2}O{sub 3}, Ti{sub 3}O{sub 5}, and TiO{sub 2}. Apparition of oxide crystallites is associated with the beginning of xenon release. TiC surface is completely covered by the oxide phases at P{sub O{sub 2}}=2x10{sup -4} mbars up to a depth of 3 {mu}m and the xenon is then completely released. For TiN samples, the results show a progressive apparition of oxide crystallites (Ti{sub 3}O{sub 5} mainly) at the surface when P{sub O{sub 2}} increases. The presence of the oxide crystallites is also directly correlated with xenon release, the more oxide crystallites are growing the more xenon is released. TiN surface is completely covered by an oxide layer at P{sub O{sub 2}}=2x10{sup -4} mbars up to 1 {mu}m. A correlation between the initial fine microstructure of TiN and the properties of the growing layer is suggested.« less

Very Long Term Oxidation of Ti-48Al-2Cr-2Nb at 704 C In Air

NASA Technical Reports Server (NTRS)

Locci, I. E.; Brady, M. P.; MacKay, R. A.; Smith, J. W.

1997-01-01

Introduction Titanium aluminides are of great interest for intermediate-temperature (600 C - 850 C) aerospace and power generation applications because of their high specific properties. Replacement of conventional superalloys by titanium aluminides offers the potential of significant weight savings. Extensive development efforts over the past IO years have led to the identification of y (TiAl) + alpha(sub 2) (Ti3Al) alloys, such as the G.E. alloy Ti48Al-2Cr-2Nb (all composition in at. %), which offer a balance of room temperature mechanical properties and high-temperature strength retention. The two phase gamma + alpha(sub 2) class of titanium aluminides also offers superior oxidation and embrittlement resistance compared to the alpha(sub 2) and orthorhombic classes of titanium aluminides. However, environmental durability is still a major concern. Significant progress has recently been made in understanding the fundamental aspects of the oxidation behavior of binary gamma + alpha(sub 2) Ti-Al alloys. However, most of this work has concentrated on short term (less than 1000 hours), high temperature (900 C - 1000 C) exposures. Also little data are available in the literature regarding the oxidation behavior of the quaternary and higher order gamma + alpha(sub 2) engineering alloys. This is especially true for the very long-term, low temperature conditions likely to be experienced during engineering applications. The present work addresses this regime to fill this gap by characterizing the oxidation behavior of Ti48Al-2Cr-2Nb for periods up to 9000 h at 704 C in air.

Y,REE,Nb,Ta,Ti-oxide (AB 2O 6) minerals from REL-REE euxenite-subtype pegmatites of the Třebíč Pluton, Czech Republic; substitutions and fractionation trends

NASA Astrophysics Data System (ADS)

Škoda, Radek; Novák, Milan

2007-04-01

Aeschynite-group minerals (AGM) and euxenite-group minerals (EGM) occur in REL-REE euxenite-subtype pegmatites from the Třebíč Pluton, Czech Republic. They form strongly metamictized, light brown to black, equigranular to needle-like, subhedral to anhedral grains enclosed in blocky K-feldspar and less commonly in albite, and blocky quartz, and in the graphic unit (quartz and K-feldspar). Both AGM and EGM are homogeneous to slightly heterogeneous in BSE images. They are not commonly associated with the other primary Y,REE,Ti,Nb-bearing minerals, i.e. allanite-(Ce), monazite-(Ce), titanite, and ilmenite, which occur within the same textural-paragenetic unit. Aeschynite-(Y), aeschynite-(Ce), aeschynite-(Nd), nioboaeschynite-(Ce), tantalaeschynite-(Ce), vigezzite and polycrase-(Y) were identified using EMP and canonical discrimination analysis [Ercit, T.S., 2005a. Identification and alteration trends of granitic-pegmatite-hosted (Y,REE,U,Th)-(Nb,Ta,Ti) oxide minerals: a statistical approach. Can. Mineral. 43, 4 1291-1303.]. The exchange vector ACa B(Nb,Ta) A(Y,REE) - 1 BTi - 1 or its combination with the exchange vector ACa 2B(Nb,Ta) 3A(U,Th) - 1 A(Y,REE) - 1 BTi - 3 have been elucidated for the AGM. The exchange vector ACa A(U,Th) A(Y,REE) - 2 is predominant in the EGM. The AGM are enriched in HREE, whereas LREE are concentrated in the EGM. Weak to none-existent geochemical fractionations, as expressed by the U/(U + Th), Y/(Y + REE), Ta/(Ta + Nb) and (Nb + Ta)/(Ti + Nb + Ta) ratios, were noted for single grains from both the AGM and EGM, as well as in grains of polycrase-(Y) from four different textural-paragenetic units located in the Vladislav pegmatite. Simultaneous increase of U/(U + Th) and Y/(Y + REE) in the AGM during fractionation is typical. The Ta/(Ta + Nb) fractionation is usually weak and contradicts the Y/(Y + REE) and U/(U + Th) fractionation trends. This unusual behavior of Nb and Ta may be controlled by associated Ti-rich minerals (titanite

Microstructure, Wear Resistance and Oxidation Behavior of Ni-Ti-Si Coatings Fabricated on Ti6Al4V by Laser Cladding.

PubMed

Zhuang, Qiaoqiao; Zhang, Peilei; Li, Mingchuan; Yan, Hua; Yu, Zhishui; Lu, Qinghua

2017-10-30

The Ni-Ti-Si composite coatings were successfully fabricated on Ti6Al4V by laser cladding. The microstructure were studied by SEM (scanning electron microscopy) and EDS (energy dispersive spectrometer). It has been found that Ti₂Ni and Ti₅Si₃ phases exist in all coatings, and some samples have TiSi₂ phases. Moreover, due to the existence of these phases, coatings presented relatively higher microhardness than that of the substrate (826 HV (Vickers hardness)) and the microhardness value of coating 3 is about twice larger than that of the substrate. During the dry sliding friction and wear test, due to the distribution of the relatively ductile phase of Ti₂Ni and reinforcement phases of Ti₅Si₃ and TiSi₂, the coatings performed good wear resistance. The oxidation process contains two stages: the rapid oxidation and slow oxidation by high temperature oxidation test at 800 °C for 50 h. Meanwhile, the value of the oxidation weight gain of the substrate is approximately three times larger than that of the coating 4. During the oxidation process, the oxidation film formed on the coating is mainly consisted of TiO₂, Al₂O₃ and SiO₂. Phases Ti₂Ni, Ti₅Si₃, TiSi₂ and TiSi were still found and it could be responsible for the improvement in oxidation resistance of the coatings by laser cladding.

Compositionally Dependent Nonlinear Optical Bandgap Behavior of Mixed Anodic Oxides in Niobium-Titanium System.

PubMed

Bleckenwegner, Petra; Mardare, Cezarina Cela; Cobet, Christoph; Kollender, Jan Philipp; Hassel, Achim Walter; Mardare, Andrei Ionut

2017-02-13

Optical bandgap mapping of Nb-Ti mixed oxides anodically grown on a thin film parent metallic combinatorial library was performed via variable angle spectroscopic ellipsometry (VASE). A wide Nb-Ti compositional spread ranging from Nb-90 at.% Ti to Nb-15 at.% Ti deposited by cosputtering was used for this purpose. The Nb-Ti library was stepwise anodized at potentials up to 10 V SHE, and the anodic oxides optical properties were mapped along the Nb-Ti library with 2 at.% resolution. The surface dissimilarities along the Nb-Ti compositional gradient were minimized by tuning the deposition parameters, thus allowing a description of the mixed Nb-Ti oxides based on a single Tauc-Lorentz oscillator for data fitting. Mapping of the Nb-Ti oxides optical bandgap along the entire compositional spread showed a clear deviation from the linear model based on mixing individual Nb and Ti electronegativities proportional to their atomic fractions. This is attributed to the strong amorphization and an in-depth compositional gradient of the mixed oxides. A systematic optical bandgap decrease toward values as low as 2.0 eV was identified at approximately 50 at.% Nb. Mixing of Nb 2 O 5 and TiO 2 with both amorphous and crystalline phases is concluded, whereas the possibility of complex Nb a Ti b O y oxide formation during anodization is unlikely.

Preparation of TiO(2) layers on cp-Ti and Ti6Al4V by thermal and anodic oxidation and by sol-gel coating techniques and their characterization.

PubMed

Velten, D; Biehl, V; Aubertin, F; Valeske, B; Possart, W; Breme, J

2002-01-01

The excellent biocompatibility of titanium and its alloys used, for example, for medical devices, is associated with the properties of their surface oxide. For a better understanding of the tissue reaction in contact with the oxide layer, knowledge of the chemical and physical properties of this layer is of increasing interest. In this study, titania films were produced on cp-Ti and Ti6Al4V substrates by thermal oxidation, anodic oxidation, and by the sol-gel process. The thickness and structure of the films produced under different conditions were determined by ellipsometry, infrared spectroscopy, and X-ray diffraction measurements. The corrosion properties of these layers were investigated by current density-potential curves under physiological conditions. The oxide layers produced on cp-Ti and Ti6Al4V by thermal oxidation consist of TiO(2) in the rutile structure. For the anodized samples the structure of TiO(2) is a mixture of amorphous phase and anatase. The structure of the coatings produced by the sol-gel process for a constant annealing time depends on the annealing temperature, and with increasing temperature successively amorphous, anatase, and rutile structure is observed. Compared to the uncoated, polished substrate with a natural oxide layer, the corrosion resistance of cp-Ti and Ti6Al4V is increased for the samples with an oxide layer thickness of about 100 nm, independent of the oxidation procedure. Copyright 2001 John Wiley & Sons, Inc.

Cp2 TiX Complexes for Sustainable Catalysis in Single-Electron Steps.

PubMed

Richrath, Ruben B; Olyschläger, Theresa; Hildebrandt, Sven; Enny, Daniel G; Fianu, Godfred D; Flowers, Robert A; Gansäuer, Andreas

2018-04-25

We present a combined electrochemical, kinetic, and synthetic study with a novel and easily accessible class of titanocene catalysts for catalysis in single-electron steps. The tailoring of the electronic properties of our Cp 2 TiX-catalysts that are prepared in situ from readily available Cp 2 TiX 2 is achieved by varying the anionic ligand X. Of the complexes investigated, Cp 2 TiOMs proved to be either equal or substantially superior to the best catalysts developed earlier. The kinetic and thermodynamic properties pertinent to catalysis have been determined. They allow a mechanistic understanding of the subtle interplay of properties required for an efficient oxidative addition and reduction. Therefore, our study highlights that efficient catalysts do not require the elaborate covalent modification of the cyclopentadienyl ligands. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Conducting interface in oxide homojunction: Understanding of superior properties in black TiO 2

DOE PAGES

Lu, Xujie; Chen, Aiping; Luo, Yongkang; ...

2016-09-14

Black TiO 2 nanoparticles with a crystalline core and amorphous-shell structure exhibit superior optoelectronic properties in comparison with pristine TiO 2. The fundamental mechanisms underlying these enhancements, however, remain unclear, largely due to the inherent complexities and limitations of powder materials. Here, we fabricate TiO 2 homojunction films consisting of an oxygen-deficient amorphous layer on top of a highly crystalline layer, to simulate the structural/functional configuration of black TiO 2 nanoparticles. Metallic conduction is achieved at the crystalline–amorphous homointerface via electronic interface reconstruction, which we show to be the main reason for the enhanced electron transport of black TiO 2.more » As a result, this work not only achieves an unprecedented understanding of black TiO 2 but also provides a new perspective for investigating carrier generation and transport behavior at oxide interfaces, which are of tremendous fundamental and technological interest.« less

Au/MxOy/TiO2 catalysts for CO oxidation: promotional effect of main-group, transition, and rare-earth metal oxide additives.

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

Ma, Zhen; Overbury, Steven; Dai, Sheng

Au/TiO2 catalysts are active for CO oxidation, but they suffer from high-temperature sintering of the gold particles, and few attempts have been made to promote or stabilize Au/TiO2. Our recent communication addressed these issues by loading gold onto Al2O3/TiO2 prepared via surface-sol-gel processing of Al(sec-OC4H9)3 on TiO2. In our current full paper, Au/Al2O3/TiO2 catalysts were prepared alternatively by thermal decomposition of Al(NO3)3 on TiO2 followed by loading gold, and the influences of the decomposition temperature and Al2O3 content were systematically surveyed. This facile method was subsequently extended to the preparation of a battery of metal oxide-modified Au/TiO2 catalysts virtually notmore » reported. It was found that Au/TiO2 modified by CaO, NiO, ZnO, Ga2O3, Y2O3, ZrO2, La2O3, Pr2O3, Nd2O3, Sm2O3, Eu2O3, Gd2O3, Dy2O3, Ho2O3, Er2O3, or Yb2O3 could retain significant activity at ambient temperature even after aging in O2-He at 500 C, whereas unmodified Au/TiO2 lost its activity. Moreover, some 200 C-calcined promoted catalysts showed high activity even at about -100 C. The deactivation and regeneration of some of these new catalysts were studied. This work furnished novel catalysts for further fundamental and applied research.« less

Halogen effect for improving high temperature oxidation resistance of Ti-50Al by anodization

NASA Astrophysics Data System (ADS)

Mo, Min-Hua; Wu, Lian-Kui; Cao, Hua-Zhen; Lin, Jun-Pin; Zheng, Guo-Qu

2017-06-01

The high temperature oxidation resistance of Ti-50Al was significantly improved via halogen effect which was achieved by anodizing in an ethylene glycol solution containing with fluorine ion. The anodized Ti-50Al with holes and micro-cracks could be self-repaired during oxidation at 1000 °C. The thickness of the oxide scale increases with the prolonging of oxidation time. On the basis of halogen effect for improving the high temperature oxidation resistance of Ti-50Al by anodization, only fluorine addition into the electrolyte can effectively improve the high temperature oxidation resistance of Ti-50Al.

Characterization of stainless steel surface processed using electrolytic oxidation and titanium complex ion solution

NASA Astrophysics Data System (ADS)

Kang, Yubin; Choi, Jaeyoung; Park, Jinju; Kim, Woo-Byoung; Lee, Kun-Jae

2017-09-01

This study attempts to improve the physical and chemical adhesion between metals and ceramics by using electrolytic oxidation and a titanium organic/inorganic complex ion solution on the SS-304 plate. Surface analysis confirmed the existence of the Tisbnd Osbnd Mx bonds formed by the bonding between the metal ions and the Ti oxide at the surface of the pre-processed SS plate, and improved chemical adhesion during ceramic coating was expected by confirming the presence of the carboxylic group. The adhesion was evaluated by using the ceramic coating solution in order to assess the improved adhesion of the SS plate under conditions. The results showed that both the adhesion and durability were largely improved in the sample processed with all the pre-processing steps, thus confirming that the physical and chemical adhesion between metals and ceramics can be improved by enhancing the physical roughness via electrolytic oxidation and pre-processing using a Ti complex ion solution.

Formation of hydroxyl radicals and kinetic study of 2-chlorophenol photocatalytic oxidation using C-doped TiO2, N-doped TiO2, and C,N Co-doped TiO2 under visible light.

PubMed

Ananpattarachai, Jirapat; Seraphin, Supapan; Kajitvichyanukul, Puangrat

2016-02-01

This work reports on synthesis, characterization, adsorption ability, formation rate of hydroxyl radicals (OH(•)), photocatalytic oxidation kinetics, and mineralization ability of C-doped titanium dioxide (TiO2), N-doped TiO2, and C,N co-doped TiO2 prepared by the sol-gel method. X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), and UV-visible spectroscopy were used to analyze the titania. The rate of formation of OH(•) for each type of titania was determined, and the OH-index was calculated. The kinetics of as-synthesized TiO2 catalysts in photocatalytic oxidation of 2-chlorophenol (2-CP) under visible light irradiation were evaluated. Results revealed that nitrogen was incorporated into the lattice of titania with the structure of O-Ti-N linkages in N-doped TiO2 and C,N co-doped TiO2. Carbon was joined to the Ti-O-C bond in the C-doped TiO2 and C,N co-doped TiO2. The 2-CP adsorption ability of C,N co-doped TiO2 and C-doped TiO2 originated from a layer composed of a complex carbonaceous mixture at the surface of TiO2. C,N co-doped TiO2 had highest formation rate of OH(•) and photocatalytic activity due to a synergistic effect of carbon and nitrogen co-doping. The order of photocatalytic activity per unit surface area was the same as that of the formation rate of OH(•) unit surface area in the following order: C,N co-doped TiO2 > C-doped TiO2 > N-doped TiO2 > undoped TiO2.

Air Oxidation Behavior of Two Ti-Base Alloys Synthesized by HIP

NASA Astrophysics Data System (ADS)

Liu, S.; Guo, Q. Q.; Liu, L. L.; Xu, L.; Liu, Y. Y.

2016-04-01

The oxidation behavior of Ti-5Al-2.5Sn and Ti-6Al-4V produced by hot isostatic pressing (HIP) has been studied at 650-850°C in air for 24 h. The oxidation kinetics of both alloys followed the parabolic law with good approximation, except for Ti-5Al-2.5Sn oxidized at 850°C. Multi-layered scales formed on both alloys at 750°C and 850°C. Ternary additions of Sn and V accounted for the different morphology of the scales formed on these two alloys. In addition, the oxidation behavior of HIP alloys is compared with that of the corresponding cast alloys and the scaling mechanism is discussed.

Role of Y-Al oxides during extended recovery process of a ferritic ODS alloy

DOE PAGES

Capdevila, C.; Pimentel, G.; Aranda, M. M.; ...

2015-08-04

The microstructural stability of Y-Al oxides during the recrystallization of Fe-Cr-Al oxide dispersion strengthened alloy is studied in this work. The goal is to determine the specific distribution pattern of oxides depending where they are located: in the matrix or at the grain boundaries. It was concluded that those located at the grain boundaries yielded a faster coarsening than the ones in the matrix, although no significant differences in composition and/or crystal structure were observed. However, the recrystallization heat treatment leads to the dissolution of the Y 2O 3 and its combination with Al to form the YAlO 3 perovskitemore » oxide particles process, mainly located at the grain boundaries. Lastly, atom probe tomography analysis revealed a significant Ti build-up at the grain boundaries that might affect subsequent migration during recrystallization.« less

Role of Y-Al Oxides During Extended Recovery Process of a Ferritic ODS Alloy

NASA Astrophysics Data System (ADS)

Capdevila, C.; Pimentel, G.; Aranda, M. M.; Rementeria, R.; Dawson, K.; Urones-Garrote, E.; Tatlock, G. J.; Miller, M. K.

2015-08-01

The microstructural stability of Y-Al oxides during the recrystallization of Fe-Cr-Al oxide dispersion strengthened alloy is studied in this work. The goal is to determine the specific distribution pattern of oxides depending where they are located: in the matrix or at the grain boundaries. It was concluded that those located at the grain boundaries yielded a faster coarsening than the ones in the matrix, although no significant differences in composition and/or crystal structure were observed. However, the recrystallization heat treatment leads to the dissolution of the Y2O3 and its combination with Al to form the YAlO3 perovskite oxide particles process, mainly located at the grain boundaries. Finally, atom probe tomography analysis revealed a significant Ti build-up at the grain boundaries that might affect subsequent migration during recrystallization.

Effect of TiN Addition on 3Y-TZP Ceramics with Emphasis on Making EDM-Able Bodies

NASA Astrophysics Data System (ADS)

Khosravifar, Mahnoosh; Mirkazemi, Seyyed Mohammad; Taheri, Mahdiar; Golestanifard, Farhad

2018-05-01

In this study, to produce electrically conductive ceramics, rapid hot press (RHP) sintering of 3 mol.% yttria-stabilized tetragonal zirconia polycrystal (3Y-TZP) and 3Y-TZP/TiN composites with TiN amounts of 25, 35, and 45 vol.% was performed at 1300, 1350, and 1400 °C. Interestingly, the toughness and hardness were improved in the presence of TiN up to 35 vol.% and maximum fracture toughness and hardness of 5.40 ± 0.05 MPa m1/2 and 14.50 ± 0.06 GPa, respectively, were obtained. However, the bending strength was decreased which could be attributed to the rather weak interfaces of nitride and oxide phases. Regarding the zirconia matrix, the effect of grain size on fracture toughness of the samples has been studied using x-ray diffraction and field emission scanning electron microscope (FESEM) analysis. It was also found that electrical resistivity decreased to the value of 6.88 × 10-6 Ω m at 45 vol.% of TiN. It seems the TiN grains form a network to impose conductivity on the ZrO2 body; however, below 35 vol.% TiN, due to lack of percolation effect, this conductivity could not be maintained according to FESEM studies. Finally, electrically conductive samples were successfully machined by electrical discharge machining (EDM).

Group 4 Metalloporphyrin diolato Complexes and Catalytic Application of Metalloporphyrins and Related Transition Metal Complexes

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

Du, Guodong

In this work, the first examples of group 4 metalloporphyrin 1,2-diolato complexes were synthesized through a number of strategies. In general, treatment of imido metalloporphyrin complexes, (TTP)M=NR, (M = Ti, Zr, Hf), with vicinal diols led to the formation of a series of diolato complexes. Alternatively, the chelating pinacolate complexes could be prepared by metathesis of (TTP)MCl 2 (M = Ti, Hf) with disodium pinacolate. These complexes were found to undergo C-C cleavage reactions to produce organic carbonyl compounds. For titanium porphyrins, treatment of a titanium(II) alkyne adduct, (TTP)Ti(η 2-PhC≡CPh), with aromatic aldehydes or aryl ketones resulted in reductive couplingmore » of the carbonyl groups to produce the corresponding diolato complexes. Aliphatic aldehydes or ketones were not reactive towards (TTP)Ti(η 2-PhC≡CPh). However, these carbonyl compounds could be incorporated into a diolato complex on reaction with a reactive precursor, (TTP)Ti[O(Ph) 2C(Ph) 2O] to provide unsymmetrical diolato complexes via cross coupling reactions. In addition, an enediolato complex (TTP)Ti(OCPhCPhO) was obtained from the reaction of (TTP)Ti(η 2-PhC≡CPh) with benzoin. Titanium porphyrin diolato complexes were found to be intermediates in the (TTP)Ti=O-catalyzed cleavage reactions of vicinal diols, in which atmospheric oxygen was the oxidant. Furthermore, (TTP)Ti=O was capable of catalyzing the oxidation of benzyl alcohol and α-hydroxy ketones to benzaldehyde and α-diketones, respectively. Other high valent metalloporphyrin complexes also can catalyze the oxidative diol cleavage and the benzyl alcohol oxidation reactions with dioxygen. A comparison of Ti(IV) and Sn(IV) porphyrin chemistry was undertaken. While chelated diolato complexes were invariably obtained for titanium porphyrins on treatment with 1,2-diols, the reaction of vicinal diols with tin porphyrins gave a number of products, including mono-, bis-alkoxo, and chelating diolato complexes

Magnesiothermic reduction for direct synthesis of Ti-Nb alloy at 1073 K (800 °C)

NASA Astrophysics Data System (ADS)

Choi, Kyunsuk; Lee, Kwang Hee; Ali, Basit; Choi, Sang-Hoon; Park, Kyoung-Tae; Sohn, Il

2017-09-01

Direct fabrication of titanium (Ti) and niobium (Nb) alloys by direct magnesiothermic reduction from the respective initial metal oxides and complex oxides has been studied. TiO2, Nb2O5, and complex TiNb2O7 oxides were used as raw materials with Mg used as a reductant. To ensure a high chemical potential of the reactants to drive the spontaneous magnesiothermic reduction of the oxide mixtures, excess Mg five times higher than the required stoichiometric molar ratio was added. Samples were heated in a glove box under recycled and purified Ar atmosphere at 1073 K (800 °C) for 10 h. After the reduction of TiO2, intermediate oxide phases of Ti6O could still be observed, but reduction of Nb2O5 and TiNb2O7 showed metallic Nb and Ti-Nb to be present with negligible oxides according to the scanning electron microscope-energy dispersive spectroscopy and x ray diffraction analysis. This indicated that direct fabrication of Ti-Nb alloys through a complex TiNb2O7 oxide is possible and can be more efficient than alloying pure metallic elements of Ti and Nb.

Novel thermoelectric properties of complex transition-metal oxides.

PubMed

Terasaki, Ichiro; Iwakawa, Manabu; Nakano, Tomohito; Tsukuda, Akira; Kobayashi, Wataru

2010-01-28

We report how the thermopower of complex transition-metal oxides is susceptible to small changes in material parameters. In the A-site ordered perovskite oxide R(2/3)Cu(3)Ti(3.6)Ru(0.4)O(12), the thermopower changes from 15 to -100 microV K(-1) at 300 K in going from R = La to Er. We associate this with the hybridization between Cu 3d and Ru 4d electrons, which depends on R. For stronger hybridization, the Cu 3d electrons become more itinerant leading to positive thermopower. In the A-site ordered perovskite cobalt oxide Sr(3)YCo(4)O(10.5), the spin state of the Co(3+) ions determines the magnitude of the thermopower, where partial isovalent substitution (Ca for Sr and Rh for Co) enhances the thermopower whilst keeping the resistivity intact. These substitutions stabilize the low spin state of the Co(3+) ions, which affects the thermopower through the entropy of the background for the carriers. We propose that the control of the magnetism plays a pivotal role in determining the thermopower in a certain class of complex oxides.

Evaluation of the tratment of metal-EDTA complexes using Ti0{sub 2} photocatalysis

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

Madden, T.; Datyte, A.K.; Prairie, M.R.

1996-03-01

This study has demonstrated the feasibility of TiO{sub 2} photocatalysis to treat EDTA and several metal-EDTA complexes that can be found in industrial wastewaters. For the EDTA complexes of metals capable of photodeposition, such as Cu and Pb, certain reaction conditions were shown to facilitate the simultaneous complex degradation and photodeposition of these metals onto the catalyst. With metals that do not easily photodeposit, such as Ni and Cd, it is shown that the complex degradation is still facilitated, and can enhance other metals removal processes after photocatalytic treatment. Because the treatment of these metal-EDTA complexes typically requires special measures,more » there may exist situations where TiO{sub 2} photocatalysis could actually be the preferred method of treatment. However, its use should be compared economically to other more established advanced oxidation technologies. This necessity is demonstrated in the economic comparison to ozone treatment for EDTA degradation alone, where ozone treatment appears to be the clear choice in this application.« less

Effect of surface oxidation on thermomechanical behavior of NiTi shape memory alloy wire

NASA Astrophysics Data System (ADS)

Ng, Ching Wei; Mahmud, Abdus Samad

2017-12-01

Nickel titanium (NiTi) alloy is a unique alloy that exhibits special behavior that recovers fully its shape after being deformed to beyond elastic region. However, this alloy is sensitive to any changes of its composition and introduction of inclusion in its matrix. Heat treatment of NiTi shape memory alloy to above 600 °C leads to the formation of the titanium oxide (TiO2) layer. Titanium oxide is a ceramic material that does not exhibit shape memory behaviors and possess different mechanical properties than that of NiTi alloy, thus disturbs the shape memory behavior of the alloy. In this work, the effect of formation of TiO2 surface oxide layer towards the thermal phase transformation and stress-induced deformation behaviors of the NiTi alloy were studied. The NiTi wire with composition of Ti-50.6 at% Ni was subjected to thermal oxidation at 600 °C to 900 °C for 30 and 60 minutes. The formation of the surface oxide layers was characterized by using the Scanning Electron Microscope (SEM). The effect of surface oxide layers with different thickness towards the thermal phase transformation behavior was studied by using the Differential Scanning Calorimeter (DSC). The effect of surface oxidation towards the stress-induced deformation behavior was studied through the tensile deformation test. The stress-induced deformation behavior and the shape memory recovery of the NiTi wire under tensile deformation were found to be affected marginally by the formation of thick TiO2 layer.

Experimental Verification of the Decomposition of Y2O3 in Fe-Based ODS Alloys During Mechanical Alloying Process

NASA Astrophysics Data System (ADS)

Byun, Jong Min; Park, Chun Woong; Do Kim, Young

2018-06-01

In this study, we investigated the state of Y2O3, as a major additive element in Fe-based ODS alloys, during mechanical alloying (MA) processes by thermodynamic approaches and experimental verification. For this purpose, we introduced Ti2O3 that formed different reaction products depending on the state of Y2O3 into the Fe-based ODS alloys. In addition, the reaction products of Ti2O3, Y, and Y2O3 powders were predicted approximately based on their formation enthalpy. The experimental results relating to the formation of Y-based complex oxides revealed that YTiO3 and Y2Ti2O7 were formed when Ti2O3 reacted with Y; in contrast, only Y2Ti2O7 was detected during the reaction between Ti2O3 and Y2O3. In the alloy of Fe-Cr-Y2O3 with Ti2O3, YTiO3 (formed by the reaction of Ti2O3 with Y) was detected after the MA and heat treatment processes were complete, even though Y2O3 was present in the system. Using these results, it was proved that Y2O3 decomposed into monoatomic Y and O during the MA process.

Effect of yttrium on martensite-austenite phase transformation temperatures and high temperature oxidation kinetics of Ti-Ni-Hf high-temperature shape memory alloys

NASA Astrophysics Data System (ADS)

Kim, Jeoung Han; Kim, Kyong Min; Yeom, Jong Taek; Young, Sung

2016-03-01

The effect of yttrium (< 5.5 at%) on the martensite-austenite phase transformation temperatures, microstructural evolution, and hot workability of Ti-Ni-Hf high-temperature shape memory alloys is investigated. For these purposes, differential scanning calorimetry, hot compression, and thermo-gravimetric tests are conducted. The phase transformation temperatures are not noticeably influenced by the addition of yttrium up to 4.5 at%. Furthermore, the hot workability is not significantly affected by the yttrium addition up to 1.0 at%. However, when the amount of yttrium addition exceeds 1.0 at%, the hot workability deteriorates significantly. In contrast, remarkable improvement in the high temperature oxidation resistance due to the yttrium addition is demonstrated. The total thickness of the oxide layers is substantially thinner in the Y-added specimen. In particular, the thickness of (Ti,Hf) oxide layer is reduced from 200 µm to 120 µm by the addition of 0.3 at% Y.

Elemental Mercury Oxidation over Fe-Ti-Mn Spinel: Performance, Mechanism, and Reaction Kinetics.

PubMed

Xiong, Shangchao; Xiao, Xin; Huang, Nan; Dang, Hao; Liao, Yong; Zou, Sijie; Yang, Shijian

2017-01-03

The design of a high-performance catalyst for Hg 0 oxidation and predicting the extent of Hg 0 oxidation are both extremely limited due to the uncertainties of the reaction mechanism and the reaction kinetics. In this work, Fe-Ti-Mn spinel was developed as a high-performance catalyst for Hg 0 oxidation, and the reaction mechanism and the reaction kinetics of Hg 0 oxidation over Fe-Ti-Mn spinel were studied. The reaction orders of Hg 0 oxidation over Fe-Ti-Mn spinel with respect to gaseous Hg 0 concentration and gaseous HCl concentration were approximately 1 and 0, respectively. Therefore, Hg 0 oxidation over Fe-Ti-Mn spinel mainly followed the Eley-Rideal mechanism (i.e., the reaction of gaseous Hg 0 with adsorbed HCl), and the rate of Hg 0 oxidation mainly depended on Cl • concentration on the surface. As H 2 O, SO 2 , and NO not only inhibited Cl • formation on the surface but also interfered with the interface reaction between gaseous Hg 0 and Cl • on the surface, Hg 0 oxidation over Fe-Ti-Mn spinel was obviously inhibited in the presence of H 2 O, SO 2 , and NO. Furthermore, the extent of Hg 0 oxidation over Fe-Ti-Mn spinel can be predicted according to the kinetic parameter k E-R , and the predicted result was consistent with the experimental result.

Formation of thick stratiform Fe-Ti oxide layers in layered intrusion and frequent replenishment of fractionated mafic magma: Evidence from the Panzhihua intrusion, SW China

NASA Astrophysics Data System (ADS)

Song, Xie-Yan; Qi, Hua-Wen; Hu, Rui-Zhong; Chen, Lie-Meng; Yu, Song-Yue; Zhang, Jia-Fei

2013-03-01

Panzhihua intrusion is one of the largest layered intrusions that hosts huge stratiform Fe-Ti oxide layers in the central part of the Emeishan large igneous province, SW China. Up to 60 m thick stratiform massive Fe-Ti oxide layers containing 85 modal% of magnetite and ilmenite and overlying magnetite gabbro compose cyclic units of the Lower Zone of the intrusion. The cyclic units of the Middle Zone consist of magnetite gabbro and overlying gabbro. In these cyclic units, contents of Fe2O3(t), TiO2 and Cr and Fe3+/Ti4+ ratio of the rocks decrease upward, Cr content of magnetite and forsterite percentage of olivine decrease as well. The Upper Zone consists of apatite gabbro characterized by enrichment of incompatible elements (e.g., 12-18 ppm La, 20-28 ppm Y) and increasing of Fe3+/Ti4+ ratio (from 1.3 to 2.3) upward. These features indicate that the Panzhihua intrusion was repeatedly recharged by more primitive magma and evolved magmas had been extracted. Calculations using MELTS indicate that extensive fractionation of olivine and clinopyroxene in deep level resulted in increasing Fe and Ti contents in the magma. When these Fe-Ti-enriched magmas were emplaced along the base of the Panzhihua intrusion, Fe-Ti oxides became an early crystallization phase, leading to a residual magma of lower density. We propose that the unusually thick stratiform Fe-Ti oxide layers resulted from coupling of gravity settling and sorting of the crystallized Fe-Ti oxides from Fe-Ti-enriched magmas and frequent magma replenishment along the floor of the magma chamber.

Microstructure and Oxidation of (La,Sr)CrO3-Added Ti3SiC2 Composites.

PubMed

Lee, Dong Bok

2015-11-01

Composites of Ti3SiC2-(10, 20, 40)wt% La0.8Sr0.2CrO3 were synthesized by hot pressing powders of Ti3SiC2 and La0.8Sr0.2CrO3. These powders reacted to form stable TiC carbides and LaTiO3, Cr2Ti4O11, La2O3, and SrCrO4 oxides during hot pressing. The composites consisted primarily of a fine TiC-rich matrix phase and coarse Ti3SiC2 dispersoids. The addition of oxidation-immune La0.8Sr0.2CrO3 into Ti3SiC2 increased the oxidation rate because TiC formed during hot pressing. During oxidation of the composites at 800-1000 degrees C for 100 h in air, Ti diffused outward to form an outer rutile-TiO2 layer, and oxygen transported inward to form an inner oxide layer.

Fabrication of band gap engineered nanostructured tri-metallic (Mn-Co-Ti) oxide thin films

NASA Astrophysics Data System (ADS)

Mansoor, Muhammad Adil; Yusof, Farazila Binti; Nay-Ming, Huang

2018-04-01

In continuation of our previous studies on photoelectrochemical (PEC) properties of titanium based composite oxide thin films, an effort is made to develop thin films of 1:1:2 manganese-cobalt-titanium oxide composite, Mn2O3-Co2O3-4TiO2 (MCT), using Co(OAc)2 and a bimetallic manganese-titanium complex, [Mn2Ti4(TFA)8(THF)6(OH)4(O)2].0.4THF (1), where OAc = acetato, TFA = trifluoroacetato and THF = tetrahydrofuran, via aerosol-assisted chemical vapour deposition (AACVD) technique. The X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM) and energy dispersive X-ray (EDX) spectroscopic analyses confirmed formation of thin film of Mn2O3-Co2O3-4TiO2 composite material with uniformly distributed agglomerated particles. The average size of 39.5 nm, of the particles embedded inside agglomerates, was estimated by Scherer's equation. Further, UV-Vis spectroscopy was used to estimate the band gap of 2.62 eV for MCT composite thin film.

Comparison study on photocatalytic oxidation of pharmaceuticals by TiO2-Fe and TiO2-reduced graphene oxide nanocomposites immobilized on optical fibers.

PubMed

Lin, Lu; Wang, Huiyao; Jiang, Wenbin; Mkaouar, Ahmed Radhi; Xu, Pei

2017-07-05

Incorporating reduced graphene oxide (rGO) or Fe 3+ ions in TiO 2 photocatalyst could enhance photocatalytic degradation of organic contaminants in aqueous solutions. This study characterized the photocatalytic activities of TiO 2 -Fe and TiO 2 -rGO nanocomposites immobilized on optical fibers synthesized by polymer assisted hydrothermal deposition method. The photocatalysts presented a mixture phase of anatase and rutile in the TiO 2 -rGO and TiO 2 -Fe nanocomposites. Doping Fe into TiO 2 particles (2.40eV) could reduce more band gap energy than incorporating rGO (2.85eV), thereby enhancing utilization efficiency of visible light. Incorporating Fe and rGO in TiO 2 decreased significantly the intensity of TiO 2 photoluminescence signals and enhanced the separation rate of photo-induced charge carriers. Photocatalytic performance of the synthesized nanocomposites was measured by the degradation of three pharmaceuticals under UV and visible light irradiation, including carbamazepine, ibuprofen, and sulfamethoxazole. TiO 2 -rGO exhibited higher photocatalytic activity for the degradation of pharmaceuticals under UV irradiation, while TiO 2 -Fe demonstrated more suitable for visible light oxidation. The results suggested that the enhanced photocatalytic performance of TiO 2 -rGO could be attributed to reduced recombination rate of photoexcited electrons-hole pairs, but for TiO 2 -Fe nanocomposite, narrower band gap would contribute to increased photocatalytic activity. Copyright © 2017 Elsevier B.V. All rights reserved.

Evolution and Control of Electronic Structures near the Interface of Complex Oxide Heterostructure SmTiO3/SrTiO3

NASA Astrophysics Data System (ADS)

Mori, Ryo; Marshall, Patrick; Isaac, Brandon; Denlinger, Jonathan; Stemmer, Susanne; Lanzara, Alessandra

The confined electron system in the quantum well of the transition metal oxide, SrTiO3, embedded in the rare earth titanate, SmTiO3, shows unique properties, such as high carrier density, fermi liquid to non-fermi liquid transition, and pseudo-gap, which can be controlled by changing the shape of the quantum well. We will present a distinct difference in the electronic structures between the different quantum well structures obtained by angle-resolved photoemission spectroscopy (ARPES) measurements, suggesting the possibility to control the orbital character and the electron correlation near the interface as well as carrier density. The work was supported by the Quantum Materials Program at LBNL, funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Materials Sciences and Engineering Division, under Contract No. DE-AC02-05CH11231.

Stoichiometry control of complex oxides by sequential pulsed-laser deposition from binary-oxide targets

DOE PAGES

Herklotz, Andreas; Dorr, Kathrin; Ward, Thomas Zac; ...

2015-04-03

To have precise atomic layer control over interfaces, we examine the growth of complex oxides through the sequential deposition from binary targets by pulsed laser deposition. In situ reflection high-energy electron diffraction (RHEED) is used to control the growth and achieve films with excellent structural quality. The growth from binary oxide targets is fundamentally different from single target growth modes and shows more similarities to shuttered growth by molecular beam epitaxy. The RHEED intensity oscillations of non-stoichiometric growth are consistent with a model of island growth and accumulation of excess material on the surface that can be utilized to determinemore » the correct stoichiometry for growth. Correct monolayer doses can be determined through an envelope frequency in the RHEED intensity oscillations. In order to demonstrate the ability of this growth technique to create complex heterostructures, the artificial n = 2 and 3 Sr n+1Ti nO 3 n+1 Ruddlesden-Popper phases are grown with good long-range order. Furthermore, this method enables the precise unit-cell level control over the structure of perovskite-type oxides, and thus the growth of complex materials with improved structural quality and electronic functionality.« less

Stable Water Oxidation in Acid Using Manganese-Modified TiO2 Protective Coatings.

PubMed

Siddiqi, Georges; Luo, Zhenya; Xie, Yujun; Pan, Zhenhua; Zhu, Qianhong; Röhr, Jason A; Cha, Judy J; Hu, Shu

2018-06-06

Accomplishing acid-stable water oxidation is a critical matter for achieving both long-lasting water-splitting devices and other fuel-forming electro- and photocatalytic processes. Because water oxidation releases protons into the local electrolytic environment, it becomes increasingly acidic during device operation, which leads to corrosion of the photoactive component and hence loss in device performance and lifetime. In this work, we show that thin films of manganese-modified titania, (Ti,Mn)O x , topped with an iridium catalyst, can be used in a coating stabilization scheme for acid-stable water oxidation. We achieved a device lifetime of more than 100 h in pH = 0 acid. We successfully grew (Ti,Mn)O x coatings with uniform elemental distributions over a wide range of manganese compositions using atomic layer deposition (ALD), and using X-ray photoelectron spectroscopy, we show that (Ti,Mn)O x films grown in this manner give rise to closer-to-valence-band Fermi levels, which can be further tuned with annealing. In contrast to the normally n-type or intrinsic TiO 2 coatings, annealed (Ti,Mn)O x films can make direct charge transfer to a Fe(CN) 6 3-/4- redox couple dissolved in aqueous electrolytes. Using the Fe(CN) 6 3-/4- redox, we further demonstrated anodic charge transfer through the (Ti,Mn)O x films to high work function metals, such as iridium and gold, which is not previously possible with ALD-grown TiO 2 . We correlated changes in the crystallinity (amorphous to rutile TiO 2 ) and oxidation state (2+ to 3+) of the annealed (Ti,Mn)O x films to their hole conductivity and electrochemical stability in acid. Finally, by combining (Ti,Mn)O x coatings with iridium, an acid-stable water-oxidation anode, using acid-sensitive conductive fluorine-doped tin oxides, was achieved.

Synthesis of nitrosobenzene via photocatalytic oxidation of aniline over MgO/TiO2 under visible light irradiation

NASA Astrophysics Data System (ADS)

Chen, Jinsong; Xiong, Jinhua; Song, Yujie; Yu, Yan; Wu, Ling

2018-05-01

MgO/TiO2 (Degussa P25 TiO2) composites were prepared and were used as visible-light-driven photocatalysts for the oxidation of aniline to nitrosobenzene under oxygen atmosphere. The typical sample with 5 wt% MgO loaded P25 (MP5) shows comparable photocatalytic activity with 2 wt% Pt/P25. The analyzed results of XPS indicate that the lattice oxygen in the MP5 possess higher electron density than those in P25. The electron-rich lattice oxygen, formed as a result of MgO loaded, would facilitate the deprontonation of aniline. A new peak at 3310 cm-1 was observed in in-situ FTIR spectrum for aniline adsorbed on the sample MP5, suggesting that anilino species were formed. These species may be produced via the deprontonation of aniline and result in the formation of the surface complexes. Further XPS studies for aniline adsorbed on the catalysts also indicate the existence of the surface complexes. Under visible light irradiation, the electrons may excite from the surface complexes and initiate the oxidation processes. Finally, speculated photocatalytic processes for the oxidation of aniline to nitrosobenzene were proposed at molecular level.

Spin-polarized two-dimensional electron gas at GdTi O3/SrTi O3 interfaces: Insight from first-principles calculations

NASA Astrophysics Data System (ADS)

Betancourt, J.; Paudel, T. R.; Tsymbal, E. Y.; Velev, J. P.

2017-07-01

Two-dimensional electron gases (2DEGs) at oxide interfaces have been a topic of intensive research due to their high carrier mobility and strong confinement. Additionally, strong correlations in the oxide materials can give rise to new and interesting physics, such as magnetism and metal-insulator transitions at the interface. Using first-principles calculations based on density functional theory, we demonstrate the presence of a highly spin-polarized 2DEG at the interface between the Mott insulator GdTi O3 and a band insulator SrTi O3 . The strong correlations in the dopant cause ferromagnetic alignment of the interface Ti atoms and result in a fully spin-polarized 2DEG. The 2DEG consists of two types of carriers distinguished by their orbital character. The majority of the interface charge is strongly localized on the Ti dx y orbitals at the interface and a smaller fraction resides on the delocalized Ti dx z ,y z states.

Hierarchical FeTiO3-TiO2 hollow spheres for efficient simulated sunlight-driven water oxidation.

PubMed

Han, Taoran; Chen, Yajie; Tian, Guohui; Wang, Jian-Qiang; Ren, Zhiyu; Zhou, Wei; Fu, Honggang

2015-10-14

Oxygen generation is the key step for the photocatalytic overall water splitting and considered to be kinetically more challenging than hydrogen generation. Here, an effective water oxidation catalyst of hierarchical FeTiO3-TiO2 hollow spheres are prepared via a two-step sequential solvothermal processes and followed by thermal treatment. The existence of an effective heterointerface and built-in electric field in the surface space charge region in FeTiO3-TiO2 hollow spheres plays a positive role in promoting the separation of photoinduced electron-hole pairs. Surface photovoltage, transient-state photovoltage, fluorescence and electrochemical characterization are used to investigate the transfer process of photoinduced charge carriers. The photogenerated charge carriers in the hierarchical FeTiO3-TiO2 hollow spheres with a proper molar ratio display much higher separation efficiency and longer lifetime than those in the FeTiO3 alone. Moreover, it is suggested that the hierarchical porous hollow structure can contribute to the enhancement of light utilization, surface active sites and material transportation through the framework walls. This specific synergy significantly contributes to the remarkable improvement of the photocatalytic water oxidation activity of the hierarchical FeTiO3-TiO2 hollow spheres under simulated sunlight (AM1.5).

Effects of substrate microstructure on the formation of oriented oxide nanotube arrays on Ti and Ti alloys

NASA Astrophysics Data System (ADS)

Ferreira, C. P.; Gonçalves, M. C.; Caram, R.; Bertazzoli, R.; Rodrigues, C. A.

2013-11-01

The formation of nanotubular oxide layers on Ti and Ti alloys has been widely investigated for the photocatalytic degradation of organic compounds due to their excellent catalytic efficiency, chemical stability, and low cost and toxicity. Aiming to improve the photocatalytic efficiency of this nanostructured oxide, this work investigated the influence of substrate grain size on the growth of nanotubular oxide layers. Ti and Ti alloys (Ti-6Al, Ti-6Al-7Nb) were produced by arc melting with non-consumable tungsten electrode and water-cooled copper hearth under argon atmosphere. Some of the ingots were heat-treated at 1000 °C for 12 and 24 h in argon atmosphere, followed by slow cooling rates to reduce crystalline defects and increase the grain size of their microstructures. Three types of samples were anodized: commercial substrate, as-prepared and heat-treated samples. The anodization was performed using fluoride solution and a cell potential of 20 V. The samples were characterized by optical microscopy, field-emission scanning electron microscopy and X-ray diffraction. The heat treatment preceding the anodization process increased the grain size of pure Ti and Ti alloys and promoted the formation of Widmanstätten structures in Ti6Al7Nb. The nanotubes layers grown on smaller grain and thermally untreated samples were more regular and homogeneous. In the case of Ti-6Al-7Nb alloy, which presents a α + β phase microstructure, the morphology of nanotubes nucleated on α matrix was more regular than those of nanotubes nucleated on β phase. After the annealing process, the Ti-6Al-7Nb alloy presented full diffusion process and the growth of equilibrium phases resulting in the appearance of regions containing higher concentrations of Nb, i.e. beta phase. In those regions the dissolution rate of Nb2O5 is lower than that of TiO2, resulting in a nanoporous layer. In general, heat treating reduces crystalline defects and promotes the increasing of the grain sizes, not

Ferrate(VI) enhanced photocatalytic oxidation of pollutants in aqueous TiO2 suspensions.

PubMed

Sharma, Virender K; Graham, Nigel J D; Li, Xiang-Zhong; Yuan, Bao-Ling

2010-02-01

ferrate/photocatalysis system. In the study of microcystin-LR, it was evident that an optimal ferrate concentration exists, whereby higher Fe(VI) concentrations above the optimum leads to a reduction in microcystin-LR degradation. In addition, the rate of microcystin-LR degradation was found to be strongly dependent on pH and was greatest at pH 6. The initial rate of photocatalytic reduction under different conditions was analysed using a Langmuirian form. Decrease in rates in the presence of dissolved oxygen may be due to competition between oxygen and ferrate as electron scavengers and to non-productive radical species interactions. The reaction between ferrate(VI) and microcystins-LR in the pH range of 6.0-10.0 is most likely controlled by the protonated Fe(VI) species, HFeO(4)(-). The photocatalytic oxidation of selected, recalcitrant contaminants was found to be significantly greater in the presence of ferrate, arising from the role of ferrate in inhibiting the h(vb)(+)-e(-)(cb) pair recombination on TiO(2) surfaces and the corresponding generation of highly oxidative Fe(V) species. The performance of the ferrate/photocatalysis system is strongly influenced by the reaction conditions, particularly the pH and dissolved oxygen concentration, arising from the complex nature of the interactions between the catalyst and the solution. Overall, the treatment performance of the Fe(VI)-TiO(2)-UV system is generally superior to alternative chemical oxidation methods. The formation of intermediate Fe(V) species in the photocatalytic reduction of ferrate(VI) requires confirmation, and a method involving electron paramagnetic resonance spectroscopy could be applied for this. The reactivity of Fe(V) with the selected contaminants is required in order to better understand the role of ferrate in the Fe(VI)-TiO(2)-UV oxidation system. To increase the practical utility of the system, it is recommended that future studies involving the photocatalytic oxidation of pollutants in the

Zeolite Y encapsulated with Fe-TiO2 for ultrasound-assisted degradation of amaranth dye in water.

PubMed

Alwash, Atheel Hassan; Abdullah, Ahmad Zuhairi; Ismail, Norli

2012-09-30

A new heterogeneous catalyst for sonocatalytic degradation of amaranth dye in water was synthesized by introducing titania into the pores of zeolite (NaY) through ion exchange method while Fe (III) was immobilized on the encapsulated titanium via impregnation method. XRD results could not detect any peaks for titanium oxide or Fe(2)O(3) due to its low loading. The UV-vis analysis proved a blue shift toward shorter wavelength after the loading of Ti into NaY while a red shift was detected after the loading of Fe into the encapsulated titanium. Different reaction variables such as TiO(2) content, amount of Fe, pH values, amount of hydrogen peroxide, catalyst loading and the initial dye concentration were studied to estimate their effect on the decolorization efficiency of amaranth. The maximum decolorization efficiency achieved was 97.5% at a solution pH of 2.5, catalyst dosage of 2 g/L, 20 mmol/100 mL of H(2)O(2) and initial dye concentration of 10 mg/L. The new heterogeneous catalyst Fe/Ti-NaY was a promising catalyst for this reaction and showed minimum Fe leaching at the end of the reaction. Copyright © 2012 Elsevier B.V. All rights reserved.

The Reactivity and Structure of Size Selected VxO y Clusters on a TiO2 (110)-(1 X 1) Surface of Variable Oxidation State

NASA Astrophysics Data System (ADS)

Neilson, Hunter L.

The Reactivity and Structure of Size Selected VxOy Clusters on a TiO2 (110) Surface of Variable Oxidation State by Hunter L Neilson The selective oxidative dehydrogenation of methanol by vanadium oxide/TiO2 model systems has received a great deal of interest in the surface science community. Previous studies using temperature programmed desorption and reaction (TPD/R) to probe the oxidation of methanol to formaldehyde by vanadia/TiO2 model catalysts have shown that the activity of these systems vary considerably based on the way in which the model system is prepared with formaldehyde desorption temperatures observed anywhere from room temperature to 660 K. The principle reason for this variation is that the preparation of sub-monolayer films of vanadia on TiO2 produces clusters with a multitude of VxOy structures and a mixture of vanadium oxidation states. As a result the stoichiometry of the active vanadium oxide catalyst as well as the oxidation state of vanadium in the active catalyst remain unknown. To better understand this system, our group has probed the reactivity and structure of size-selected Vx, VOy and VxOy clusters on a reduced TiO2 (110) support in ultra-high vacuum (UHV) via TPD/R and scanning tunneling microscopy (STM). Ex situ preparation of these clusters in the gas phase prior to deposition has allowed us to systematically vary the stoichiometry of the vanadia clusters; a layer of control not available via the usual routes to vanadium oxide. The most active catalysts are shown to have (VO3)n stoichiometry in agreement with the theoretical models of the Metiu group. We have shown that both the activity and selectivity of V2O6 and V3O9 cluster catalysts depend sensitively on the oxidation state of the TiO2 (110) support. For example, V2O6 on a reduced surface is selective for the oxidation of methanol to formaldehyde while the selectivity shifts to favor methyl formate as the surface becomes increasingly oxidized. STM studies show that the

Influence of temperature on oxidation mechanisms of fiber-textured AlTiTaN coatings.

PubMed

Khetan, Vishal; Valle, Nathalie; Duday, David; Michotte, Claude; Delplancke-Ogletree, Marie-Paule; Choquet, Patrick

2014-03-26

The oxidation kinetics of AlTiTaN hard coatings deposited at 265 °C by DC magnetron sputtering were investigated between 700 and 950 °C for various durations. By combining dynamic secondary ion mass spectrometry (D-SIMS), X-ray diffraction (XRD), and transmission electron microscopy (TEM) investigations of the different oxidized coatings, we were able to highlight the oxidation mechanisms involved. The TEM cross-section observations combined with XRD analysis show that a single amorphous oxide layer comprising Ti, Al, and Ta formed at 700 °C. Above 750 °C, the oxide scale transforms into a bilayer oxide comprising an Al-rich upper oxide layer and a Ti/Ta-rich oxide layer at the interface with the coated nitride layer. From the D-SIMS analysis, it could be proposed that the oxidation mechanism was governed primarily by inward diffusion of O for temperatures of ≤700 °C, while at ≥750 °C, it is controlled by outward diffusion of Al and inward diffusion of O. Via a combination of structural and chemical analysis, it is possible to propose that crystallization of rutile lattice favors the outward diffusion of Al within the AlTiTa mixed oxide layer with an increase in the temperature of oxidation. The difference in the mechanisms of oxidation at 700 and 900 °C also influences the oxidation kinetics with respect to oxidation time. Formation of a protective alumina layer decreases the rate of oxidation at 900 °C for long durations of oxidation compared to 700 °C. Along with the oxidation behavior, the enhanced thermal stability of AlTiTaN compared to that of the TiAlN coating is illustrated.

Electrochemical oxidation of 2,4,5-trichlorophenoxyacetic acid by metal-oxide-coated Ti electrodes.

PubMed

Maharana, Dusmant; Xu, Zesheng; Niu, Junfeng; Rao, Neti Nageswara

2015-10-01

Electrochemical oxidation of 2,4,5-trichlorophenoxyacetic acid (2,4,5-T) over metal-oxide-coated Ti anodes, i.e., Ti/SnO2-Sb/Ce-PbO2, Ti/SnO2-Sb and Ti/RuO2, was examined. The degradation efficiency of over 90% was attained at 20 min at different initial concentrations (0.5-20 mg L(-1)) and initial pH values (3.1-11.2). The degradation efficiencies of 2,4,5-T on Ti/SnO2-Sb/Ce-PbO2, Ti/SnO2-Sb and Ti/RuO2 anodes were higher than 99.9%, 97.2% and 91.5% at 30 min, respectively, and the respective total organic carbon removal ratios were 65.7%, 54.6% and 37.2%. The electrochemical degradation of 2,4,5-T in aqueous solution followed pseudo-first-order kinetics. The compounds, i.e., 2,5-dichlorohydroquinone and 2,5-dihydroxy-p-benzoquinone, have been identified as the main aromatic intermediates by liquid chromatography-mass spectrometry. The results showed that the energy efficiencies of 2,4,5-T (20 mg L(-1)) degradation with Ti/SnO2-Sb/Ce-PbO2 anode at the optimal current densities from 2 to 16 mA cm(-2) ranged from 8.21 to 18.73 kWh m(-3). Copyright © 2015 Elsevier Ltd. All rights reserved.

Oxidation Kinetics of a NiPtTi High Temperature Shape Memory Alloy

NASA Technical Reports Server (NTRS)

Smialek, James L.; Humphrey, Donald L.; Noebe, Ronald D.

2007-01-01

A high temperature shape memory alloy (HTSMA), Ni30Pt50Ti, with an M(sub s) near 600 C, was isothermally oxidized in air for 100 hr over the temperature range of 500 to 900 C. Parabolic kinetics were confirmed by log-log and parabolic plots and showed no indication of fast transient oxidation. The overall behavior could be best described by the Arrhenius relationship: k(sub p) = 1.64 x 10(exp 12)[(-250 kJ/mole)/RT] mg(sup 2)/cm(sup 4)hr. This is about a factor of 4 reduction compared to values measured here for a binary Ni47Ti commercial SMA. The activation energy agreed with most literature values for TiO2 scale growth measured for elemental Ti and other NiTi alloys. Assuming uniform alloy depletion of a 20 mil (0.5 mm) dia. HTSMA wire, approx. 1 percent Ti reduction is predicted after 20,000 hr oxidation at 500 C, but becomes much more serious at higher temperatures.

High- T c superconductivity at the interface between the CaCuO 2 and SrTiO 3 insulating oxides

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

Di Castro, D.; Cantoni, C.; Ridolfi, F.

2015-09-28

At interfaces between complex oxides it is possible to generate electronic systems with unusual electronic properties, which are not present in the isolated oxides. One important example is the appearance of superconductivity at the interface between insulating oxides, although, until now, with very low T c. We report the occurrence of high T c superconductivity in the bilayer CaCuO 2/SrTiO 3, where both the constituent oxides are insulating. In order to obtain a superconducting state, the CaCuO 2/SrTiO 3 interface must be realized between the Ca plane of CaCuO 2 and the TiO 2 plane of SrTiO 3. Only inmore » this case can oxygen ions be incorporated in the interface Ca plane, acting as apical oxygen for Cu and providing holes to the CuO 2 planes. In addition, a detailed hole doping spatial profile can be obtained by scanning transmission electron microscopy and electron-energy-loss spectroscopy at the O K edge, clearly showing that the (super)conductivity is confined to about 1–2 CaCuO 2 unit cells close to the interface with SrTiO 3. The results obtained for the CaCuO 2/SrTiO 3 interface can be extended to multilayered high T c cuprates, contributing to explaining the dependence of T c on the number of CuO 2 planes in these systems.« less

Electrolytic Production of Ti5Si3/TiC Composites by Solid Oxide Membrane Technology

NASA Astrophysics Data System (ADS)

Zheng, Kai; Zou, Xingli; Xie, Xueliang; Lu, Changyuan; Chen, Chaoyi; Xu, Qian; Lu, Xionggang

2017-12-01

This paper investigated the electrolytic production of Ti5Si3/TiC composites from TiO2/SiO2/C in molten CaCl2. The solid-oxide oxygen-ion-conducting membrane tube filled with carbon-saturated liquid tin was served as the anode, and the pressed spherical TiO2/SiO2/C pellet was used as the cathode. The electrochemical reduction process was carried out at 1273 K and 3.8 V. The characteristics of the obtained cathode products and the reaction mechanism of the electroreduction process were studied by a series of time-dependent electroreduction experiments. It was found that the electroreduction process generally proceeds through the following steps: TiO2/SiO2/C → Ti2O3, CaTiO3, Ca2SiO4, SiC → Ti5Si3, TiC. The morphology observation and the elemental distribution analysis indicate that the reaction routes for Ti5Si3 and TiC products are independent during the electroreduction process.

Electrolytic Production of Ti5Si3/TiC Composites by Solid Oxide Membrane Technology

NASA Astrophysics Data System (ADS)

Zheng, Kai; Zou, Xingli; Xie, Xueliang; Lu, Changyuan; Chen, Chaoyi; Xu, Qian; Lu, Xionggang

2018-02-01

This paper investigated the electrolytic production of Ti5Si3/TiC composites from TiO2/SiO2/C in molten CaCl2. The solid-oxide oxygen-ion-conducting membrane tube filled with carbon-saturated liquid tin was served as the anode, and the pressed spherical TiO2/SiO2/C pellet was used as the cathode. The electrochemical reduction process was carried out at 1273 K and 3.8 V. The characteristics of the obtained cathode products and the reaction mechanism of the electroreduction process were studied by a series of time-dependent electroreduction experiments. It was found that the electroreduction process generally proceeds through the following steps: TiO2/SiO2/C → Ti2O3, CaTiO3, Ca2SiO4, SiC → Ti5Si3, TiC. The morphology observation and the elemental distribution analysis indicate that the reaction routes for Ti5Si3 and TiC products are independent during the electroreduction process.

Microstructure/Oxidation/Microhardness Correlations in Gamma-Based and Tau-Based Al-Ti-Cr Alloys

NASA Technical Reports Server (NTRS)

Brady, Michael P.; Smialek, J. L.; Humphrey, D. L.

1994-01-01

The relationships between alloy microstructure and air oxidation kinetics and alloy microstructure and microhardness in the Al-Ti-Cr system for exposures at 800 C and 1000 C were investigated. The relevant phases were identified as tau (Ll2), gamma (LIO), r-Al2Ti, TiCrAl (laves), and Cr2AI. Protective alumina formation was associated with tau, Al-rich TiCrAl, and gamma/TiCrAl mixtures. Brittleness was associated with the TiCrAl phase and tau decomposition to A12Ti + Cr2AI. It was concluded that two-phase gamma + TiCrAl alloys offer the greatest potential for oxidation resistance and room temperature ductility in the Al-Ti-Cr system.

Occurrence and possible significance of rare Ti oxides (Magneli phases) in carbonaceous chondrite matrices

NASA Technical Reports Server (NTRS)

Brearley, Adrian J.

1993-01-01

Rare, ultrafine-grained Ti oxides (Ti3O5 and the Magneli phases, Ti5O9 and Ti8O15) have been identified by TEM in the CM2 carbonaceous chondrite, Bells, and a carbonaceous chondrite matrix clast from the Nilpena polymict ureilite. In both meteorites the Ti oxides occur in the matrix as isolated grains and clusters of two or more grains. They are euhedral in shape and have grain sizes of 0.05-0.3 micron. Magneli phases have been recently shown to be a common component in some interplanetary dust particles, but this is the first reported occurrence in a meteorite. The morphological properties and grain size of the Ti oxides are consistent with formation by vapor phase condensation either within the solar nebula or possibly in a presolar environment.

Stoichiometry control of complex oxides by sequential pulsed-laser deposition from binary-oxide targets

DOE PAGES

Herklotz, A.; Dörr, Kathrin; Ward, T. Z.; ...

2015-04-03

In this paper, to have precise atomic layer control over interfaces, we examine the growth of complex oxides through the sequential deposition from binary targets by pulsed laser deposition. In situ reflection high-energy electron diffraction (RHEED) is used to control the growth and achieve films with excellent structural quality. The growth from binary oxide targets is fundamentally different from single target growth modes and shows more similarities to shuttered growth by molecular beam epitaxy. The RHEED intensity oscillations of non-stoichiometric growth are consistent with a model of island growth and accumulation of excess material on the surface that can bemore » utilized to determine the correct stoichiometry for growth. Correct monolayer doses can be determined through an envelope frequency in the RHEED intensity oscillations. In order to demonstrate the ability of this growth technique to create complex heterostructures, the artificial n = 2 and 3 Sr n +1Ti n O 3 n +1 Ruddlesden-Popper phases are grown with good long-range order. Finally, this method enables the precise unit-cell level control over the structure of perovskite-type oxides, and thus the growth of complex materials with improved structural quality and electronic functionality.« less

Synthesis of [(Ca1-xSrx)2-2y](Ti2-2yLi2y)Si2yO6-y Ceramic and its Application in Efficient Plasma Decomposition of CO2

NASA Astrophysics Data System (ADS)

Li, Ruixing; Tang, Qing; Yin, Shu; Sato, Tsugio

According to both the first principle and materials chemistry, a method for fabricating [(Ca1-xSrx)2-2y](Ti2-2yLi2y)Si2yO6-y ceramic was investigated. It was considered that the sintering was promoted by self-accelerated diffusion due to the formation of point defects caused by doping with Li2Si2O5. Consequently, a concept of non-stoichiometrically activated sintering, which was enhanced by point defects without the help of a grain boundary phase, was systematically studied in the Ca1-xSrxTiO3-Li2Si2O5 system. The mechanical and dielectric properties of [(Ca1-xSrx)2-2y](Ti2-2yLi2y)Si2yO6-y were greatly enhanced by adding Li2Si2O5. To improve CO2 decomposition activity, [(Ca1-xSrx)2-2y](Ti2-2yLi2y)Si2yO6-y, which possesses both high permittivity and high dielectric strength was used as a dielectric barrier to decompose CO2 by dielectric barrier discharges (DBDs) plasma without using any catalyst and auxiliary substance. It successfully generated DBDs plasma and the CO2 conversion was much higher than that using an alumina or a silica glass barrier which was widely used as the dielectric barrier in previous studies.

Rapid synthesis of rutile TiO2 nano-flowers by dealloying Cu60Ti30Y10 metallic glasses

NASA Astrophysics Data System (ADS)

Wang, Ning; Pan, Ye; Wu, Shikai; Zhang, Enming; Dai, Weiji

2018-01-01

The 3D nanostructure rutile TiO2 photocatalyst was rapidly synthesized by dealloying method using Cu60Ti30Y10 amorphous ribbons as precursors. The preparation period was kept down to just 3 h, which is much shorter than those of the samples by dealloying Cu60Ti30Al10, Cu70Ti30 and Cu60Ti30Sn10. The synthesized sample was characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS). XRD and XPS reveal the successful synthesis of rutile TiO2. The SEM and TEM images show that the synthesized rutile TiO2 nano-material presents homogeneous distributed 3D nanoflowers structure, which is composed of large quantities of fine rice-like nanorods (40-150 nm in diameter and 100-250 nm in length). BET specific surface areas of the samples were investigated by N2 adsorption-desorption isotherms, the fabricated rutile TiO2 exhibits very high specific surface area (194.08 m2/g). The photocatalytic activities of the samples were evaluated by degrading rhodamine B (RhB) dye (10 mg/L) under the irradiation of both simulated visible light (λ > 420 nm) and ultraviolet (UV) light (λ = 365 nm). The results show that the photocatalytic activity of rutile TiO2 prepared by dealloying Cu60Ti30Y10 amorphous ribbons is higher than those of commercial rutile and the sample synthesized by dealloying Cu70Ti30 precursors. The advantages of both short preparation period and superior photocatalytic activity suggest that Cu60Ti30Y10 metallic glasses are really a kind of perfect titanium source for rapidly fabricating high efficient TiO2 nano-materials. In addition, the influence of chemical composition of the amorphous precursors on preparation period of the rutile TiO2 nano-material was investigated from the point of view of standard electrode potentials.

Evaluating tetracycline degradation pathway and intermediate toxicity during the electrochemical oxidation over a Ti/Ti4O7 anode.

PubMed

Wang, Jianbing; Zhi, Dan; Zhou, Hao; He, Xuwen; Zhang, Dayi

2018-06-15

Tetracycline (TC) is one of the most widely used antibiotics with significant impacts on human health and thus it needs appropriate approaches for its removal. In the present study, we evaluated the performance and complete pathway of the TC electrochemical oxidation on a Ti/Ti 4 O 7 anode prepared by plasma spraying. Morphological data and composition analysis indicated a compact coating layer on the anode, which had the characteristic peaks of Ti 4 O 7 as active constituent. The TC electrochemical oxidation on the Ti/Ti 4 O 7 anode followed a pseudo-first-order kinetics, and the TC removal efficiency reached 95.8% in 40 min. The influential factors on TC decay kinetics included current density, anode-cathode distance and initial TC concentration. This anode also had high durability and the TC removal efficiency was maintained over 95% after five times reuse. For the first time, we unraveled the complete pathway of the TC electrochemical oxidation using high-performance liquid chromatograph (HPLC) and gas chromatograph (GC) coupled with mass spectrometer (MS). ·OH radicals produced from electrochemical oxidation attack the double bond, phenolic group and amine group of TC, forming a primary intermediate (m/z = 461), secondary intermediates (m/z = 432, 477 and 509) and tertiary intermediates (m/z = 480, 448 and 525). The latter were further oxidized to the key downstream intermediate (m/z = 496), followed by further downstream intermediates (m/z = 451, 412, 396, 367, 351, 298 and 253) and eventually short-chain carboxylic acids. We also evaluated the toxicity change during the electrochemical oxidation process with bioluminescent bacteria. The bioluminescence inhibition ratio peaked at 10 min (55.41%), likely owing to the high toxicity of intermediates with m/z = 461, 432 and 477 as obtained from quantitative structure activity relationship (QSAR) analysis. The bioluminescence inhibition ratio eventually decreased to 16.78% in 40�

Heterobimetallic Ti/Co Complexes That Promote Catalytic N-N Bond Cleavage.

PubMed

Wu, Bing; Gramigna, Kathryn M; Bezpalko, Mark W; Foxman, Bruce M; Thomas, Christine M

2015-11-16

Treatment of the tris(phosphinoamide) titanium precursor ClTi(XylNP(i)Pr2)3 (1) with CoI2 leads to the heterobimetallic complex (η(2)-(i)Pr2PNXyl)Ti(XylNP(i)Pr2)2(μ-Cl)CoI (2). One-electron reduction of 2 affords (η(2)-(i)Pr2PNXyl)Ti(XylNP(i)Pr2)2CoI (3), which can be reduced by another electron under dinitrogen to generate the reduced diamagnetic complex (THF)Ti(XylNP(i)Pr2)3CoN2 (4). The removal of the dinitrogen ligand from 4 under vacuum affords (THF)Ti(XylNP(i)Pr2)3Co (5), which features a Ti-Co triple bond. Treatment of 4 with hydrazine or methyl hydrazine results in N-N bond cleavage and affords the new diamagnetic complexes (L)Ti(XylNP(i)Pr2)3CoN2 (L = NH3 (6), MeNH2 (7)). Complexes 4, 5, and 6 have been shown to catalyze the disproportionation of hydrazine into ammonia and dinitrogen gas through a mechanism involving a diazene intermediate.

High-temperature wear and oxidation behaviors of TiNi/Ti2Ni matrix composite coatings with TaC addition prepared on Ti6Al4V by laser cladding

NASA Astrophysics Data System (ADS)

Lv, Y. H.; Li, J.; Tao, Y. F.; Hu, L. F.

2017-04-01

TiNi/Ti2Ni matrix composite coatings were produced on Ti6Al4V surfaces by laser cladding the mixed powders of Ni-based alloy and different contents of TaC (0, 5, 10, 15, 20, 30 and 40 wt.%). Microstructures of the coatings were investigated. High-temperature wear tests of the substrate and the coatings were carried out at 600 °C in air for 30 min. High-temperature oxidation tests of the substrate and the coatings were performed at 1000 °C in air for 50 h. Wear and oxidation mechanisms were revealed in detail. The results showed that TiNi/Ti2Ni as the matrix and TiC/TiB2/TiB as the reinforcements are the main phases of the coatings. The friction coefficients of the substrate and the coatings with different contents of TaC were 0.431 (the substrate), 0.554 (0 wt.%), 0.486 (5 wt.%), 0.457 (10 wt.%), 0.458 (15 wt.%), 0.507 (20 wt.%), 0.462 (30 wt.%) and 0.488 (40 wt.%). The wear rates of the coatings were decreased by almost 83%-98% than that of the substrate and presented a decreasing tendency with increasing TaC content. The wear mechanism of the substrate was a combination of serious oxidation, micro-cutting and brittle debonding. For the coatings, oxidation and slight scratching were predominant during wear, accompanied by slight brittle debonding in partial zones. With the increase in content of TaC, the oxidation film better shielded the coatings from destruction due to the effective friction-reducing role of Ta2O5. The oxidation rates of the substrate and the coatings with different contents of TaC at 1000 °C were 12.170 (the substrate), 5.886 (0 wt.%), 4.937 (5 wt.%), 4.517 (10 wt.%), 4.394 (15 wt.%), 3.951 (20 wt.%), 4.239 (30 wt.%) and 3.530 (40 wt.%) mg2 cm-4 h-1, respectively. The oxidation film formed outside the coating without adding TaC was composed of TiO2, NiO, Cr2O3, Al2O3 and SiO2. When TaC was added, Ta2O5 and TaC were also detected, which effectively improved the oxidation resistance of the coatings. The addition of TaC contributed to the

Selective CO Production by Photoelectrochemical Methane Oxidation on TiO2.

PubMed

Li, Wei; He, Da; Hu, Guoxiang; Li, Xiang; Banerjee, Gourab; Li, Jingyi; Lee, Shin Hee; Dong, Qi; Gao, Tianyue; Brudvig, Gary W; Waegele, Matthias M; Jiang, De-En; Wang, Dunwei

2018-05-23

The inertness of the C-H bond in CH 4 poses significant challenges to selective CH 4 oxidation, which often proceeds all the way to CO 2 once activated. Selective oxidation of CH 4 to high-value industrial chemicals such as CO or CH 3 OH remains a challenge. Presently, the main methods to activate CH 4 oxidation include thermochemical, electrochemical, and photocatalytic reactions. Of them, photocatalytic reactions hold great promise for practical applications but have been poorly studied. Existing demonstrations of photocatalytic CH 4 oxidation exhibit limited control over the product selectivity, with CO 2 as the most common product. The yield of CO or other hydrocarbons is too low to be of any practical value. In this work, we show that highly selective production of CO by CH 4 oxidation can be achieved by a photoelectrochemical (PEC) approach. Under our experimental conditions, the highest yield for CO production was 81.9%. The substrate we used was TiO 2 grown by atomic layer deposition (ALD), which features high concentrations of Ti 3+ species. The selectivity toward CO was found to be highly sensitive to the substrate types, with significantly lower yield on P25 or commercial anatase TiO 2 substrates. Moreover, our results revealed that the selectivity toward CO also depends on the applied potentials. Based on the experimental results, we proposed a reaction mechanism that involves synergistic effects by adjacent Ti sites on TiO 2 . Spectroscopic characterization and computational studies provide critical evidence to support the mechanism. Furthermore, the synergistic effect was found to parallel heterogeneous CO 2 reduction mechanisms. Our results not only present a new route to selective CH 4 oxidation, but also highlight the importance of mechanistic understandings in advancing heterogeneous catalysis.

Preparation and photoelectrocatalytic performance of N-doped TiO2/NaY zeolite membrane composite electrode material.

PubMed

Cheng, Zhi-Lin; Han, Shuai

2016-01-01

A novel composite electrode material based on a N-doped TiO2-loaded NaY zeolite membrane (N-doped TiO2/NaY zeolite membrane) for photoelectrocatalysis was presented. X-ray diffraction (XRD), scanning electron microscopy (SEM), UV-visible (UV-vis) and X-ray photoelectron spectroscopy (XPS) characterization techniques were used to analyze the structure of the N-doped TiO2/NaY zeolite membrane. The XRD and SEM results verified that the N-doped TiO2 nanoparticles with the size of ca. 20 nm have been successfully loaded on the porous stainless steel-supported NaY zeolite membrane. The UV-vis result showed that the N-doped TiO2/NaY zeolite membrane exhibited a more obvious red-shift than that of N-TiO2 nanoparticles. The XPS characterization revealed that the doping of N element into TiO2 was successfully achieved. The photoelectrocatalysis performance of the N-doped TiO2/NaY zeolite membrane composite electrode material was evaluated by phenol removal and also the effects of reaction conditions on the catalytic performance were investigated. Owing to exhibiting an excellent catalytic activity and good recycling stability, the N-doped TiO2/NaY zeolite membrane composite electrode material was of promising application for photoelectrocatalysis in wastewater treatment.

Tetrahedral silsesquioxane-C2H2Ti complex for hydrogen storage

NASA Astrophysics Data System (ADS)

Konda, Ravinder; Tavhare, Priyanka; Ingale, Nilesh; Chaudhari, Ajay

2018-04-01

The interaction of molecular hydrogen with tetrahedral silsesquioxane (T4)-C2H2Ti complex has been studied using Density Functional Theory with M06-2X functional and MP2 method with 6-311++G** basis set. T4-C2H2Ti complex can absorb maximum five hydrogen molecules with the gravimetric hydrogen storage capacity of 3.4 wt %. Adsorption energy calculations show that H2 adsorption on T4-C2H2Ti complex is favorable at room temperature by both the methods. We have studied the effect of temperature and pressure on Gibbs free energy corrected adsorption energies. Molecular dynamics simulations for H2 adsorbed T4-C2H2Ti complex have also been performed at 300K and show that loosely bonded H2 molecule flies away within 1fs. Various interaction energies within the complex are studied. Stability of a complex is predicted by means of a gap between Highest Occupied Molecular Orbital (HUMO) and Lowest Unoccupied Molecular Orbital (LUMO). The H2 desorption temperature for T4-C2H2Ti complex is calculated with Van't Hoff equation and it is found to be 229K.

First-principles analysis of X-ray magnetic circular dichroism for transition metal complex oxides

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

Ikeno, Hidekazu, E-mail: h-ikeno@21c.osakafu-u.ac.jp

2016-10-14

X-ray magnetic circular dichroism (XMCD) is widely used for the characterization of magnetism of materials. However, information from XMCD related to the atomic, electronic, and magnetic structures is not fully utilized due to the lack of reliable theoretical tools for spectral analysis. In this work, the first-principles configuration interaction (CI) calculations for X-ray absorption spectra developed by the author were extended for the calculation of XMCD, where the Zeeman energy was taken into the Hamiltonian of the CI to mimic magnetic polarization in the solid state. This technique was applied to interpret the L{sub 2,3} XMCD from 3d transition metalmore » complex oxides, such as NiFe{sub 2}O{sub 4} and FeTiO{sub 3}. The experimental XMCD spectra were quantitatively reproduced using this method. The oxidation states as well as the magnetic ordering between transition metal ions on crystallographically different sites in NiFe{sub 2}O{sub 4} can be unambiguously determined. A first-principles analysis of XMCD in FeTiO{sub 3} revealed the presence of Fe{sup 3+} and Ti{sup 3+} ions, which indicates that the charge transfer from Fe to Ti ions occurs. The origin of magnetic polarization of Ti ions in FeTiO{sub 3} was also discussed.« less

Modifications of structural and physical properties induced by swift heavy ions in Gd2Ti2O7 and Y2Ti2O7 pyrochlores

NASA Astrophysics Data System (ADS)

Sellami, N.; Sattonnay, G.; Grygiel, C.; Monnet, I.; Debelle, A.; Legros, C.; Menut, D.; Miro, S.; Simon, P.; Bechade, J. L.; Thomé, L.

2015-12-01

The structural transformations induced by ionization processes in Gd2Ti2O7 and Y2Ti2O7 pyrochlores irradiated with swift heavy ions have been studied using XRD and Raman experiments. Results show that irradiation induces amorphization and that the phase transformation build-up can be accounted for in the framework of a model involving a single-impact mechanism. The radiation induced amorphization build-up is faster in Gd2Ti2O7 than in Y2Ti2O7. Moreover, a decrease of the thermal conductivity (measured by the laser flash method) is induced by irradiation both in Gd2Ti2O7 and Y2Ti2O7.

Antiferromagnetic-ferromagnetic crossover in UO 2-TiO x multi-phase systems

NASA Astrophysics Data System (ADS)

Nakamura, Akio; Tsutsui, Satoshi; Yoshii, Kenji

2001-05-01

An antiferromagnetic (AF)-weakly ferromagnetic (WF) crossover has been found for UO 2-TiO x multi-phase systems, (1- y)UO 2+ yTiO x ( y=0.05-0.72, x=0, 1.0, 1.5 and 2.0), when these mixtures are heat treated at high temperature in vacuum. From the powder X-ray diffraction and electron-microprobe analyses, their phase assemblies were as follows: for x=0, 1.0 and 1.5, a heterogeneous two-phase mixture of UO 2+TiO x; for x=2.0, that of UO 2+UTi 2O 6 for y<0.67, showing characteristic microstructures, and for y>0.67 that of UTi 2O 6+TiO 2 (plus residual minor UO 2). Magnetic susceptibility ( χ) of the present UO 2 powder was confirmed to exhibit an antiferromagnetic sharp drop at TN (=30.5 K). In contrast, χ of these multi-phase systems was found to exhibit a sharp upturn at the respective TN, while their TN values remained almost constant with varying y. This χ upturn at TN is most pronounced for UO 2+Ti-oxide (titania) systems ( x=1.0, 1.5 and 2.0) over the wide mixture ratio above y˜0.10. These observations indicate that an AF-WF crossover is induced for these multi-phase systems, plausibly due to the interfacial magnetic modification of UO 2 in contact with the oxide partners.

Nano-sized TiO2 (nTiO2) induces metabolic perturbations in Physarum polycephalum macroplasmodium to counter oxidative stress under dark conditions.

PubMed

Zhang, Zhi; Liang, Zhi Cheng; Zhang, Jian Hua; Tian, Sheng Li; Le Qu, Jun; Tang, Jiao Ning; De Liu, Shi

2018-06-15

Nano-sized TiO 2 (nTiO 2 ) exerts an oxidative effect on cells upon exposure to solar or UV irradiation and ecotoxicity of the nTiO 2 is an urgent concern. Little information is available regarding the effect of TiO 2 on cells under dark conditions. Metabolomics is a unique approach to the discovery of biomarkers of nTiO 2 cytotoxicity, and leads to the identification of perturbed metabolic pathways and the mechanism underlying nTiO 2 toxicity. In the present study, gas chromatography mass spectrometry (GC/MS)-based metabolomics was performed to investigate the effect of nTiO 2 on sensitive cells (P. polycephalum macroplasmodium) under dark conditions. According to the multivariate pattern recognition analysis, at least 60 potential metabolic biomarkers related to sugar metabolism, amino acid metabolism, nucleotide metabolism, polyamine biosynthesis, and secondary metabolites pathways were significantly perturbed by nTiO 2 . Notably, many metabolic biomarkers and pathways were related to anti-oxidant mechanisms in the living organism, suggesting that nTiO 2 may induce oxidative stress, even under dark conditions. This speculation was further validated by the biochemical levels of reactive oxygen species (ROS), 8-hydroxy-2-deoxyguanosine (8-OHdG), and total soluble phenols (TSP). We inferred that the oxidative stress might be related to nTiO 2 -induced imbalance of cellular ROS. To the best of our knowledge, the present study is the first to investigate the nTiO 2 -induced metabolic perturbations in slime mold, provide a new perspective of the mechanism underlying nTiO 2 toxicity under dark conditions, and show that metabolomics can be employed as a rapid, reliable and powerful tool to investigate the interaction among organisms, the environment, and nanomaterials. Copyright © 2018 Elsevier Inc. All rights reserved.

Oxidation State of Nakhlites as inferred from Fe-Ti oxide Equilibria and Augite/Melt Europium Partitioning

NASA Technical Reports Server (NTRS)

Makishima, J.; McKay, G.; Le, L.; Miyamoto, M.; Mikouchi, T.

2007-01-01

Recent studies have shown that Martian magmas had wide range of oxygen fugacities (fO2) and that this variation is correlated with the variation of La/Yb ratio and isotopic characteristics of the Martian basalts, shergottite meteorites. The origin of this correlation must have important information about mantle sources and Martian evolution. In order to understand this correlation, it is necessary to know accurate value of oxidation state of other Martian meteorite groups. Nakhlites, cumulate clinopyroxenites, are another major group of Martian meteorites and have distinctly different trace element and isotopic characteristics from shergottites. Thus, estimates of oxidation state of nakhlites will give us important insight into the mantle source in general. Several workers have estimated oxidation state of nakhlites by using Fe-Ti oxide equilibrium. However, Fe-Ti oxides may not record the oxidation state of the parent melt of the nakhlite because it is a late-stage mineral. Furthermore, there is no comprehensive study which analyzed all nakhlite samples at the same time. Therefore, in this study (1) we reduced the uncertainty of the estimate using the same electron microprobe and the same standards under the same condition for Fe-Ti oxide in 6 nakhlites and (2) we also performed crystallization experiments to measure partition coefficients of Eu into pyroxene in the nakhlite system in order to estimate fO2 when the pyroxene core formed (i.e. Eu oxybarometer [e.g. 2,6]).

Development of a Novel Melt Spinning-Based Processing Route for Oxide Dispersion-Strengthened Steels

NASA Astrophysics Data System (ADS)

Hong, Zuliang; Morrison, Alasdair P. C.; Zhang, Hongtao; Roberts, Steve G.; Grant, Patrick S.

2018-02-01

Melt spinning of an Fe-5Y and Fe-1Y-1Ti (wt pct) alloy produced a relatively uniform spatial distribution of Y and Ti in solid solution and ribbons with consistent yield (> 60 pct by weight), fast processing time (< 10 seconds), good scalability (up to > 100 g feedstock material), and repeatability. Heat treatment in the presence of Fe2O3 as an oxygen source (Rhines pack method) at 973 K validated the potential of forming < 20 nm Y-rich oxides in the Fe-5Y ribbons. Pulverized Fe-1Y-1Y ribbons were consolidated to bulk using the field-assisted sintering technique (FAST) incorporating nano-sized Fe3O4 powder as the oxygen source. After FAST at 1273 K, 50 MPa, and 30 minutes, a comparatively high number density of sub-micron Y and/or Ti-rich oxides were developed. Further formation of fine-scale oxides took place during post-FAST annealing, resulting in an approximate 20 pct increase in hardness at temperatures below 573 K, but with a reduced hardening effect above 673 K due to a small fraction of persistent porosity and mechanically weak prior ribbon boundaries that were decorated with Ti-rich oxides.

Varying the Lewis base coordination of the Y2N2 core in the reduced dinitrogen complexes {[(Me3Si)2N]2(L)Y}2(μ-η2:η2-N2) (L = benzonitrile, pyridines, triphenylphosphine oxide, and trimethylamine N-oxide).

PubMed

Corbey, Jordan F; Farnaby, Joy H; Bates, Jefferson E; Ziller, Joseph W; Furche, Filipp; Evans, William J

2012-07-16

The effect of the neutral donor ligand, L, on the Ln(2)N(2) core in the (N═N)(2-) complexes, [A(2)(L)Ln](2)(μ-η(2):η(2)-N(2)) (Ln = Sc, Y, lanthanide; A = monoanion; L = neutral ligand), is unknown since all of the crystallographically characterized examples were obtained with L = tetrahydrofuran (THF). To explore variation in L, displacement reactions between {[(Me(3)Si)(2)N](2)(THF)Y}(2)(μ-η(2):η(2)-N(2)), 1, and benzonitrile, pyridine (py), 4-dimethylaminopyridine (DMAP), triphenylphosphine oxide, and trimethylamine N-oxide were investigated. THF is displaced by all of these ligands to form {[(Me(3)Si)(2)N](2)(L)Y}(2)(μ-η(2):η(2)-N(2)) complexes (L = PhCN, 2; py, 3; DMAP, 4; Ph(3)PO, 5; Me(3)NO, 6) that were fully characterized by analytical, spectroscopic, density functional theory, and X-ray crystallographic methods. The crystal structures of the Y(2)N(2) cores in 2-5 are similar to that in 1 with N-N bond distances between 1.255(3) Å and 1.274(3) Å, but X-ray analysis of the N-N distance in 6 shows it to be shorter: 1.198(3) Å.

Rapid and direct synthesis of complex perovskite oxides through a highly energetic planetary milling

PubMed Central

Lee, Gyoung-Ja; Park, Eun-Kwang; Yang, Sun-A; Park, Jin-Ju; Bu, Sang-Don; Lee, Min-Ku

2017-01-01

The search for a new and facile synthetic route that is simple, economical and environmentally safe is one of the most challenging issues related to the synthesis of functional complex oxides. Herein, we report the expeditious synthesis of single-phase perovskite oxides by a high-rate mechanochemical reaction, which is generally difficult through conventional milling methods. With the help of a highly energetic planetary ball mill, lead-free piezoelectric perovskite oxides of (Bi, Na)TiO3, (K, Na)NbO3 and their modified complex compositions were directly synthesized with low contamination. The reaction time necessary to fully convert the micron-sized reactant powder mixture into a single-phase perovskite structure was markedly short at only 30–40 min regardless of the chemical composition. The cumulative kinetic energy required to overtake the activation period necessary for predominant formation of perovskite products was ca. 387 kJ/g for (Bi, Na)TiO3 and ca. 580 kJ/g for (K, Na)NbO3. The mechanochemically derived powders, when sintered, showed piezoelectric performance capabilities comparable to those of powders obtained by conventional solid-state reaction processes. The observed mechanochemical synthetic route may lead to the realization of a rapid, one-step preparation method by which to create other promising functional oxides without time-consuming homogenization and high-temperature calcination powder procedures. PMID:28387324

Fe-Ti-oxide textures and microstructures in shear zones from oceanic gabbros at Atlantis Bank, Southwest Indian Ridge

NASA Astrophysics Data System (ADS)

Till, Jessica; Morales, Luiz F. G.; Rybacki, Erik

2016-04-01

Ocean drilling expeditions at several oceanic core complexes formed at slow- and ultra-slow-spreading ridges have recovered cores containing numerous zones of oxide-rich gabbros containing ilmenite and magnetite. In these cores, high modal concentrations of Fe-Ti-oxides are systematically associated with high-temperature plastic deformation features in silicates. We present observations of Fe-Ti-oxide mineral structures and textural characteristics from a series of oxide-rich shear zones from Atlantis Bank (ODP Site 735B) on the Southwest Indian Ridge aimed at determining how oxide mineral abundances relate to strain localization. Fe-Ti-oxide minerals in undeformed oxide gabbros and in highly deformed samples from natural shear zones generally have morphologies characteristic of crystallized melt, including highly cuspate grains and low dihedral angles. Anisotropy of magnetic susceptibility in oxide-rich shear zones is very strong, with fabrics mainly characterized by strong magnetic foliations parallel to the macroscopic foliation. Crystallographic preferred orientations (CPO) in magnetite are generally weak, with occasionally well-defined textures. Ilmenite typically displays well-developed CPOs, however, the melt-like ilmenite grain shapes indicate that at least part of the crystallographic texture results from oriented ilmenite growth during post-deformation crystallization. The oxides are hypothesized to have initially been present as isolated pockets of trapped melt (intercumulus liquid) in a load-bearing silicate framework. Progressive plastic deformation of silicate phases at high-temperature mainly produced two features: (i) elongated melt pockets, which crystallized to form strings of opaque minerals and (ii), interconnected networks of melt regions. The latter lead to intense strain localization of the rock, which appears as oxide-rich mylonites in the samples. In some samples, abundant low-angle grain boundaries in both magnetite and ilmenite suggest

Fe and C doped TiO2 with different aggregate architecture: Synthesis, optical, spectral and photocatalytic properties, first-principle calculation

NASA Astrophysics Data System (ADS)

Baklanova, I. V.; Zhukov, V. P.; Krasil'nikov, V. N.; Gyrdasova, O. I.; Buldakova, L. Yu.; Shalaeva, E. V.; Polyakov, E. V.; Kuznetsov, M. V.; Shein, I. R.; Vovkotrub, E. G.

2017-12-01

Iron and carbon doped nanostructured titanium dioxide with different morphology of aggregates was synthesized using the developed precursor technique. Glycolate of the general composition Ti1-xFex(OCH2CH2O)2-x/2 (0 ≤ x ≤ 0.1) was used as a precursor. The synthesized samples of the compositions Ti1-xFexO2, Ti1-xFexO(2-x/2)-yCy and Ti1-xFexO(2-x/2)-yCy:nC were characterized by X-ray diffraction, scanning electron microscopy, ultraviolet and visible absorption spectroscopy, as well as by vibration and X-ray photoelectron spectroscopy methods. In addition, they were tested as photocatalysts in the hydroquinone oxidation reaction under ultraviolet and visible irradiation. It is established that the insertion of iron into the structure of carbon-doped anatase (TiO2-yCy) suppresses its photocatalytic activity in the visible range of the spectrum, but leads to no change under ultraviolet irradiation. Globular samples of Ti1-xFexO(2-x/2)-yCy containing no more than 2.5 at% Fe show the maximum photocatalytic activity. To clarify the reasons for the observed complex dependence of photocatalytic activity on the concentration of the dopant first-principles, calculations of the electronic band structure and optical absorption of anatase doped with iron and carbon are performed and discussed.

Electronic structure of charge- and spin-controlled Sr(1-(x+y))La(x+y)Ti(1-x)Cr(x)O3.

PubMed

Iwasawa, H; Yamakawa, K; Saitoh, T; Inaba, J; Katsufuji, T; Higashiguchi, M; Shimada, K; Namatame, H; Taniguchi, M

2006-02-17

We present the electronic structure of Sr(1-(x+y))La(x+y)Ti(1-x)Cr(x)O3 investigated by high-resolution photoemission spectroscopy. In the vicinity of the Fermi level, it was found that the electronic structure was composed of a Cr 3d local state with the t(2g)3 configuration and a Ti 3d itinerant state. The energy levels of these Cr and Ti 3d states are well interpreted by the difference of the charge-transfer energy of both ions. The spectral weight of the Cr 3d state is completely proportional to the spin concentration x irrespective of the carrier concentration y, indicating that the spin density can be controlled by x as desired. In contrast, the spectral weight of the Ti 3d state is not proportional to y, depending on the amount of Cr doping.

Bi-functional anodic TiO2 oxide: Nanotubes for wettability control and barrier oxide for uniform coloring

NASA Astrophysics Data System (ADS)

Kim, Sunkyu; Jung, Minkyeong; Kim, Moonsu; Choi, Jinsub

2017-06-01

A uniformly colored TiO2, on which the surface is functionalized with nanotubes to control wettability, was prepared by a two-step anodization; the first anodization was carried out to prepare nanotubes for a super-hydrophilic or -hydrophobic surface and the second anodization was performed to fabricate a thin film barrier oxide to ensure uniform coloring. The effect of the nanotubes on barrier oxide coloring was examined by spectrophotometry and UV-vis-IR spectroscopy. We found four different regimes governing the color changes in terms of anodization voltage, indicating that the color of the duplex TiO2 was primarily determined by the thickness of the barrier oxide layer formed during the second anodization step. The surface wettability, as confirmed by the water contact angle, revealed that the single barrier TiO2 yielded 74.6° ± 2.1, whereas the nanotubes on the barrier oxide imparted super-hydrophilic properties as a result of increasing surface roughness as well as imparting a higher hydrophobicity after organic acid treatment.

Role of flue gas components in mercury oxidation over TiO2 supported MnOx-CeO2 mixed-oxide at low temperature.

PubMed

Li, Hailong; Wu, Chang-Yu; Li, Ying; Li, Liqing; Zhao, Yongchun; Zhang, Junying

2012-12-01

MnO(x)-CeO(2) mixed-oxide supported on TiO(2) (Mn-Ce/Ti) was synthesized by an ultrasound-assisted impregnation method and employed to oxidize elemental mercury (Hg(0)) at 200°C in simulated coal combustion flue gas. Over 90% of Hg(0) oxidation was achieved on the Mn-Ce/Ti catalyst at 200°C under simulated flue gas representing those from burning low-rank coals with a high gas hourly space velocity of 60,000 h(-1). Gas-phase O(2) regenerated the lattice oxygen and replenished the chemisorbed oxygen, which facilitated Hg(0) oxidation. HCl was the most effective flue gas component responsible for Hg(0) oxidation. 10 ppm HCl plus 4% O(2) resulted in 100% Hg(0) oxidation under the experimental conditions. SO(2) competed with Hg(0) for active sites, thus deactivating the catalyst's capability in oxidizing Hg(0). NO covered the active sites and consumed surface oxygen active for Hg(0) oxidation, hence limiting Hg(0) oxidation. Water vapor showed prohibitive effect on Hg(0) oxidation due to its competition with HCl and Hg(0) for active adsorption sites. This study provides information about the promotional or inhibitory effects of individual flue gas components on Hg(0) oxidation over a highly effective Mn-Ce/Ti catalyst. Such knowledge is of fundamental importance for industrial applications of the Mn-Ce/Ti catalyst in coal-fired power plants. Copyright © 2012 Elsevier B.V. All rights reserved.

Oxygen-storage behavior and local structure in Ti-substituted YMnO3

NASA Astrophysics Data System (ADS)

Levin, I.; Krayzman, V.; Vanderah, T. A.; Tomczyk, M.; Wu, H.; Tucker, M. G.; Playford, H. Y.; Woicik, J. C.; Dennis, C. L.; Vilarinho, P. M.

2017-02-01

Hexagonal manganates RMnO3 (R=Y, Ho, Dy) have been recently shown to exhibit oxygen-storage capacities promising for three-way catalysts, air-separation, and related technologies. Here, we demonstrate that Ti substitution for Mn can be used to chemically tune the oxygen-breathing properties of these materials towards practical applications. Specifically, Y(Mn1-xTix)O3 solid solutions exhibit facile oxygen absorption/desorption via reversible Ti3+↔Ti4+ and Mn3+↔Mn4+ reactions already in ambient air at ≈400 °C and ≈250 °C, respectively. On cooling, the oxidation of both cations is accompanied by oxygen uptake yielding a formula YMn3+1-x-yMn4+yTi4+xO3+δ. The presence of Ti promotes the oxidation of Mn3+ to Mn4+, which is almost negligible for YMnO3 in air, thereby increasing the uptake of oxygen beyond that required for a given Ti4+ concentration. The reversibility of the redox reactions is limited by sluggish kinetics; however, the oxidation process continues, if slowly, even at room temperature. The extra oxygen atoms are accommodated by the large interstices within a triangular lattice formed by the [MnO5] trigonal bipyramids. According to bond distances from Rietveld refinements using the neutron diffraction data, the YMnO3 structure features under-bonded Mn and even more severely under-bonded oxygen atoms that form the trigonal bases of the [MnO5] bipyramids. The tensile bond strain around the 5-fold coordinated Mn site and the strong preference of Ti4+(and Mn4+) for higher coordination numbers likely provide driving forces for the oxidation reaction. Reverse Monte Carlo refinements of the local atomic displacements using neutron total scattering revealed how the excess oxygen atoms are accommodated in the structure by correlated local displacements of the host atoms. Large displacements of the under-bonded host oxygen atoms play a key part in this lattice-relaxation process, facilitating reversible exchange of significant amounts of oxygen with

Structural, Morphological, Optical and Photocatalytic Properties of Y, N-Doped and Codoped TiO₂ Thin Films.

PubMed

Hamden, Zeineb; Conceição, David; Boufi, Sami; Vieira Ferreira, Luís Filipe; Bouattour, Soraa

2017-05-31

Pure TiO₂, Y-N single-doped and codoped TiO₂ powders and thin films deposited on glass beads were successfully prepared using dip-coating and sol-gel methods. The samples were analyzed using grazing angle X-ray diffraction (GXRD), Raman spectroscopy, time resolved luminescence, ground state diffuse reflectance absorption and scanning electron microscopy (SEM). According to the GXRD patterns and micro-Raman spectra, only the anatase form of TiO₂ was made evident. Ground state diffuse reflectance absorption studies showed that doping with N or codoping with N and Y led to an increase of the band gap. Laser induced luminescence analysis revealed a decrease in the recombination rate of the photogenerated holes and electrons. The photocatalytic activity of supported catalysts, toward the degradation of toluidine, revealed a meaningful enhancement upon codoping samples at a level of 2% (atomic ratio). The photocatalytic activity of the material and its reactivity can be attributed to a reduced, but significant, direct photoexcitation of the semiconductor by the halogen lamp, together with a charge-transfer-complex mechanism, or with the formation of surface oxygen vacancies by the N dopant atoms.

Catalytic evaluation on liquid phase oxidation of vanillyl alcohol using air and H2O2 over mesoporous Cu-Ti composite oxide

NASA Astrophysics Data System (ADS)

Saha, Subrata; Hamid, Sharifah Bee Abd; Ali, Tammar Hussein

2017-02-01

A mesoporous, highly crystalline Cu-Ti composite oxide catalyst was prepared via facile, simple and modified solution method varying Cu and Ti ratio for selective liquid phase oxidation of vanillyl alcohol. Various spectroscopic procedures were employed to systematically characterize the catalyst structural and physicochemical properties. The defect chemistry of the catalyst was confirmed from the presence of surface defects revealed through HRTEM imagery between the TiO2 (101) and Cu3TiO4 (012) planes, complemented by the XRD profiling. Further, presence of oxygen vacancy evidenced by O 1s XPS spectra were observed on the catalyst surface. Moreover, the stoichiometry of Cu and Ti in the catalyst synthesis protocol was notably found to be the vital determinant to alter the redox properties of Cu-Ti composite oxide catalyst supported by H2-TPR. O2-TPD analysis. Moreover, a rational investigation was done using different oxidants such as air and H2O2 with variables reaction conditions. The catalyst was active for liquid phase oxidation of vanillyl alcohol to vanillin with performance of 66% conversion and 71% selectivity using H2O2 in base free condition. And also, catalytic activity was significantly improved by 94% conversion with 86% selectivity to vanillin in liquid phase aerobic oxidation at the optimum reaction conditions. To expand the superiority of the catalyst, three times reusability study was also examined with appreciable catalytic activity.

Photocatalytic oxidation of nitrogen oxides using TiO2 loading on woven glass fabric.

PubMed

Wang, Haiqiang; Wu, Zhongbiao; Zhao, Weirong; Guan, Baohong

2007-01-01

TiO2 loading on woven glass fabric is applied to treat nitrogen oxides (NOx) by photocatalytic oxidation (PCO). In this paper, the PCO behavior of NO at high concentrations was studied by PCO of NOx at source levels (20-168 ppm). The PCO efficiency reached 27% in this experiment, while the inlet NOx concentration was 168 ppm (147 ppm NO). The dependency of the reaction rate on several key influencing factors (relative humidity, space time, inlet concentration, oxygen percentage) was also studied. The results illustrate that the resulting hydroxyl radical and active oxide play an important role in the oxidation of NOx. The reactions are limited by the thermodynamic equilibrium after ca. 15s space time. A possible explanation for the catalyst deactivation is the accumulation of nitric acid and nitrous acid on the TiO2 surface during the PCO of NOx. However, the photocatalytic activity can be recovered with a simple heat treatment. The results from the study of the effect of the inlet concentration were described with the Langmuir-Hinshelwood model.

Electronic phase separation at the LaAlO₃/SrTiO₃ interface.

PubMed

Ariando; Wang, X; Baskaran, G; Liu, Z Q; Huijben, J; Yi, J B; Annadi, A; Barman, A Roy; Rusydi, A; Dhar, S; Feng, Y P; Ding, J; Hilgenkamp, H; Venkatesan, T

2011-02-08

There are many electronic and magnetic properties exhibited by complex oxides. Electronic phase separation (EPS) is one of those, the presence of which can be linked to exotic behaviours, such as colossal magnetoresistance, metal-insulator transition and high-temperature superconductivity. A variety of new and unusual electronic phases at the interfaces between complex oxides, in particular between two non-magnetic insulators LaAlO(3) and SrTiO(3), have stimulated the oxide community. However, no EPS has been observed in this system despite a theoretical prediction. Here, we report an EPS state at the LaAlO(3)/SrTiO(3) interface, where the interface charges are separated into regions of a quasi-two-dimensional electron gas, a ferromagnetic phase, which persists above room temperature, and a (superconductor like) diamagnetic/paramagnetic phase below 60 K. The EPS is due to the selective occupancy (in the form of 2D-nanoscopic metallic droplets) of interface sub-bands of the nearly degenerate Ti orbital in the SrTiO(3). The observation of this EPS demonstrates the electronic and magnetic phenomena that can emerge at the interface between complex oxides mediated by the Ti orbital.

Structural, thermal and electrical conductivity characteristics of Ln{sub 0.5}Sr{sub 0.5}Ti{sub 0.5}Mn{sub 0.5}O{sub 3±d} (Ln: La, Nd and Sm) complex perovskites as anode materials for solid oxide fuel cell

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

Jeong, Jihoon; Department of Mechanical Engineering, The University of Texas at Austin, Austin, TX 78712; Azad, Abul K.

2015-03-15

The Ti and Mn replaced complex perovskites, Ln{sub 0.5}Sr{sub 0.5}Ti{sub 0.5}Mn{sub 0.5}O{sub 3±d} (Ln: La, Nd and Sm), were reported as potential anode materials for high temperature-operating solid oxide fuel cells (HT-SOFCs). For the present research study, synthesis, crystallographic, thermal and electrical conductivity properties of Ln{sub 0.5}Sr{sub 0.5}Ti{sub 0.5}Mn{sub 0.5}O{sub 3±d} complex perovskites were investigated using X-ray diffraction (XRD), Rietveld method, thermogravimetric analysis (TGA) and electrical conductivity to apply these oxide materials for the HT-SOFC anode materials. XRD results showed that Ln{sub 0.5}Sr{sub 0.5}Ti{sub 0.5}Mn{sub 0.5}O{sub 3±d} oxide systems synthesized as single phases did not react with 8 mol% yttriamore » stabilized zirconia (8YSZ) and 10 mol% Gd-doped cerium oxide (CGO91) up to 1500 °C and did not decompose under dry 3.9% hydrogen at 850 °C. The crystal structures of La{sub 0.5}Sr{sub 0.5}Ti{sub 0.5}Mn{sub 0.5}O{sub 3±d} (LSTM), Nd{sub 0.5}Sr{sub 0.5}Ti{sub 0.5}Mn{sub 0.5}O{sub 3±d} (NSTM) and Sm{sub 0.5}Sr{sub 0.5}Ti{sub 0.5}Mn{sub 0.5}O{sub 3±d} (SSTM) showed orthorhombic symmetry with the space group Pbnm and SSTM showed a more distorted structure. Thermogravimetric analysis (TGA) proved weight gains in these three sample occurred under oxidizing conditions and weight loss under reducing conditions. Electrical conductivity values of NSTM were higher than those of LSTM and SSTM under oxidizing and reducing conditions. - Graphical abstract: The B-site cations (Ti/Mn) are surrounded by regular octahedra of oxygen in Nd{sub 0.5}Sr{sub 0.5}Ti{sub 0.5}Mn{sub 0.5}O{sub 3±d}(NSTM). These octahedra are linked together in a corner sharing three dimensional framework, while Nd/Sr ion occupies 12-coordinated A-site between these octahedra. The Ti/Mn–O{sub 6} octahedra are elongated along the c-axis. The crystal structure distortion was due to the smaller ionic radius of the A-site cations, which force the (Ti

Synthesis of reduced graphene oxide-anatase TiO2 nanocomposite and its improved photo-induced charge transfer properties.

PubMed

Wang, Ping; Zhai, Yueming; Wang, Dejun; Dong, Shaojun

2011-04-01

The construction of reduced graphene oxide or graphene oxide with semiconductor has gained more and more attention due to its unexpected optoelectronic and electronic properties. The synthesis of reduced graphene oxide (RGO) or graphene oxide-semiconductor nanocomposite with well-dispersed decorated particles is still a challenge now. Herein, we demonstrate a facile method for the synthesis of graphene oxide-amorphous TiO(2) and reduced graphene oxide-anatase TiO(2) nanocomposites with well-dispersed particles. The as-synthesized samples were characterized by transmission electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy, UV-Vis absorption spectroscopy, Fourier transform infrared spectrometry, and thermogravimetric analysis. The photovoltaic properties of RGO-anatase TiO(2) were also compared with that of similar sized anatase TiO(2) by transient photovoltage technique, and it was interesting to find that the combination of reduced graphene oxide with anatase TiO(2) will significantly increase the photovoltaic response and retard the recombination of electron-hole pairs in the excited anatase TiO(2).

Effect of different processes and Ti/Zn molar ratios on the structure, morphology, and enhanced photoelectrochemical and photocatalytic performance of Ti3+ self-doped titanium-zinc hybrid oxides

NASA Astrophysics Data System (ADS)

Fu, Rongrong; Wang, Qingyao; Gao, Shanmin; Wang, Zeyan; Huang, Baibiao; Dai, Ying; Lu, Jun

2015-07-01

Ti3+ self-doped titanium-zinc hybrid oxides with different phase compositions and morphologies were successfully synthesized using Zn powder as the reductant and Zn source by a chemical-reduction precipitation method with subsequent thermal treatment. The fabricated Ti3+ self-doped TiO2(A)/TiO2(R), TiO2(A)/TiO2(R)/ZnTiO3, and TiO2(A)/ZnO heterojunctions were characterized by X-ray diffraction, transmission electron microscopy, high-resolution transmission electron microscopy, X-ray photoelectron spectroscopy, and UV-Vis diffuse reflectance spectroscopy. The effects of various Ti/Zn molar ratios and preparation processes on the structural, morphological, optical, photocurrent and photocatalytic properties of the resultant samples were investigated systematically. Results reveal that Ti3+ self-doping enhances the photoabsorption capability of titanium-zinc hybrid oxides in the visible-light region. Moreover, different processes and Ti/Zn molar ratios play great influences on the structure, morphology, optical, photocurrent and photocatalytic properties of the final products. Ti3+ self-doped titanium-zinc hybrid oxides exhibit excellent photocurrent and photocatalytic activity than pure TiO2 and ZnTiO3 under visible-light irradiation (λ ≥ 400 nm). The most active Ti3+ self-doped titanium-zinc hybrid oxides photoanode presents significantly improved water splitting performance. The synergistic effect between the Ti3+ self-doped and heterojunctions is responsible for the enhanced performance of these materials.

Combinatorial assessment of the influence of composition and exposure time on the oxidation behavior and concurrent oxygeninduced phase transformations of binary Ti-x systems

NASA Astrophysics Data System (ADS)

Samimi, Peyman

The relatively low oxidation resistance and subsequent surface embrittlement have often limited the use of titanium alloys in elevated temperature structural applications. Although extensive effort is spent to investigate the high temperature oxidation performance of titanium alloys, the studies are often constrained to complex technical titanium alloys and neither the mechanisms associated with evolution of the oxide scale nor the effect of oxygen ingress on the microstructure of the base metal are well-understood. In addition lack of systematic oxidation studies across a wider domain of the alloy composition has complicated the determination of composition-mechanism-property relationships. Clearly, it would be ideal to assess the influence of composition and exposure time on the oxidation resistance, independent of experimental variabilities regarding time, temperature and atmosphere as the potential source of error. Such studies might also provide a series of metrics (e.g., hardness, scale, etc) that could be interpreted together and related to the alloy composition. In this thesis a novel combinatorial approach was adopted whereby a series of compositionally graded specimens, (Ti-xMo, Ti-xCr, Ti-xAl and Ti-xW) were prepared using Laser Engineered Net Shaping (LENS(TM)) technology and exposed to still-air at 650 °C. (Abstract shortened by ProQuest.).

Application of Ni-Oxide@TiO₂ Core-Shell Structures to Photocatalytic Mixed Dye Degradation, CO Oxidation, and Supercapacitors.

PubMed

Lee, Seungwon; Lee, Jisuk; Nam, Kyusuk; Shin, Weon Gyu; Sohn, Youngku

2016-12-20

Performing diverse application tests on synthesized metal oxides is critical for identifying suitable application areas based on the material performances. In the present study, Ni-oxide@TiO₂ core-shell materials were synthesized and applied to photocatalytic mixed dye (methyl orange + rhodamine + methylene blue) degradation under ultraviolet (UV) and visible lights, CO oxidation, and supercapacitors. Their physicochemical properties were examined by field-emission scanning electron microscopy, X-ray diffraction analysis, Fourier-transform infrared spectroscopy, and UV-visible absorption spectroscopy. It was shown that their performances were highly dependent on the morphology, thermal treatment procedure, and TiO₂ overlayer coating.

Fabrication of TiO2 Crystalline Coatings by Combining Ti-6Al-4V Anodic Oxidation and Heat Treatments

PubMed Central

Schvezov, Carlos Enrique; Ares, Alicia Esther

2015-01-01

The bio- and hemocompatibility of titanium alloys are due to the formation of a TiO2 layer. This natural oxide may have fissures which are detrimental to its properties. Anodic oxidation is used to obtain thicker films. By means of this technique, at low voltages oxidation, amorphous and low roughness coatings are obtained, while, above a certain voltage, crystalline and porous coatings are obtained. According to the literature, the crystalline phases of TiO2, anatase, and rutile would present greater biocompatibility than the amorphous phase. On the other hand, for hemocompatible applications, smooth and homogeneous surfaces are required. One way to obtain crystalline and homogeneous coatings is by heat treatments after anodic oxidation. The aim of this study is to evaluate the influence of heat treatments on the thickness, morphology, and crystalline structure of the TiO2 anodic coatings. The characterization was performed by optical and scanning electron microscopy, X-ray diffraction, and X-ray reflectometry. Coatings with different colors of interference were obtained. There were no significant changes in the surface morphology and roughness after heat treatment of 500°C. Heat treated coatings have different proportions of the crystalline phases, depending on the voltage of anodic oxidation and the temperature of the heat treatment. PMID:25784939

Visible light assisted photodecolorization of eosin-Y in aqueous solution using hesperidin modified TiO2 nanoparticles

NASA Astrophysics Data System (ADS)

Vignesh, K.; Suganthi, A.; Rajarajan, M.; Sakthivadivel, R.

2012-03-01

Hesperidin a flavanoid, modified TiO2 nanoparticles (Hes-TiO2) was synthesized to improve the visible light driven photocatalytic performance of TiO2. The synthesized nanoparticles were characterized by UV-visible diffuse reflectance spectroscopy (UV-vis-DRS), FT-IR, powder X-ray diffraction (XRD) and scanning electron microscopy (SEM). The photocatalytic activity of Hes-TiO2 was investigated based on the decolorization of eosin-Y under visible light irradiation. Hes-TiO2 showed high efficiency for the decolorization of eosin-Y. The influences of various reaction parameters like effect of pH, catalyst dosage and initial dye concentration on the photocatalytic efficiency were investigated. The adsorption of eosin-Y on Hes-TiO2 was found favorable by the Langmuir approach. The removal percentage of chemical oxygen demand (COD) was determined to evaluate the mineralization of eosin-Y during photodecolorization. Based on the intermediates obtained in the GC-MS spectroscopic technique, a probable degradation mechanism has been proposed.

Interfacial charge-transfer transitions in a TiO2-benzenedithiol complex with Ti-S-C linkages.

PubMed

Fujisawa, Jun-ichi; Muroga, Ryuki; Hanaya, Minoru

2015-11-28

Interfacial charge-transfer (ICT) transitions between organic materials and inorganic semiconductors are a new mechanism for light absorption at organic-semiconductor interfaces. ICT transitions cause one-step interfacial charge separation without loss of energy. This feature is potentially useful to realize efficient organic-inorganic hybrid solar cells. ICT transitions have been examined by employing titanium dioxide (TiO2) nanoparticles chemisorbed with π-conjugated molecules via Ti-O-C linkages. Here, we report ICT transitions in a TiO2 and 1,2-benzenedithiol (BDT) complex with Ti-S-C linkages. BDT adsorbs on TiO2 by the bridging bidentate coordination of the sulfur atoms to surface titanium atoms. The TiO2-BDT complex shows ICT transitions from the BDT moiety to the conduction band of TiO2 in the visible region. The ICT transitions occur by orbital overlaps between the d orbitals of the surface titanium atoms and the π orbitals of the benzene ring. Our density-functional-theory (DFT) analysis reveals that the 3p valence orbitals of the sulfur bridging atoms contribute to more than 50% of the highest occupied molecular orbital (HOMO) and the 3d-3p(sulfur)-π interaction via the Ti-S-C linkage enhances the electronic mixing between the titanium atoms and the benzene moiety as compared to the 3d-2p(oxygen)-πvia the Ti-O-C linkage. This result indicates the important role of the heavier-atom linkers for strong organic-inorganic electronic couplings.

Structural, Morphological, Optical and Photocatalytic Properties of Y, N-Doped and Codoped TiO2 Thin Films

PubMed Central

Hamden, Zeineb; Conceição, David; Boufi, Sami; Vieira Ferreira, Luís Filipe; Bouattour, Soraa

2017-01-01

Pure TiO2, Y-N single-doped and codoped TiO2 powders and thin films deposited on glass beads were successfully prepared using dip-coating and sol-gel methods. The samples were analyzed using grazing angle X-ray diffraction (GXRD), Raman spectroscopy, time resolved luminescence, ground state diffuse reflectance absorption and scanning electron microscopy (SEM). According to the GXRD patterns and micro-Raman spectra, only the anatase form of TiO2 was made evident. Ground state diffuse reflectance absorption studies showed that doping with N or codoping with N and Y led to an increase of the band gap. Laser induced luminescence analysis revealed a decrease in the recombination rate of the photogenerated holes and electrons. The photocatalytic activity of supported catalysts, toward the degradation of toluidine, revealed a meaningful enhancement upon codoping samples at a level of 2% (atomic ratio). The photocatalytic activity of the material and its reactivity can be attributed to a reduced, but significant, direct photoexcitation of the semiconductor by the halogen lamp, together with a charge-transfer-complex mechanism, or with the formation of surface oxygen vacancies by the N dopant atoms. PMID:28772962

Effect of modification of oxide layer on NiTi stent corrosion resistance.

PubMed

Trépanier, C; Tabrizian, M; Yahia, L H; Bilodeau, L; Piron, D L

1998-01-01

Because of its good radiopacity, superelasticity, and shape memory properties, nickel-titanium (NiTi) is a potential material for fabrication of stents because these properties can facilitate their implantation and precise positioning. However, in vitro studies of NiTi alloys report the dependence of alloy biocompatibility and corrosion behavior on surface conditions. Surface oxidation seems to be very promising for improving the corrosion resistance and biocompatibility of NiTi. In this work, we studied the effect on corrosion resistance and surface characteristics of electropolishing, heat treatment, and nitric acid passivation of NiTi stents. Characterization techniques such as potentiodynamic polarization tests, scanning electron microscopy, Auger electron spectroscopy, and X-ray photoelectron spectroscopy were used to relate corrosion behavior to surface characteristics and surface treatments. Results show that all of these surface treatments improve the corrosion resistance of the alloy. This improvement is attributed to the plastically deformed native oxide layer removal and replacement by a newly grown, more uniform one. The uniformity of the oxide layer, rather than its thickness and composition, seems to be the predominant factor to explain the corrosion resistance improvement.

Ti-Catalyzed Multicomponent Oxidative Carboamination of Alkynes with Alkenes and Diazenes

PubMed Central

Davis-Gilbert, Zachary W.; Yao, Letitia J.; Tonks, Ian A.

2017-01-01

The inter- or intramolecular oxidative carboamination of alkynes catalyzed by [py2TiCl2NPh]2 is reported. These multicomponent reactions couple alkenes, alkynes and diazenes to form either α,β-unsaturated imines or α-(iminomethyl)cyclopropanes via a TiII/TiIV redox cycle. Each of these products is formed from a common azatitanacyclohexene intermediate that undergoes either β-H elimination or α,γ-coupling, wherein the selectivity is under substrate control. PMID:27790910

Thermal Shock and Oxidation Behavior of HiPIMS TiAlN Coatings Grown on Ti-48Al-2Cr-2Nb Intermetallic Alloy

PubMed Central

Badini, Claudio; Deambrosis, Silvia M.; Padovano, Elisa; Fabrizio, Monica; Ostrovskaya, Oxana; Miorin, Enrico; D’Amico, Giuseppe C.; Montagner, Francesco; Biamino, Sara; Zin, Valentina

2016-01-01

A High Power Impulse Magnetron Sputtering (HiPIMS) method for depositing TiAlN environmental barrier coatings on the surface of Ti-48Al-2Cr-2Nb alloy was developed in view of their exploitation in turbine engines. Three differently engineered TiAlN films were processed and their performance compared. Bare intermetallic alloy coupons and coated specimens were submitted to thermal cycling under oxidizing atmosphere up to 850 °C or 950 °C, at high heating and cooling rates. For this purpose, a burner rig able to simulate the operating conditions of the different stages of turbine engines was used. Microstructures of the samples were compared before and after each test using several techniques (microscopy, XRD, and XPS). Coating-intermetallic substrate adhesion and tribological properties were investigated too. All the TiAlN films provided a remarkable increase in oxidation resistance. Good adhesion properties were observed even after repeated thermal shocks. HiPIMS pretreatments of the substrate surfaces performed before the coating deposition significantly affected the oxidation rate, the oxide layer composition and the coating/substrate adhesion. PMID:28774082

Composite TiO2/clays materials for photocatalytic NOx oxidation

NASA Astrophysics Data System (ADS)

Todorova, N.; Giannakopoulou, T.; Karapati, S.; Petridis, D.; Vaimakis, T.; Trapalis, C.

2014-11-01

TiO2 photocatalyst received much attention for air purification applications especially for removal of air pollutants like NOx, VOCs etc. It has been established that the activity of the photocatalyst can be significantly enhanced by its immobilization onto suitable substrates like inorganic minerals, porous silica, hydroxyapatite, adsorbent materials like activated carbon, various co-catalysts such as semiconductors, graphene, reduced graphite oxide, etc. In the present work, photocatalytic composite materials consisted of mineral substrate and TiO2 in weight ratio 1:1 were manufactured and examined for oxidation and removal of nitric oxides NOx (NO and NO2). Commercial titania P25 (Evonik-Degussa) and urea-modified P25 were used as photocatalytically active components. Inorganic minerals, namely kunipia, talk and hydrotalcite were selected as supporting materials due to their layered structure and expected high NOx adsorption capability. Al3+ and Ca2+ intercalation was applied in order to improve the dispersion of TiO2 and its loading into the supporting matrix. The X-ray diffraction analysis and Scanning Electron Microscopy revealed the binary structure of the composites and homogeneous dispersion of the photocatalyst into the substrates. The photocatalytic behavior of the materials in NOx oxidation and removal was investigated under UV and visible light irradiation. The composite materials exhibited superior photocatalytic activity than the bare titania under both types of irradiation. Significant visible light activity was recorded for the composites containing urea-modified titania that was accredited to the N-doping of the semiconductor. Among the different substrates, the hydrotalcite caused highest increase in the NOx removal, while among the intercalation ions the Ca2+ was more efficient. The results were related to the improved dispersion of the TiO2 and the synergetic activity of the substrates as NOx adsorbers.

S-TiO2/S-reduced graphene oxide for enhanced photoelectrochemical water splitting

NASA Astrophysics Data System (ADS)

Elbakkay, Mohamed H.; El Rouby, Waleed M. A.; El-Dek, S. I.; Farghali, Ahmed A.

2018-05-01

Sulfur-doped titanium oxide on the surface of sulfur-doped reduced graphene oxide nanocomposites (S-TiO2/S-RGO) were successfully synthesized for the first time through a simple low cost solvothermal reaction process. The sulfur doping was detected in both TiO2 matrix and carbon framework structure of reduced graphene oxide using X-ray photoelectron spectroscopy (XPS) and Energy-dispersive X-ray spectroscopy (EDX). Cross-sectional AFM analysis of S-RGO nanosheets reveals a thickness of 0.51 nm which is much thinner than those previously reported of heteroatom doped-RGO, confirming the single-layer feature. When the as-prepared (S-TiO2/S-RGO) nanocomposites are utilized as photoanodes for photoelectrochemical (PEC) water splitting, they exhibited an enhanced photoelectrochemical performance and long-term stability. The photocurrent density of S-TiO2/S-RGO(0.2) photoanode revealed 3.36 mA/cm2 at 1 V vs Ag/AgCl which is considered 3 times compared to bare synthesized TiO2. This improvement in the photocurrent density was attributed to the increased separation rate of photogenerated electrons and holes and efficient visible light harvesting as a result of the successful combination of the S-TiO2 and the S-RGO in the same nanocomposite photoanode. This promising result presents a new approach for the synthesis of high-efficient future metal-free photoelectrocatalysts.

Reduced TiO2-Graphene Oxide Heterostructure As Broad Spectrum-Driven Efficient Water-Splitting Photocatalysts.

PubMed

Li, Lihua; Yu, Lili; Lin, Zhaoyong; Yang, Guowei

2016-04-06

The reduced TiO2-graphene oxide heterostructure as an alternative broad spectrum-driven efficient water splitting photocatalyst has become a really interesting topic, however, its syntheses has many flaws, e.g., tedious experimental steps, time-consuming, small scale production, and requirement of various additives, for example, hydrazine hydrate is widely used as reductant to the reduction of graphene oxide, which is high toxicity and easy to cause the second pollution. For these issues, herein, we reported the synthesis of the reduced TiO2-graphene oxide heterostructure by a facile chemical reduction agent-free one-step laser ablation in liquid (LAL) method, which achieves extended optical response range from ultraviolet to visible and composites TiO(2-x) (reduced TiO2) nanoparticle and graphene oxide for promoting charge conducting. 30.64% Ti(3+) content in the reduced TiO2 nanoparticles induces the electronic reconstruction of TiO2, which results in 0.87 eV decrease of the band gap for the visible light absorption. TiO(2-x)-graphene oxide heterostructure achieved drastically increased photocatalytic H2 production rate, up to 23 times with respect to the blank experiment. Furthermore, a maximum H2 production rate was measured to be 16 mmol/h/g using Pt as a cocatalyst under the simulated sunlight irradiation (AM 1.5G, 135 mW/cm(2)), the quantum efficiencies were measured to be 5.15% for wavelength λ = 365 ± 10 nm and 1.84% for λ = 405 ± 10 nm, and overall solar energy conversion efficiency was measured to be 14.3%. These findings provided new insights into the broad applicability of this methodology for accessing fascinate photocatalysts.

Influence of silicon oxide on the performance of TiN bottom electrode in phase change memory

NASA Astrophysics Data System (ADS)

Gao, Dan; Liu, Bo; Xu, Zhen; Wang, Heng; Xia, Yangyang; Wang, Lei; Zhu, Nanfei; Li, Ying; Zhan, Yipeng; Song, Zhitang; Feng, Songlin

2016-10-01

The stability of TiN which is the preferred bottom electrode contact (BEC) of phase change memory (PCM) due to its low thermal conductivity and suitable electrical conductivity, is very essential to the reliability of PCM devices. In this work, in order to investigate the effect of high aspect ratio process (HARP) SiO2 on the performance of TiN, both TiN/SiO2, TiN/SiN thin films and TiN BEC device structures are analyzed. By combining transmission electron microscopy (TEM) and energy dispersive X-ray spectroscopy (EDS), we found that the TiN would be oxidized after the deposition of HARP SiO2 and there exist a thin ( 4 nm) oxidation interfacial layer between TiN and SiO2. Electrical measurements were performed on the 1R PCM test-key die with 7 nm and 10 nm BEC-only cells. The statistical initial resistances of BEC have wide distribution and it is confirmed that the non-uniform oxidation of TiN BEC affects the astringency of the resistance of TiN BEC. The experimental results help to optimize the process of TiN BEC, and SiN is recommended as a better choice as the linear layer.

Effect of oxidative stress from nanoscale TiO2 particles on a Physarum polycephalum macroplasmodium under dark conditions.

PubMed

Zhang, Zhi; Zhang, Jianhua; Shi, Caixia; Guo, Heng; Ni, RuiYang; Qu, Junle; Tang, Jiaoning; Liu, Shide

2017-07-01

Information regarding the effect of nanoscale titanium dioxide particles (nTiO 2 ) on the environment under dark conditions is scarce, and the effect of nTiO 2 on fungi is largely unknown. Due to its huge size and high sensitivity to external stimuli, the slime mold fungi cell, Physarum polycephalum macroplasmodium, was utilized as a novel subject for the toxicity investigations in the present study, and oxidative stress from nTiO 2 on the macroplasmodium was assessed under dark conditions. Short exposure (2-3 h) caused an intracellular reactive oxygen species (ROS) imbalance, and an anti-oxidative mechanism was activated from intermediate doses of nTiO 2 (5-18 mg/mL). At long exposure times (~3 days), relatively low doses of nTiO 2 (≤9 mg/mL) stimulated the growth of macroplasmodium and oxidative stress without DNA damage, whereas higher doses of nTiO 2 (≥15 mg/mL) led to growth inhibition, significant DNA oxidative damage, and activation of the DNA single-strand repairing system. Although DNA oxidative damage was decreased to the same level as the control group by the supplementation of the anti-oxidant vitamin C, growth of the macroplasmodium failed to be completely restored. We inferred that nTiO 2 induced a complicated toxicity effect on P. polycephalum in addition to DNA oxidative damage. Taken as a whole, the present study implied the probability of using P. polycephalum macroplasmodium for toxicity studies at the single-cell level, indicating that nTiO 2 could induce oxidative stress or damage in P. polycephalum even under dark conditions and suggesting that the release of nTiO 2 could lead to a growth imbalance of slime molds in the environment.

Application of Ni-Oxide@TiO2 Core-Shell Structures to Photocatalytic Mixed Dye Degradation, CO Oxidation, and Supercapacitors

PubMed Central

Lee, Seungwon; Lee, Jisuk; Nam, Kyusuk; Shin, Weon Gyu; Sohn, Youngku

2016-01-01

Performing diverse application tests on synthesized metal oxides is critical for identifying suitable application areas based on the material performances. In the present study, Ni-oxide@TiO2 core-shell materials were synthesized and applied to photocatalytic mixed dye (methyl orange + rhodamine + methylene blue) degradation under ultraviolet (UV) and visible lights, CO oxidation, and supercapacitors. Their physicochemical properties were examined by field-emission scanning electron microscopy, X-ray diffraction analysis, Fourier-transform infrared spectroscopy, and UV-visible absorption spectroscopy. It was shown that their performances were highly dependent on the morphology, thermal treatment procedure, and TiO2 overlayer coating. PMID:28774145

Oxidation behavior of Al/Cr coating on Ti2AlNb alloy at 900 °C

NASA Astrophysics Data System (ADS)

Yang, Zhengang; Liang, Wenping; Miao, Qiang; Chen, Bowen; Ding, Zheng; Roy, Nipon

2018-04-01

In this paper, the Al/Cr coating was fabricated on the surface of Ti2AlNb alloy via rf magnetron sputtering and double glow treatment to enhance oxidation resistance. The protective coating with an outer layer of Al and inner layer of Cr has great bonding strength due to the in-diffusion of Cr and the inter-diffusion between Al and Cr to form Al-Cr alloyed layer which has great hardness. Acoustic emission curve which was detected via WS-2005 scratch tester indicates the bonding strength between Al/Cr coating and substrate is great. Morphology of Ti2AlNb alloy with Al/Cr coating after scratch test shows that the scratch is smooth without disbanding, and the depth and breadth of scratch are changed uniformly. The mass change was reduced after oxidation test due to the Al/Cr protective coating. Isothermal oxidation test at 900 °C was researched. Results indicate that Al/Cr coating provided oxidation resistance of Ti2AlNb alloy with prolonged air exposure at 900 °C. Al2O3 was detected by XRD patterns and SEM images, and was formed on the surface of Ti2AlNb alloy to protect substrate during oxidation test. A certain content of Cr is beneficial for the formation of Al2O3. Besides, Cr2O3 was produced under Al2O3 by outward diffusion of Cr to protect substrate sequentially, no cracks were discovered on Al/Cr protective coating. The process of Ti outward diffusion into surface was suppressive due to integration of Cr-Ti and Al-Ti intermetallics. A steady, adherent and continuous coated layer of Al/Cr on Ti2AlNb alloy increases oxidation resistance.

Composition and structure of acid leached LiMn 2-yTi yO 4 (0.2≤ y≤1.5) spinels

NASA Astrophysics Data System (ADS)

Avdeev, Georgi; Amarilla, José Manuel; Rojo, José María; Petrov, Kostadin; Rojas, Rosa María

2009-12-01

Lithium manganese titanium spinels, LiMn 2-yTi yO 4, (0.2≤ y≤1.5) have been synthesized by solid-state reaction between TiO 2 (anatase), Li 2CO 3 and MnCO 3. Li + was leached from the powdered reaction products by treatment in excess of 0.2 N HCl at 85 °C for 6 h, under reflux. The elemental composition of the acidic solution and solid residues of leaching has been determined by complexometric titration, atomic absorption spectroscopy and X-ray fluorescence analysis. Powder X-ray diffraction was used for structural characterization of the crystalline fraction of the solid residues. It has been found that the amount of Li + leached from LiMn 2-yTi yO 4 decreases monotonically with increasing y in the interval 0.2≤ y≤1.0 and abruptly drops to negligibly small values for y>1.0. The content of Mn and Li in the liquid phase and of Mn and Ti in the solid (amorphous plus crystalline) residue, were related to the composition and cation distribution in the pristine compounds. A new formal chemical equation describing the process of leaching and a mechanism of the structural transformation undergone by the initial solids as a result of Li + removal has been proposed.

Photocatalytic degradation of diclofenac using TiO2-SnO2 mixed oxide catalysts.

PubMed

Mugunthan, E; Saidutta, M B; Jagadeeshbabu, P E

2017-12-26

The complex nature of diclofenac limits its biological degradation, posing a serious threat to aquatic organisms. Our present work aims to eliminate diclofenac from wastewater through photocatalytic degradation using TiO 2 -SnO 2 mixed-oxide catalysts under various operating conditions such as catalyst loading, initial diclofenac concentration and initial pH. Different molar ratios of Ti-Sn (1:1, 5:1, 10:1, 20:1 and 30:1) were prepared by the hydrothermal method and were characterized. The results indicated that addition of Sn in small quantity enhances the catalytic activity of TiO 2 . Energy Band gap of the TiO 2 -SnO 2 catalysts was found to increase with an increase in Tin content. TiO 2 -SnO 2 catalyst with a molar ratio of 20:1 was found to be the most effective when compared to other catalysts. The results suggested that initial drug concentration of 20 mg/L, catalyst loading of 0.8 g/L and pH 5 were the optimum operating conditions for complete degradation of diclofenac. Also, the TiO 2 -SnO 2 catalyst was effective in complete mineralization of diclofenac with a maximum total organic carbon removal of 90% achieved under ultraviolet irradiation. The repeatability and stability results showed that the TiO 2 -SnO 2 catalyst exhibited an excellent repeatability and better stability over the repeated reaction cycles. The photocatalytic degradation of diclofenac resulted in several photoproducts, which were identified through LC-MS.

TiO2-Based Advanced Oxidation Nanotechnologies For Water Purification And Reuse

EPA Science Inventory

TiO₂ photocatalysis, one of the UV-based advanced oxidation technologies (AOTs) and nanotechnologies (AONs), has attracted great attention for the development of efficient water treatment and purification systems due to the effectiveness of TiO₂ to generate ...

Peculiarities of structure formation of layered metal-oxide system Ti-Ta-(Ti,Ta)xOy during electro-spark alloying and thermally stimulated modification

NASA Astrophysics Data System (ADS)

Fomina, Marina A.; Koshuro, Vladimir A.; Fomin, Aleksandr A.; Rodionov, Igor V.; Skaptsov, Aleksandr A.; Zakharevich, Andrey M.; Aman, Alexander; Oseev, Aleksandr; Hirsch, Soeren; Majcherek, Soeren

2016-04-01

The study focuses on high-performance combined electro-spark alloying of titanium and titanium alloy (VT1-0, VT16) surface and porous matrix structure oxidation. The metal-oxide coatings morphology is the result of melt drop transfer, heat treatment, and oxidation. The study establishes the influence of technological regimes of alloying and oxidation on morphological heterogeneity of biocompatible layered metal-oxide system Ti-Ta-(Ti,Ta)xOy. It was found that during electro-spark alloying the concentration of tantalum on the titanium surface ranges from 0.1 to 3.2 at.%. Morphology of the deposited splats is represented by uniformly grown crystals of titanium and tantalum oxides, which increase from nano- to submicron size.

Oxygen-storage behavior and local structure in Ti-substituted YMnO 3

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

Levin, I.; Krayzman, V.; Vanderah, T. A.

Hexagonal manganates RMnO3 (R=Y, Ho, Dy) have been recently shown to exhibit oxygen-storage capacities promising for three-way catalysts, air-separation, and related technologies. Here, we demonstrate that Ti substitution for Mn can be used to chemically tune the oxygen-breathing properties of these materials towards practical applications. Specifically, Y(Mn1-xTix)O3 solid solutions exhibit facile oxygen absorption/desorption via reversible Ti3+↔Ti4+ and Mn3+↔Mn4+ reactions already in ambient air at ≈400 °C and ≈250 °C, respectively. On cooling, the oxidation of both cations is accompanied by oxygen uptake yielding a formula YMn3+1-x-yMn4+yTi4+xO3+δ. The presence of Ti promotes the oxidation of Mn3+ to Mn4+, which is almostmore » negligible for YMnO3 in air, thereby increasing the uptake of oxygen beyond that required for a given Ti4+ concentration. The reversibility of the redox reactions is limited by sluggish kinetics; however, the oxidation process continues, if slowly, even at room temperature. The extra oxygen atoms are accommodated by the large interstices within a triangular lattice formed by the [MnO5] trigonal bipyramids. According to bond distances from Rietveld refinements using the neutron diffraction data, the YMnO3 structure features under-bonded Mn and even more severely under-bonded oxygen atoms that form the trigonal bases of the [MnO5] bipyramids. The tensile bond strain around the 5-fold coordinated Mn site and the strong preference of Ti4+(and Mn4+) for higher coordination numbers likely provide driving forces for the oxidation reaction. Reverse Monte Carlo refinements of the local atomic displacements using neutron total scattering revealed how the excess oxygen atoms are accommodated in the structure by correlated local displacements of the host atoms. Large displacements of the under-bonded host oxygen atoms play a key part in this lattice-relaxation process, facilitating reversible exchange of significant amounts of oxygen

Evolutionary search for novel superhard phases, or can TiO2 be the hardest oxide? (Invited)

NASA Astrophysics Data System (ADS)

Oganov, A. R.; Lyakhov, A. O.

2010-12-01

Synthesis of novel superhard materials, frequently achieved with high-pressure experimental techniques, is a difficult task. Study of such materials, usually first obtained in very small quantities, is complicated, and this field is full of controversies and artefacts (see, e.g. [1]). Hardness was long believed to be an exceedingly difficult property to model or predict; however, a number of simple models have recently been proposed and shown to yield surprisingly accurate results (see reviews in [2]). We have found [3] a way to further improve these models, by augmenting them with bond-valence model and graph theory. Combining such models with our structure prediction method [4], we have developed a powerful [5] approach for computational design of novel superhard materials. Using this method, we recently addressed [3] the previously proposed [6] possibility that C3N4 may be harder than diamond, and the claim [7] that TiO2-cotunnite is the hardest oxide with the Vickers hardness of 38 GPa. Our results unequivocally suggest that the latter suggestion is incorrect. No TiO2 polymorph can attain hardness greater than 17 GPa [3], i.e. all possible structures of TiO2 are softer than common corundum (Al2O3). Furthermore, TiO2-cotunnite is dynamically unstable at atmospheric pressure [8]. REFERENCES: [1] Oganov A.R., Solozhenko V.L., Kurakevych O.O., Gatti C., Ma Y., Chen J., Liu Z., and Hemley R.J., http://arxiv.org/abs/ 0908.2126 (2009). [2] Theory of Superhard Materials (Special Issue), J. Superhard Materials, issue 3 (2010). [3] Lyakhov A.O., Oganov A.R., in prep. (2010). [4] Oganov A.R., Glass C.W., J. Chem. Phys. 124, 244704 (2006). [5] Oganov A.R., Lyakhov A.O., J. Superhard Mater. 32, 143-147 (2010). [6] Liu A.Y., Cohen M.L., Science 245, 841-842 (1989). [7] Dubrovinsky L.S., Dubrovinskaia N.A., et al., Nature 410, 653-654 (2001). [8] Kim D.Y., et al., Appl. Phys. Lett. 90, 171903 (2007).

Thermoelectric and structural correlations in (S r1 -x -yC axN dy) Ti O3 perovskites

NASA Astrophysics Data System (ADS)

Somaily, H.; Kolesnik, S.; Dabrowski, B.; Chmaissem, O.

2017-08-01

Structural and thermoelectric properties are reported for a specially designed class of A -site substituted perovskite titanates, (S r1 -x -yC axN dy) Ti O3 . Two series synthesized with various A -site Sr-rich or Ca-rich (Sr-poor) concentrations were investigated using high-resolution neutron powder diffraction as a function of temperature and Nd doping. Each series was designed to have a nominally constant tolerance factor at room temperature. We determine the room temperature structures as tetragonal I 4 /m c m and orthorhombic P b n m for the Sr-rich and Ca-rich series, respectively. Three low-temperature orthorhombic structures, P b n m , I b m m , and P b c m were also observed for the Sr-rich series, whereas the symmetry of the Ca-rich series remains unchanged throughout the full measured temperature range. Thermoelectric properties of (S r1 -x -yC axN dy) Ti O3 were investigated and correlated with the structural variables. We succeeded in achieving a relatively high figure of merit Z T =0.07 at ˜400 K in the Sr-rich S r0.76C a0.16N d0.08Ti O3 composition which is comparable to that of the best n -type TE SrT i0.80N b0.20O3 oxide material reported to date. For a fixed tolerance factor, the Nd doping enhances the carrier density and effective mass at the expense of the Seebeck coefficient. Thermal conductivity greatly reduces upon Nd doping in the Ca-rich series. With an enhanced Seebeck coefficient at elevated temperatures and reduced thermal conductivity, we predict that S r0.76C a0.16N d0.08Ti O3 and similar compositions have the potential to become some of the best materials in their class of thermoelectric oxides.

Novel Au-TiC Catalysts for CO Oxidation and Desulfurization Processes

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

Rodriguez, J.A.; Liu, P.; Takahashi, Y.

2011-05-30

Recent articles dealing with the physical and chemical properties of novel Au-TiC catalysts are reviewed. High-resolution photoemission, scanning tunneling microscopy and first-principles periodic density-functional calculations were used to study the deposition of gold on a TiC(0 0 1) surface. Gold grows forming two-dimensional (very low coverage) and three-dimensional (medium and large coverage) islands on the carbide substrate. A positive shift in the binding energy of the C 1s core level is observed after the deposition of Au on TiC(0 0 1). The results of the density-functional calculations corroborate the formation of Au-C bonds. In general, the bond between Au andmore » the TiC(0 0 1) surface exhibits very little ionic character, but there is a substantial polarization of electrons around Au that facilitates bonding of the adatoms with electron-acceptor molecules (CO, O{sub 2}, C{sub 2}H{sub 4}, SO{sub 2}, thiophene, etc.). Experimental measurements indicate that Au/TiC(0 0 1) is a very good catalysts for the oxidation of CO, the destruction of SO{sub 2} and the hydrodesulfurization of thiophene. At temperatures below 200 K, Au/TiC(0 0 1) is able to perform the 2CO + O{sub 2} {yields} 2CO{sub 2} reaction and the full decomposition of SO{sub 2}. Furthermore, in spite of the very poor hydrodesulfurization performance of TiC(0 0 1) or Au(1 1 1), a Au/TiC(0 0 1) surface displays a hydrodesulfurization activity higher than that of conventional Ni/MoS{sub x} catalysts. Metal carbides are excellent supports for enhancing the chemical reactivity of gold. The Au/TiC system is more chemically active than systems generated by depositing Au nanoparticles on oxide surfaces.« less

Novel Au-TiC Catalysts for CO Oxidation and Desulfurization Processes

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

J Rodriguez; P Liu; Y Takahashi

2011-12-31

Recent articles dealing with the physical and chemical properties of novel Au-TiC catalysts are reviewed. High-resolution photoemission, scanning tunneling microscopy and first-principles periodic density-functional calculations were used to study the deposition of gold on a TiC(0 0 1) surface. Gold grows forming two-dimensional (very low coverage) and three-dimensional (medium and large coverage) islands on the carbide substrate. A positive shift in the binding energy of the C 1s core level is observed after the deposition of Au on TiC(0 0 1). The results of the density-functional calculations corroborate the formation of Au-C bonds. In general, the bond between Au andmore » the TiC(0 0 1) surface exhibits very little ionic character, but there is a substantial polarization of electrons around Au that facilitates bonding of the adatoms with electron-acceptor molecules (CO, O{sub 2}, C{sub 2}H{sub 4}, SO{sub 2}, thiophene, etc.). Experimental measurements indicate that Au/TiC(0 0 1) is a very good catalysts for the oxidation of CO, the destruction of SO{sub 2} and the hydrodesulfurization of thiophene. At temperatures below 200 K, Au/TiC(0 0 1) is able to perform the 2CO + O{sub 2} {yields} 2CO{sub 2} reaction and the full decomposition of SO{sub 2}. Furthermore, in spite of the very poor hydrodesulfurization performance of TiC(0 0 1) or Au(1 1 1), a Au/TiC(0 0 1) surface displays a hydrodesulfurization activity higher than that of conventional Ni/MoS{sub x} catalysts. Metal carbides are excellent supports for enhancing the chemical reactivity of gold. The Au/TiC system is more chemically active than systems generated by depositing Au nanoparticles on oxide surfaces.« less

Investigation of TiO2 based Mixed-metal Oxide Catalysts for the Production of Hydrogen

NASA Astrophysics Data System (ADS)

Luo, Si

Abstract of the Dissertation. Investigation of TiO2 based Mixed-metal Oxide Catalysts for the Production of Hydrogen. by. Si Luo. Doctor of Philosophy. in. Chemistry. Stony Brook University. 2017. The environmental impacts of fossil fuel consumption and the resulting global warming have attracted increasing attention to technologies and fuels that are both sustainable and renewable in the 21st century. To date, hydrogen has been proposed as an encouraging candidate of the next generation of chemical fuels, which meets all demands for carbon free and efficient chemistries that could be produced from a variety of sources. However, despite tremendous efforts, there is a clear need to develop new catalysts for the production of hydrogen through catalytic processes that are sustainable, such as in the photocatalytic splitting of water (PCS: H2O → H2 + 0.5O2) and the water-gas shift process (WGS: CO + H2O → H2 + CO2). This thesis is primarily motivated by this challenge and has focused on the photochemical and thermal production of H2 by the employment of novel TiO2 based catalysts. TiO2 is one of the most widely studied photocatalysts in all history, due to its relatively high activity, robust stability, safety and low cost. In this thesis, several TiO2-based mixed metal oxide nano catalysts (CeOx-TiO2, Ru-TiO2, Ga-TiO2) have been synthesized with carefully controlled morphology/structure and with inclusion of co-catalysts (Pt). These novel materials were comprehensively characterized to better understand their morphology, crystal structure, and electronic properties in an attempt to unravel phenomena responsible for high catalytic performance for the production of H2 from H2O. We have discovered the importance of low-dimensional metal oxide and interfacial stabilized nano-scaled mixed metal oxides for H2 production, while learning how best to tune such structure to optimize both thermal and photochemical conversion. Optimized structure and/or composition have been

Enhanced oxidation of naphthalene using plasma activation of TiO2/diatomite catalyst.

PubMed

Wu, Zuliang; Zhu, Zhoubin; Hao, Xiaodong; Zhou, Weili; Han, Jingyi; Tang, Xiujuan; Yao, Shuiliang; Zhang, Xuming

2018-04-05

Non-thermal plasma technology has great potential in reducing polycyclic aromatic hydrocarbons (PAHs) emission. But in plasma-alone process, various undesired by-products are produced, which causes secondary pollutions. Here, a dielectric barrier discharge (DBD) reactor has been developed for the oxidation of naphthalene over a TiO 2 /diatomite catalyst at low temperature. In comparison to plasma-alone process, the combination of plasma and TiO 2 /diatomite catalyst significantly enhanced naphthalene conversion (up to 40%) and CO x selectivity (up to 92%), and substantially reduced the formation of aerosol (up to 90%) and secondary volatile organic compounds (up to near 100%). The mechanistic study suggested that the presence of the TiO 2 /diatomite catalyst intensified the electron energy in the DBD. Meantime, the energized electrons generated in the discharge activated TiO 2 , while the presence of ozone enhanced the activity of the TiO 2 /diatomite catalyst. This plasma-catalyst interaction led to the synergetic effect resulting from the combination of plasma and TiO 2 /diatomite catalyst, consequently enhanced the oxidation of naphthalene. Importantly, we have demonstrated the effectiveness of plasma to activate the photocatalyst for the deep oxidation of PAH without external heating, which is potentially valuable in the development of cost-effective gas cleaning process for the removal of PAHs in vehicle applications during cold start conditions. Copyright © 2017 Elsevier B.V. All rights reserved.

Titanium oxide (TiO2) nanoparticles in induction of apoptosis and inflammatory response in brain

NASA Astrophysics Data System (ADS)

Meena, Ramovatar; Kumar, Sumit; Paulraj, R.

2015-01-01

The ever increasing applications of engineered nanoparticles in 21st century cause serious concern about its potential health risks on living being. Regulatory health risk assessment of such particles has become mandatory for the safe use of nanomaterials in consumer products and medicines. In order to study the mechanism underlying the effects of nano-TiO2 (TiO2 nanoparticles) on the brain, wistar rats were administrated intravenously with various doses of nano-TiO2 (21 nm) through the caudal vein, once a week for 4 weeks and different parameters such as bioaccumulation of nano-TiO2, oxidative stress-mediated response, level of inflammatory markers such as NF-κB (p65), HSP 60, p38, nitric oxide, IFN-γ and TNF-α, and level of neurochemicals in brain as well as DNA damage and expression of apoptosis markers (p53, Bax, Bcl-2, and cyto c) were evaluated. Results show that the concentration of nano-TiO2 in the brain increased with increasing the doses of nano-TiO2. Oxidative stress and injury of the brain occurred as nano-TiO2 appeared to trigger a cascade of reactions such as inflammation, lipid peroxidation, decreases the activities of antioxidative enzymes and melatonin level, the reduction of glutamic acid, downregulated levels of acetylcholinesterase activities, and the increase in caspase-3 activity (a biomarker of apoptosis), DNA fragmentation, and apoptosis. It may be concluded that nano-TiO2 induces oxidative stress that leads to activation of inflammatory cytokines and an alteration in the level of neurotransmitters resulted in the induction of mitochondrial-mediated apoptosis.

Investigation of physicochemical and tribological properties of transparent oxide semiconducting thin films based on Ti-V oxides

NASA Astrophysics Data System (ADS)

Mazur, M.; Sieradzka, K.; Kaczmarek, D.; Domaradzki, J.; Wojcieszak, D.; Domanowski, P.

2013-08-01

In this paper investigations of structural and optical properties of nanocrystalline Ti-V oxide thin films are described. The films were deposited onto Corning 7059 glass using a modified reactive magnetron sputtering method. Structural investigations of prepared Ti-V oxides with vanadium addition of 19 at. % revealed amorphous structure, while incorporation of 21 and 23 at. % of vanadium resulted in V2O5 formation with crystallites sizes of 12.7 and 32.4 nm, respectively. All prepared thin films belong to transparent oxide semiconductors due to their high transmission level of ca. 60-75 % in the visible light range, and resistivity in the range of 3.3·102-1.4·105 Ωcm. Additionally, wettability and hardness tests were performed in order to evaluate the usefulness of the films for functional coatings.

Surface XPS characterization of NiTi shape memory alloy after advanced oxidation processes in UV/H 2O 2 photocatalytic system

NASA Astrophysics Data System (ADS)

Wang, R. M.; Chu, C. L.; Hu, T.; Dong, Y. S.; Guo, C.; Sheng, X. B.; Lin, P. H.; Chung, C. Y.; Chu, P. K.

2007-08-01

Surface structure of NiTi shape memory alloy (SMA) was modified by advanced oxidation processes (AOP) in an ultraviolet (UV)/H 2O 2 photocatalytic system, and then systematically characterized with x-ray photoelectron spectroscopy (XPS). It is found that the AOP in UV/H 2O 2 photocatalytic system leads to formation of titanium oxides film on NiTi substrate. Depth profiles of O, Ni and Ti show such a film possesses a graded interface structure to NiTi substrate and there is no intermediate Ni-rich layer like that produced in conventional high temperature oxidation. Except TiO 2 phase, some titanium suboxides (TiO, Ti 2O 3) may also exist in the titanium oxides film. Oxygen mainly presents in metal oxides and some chemisorbed water and OH - are found in titanium oxides film. Ni nearly reaches zero on the upper surface and relatively depleted in the whole titanium oxides film. The work indicates the AOP in UV/H 2O 2 photocatalytic system is a promising way to favor the widespread application of biomedical NiTi SMA by improving its biocompatibility.

TiO2-photocatalyzed As(III) oxidation in a fixed-bed, flow-through reactor.

PubMed

Ferguson, Megan A; Hering, Janet G

2006-07-01

Compliance with the U.S. drinking water standard for arsenic (As) of 10 microg L(-1) is required in January 2006. This will necessitate implementation of treatment technologies for As removal by thousands of water suppliers. Although a variety of such technologies is available, most require preoxidation of As(III) to As(V) for efficient performance. Previous batch studies with illuminated TiO2 slurries have demonstrated that TiO2-photocatalyzed AS(III) oxidation occurs rapidly. This study examined reaction efficiency in a flow-through, fixed-bed reactor that provides a better model for treatment in practice. Glass beads were coated with mixed P25/sol gel TiO2 and employed in an upflow reactor irradiated from above. The reactor residence time, influent As(III) concentration, number of TiO2 coatings on the beads, solution matrix, and light source were varied to characterize this reaction and determine its feasibility for water treatment. Repeated usage of the same beads in multiple experiments or extended use was found to affect effluent As(V) concentrations but not the steady-state effluent As(III) concentration, which suggests that As(III) oxidation at the TiO2 surface undergoes dynamic sorption equilibration. Catalyst poisoning was not observed either from As(V) or from competitively adsorbing anions, although the higher steady-state effluent As(III) concentrations in synthetic groundwater compared to 5 mM NaNO3 indicated that competitive sorbates in the matrix partially hinder the reaction. A reactive transport model with rate constants proportional to incident light at each bead layer fit the experimental data well despite simplifying assumptions. TiO2-photocatalyzed oxidation of As(III) was also effective under natural sunlight. Limitations to the efficiency of As(III) oxidation in the fixed-bed reactor were attributable to constraints of the reactor geometry, which could be overcome by improved design. The fixed-bed TiO2 reactor offers an environmentally

Oxidation of refractory sulfur compounds over Ti-containing mesoporous molecular sieves prepared by using a fluorosilicon compound.

PubMed

Jeong, Kwang-Eun; Cho, Chin-Soo; Chae, Ho-Jeong; Kim, Chul-Ung; Jeong, Soon-Yong

2010-05-01

Titanium containing mesoporous molecular sieve (Ti-MMS) catalysts were studied for the oxidative desulfurization of refractory sulfur compounds. Ti-MMS catalysts were synthesized from fluorosilicon compounds and Ti with the hydrolysis reaction of H2SiF6 in an ammonia-surfactant mixed solution. The solid products were characterized by XRD, XRF, nitrogen adsorption, and diffuse reflectance UV-vis spectroscopy. Effects of Ti loading and oxidant/sulfur mole ratio, and sulfur species on ODS activity were investigated.

Ab Initio Study of the Atomic Level Structure of the Rutile TiO2(110)-Titanium Nitride (TiN) Interface.

PubMed

Gutiérrez Moreno, José Julio; Nolan, Michael

2017-11-01

Titanium nitride (TiN) is widely used in industry as a protective coating due to its hardness and resistance to corrosion and can spontaneously form a thin oxide layer when it is exposed to air, which could modify the properties of the coating. With limited understanding of the TiO 2 -TiN interfacial system at present, this work aims to describe the structural and electronic properties of oxidized TiN based on a density functional theory (DFT) study of the rutile TiO 2 (110)-TiN(100) interface model system, also including Hubbard +U correction on Ti 3d states. The small lattice mismatch gives a good stability to the TiO 2 -TiN interface after depositing the oxide onto TiN through the formation of interfacial Ti-O bonds. Our DFT+U study shows the presence of Ti 3+ cations in the TiO 2 region, which are preferentially located next to the interface region as well as the rotation of the rutile TiO 2 octahedra in the interface structure. The DFT+U TiO 2 electronic density of states (EDOS) shows localized Ti 3+ defect states forming in the midgap between the top edge of the valence and the bottom of the conduction band. We increase the complexity of our models by the introduction of nonstoichiometric compositions. Although the vacancy formation energies for Ti in TiN (E vac (Ti) ≥ 4.03 eV) or O in the oxide (E vac (O) ≥ 3.40 eV) are quite high relative to perfect TiO 2 -TiN, defects are known to form during the oxide growth and can therefore be present after TiO 2 formation. Our results show that a structure with exchanged O and N can lie 0.82 eV higher in energy than the perfect system, suggesting the stability of structures with interdiffused O and N anions at ambient conditions. The presence of N in TiO 2 introduces N 2p states localized between the top edge of the O 2p valence states and the midgap Ti 3+ 3d states, thus reducing the band gap in the TiO 2 region for the exchanged O/N interface EDOS. The outcomes of these simulations give us a most comprehensive

Effect of different processes and Ti/Zn molar ratios on the structure, morphology, and enhanced photoelectrochemical and photocatalytic performance of Ti3+ self-doped titanium–zinc hybrid oxides

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

Fu, Rongrong; Wang, Qingyao; Gao, shanmin

2015-07-01

Ti3+ self-doped titanium–zinc hybrid oxides with different phase compositions and morphologies were successfully synthesized using Zn powder as the reductant and Zn source by a chemical-reduction precipitation method with subsequent thermal treatment. The fabricated Ti3+ self-doped TiO2(A)/TiO2(R), TiO2(A)/TiO2(R)/ZnTiO3, and TiO2(A)/ZnO heterojunctions were characterized by X-ray diffraction, transmission electron microscopy, high-resolution transmission electron microscopy, X-ray photoelectron spectroscopy, and UV–Vis diffuse reflectance spectroscopy. The effects of various Ti/Zn molar ratios and preparation processes on the structural, morphological, optical, photocurrent and photocatalytic properties of the resultant samples were investigated systematically. Results reveal that Ti3+ self-doping enhances the photoabsorption capability of titanium–zinc hybrid oxidesmore » in the visible-light region. Moreover, different processes and Ti/Zn molar ratios play great influences on the structure, morphology, optical, photocurrent and photocatalytic properties of the final products. Ti3+ self-doped titanium–zinc hybrid oxides exhibit excellent photocurrent and photocatalytic activity than pure TiO2 and ZnTiO3 under visible-light irradiation (λ ≥ 400 nm). The most active Ti3+ self-doped titanium–zinc hybrid oxides photoanode presents significantly improved water splitting performance. The synergistic effect between the Ti3+ self-doped and heterojunctions is responsible for the enhanced performance of these materials.« less

New ramsdellites LiTi 2-yV yO 4 (0≤ y≤1): Synthesis, structure, magnetic properties and electrochemical performances as electrode materials for lithium batteries

NASA Astrophysics Data System (ADS)

Kuhn, Alois; Martín, María; García-Alvarado, Flaviano

2010-01-01

The new ramsdellite series LiTi 2-yV yO 4 (0≤ y≤1) has been prepared by conventional solid state chemistry techniques and was characterized by X-ray powder diffraction and electron diffraction. To our knowledge, this is the first report on ramsdellites containing vanadium. The magnetic behaviour of these ramsdellites is strongly influenced by its vanadium content. In this sense, LiTi 2O 4 ( y=0) exhibits metallic-like temperature independent paramagnetism, but d electrons tend to localize with increasing V content. LiTiVO 4, though also paramagnetic, follows then the Curie-Weiss law. The crossover from delocalized to localized electrons is observed between compositions y=0.6 and 0.8. For y≥0.8 the magnetic results evidence an isovalent substitution mechanism of trivalent Ti by V. The electrochemical lithium intercalation and deintercalation chemistry of LiTi 2-yV yO 4 is grouped into two different operating voltage regions. Reversible lithium deintercalation of vanadium-substituted ramsdellite titanates LiTi 2-yV yO 4 in the high voltage range 2-3 V vs. Li occurs in two main steps, one at about 2 V and the other at about 3 V. The 3 V process capacity increases with the vanadium content, while the 2 V capacity decreases at the same time. The vanadium to titanium substitution rate in LiTi 2O 4 was found to be beneficial to the specific energy in as much as a 50% increase (1 V) of the working voltage is observed. On the other hand, reversible lithium intercalation in vanadium-substituted ramsdellite titanates LiTi 2-yV yO 4 in the low voltage range 1-2 V vs. Li occurs in one main single step, in which the capacity is not affected by the vanadium content, although vanadium-doping produces an improved capacity retention with an excellent cycling behaviour observed for y≤0.6.

Rapid photo-degradation of 2-chlorophenol under visible light irradiation using cobalt oxide-loaded TiO2/reduced graphene oxide nanocomposite from aqueous media.

PubMed

Sharma, Ajit; Lee, Byeong-Kyu

2016-01-01

The photocatalytic removal of 2-chlorophenol (2-CP) from water environment was investigated by TiO2-RGO-CoO. Cobalt oxide-loaded TiO2 (TiO2-CoO) supported with reduced graphene oxide (RGO) was synthesized using a sol-gel method and then annealed at 500 °C for 5 min. The material characteristics were analyzed by UV-Vis analysis, Fourier transform infrared (FTIR) spectroscopy, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM) and energy dispersive X-ray (EDX) spectroscopy. Incorporation of cobalt oxide and RGO into the TiO2 system (TiO2-RGO-CoO) lowered the band gap energy to 2.83 eV, which greatly enhanced the visible light absorption. The TiO2-RGO-CoO photocatalyst showed complete removal of 20 mg/L 2-CP within 8 h with the addition of 0.01% H2O2 under 100 W visible light irradiation. The photo-degradation efficiency of 2-CP (10 mg/L) was 35.2, 48.9, 58.9 and 98.2% for TiO2, TiO2-RGO, TiO2-CoO and TiO2-RGO-CoO, respectively, in the presence of visible light irradiation at solution pH of 6.0. The TiO2-RGO-CoO photocatalyst retained its high removal efficiency even after five photocatalytic cycles. Copyright © 2015 Elsevier Ltd. All rights reserved.

Plasma-induced synthesis of Pt nanoparticles supported on TiO2 nanotubes for enhanced methanol electro-oxidation

NASA Astrophysics Data System (ADS)

Su, Nan; Hu, Xiulan; Zhang, Jianbo; Huang, Huihong; Cheng, Jiexu; Yu, Jinchen; Ge, Chao

2017-03-01

A Pt/C/TiO2 nanotube composite catalyst was successfully prepared for enhanced methanol electro-oxidation. Pt nanoparticles with a particle size of 2 nm were synthesized by plasma sputtering in water, and anatase TiO2 nanotubes with an inner diameter of approximately 100 nm were prepared by a simple two-step anodization method and annealing process. Field-emission scanning electron microscopy images indicated that the different morphologies of TiO2 synthesized on the surface of Ti foils were dependent on the different anodization parameters. The electrochemical performance of Pt/C/TiO2 catalysts for methanol oxidation showed that TiO2 nanotubes were more suitable for use as Pt nanoparticle support materials than irregular TiO2 short nanorods due to their tubular morphology and better electronic conductivity. X-ray photoelectron spectroscopy characterization showed that the binding energies of the Pt 4f of the Pt/C/TiO2 nanotubes exhibited a slightly positive shift caused by the relatively strong interaction between Pt and the TiO2 nanotubes, which could mitigate the poisoning of the Pt catalyst by COads, and further enhance the electrocatalytic performance. Thus, the as-obtained Pt/C/TiO2 nanotubes composites may become a promising catalyst for methanol electro-oxidation.

Simple synthesized Pt/GNs/TiO2 with good mass activity and stability for methanol oxidation

NASA Astrophysics Data System (ADS)

Zhang, Jianbo; Hu, Xiulan; Zhu, Faquan; Su, Nan; Huang, Huihong; Cheng, Jiexu; Yang, Hui

2017-12-01

Pt/GNs/TiO2 (GNs, graphene nanosheets) catalyst was synthesized by a simple two-step method, including a rapid solution plasma technique to obtained Pt nanoparticles with a size of 2-5 nm and followed by an ultrasonic mixing of the Pt, GNs and TiO2 nanoparticles. After coupling with TiO2 nanoparticles, the Pt/GNs/TiO2 catalyst exhibited a promoting catalytic activity towards methanol oxidation, which was superior to the Pt/GNs catalyst. The mass activity of the Pt/GNs/TiO2 catalyst was 3464 mA mgPt -1, which was 3.5 and 3.4 times higher than those of the Pt/GNs and the commercial Pt/C, respectively. And the Pt/GNs/TiO2 showed a strongly negative shift onset potential of methanol oxidation. The results of long-term cyclic voltammetry and CO-stripping tests showed an improved CO tolerance of the Pt/GNs/TiO2. Moreover, the mass activity of the Pt/GNs/TiO2 was further enhanced under light irradiation, with the mass activity of 4715 mA mgPt -1, which was 1.4 times higher than that of in dark. This work provides new opportunities for exploiting efficient visible photo-assisted electro-catalytic methanol oxidation.

Facile synthesis of polyaniline/TiO2/graphene oxide composite for high performance supercapacitors

NASA Astrophysics Data System (ADS)

Su, Haifang; Wang, Teng; Zhang, Shengyi; Song, Jiming; Mao, Changjie; Niu, Helin; Jin, Baokang; Wu, Jieying; Tian, Yupeng

2012-06-01

The polyaniline/TiO2/graphene oxide (PANI/TiO2/GO) composite, as a novel supercapacitor material, is synthesized by in situ hydrolyzation of tetrabutyl titanate and polymerization of aniline monomer in the presence of graphene oxide. The morphology, composition and structure of the composites as-obtained are characterized by SEM, TEM, XRD and TGA. The electrochemical property and impedance of the composites are studied by cyclic voltammetry and Nyquist plot, respectively. The results show that the introduction of the GO and TiO2 enhanced the electrode conductivity and stability, and then improved the supercapacitive behavior of PANI/TiO2/GO composite. Significantly, the electrochemical measurement results show that the PANI/TiO2/GO composite has a high specific capacitance (1020 F g-1 at 2 mV s-1, 430 F g-1 at 1 A g-1) and long cycle life (over 1000 times).

New oxidation treatment of NiTi shape memory alloys to obtain Ni-free surfaces and to improve biocompatibility.

PubMed

Michiardi, A; Aparicio, C; Planell, J A; Gil, F J

2006-05-01

Various oxidation treatments were applied to nearly equiatomic NiTi alloys so as to form a Ni-free protective oxide on the surface. Sample surfaces were analyzed by X-ray Photoelectron Spectroscopy, and NiTi transformation temperatures were determined by differential scanning calorimetry (DSC) before and after the surface treatment. An ion release experiment was carried out up to one month of immersion in SBF for both oxidized and untreated surfaces. The results show that oxidation treatment in a low-oxygen pressure atmosphere leads to a high surface Ti/Ni ratio, a very low Ni surface concentration and a thick oxide layer. This oxidation treatment does not significantly affect the shape memory properties of the alloy. Moreover, the oxide formed significantly decreases Ni release into exterior medium comparing with untreated surfaces. As a consequence, this new oxidation treatment could be of great interest for biomedical applications, as it could minimize sensitization and allergies and improve biocompatibility and corrosion resistance of NiTi shape memory alloys. (c) 2005 Wiley Periodicals, Inc.

Preparation and self-sterilizing properties of Ag@TiO2-styrene-acrylic complex coatings.

PubMed

Zhou, Xiang-dong; Chen, Feng; Yang, Jin-tao; Yan, Xiao-hui; Zhong, Ming-qiang

2013-04-01

In this study, we report a simple and cost-effective method for self-sterilized complex coatings obtained by Ag@TiO2 particle incorporation into styrene-acrylic latex. The Ag@TiO2 particles were prepared via a coupling agent modification process. The composite latices characterized by transmission electron microscopy (TEM) study were highly homogeneous at the nanometric scale, and the Ag@TiO2 particles were well dispersed and exhibited an intimate contact between both the organic and inorganic components. The Ag@TiO2 nanoparticles significantly enhanced the absorption in the visible region and engendered a good heat-insulating effect of the complex coatings. Moreover, the Ag@TiO2 nanoparticle incorporation into this polymer matrix renders self-sterilized nanocomposite materials upon light excitation, which are tested against Escherichia coli and Staphylococcus aureus. The complex coatings display an impressive performance in the killing of all micro-organisms with a maximum for a Ag@TiO2 loading concentration of 2-5 wt.%. The weathering endurance of the complex coating was also measured. Copyright © 2012 Elsevier B.V. All rights reserved.

Magnetic dilution and domain selection in the X Y pyrochlore antiferromagnet Er2Ti2O7

NASA Astrophysics Data System (ADS)

Gaudet, J.; Hallas, A. M.; Maharaj, D. D.; Buhariwalla, C. R. C.; Kermarrec, E.; Butch, N. P.; Munsie, T. J. S.; Dabkowska, H. A.; Luke, G. M.; Gaulin, B. D.

2016-08-01

Below TN=1.1 K, the X Y pyrochlore Er2Ti2O7 orders into a k =0 noncollinear, antiferromagnetic structure referred to as the ψ2 state. The magnetic order in Er2Ti2O7 is known to obey conventional three-dimensional (3D) percolation in the presence of magnetic dilution, and in that sense is robust to disorder. Recently, however, two theoretical studies have predicted that the ψ2 structure should be unstable to the formation of a related ψ3 magnetic structure in the presence of magnetic vacancies. To investigate these theories, we have carried out systematic elastic and inelastic neutron scattering studies of three single crystals of Er2 -xYxTi2O7 with x =0 (pure), 0.2 (10 %Y ) and 0.4 (20 % Y ), where magnetic Er3 + is substituted by nonmagnetic Y3 +. We find that the ψ2 ground state of pure Er2Ti2O7 is significantly affected by magnetic dilution. The characteristic domain selection associated with the ψ2 state, and the corresponding energy gap separating ψ2 from ψ3, vanish for Y3 + substitutions between 10 % Y and 20 % Y , far removed from the three-dimensional percolation threshold of ˜60 % Y . The resulting ground state for Er2Ti2O7 with magnetic dilutions from 20 % Y up to the percolation threshold is naturally interpreted as a frozen mosaic of ψ2 and ψ3 domains.

Hierarchical Ti-Nb oxide microspheres with synergic multiphase structure as ultra-long-life anode materials for lithium-ion batteries

NASA Astrophysics Data System (ADS)

Wang, Guanqin; Wen, Zhongsheng; Du, Lulu; Yang, Yan-E.; Li, Song; Sun, Juncai; Ji, Shijun

2017-11-01

Titanium/niobium oxides have drawn wide attention due to their attractive high lithium-intercalation voltage avoiding the formation of solid electrochemical interface. However, their poor electronic conductivity hinders the commercial applications because of the low electrochemical kinetics in lithiating and de-lithiating process. In the study, new approach to improving the low conductivity of the conventional oxides in micrometers are tactically proposed via the synergic effect of highly mixed multiphase oxide nanocrystals. Ti-Nb oxide composite microspheres with hierarchical microstructure are fabricated successfully via a very facile method combined solvothermal process and calcination. Interconnected crystalline nanoparticles of TiO2, Nb2O5 and TiNb2O7 nanocrystals are involved in the obtained Ti-Nb oxides, demonstrating high structure stability during electrochemical reaction. Meanwhile, the ionic/electronic conductivity is remarkably enhanced by the defects of O2- vacancies and Ti3+/Nb4+ ions. The remained specific capacity of the multiphase Ti-Nb oxides is up to 185.3 mAh g-1 at 5 C with very weak capacity fade of 5.3% after 1800 cycles, showing a very long cycling stability.

Development of an E-H2O2/TiO2 photoelectrocatalytic oxidation system for water and wastewater treatment.

PubMed

Li, X Z; Liu, H S

2005-06-15

In this study, an innovative E-H2O2/TiO2 (E-H2O2 = electrogenerated hydrogen peroxide) photoelectrocatalytic (PEC) oxidation system was successfully developed for water and wastewater treatment. A TiO2/Ti mesh electrode was applied in this photoreactor as the anode to conduct PEC oxidation, and a reticulated vitreous carbon (RVC) electrode was used as the cathode to electrogenerate hydrogen peroxide simultaneously. The TiO2/Ti mesh electrode was prepared with a modified anodic oxidation process in a quadrielectrolyte (H2SO4-H3PO4-H2O2-HF) solution. The crystal structure, surface morphology, and film thickness of the TiO2/Ti mesh electrode were characterized by X-ray diffraction and scanning electron microscopy. The analytical results showed that a honeycomb-type anatase film with a thickness of 5 microm was formed. Photocatalytic oxidation (PC) and PEC oxidation of 2,4,6-trichlorophenol (TCP) in an aqueous solution were performed under various experimental conditions. Experimental results showed that the TiO2/Ti electrode, anodized in the H2SO4-H3PO4-H2O2-HF solution, had higher photocatalytic activity than the TiO2/Ti electrode anodized in the H2SO4 solution. It was found that the maximum applied potential would be around 2.5 V, corresponding to an optimum applied current density of 50 microA cm(-2) under UV-A illumination. The experiments confirmed that the E-H2O2 on the RVC electrode can significantly enhance the PEC oxidation of TCP in aqueous solution. The rate of TCP degradation in such an E-H2O2-assisted TiO2 PEC reaction was 5.0 times that of the TiO2 PC reaction and 2.3 times that of the TiO2 PEC reaction. The variation of pH during the E-H2O2-assisted TiO2 PEC reaction, affected by individual reactions, was also investigated. It was found that pH was well maintained during the TCP degradation in such an E-H2O2/TiO2 reaction system. This is beneficial to TCP degradation in an aqueous solution.

The effect of site geometry, Ti content and Ti oxidation state on the Ti K-edge XANES spectrum of synthetic hibonite

NASA Astrophysics Data System (ADS)

Doyle, P. M.; Berry, A. J.; Schofield, P. F.; Mosselmans, J. F. W.

2016-08-01

The Al-rich oxide hibonite (CaAl12O19) is modeled to be the second mineral to condense from a gas of solar composition and is found within calcium-aluminum-rich inclusions and the matrix of chondritic meteorites. Both Ti3+ and Ti4+ are reported in meteoritic hibonite, so hibonite has been proposed as a single mineral oxybarometer that could be used to elucidate conditions within the first 0.2 Myrs of the Solar System. Synthetic hibonites with Ti3+/(Ti3+ + Ti4+) (hereafter Ti3+/ΣTi) ranging between 0 and 1 were prepared as matrix-matched standards for meteoritic hibonite. The largest yield of both Ti-free and Ti-bearing hibonite at ∼1300 and ∼1400 °C was obtained by a single sinter under reducing conditions. In situ micro-beam Ti K-edge X-ray absorption near edge structure (XANES) spectra were recorded from the synthetic hibonites, as well as from terrestrial hibonite. Spectral features in the post-crest region were shown to correlate with the Ti4+ content. Furthermore, Ti4+ on the M2 trigonal bipyramidal and the adjoining M4 octahedral sites appears to cause variability in the post-crest region as a function of orientation. For this suite of synthetic hibonites it was observed that the pre-edge peak region is not influenced by orientation, but is controlled by Ti3+/ΣTi, site geometry and/or Ti concentration. In particular, the pre-edge peak intensities reflect Ti coordination environment and distortion of the M4 octahedral site. Therefore, although pre-edge peak intensities have previously been used to determine Ti3+/ΣTi in meteoritic minerals, we excluded use of the pre-edge peak intensities for quantifying Ti valence states in hibonite. The energy of the absorption edge at a normalized intensity of 0.8 (E0.8) and the energy of the minimum between the pre-edge region and the absorption edge (Em1) were found to vary systematically with Ti3+/ΣTi. Ti3+/ΣTi in hibonite as a function of Em1 was modeled by a quadratic function that may be used to quantify Ti3

Complex oxides: Intricate disorder

DOE PAGES

Uberuaga, Blas Pedro

2016-02-29

In this study, complex oxides such as pyrochlores have a myriad of potential technological applications, including as fast ion conductors and radiation-tolerant nuclear waste forms. They are also of interest for their catalytic and spin ice properties. Many of these functional properties are enabled by the atomic structure of the cation sublattices. Pyrochlores (A2B2O7) contain two different cations (A and B), typically a 3+ rare earth and a 4+ transition metal such as Hf, Zr, or Ti. The large variety of chemistries that can form pyrochlores leads to a rich space in which to search for exotic new materials. Furthermore,more » how cations order or disorder on their respective sublattices for a given chemical composition influences the functional properties of the oxide. For example, oxygen ionic conductivity is directly correlated with the level of cation disorder — the swapping of A and B cations 1. Further, the resistance of these materials against amorphization has also been connected with the ability of the cations to disorder 2, 3. These correlations between cation structure and functionality have spurred great interest in the structure of the cation sublattice under irradiation, with significant focus on the disordering mechanisms and disordered structure. Previous studies have found that, upon irradiation, pyrochlores often undergo an order-to-disorder transformation, in which the resulting structure is, from a diffraction point of view, indistinguishable from fluorite (AO2) (ref. 3). Shamblin et al. now reveal that the structure of disordered pyrochlore is more complicated than previously thought 4.« less

Microstructures and Properties of Plasma Electrolytic Oxidized Ti Alloy (Ti-6Al-4V) for Bio-implant Application

NASA Astrophysics Data System (ADS)

Kumari, Renu; Blawert, Carsten; Majumdar, J. Dutta

2016-02-01

In the present study, plasma electrolytic oxidation (PEO) of Ti6Al4V has been performed in an electrolyte containing 20 g/L of Na2SiO3, 10 g/L of Na3PO4, 2 g/L of KOH, and 5 g/L of hydroxyapatite at an optimum constant potential of 430 V for 10 minutes. Followed by PEO treatment, surface roughness was measured using non-contact optical profilometer. A detailed characterization of microstructure, composition and phase analysis was carried out using scanning electron microscopy, energy-dispersive X-ray spectroscopic analysis, Fourier-transform infrared, and X-ray diffraction study. The mechanical properties of the surface have been evaluated by measuring nano-hardness and wear resistance. The effect of surface modification on corrosion resistance property has also been evaluated in Hank's solution. Finally, wettability and bioactivity test have been also performed. PEO developed a thick (150 μm) porous (35 pct) oxide film on the surface of Ti-6Al-4V consisting of anatase, rutile, and SiO2. The nano-hardness of the PEO-treated surface is increased to 8 ± 0.5 GPa as compared to 2 ± 0.4 GPa of the as-received Ti-6Al-4V. Wear and corrosion resistance were improved following oxidation. There is an improvement in wettability in terms of decrease in contact angle from 60 ± 1.5 to 45 ± 1 deg. Total surface energy and its polar component were also increased significantly on PEO-treated surface as compared to the as-received Ti6Al4V.

Cationic (V, Y)-codoped TiO2 with enhanced visible light induced photocatalytic activity: A combined experimental and theoretical study

NASA Astrophysics Data System (ADS)

Khan, Matiullah; Cao, Wenbin

2013-11-01

To employ TiO2 as an efficient photocatalyst, high reactivity under visible light and improved separation of photoexcited carriers are required. An effective co-doping approach is applied to modify the photocatalytic properties of TiO2 by doping vanadium (transition metal) and yttrium (rare earth element). V and/or Y codoped TiO2 was prepared using hydrothermal method without any post calcination for crystallization. Based on density functional theory, compensated and noncompensated V, Y codoped TiO2 models were constructed and their structural, electronic, and optical properties were calculated. Through combined experimental characterization and theoretical modeling, V, Y codoped TiO2 exhibited high absorption coefficient with enhanced visible light absorption. All the prepared samples showed pure anatase phase and spherical morphology with uniform particle distribution. Electronic band structure demonstrates that V, Y codoping drastically reduced the band gap of TiO2. It is found that both the doped V and Y exist in the form of substitutional point defects replacing Ti atom in the lattice. The photocatalytic activity, evaluated by the degradation of methyl orange, displays that the codoped TiO2 sample exhibits enhanced visible light photocatalytic activity. The synergistic effects of V and Y drastically improved the Brunauer-Emmett-Teller specific surface area, visible light absorption, and electron-hole pair's separation leading to the enhanced visible light catalytic activity.

Oxygen-storage behavior and local structure in Ti-substituted YMnO{sub 3}

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

Levin, I., E-mail: igor.levin@nist.gov; Krayzman, V.; Vanderah, T.A.

Hexagonal manganates RMnO{sub 3} (R=Y, Ho, Dy) have been recently shown to exhibit oxygen-storage capacities promising for three-way catalysts, air-separation, and related technologies. Here, we demonstrate that Ti substitution for Mn can be used to chemically tune the oxygen-breathing properties of these materials towards practical applications. Specifically, Y(Mn{sub 1−x}Ti{sub x})O{sub 3} solid solutions exhibit facile oxygen absorption/desorption via reversible Ti{sup 3+}↔Ti{sup 4+} and Mn{sup 3+}↔Mn{sup 4+} reactions already in ambient air at ≈400 °C and ≈250 °C, respectively. On cooling, the oxidation of both cations is accompanied by oxygen uptake yielding a formula YMn{sup 3+}{sub 1−x-y}Mn{sup 4+}{sub y}Ti{sup 4+}{sub x}O{submore » 3+δ}. The presence of Ti promotes the oxidation of Mn{sup 3+} to Mn{sup 4+}, which is almost negligible for YMnO{sub 3} in air, thereby increasing the uptake of oxygen beyond that required for a given Ti{sup 4+} concentration. The reversibility of the redox reactions is limited by sluggish kinetics; however, the oxidation process continues, if slowly, even at room temperature. The extra oxygen atoms are accommodated by the large interstices within a triangular lattice formed by the [MnO{sub 5}] trigonal bipyramids. According to bond distances from Rietveld refinements using the neutron diffraction data, the YMnO{sub 3} structure features under-bonded Mn and even more severely under-bonded oxygen atoms that form the trigonal bases of the [MnO{sub 5}] bipyramids. The tensile bond strain around the 5-fold coordinated Mn site and the strong preference of Ti{sup 4+}(and Mn{sup 4+}) for higher coordination numbers likely provide driving forces for the oxidation reaction. Reverse Monte Carlo refinements of the local atomic displacements using neutron total scattering revealed how the excess oxygen atoms are accommodated in the structure by correlated local displacements of the host atoms. Large displacements of the

The interfacial orientation relationship of oxide nanoparticles in a hafnium-containing oxide dispersion-strengthened austenitic stainless steel

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

Miao, Yinbin, E-mail: miao2@illinois.edu; Mo, Kun; Cui, Bai

2015-03-15

This work reports comprehensive investigations on the orientation relationship of the oxide nanoparticles in a hafnium-containing austenitic oxide dispersion-strengthened 316 stainless steel. The phases of the oxide nanoparticles were determined by a combination of scanning transmission electron microscopy–electron dispersive X-ray spectroscopy, atom probe tomography and synchrotron X-ray diffraction to be complex Y–Ti–Hf–O compounds with similar crystal structures, including bixbyite Y{sub 2}O{sub 3}, fluorite Y{sub 2}O{sub 3}–HfO{sub 2} solid solution and pyrochlore (or fluorite) Y{sub 2}(Ti,Hf){sub 2−x}O{sub 7−x}. High resolution transmission electron microscopy was used to characterize the particle–matrix interfaces. Two different coherency relationships along with one axis-parallel relation between themore » oxide nanoparticles and the steel matrix were found. The size of the nanoparticles significantly influences the orientation relationship. The results provide insight into the relationship of these nanoparticles with the matrix, which has implications for interpreting material properties as well as responses to radiation. - Highlights: • The oxide nanoparticles in a hafnium-containing austenitic ODS were characterized. • The nanoparticles are Y–Hf–Ti–O enriched phases according to APT and STEM–EDS. • Two coherency and an axis-parallel orientation relationships were found by HR-TEM. • Particle size has a prominent effect on the orientation relationship (OR). • Formation mechanism of the oxide nanoparticles was discussed based on the ORs.« less

Investigation on the Oxidation and Reduction of Titanium in Molten Salt with the Soluble TiC Anode

NASA Astrophysics Data System (ADS)

Wang, Shulan; Wan, Chaopin; Liu, Xuan; Li, Li

2015-12-01

To reveal the oxidation process of titanium from TiC anode and the reduction mechanism of titanium ions in molten NaCl-KCl, the polarization curve of TiC anode in molten NaCl-KCl and cyclic voltammograms of the molten salt after polarization were studied. Investigation on the polarization curve shows that titanium can be oxidized and dissociated from the TiC anode at very low potential. The cyclic voltammograms demonstrated that the reduction reaction of titanium ions in the molten salt is a one-step process. By potentiostatic electrolysis, dendritic titanium is obtained on the steel plate. The work promotes the understanding on the process of electrochemical oxidization/dissociation of titanium from TiC anode and the reduction mechanism of titanium ions in molten salt.

Oxidation of Sulfonamides in Aqueous Solution by UV-TiO2-Fe(VI).

PubMed

Ma, Yan; Zhang, Kejia; Li, Cong; Zhang, Tuqiao; Gao, Naiyun

2015-01-01

The photocatalytic degradation of sulfonamides in aqueous TiO2 suspension under UV irradiation has been investigated using potassium ferrate as electron acceptors. The results showed that the stability of Fe(VI) is dependent on pH significantly, and the stability reduces obviously in the presence of UV-TiO2. The experiments indicated that Fe(VI) could effectively scavenge the conduction band electrons from the surface of TiO2. The photocatalytic oxidation of sulfonamides with Fe(VI) was found to be much faster than that without Fe(VI). The SD, SM, and SMX concentration was greatly reduced by 89.2%, 83.4%, and 82.0%, respectively, after 10 min with UV-TiO2-Fe(VI), comparing to 65.2%, 66.0%, and 71.9%, respectively, with Fe(VI) only in the dark and 71.3%, 72.7%, and 76.0%, respectively, with UV-TiO2. The pH value of solution significantly influenced the sulfonamides degradation in UV-TiO2-Fe(VI) system. The degradation amount of sulfonamides after 10 min was a maximum at pH 7. The intermediate products of sulfonamides oxidation by UV-TiO2-Fe(VI) were analysed by LC-HESI-MS-MS and the results suggested that a majority of sulfonamides turned into large-molecule products without complete mineralization.

Oxidation of Sulfonamides in Aqueous Solution by UV-TiO2-Fe(VI)

PubMed Central

Ma, Yan; Zhang, Kejia; Li, Cong; Zhang, Tuqiao; Gao, Naiyun

2015-01-01

The photocatalytic degradation of sulfonamides in aqueous TiO2 suspension under UV irradiation has been investigated using potassium ferrate as electron acceptors. The results showed that the stability of Fe(VI) is dependent on pH significantly, and the stability reduces obviously in the presence of UV-TiO2. The experiments indicated that Fe(VI) could effectively scavenge the conduction band electrons from the surface of TiO2. The photocatalytic oxidation of sulfonamides with Fe(VI) was found to be much faster than that without Fe(VI). The SD, SM, and SMX concentration was greatly reduced by 89.2%, 83.4%, and 82.0%, respectively, after 10 min with UV-TiO2-Fe(VI), comparing to 65.2%, 66.0%, and 71.9%, respectively, with Fe(VI) only in the dark and 71.3%, 72.7%, and 76.0%, respectively, with UV-TiO2. The pH value of solution significantly influenced the sulfonamides degradation in UV-TiO2-Fe(VI) system. The degradation amount of sulfonamides after 10 min was a maximum at pH 7. The intermediate products of sulfonamides oxidation by UV-TiO2-Fe(VI) were analysed by LC-HESI-MS-MS and the results suggested that a majority of sulfonamides turned into large-molecule products without complete mineralization. PMID:26347888

Phase inversion and frequency doubling of reflection high-energy electron diffraction intensity oscillations in the layer-by-layer growth of complex oxides

NASA Astrophysics Data System (ADS)

Mao, Zhangwen; Guo, Wei; Ji, Dianxiang; Zhang, Tianwei; Gu, Chenyi; Tang, Chao; Gu, Zhengbin; Nie*, Yuefeng; Pan, Xiaoqing

In situ reflection high-energy electron diffraction (RHEED) and its intensity oscillations are extremely important for the growth of epitaxial thin films with atomic precision. The RHEED intensity oscillations of complex oxides are, however, rather complicated and a general model is still lacking. Here, we report the unusual phase inversion and frequency doubling of RHEED intensity oscillations observed in the layer-by-layer growth of SrTiO3 using oxide molecular beam epitaxy. In contacts to the common understanding that the maximum(minimum) intensity occurs at SrO(TiO2) termination, respectively, we found that both maximum or minimum intensities can occur at SrO, TiO2, or even incomplete terminations depending on the incident angle of the electron beam, which raises a fundamental question if one can rely on the RHEED intensity oscillations to precisely control the growth of thin films. A general model including surface roughness and termination dependent mean inner potential qualitatively explains the observed phenomena, and provides the answer to the question how to prepare atomically and chemically precise surface/interfaces using RHEED oscillations for complex oxides. We thank National Basic Research Program of China (No. 11574135, 2015CB654901) and the National Thousand-Young-Talents Program.

Photocatalytic Oxidation of Oil Contaminated Water Using TiO2/UV

NASA Astrophysics Data System (ADS)

Vargas Solla, Monica; Romero Rojas, Jairo

2017-04-01

Currently, oil is one of the most used energy sources all around the world, for example to make motor engines work. That prevailing usage of oil is the reason why water sources are under serious pollution risks with compounds that are hard to remove, such as hydrocarbons. There are a few water treatment processes known as Advanced Oxidation Processes, which search for a way to treat polluted water with toxic refractory compounds, to make its reuse more feasible and to avoid or at least appease the injurious effects of pollution over ecosystems. A heterogeneous photocatalysis water treatment technology, sorted as an Advanced Oxidation Process, which is intended to treat refractory compound polluted water by the use of TiO2 and UV light, is presented in this investigation. The evidence about its efficiency in hydrocarbon removal from used motor oil polluted water, since it is an extremely important pollutant due to its complexity, toxicity and recalcitrant characteristics, is also presented through COD, Oil and Grease and Hydrocarbons analysis.

Spectroelectrochemical studies of hole percolation on functionalised nanocrystalline TiO2 films: a comparison of two different ruthenium complexes.

PubMed

Li, Xiaoe; Nazeeruddin, Mohammad K; Thelakkat, Mukundan; Barnes, Piers R F; Vilar, Ramón; Durrant, James R

2011-01-28

We report the application of spectroelectrochemical techniques to compare the hole percolation dynamics of molecular networks of two ruthenium bipyridyl complexes adsorbed onto mesoporous, nanocrystalline TiO(2) films. The percolation dynamics of the ruthenium complex cis-di(thiocyanato)(2,2'-bipyridyl-4,4'-dicarboxylic acid)-(2,2'-bipyridyl-4,4'-tridecyl) ruthenium(II), N621, is compared with those observed for an analogous dye with an additional tri-phenyl amine (TPA) donor moiety, cis-di(thiocyanato)(2,2'-bipyridyl-4,4'-dicarboxylic acid)-(2,2'-bipyridyl-4,4'-bis(vinyltriphenylamine)) ruthenium(II), HW456. The in situ oxidation of these ruthenium complexes adsorbed to the TiO(2) films is monitored by cyclic voltammetry and voltabsorptometry, whilst the dynamics of hole (cation) percolation between adsorbed ruthenium complexes is monitored by potentiometric spectroelectrochemistry and chronoabsorptometry. The hole diffusion coefficient, D(eff), is shown to be dependent on the dye loading on the nanocrystalline TiO(2) film, with a threshold observed at ∼60% monolayer surface coverage for both dyes. The hole diffusion coefficient of HW456 is estimated to be 2.6 × 10(-8) cm(2)/s, 20-fold higher than that obtained for the control N621, attributed to stronger electronic coupling between the TPA moieties of HW456 accelerating the hole percolation dynamics. The presence of mercuric ions, previously shown to bind to the thiocyanates of analogous ruthenium complexes, resulted in a quenching of the hole percolation for N621/TiO(2) films and an enhancement for HW456/TiO(2) films. These results strongly suggest that the hole percolation pathway is along the overlapped neighbouring -NCS groups for the N621 molecules, whereas in HW456 molecules cation percolation proceeds between intermolecular TPA ligands. These results are discussed in the context of their relevance to the process of dye regeneration in dye sensitised solar cells, and to the molecular wiring of wide

Optical properties of Y and Ti co-substituted BiFeO{sub 3} multiferroics

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

Singh, Vikash, E-mail: rk.dwivedi@jiit.ac.in; Sharma, Subhash, E-mail: rk.dwivedi@jiit.ac.in; Kumar, Manoj, E-mail: rk.dwivedi@jiit.ac.in

2014-04-24

Pure and co substituted Bi{sub 1−x}Y{sub x}Fe{sub 1−x}Ti{sub x}O{sub 3} (x ≤ 0.24) ceramics were synthesized by solid state reaction method. X-ray diffraction patterns of Y and Ti codoped samples have shown single phase formation. Increasing Y and Ti concentration reveals structural transition from rhombohedral phase (R3c) for x ≤ 0.16 to orthorhombic phase (Pnma) for x = 0.24. FT-IR spectra exhibit broad absorption bands, which may be due to the overlapping of Fe-O and Bi-O vibrations. UV-visible spectroscopy results show strong absorption of light in the spectral range of 400-720 nm, indicating optical band gap in the visible regionmore » for these samples. These interesting optical properties of co-substituted BFO samples in visible region may find potential applications in optoelectronic devices.« less

Interaction of TiO2 nanocluster with graphene oxide: Experimental and theoretical investigations

NASA Astrophysics Data System (ADS)

Yadav, A.; Gangan, A. S.; Chakraborty, B.; Ramaniah, L. M.; Patel, N.; Yadav, M.; Dashora, A.; Kothari, D. C.; Press, M.

2017-05-01

Go-TiO2 composites are gaining importance because of their applications in various fields and also due to their stability. In this work, we have reported for the first time, interaction of Graphene Oxide (GO) with TiO2 nanocluster. To understand the interfacial interaction between GO and TiO2, we have proposed GO-TiO2 models through simulations. The calculated optical properties of theoretical models were compared with experimentally synthesized RGO-TiO2 composite. Optical absorption spectra indicated enhancement in visible region for RGO-TiO2 nanocomposite when compared to that of TiO2. The variation in optical properties of RGO-TiO2 cluster with degree of functionalization was also studied. It was observed that in GO-TiO2 model with optimum OH groups, new states were formed within the band gap which could be responsible for enhanced absorption in visible region.

High Activity of Au/K/TiO 2(110) for CO Oxidation: Alkali-Metal-Enhanced Dispersion of Au and Bonding of CO

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

Rodriguez, Jose A.; Grinter, David C.; Ramirez, Pedro J.

In this paper, images from scanning tunneling microscopy show high mobility for potassium (K) on an oxidized TiO 2(110) surface. At low coverages, the alkali metal occupies mainly terrace sites of the o-TiO 2(110) system. The results of X-ray photoelectron spectroscopy indicate that K is fully ionized. The electron transferred from K to the titania affects the reactivity of this oxide, favoring the dispersion of Au particles on the terraces of the o-TiO 2(110) surface. When small coverages of K and Au are present on the o-TiO 2(110) system, only a few K–Au pairs are formed and the alkali metalmore » affects Au chemisorption mainly through the oxide interactions. Addition of K to Au/o-TiO 2(110) enhances the reactivity of the system, opening new reaction paths for the adsorption and oxidation of carbon monoxide. CO can undergo disproportionation (2CO → C ads + CO 2,ads) on K/o-TiO 2(110) and Au/K/o-TiO 2(110) surfaces. The Au–KO x interface binds CO much better than plain Au–TiO 2, increasing the surface coverage of CO and facilitating its oxidation. Kinetic tests show that K promotes CO oxidation on Au/TiO 2. Finally, turnover frequencies of 2.1 and 10.8 molecules (Au site) -1 s –1 were calculated for oxidation of CO on Au/o-TiO 2(110) and Au/K/o-TiO 2(110) catalysts, respectively.« less

High Activity of Au/K/TiO 2(110) for CO Oxidation: Alkali-Metal-Enhanced Dispersion of Au and Bonding of CO

DOE PAGES

Rodriguez, Jose A.; Grinter, David C.; Ramirez, Pedro J.; ...

2018-02-14

In this paper, images from scanning tunneling microscopy show high mobility for potassium (K) on an oxidized TiO 2(110) surface. At low coverages, the alkali metal occupies mainly terrace sites of the o-TiO 2(110) system. The results of X-ray photoelectron spectroscopy indicate that K is fully ionized. The electron transferred from K to the titania affects the reactivity of this oxide, favoring the dispersion of Au particles on the terraces of the o-TiO 2(110) surface. When small coverages of K and Au are present on the o-TiO 2(110) system, only a few K–Au pairs are formed and the alkali metalmore » affects Au chemisorption mainly through the oxide interactions. Addition of K to Au/o-TiO 2(110) enhances the reactivity of the system, opening new reaction paths for the adsorption and oxidation of carbon monoxide. CO can undergo disproportionation (2CO → C ads + CO 2,ads) on K/o-TiO 2(110) and Au/K/o-TiO 2(110) surfaces. The Au–KO x interface binds CO much better than plain Au–TiO 2, increasing the surface coverage of CO and facilitating its oxidation. Kinetic tests show that K promotes CO oxidation on Au/TiO 2. Finally, turnover frequencies of 2.1 and 10.8 molecules (Au site) -1 s –1 were calculated for oxidation of CO on Au/o-TiO 2(110) and Au/K/o-TiO 2(110) catalysts, respectively.« less

Oxygen deficient Ti oxides (natural magnéli phases) from mudstone xenoliths with native iron from Disko, central West Greenland

NASA Astrophysics Data System (ADS)

Pedersen, A. K.; Rønsbo, J. G.

1987-05-01

Mudstone xenoliths in a strongly reduced andesitic subaquatic breccia with native iron from the Asuk Member on Disko contain Ti oxides which are oxygen deficient relative to rutile. Ore microscopy reveals that the mudstone xenoliths contain former clastic oxide grains which have equilibrated to blue Ti oxides and grey aluminous Ti oxides. They also contain still immature coal fragments in a glassy matrix with native iron. The blue oxides are compositionally similar to magnéli phases TinO2n-1 within the range n=4 to 7, and several grains contain more than one natural magnéli phase. Two other phases found are 1) pale orange blebs in magnéli phases with a composition approaching Al1Ti{1/3+}Ti{2/4+}O7 (AlTi phase B) and 2) grey oxide rims on magnéli phases or independent grains of the compositional series Al2-x(Ti{0.5/4+}(Mg,Fe)0.5)xTi{n-2/4+}O2n-1 with n mostly between 7 and 10 (AlTi phase A). The natural magnéli phases equilibrated at oxygen fugacities 4 to 5 log units below the Fe-W oxygen buffer at igneous temperatures and represent the most reduced high-temperature environment yet recorded among native iron bearing rocks from Disko. The extremely reducing conditions were met in rocks where coal fragments were still in a state of degassing hydrocarbon components at the time of quenching. Field geology and carbon barometry indicate equilibration at pressures of less than 10 bars.

The influence of the substrate on the adhesive strength of the micro-arc oxidation coating developed on TiNi shape memory alloy

NASA Astrophysics Data System (ADS)

Hsieh, Shy-Feng; Ou, Shih-Fu; Chou, Chia-Kai

2017-01-01

TiNi shape memory alloys (SMAs), used as long-term implant materials, have a disadvantage. Ni-ion release from the alloys may trigger allergies in the human body. Micro-arc oxidation has been utilized to modify the surface of the TiNi SMA for improving its corrosion resistance and biocompatibility. However, there are very few reports investigating the essential adhesive strength between the micro-arc oxidized film and TiNi SMA. Two primary goals were attained by this study. First, Ti50Ni48.5Mo1.5 SMA having a phase transformation temperature (Af) less than body temperature and good shape recovery were prepared. Next, the Ti50Ni50 and Ti50Ni48.5Mo1.5 SMA surfaces were modified by micro-arc oxidation in phosphoric acid by applying relatively low voltages to maintain the adhesive strength. The results indicated that the pore size, film thickness, and P content increased with applied voltage. The micro-arc oxidized film, comprising Ti oxides, Ni oxide, and phosphate compounds, exhibited a glassy amorphous structure. The outmost surface of the micro-arc oxidized film contained a large amount of P (>12 at%) but only a trace of Ni (<5 at%). The adhesive strengths of all the micro-arc oxidized films exceeded the requirements of ISO 13779. Furthermore, Mo addition into TiNi SMAs was found to be favorable for improving the adhesive strength of the micro-arc oxidized film.

Characterization of oxide nanoparticles in Al-free and Al-containing oxide dispersion strengthened ferritic steels.

PubMed

Lee, Jae Hoon; Kim, Jeoung Han

2013-09-01

Oxide nanoparticles in oxide dispersion strengthened (ODS) ferritic steels with and without Al have been characterized by transmission electron microscopy. It is confirmed that most of the complex oxide particles consist of Y2TiO5 for 18Cr-ODS steel and YAlO3 or YAl5O12 for 18Cr5Al-ODS steel, respectivley. The addition of 5% Al in 18Cr-ODS steel leads to the formation of larger oxide particles and the reduction in their number density. For 18Cr-ODS steel, 87% of the oxide particles are coherent. The misfit strain of the coherent particles and a few semi-coherent particles is about 0.034 and 0.056, respectively. For 18Cr5Al-ODS steel, 75% of the oxide particles are semi-coherent, of which the misfit strain is 0.091 and 0.125, respectively. These results suggest that for the Al-containing ODS steel the Al addition accelerates the formation of semi-coherent oxide particles and its larger coherent and semi-coherent particles result in the larger misfit strain between the oxide particle and alloy matrix, indicating that the coherence of oxide nanoparticles in ODS steels is size-dependent.

Oxidation Resistance of Materials Based on Ti3AlC2 Nanolaminate at 600 °C in Air

NASA Astrophysics Data System (ADS)

Ivasyshyn, Andrij; Ostash, Orest; Prikhna, Tatiana; Podhurska, Viktoriya; Basyuk, Tatiana

2016-08-01

The oxidation behavior of Ti3AlC2-based materials had been investigated at 600 °C in static air for 1000 h. It was shown that the intense increase of weight gain per unit surface area for sintered material with porosity of 22 % attributed to oxidation of the outer surface of the specimen and surfaces of pores in the bulk material. The oxidation kinetics of the hot-pressed Ti3AlC2-based material with 1 % porosity remarkably increased for the first 15 h and then slowly decreased. The weight gain per unit surface area for this material was 1.0 mg/cm2 after exposition for 1000 h. The intense initial oxidation of Ti3AlC2-based materials can be eliminated by pre-oxidation treatment at 1200 °C in air for 2 h. As a result, the weight gain per unit surface area for the pre-oxidized material did not exceed 0.11 mg/cm2 after 1000 h of exposition at 600 °C in air. It was demonstrated that the oxidation resistance of Ti3AlC2-based materials can be significantly improved by niobium addition.

Niobium oxide compositions and methods for using same

DOEpatents

Goodenough, John B; Han, Jian-Tao

2014-02-11

The disclosure relates a niobium oxide useful in anodes of secondary lithium ion batteries. Such niobium oxide has formula Li.sub.xM.sub.1-yNb.sub.yNb.sub.2O.sub.7, wherein 0.ltoreq.x.ltoreq.3, 0.ltoreq.y.ltoreq.1, and M represents Ti or Zr. The niobium oxide may be in the form of particles, which may be carbon coated. The disclosure also relates to an electrode composition containing at least one or more niobium oxides of formula Li.sub.xM.sub.1-yNb.sub.yNb.sub.2O.sub.7. The disclosure further relates to electrodes, such as anodes, and batteries containing at least one or more niobium oxides of formula Li.sub.xM.sub.1-yNb.sub.yNb.sub.2O.sub.7. Furthermore, the disclosure relates to methods of forming the above.

Pulsed laser ablation of complex oxides: The role of congruent ablation and preferential scattering for the film stoichiometry

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

Wicklein, S.; Koehl, A.; Dittmann, R.

2012-09-24

By combining structural and chemical thin film analysis with detailed plume diagnostics and modeling of the laser plume dynamics, we are able to elucidate the different physical mechanisms determining the stoichiometry of the complex oxides model material SrTiO{sub 3} during pulsed laser deposition. Deviations between thin film and target stoichiometry are basically a result of two effects, namely, incongruent ablation and preferential scattering of lighter ablated species during their motion towards the substrate in the O{sub 2} background gas. On the one hand, a progressive preferential ablation of the Ti species with increasing laser fluence leads to a regime ofmore » Ti-rich thin film growth at larger fluences. On the other hand, in the low laser fluence regime, a more effective scattering of the lighter Ti plume species results in Sr rich films.« less

Comparative optical studies of ZnO and ZnO-TiO2 - Metal oxide nanoparticle

NASA Astrophysics Data System (ADS)

Vijayalakshmi, R. Vanathi; Asvini, V.; Kumar, P. Praveen; Ravichandran, K.

2018-05-01

A comparative study was carried out to show the enhancement in optical activity of bimetal oxide nanoparticle (ZnO - TiO2) than metal oxide nanoparticle (ZnO), which can preferably be used for optical applications. The samples were prepared by wet chemical method and crystalline structure of the samples as hexagonal - primitive for ZnO and tetragonal - bcc for ZnO-TiO2 was confirmed by XRD measurements. The average grain size of ZnO - 19.89nm and ZnO-TiO2- 49.89 nm was calculated by Debye- Scherrer formula. The structure and particle size of the sample was analyzed by FESEM images. The direct band gap energy of ZnO (3.9eV) and ZnO - TiO2(4.68eV) was calculated by Kubelka-Munk Function, from which it is clear that the band gap energy increases in bimetal oxide to a desired level than in its pure form. The photoluminescence study shows that the emitted wavelength of the samples lies exactly around the visible region.

Phase relationships in the CeFe 8 Co 3 Ti 1 - y Si y system

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

Conner, B. S.; McGuire, M. A.; Susner, M. A.

We investigated the phase formation behavior of the nominal CeFe 8Co 3Ti 1-ySi y system for 0 ≤ y ≤ 0.6 by powder x-ray diffraction and scanning electron microscopy with energy dispersive x-ray spectroscopy for ingots formed by arc-melting then annealing at 1000 °C and quenching to room temperature. The ingots are seen to nearly single phase for y ≤ 0.4 and are multi-phase for y ≥ 0.5 though a compound of the ThMn 12 type does indeed form for all values of y. We also measured the saturation magnetizations (M s), Curie temperatures (T C), and magnetic anisotropy fieldsmore » (H a) for the y ≤ 0.4 samples and the values of Ms and Ha appear to be nearly identical for all y 0.4. TC, but, is seen to increase about 20 °C in this range for increasing y.« less

Phase relationships in the CeFe 8 Co 3 Ti 1 - y Si y system

DOE PAGES

Conner, B. S.; McGuire, M. A.; Susner, M. A.; ...

2017-04-07

We investigated the phase formation behavior of the nominal CeFe 8Co 3Ti 1-ySi y system for 0 ≤ y ≤ 0.6 by powder x-ray diffraction and scanning electron microscopy with energy dispersive x-ray spectroscopy for ingots formed by arc-melting then annealing at 1000 °C and quenching to room temperature. The ingots are seen to nearly single phase for y ≤ 0.4 and are multi-phase for y ≥ 0.5 though a compound of the ThMn 12 type does indeed form for all values of y. We also measured the saturation magnetizations (M s), Curie temperatures (T C), and magnetic anisotropy fieldsmore » (H a) for the y ≤ 0.4 samples and the values of Ms and Ha appear to be nearly identical for all y 0.4. TC, but, is seen to increase about 20 °C in this range for increasing y.« less

Photocatalytic oxidation of propylene on La and N codoped TiO2 nanoparticles

NASA Astrophysics Data System (ADS)

Liu, Jinfeng; Li, Haiyan; Zong, Lanlan; Li, Qiuye; Wang, Xiaodong; Zhang, Min; Yang, Jianjun

2015-02-01

Lanthanum- and nitrogen-codoped TiO2 photocatalysts was synthesized using orthorhombic nanotubes titanic acid as the precursor by a simple impregnation and subsequent calcination method. The morphology, phase structure, and properties of La- and N-codoped TiO2 were well characterized by transmission electron microscopy, X-ray diffraction, Raman spectra, X-ray photoelectron spectroscopy, and UV-Vis diffuse reflectance spectra. The La-/N-codoped TiO2 showed excellent photoactivity of propylene oxidation compared with the single-doped TiO2 and La-/N-codoped P25 TiO2 nanoparticles under visible light irradiation. The origin of the enhancement of the visible light-responsive photocatalytic activity was discussed in detail.

A new recipe for preparing oxidized TiO2(1 1 0) surfaces: An STM study

NASA Astrophysics Data System (ADS)

Hansen, Jonas Ø.; Matthiesen, Jesper; Lira, Estephania; Lammich, Lutz; Wendt, Stefan

2017-12-01

Using high-resolution scanning tunneling microscopy (STM), we have studied the oxidation of rutile TiO2(1 1 0)-(1 × 1) surfaces with Had species at room temperature. We followed the evolution of various stable species as function of the O2 exposure, and the nature of the ultimately dominating species in the Ti troughs is described. When O2 saturation was accomplished using a glass-capillary array doser, we found that on-top O (Oot) adatoms are the predominant surface species. In contrast, when O2 was supplied via backfilling of the chamber the predominant surface species are tentatively assigned to terminal OH groups. We argue that unintended reactions with the chamber walls have a strong influence on the formed surface species, explaining scattered results in the literature. On the basis of our STM data we propose an alternative, easy way of preparing oxidized TiO2(1 1 0) surfaces with Oot adatoms (o-TiO2). It is certain that o-TiO2(1 1 0) surfaces prepared according to this recipe do not have any residual surface O vacancies. This contradicts the situation when oxidizing reduced TiO2(1 1 0) surfaces with O vacancies, where some O vacancies persist.

TEM and HRTEM study of oxide particles in an Al-alloyed high-Cr oxide dispersion strengthened ferritic steel with Hf addition

NASA Astrophysics Data System (ADS)

Dou, Peng; Kimura, Akihiko; Kasada, Ryuta; Okuda, Takanari; Inoue, Masaki; Ukai, Shigeharu; Ohnuki, Somei; Fujisawa, Toshiharu; Abe, Fujio; Jiang, Shan; Yang, Zhigang

2017-03-01

The nanoparticles in an Al-alloyed high-Cr oxide dispersion strengthened (ODS) ferritic steel with Hf addition, i.e., SOC-16 (Fe-15Cr-2W-0.1Ti-4Al-0.62Hf-0.35Y2O3), have been examined by transmission electron microscopy (TEM) and high resolution transmission electron microscopy (HRTEM). Relative to an Al-alloyed high-Cr ODS ferritic steel without Hf addition, i.e., SOC-9 (Fe-15.5Cr-2W-0.1Ti-4Al-0.35Y2O3), the dispersion morphology and coherency of the oxide nanoparticles in SOC-16 were significantly improved. Almost all the small nanoparticles (diameter <10 nm) in SOC-16 were found to be consistent with cubic Y2Hf2O7 oxides with the anion-deficient fluorite structure and coherent with the bcc steel matrix. The larger particles (diameter >10 nm) were also mainly identified as cubic Y2Hf2O7 oxides with the anion-deficient fluorite structure. The results presented here are compared with those of SOC-9 with a brief discussion of the underlying mechanisms of the unusual thermal and irradiation stabilities of the oxides as well as the superior strength, excellent irradiation tolerance and extraordinary corrosion resistance of SOC-16.

Photoluminescent properties of complex metal oxide nanopowders for gas sensing

NASA Astrophysics Data System (ADS)

Bovhyra, R. V.; Mudry, S. I.; Popovych, D. I.; Savka, S. S.; Serednytski, A. S.; Venhryn, Yu. I.

2018-03-01

This work carried out research on the features of photoluminescence of the mixed and complex metal oxide nanopowders (ZnO/TiO2, ZnO/SnO2, Zn2SiO4) in vacuum and gaseous ambient. The nanopowders were obtained using pulsed laser reactive technology. The synthesized nanoparticles were characterized by X-ray diffractometry, energy-dispersive X-ray analysis, and scanning and transmission electron microscopy analysis for their sizes, shapes and collocation. The influence of gas environment on the photoluminescence intensity was investigated. A change of ambient gas composition leads to a rather significant change in the intensity of the photoluminescence spectrum and its deformation. The most significant changes in the photoluminescent spectrum were observed for mixed ZnO/TiO2 nanopowders. This obviously is the result of a redistribution of existing centers of luminescence and the appearance of new adsorption centers of luminescence on the surface of nanopowders. The investigated nanopowders can be effectively used as sensing materials for the construction of the multi-component photoluminescent sensing matrix.

Biofilm Formation by Pseudomonas Species Onto Graphene Oxide-TiO2 Nanocomposite-Coated Catheters: In vitro Analysis

NASA Astrophysics Data System (ADS)

Deb, Ananya; Vimala, R.

The present study focuses on the development of an in vitro model system for biofilm growth by Pseudomonas aerouginosa onto small discs of foley catheter. Catheter disc used for the study was coated with graphene oxide-titanium oxide composite (GO-TiO2) and titanium oxide (TiO2) and characterized through XRD, UV-visible spectroscopy. Morphological analysis was done by scanning electron microscopy (SEM). The biofilm formed on the catheter surface was quantified by crystal violet (CV) staining method and a colorimetric assay (MTT assay) which involves the reduction of tetrazolium salt. The catheter coated with GO-TiO2 showed reduced biofilm growth in comparison to the TiO2-coated and uncoated catheter, thus indicating that it could be successfully used in coating biomedical devices to prevent biofilm formation which is a major cause of nosocomial infection.

The disclosed transformation of pre-sputtered Ti films into nanoparticles via controlled thermal oxidation

NASA Astrophysics Data System (ADS)

Awad, M. A.; Raaif, M.

2018-05-01

Nanoparticles of TiO2 were successfully prepared from pre-sputtered Ti films using the controlled thermal oxidation. The effect of oxidation temperature on structural, morphological and optical properties in addition to photocatalysis activity of the sputtered films was tested and explained. Analysis of XRD and EDAX elucidated the enhancement in crystallization and oxygen content with the increase of oxidation temperature. SEM depicted the formation of very fine nanoparticles with no specific border on the films oxidized at 550 and 600 °C, whilst crystallites with larger size of approximately from 16 to 23 nm have been observed for the film oxidized at 650 °C. Both optical transmission and refractive index were increased with increasing the oxidation temperature. A red shift in the absorption edge was obtained for the films oxidized at 650 °C compared to that oxidized at 600 °C. The photocatalysis tests demonstrated the priority of 600 °C nanoparticle films to decompose methyl orange (MO) more than 650 °C treated film.

Interdiffusion-driven synthesis of tetragonal chromium (III) oxide on BaTi O3

NASA Astrophysics Data System (ADS)

Asa, M.; Vinai, G.; Hart, J. L.; Autieri, C.; Rinaldi, C.; Torelli, P.; Panaccione, G.; Taheri, M. L.; Picozzi, S.; Cantoni, M.

2018-03-01

Interfaces play a crucial role in the study of novel phenomena emerging at heterostructures comprising metals and functional oxides. For this reason, attention should be paid to the interface chemistry, which can favor the interdiffusion of atomic species and, under certain conditions, lead to the formation of radically different compounds with respect to the original constituents. In this work, we consider Cr/BaTi O3 heterostructures grown on SrTi O3 (100) substrates. Chromium thin films (1-2 nm thickness) are deposited by molecular beam epitaxy on the BaTi O3 layer, and subsequently annealed in vacuum at temperatures ranging from 473 to 773 K. A disordered metallic layer is detected for annealing temperatures up to 573 K, whereas, at higher temperatures, we observe a progressive oxidation of chromium, which we relate to the thermally activated migration of oxygen from the substrate. The chromium oxidation state is +3 and the film shows a defective rocksalt structure, which grows lattice matched on the underlying BaTi O3 layer. One out of every three atoms of chromium is missing, producing an uncommon tetragonal phase with C r2O3 stoichiometry. Despite the structural difference with respect to the ordinary corundum α-C r2O3 phase, we demonstrate both experimentally and theoretically that the electronic properties of the two phases are, to a large extent, equivalent.

Magnetic hardening of Ce 1+xFe 11–yCo yTi with ThMn 12 structure by melt spinning

DOE PAGES

Zhou, Chen; Sun, Kewei; Pinkerton, Frederick E.; ...

2015-04-15

A recent study on the intrinsic magnetic properties of CeFe 11–yCo yTi has revealed that substituting one Co for Fe retains the favorable magnetocrystalline anisotropy H a found in the ternary Fe end member, while enhancing the Curie temperature T c and saturation magnetization 4πM s. These findings warrant further optimization around Co substitution y = 1 to try to exploit the hard magnetic properties of these Ce-based magnets. Both Ce and Co concentrations in Ce 1+xFe 11–yCo yTi have been optimized in the range of x = 0 – 0.2 and y = 0 –1.5. It was found thatmore » Co substitution effectively enhances all hard magnetic properties, although the values are still lower than those predicted from the intrinsic magnetic properties. Specifically, T c increases from 210 °C to 285 – 350 °C; 4πM 19 (magnetization at 19 kOe) from 8.9 kG to 10.5 – 11.5 kG, remanence Br from 3.1 kG to 4.1 – 4.5 kG, and most importantly, H ci from 1.1 kOe to 1.5 kOe. As a result, the room temperature energy product (BH) max has been increased by over 100% from 0.7 MGOe in Ce 1.1Fe 11Ti to 1.5 MGOe in Ce 1.05Fe 9.75Co 1.25Ti. Microscopy analysis indicates that the addition of Co refines the grain size and promotes chemical homogeneity at the microscopic scale. As a result, the beneficial effect of Co on the microstructure contributes to the improved hard magnetic properties.« less

H2O2/TiO2 photocatalytic oxidation of metol. Identification of intermediates and reaction pathways.

PubMed

Aceituno, Mónica; Stalikas, Constantine D; Lunar, Loreto; Rubio, Soledad; Pérez-Bendito, Dolores

2002-08-01

The applicability of H2O2 to increase the efficiency of TiO2 photocatalytic degradations was investigated. The photographic developer metol [N-methyl-p-aminophenol] that does not adsorb on the surface of TiO2 particulates was used as a model for this purpose. It was proved that metol was mineralised under oxidation with H2O2/TiO2/UV through different thermal and photochemical reactions. Identification of intermediates by both HPLC-electron impact-MS and HPLC-electrospray ionisation-MS helped to elucidate the role of H2O2 and TiO2 in the degradation process and to establish degradation pathways. Intermediates yielded were partially oxygenated aromatic species and dimers, which were amenable to oxidation. The optimal degradation conditions found for mineralisation were 0.4 M H2O2, 5 mg/ml TiO2, pH 9 and irradiation centred at 360 nm (4.9 mW/cm2). The use of oxidants opens an interesting medium to the treatment of effluents containing a diversity of organics since they increase substantially the efficiency of TiO2 photocatalytic degradations.

Adsorption process of fluoride from drinking water with magnetic core-shell Ce-Ti@Fe3O4 and Ce-Ti oxide nanoparticles.

PubMed

Abo Markeb, Ahmad; Alonso, Amanda; Sánchez, Antoni; Font, Xavier

2017-11-15

Synthesized magnetic core-shell Ce-Ti@Fe 3 O 4 nanoparticles were tested, as an adsorbent, for fluoride removal and the adsorption studies were optimized. Adsorption capacity was compared with the synthesized Ce-Ti oxide nanoparticles. The adsorption equilibrium for the Ce-Ti@Fe 3 O 4 adsorbent was found to occur in <15min and it was demonstrated to be stable and efficient in a wide pH range of 5-11 with high fluoride removal efficiency over 80% of all cases. Furthermore, isotherm data were fitted using Langmuir and Freundlich models, and the adsorption capacities resulted in 44.37 and 91.04mg/g, at pH7, for Ce-Ti oxides and Ce-Ti@Fe 3 O 4 nanoparticles, respectively. The physical sorption mechanism was estimated using the Dubinin-Radushkevich model. An anionic exchange process between the OH - group on the surface of the Ce-Ti@Fe 3 O 4 nanomaterial and the F - was involved in the adsorption. Moreover, thermodynamic parameters proved the spontaneous process for the adsorption of fluoride on Ce-Ti@Fe 3 O 4 nanoparticles. The reusability of the material through magnetic recovery was demonstrated for five cycles of adsorption-desorption. Although the nanoparticles suffer slight structure modifications after their reusability, they keep their adsorption capacity. Likewise, the efficiency of the Ce-Ti@Fe 3 O 4 was demonstrated when applied to real water to obtain a residual concentration of F - below the maximum contaminated level, 1.5mg/L (WHO, 2006). Copyright © 2017 Elsevier B.V. All rights reserved.

Investigation of TiN thin film oxidation depending on the substrate temperature at vacuum break

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

Piallat, Fabien, E-mail: fabien.piallat@gmail.com; CEA, LETI, Campus Minatec, F-38054 Grenoble; LTM-CNRS, 17 rue des Martyrs, 38054 Grenoble

2016-09-15

Due to the reduction of the thickness of the layers used in the advanced technology nodes, there is a growing importance of the surface phenomena in the definition of the general properties of the materials. One of the least controlled and understood phenomenon is the oxidation of metals after deposition, at the vacuum break. In this study, the influence of the sample temperature at vacuum break on the oxidation level of TiN deposited by metalorganic chemical vapor deposition is investigated. TiN resistivity appears to be lower for samples which underwent vacuum break at high temperature. Using X-ray photoelectron spectrometry analysis,more » this change is correlated to the higher oxidation of the TiN layer. Moreover, angle resolved XPS analysis reveals that higher is the temperature at the vacuum break, higher is the surface oxidation of the sample. This surface oxidation is in turn limiting the diffusion of oxygen in the volume of the layer. Additionally, evolution of TiN layers resistivity was monitored in time and it shows that resistivity increases until a plateau is reached after about 10 days, with the lowest temperature at vacuum break resulting in the highest increase, i.e., the resistivity of the sample released to atmosphere at high temperature increased by a factor 1.7 whereas the resistivity of the sample cooled down under vacuum temperature increased by a factor 2.7.« less

Electrical and morphological characterization of transfer-printed Au/Ti/TiO{sub x}/p{sup +}-Si nano- and microstructures with plasma-grown titanium oxide layers

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

Weiler, Benedikt, E-mail: benedikt.weiler@nano.ei.tum.de; Nagel, Robin; Albes, Tim

2016-04-14

Highly-ordered, sub-70 nm-MOS-junctions of Au/Ti/TiO{sub x}/p{sup +}-Si were efficiently and reliably fabricated by nanotransfer-printing (nTP) over large areas and their functionality was investigated with respect to their application as MOS-devices. First, we used a temperature-enhanced nTP process and integrated the plasma-oxidation of a nm-thin titanium film being e-beam evaporated directly on the stamp before the printing step without affecting the p{sup +}-Si substrate. Second, morphological investigations (scanning electron microscopy) of the nanostructures confirm the reliable transfer of Au/Ti/TiO{sub x}-pillars of 50 nm, 75 nm, and 100 nm size of superior quality on p{sup +}-Si by our transfer protocol. Third, the fabricated nanodevices are alsomore » characterized electrically by conductive AFM. Fourth, the results are compared to probe station measurements on identically processed, i.e., transfer-printed μm-MOS-structures including a systematic investigation of the oxide formation. The jV-characteristics of these MOS-junctions demonstrate the electrical functionality as plasma-grown tunneling oxides and the effectivity of the transfer-printing process for their large-scale fabrication. Next, our findings are supported by fits to the jV-curves of the plasma-grown titanium oxide by kinetic-Monte-Carlo simulations. These fits allowed us to determine the dominant conduction mechanisms, the material parameters of the oxides and, in particular, a calibration of the thickness depending on applied plasma time and power. Finally, also a relative dielectric permittivity of 12 was found for such plasma-grown TiO{sub x}-layers.« less

Comparative study on the effect of H2 pre-adsorption on CO oxidation in O2-poor atmosphere over Au/TiO2 and TiO2: Temperature programmed surface reaction by a multiplexed mass spectrometer testing

NASA Astrophysics Data System (ADS)

Si, Ruiru; Liu, Junfeng; Zhang, Yujuan; Chen, Xun; Dai, Wenxin; Fu, Xianzhi

2016-11-01

The behaviors of H2 pre-adsorption on CO oxidation in an O2-poor stream containing a trace H2O over Au/TiO2 and TiO2 have been investigated by a temperature programmed surface reaction testing, respectively. It was found that the H2 pre-adsorption could keep CO oxidation without H2O consumption over Au/TiO2, but suppress CO oxidation over TiO2. The chemisorption testing showed that the H2 adsorption at Au/TiO2 could benefit to the formation of Ti-bonded hydroxyl species (Ti4+-OH), while the H2 adsorption at TiO2 would consume the Ti-bonded hydroxyl species and form the bridge hydroxyl species (Ti4+-OH-Ti4+). These results show that only the Ti-bonded hydroxyl species (not all kinds of hydroxyl species) could act as the active species of oxidizing CO. Furthermore, it is suggested that the dissociative hydrogen adsorbed at Au sites could activate the lattice oxygen of TiO2 to form the active Ti-bonded hydroxyl species (hydrogen spillover from Au to TiO2), which exhibit a strong reducibility than the H directly adsorbed at TiO2.

Electrochemical oxidation of 4-chlorophenol for wastewater treatment using highly active UV treated TiO2 nanotubes.

PubMed

Tian, Min; Thind, Sapanbir S; Dondapati, Jesse S; Li, Xinyong; Chen, Aicheng

2018-06-07

In the present work, we report on a facile UV treatment approach for enhancing the electrocatalytic activity of TiO 2 nanotubes. The TiO 2 nanotubes were prepared using an anodization oxidation method by applying a voltage of 40 V for 8 h in a DMSO + 2% HF solution, and further treated under UV light irradiation. Compared with Pt and untreated TiO 2 nanotubes, the UV treated electrode exhibited a superior electrocatalytic activity toward the oxidation of 4-chlorophenol (4-ClPh). The effects of current density and temperature on the electrochemical oxidation of the 4-ClPh were also systematically investigated. The high electrocatalytic activity of the UV treated TiO 2 nanotubes was further confirmed by the electrochemical oxidation of other persistent organic pollutants including phenol, 2-, 3-, 4-nitrophenol, and 4-aminophenol. The total organic carbon (TOC) analysis revealed that over 90% 4-ClPh was removed when the UV treated TiO 2 electrode was employed and the rate constant was 16 times faster than that of the untreated TiO 2 electrode; whereas only 60% 4-ClPh was eliminated at the Pt electrode under the same conditions. This dramatically improved electrocatalytic activity might be attributed to the enhanced donor density, conductivity, and high overpotential for oxygen evolution. Our results demonstrated that the application of the UV treatment to the TiO 2 nanotubes enhanced their electrochemical activity and energy consumption efficiency significantly, which is highly desirable for the abatement of persistent organic pollutants. Copyright © 2018 Elsevier Ltd. All rights reserved.

The atomic level structure of the TiO(2)-NiTi interface.

PubMed

Nolan, M; Tofail, S A M

2010-09-07

The biocompatibility of NiTi shape memory alloys (SMA) has made possible applications in invasive and minimally invasive biomedical devices. The NiTi intermetallic alloy spontaneously forms a thin passive layer of TiO(2), which provides its biocompatibility. The oxide layer is thought to form as Ti in the alloy reacts with oxygen. In this paper, we study the details of the oxide-alloy interface. The atomic model is the (110) NiTi surface interfaced with the (100) rutile TiO(2) surface; this combination provides the best lattice match of alloy and oxide. When the interface forms, static minimisations and molecular dynamics show that there is no migration of atoms between the alloy and the oxide. In the alloy there are some notable structural relaxations. We find that a columnar structure appears in which alternating long and short Ni-Ti bonds are present in each surface and subsurface plane into the fourth subsurface layer. The oxide undergoes some structural changes as a result of terminal oxygen coordinating to Ti in the NiTi surface. The electronic structure shows that Ti(3+) species are present at the interface, with Ti(4+) in the bulk of the oxide layer and that the metallic character of the alloy is unaffected by the interaction with oxygen, all of which is consistent with experiment. A thermodynamic analysis is used to examine the stability of different possible structures-a perfect interface and one with Ti and O vacancies. We find that under conditions typical of oxidation and shape memory treatments, the most stable interface structure is that with Ti vacancies in the alloy surface, leaving an Ni-rich layer, consistent with the experimental findings for this interface.

Oxidative stress response of the aquatic macrophyte Hydrilla verticillata exposed to TiO2 nanoparticles.

PubMed

Okupnik, Annette; Pflugmacher, Stephan

2016-11-01

The present study investigated the effects of titanium dioxide nanoparticles (TiO 2 -NPs) on the oxidative stress response in Hydrilla verticillata. Macrophytes were exposed to different concentrations of TiO 2 -NPs (0 mg/L, 0.01 mg/L, 0.1 mg/L, 1 mg/L, and 10 mg/L) for 24 h, based on currently predicted levels of nano-TiO 2 in surface waters. In addition, TiO 2 -NPs with varying crystalline status were used to assess the potential influence of crystalline phases on oxidative stress responses. The level of hydrogen peroxide (H 2 O 2 ), reduced and oxidized glutathione (GSH and GSSG), and activities of the antioxidative enzymes peroxidase (POD), catalase (CAT), and glutathione reductase (GR) were measured and compared with a bulk counterpart. Although POD was not considered to be active, the results imply an activation of the enzymatic defense system, because increased CAT and GR activities were observed. Exposure to bulk TiO 2 revealed lower enzyme activities at all exposure concentrations, suggesting a nano-specific influence on the antioxidative defense mechanisms in H. verticillata. Moreover, all TiO 2 -NP concentrations resulted in a decreased GSH/GSSG ratio, indicating high GSH-dependent metabolic activity to protect against the destructive effects of reactive oxygen species (ROS) generated during nano-TiO 2 exposure. As the level of H 2 O 2 was solely elevated after exposure to 10 mg/L of P25, it appears plausible that the adaptive metabolic mechanisms of H. verticillata are able to cope with environmentally relevant concentrations of TiO 2 -NPs. Environ Toxicol Chem 2016;35:2859-2866. © 2016 SETAC. © 2016 SETAC.

Novel Combination of Efficient Perovskite Solar Cells with Low Temperature Processed Compact TiO2 Layer via Anodic Oxidation.

PubMed

Du, Yangyang; Cai, Hongkun; Wen, Hongbin; Wu, Yuxiang; Huang, Like; Ni, Jian; Li, Juan; Zhang, Jianjun

2016-05-25

In this work, a facile and low temperature processed anodic oxidation approach is proposed for fabricating compact and homogeneous titanium dioxide film (AO-TiO2). In order to realize morphology and thickness control of AO-TiO2, the theory concerning anodic oxidation (AO) is unveiled and the influence of relevant parameters during the process of AO such as electrolyte ingredient and oxidation voltage on AO-TiO2 formation is observed as well. Meanwhile, we demonstrate that the planar perovskite solar cells (p-PSCs) fabricated in ambient air and utilizing optimized AO-TiO2 as electron transport layer (ETL) can deliver repeatable power conversion efficiency (PCE) over 13%, which possess superior open-circuit voltage (Voc) and higher fill factor (FF) compared to its counterpart utilizing conventional high temperature processed compact TiO2 (c-TiO2) as ETL. Through a further comparative study, it is indicated that the improvement of device performance should be attributed to more effective electron collection from perovskite layer to AO-TiO2 and the decrease of device series resistance. Furthermore, hysteresis effect about current density-voltage (J-V) curves in TiO2-based p-PSCs is also unveiled.

Effect of calcination temperature on formaldehyde oxidation performance of Pt/TiO2 nanofiber composite at room temperature

NASA Astrophysics Data System (ADS)

Xu, Feiyan; Le, Yao; Cheng, Bei; Jiang, Chuanjia

2017-12-01

Catalytic oxidation at room temperature over well-designed catalysts is an environmentally friendly method for the abatement of indoor formaldehyde (HCHO) pollution. Herein, nanocomposites of platinum (Pt) and titanium dioxide (TiO2) nanofibers with various phase compositions were prepared by calcining the electrospun TiO2 precursors at different temperatures and subsequently depositing Pt nanoparticles (NPs) on the TiO2 through a NaBH4-reduction process. The phase compositions and structures of Pt/TiO2 can be easily controlled by varying the calcination temperature. The Pt/TiO2 nanocomposites showed a phase-dependent activity towards the catalytic HCHO oxidation. Pt/TiO2 containing pure rutile phase showed enhanced activity with a turnover frequency (TOF) of 16.6 min-1 (for a calcination temperature of 800 °C) as compared to those containing the anatase phase or mixed phases. Density functional theory calculation shows that TiO2 nanofibers with pure rutile phase have stronger adsorption ability to Pt atoms than anatase phase, which favors the reduction of Pt over rutile phase TiO2, leading to higher contents of metallic Pt in the nanocomposite. In addition, the Pt/TiO2 with rutile phase possesses more abundant oxygen vacancies, which is conducive to the activation of adsorbed oxygen. Consequently, the Pt/rutile-TiO2 nanocomposite exhibited better catalytic activity towards HCHO oxidation at room temperature.

Evolution of Microstructure and Mechanical Properties of Oxide Dispersion Strengthened Steels Made from Water-Atomized Ferritic Powder

NASA Astrophysics Data System (ADS)

Arkhurst, Barton Mensah; Kim, Jeoung Han

2018-05-01

Nano-structured oxide dispersion strengthened (ODS) steels produced from a 410L stainless steel powder prepared by water-atomization was studied. The influences of Ti content and milling time on the microstructure and the mechanical properties were analysed. It was found that the ODS steels made from the Si bearing 410L powder contained Y-Ti-O, Y-Ti-Si-O, Y-Si-O, and TiO2 oxides. Most nanoparticles produced after 80 h of milling were aggregated nanoparticles; however, after 160 h of milling, most aggregated nanoparticles dissociated into smaller individual nanoparticles. Perfect mixing of Y and Ti was not achieved even after the longer milling time of 160 h; instead, the longer hours of milling rather resulted in Si incorporation into the Y-Ti-O rich nanoparticles and a change in the matrix morphology from an equiaxed microstructure to a tempered martensite-like microstructure. The overall micro-hardness of the ODS steel increased with the increase of milling time. After 80 and 160 h, the microhardnesses were over 400 HV, which primarily resulted from the finer dispersed nanoparticles and in part to the formation of martensitic phases. Tensile strength of the 410L ODS steels was comparable with that of ODS steel produced from gas-atomized powder.

Novel Montmorillonite/TiO₂/MnAl-Mixed Oxide Composites Prepared from Inverse Microemulsions as Combustion Catalysts.

PubMed

Napruszewska, Bogna D; Michalik-Zym, Alicja; Rogowska, Melania; Bielańska, Elżbieta; Rojek, Wojciech; Gaweł, Adam; Wójcik-Bania, Monika; Bahranowski, Krzysztof; Serwicka, Ewa M

2017-11-19

A novel design of combustion catalysts is proposed, in which clay/TiO₂/MnAl-mixed oxide composites are formed by intermixing exfoliated organo-montmorillonite with oxide precursors (hydrotalcite-like in the case of Mn-Al oxide) obtained by an inverse microemulsion method. In order to assess the catalysts' thermal stability, two calcination temperatures were employed: 450 and 600 °C. The composites were characterized with XRF (X-ray fluorescence), XRD (X-ray diffraction), HR SEM (high resolution scanning electron microscopy, N₂ adsorption/desorption at -196 °C, and H₂ TPR (temperature programmed reduction). Profound differences in structural, textural and redox properties of the materials were observed, depending on the presence of the TiO₂ component, the type of neutralization agent used in the titania nanoparticles preparation (NaOH or NH₃ (aq)), and the temperature of calcination. Catalytic tests of toluene combustion revealed that the clay/TiO₂/MnAl-mixed oxide composites prepared with the use of ammonia showed excellent activity, the composites obtained from MnAl hydrotalcite nanoparticles trapped between the organoclay layers were less active, but displayed spectacular thermal stability, while the clay/TiO₂/MnAl-mixed oxide materials obtained with the aid of NaOH were least active. The observed patterns of catalytic activity bear a direct relation to the materials' composition and their structural, textural, and redox properties.

Fe-Ti-Cr-Oxides in Martian Meteorite EETA79001 Studied by Point-counting Procedure Using Raman Spectroscopy

NASA Technical Reports Server (NTRS)

Wang, Alian; Kuebler, Karla E.; Jolliff, Bradley L.; Haskin, Larry A.

2003-01-01

Fe-Ti-Cr-Oxide minerals contain much information about rock petrogenesis and alteration. Among the most important in the petrology of common intrusive and extrusive rocks are those of the FeO-TiO2-Cr2O3 compositional system chromite, ulv spinel-magnetite, and ilmenite-hematite. These minerals retain memories of oxygen fugacity. Their exsolution into companion mineral pairs give constraints on formation temperature and cooling rate. Laser Raman spectroscopy is anticipated to be a powerful technique for characterization of materials on the surface of Mars. A Mars Microbeam Raman Spectrometer (MMRS) is under development. It combines a micro sized laser beam and an automatic point-counting mechanism, and so can detect minor minerals or weak Raman-scattering phases such as Fe- Ti-Cr-oxides in mixtures (rocks & soils), and provide information on grain size and mineral mode. Most Fe-Ti-Cr-oxides produce weaker Raman signals than those from oxyanionic minerals, e.g. carbonates, sulfates, phosphates, and silicates, partly because most of them are intrinsically weaker Raman scatters, and partly because their dark colors limit the penetration depth of the excitation laser beam (visible wavelength) and of the Raman radiation produced. The purpose of this study is to show how well the Fe-Ti-Cr-oxides can be characterized by on-surface planetary exploration using Raman spectroscopy. We studied the basic Raman features of common examples of these minerals using well-characterized individual mineral grains. The knowledge gained was then used to study the Fe-Ti-Cr-oxides in Martian meteorite EETA79001, especially effects of compositional and structural variations on their Raman features.

Pinhole mediated electrical transport across LaTiO3/SrTiO3 and LaAlO3/SrTiO3 oxide hetero-structures

NASA Astrophysics Data System (ADS)

Kumar, Pramod; Dogra, Anjana; Toutam, Vijaykumar

2013-11-01

Metal-insulator-metal configuration of LaTiO3/SrTiO3 and LaAlO3/SrTiO3 hetero-structures between two dimensional electron gas formed at the interface and different area top electrodes is employed for Conductive Atomic force microscopy (CAFM) imaging, Current-Voltage (I-V), and Capacitance-Voltage (C-V) spectroscopy. Electrode area dependent I-V characteristics are observed for these oxide hetero-structures. With small area electrodes, rectifying I-V characteristics are observed, compared to, both tunneling and leakage current characteristics for large area electrodes. CAFM mapping confirmed the presence of pinholes on both surfaces. Resultant I-V characteristics have a contribution from both tunneling and leakage due to pinholes.

Enhancing visible light photo-oxidation of water with TiO2 nanowire arrays via cotreatment with H2 and NH3: synergistic effects between Ti3+ and N.

PubMed

Hoang, Son; Berglund, Sean P; Hahn, Nathan T; Bard, Allen J; Mullins, C Buddie

2012-02-29

We report a synergistic effect involving hydrogenation and nitridation cotreatment of TiO(2) nanowire (NW) arrays that improves the water photo-oxidation performance under visible light illumination. The visible light (>420 nm) photocurrent of the cotreated TiO(2) is 0.16 mA/cm(2) and accounts for 41% of the total photocurrent under simulated AM 1.5 G illumination. Electron paramagnetic resonance (EPR) spectroscopy reveals that the concentration of Ti(3+) species in the bulk of the TiO(2) following hydrogenation and nitridation cotreatment is significantly higher than that of the sample treated solely with ammonia. It is believed that the interaction between the N-dopant and Ti(3+) is the key to the extension of the active spectrum and the superior visible light water photo-oxidation activity of the hydrogenation and nitridation cotreated TiO(2) NW arrays. © 2012 American Chemical Society

Ti4O7/g-C3N4 visible light photocatalytic performance on hypophosphite oxidation: Effect of annealing temperature

NASA Astrophysics Data System (ADS)

Guan, Wei; Sun, Gaoge; Yin, Lei; Zhang, Zhenghua; Tian, Shichao

2018-03-01

The oxidation of hypophosphite to phosphate is the key to recover the phosphorus resource from the hypophosphite wastewater. In the present work, Ti4O7/g-C3N4 composites were synthesized at two different temperatures (100 and 160 °C) and their performance on photocatalytic oxidation of hypophosphite under visible light irradiation and the corresponding mechanism were evaluated. A hydrolysis method using g-C3N4 and Ti4O7 was applied to synthesize the Ti4O7/g-C3N4 composites with their hybrid structure and morphology confirmed by XRD, SEM and XPS. The annealing temperature significantly affected the photocatalytic performance of Ti4O7/g-C3N4 that the 160-Ti4O7/g-C3N4 composite (fabricated at 160 °C) showed the highest oxidation efficiency of hypophosphite of 81% and the highest photocatalytic oxidation rate of 0.467 h-1 comparing with the 100-Ti4O7/g-C3N4 composite (fabricated at 100 °C) and pure g-C3N4. The enhanced photocatalytic performance of 160-Ti4O7/g-C3N4 could be ascribed to the effective charge separation and enhanced photoabsorption efficiency. Additionally, electron spin resonance (ESR) results showed that hydroxyl radicals and superoxide anion radicals were mainly responsible to the oxidation of hypophosphite with superoxide anion radicals accounting for a more significant contribution. Moreover, Ti4O7/g-C3N4 photocatalysts showed the remarkable stability in the repetitive experiments.

Density functional theory simulation of titanium migration and reaction with oxygen in the early stages of oxidation of equiatomic NiTi alloy.

PubMed

Nolan, Michael; Tofail, Syed A M

2010-05-01

The biocompatibility of NiTi shape memory alloys (SMA) has made possible applications in self-expandable cardio-vascular stents, stone extraction baskets, catheter guide wires and other invasive and minimally invasive biomedical devices. The NiTi intermetallic alloy spontaneously forms a thin passive layer of TiO(2), which provides its biocompatibility. The oxide layer is thought to form as the Ti in the alloy surface reacts with oxygen, resulting in a depletion of Ti in the subsurface region - experimental evidence indicates formation of a Ni-rich layer below the oxide film. In this paper, we study the initial stages of oxide growth on the (110) surface of the NiTi alloy to understand the formation of alloy/oxide interface. We initially adsorb atomic and molecular oxygen on the (110) surface and then successively add O(2) molecules, up to 2 monolayer of O(2). Oxygen adsorption always results in a large energy gain. With atomic oxygen, Ti is pulled out of the surface layer leaving behind a Ni-rich subsurface region. Molecular O(2), on the other hand adsorbs dissociatively and pulls a Ti atom farther out of the surface layer. The addition of further O(2) up to 1 monolayer is also dissociative and results in complete removal of Ti from the initial surface layer. When further O(2) is added up to 2 monolayer, Ti is pulled even further out of the surface and a single thin layer of composition O-Ti-O is formed. The electronic structure shows that the metallic character of the alloy is unaffected by interaction with oxygen and formation of the oxide layer, consistent with the oxide layer being a passivant. Copyright 2010 Elsevier Ltd. All rights reserved.

Novel technique for preparing Ca- and P-containing ceramic coating on Ti-6Al-4V by micro-arc oxidation.

PubMed

Yu, Sirong; Yang, Xizhen; Yang, Long; Liu, Yaohui; Yu, Yingjie

2007-11-01

A novel technique for preparing the Ca- and P-containing ceramic coating on Ti-6Al-4V alloy by micro-arc oxidation (MAO) was developed successfully in this paper. In the new technique, Ti alloy first was micro-arc oxidated in P-containing electrolyte, and then it was micro-arc oxidated in Ca-containing electrolyte. This technique can avoid the undesired chemical reaction between Ca-containing salt and P-containing salt in electrolyte. The surface morphologies, composition, and phases of MAO coatings were studied by means of SEM, EDS, and XRD. The results show that the P- and Ca-containing coating on Ti-6Al-4V alloy contains Ti, TiO(2) (rutile), alpha-Ca(PO(3))(2), CaTiO(3), and AlTi(3). There are many small and uniform pores in the coating. Most of these pores are coterminous. The microhardness of the coating is 720 HV and higher than that of Ti-6Al-4V alloy (220 HV). The coating is more wear-resistant than Ti-6Al-4V alloy under the lubricant of the artificial saliva and not easy to desquamate from the substrate of Ti-6Al-4V alloy.

Improved Osteoblast and Chondrocyte Adhesion and Viability by Surface-Modified Ti6Al4V Alloy with Anodized TiO₂ Nanotubes Using a Super-Oxidative Solution.

PubMed

Beltrán-Partida, Ernesto; Moreno-Ulloa, Aldo; Valdez-Salas, Benjamín; Velasquillo, Cristina; Carrillo, Monica; Escamilla, Alan; Valdez, Ernesto; Villarreal, Francisco

2015-03-02

Titanium (Ti) and its alloys are amongst the most commonly-used biomaterials in orthopedic and dental applications. The Ti-aluminum-vanadium alloy (Ti6Al4V) is widely used as a biomaterial for these applications by virtue of its favorable properties, such as high tensile strength, good biocompatibility and excellent corrosion resistance. TiO₂ nanotube (NTs) layers formed by anodization on Ti6Al4V alloy have been shown to improve osteoblast adhesion and function when compared to non-anodized material. In his study, NTs were grown on a Ti6Al4V alloy by anodic oxidation for 5 min using a super-oxidative aqueous solution, and their in vitro biocompatibility was investigated in pig periosteal osteoblasts and cartilage chondrocytes. Scanning electron microscopy (SEM), energy dispersion X-ray analysis (EDX) and atomic force microscopy (AFM) were used to characterize the materials. Cell morphology was analyzed by SEM and AFM. Cell viability was examined by fluorescence microscopy. Cell adhesion was evaluated by nuclei staining and cell number quantification by fluorescence microscopy. The average diameter of the NTs was 80 nm. The results demonstrate improved cell adhesion and viability at Day 1 and Day 3 of cell growth on the nanostructured material as compared to the non-anodized alloy. In conclusion, this study evidences the suitability of NTs grown on Ti6Al4V alloy using a super-oxidative water and a short anodization process to enhance the adhesion and viability of osteoblasts and chondrocytes. The results warrant further investigation for its use as medical implant materials.

Effect of different alloyed layers on the high temperature oxidation behavior of newly developed Ti 2AlNb-based alloys

NASA Astrophysics Data System (ADS)

Wu, Hongyan; Zhang, Pingze; Zhao, Haofeng; Wang, Ling; Xie, Aigen

2011-01-01

The application of titanium aluminide orthorhombic alloys (O-phase alloys) as potential materials in aircraft and jet engines was limited by their poor oxidation resistance at high temperature. The Ti 2AlNb-based alloys were chromised (Cr), chromium-tungstened (Cr-W) and nickel-chromised (Ni-Cr) by the double glow plasma surface alloying process to improve their high temperature oxidation resistance. The discontinuous oxidative behavior of Cr, Cr-W and Ni-Cr alloyed layers on Ti 2AlNb-based alloy at 1093 K was explored in this study. After exposing at 1093 K, the TiO 2 layer was formed on the bare alloy and accompanied by the occurrence of crack, which promoted oxidation rate. The oxidation behavior of Ti 2AlNb-based alloys was improved by surface alloying due to the formation of protective Al 2O 3 scale or continuous and dense NiCr 2O 4 film. The Ni-Cr alloyed layer presented the best high-temperature oxidation resistance among three alloyed layers.

Oxidation Resistance of Materials Based on Ti3AlC2 Nanolaminate at 600 °C in Air.

PubMed

Ivasyshyn, Andrij; Ostash, Orest; Prikhna, Tatiana; Podhurska, Viktoriya; Basyuk, Tatiana

2016-12-01

The oxidation behavior of Ti3AlC2-based materials had been investigated at 600 °C in static air for 1000 h. It was shown that the intense increase of weight gain per unit surface area for sintered material with porosity of 22 % attributed to oxidation of the outer surface of the specimen and surfaces of pores in the bulk material. The oxidation kinetics of the hot-pressed Ti3AlC2-based material with 1 % porosity remarkably increased for the first 15 h and then slowly decreased. The weight gain per unit surface area for this material was 1.0 mg/cm(2) after exposition for 1000 h. The intense initial oxidation of Ti3AlC2-based materials can be eliminated by pre-oxidation treatment at 1200 °C in air for 2 h. As a result, the weight gain per unit surface area for the pre-oxidized material did not exceed 0.11 mg/cm(2) after 1000 h of exposition at 600 °C in air. It was demonstrated that the oxidation resistance of Ti3AlC2-based materials can be significantly improved by niobium addition.

Effect of the Combined Addition of Y and Ti on the Second Phase and Mechanical Properties of China Low-Activation Martensitic Steel

NASA Astrophysics Data System (ADS)

Zhang, Yangpeng; Zhan, Dongping; Qi, Xiwei; Jiang, Zhouhua; Zhang, Huishu

2018-05-01

In this study, approximately 0.35% Ti and two different Y contents were added to China low-activation martensitic (CLAM) steel during melting in a vacuum induction melting furnace. Scanning electron microscopy, transmission electron microscopy, x-ray diffraction, tensile tests, and Charpy impact tests were used to investigate the effects of the combined addition of Y and Ti on the second phase and mechanical properties. The results indicated that Y and Fe formed the large intermetallic compound Fe-Y; the compound easily aggregated in the grain boundaries and exhibited the strength of CLAM steel. Ti did not combine with Y to form the Y-Ti-O phase; however, it could combine with Ta and W to form MC precipitates, which were generally in the 20-50 nm size range. The CLAM steel with a higher Y content exhibited lower yield and tensile strengths at room temperature, with both steels yielding almost identical strengths at 600 °C.

Effect of the Combined Addition of Y and Ti on the Second Phase and Mechanical Properties of China Low-Activation Martensitic Steel

NASA Astrophysics Data System (ADS)

Zhang, Yangpeng; Zhan, Dongping; Qi, Xiwei; Jiang, Zhouhua; Zhang, Huishu

2018-04-01

In this study, approximately 0.35% Ti and two different Y contents were added to China low-activation martensitic (CLAM) steel during melting in a vacuum induction melting furnace. Scanning electron microscopy, transmission electron microscopy, x-ray diffraction, tensile tests, and Charpy impact tests were used to investigate the effects of the combined addition of Y and Ti on the second phase and mechanical properties. The results indicated that Y and Fe formed the large intermetallic compound Fe-Y; the compound easily aggregated in the grain boundaries and exhibited the strength of CLAM steel. Ti did not combine with Y to form the Y-Ti-O phase; however, it could combine with Ta and W to form MC precipitates, which were generally in the 20-50 nm size range. The CLAM steel with a higher Y content exhibited lower yield and tensile strengths at room temperature, with both steels yielding almost identical strengths at 600 °C.

Highly Ordered Periodic Au/TiO₂ Hetero-Nanostructures for Plasmon-Induced Enhancement of the Activity and Stability for Ethanol Electro-oxidation.

PubMed

Jin, Zhao; Wang, Qiyu; Zheng, Weitao; Cui, Xiaoqiang

2016-03-02

The catalytic electro-oxidation of ethanol is the essential technique for direct alcohol fuel cells (DAFCs) in the area of alternative energy for the ability of converting the chemical energy of alcohol into the electric energy directly. Developing highly efficient and stable electrode materials with antipoisoning ability for ethanol electro-oxidation remains a challenge. A highly ordered periodic Au-nanoparticle (NP)-decorated bilayer TiO2 nanotube (BTNT) heteronanostructure was fabricated by a two-step anodic oxidation of Ti foil and the subsequent photoreduction of HAuCl4. The plasmon-induced charge separation on the heterointerface of Au/TiO2 electrode enhances the electrocatalytic activity and stability for the ethanol oxidation under visible light irradiation. The highly ordered periodic heterostructure on the electrode surface enhanced the light harvesting and led to the greater performance of ethanol electro-oxidation under irradiation compared with the ordinary Au NPs-decorated monolayer TiO2 nanotube (MTNT). This novel Au/TiO2 electrode also performed a self-cleaning property under visible light attributed to the enhanced electro-oxidation of the adsorbed intermediates. This light-driven enhancement of the electrochemical performances provides a development strategy for the design and construction of DAFCs.

Degradation of 2,4-dichlorophenol with a novel TiO2/Ti-Fe-graphite felt photoelectrocatalytic oxidation process.

PubMed

Zhao, Bao-xiu; Li, Xiang-zhong; Wang, Peng

2007-01-01

Degradation of 2,4-dichlorophenol (2,4-DCP) was studied in a novel three-electrode photoelectrocatalytic (PEC) integrative oxidation process, and the factors influencing the degradation rate, such as applied current, flow speed of O2, pH, adscititious voltage and initial 2,4-DCP concentration were investigated and optimized. H2O2 was produced nearby cathode and Fe2+ continuously generated from Fe anode in solution when current and O2 were applied, so, main reactions, H2O2-assisted TiO2 PEC oxidation and E-Fenton reaction, occurred during degradation of 2,4-DCP in this integrative system. The degradation ratio of 2,4-DCP was 93% in this integrative oxidation process, while it was only 31% in E-Fenton process and 46% in H2O2-assisted TiO2 PEC process. So, it revealed that the degradation of 2,4-DCP was improved greatly by photoelectrical cooperation effect. By the investigation of pH, it showed that this integrative process could work well in a wide pH range from pH 3 to pH 9.

The phases and magnetic properties of (Ti, Co), and Cr doped Zn 2Y-type hexagonal ferrite

NASA Astrophysics Data System (ADS)

Chang, Y. H.; Wang, C. C.; Chin, T. S.; Yen, F. S.

1988-04-01

The phases and magnetic properties of Y-type hexagonal ferrite, Ba 2Zn 2 (Ti, Co) yFe 12-2 yO 22 doped with two sets of ions, (Ti, Co) and Cr were studied. In (Ti, Co) - doped ferrites the second phase appears at y ⩾ 0.6, which is a spinel type with the formula of (Zn 1-ηCo η)(Fe 2-δCo δ)O 4. Two resonant peaks are observed in ESR studies at the fields of 1020 and 2430 Oe, respectively, at a frequency of 9.684 GHz. The linewidth increases with the addition of the dopants. In chromium doped ferrite, two phases are identified as the amount of chromium is up to 0.2: spinel type of Zn(Fe 2-ɛCr ɛ)O 4 and orthorhombic BaCr 2O 4. Although the amount of Cr used does not influence the resonant field of the unique peak of the derivative curves from ESR, it eventually enlarges the linewidth.

Evolution of ferromagnetism in two-dimensional electron gas of LaTiO3/SrTiO3

NASA Astrophysics Data System (ADS)

Wen, Fangdi; Cao, Yanwei; Liu, Xiaoran; Pal, B.; Middey, S.; Kareev, M.; Chakhalian, J.

2018-03-01

Understanding, creating, and manipulating spin polarization of two-dimensional electron gases at complex oxide interfaces present an experimental challenge. For example, despite almost a decade long research effort, the microscopic origin of ferromagnetism in LaAlO3/SrTiO3 heterojunctions is still an open question. Here, by using a prototypical two-dimensional electron gas (2DEG) which emerges at the interface between band insulator SrTiO3 and antiferromagnetic Mott insulator LaTiO3, the experiment reveals the evidence for magnetic phase separation in a hole-doped Ti d1 t2g system, resulting in spin-polarized 2DEG. The details of electronic and magnetic properties of the 2DEG were investigated by temperature-dependent d.c. transport, angle-dependent X-ray photoemission spectroscopy, and temperature-dependent magnetoresistance. The observation of clear hysteresis in magnetotransport at low magnetic fields implies spin-polarization from magnetic islands in the hole rich LaTiO3 near the interface. These findings emphasize the role of magnetic instabilities in doped Mott insulators, thus providing another path for designing all-oxide structures relevant to spintronic applications.

Ti4O7/g-C3N4 Visible Light Photocatalytic Performance on Hypophosphite Oxidation: Effect of Annealing Temperature

PubMed Central

Guan, Wei; Sun, Gaoge; Yin, Lei; Zhang, Zhenghua; Tian, Shichao

2018-01-01

The oxidation of hypophosphite to phosphate is the key to recover the phosphorus resource from the hypophosphite wastewater. In the present work, Ti4O7/g-C3N4 composites were synthesized at two different temperatures (100 and 160°C) and their performance on photocatalytic oxidation of hypophosphite under visible light irradiation and the corresponding mechanism were evaluated. A hydrolysis method using g-C3N4 and Ti4O7 was applied to synthesize the Ti4O7/g-C3N4 composites with their hybrid structure and morphology confirmed by X-ray diffraction (XRD), scanning electron microscopy (SEM), and X-ray photoelectron spectra (XPS). The annealing temperature significantly affected the photocatalytic performance of Ti4O7/g-C3N4 that the 160-Ti4O7/g-C3N4 composite (fabricated at 160°C) showed the highest oxidation efficiency of hypophosphite of 81% and the highest photocatalytic oxidation rate of 0.467 h−1 comparing with the 100-Ti4O7/g-C3N4 composite (fabricated at 100°C) and pure g-C3N4. The enhanced photocatalytic performance of 160-Ti4O7/g-C3N4 could be ascribed to the effective charge separation and enhanced photoabsorption efficiency. Additionally, electron spin resonance (ESR) results showed that hydroxyl radicals and superoxide anion radicals were mainly responsible to the oxidation of hypophosphite with superoxide anion radicals accounting for a more significant contribution. Moreover, Ti4O7/g-C3N4 photocatalysts showed the remarkable stability in the repetitive experiments. PMID:29546041

Ti4O7/g-C3N4 Visible Light Photocatalytic Performance on Hypophosphite Oxidation: Effect of Annealing Temperature.

PubMed

Guan, Wei; Sun, Gaoge; Yin, Lei; Zhang, Zhenghua; Tian, Shichao

2018-01-01

The oxidation of hypophosphite to phosphate is the key to recover the phosphorus resource from the hypophosphite wastewater. In the present work, Ti 4 O 7 /g-C 3 N 4 composites were synthesized at two different temperatures (100 and 160°C) and their performance on photocatalytic oxidation of hypophosphite under visible light irradiation and the corresponding mechanism were evaluated. A hydrolysis method using g-C 3 N 4 and Ti 4 O 7 was applied to synthesize the Ti 4 O 7 /g-C 3 N 4 composites with their hybrid structure and morphology confirmed by X-ray diffraction (XRD), scanning electron microscopy (SEM), and X-ray photoelectron spectra (XPS). The annealing temperature significantly affected the photocatalytic performance of Ti 4 O 7 /g-C 3 N 4 that the 160-Ti 4 O 7 /g-C 3 N 4 composite (fabricated at 160°C) showed the highest oxidation efficiency of hypophosphite of 81% and the highest photocatalytic oxidation rate of 0.467 h -1 comparing with the 100-Ti 4 O 7 /g-C 3 N 4 composite (fabricated at 100°C) and pure g-C 3 N 4 . The enhanced photocatalytic performance of 160-Ti 4 O 7 /g-C 3 N 4 could be ascribed to the effective charge separation and enhanced photoabsorption efficiency. Additionally, electron spin resonance (ESR) results showed that hydroxyl radicals and superoxide anion radicals were mainly responsible to the oxidation of hypophosphite with superoxide anion radicals accounting for a more significant contribution. Moreover, Ti 4 O 7 /g-C 3 N 4 photocatalysts showed the remarkable stability in the repetitive experiments.

Structural and characteristic variation of anodic oxide on pure Ti with anodization duration

NASA Astrophysics Data System (ADS)

Mizukoshi, Yoshiteru; Ohtsu, Naofhumi; Masahashi, Naoya

2013-10-01

Change in the structural and characteristic of the anodic oxide on pure Ti with the duration of anodization time was investigated. With the progress of the anodization, the phase of the formed TiO2 successively changed from anatase phase to rutile phase. In the transition process, peak intensities of rutile TiO2 1 0 1, 1 1 1 and 2 1 1 planes of X-ray diffraction characteristically increased. The contact angles of water droplets on the anodize TiO2 were monotonously decreased with the progress of the anodization except on the characteristically oriented rutile surface. In the evaluations of acetaldehyde photocatalysis under UV illumination, the anatase TiO2 anodized for short period exhibited high activities. On the other hand, when illuminated with visible light (>422 nm), rutile-structured TiO2 formed by anodization with a long duration exhibited superior photocatalytic activities probably due to high rutile fraction and sulfur incorporation from the electrolyte.

Influences of ultra-thin Ti seed layers on the dewetting phenomenon of Au films deposited on Si oxide substrates

NASA Astrophysics Data System (ADS)

Kamiko, Masao; Kim, So-Mang; Jeong, Young-Seok; Ha, Jae-Ho; Koo, Sang-Mo; Ha, Jae-Geun

2018-05-01

The influences of a Ti seed layer (1 nm) on the dewetting phenomenon of Au films (5 nm) grown onto amorphous SiO2 substrates have been studied and compared. Atomic force microscopy results indicated that the introduction of Ti between the substrate and Au promoted the dewetting phenomenon. X-ray diffraction measurements suggested that the initial deposition of Ti promoted crystallinity of Au. A series of Auger electron spectroscopy and X-ray photoelectron spectroscopy results revealed that Ti transformed to a Ti oxide layer by reduction of the amorphous SiO2 substrate surface, and that the Ti seed layer remained on the substrate, without going through the dewetting process during annealing. We concluded that the enhancement of Au dewetting and the improvement in crystallinity of Au by the insertion of Ti could be attributed to the fact that Au location was changed from the surface of the amorphous SiO2 substrate to that of the Ti oxide layer.

Ab initio calculation of Ti NMR shieldings for titanium oxides and halides

NASA Astrophysics Data System (ADS)

Tossell, J. A.

Titanium NMR shielding constants have been calculated using ab initio coupled Hartree-Fock perturbation theory and polarized double-zeta basis sets for TiF 4, TiF 62-, TiCI 4, Ti(OH) 4, Ti(OH 2) 64+, Ti(OH) 4O, and Ti(OH) 3O -. In all cases the calculations were performed at Hartree-Fuck energy-optimized geometries. For Ti(OH) 4 a S4-symmetry geometry with nonlinear ∠ TiOH was employed. Relative shieldings are in reasonable agreement with experiment for TiF 62-, TiCI 4, and Ti(OR) 4, where R = H or alkyl. Ti(OH 2) 64+ is predicted to be more highly shielded than Ti(OH) 4 by about 340 ppm. The five-coordinate complex Ti(OH) 4O, whose calculated structure matches well that measured by extended X-ray absorption fine structure in K 2O · TiO 2 · SiO 2 glass, is actually deshielded compared to Ti(OH) 4 by about 40 ppm. X-ray absorption-near-edge spectral energies have also been calculated for TiF 4, TiCI 4, Ti(OH) 4, and Ti(OH) 4O using an equivalent ionic core virtual-orbital method and the observed reduction in term energy for the five-coordinate species compared to Ti(OH) 4 has been reproduced. Replacement of the H atoms in Ti(OH) 4 by point charges has only a slight effect upon σTi, suggesting a possible means of incorporating second-neighbor effects in NMR calculations for condensed phases.

Sacrificial hydrogen generation from aqueous triethanolamine with Eosin Y-sensitized Pt/TiO2 photocatalyst in UV, visible and solar light irradiation.

PubMed

Chowdhury, Pankaj; Gomaa, Hassan; Ray, Ajay K

2015-02-01

In this paper, we have studied Eosin Y-sensitized sacrificial hydrogen generation with triethanolamine as electron donor in UV, visible, and solar light irradiation. Aeroxide TiO2 was loaded with platinum metal via solar photo-deposition method to reduce the electron hole recombination process. Photocatalytic sacrificial hydrogen generation was influenced by several factors such as platinum loading (wt%) on TiO2, solution pH, Eosin Y to Pt/TiO2 mass ratio, triethanolamine concentration, and light (UV, visible and solar) intensities. Detailed reaction mechanisms in visible and solar light irradiation were established. Oxidation of triethanolamine and formaldehyde formation was correlated with hydrogen generation in both visible and solar lights. Hydrogen generation kinetics followed a Langmuir-type isotherm with reaction rate constant and adsorption constant of 6.77×10(-6) mol min(-1) and 14.45 M(-1), respectively. Sacrificial hydrogen generation and charge recombination processes were studied as a function of light intensities. Apparent quantum yields (QYs) were compared for UV, visible, and solar light at four different light intensities. Highest QYs were attained at lower light intensity because of trivial charge recombination. At 30 mW cm(-2) we achieved QYs of 10.82%, 12.23% and 11.33% in UV, visible and solar light respectively. Copyright © 2014 Elsevier Ltd. All rights reserved.

CdS Nanoparticle-Modified α-Fe2O3/TiO2 Nanorod Array Photoanode for Efficient Photoelectrochemical Water Oxidation.

PubMed

Yin, Ruiyang; Liu, Mingyang; Tang, Rui; Yin, Longwei

2017-09-02

In this work, we demonstrate a facile successive ionic layer adsorption and reaction process accompanied by hydrothermal method to synthesize CdS nanoparticle-modified α-Fe 2 O 3 /TiO 2 nanorod array for efficient photoelectrochemical (PEC) water oxidation. By integrating CdS/α-Fe 2 O 3 /TiO 2 ternary system, light absorption ability of the photoanode can be effectively improved with an obviously broadened optical-response to visible light region, greatly facilitates the separation of photogenerated carriers, giving rise to the enhancement of PEC water oxidation performance. Importantly, for the designed abnormal type-II heterostructure between Fe 2 O 3 /TiO 2 , the conduction band position of Fe 2 O 3 is higher than that of TiO 2 , the photogenerated electrons from Fe 2 O 3 will rapidly recombine with the photogenerated holes from TiO 2 , thus leads to an efficient separation of photogenerated electrons from Fe 2 O 3 /holes from TiO 2 at the Fe 2 O 3 /TiO 2 interface, greatly improving the separation efficiency of photogenerated holes within Fe 2 O 3 and enhances the photogenerated electron injection efficiency in TiO 2 . Working as the photoanodes of PEC water oxidation, CdS/α-Fe 2 O 3 /TiO 2 heterostucture electrode exhibits improved photocurrent density of 0.62 mA cm - 2 at 1.23 V vs. reversible hydrogen electrode (RHE) in alkaline electrolyte, with an obviously negatively shifted onset potential of 80 mV. This work provides promising methods to enhance the PEC water oxidation performance of the TiO 2 -based heterostructure photoanodes.

Novel photoinduced phase transitions in transition metal oxides and diluted magnetic semiconductors.

PubMed

Mizokawa, Takashi

2012-10-23

Some transition metal oxides have frustrated electronic states under multiphase competition due to strongly correlated d electrons with spin, charge, and orbital degrees of freedom and exhibit drastic responses to external stimuli such as optical excitation. Here, we present photoemission studies on Pr0.55(Ca1 - ySry)0.45MnO3 (y = 0.25), SrTiO3, and Ti1 - xCoxO2 (x = 0.05, 0.10) under laser illumination and discuss electronic structural changes induced by optical excitation in these strongly correlated oxides. We discuss the novel photoinduced phase transitions in these transition metal oxides and diluted magnetic semiconductors on the basis of polaronic pictures such as orbital, ferromagnetic, and ferroelectric polarons.

X-ray analyses of thermally grown and reactively sputtered tantalum oxide films on NiTi alloy

NASA Astrophysics Data System (ADS)

McNamara, Karrina; Tofail, Syed A. M.; Conroy, Derek; Butler, James; Gandhi, Abbasi A.; Redington, Wynette

2012-08-01

Sputter deposition of tantalum (Ta) on the surface of NiTi alloy is expected to improve the alloy's corrosion resistance and biocompatibility. Tantalum is a well-known biomaterial which is not affected by body fluids and is not irritating to human tissue. Here we compare the oxidation chemistry crystal structure evolution of tantalum oxide films grown on NiTi by reactive O2 sputtering and by thermal oxidation of sputter deposited Ta films. The effect of sputtering parameters and post-sputtering treatments on the morphology, oxidation state and crystal structure of the tantalum oxide layer have been investigated by field-emission scanning electron microscopy (FE-SEM), X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD). The study has found that it may be better to avoid oxidation at and above 600 °C. The study establishes that reactive sputtering in presence of low oxygen mixture yields thicker film with better control of the film quality except that the surface oxidation state of Ta is slightly lower.

Catalytic formal [2+2+1] synthesis of pyrroles from alkynes and diazenes via Ti(II)/Ti(IV) redox catalysis.

PubMed

Gilbert, Zachary W; Hue, Ryan J; Tonks, Ian A

2016-01-01

Pyrroles are structurally important heterocycles. However, the synthesis of polysubstituted pyrroles is often challenging. Here, we report a multicomponent, Ti-catalysed formal [2+2+1] reaction of alkynes and diazenes for the oxidative synthesis of penta- and trisubstituted pyrroles: a nitrenoid analogue to classical Pauson-Khand-type syntheses of cyclopentenones. Given the scarcity of early transition-metal redox catalysis, preliminary mechanistic studies are presented. Initial stoichiometric and kinetic studies indicate that the mechanism of this reaction proceeds through a formally Ti(II)/Ti(IV) redox catalytic cycle, in which an azatitanacyclobutene intermediate, resulting from [2+2] alkyne + Ti imido coupling, undergoes a second alkyne insertion followed by reductive elimination to yield pyrrole and a Ti(II) species. The key component for catalytic turnover is the reoxidation of the Ti(II) species to a Ti(IV) imido via the disproportionation of an η(2)-diazene-Ti(II) complex.

Catalytic formal [2+2+1] synthesis of pyrroles from alkynes and diazenes via TiII/TiIV redox catalysis

NASA Astrophysics Data System (ADS)

Gilbert, Zachary W.; Hue, Ryan J.; Tonks, Ian A.

2016-01-01

Pyrroles are structurally important heterocycles. However, the synthesis of polysubstituted pyrroles is often challenging. Here, we report a multicomponent, Ti-catalysed formal [2+2+1] reaction of alkynes and diazenes for the oxidative synthesis of penta- and trisubstituted pyrroles: a nitrenoid analogue to classical Pauson-Khand-type syntheses of cyclopentenones. Given the scarcity of early transition-metal redox catalysis, preliminary mechanistic studies are presented. Initial stoichiometric and kinetic studies indicate that the mechanism of this reaction proceeds through a formally TiII/TiIV redox catalytic cycle, in which an azatitanacyclobutene intermediate, resulting from [2+2] alkyne + Ti imido coupling, undergoes a second alkyne insertion followed by reductive elimination to yield pyrrole and a TiII species. The key component for catalytic turnover is the reoxidation of the TiII species to a TiIV imido via the disproportionation of an η2-diazene-TiII complex.

Improved Osteoblast and Chondrocyte Adhesion and Viability by Surface-Modified Ti6Al4V Alloy with Anodized TiO2 Nanotubes Using a Super-Oxidative Solution

PubMed Central

Beltrán-Partida, Ernesto; Moreno-Ulloa, Aldo; Valdez-Salas, Benjamín; Velasquillo, Cristina; Carrillo, Monica; Escamilla, Alan; Valdez, Ernesto; Villarreal, Francisco

2015-01-01

Titanium (Ti) and its alloys are amongst the most commonly-used biomaterials in orthopedic and dental applications. The Ti-aluminum-vanadium alloy (Ti6Al4V) is widely used as a biomaterial for these applications by virtue of its favorable properties, such as high tensile strength, good biocompatibility and excellent corrosion resistance. TiO2 nanotube (NTs) layers formed by anodization on Ti6Al4V alloy have been shown to improve osteoblast adhesion and function when compared to non-anodized material. In his study, NTs were grown on a Ti6Al4V alloy by anodic oxidation for 5 min using a super-oxidative aqueous solution, and their in vitro biocompatibility was investigated in pig periosteal osteoblasts and cartilage chondrocytes. Scanning electron microscopy (SEM), energy dispersion X-ray analysis (EDX) and atomic force microscopy (AFM) were used to characterize the materials. Cell morphology was analyzed by SEM and AFM. Cell viability was examined by fluorescence microscopy. Cell adhesion was evaluated by nuclei staining and cell number quantification by fluorescence microscopy. The average diameter of the NTs was 80 nm. The results demonstrate improved cell adhesion and viability at Day 1 and Day 3 of cell growth on the nanostructured material as compared to the non-anodized alloy. In conclusion, this study evidences the suitability of NTs grown on Ti6Al4V alloy using a super-oxidative water and a short anodization process to enhance the adhesion and viability of osteoblasts and chondrocytes. The results warrant further investigation for its use as medical implant materials. PMID:28787976

The complex metal-rich boride Ti1+xRh2-x+yIr3-yB3 (x=0.68, y=1.06) with a new structure type containing B4 zigzag fragments: Synthesis, crystal chemistry and theoretical calculations

NASA Astrophysics Data System (ADS)

Goerens, Christian; Fokwa, Boniface P. T.

2012-08-01

Polycrystalline samples and single crystals of the new complex boride Ti1+xRh2-x+yIr3-yB3 (x=0.68; y=1.06) were synthesized by arc-melting the elements in a water-cooled copper crucible under an argon atmosphere and characterized by X-Ray diffraction as well as EDX measurements. The crystal structure was refined on the basis of single crystal data. The new phase, which represents a new structure type containing trans zigzag B4 fragments as well as isolated boron atoms crystallizes in the orthorhombic space group Pbam (Nr. 55) with the lattice parameters a=8.620(1) Å, b=14.995(2) Å and c=3.234(1) Å. First-principles density functional theory calculations using the Vienna ab-initio simulation package (VASP) were performed on an appropriate structural model (using a supercell approach) and the experimental crystallographic data could be reproduced accurately. Based on this model, the density of states and crystal orbital Hamilton population (for bonding analysis) were calculated, using the linear muffin-tin orbital atomic sphere approximation (LMTO-ASA) method. According to these calculations, this metal-rich compound should be metallic, as expected. Furthermore, very strong boron-boron interactions are observed in the trans zigzag B4 fragment, which induce a clear differentiation of two types of metal-boron contacts with different strength. The observed three-dimensional metal-metal interaction is in good agreement with the predicted metallic behavior.

First-principles studies of magnetic complex oxide heterointerfaces

NASA Astrophysics Data System (ADS)

Rondinelli, James M.

Despite the technological advancements driven by conventional semiconductors, continued improvements in nanoelectronics will require new materials with greater functionality. Perovskite-structured transition metal oxides with ABO3 stoichiometry are leading candidates that display amyriad of useful phenomena: ferroelectricity, magnetism, and superconductivity. Since these properties arise from correlated electronic interactions, field-tuning techniques make possible ultra-fast phase transitions between dramatically different states. Unfortunately, the integration of these materials into microelectronics has not yet occurred because of a fundamental lack in understanding how to predict and control these phase transitions at oxide--oxide heterointerfaces. The exceedingly difficult challenge of identifying the microscopic origins of interface electronic behavior is crucial to the functional design and discovery of next generation electronic materials. This dissertation focuses on developing that understanding at magnetic perovskite oxide heterointerfaces using first-principles (parameter free) density functional calculations. New ideas for oxide-oxide superlattice design emerge by considering the interfaces as entirely new complex materials: the interfacial electronic and magnetic structure in artificial geometries is genuinely different from those of the parent bulk materials due to changes in symmetry- and size-dependent properties. By isolating the role of the interacting electron-, orbital-, and spin-lattice degrees of freedom at the interfaces, I identify that the primary interaction governing the ground state derives from latent instabilities present in the bulk phases. The heteroepitaxial structural constraints enhance these modes to re-normalize the low energy electronic structure. To develop insight into the role of thin film thickness and strain effects, I explore how the electronic and magnetic structures of single component films respond to the elastic

Copper doping enhanced the oxidative stress-mediated cytotoxicity of TiO2 nanoparticles in A549 cells.

PubMed

Ahmad, J; Siddiqui, M A; Akhtar, M J; Alhadlaq, H A; Alshamsan, A; Khan, S T; Wahab, R; Al-Khedhairy, A A; Al-Salim, A; Musarrat, J; Saquib, Q; Fareed, M; Ahamed, M

2018-05-01

Physicochemical properties of titanium dioxide nanoparticles (TiO 2 NPs) can be tuned by doping with metals or nonmetals. Copper (Cu) doping improved the photocatalytic behavior of TiO 2 NPs that can be applied in various fields such as environmental remediation and nanomedicine. However, interaction of Cu-doped TiO 2 NPs with human cells is scarce. This study was designed to explore the role of Cu doping in cytotoxic response of TiO 2 NPs in human lung epithelial (A549) cells. Characterization data demonstrated the presence of both TiO 2 and Cu in Cu-doped TiO 2 NPs with high-quality lattice fringes without any distortion. The size of Cu-doped TiO 2 NPs (24 nm) was lower than pure TiO 2 NPs (30 nm). Biological results showed that both pure and Cu-doped TiO 2 NPs induced cytotoxicity and oxidative stress in a dose-dependent manner. Low mitochondrial membrane potential and higher caspase-3 enzyme (apoptotic markers) activity were also observed in A549 cells exposed to pure and Cu-doped TiO 2 NPs. We further observed that cytotoxicity caused by Cu-doped TiO 2 NPs was higher than pure TiO 2 NPs. Moreover, antioxidant N-acetyl cysteine effectively prevented the reactive oxygen species generation, glutathione depletion, and cell viability reduction caused by Cu-doped TiO 2 NPs. This is the first report showing that Cu-doped TiO 2 NPs induced cytotoxicity and oxidative stress in A549 cells. This study warranted further research to explore the role of Cu doping in toxicity mechanisms of TiO 2 NPs.

Radiation response of ODS ferritic steels with different oxide particles under ion-irradiation at 550 °C

NASA Astrophysics Data System (ADS)

Song, Peng; Morrall, Daniel; Zhang, Zhexian; Yabuuchi, Kiyohiro; Kimura, Akihiko

2018-04-01

In order to investigate the effects of oxide particles on radiation response such as hardness change and microstructural evolution, three types of oxide dispersion strengthened (ODS) ferritic steels (named Y-Ti-ODS, Y-Al-ODS and Y-Al-Zr-ODS), mostly strengthened by Y-Ti-O, Y-Al-O and Y-Zr-O dispersoids, respectively, were simultaneously irradiated with iron and helium ions at 550 °C up to a damage of 30 dpa and a corresponding helium (He) concentration of ∼3500 appm to a depth of 1000-1300 nm. A single iron ion beam irradiation was also performed for reference. Transmission electron microscopy revealed that after the dual ion irradiation helium bubbles of 2.8, 6.6 and 4.5 nm in mean diameter with the corresponding number densities of 1.1 × 1023, 2.7 × 1022 and 3.6 × 1022 m-3 were observed in Y-Ti-ODS, Y-Al-ODS and Y-Al-Zr-ODS, respectively, while no such bubbles were observed after single ion irradiation. About 80% of intragranular He bubbles were adjacent to oxide particles in the ODS ferritic steels. Although the high number density He bubbles were observed in the ODS steels, the void swelling in Y-Ti-ODS, Y-Al-ODS and Y-Al-Zr-ODS was still small and estimated to be 0.13%, 0.53% and 0.20%, respectively. The excellent swelling resistance is dominantly attributed to the high sink strength of oxide particles that depends on the morphology of particle dispersion rather than the crystal structure of the particles. In contrast, no dislocation loops were produced in any of the irradiated steels. Nanoindentation measurements showed that no irradiation hardening but softening was found in the ODS ferritic steels, which was probably due to irradiation induced dislocation recovery. The helium bubbles in high number density never contributed to the irradiation hardening of the ODS steels at these irradiation conditions.

Complex oxide ferroelectrics: Electrostatic doping by domain walls

DOE PAGES

Maksymovych, Petro

2015-06-19

Electrically conducting interfaces can form, rather unexpectedly, by breaking the translational symmetry of electrically insulating complex oxides. For example, a nanometre-thick heteroepitaxial interface between electronically insulating LaAlO 3 and SrTiO 3 supports a 2D electron gas1 with high mobility of >1,000 cm 2 V -1 s -1 (ref. 2). Such interfaces can exhibit magnetism, superconductivity and phase transitions that may form the functional basis of future electronic devices2. A peculiar conducting interface can be created within a polar ferroelectric oxide by breaking the translational symmetry of the ferroelectric order parameter and creating a so-called ferroelectric domain wall (Fig. 1a,b). Ifmore » the direction of atomic displacements changes at the wall in such a way as to create a discontinuity in the polarization component normal to the wall (Fig. 1a), the domain wall becomes electrostatically charged. It may then attract compensating mobile charges of opposite sign produced by dopant ionization, photoexcitation or other effects, thereby locally, electrostatically doping the host ferroelectric film. In contrast to conductive interfaces between epitaxially grown oxides, domain walls can be reversibly created, positioned and shaped by electric fields, enabling reconfigurable circuitry within the same volume of the material. Now, writing in Nature Nanotechnology, Arnaud Crassous and colleagues at EPFL and University of Geneva demonstrate control and stability of charged conducting domain walls in ferroelectric thin films of BiFeO 3 down to the nanoscale.« less

Synthesis, characterization and photocatalytic activity of mixed oxides derived from ZnAlTi ternary layered double hydroxides

NASA Astrophysics Data System (ADS)

Sahu, R. K.; Mohanta, B. S.; Das, N. N.

2013-09-01

A new series of Ti4+ containing ZnAl-LDHs with varying Zn:Al:Ti (~3:1:0-3:0.5:0.5) ratio were prepared by coprecipitation of homogeneous solution metal salts and characterized by various physicochemical methods. Powder XRD revealed the formation of well crystallized LDH even at the highest Ti4+ content. On thermal treatment at 450 °C, the well crystallized LDH precursors yielded mixed oxides with BET surface area in the range 92-118 m2/g. UV-vis diffuse reflection spectroscopy (DRS) showed a marginal decrease of band gap energy for calcined ZnAlTi-LDHs in comparison to either ZnO or TiO2-P25. The TEM analyses of a representative sample (as-synthesized and calcined) indicated more or less uniform distribution of titanium species. The derived mixed oxides from titanium containing LDH precursors demonstrated better activity toward photodegradation of methylene blue and rhodamine B than those of a physical mixture of ZnO and TiO2. Moreover, the present work not only provided a first hand understanding about semiconductor properties of ZnAlTi-LDHs but also demonstrated their potential as photocatalysts for degradation of organic pollutants.

Al-doped TiO{sub 2} mesoporous material supported Pd with enhanced catalytic activity for complete oxidation of ethanol

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

Zhu, Jing, E-mail: mlczjsls123@163.com; Mu, Wentao, E-mail: mwt15035687833@163.com; Su, Liqing, E-mail: suliqing0163@163.com

Pd catalysts supported on Al-doped TiO{sub 2} mesoporous materials were evaluated in complete oxidation of ethanol. The catalysts synthesized by wet impregnation based on evaporation-induced self-assembly were characterized by X-ray diffraction, measurement of pore structure, XPS, FT-IR, temperature programmed reduction and TEM. Characteristic results showed that the aluminium was doped into the lattice of mesoporous anatase TiO{sub 2} to form Al-O-Ti defect structure. Catalytic results revealed that Al-doped catalysts were much more active than the pristine one, especially at low temperature (≤200 °C). This should be ascribed to the introduction of aluminium ions that suppressed the strong metal-support interaction andmore » increased the active sites of Pd oxides, enhanced the stabilized anatase TiO{sub 2}, improved well dispersed high valence palladium species with high reducibility and enriched chemisorption oxygen. - Graphical abstract: Al-doped Pd/TiO{sub 2} exhibited optimal catalytic performance for ethanol oxidation and CO{sub 2} yield by the suppression of SMSI. - Highlights: • Palladium catalysts supported on Al-doped TiO{sub 2} mesoporous materials were studied. • The introduction of Al can enhance anatase stabilization and increase defect TiO{sub 2}. • The Pd/Al-TiO{sub 2} catalysts show higher ethanol conversion and CO{sub 2} yield than Pd/TiO{sub 2}. • The influence of Al on SMSI and catalytic performance were evaluated by TPR and XPS.« less

Partitioning of Cu between mafic minerals, Fe-Ti oxides and intermediate to felsic melts

NASA Astrophysics Data System (ADS)

Liu, Xingcheng; Xiong, Xiaolin; Audétat, Andreas; Li, Yuan

2015-02-01

This study used improved capsule technique i.e., Pt95Cu05 or Au95Cu05 alloy capsules as Cu sources to determine Cu partitioning between mafic minerals, Fe-Ti oxides and intermediate to felsic melts at 0.5-2.5 GPa, 950-1100 °C and various oxygen fugacities (fO2). In combination with the data from the mafic composition systems, the results demonstrate that Cu is generally highly incompatible in mafic minerals and moderately incompatible to compatible in Fe-Ti oxides. The general order of mineral/melt Cu partition coefficients (DCu) is garnet (0.01-0.06) ⩽ olivine (0.04-0.20) ≈ opx (0.04-0.24) ≈ amphibole (0.04-0.20) ⩽ cpx (0.04-0.45) ⩽ magnetite, titanomagnetite and Cr-spinel (0.18-1.83). The variations in DCu depend mainly on temperature, fO2 or mineral composition. In general, DCu for olivine (and perhaps opx) increases with decreasing temperature and increasing fO2. DCu increases for cpx with Na+ (pfu) in cpx, for magnetite and Cr-spinel with Fe3+ (pfu) in these phases and for titanomagnetite with Ti4+ (pfu) in this phase. The large number of DCu data (99 pairs) serves as a foundation for quantitatively understanding the behavior of Cu during magmatic processes. The generation of intermediate to felsic magmas via fractional crystallization or partial melting of mafic rocks (magmas) at deep levels of crust involves removal of or leaving assemblages of mafic minerals + Fe-Ti oxides ± sulfides. With our DCu data on mafic minerals and Fe-Ti oxides, DCubulk values around 0.2 were obtained for the sulfide-free assemblages. Cu will thus be concentrated efficiently in the derived melts during these two processes if sulfides are absent or negligible, explaining that high fO2 and sulfide-destabilization are favorable to formation of the porphyry Cu system.

Catalytic oxidation of VOCs over Mn/TiO2/activated carbon under 185 nm VUV irradiation.

PubMed

Shu, Yajie; Xu, Yin; Huang, Haibao; Ji, Jian; Liang, Shimin; Wu, Muyan; Leung, Dennis Y C

2018-06-04

Volatile organic compounds (VOCs) are regarded as the major contributors to air pollution, and should be strictly regulated. Photocatalytic oxidation (PCO) is of great interest for the removal of VOCs owing to its strong oxidation capability. However, its application is greatly limited by catalytic deactivation. Vacuum Ultraviolet (VUV) irradiation provides a novel way to improve the photocatalytic activity while much O 3 will be generated which may cause secondary pollution. In this study, a multi-functional catalyst of Mn/TiO 2 /activated carbon (AC) was developed to eliminate and utilize O 3 , as well as enhance catalytic oxidation of VOC degradation via ozone-assisted catalytic oxidation (OZCO). The results indicate that Mn modified TiO 2 /AC (i.e. 0.1%Mn/20%TiO 2 /AC) achieved a toluene removal efficiency of nearly 86% with 100% elimination rate of O 3 . With the help of Mn/TiO 2 /AC catalyst, O 3 was catalytically decomposed and transformed into active species of O ( 1 D) and OH, thus enhancing toluene removal. The combination of VUV irradiation with multi-functional catalyst provides a novel and efficient way for the degradation of VOCs. Copyright © 2018 Elsevier Ltd. All rights reserved.

Fabrication of hydroxyapatite and TiO 2 nanorods on microarc-oxidized titanium surface using hydrothermal treatment

NASA Astrophysics Data System (ADS)

Song, Ho-Jun; Kim, Ji-Woo; Kook, Min-Suk; Moon, Won-Jin; Park, Yeong-Joon

2010-09-01

AC-type microarc oxidation (MAO) and hydrothermal treatment techniques were used to enhance the bioactivity of commercially pure titanium (CP-Ti). The porous TiO 2 layer fabricated by the MAO treatment had a dominant anatase structure and contained Ca and P ions. The MAO-treated specimens were treated hydrothermally to form HAp crystallites on the titanium oxide layer in an alkaline aqueous solution (OH-solution) or phosphorous-containing alkaline solution (POH-solution). A small number of micro-sized hydroxyapatite (HAp) crystallites and a thin layer composed of nano-sized HAps were formed on the Ti-MAO-OH group treated hydrothermally in an OH-solution, whereas a large number of micro-sized HAp crystallites and dense anatase TiO 2 nanorods were formed on the Ti-MAO-POH group treated hydrothermally in a POH-solution. The layer of bone-like apatite that formed on the surface of the POH-treated sample after soaking in a modified simulated body fluid was thicker than that on the OH-treated samples.

Pt-Au/MOx-CeO₂ (M = Mn, Fe, Ti) Catalysts for the Co-Oxidation of CO and H₂ at Room Temperature.

PubMed

Hong, Xiaowei; Sun, Ye; Zhu, Tianle; Liu, Zhiming

2017-02-27

A series of nanostructured Pt-Au/MO x -CeO₂ (M = Mn, Fe, Ti) catalysts were prepared and their catalytic performance for the co-oxidation of carbon monoxide (CO) and hydrogen (H₂) were evaluated at room temperature. The results showed that MO x promoted the CO oxidation of Pt-Au/CeO₂, but only the TiO₂ could enhance co-oxidation of CO and H₂ over Pt-Au/CeO₂. Related characterizations were conducted to clarify the promoting effect of MO x . Temperature-programmed reduction of hydrogen (H₂-TPR) and X-ray photoelectron spectroscopy (XPS) results suggested that MO x could improve the charge transfer from Au sites to CeO₂, resulting in a high concentration of Ce 3+ and cationic Au species which benefits for the CO oxidation. In-situ diffuse reflectance infrared Fourier transform spectroscopy (In-situ DRIFTS) results indicated that TiO₂ could facilitate the oxidation of H₂ over the Pt-Au/TiO₂-CeO₂ catalyst.

Preparation of core-shell Ti-Nb oxide nanocrystals

NASA Astrophysics Data System (ADS)

Simakov, David S. A.; Tsur, Yoed

2008-01-01

Nanosized powders of Ti-Nb oxide core-shell nanocrystals with atomic ratios of Nb/Ti = 0.11, 0.25, and 0.38 have been prepared by two preparation routes. The first route was co-precipitation, followed by␣annealing, using NbCl5 as a source of Nb. The second route was coating of pure TiO2 nanocrystals by Nb-isopropoxide in liquid medium, followed by impregnation of the Nb into the nanoparticles by annealing. Both methods yielded anatase nanocrystals with a Nb-rich shell and a core, which had much lower Nb loadings. The anatase structure solid solution (with Nb incorporated) was stable under annealing up to 760°C. The particle size remained within the nanometric scale ( <50 nm) under heat-treatment up to 760°C. It has been shown that the fabricated powders can be redispersed in aqueous media by simple ultrasound treatment, resulting in nanosized dispersions. Using a variety of analytical techniques, including depth profiling of single nanocrystallites by AES combined with sputtering by Ar ions, the mechanism of the core-shell structure creation was studied. It is proposed that the formation of the core-shell structure is governed by solubility limitations in the co-precipitation route and by solubility and diffusion limitations in the coating-incorporation route.

The plasma electrolytic oxidation micro-discharge channel model and its microstructure characteristic based on Ti tracer

NASA Astrophysics Data System (ADS)

Gao, Fangyuan; Hao, Li; Li, Guang; Xia, Yuan

2018-02-01

This study focuses on the individual discharge channel of ceramic coating prepared by plasma electrolytic oxidation (PEO), and attempts to reveal the mechanism of breakdown discharge at low voltage. Titanium (Ti) was employed as a substrate with the layer of aluminum deposited on it (aluminized Ti). The shape and microstructure of the discharge channels in PEO coatings were investigated using transmission electron microscope (TEM) and scanning electron microscopy (SEM). A schematic model of the individual discharge channel was proposed based on Ti tracer method. The shape of the discharge channel was mainly cylinder-shaped in the compact coating, with a groove-like oxidation region existed at the coating/substrate interface. In the groove-like oxidation region, the phase composition mainly composed of amorphous and mixed polycrystalline (aluminum titanate and mullite). β-Al2O3 was found in the ceramic coating. TEM morphology showed that nanometer sized micro channels existed in the ceramic coatings.

Band Alignment and Charge Transfer in Complex Oxide Interfaces

NASA Astrophysics Data System (ADS)

Zhong, Zhicheng; Hansmann, Philipp

2017-01-01

The synthesis of transition metal heterostructures is currently one of the most vivid fields in the design of novel functional materials. In this paper, we propose a simple scheme to predict band alignment and charge transfer in complex oxide interfaces. For semiconductor heterostructures, band-alignment rules like the well-known Anderson or Schottky-Mott rule are based on comparison of the work function or electron affinity of the bulk components. This scheme breaks down for oxides because of the invalidity of a single work-function approximation as recently shown in [Phys. Rev. B 93, 235116 (2016), 10.1103/PhysRevB.93.235116; Adv. Funct. Mater. 26, 5471 (2016), 10.1002/adfm.201600243]. Here, we propose a new scheme that is built on a continuity condition of valence states originating in the compounds' shared network of oxygen. It allows for the prediction of sign and relative amplitude of the intrinsic charge transfer, taking as input only information about the bulk properties of the components. We support our claims by numerical density functional theory simulations as well as (where available) experimental evidence. Specific applications include (i) controlled doping of SrTiO3 layers with the use of 4 d and 5 d transition metal oxides and (ii) the control of magnetic ordering in manganites through tuned charge transfer.

Nanocrystallized SrHA/SrHA SrTiO3/SrTiO3 TiO2 multilayer coatings formed by micro-arc oxidation for photocatalytic application

NASA Astrophysics Data System (ADS)

Han, Y.; Chen, D. H.; Zhang, L.

2008-08-01

Novel photocatalytic coatings containing strontium hydroxyapatite (SrHA), strontium titanate (SrTiO3), and TiO2 were formed by micro-arc oxidation (MAO) in an aqueous electrolyte containing strontium acetate and β-glycerophosphate disodium at 530 V for 0.1-5 min. The structure evolution of the coatings was investigated as a function of processing time, and the photocatalytic activity of the coatings was evaluated by measuring the decomposition rate of methyl orange under ultraviolet irradiation. During the MAO processing of the coatings, it was observed that some granules appeared in the electrolyte adjacent to the anode and they increased in amount as the processing time was prolonged. The obtained results show that the granules are amorphous and poorly crystallized SrHA with negative charges. The coating prepared for 5 min presents a microporous structure of SrHA/SrHA-SrTiO3/SrTiO3-TiO2 multilayers, in which the SrHA outermost layer and the SrHA-SrTiO3 intermediate layer are nanocrystallized. It is suggested that formation of the granules, electro-migration of the granules onto the pre-formed layer, and crystallization of the adhered granules are possible mechanisms for the formation of a SrHA/SrHA-SrTiO3/SrTiO3-TiO2 multilayer coating. This coating shows much higher photocatalytic decomposition efficiency relative to the MAO-formed TiO2 coating, and is expected to have an important photocatalytic application.

Porous TiO₂ surface formed on nickel-titanium alloy by plasma electrolytic oxidation: a prospective polymer-free reservoir for drug eluting stent applications.

PubMed

Huan, Zhiguang; Fratila-Apachitei, Lidy E; Apachitei, Iulian; Duszczyk, Jurek

2013-07-01

In this study, a porous oxide layer was formed on the surface of nickel-titanium alloy (NiTi) by plasma electrolytic oxidation (PEO) with the aim to produce a polymer-free drug carrier for drug eluting stent (DES) applications. The oxidation was performed galvanostatically in concentrated phosphoric acid electrolyte at low temperature. It was found that the response of NiTi substrate during the PEO process was different from that of bulk Ti, since the presence of large amount of Ni delayed the initial formation of a compact oxide layer that is essential for the PEO to take place. Under optimized PEO conditions, the resultant surface showed porosity, pore density and oxide layer thickness of 14.11%, 2.40 × 10⁵ pores/mm² and 0.8 μm, respectively. It was additionally noted that surface roughness after PEO did not significantly increase as compared with that of original NiTi substrate and the EDS analyses revealed a decrease in Ni/Ti ratio on the surface after PEO. The cross-section morphology showed no discontinuity between the PEO layer and the NiTi substrate. Furthermore, wettability and surface free energy of the NiTi substrate increased significantly after PEO treatment. The PEO process could be successfully translated to NiTi stent configuration proving for the first time its feasibility for such a medical device and offering potential for development of alternative, polymer-free drug carriers for NiTi DES. Copyright © 2013 Wiley Periodicals, Inc.

Preparation of atomically flat rutile TiO 2(001) surfaces for oxide film growth

DOE PAGES

Wang, Yang; Lee, Shinbuhm; Vilmercati, P.; ...

2016-01-01

The availability of low-index rutile TiO 2 single crystal substrates with atomically flat surfaces is essential for enabling epitaxialgrowth of rutile transition metal oxide films. The high surface energy of the rutile (001) surface often leads to surface faceting, which precludes the sputter and annealing treatment commonly used for the preparation of clean and atomically flat TiO 2(110) substrate surfaces. In this work, we reveal that stable and atomically flat rutile TiO 2(001) surfaces can be prepared with an atomically ordered reconstructedsurface already during a furnace annealing treatment in air. We tentatively ascribe this result to the decrease in surfacemore » energy associated with the surface reconstruction, which removes the driving force for faceting. Despite the narrow temperature window where this morphology can initially be formed, we demonstrate that it persists in homoepitaxialgrowth of TiO 2(001) thin films. The stabilization of surface reconstructions that prevent faceting of high-surface-energy crystal faces may offer a promising avenue towards the realization of a wider range of high quality epitaxial transition metal oxide heterostructures.« less

Thermoelectric properties of the ceramic oxide Sr1- x La x TiO3

NASA Astrophysics Data System (ADS)

Mahmud, Iqbal; Yoon, Man-Soon; Kim, Il-Ho; Choi, Moon-Kwan; Ur, Soon-Chul

2016-01-01

The effect of lanthanum on the electric and the thermoelectric properties of the ceramic oxide Sr1- x La x TiO3 (where x = 0.0, 0.04, 0.06, 0.08 and 0.12 mole) have been studied. La-doped SrTiO3 was prepared by using the conventional mixed-oxide reaction method. XRD patterns indicated that almost all the La atoms incorporated into the SrTiO3 crystal provided charge carriers. The lattice parameter increases with increasing La doping content. The relative densities of all the samples varied from 89.6% to 94.8%. The electrical conductivity increased with La doping up to 0.08 moles and then decreased as the content of La was increased above 0.08 moles. The thermal conductivity decreased with increasing La content. The largest absolute value of the Seebeck coefficient, 394 μVK-1 at 973 K, was observed at x = 0.04. The Sr0.92La0.08TiO3 sample showed its maximum electrical conductivity at 773 K and its largest ZT value of 0.20 at 973 K.

Sodium-promoted Pd/TiO2 for catalytic oxidation of formaldehyde at ambient temperature.

PubMed

Zhang, Changbin; Li, Yaobin; Wang, Yafei; He, Hong

2014-05-20

Catalytic oxidation of formaldehyde (HCHO) to CO2 at ambient conditions is of great interest for indoor HCHO purification. Here, we report that sodium-doped Pd/TiO2 is a highly effective catalyst for the catalytic oxidation of HCHO at room temperature. It was observed that Na doping has a dramatic promotion effect on the Pd/TiO2 catalyst and that nearly 100% HCHO conversion could be achieved over the 2Na-Pd/TiO2 catalyst at a GHSV of 95000 h(-1) and HCHO inlet concentration of 140 ppm at 25 °C. The mechanism of the Na-promotion effect was investigated by using Brunauer-Emmett-Teller (BET), X-ray diffraction (XRD), CO chemisorption, Temperature-programmed reduction by H2 (H2-TPR), X-ray photoelectron spectroscopy (XPS) and temperature-programmed desorption of O2 (O2-TPD) methods. The results showed that Na species addition can induce and further stabilize a negatively charged and well-dispersed Pd species, which then facilitates the activation of H2O and chemisorbed oxygen, therefore resulting in the high performance of the 2Na-Pd/TiO2 catalyst for the ambient HCHO destruction.

On the electron affinities of the Ca, Sc, Ti and Y atoms

NASA Technical Reports Server (NTRS)

Bauschlicher, Charles W., Jr.; Langhoff, Stephen R.; Taylor, Peter R.

1988-01-01

For the Ca, Sc, Ti and Y atoms calculations are performed for the ground states of the neutrals and the ground and several low-lying excited states of the negative ions. Overall the computed electron affinities are in good accord with experiment. The calculations show the rapid stabilization of the 3d orbital relative to the 4p as the nuclear charge increases. The 3F(0) and 3D(0) terms are found to be close in energy in Sc(-) and in Y(-). This confirms earlier speculation that some of the peaks in the photodetachment spectra of Y(-) originate from the bound excited 3F(0) term of Y(-).

Effect of thermal oxidation on corrosion and corrosion-wear behaviour of a Ti-6Al-4V alloy.

PubMed

Güleryüz, Hasan; Cimenoğlu, Hüseyin

2004-07-01

In this study, comparative investigation of thermal oxidation treatment for Ti-6Al-4V was carried out to determine the optimum oxidation conditions for further evaluation of corrosion-wear performance. Characterization of modified surface layers was made by means of microscopic examinations, hardness measurements and X-ray diffraction analysis. Optimum oxidation condition was determined according to the results of accelerated corrosion tests made in 5m HCl solution The examined Ti-6Al-4V alloy exhibited excellent resistance to corrosion after oxidation at 600 degrees C for 60 h. This oxidation condition achieved 25 times higher wear resistance than the untreated alloy during reciprocating wear test conducted in a 0.9% NaCl solution.

Instrumentation for Epitaxial Growth of Complex Oxides

DTIC Science & Technology

2015-12-17

synthesis of complex oxide heterostructures. A RF oxygen plasma source was acquired to increase the oxidizing ability of the growth environment, an...improvement that will prove critical in stabilizing materials with high oxidization states. The plasma source and accompanying electronics were purchased...2014 14-Aug-2015 Approved for Public Release; Distribution Unlimited Final Report: Instrumentation for Epitaxial Growth of Complex Oxides The views

TiO2 Nanoparticle-Induced Oxidation of the Plasma Membrane: Importance of the Protein Corona.

PubMed

Runa, Sabiha; Lakadamyali, Melike; Kemp, Melissa L; Payne, Christine K

2017-09-21

Titanium dioxide (TiO 2 ) nanoparticles, used as pigments and photocatalysts, are widely present in modern society. Inhalation or ingestion of these nanoparticles can lead to cellular-level interactions. We examined the very first step in this cellular interaction, the effect of TiO 2 nanoparticles on the lipids of the plasma membrane. Within 12 h of TiO 2 nanoparticle exposure, the lipids of the plasma membrane were oxidized, determined with a malondialdehyde assay. Lipid peroxidation was inhibited by surface passivation of the TiO 2 nanoparticles, incubation with an antioxidant (Trolox), and the presence of serum proteins in solution. Subsequent experiments determined that serum proteins adsorbed on the surface of the TiO 2 nanoparticles, forming a protein corona, inhibit lipid peroxidation. Super-resolution fluorescence microscopy showed that these serum proteins were clustered on the nanoparticle surface. These protein clusters slow lipid peroxidation, but by 24 h, the level of lipid peroxidation is similar, independent of the protein corona or free serum proteins. Additionally, over 24 h, this corona of proteins was displaced from the nanoparticle surface by free proteins in solution. Overall, these experiments provide the first mechanistic investigation of plasma membrane oxidation by TiO 2 nanoparticles, in the absence of UV light and as a function of the protein corona, approximating a physiological environment.

Microstructural Analysis of TiAl x N y O z Coatings Fabricated by DC Reactive Sputtering

NASA Astrophysics Data System (ADS)

García-González, L.; Hernández-Torres, J.; Flores-Ramírez, N.; Martínez-Castillo, J.; García-Ramírez, P. J.; Muñoz-Saldaña, J.; Espinoza-Beltrán, F. J.

2009-02-01

TiAl x N y O z coatings were prepared by DC reactive sputtering on AISI D2 tool steel substrates, using a target of Ti-Al-O fabricated from a mixture of powders of Ti (22.60 wt.%), Al (24.77 wt.%), and O (52.63 wt.%). The coatings were deposited on substrates at room temperature in a reactive atmosphere of nitrogen and argon under a pressure of 8.5 × 10-3 mbar. X-ray diffraction, electron dispersive spectroscopy, Raman scattering, and nanoindentation techniques were employed to investigate the coatings. The results show that the increment in the nitrogen flow affects the structure and the mechanical properties of the coatings. The sample with the lowest nitrogen flow presented the highest hardness (10.5 GPa) and the Young’s modulus (179.5 GPa). The hardness of the coatings TiAl x N y O z as a function of crystalline grain size shows a behavior consistent with the Hall-Petch relation.

Memory effects in a Al/Ti:HfO2/CuPc metal-oxide-semiconductor device

NASA Astrophysics Data System (ADS)

Tripathi, Udbhav; Kaur, Ramneek

2016-05-01

Metal oxide semiconductor structured organic memory device has been successfully fabricated. Ti doped hafnium oxide (Ti:HfO2) nanoparticles has been fabricated by precipitation method and further calcinated at 800 °C. Copper phthalocyanine, a hole transporting material has been utilized as an organic semiconductor. The electrical properties of the fabricated device have been studied by measuring the current-voltage and capacitance-voltage characteristics. The amount of charge stored in the nanoparticles has been calculated by using flat band condition. This simple approach for fabricating MOS memory device has opens up opportunities for the development of next generation memory devices.

Photo-catalytic oxidation of acetone on a TiO2 powder: An in situ FTIR investigation

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

Szanyi, János; Kwak, Ja Hun

2015-09-01

In situ transmission infrared spectroscopy was used to investigate the photo-oxidation of acetone on a commercial, oxidized TiO2 (P25) powder catalyst under UV irradiation at ambient temperature, in the absence and presence of gas phase O2. The photochemistry of a number of organic molecules (1-butanone, methanol and acetic acid,) under the same conditions was also studied in order to identify reaction intermediates and products formed in the photo-oxidation of acetone. Under anaerobic conditions (in the absence of gas phase oxygen) limited extent of photo-oxidation of acetone took place on the oxidized TiO2 sample. In the presence of O2 in themore » gas phase, however, acetone was completely converted to acetates and formates, and ultimately CO2. The initial step in the sequence of photo-induced reactions is the ejection of a methyl radical, resulting in the formation of surface acetates (from the acetyl group) and formates (from the methyl radicals). Acetate ions are also converted to formates, that, in turn, photo-oxidized to CO2. Under the experimental conditions applied the accumulation of carbonates and bicarbonates were observed on the TiO2 surface as the photo-oxidation of acetone proceeded (this was also observed during the course of photo-oxidation of all the other organics studied here). When the initial radical ejection step produced hydrocarbons containing more than one C atoms (as in the case in 2-butanone and mesytil oxide), the formation of aldehydes on the catalyst surface was also observed as a result of secondary reactions. This work was supported by the US Department of Energy, Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences & Biosciences. Pacific Northwest National Laboratory is operated by Battelle for the US Department of Energy. JHK also acknowledges the support of this work by the 2014 Research Fund of UNIST (Ulsan National Institute of Science and Technology, Ulsan, Korea). The authors thank

Iron(III)-oxo centers on TiO{sub 2} for visible light photocatalysis.

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

Libera, J. A.; Elam, J. W.; Sather, N. F.

Isolated iron(III)-oxo clusters were synthesized onto TiO{sub 2} using atomic layer deposition. The Fe{sub x}O{sub y}/TiO{sub 2} nanocomposites have unique properties that enable not only absorption of visible light, but efficient photocatalysis as demonstrated by methylene blue degradation. The localization of photogenerated electrons in core TiO{sub 2} nanocrystallites upon visible light excitation demonstrates coupling of conduction bands of mixed oxides. The redox properties of photogenerated charges in nanocomposites were studied using in situ electron paramagnetic resonance spectroscopy.

Quantification of oxide particle composition in model oxide dispersion strengthened steel alloys.

PubMed

London, A J; Lozano-Perez, S; Moody, M P; Amirthapandian, S; Panigrahi, B K; Sundar, C S; Grovenor, C R M

2015-12-01

Oxide dispersion strengthened ferritic steels (ODS) are being considered for structural components of future designs of fission and fusion reactors because of their impressive high-temperature mechanical properties and resistance to radiation damage, both of which arise from the nanoscale oxide particles they contain. Because of the critical importance of these nanoscale phases, significant research activity has been dedicated to analysing their precise size, shape and composition (Odette et al., Annu. Rev. Mater. Res. 38 (2008) 471-503 [1]; Miller et al., Mater. Sci. Technol. 29(10) (2013) 1174-1178 [2]). As part of a project to develop new fuel cladding alloys in India, model ODS alloys have been produced with the compositions, Fe-0.3Y2O3, Fe-0.2Ti-0.3Y2O3 and Fe-14Cr-0.2Ti-0.3Y2O3. The oxide particles in these three model alloys have been studied by APT in their as-received state and following ion irradiation (as a proxy for neutron irradiation) at various temperatures. In order to adequately quantify the composition of the oxide clusters, several difficulties must be managed, including issues relating to the chemical identification (ranging and variable peak-overlaps); trajectory aberrations and chemical structure; and particle sizing. This paper presents how these issues can be addressed by the application of bespoke data analysis tools and correlative microscopy. A discussion follows concerning the achievable precision in these measurements, with reference to the fundamental limiting factors. Copyright © 2015 Elsevier B.V. All rights reserved.

Role of Zn doping in oxidative stress mediated cytotoxicity of TiO2 nanoparticles in human breast cancer MCF-7 cells

NASA Astrophysics Data System (ADS)

Ahamed, Maqusood; Khan, M. A. Majeed; Akhtar, Mohd Javed; Alhadlaq, Hisham A.; Alshamsan, Aws

2016-07-01

We investigated the effect of Zn-doping on structural and optical properties as well as cellular response of TiO2 nanoparticles (NPs) in human breast cancer MCF-7 cells. A library of Zn-doped (1-10 at wt%) TiO2 NPs was prepared. Characterization data indicated that dopant Zn was incorporated into the lattice of host TiO2. The average particle size of TiO2 NPs was decreases (38 to 28 nm) while the band gap energy was increases (3.35 eV-3.85 eV) with increasing the amount of Zn-doping. Cellular data demonstrated that Zn-doped TiO2 NPs induced cytotoxicity (cell viability reduction, membrane damage and cell cycle arrest) and oxidative stress (reactive oxygen species generation & glutathione depletion) in MCF-7 cells and toxic intensity was increases with increasing the concentration of Zn-doping. Molecular data revealed that Zn-doped TiO2 NPs induced the down-regulation of super oxide dismutase gene while the up-regulation of heme oxygenase-1 gene in MCF-7 cells. Cytotoxicity induced by Zn-doped TiO2 NPs was efficiently prevented by N-acetyl-cysteine suggesting that oxidative stress might be the primarily cause of toxicity. In conclusion, our data indicated that Zn-doping decreases the particle size and increases the band gap energy as well the oxidative stress-mediated toxicity of TiO2 NPs in MCF-7 cells.

Role of Zn doping in oxidative stress mediated cytotoxicity of TiO2 nanoparticles in human breast cancer MCF-7 cells

PubMed Central

Ahamed, Maqusood; Khan, M. A. Majeed; Akhtar, Mohd Javed; Alhadlaq, Hisham A.; Alshamsan, Aws

2016-01-01

We investigated the effect of Zn-doping on structural and optical properties as well as cellular response of TiO2 nanoparticles (NPs) in human breast cancer MCF-7 cells. A library of Zn-doped (1–10 at wt%) TiO2 NPs was prepared. Characterization data indicated that dopant Zn was incorporated into the lattice of host TiO2. The average particle size of TiO2 NPs was decreases (38 to 28 nm) while the band gap energy was increases (3.35 eV–3.85 eV) with increasing the amount of Zn-doping. Cellular data demonstrated that Zn-doped TiO2 NPs induced cytotoxicity (cell viability reduction, membrane damage and cell cycle arrest) and oxidative stress (reactive oxygen species generation & glutathione depletion) in MCF-7 cells and toxic intensity was increases with increasing the concentration of Zn-doping. Molecular data revealed that Zn-doped TiO2 NPs induced the down-regulation of super oxide dismutase gene while the up-regulation of heme oxygenase-1 gene in MCF-7 cells. Cytotoxicity induced by Zn-doped TiO2 NPs was efficiently prevented by N-acetyl-cysteine suggesting that oxidative stress might be the primarily cause of toxicity. In conclusion, our data indicated that Zn-doping decreases the particle size and increases the band gap energy as well the oxidative stress-mediated toxicity of TiO2 NPs in MCF-7 cells. PMID:27444578

The Heterogeneous Photocatalytic Oxidation of Hydrocarbons on Platinized TiO2 Powders.

DTIC Science & Technology

1980-08-28

V W DUNN, K 0 WILBOURN NOO1-78-C-OS92 UCLASSIFIE D T - 10 ML I.’ fflfllfl~fflfllflfEEEEEEEEEl IIIII 1.1 . ILL 111L25 .4~I~ ( .6III MICROCOPY...Photocatalytic Oxidation of Hydrocarbons on Platinized TiO 2 Powders O by Ikuichiro Izumi, Wendell W. Dunn, Keith 0. Wilbourn , Fu-Ren F. Fan, and Allen J. Bard...Hydrocarbons on Platinized TiO 2 Powders. Ikuichiro Izumi, Wendell W. Dunn, Keith 0. Wilbourn , Fu-Ren F. Fan, and Allen J. Bard* Department of Chemistry, The

Enhancement of wear and corrosion resistance of low modulus β-type Zr-20Nb-xTi (x=0, 3) dental alloys through thermal oxidation treatment.

PubMed

Zhang, Jianfeng; Gan, Xiaxia; Tang, Hongqun; Zhan, Yongzhong

2017-07-01

In order to obtain material with low elastic modulus, good abrasion resistance and high corrosion stability as screw for dental implant, the biomedical Zr-20Nb and Zr-20Nb-3Ti alloy with low elastic modulus were thermal oxidized respectively at 700°C for 1h and 600°C for 1.25h to obtain the compact oxidized layer to improve its wear resistance and corrosion resistance. The results show that smooth compact oxidized layer (composed of monoclinic ZrO 2 , tetragonal ZrO 2 and 6ZrO 2 -Nb 2 O 5 ) with 22.6μm-43.5μm thickness and 1252-1306HV hardness can be in-situ formed on the surface of the Zr-20Nb-xTi (x=0, 3). The adhesion of oxidized layers to the substrates is determined to be 58.35-66.25N. The oxidized Zr-20Nb-xTi alloys reveal great improvement of the pitting corrosion resistance in comparison with the un-oxidized alloys. In addition, the oxidized Zr-20Nb-3Ti exhibits sharply reduction of the corrosion rates and the oxidized Zr-20Nb shows higher corrosion rates than un-oxidized alloys, which is relevant with the content of the t-ZrO 2 . Wear test in artificial saliva demonstrates that the wear losses of the oxidized Zr-20Nb-xTi (x=0, 3) are superior to pure Ti. All of the un-oxidized Zr-20Nb-xTi (x=0, 3) alloys suffer from serious adhesive wear due to its high plasticity. Because of the protection from compact oxide layer with high adhesion and high hardness, the coefficients of friction and wear losses of the oxidized Zr-20Nb-xTi (x=0, 3) alloys decrease 50% and 95%, respectively. The defects on the oxidized Zr-20Nb have a negative effect on the friction and wear properties. In addition, after the thermal oxidation, compression test show that elastic modulus and strength of Zr-20Nb-xTi (x=0, 3) increase slightly with plastic deformation after 40% of transformation. Furthermore, stripping of the oxidized layer from the alloy matrix did not occur during the whole experiments. As the surface oxidized Zr-20Nb-3Ti alloy has a combination of excellent performance

Possible ferrimagnetism and ferroelectricity of half-substituted rare-earth titanate: A first-principles study on Y0.5La0.5TiO3

NASA Astrophysics Data System (ADS)

An, Ming; Zhang, Hui-Min; Weng, Ya-Kui; Zhang, Yang; Dong, Shuai

2016-04-01

Titanates with the perovskite structure, including ferroelectrics (e.g., BaTiO3) and ferromagnetic ones (e.g., YTiO3), are important functional materials. Recent theoretical studies predicted multiferroic states in strained EuTiO3 and titanate superlattices, the former of which has already been experimental confirmed. Here, a first-principles calculation is performed to investigate the structural, magnetic, and electronic properties of Y half-substituted LaTiO3. Our results reveal that the magnetism of Y0.5La0.5TiO3 sensitively depends on its structural details because of the inherent phase competition. The lowest energy state is the ferromagnetic state, resulting in 0.25 μ B /Ti. Furthermore, some configurations of Y0.5La0.5TiO3 exhibit hybrid improper polarizations, which can be significantly affected by magnetism, resulting in the multiferroic properties. Because of the quenching disorder of substitution, the real Y0.5La0.5TiO3 material with random A-site ions may exhibit interesting relaxor behaviors.

Dye-sensitized electron transfer from TiO 2 to oxidized triphenylamines that follows first-order kinetics

DOE PAGES

DiMarco, Brian N.; Troian-Gautier, Ludovic; Sampaio, Renato N.; ...

2018-01-01

Two sensitizers, [Ru(bpy) 2 (dcb)] 2+ ( RuC ) and [Ru(bpy) 2 (dpb)] 2+ ( RuP ), were anchored to mesoporous TiO 2 thin films and utilized to sensitize the reaction of TiO 2 electrons with oxidized triphenylamines to visible light in CH 3 CN electrolytes.

Low-temperature thermoelectric properties of the electron-doped perovskites Sr1- x Ca x Ti1- y Nb y O3

NASA Astrophysics Data System (ADS)

Okuda, Tetsuji; Fukuyado, Junichi; Narikiyo, Kurahito; Akaki, Mitsuru; Kuwahara, Hideki

2013-08-01

We have investigated the thermoelectric (TE) properties for single crystals of the perovskites Sr1- x Ca x Ti1- y Nb y O3 for 0 ≤ x ≤ 0.4 and 0 ≤ y ≤ 0.03 at temperatures below room temperature (RT). We found that SrTi0.99Nb0.01O3 showed a large power factor at low temperatures ( PF = 50 µW/K2cm at 100 K ˜ 90 µW/K2cm at 50 K) and the largest dimensionless TE figure-ofmerit at temperatures below 40 K ( ZT ˜ 0.07) among the reported materials. Such a large low-temperature TE response around a carrier concentration of 1020 cm-3 is due to a distinct phonon drag effect. We also found that the Ca2+ substitution for Sr2+ increased the ZT at 300 K for Sr1- x Ca x Ti0.97Nb0.03O3 from 0.08 to 0.105. The enhancement of the ZT around RT originates both from a large reduction of a thermal conductivity due to a randomness introduced into the crystal structure and from an unexpected enhancement of a Seebeck coefficient.

Evaluation of Ti-48Al-2Cr-2Nb Under Fretting Conditions

NASA Technical Reports Server (NTRS)

Miyoshi, Kazuhisa; Lerch, Bradley A.; Draper, Susan L.; Raj, Sai V.

2001-01-01

The fretting behavior of Ti-48Al-2Cr-2Nb (y-TiAl) in contact with the nickel-base superalloy 718 was examined in air at temperatures from 296 to 823 K (23 to 550 C). The interfacial adhesive bonds between Ti-48Al-2Cr-2Nb and superalloy 718 were generally stronger than the cohesive bonds within Ti-48Al-2Cr-2Nb. The failed Ti-48Al-2Cr-2Nb debris subsequently transferred to the superalloy 718. In reference experiments conducted with Ti-6Al-4V against superalloy 718 under identical fretting conditions, the degree of transfer was greater for Ti-6A1-4V than for Ti-48Al-2Cr-2Nb. Wear of Ti-48Al-2Cr-2Nb generally decreased with increasing fretting frequency. The increasing rate of oxidation at elevated temperatures led to a drop in wear at 473 K. However, fretting wear increased as the temperature was increased from 473 to 823 K. At 723 and 823 K, oxide film disruption generated cracks, loose wear debris, and pits on the Ti-48Al-2Cr-2Nb wear surface. Both increasing slip amplitude and increasing load tended to produce more metallic wear debris, causing severe abrasive wear in the contacting metals.

Optical, electrochemical and hydrophilic properties of Y2O3 doped TiO2 nanocomposite films.

PubMed

Zhang, Xiangchao; Yang, Huaming; Tang, Aidong

2008-12-25

The 5% Y2O3 doped TiO2 nanocomposite film (YTF) deposited on ITO glass substrate has been synthesized by the sol-gel dip-coating method. The as-synthesized samples were characterized using X-ray diffraction (XRD), atomic force microscopy (AFM), scanning electron microscope (SEM), X-ray photoelectron spectroscopy (XPS), voltage-current (V-I), electrochemical impedance spectroscopy (EIS) and ultraviolet-visible (UV-vis) analysis technologies. The crystalline structure, surface morphology and surface chemical composition of YTF sample have been primarily investigated. The results demonstrate that YTF is anatase crystalline phase with thickness of 480 nm and consists of spherical shape particles with a grain size of about 15.8 nm. The binding energy appears as a chemical shift, and relatively more Y and Ti species are present on the surface, indicating that active surfaces of the nanocomposite film have been enhanced with more oxygen vacancies Vö due to doping Y2O3 to TiO2. The absorption edge of YTF has a red shift, and the optical properties of YTF in visible light region have been obviously improved. The water contact angle is about 8 degrees after daylight lamp irradiation 60 min. An equivalent circuit model provided a reliable description for the electrochemical systems. Based on the Mott-Schottky equation, the donor concentration (ND) for YTF is 1.05 x 10(20) cm(-3), which enhances 1 order of magnitude than that for pure TiO2 film (TF), the flat-band potential (V(fb)) and the space charge layer (d(sc)) obviously decreased. With the incorporation of Y2O3 into TiO2, the optical, electrochemical and photoinduced hydrophilic properties of YTF in visible light region have obviously improved, indicating that YTF shows promising applications in solar energy conversion, self-cleaning and other potential fields.

The structure feature of layered M1/3TiNbO5 (M=Fe, Ce) and their photocatalytic oxidization performance for ethyl mercaptan

NASA Astrophysics Data System (ADS)

Dong, Rui; Wang, Yuan; Wang, Ningning; Xu, Lei; He, Jie; Wu, Shanshan; Lan, Yunxiang; Hu, Jinsong

2016-09-01

Layered photocatalytic materials M1/3TiNbO5 (M = Fe, Ce) were prepared by ion-exchange of KTiNbO5 with M(NO3)3. The parent KTiNbO5 was synthesized with titanium (IV) isopropoxide and niobium oxalate by a novel polymerized complex (PC) method. The micro-structures and spectral response features of the as-prepared samples were characterized by powder X-ray diffraction (XRD), transmission electron microscope (TEM), laser Raman spectroscopy (LRS) and UV-vis diffuse reflectance spectroscopy (UV-vis DRS). The results revealed that there was a significant interaction between the interlayer cation and the terminal Nbdbnd O (Tidbnd O) bond in the NbO6 (TiO6) unit of the laminates. Photocatalytic performance was evaluated in oxidation of ethyl mercaptan under natural and UV light irradiation. It can be deduced that the photocatalytic oxidization performance can be directly affected by the characteristics of the interlayer cations.

Synthesis of complex oxides with garnet structure by spray drying of an aqueous salt solution

NASA Astrophysics Data System (ADS)

Makeenko, A. V.; Larionova, T. V.; Klimova-Korsmik, O. G.; Starykh, R. V.; Galkin, V. V.; Tolochko, O. V.

2017-04-01

The use of spray drying to obtain powders of complex oxides with a garnet structure has demonstrated. The processes occurring during heating of the synthesized oxide-salt product, leading to the formation of a material with a garnet structure, have been investigated using DTA, TGA, XPS, and XRD. It has been shown that a single-phase garnet structure of system (Y x Gd(3- x))3Al5O12 can be synthesized over the entire range of compositions.

Apatite Formation and Biocompatibility of a Low Young’s Modulus Ti-Nb-Sn Alloy Treated with Anodic Oxidation and Hot Water

PubMed Central

Tanaka, Hidetatsu; Mori, Yu; Noro, Atsushi; Kogure, Atsushi; Kamimura, Masayuki; Yamada, Norikazu; Hanada, Shuji; Masahashi, Naoya; Itoi, Eiji

2016-01-01

Ti-6Al-4V alloy is widely prevalent as a material for orthopaedic implants because of its good corrosion resistance and biocompatibility. However, the discrepancy in Young’s modulus between metal prosthesis and human cortical bone sometimes induces clinical problems, thigh pain and bone atrophy due to stress shielding. We designed a Ti-Nb-Sn alloy with a low Young’s modulus to address problems of stress disproportion. In this study, we assessed effects of anodic oxidation with or without hot water treatment on the bone-bonding characteristics of a Ti-Nb-Sn alloy. We examined surface analyses and apatite formation by SEM micrographs, XPS and XRD analyses. We also evaluated biocompatibility in experimental animal models by measuring failure loads with a pull-out test and by quantitative histomorphometric analyses. By SEM, abundant apatite formation was observed on the surface of Ti-Nb-Sn alloy discs treated with anodic oxidation and hot water after incubation in Hank’s solution. A strong peak of apatite formation was detected on the surface using XRD analyses. XPS analysis revealed an increase of the H2O fraction in O 1s XPS. Results of the pull-out test showed that the failure loads of Ti-Nb-Sn alloy rods treated with anodic oxidation and hot water was greater than those of untreated rods. Quantitative histomorphometric analyses indicated that anodic oxidation and hot water treatment induced higher new bone formation around the rods. Our findings indicate that Ti-Nb-Sn alloy treated with anodic oxidation and hot water showed greater capacity for apatite formation, stronger bone bonding and higher biocompatibility for osteosynthesis. Ti-Nb-Sn alloy treated with anodic oxidation and hot water treatment is a promising material for orthopaedic implants enabling higher osteosynthesis and lower stress disproportion. PMID:26914329

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

PubMed

Nolan, Michael

2011-10-28

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

Constructing hierarchical interfaces: TiO 2-supported PtFe-FeO x nanowires for room temperature CO oxidation

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

Zhu, Huiyuan; Wu, Zili; Dong, Su

2015-08-05

This is a report of a facile approach to constructing catalytic active hierarchical interfaces in one-dimensional (1D) nanostructure, exemplified by the synthesis of TiO 2-supported PtFe–FeO x nanowires (NWs). The hierarchical interface, constituting atomic level interactions between PtFe and FeO x within each NW and the interactions between NWs and support (TiO 2), enables CO oxidation with 100% conversion at room temperature. We identify the role of the two interfaces by probing the CO oxidation reaction with isotopic labeling experiments. Both the oxygen atoms (Os) in FeO x and TiO 2 participate in the initial CO oxidation, facilitating the reactionmore » through a redox pathway. Moreover, the intact 1D structure leads to the high stability of the catalyst. After 30 h in the reaction stream, the PtFe–FeO x/TiO2 catalyst exhibits no activity decay. These results provide a general approach and new insights into the construction of hierarchical interfaces for advanced catalysis.« less

Synthesis and transformations of alkylphosphate and alkoxysiloxide metal complexes to multicomponent oxide materials

NASA Astrophysics Data System (ADS)

Lugmair, Claus Guenter

This thesis describes the synthesis of mixed element oxide materials utilizing oxygen rich ``single-source precursor'' molecules. The key attributes of these precursor complexes are that they possess the stoichiometry of the targeted oxide material and that they can be converted to carbon free materials by mild thermal treatment. Complexes of Al, Cu, Fe, Hf, Nb, Ta, Ti, and Zr were prepared that contain tris(tert-butoxy)siloxy ligands as precursors to silica based materials. The pyrolytic decomposition of these complexes occur under mild conditions, with onset temperatures to decomposition between 95 and 200sp°C. The resulting metal-silica or metal oxide-silica materials contain very little carbon. The solid state transformation of Zrlbrack OSi(OsptBu)sb3rbracksb4 to ZrOsb2{*}4SiOsb2 produced an open fibrous material with pores which are ca. 20 nm in diameter. The solution phase thermolysis of the various metal siloxide complexes in anhydrous organic solvents led to xerogels consisting of small spherical primary particles (≤ca. 5 nm). These xerogels typically possess very high surface areas. The ZrOsb2{*}4SiOsb2 materials are amorphous as initially formed, and subsequent crystallizations of tetragonal ZrOsb2, monoclinic ZrOsb2, and cristobalite occur at relatively high temperatures. The enhanced stabilization of the amorphous and tetragonal phases of zirconia, relative to those derived from many sol-gel systems, implies that these single-source precursors initially produce highly homogeneous materials and that subsequent crystallizations are to a large degree diffusion-controlled, Careful addition of 1 or 2 equiv of water to THF solutions of Mlbrack OSi(OsptBu)sb3rbracksb4 (M = Zr, Hf) produced the isolable aqua complexes Mlbrack OSi(OsptBu)sb3rbracksb4(Hsb2O) and Mlbrack OSi(OsptBu)sb3rbracksb4(Hsb2O)sb2. It is likely that the hydrolysis of Zrlbrack OSi(OsptBu)sb3rbracksb4(Hsb2O)sb2 also occurs by an associative mechanism via the tris(aqua) intermediate

Study of non-stoichiometric BaSrTiFeO3 oxide dedicated to semiconductor gas sensors

NASA Astrophysics Data System (ADS)

Fasquelle, D.; Verbrugghe, N.; Deputier, S.

2016-11-01

Developing instrumentation systems compatible with the European RoHS directive (restriction of hazardous substances) to monitor our environment is of great interest for our society. Our research therefore aims at developing innovating integrated systems of detection dedicated to the characterization of various environmental exposures. These systems, which integrate new gas sensors containing lead-free oxides, are dedicated to the detection of flammable and toxic gases. We have firstly chosen to study semiconductor gas sensors implemented with lead-free oxides in view to develop RoHS devices. Therefore thick films deposited by spin-coating and screen-printing have been chosen for their robustness, ease to realize and ease to finally obtain cost-effective sensors. As crystalline defects and ionic vacancies are of great interest for gas detection, we have decided to study a non-stoichiometric composition of the BaSrTiFeO3 sensible oxide. Nonstoichiometric BaSrTiFeO3 lead-free oxide thick films were deposited by screen-printing on polycrystalline AFO3 substrates covered by a layer of Ag-Pd acting as bottom electrode. The physical characterizations have revealed a crystalline structure mainly composed of BaTiO3 pseudo-cubic phase and Ba4Ti12O27 monoclinic phase for the powder, and a porous microstructure for the thick films. When compared to a BSTF thick film with a stoichiometric composition, a notable increase in the BSTF dielectric constant value was observed when taking into account of a similar microstructure and grain size. The loss tangent mean value varies more softly for the non-stoichiometric BaSrTiFeO3 films than for the perovskite BSTF film as tanδ decreases from 0.45 to 0.04 when the frequency increases from 100 Hz to 1 MHz.

Spectroscopic study of the charge-transfer complexes TiCl4/styrene and TiCl4/polystyrene

NASA Astrophysics Data System (ADS)