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Sample records for tetragonal phase oxides

  1. Finite element analysis of the tetragonal to monoclinic phase transformation during oxidation of zirconium alloys

    Energy Technology Data Exchange (ETDEWEB)

    Platt, P., E-mail: Philip.Platt@manchester.ac.uk [University of Manchester, School of Materials, Materials Performance Centre, Manchester M13 9PL (United Kingdom); Frankel, P. [University of Manchester, School of Materials, Materials Performance Centre, Manchester M13 9PL (United Kingdom); Gass, M.; Howells, R. [AMEC, Walton House, Faraday Street, Birchwood Park, Risley, Warrington WA3 6GA (United Kingdom); Preuss, M. [University of Manchester, School of Materials, Materials Performance Centre, Manchester M13 9PL (United Kingdom)

    2014-11-15

    Corrosion is a key limiting factor in the degradation of zirconium alloys in light water reactors. Developing a mechanistic understanding of the corrosion process offers a route towards improving safety and efficiency as demand increases for higher burn-up of fuel. Oxides formed on zirconium alloys are composed of both monoclinic and meta-stable tetragonal phases, and are subject to a number of potential mechanical degradation mechanisms. The work presented investigates the link between the tetragonal to monoclinic oxide phase transformation and degradation of the protective character of the oxide layer. To achieve this, Abaqus finite element analysis of the oxide phase transformation has been carried out. Study of the change in transformation strain energy shows how relaxation of oxidation induced stress and fast fracture at the metal–oxide interface could destabilise the tetragonal phase. Central to this is the identification of the transformation variant most likely to form, and understanding why twinning of the transformed grain is likely to occur. Development of transformation strain tensors and analysis of the strain components allows some separation of dilatation and shear effects. Maximum principal stress is used as an indication of fracture in the surrounding oxide layer. Study of the stress distributions shows the way oxide fracture is likely to occur and the differing effects of dilatation and shape change. Comparison with literature provides qualitative validation of the finite element simulations.

  2. Finite element analysis of the tetragonal to monoclinic phase transformation during oxidation of zirconium alloys

    Science.gov (United States)

    Platt, P.; Frankel, P.; Gass, M.; Howells, R.; Preuss, M.

    2014-11-01

    Corrosion is a key limiting factor in the degradation of zirconium alloys in light water reactors. Developing a mechanistic understanding of the corrosion process offers a route towards improving safety and efficiency as demand increases for higher burn-up of fuel. Oxides formed on zirconium alloys are composed of both monoclinic and meta-stable tetragonal phases, and are subject to a number of potential mechanical degradation mechanisms. The work presented investigates the link between the tetragonal to monoclinic oxide phase transformation and degradation of the protective character of the oxide layer. To achieve this, Abaqus finite element analysis of the oxide phase transformation has been carried out. Study of the change in transformation strain energy shows how relaxation of oxidation induced stress and fast fracture at the metal-oxide interface could destabilise the tetragonal phase. Central to this is the identification of the transformation variant most likely to form, and understanding why twinning of the transformed grain is likely to occur. Development of transformation strain tensors and analysis of the strain components allows some separation of dilatation and shear effects. Maximum principal stress is used as an indication of fracture in the surrounding oxide layer. Study of the stress distributions shows the way oxide fracture is likely to occur and the differing effects of dilatation and shape change. Comparison with literature provides qualitative validation of the finite element simulations.

  3. Finite element analysis of the tetragonal to monoclinic phase transformation during oxidation of zirconium alloys

    International Nuclear Information System (INIS)

    Platt, P.; Frankel, P.; Gass, M.; Howells, R.; Preuss, M.

    2014-01-01

    Corrosion is a key limiting factor in the degradation of zirconium alloys in light water reactors. Developing a mechanistic understanding of the corrosion process offers a route towards improving safety and efficiency as demand increases for higher burn-up of fuel. Oxides formed on zirconium alloys are composed of both monoclinic and meta-stable tetragonal phases, and are subject to a number of potential mechanical degradation mechanisms. The work presented investigates the link between the tetragonal to monoclinic oxide phase transformation and degradation of the protective character of the oxide layer. To achieve this, Abaqus finite element analysis of the oxide phase transformation has been carried out. Study of the change in transformation strain energy shows how relaxation of oxidation induced stress and fast fracture at the metal–oxide interface could destabilise the tetragonal phase. Central to this is the identification of the transformation variant most likely to form, and understanding why twinning of the transformed grain is likely to occur. Development of transformation strain tensors and analysis of the strain components allows some separation of dilatation and shear effects. Maximum principal stress is used as an indication of fracture in the surrounding oxide layer. Study of the stress distributions shows the way oxide fracture is likely to occur and the differing effects of dilatation and shape change. Comparison with literature provides qualitative validation of the finite element simulations

  4. Oxidation of zirconium alloys in steam: influence of tetragonal zirconia on oxide growth mechanism

    International Nuclear Information System (INIS)

    Godlewski, J.

    1990-07-01

    The oxidation of zirconium alloys in presence of steam, presents after a 'parabolic' growth law, an acceleration of the oxidation velocity. This phenomenon limits the use of zirconium alloys as nuclear fuel cladding element. In order to determine the physico-chemical process leading to this kinetic transition, two approaches have been carried out: the first one has consisted to determine the composition of the oxide layer and its evolution with the oxidation time; and the second one to determine the oxygen diffusion coefficients in the oxide layers of pre- and post-transition as well as their evolution with the oxidation time. The composition of the oxide layers has been determined by two analyses techniques: the X-ray diffraction and the laser Raman spectroscopy. This last method has allowed to confirm the presence of tetragonal zirconium oxide in the oxide layers. Analyses carried out by laser Raman spectroscopy on oxides oblique cuttings have revealed that the tetragonal zirconium oxide is transformed in monoclinic phase during the kinetic transition. A quantitative approach has allowed to corroborate the results obtained by these two techniques. In order to determine the oxygen diffusion coefficients in the oxides layers, two diffusion treatments have been carried out: 1)under low pressure with D 2 18 O 2 ) under high pressure in an autoclave with H 2 18 O. The oxygen 18 concentration profiles have been obtained by two analyses techniques: the nuclear microprobe and the secondary ions emission spectroscopy. The obtained profiles show that the mass transport is made by the volume and particularly by the grain boundaries. The corresponding diffusion coefficients have been calculated with the WHIPPLE and LE CLAIRE solution. The presence of tetragonal zirconium oxide, its relation with the kinetic transition, and the evolution of the diffusion coefficients with the oxidation time, are discussed in terms of internal stresses in the oxide layer and of the oxide layer

  5. Nanosize stabilization of cubic and tetragonal phases in reactive plasma synthesized zirconia powders

    Energy Technology Data Exchange (ETDEWEB)

    Jayakumar, S., E-mail: sjayakumar.physics@gmail.com [Research and Development Centre, Bharathiar University, Coimbatore 641 014 (India); Department of Physics, Pollachi Institute of Engineering and Technology, Pollachi 642 205 (India); Ananthapadmanabhan, P.V.; Thiyagarajan, T.K. [Laser and Plasma Technology Division, BARC, Trombay, Mumbai 400 085 (India); Perumal, K. [Vision for Wisdom, Temple of Consciousness, Aliyar 642 101 (India); Mishra, S.C. [Department of Metallurgical and Materials Engg, National Institute of Technology, Rourkela 769 008 (India); Suresh, G. [Department of Physics, Park College of Engineering and Technology, Coimbatore 641 659 (India); Su, L.T.; Tok, A.I.Y. [School of Materials Science and Engg, Nanyang Technological University, 50 Nanyang Avenue, Singapore 639 798 (Singapore)

    2013-06-15

    Pure zirconium oxide powders with particle size 2–33 nm are synthesized by reactive plasma processing. Transmission electron microscopy investigation of these particles revealed size dependent behavior for their phase stabilization. The monoclinic phase is found to be stable when particle size is ≥20 nm; Tetragonal is found to be stabilized in the range of 7–20 nm and as the particle size decreases to 6 nm and less, the cubic phase is stabilized. - Highlights: ► Direct conversion of micron-sized zirconium hydride powder to single crystal ZrO{sub 2} nanopowder. ► Size dependent stabilization of cubic, tetragonal and monoclinic phases in the reactive plasma synthesized ZrO{sub 2} nanopowder. ► Transmission electron microscopic investigation to identify particles of different sizes and their corresponding phase structure.

  6. Glass ceramic toughened with tetragonal zirconia

    Science.gov (United States)

    Keefer, Keith D.; Michalske, Terry A.

    1986-01-01

    A phase transformation-toughened glass ceramic and a process for making it are disclosed. A mixture of particulate network-forming oxide, network-modifying oxide, and zirconium oxide is heated to yield a homogeneous melt, and this melt is then heat-treated to precipitate an appreciable quantity of tetragonal zirconia, which is retained at ambient temperature to form a phase transformation-toughened glass ceramic. Nucleating agents and stabilizing agents may be added to the mixture to facilitate processing and improve the ceramic's properties. Preferably, the mixture is first melted at a temperature from 1200.degree. to 1700.degree. C. and is then heat-treated at a temperature within the range of 800.degree. to 1200.degree. C. in order to precipitate tetragonal ZrO.sub.2. The composition, as well as the length and temperature of the heat-treatment, must be carefully controlled to prevent solution of the precipitated tetragonal zirconia and subsequent conversion to the monoclinic phase.

  7. Pressure induced phase transitions in ceramic compounds containing tetragonal zirconia

    Energy Technology Data Exchange (ETDEWEB)

    Sparks, R.G.; Pfeiffer, G.; Paesler, M.A.

    1988-12-01

    Stabilized tetragonal zirconia compounds exhibit a transformation toughening process in which stress applied to the material induces a crystallographic phase transition. The phase transition is accompanied by a volume expansion in the stressed region thereby dissipating stress and increasing the fracture strength of the material. The hydrostatic component of the stress required to induce the phase transition can be investigated by the use of a high pressure technique in combination with Micro-Raman spectroscopy. The intensity of Raman lines characteristic for the crystallographic phases can be used to calculate the amount of material that has undergone the transition as a function of pressure. It was found that pressures on the order of 2-5 kBar were sufficient to produce an almost complete transition from the original tetragonal to the less dense monoclinic phase; while a further increase in pressure caused a gradual reversal of the transition back to the original tetragonal structure.

  8. Raman spectroscopy study of the tetragonal-to-monoclinic transition in zirconium oxide scales and determination of overall oxygen diffusion by nuclear microanalysis of O18

    International Nuclear Information System (INIS)

    Godlewski, J.; Lambertin, M.; Gros, J.P.; Wadier, J.F.; Weidinger, H.

    1991-01-01

    This paper reports on two allotropic forms of zirconium oxide, monoclinic and tetragonal that have been identified in the scales formed on zirconium alloys. The transition from tetragonal to monoclinic has been followed by Z-ray measurements and Raman laser spectroscopy. Information on the average content of the tetragonal phase was obtained by X-ray diffraction, whereas Raman laser analyses on tapered sections revealed its distribution through the scale thickness. Oxidation exposures were made in an autoclave, using H 2 O 18 and D 2 O 18 to determine the overall diffusion coefficients. In particular, oxide scales have been studied on Zircaloy-4 with three different precipitate sizes, and on a Zr-1Nb alloy, after exposure in an autoclave for between 3 and 100 days. The specimens were analyzed in detail in the vicinity of the kinetics transition point, where the acceleration of corrosion occurs. Raman spectroscopy analyses enabled the crystallographic nature of the ZrO 2 to be determined. Close to the interface, the tetragonal phase content is about 40%, when after the transition the tetragonal phase is transformed into monoclinic. The O 18 diffusion treatment was carried out in an autoclave at 400 degrees C under pressure on specimens previously oxidized for between 3 and 100 days in natural water vapor pressure. The diffusion profiles were determined by nuclear microanalysis using the O 18 (p, α) → N 15 reaction. Based on these profiles, the volume and grain boundary diffusion coefficients were calculated for each material and for each oxidation time

  9. High-pressure synthesis of fully occupied tetragonal and cubic tungsten bronze oxides

    Energy Technology Data Exchange (ETDEWEB)

    Ikeuchi, Yuya; Takatsu, Hiroshi; Tassel, Cedric; Goto, Yoshihiro; Murakami, Taito; Kageyama, Hiroshi [Graduate School of Engineering, Kyoto University (Japan)

    2017-05-15

    A high-pressure reaction yielded the fully occupied tetragonal tungsten bronze K{sub 3}W{sub 5}O{sub 15} (K{sub 0.6}WO{sub 3}). The terminal phase shows an unusual transport property featuring slightly negative temperature-dependence in resistivity (dρ/dT<0) and a large Wilson ratio of R{sub W}=3.2. Such anomalous metallic behavior possibly arises from the low-dimensional electronic structure with a van Hove singularity at the Fermi level and/or from enhanced magnetic fluctuations by geometrical frustration of the tungsten sublattice. The asymmetric nature of the tetragonal tungsten bronze K{sub x}WO{sub 3}-K{sub 0.6-y}Ba{sub y}WO{sub 3} phase diagram implies that superconductivity for x≤0.45 originates from the lattice instability because of potassium deficiency. A cubic perovskite KWO{sub 3} phase was also identified as a line phase - in marked contrast to Na{sub x}WO{sub 3} and Li{sub x}WO{sub 3} with varying quantities of x (<1). This study presents a versatile method by which the solubility limit of tungsten bronze oxides can be extended. (copyright 2017 Wiley-VCH Verlag GmbH and Co. KGaA, Weinheim)

  10. Lattice vibrations and cubic to tetragonal phase transition in ZrO2

    International Nuclear Information System (INIS)

    Negita, K.

    1989-01-01

    On the basis of analyses of phonon modes in ZrO 2 , it is suggested that condensation of a phonon X 2 - at the cubic Brillouin zone boundary X point, (0, 0, 2 π/a), is associated with the cubic to tetragonal phase transition in ZrO 2 . Free energy consideration shows that spontaneous volume and shear strains, e Alg = (e 1 +e 2 +e 3 ) and e Eg = (2e 3 - e 1 - e 2 )/ Λ3, are induced in the tetragonal phase as a result of indirect couplings of the X 2 - mode to homogeneous elastic strains; the tetragonal phase is improper ferroelastic

  11. Mechanism of the monoclinic-to-tetragonal phase transition induced in zirconia and hafnia by swift heavy ions

    International Nuclear Information System (INIS)

    Benyagoub, Abdenacer

    2005-01-01

    Recent results demonstrated that defect formation or amorphization are not the only structural changes induced by swift heavy ions in crystalline materials and that under certain circumstances crystalline-to-crystalline phase transitions can also occur. For instance, it was found that both zirconia and hafnia transform from the monoclinic to the tetragonal phase with a kinetics involving a double ion impact process. In order to understand the origin of this ion-beam induced phase transition, the behavior of these twin oxides was analyzed and compared. In fact, the likeness of these materials offered the unique opportunity to impose drastic constraints on the possible models proposed to explain the creation of atomic displacements in the wake of swift heavy ions. This comparison clearly suggests that the thermal spike is the most appropriate process which governs the transition from the monoclinic to the tetragonal phase in zirconia and hafnia

  12. Tetragonal-to-Tetragonal Phase Transition in Lead-Free (KxNa1−xNbO3 (x = 0.11 and 0.17 Crystals

    Directory of Open Access Journals (Sweden)

    Dabin Lin

    2014-06-01

    Full Text Available Lead free piezoelectric crystals of (KxNa1−xNbO3 (x = 0.11 and 0.17 have been grown by the modified Bridgman method. The structure and chemical composition of the obtained crystals were determined by X-ray diffraction (XRD and electron probe microanalysis (EPMA. The domain structure evolution with increasing temperature for (KxNa1−xNbO3 (x = 0.11 and 0.17 crystals was observed using polarized light microscopy (PLM, where distinguished changes of the domain structures were found to occur at 400 °C and 412 °C respectively, corresponding to the tetragonal to tetragonal phase transition temperatures. Dielectric measurements performed on (K0.11Na0.89NbO3 crystals exhibited tetragonal to tetragonal and tetragonal to cubic phase transitions temperatures at 405 °C and 496 °C, respectively.

  13. Tetragonal and collapsed-tetragonal phases of CaFe2As2 : A view from angle-resolved photoemission and dynamical mean-field theory

    Science.gov (United States)

    van Roekeghem, Ambroise; Richard, Pierre; Shi, Xun; Wu, Shangfei; Zeng, Lingkun; Saparov, Bayrammurad; Ohtsubo, Yoshiyuki; Qian, Tian; Sefat, Athena S.; Biermann, Silke; Ding, Hong

    2016-06-01

    We present a study of the tetragonal to collapsed-tetragonal transition of CaFe2As2 using angle-resolved photoemission spectroscopy and dynamical mean field theory-based electronic structure calculations. We observe that the collapsed-tetragonal phase exhibits reduced correlations and a higher coherence temperature due to the stronger Fe-As hybridization. Furthermore, a comparison of measured photoemission spectra and theoretical spectral functions shows that momentum-dependent corrections to the density functional band structure are essential for the description of low-energy quasiparticle dispersions. We introduce those using the recently proposed combined "screened exchange + dynamical mean field theory" scheme.

  14. Transition to collapsed tetragonal phase in CaFe2As2 single crystals as seen by 57Fe Mössbauer spectroscopy

    Science.gov (United States)

    Bud'ko, Sergey L.; Ma, Xiaoming; Tomić, Milan; Ran, Sheng; Valentí, Roser; Canfield, Paul C.

    2016-01-01

    Temperature dependent measurements of 57Fe Mössbauer spectra on CaFe2As2 single crystals in the tetragonal and collapsed tetragonal phases are reported. Clear features in the temperature dependencies of the isomer shift, relative spectra area, and quadrupole splitting are observed at the transition from the tetragonal to the collapsed tetragonal phase. From the temperature dependent isomer shift and spectral area data, an average stiffening of the phonon modes in the collapsed tetragonal phase is inferred. The quadrupole splitting increases by ˜25 % on cooling from room temperature to ˜100 K in the tetragonal phase and is only weakly temperature dependent at low temperatures in the collapsed tetragonal phase, in agreement with the anisotropic thermal expansion in this material. In order to gain microscopic insight about these measurements, we perform ab initio density functional theory calculations of the electric field gradient and the electron density of CaFe2As2 in both phases. By comparing the experimental data with the calculations we are able to fully characterize the crystal structure of the samples in the collapsed-tetragonal phase through determination of the As z coordinate. Based on the obtained temperature dependent structural data we are able to propose charge saturation of the Fe-As bond region as the mechanism behind the stabilization of the collapsed-tetragonal phase at ambient pressure.

  15. Tetragonal To Collapsed Tetragonal Phase Transition In BaFe2As2 and CaFe2As2

    International Nuclear Information System (INIS)

    Mittal, R.; Mishra, S. K.; Chaplot, S. L.; Ovsyannikov, S. V.; Trots, D. M.; Dubrovinsky, L.; Greenberg, E.; Su, Y.; Brueckel, Th.; Matsuishi, S.; Hosono, H.; Garbarino, G.

    2010-01-01

    Superconductivity in MFe 2 As 2 (M = Ba, Ca) compounds appears either at a critical doping level at ambient pressure or in the parent compound itself by application of pressure above a critical value. We report high pressure powder x-ray diffractions studies for these compounds at 300 K up to about 56 GPa using membrane diamond anvil cells. The measurements for BaFe 2 As 2 show a new tetragonal to collapsed tetragonal phase transition at about 22 GPa that remains stable upto 56 GPa. CaFe 2 As 2 is already known to transform to collapsed phase at 1.7 GPa at 300 K. Our measurements on CaFe 2 As 2 do not show any post collapsed phase transition on increase of pressure 50 GPa at 300 K. It is important to note that the transition in both compounds occurs when they are compressed to almost the same value of the unit cell volume and attain similar c t /a t ratios. We present a detailed analysis of the pressure dependence and structure phase transitions as well as equation of state in these important FeAs compounds that should be useful in the context of possible superconductivity in the collapsed phase.

  16. Evolution of tetragonal phase of ZrO2 in the corrosion of Zry-4 and Zr-2.5Nb at high pressure and temperature

    International Nuclear Information System (INIS)

    Bordoni, Roberto A.; Olmedo, Ana M.; Villegas, Marina; Maroto, Alberto J. G.; Lin, J.; Szpunar, J. A.

    1999-01-01

    The corrosion kinetics of Zr-2.5 Nb and Zircaloy-4 was studied at 350 C degrees in lithiated heavy water. The oxides grown on both alloys during the exposures were found to be strongly textured. The pole figures showed that the major orientation components of the oxide formed on Zr-2.5 Nb were (10-3) [0-10] and (10-3)[301] while (10-3) fiber was formed on Zircaloy-4. No significant change in texture was found in either alloy when increasing the thickness of the oxide film. The phases present in the film were determined and their evolution with the exposure time was followed. The results indicated that the tetragonal volume fraction decreased with increasing the thickness of the oxide layers of both materials. The tetragonal volume fraction of Zircaloy-4 was higher than that of Zr-2.5 Nb for the same oxide thickness. (author)

  17. Crystal Structure of Tetragonal Form of La2NiO4+x

    Science.gov (United States)

    Kajitani, Tsuyoshi; Hosoya, Syoichi; Hirabayashi, Makoto; Fukuda, Tsuguo; Onozuka, Takashi

    1989-10-01

    The crystal structure of the title oxide was studied by means of the X-ray and neutron single crystal diffraction measurements. At room temperature, the tetragonal crystal structure is P42/ncm-type (No. 138), which is one of the subgroup of the space group I4/mmm. The lattice parameters of a sample annealed and slowly cooled in oxygen atmosphere from 673 K are a{=}b{=}5.4640(1) Å and c{=}12.6719(2) Å, while the oxygen content, x{=}0.10(4), was determined from obtained neutron data. The title oxide undergoes a tetragonal (P42/ncm)/tetragonal (I4/mmm) phase transition at about 560 K. The transition temperature is almost identical both in the annealed and as-grown crystals.

  18. Zirconium oxide crystal phase: The role of the pH and time to attain the final pH for precipitation of the hydrous oxide

    International Nuclear Information System (INIS)

    Srinivasan, R.; Harris, M.B.; Simpson, S.F.; De Angelis, R.J.; Davis, B.H.

    1988-01-01

    Precipitated hydrous zirconium oxide can be calcined to produce either a monoclinic or tetragonal product. It has been observed that the time taken to attain the final pH of the solution in contact with the precipitate plays a dominant role in determining the crystal structure of the zirconium oxide after calcination at 500 0 C. The dependence of crystal structure on the rate of precipitation is observed only in the pH range 7--11. Rapid precipitation in this pH range yields predominately monoclinic zirconia, whereas slow (8 h) precipitation produces the tetragonal phase. At pH of approximately 13.0, only the tetragonal phase is formed from both slowly and rapidly precipitated hydrous oxide. The present results, together with earlier results, show that both the pH of the supernatant liquid and the time taken to attain this pH play dominant roles in determining the crystal structure of zirconia that is formed after calcination of the hydrous oxide. The factors that determine the crystal phase are therefore imparted in a mechanism of precipitation that depends upon the pH, and it is inferred that it is the hydroxyl concentration that is the dominant factor

  19. Phase stability of zirconium oxide films during focused ion beam milling

    Science.gov (United States)

    Baxter, Felicity; Garner, Alistair; Topping, Matthew; Hulme, Helen; Preuss, Michael; Frankel, Philipp

    2018-06-01

    Focused ion beam (FIB) is a widely used technique for preparation of electron transparent samples and so it is vital to understand the potential for introduction of FIB-induced microstructural artefacts. The bombardment of both Xe+ and Ga+ ions is observed to cause extensive monoclinic to tetragonal phase transformation in ZrO2 corrosion films, however, this effect is diminished with reduced energy and is not observed below 5 KeV. This study emphasises the importance of careful FIB sample preparation with a low energy cleaning step, and also gives insight into the stabilisation mechanism of the tetragonal phase during oxidation.

  20. Stabilization of metastable tetragonal zirconia nanocrystallites by surface modification

    DEFF Research Database (Denmark)

    Nielsen, Mette Skovgaard; Almdal, Kristoffer; Lelieveld, A. van

    2011-01-01

    Metastable tetragonal zirconia nanocrystallites were studied in humid air and in water at room temperature (RT). A stabilizing effect of different surfactants on the tetragonal phase was observed. Furthermore, the phase stability of silanized metastable tetragonal zirconia nanocrystallites was te...... exposure to humidity. Only silanes and phosphate esters of these were able to stabilize the tetragonal phase in water. Even as small amounts of silanes as 0.25 silane molecule per nm2 are able to stabilize the tetragonal phase in water at RT. Aminopropyl trimethoxy silane and γ...

  1. Nonequilibrium phase formation in oxides prepared at low temperature: Fergusonite-related phases

    International Nuclear Information System (INIS)

    Mather, S.A.; Davies, P.K.

    1995-01-01

    Sol-gel methods have been developed to prepare YNbO 4 , YTaO 4 , and other rare-earth niobates and tantalates with fergusonite-related crystal structures. At low temperatures, all of the fergusonites, with the exception of SmTaO 4 , crystallize in a metastable tetragonal (T') structure similar to that of tetragonal zirconia. Although all of the equilibrium forms of these oxides adopt a crystal structure containing an ordered distribution of the trivalent and pentavalent cations, a random cation distribution is obtained in the metastable T' phase. Metastable phase formation is often ascribed solely to kinetically limited topotactic crystallization. However, the changes in the grain size and unit-cell volumes that accompany the metastable-to-equilibrium fergusonite conversions imply that other physical phenomena induced by small-particle synthesis, namely the Gibbs-Thompson pressure effect and the increased contribution of surface energy, cannot be ignored

  2. Gradient stress induced coexistence of tetragonal and rhombohedral phases in Pb(Zr,Ti)O3 films

    International Nuclear Information System (INIS)

    Li Liben; Chen Qingdong; Li Xinzhong; Hu Zhixiang; Zhen Zhiqiang

    2009-01-01

    Thermodynamic theory has been used to explain quantitatively the coexistence of tetragonal and rhombohedral phases in Zr-rich Pb(Zr, Ti)O 3 (PZT) films grown on a compressive substrate. The key is to consider a set of gradient thermal stresses imposed on the films. The 'stress-temperature' phase diagrams were developed for PZT films of several different compositions (Ti/Zr=20/80, 30/70, 40/60, 50/50). The characteristic feature of the phase diagrams for Zr-rich PZT films is the coexistence of tetragonal and rhombohedral phases in the compressive stress region. The volume fractions of the rhombohedral phase were calculated for the Zr-rich PZT films grown on MgO substrate. The result agrees with the experiment.

  3. Raman spectroscopy analysis of air grown oxide scale developed on pure zirconium substrate

    Energy Technology Data Exchange (ETDEWEB)

    Kurpaska, L., E-mail: lukasz.kurpaska@ncbj.gov.pl [Laboratoire Roberval, UMR 7337, Université de Technologie de Compiègne, Centre de Recherche de Royallieu, CS 60319, 60203 Compiègne Cedex (France); National Center for Nuclear Research, St. A. Soltana 7/23, 05-400 Otwock-Swierk (Poland); Favergeon, J. [Laboratoire Roberval, UMR 7337, Université de Technologie de Compiègne, Centre de Recherche de Royallieu, CS 60319, 60203 Compiègne Cedex (France); Lahoche, L. [Laboratoire Roberval, UMR 7337, Université de Technologie de Compiègne, Centre de Recherche de Royallieu, CS 60319, 60203 Compiègne Cedex (France); Laboratoire des Technologies Innovantes, Université de Picardie Jules-Verne, EA 3899, Avenue des Facultés – Le Bailly, 80025 Amiens Cedex (France); El-Marssi, M. [Laboratoire de Physique de la Matière Condensée, Université de Picardie Jules-Verne, 33 rue St. Leu, 80039 Amiens Cedex (France); Grosseau Poussard, J.-L. [LaSIE UMR-CNRS 7356, Pole Sciences et Technologie, Universite de La Rochelle, av. M Crepeau, 17042 La Rochelle, Cedex (France); Moulin, G.; Roelandt, J.-M. [Laboratoire Roberval, UMR 7337, Université de Technologie de Compiègne, Centre de Recherche de Royallieu, CS 60319, 60203 Compiègne Cedex (France)

    2015-11-15

    Using Raman spectroscopy technique, external and internal parts of zirconia oxide films developed at 500 °C and 600 °C on pure zirconium substrate under air at normal atmospheric pressure have been examined. Comparison of Raman peak positions of tetragonal and monoclinic zirconia phases, recorded during the oxide growth at elevated temperature, and after cooling at room temperature have been presented. Subsequently, Raman peak positions (or shifts) were interpreted in relation with the stress evolution in the growing zirconia scale, especially closed to the metal/oxide interface, where the influence of compressive stress in the oxide is the biggest. Reported results, for the first time show the presence of a continuous layer of tetragonal zirconia phase developed in the proximity of pure zirconium substrate. Based on the Raman peak positions we prove that this tetragonal layer is stabilized by the high compressive stress and sub-stoichiometry level. Presence of the tetragonal phase located in the outer part of the scale have been confirmed, yet its Raman characteristics suggest a stress-free tetragonal phase, therefore different type of stabilization mechanism. Presented study suggest that its stabilization could be related to the lattice defects introduced by highstoichiometry of zirconia or presence of heterovalent cations. - Highlights: • The oxide layer consists of a mixture of tetragonal and monoclinic phases, clearly distinguishable by Raman spectroscopy. • The layer located close to the metal/oxide interphase consists mainly of the tetragonal phase. • Small amount of tetragonal layer located in the external oxide scale have been observed. • Stabilization mechanism of the tetragonal phase located in the external part of the oxide have been proposed.

  4. Stable tetragonal phase and magnetic properties of Fe-doped HfO2 nanoparticles

    Science.gov (United States)

    Sales, T. S. N.; Cavalcante, F. H. M.; Bosch-Santos, B.; Pereira, L. F. D.; Cabrera-Pasca, G. A.; Freitas, R. S.; Saxena, R. N.; Carbonari, A. W.

    2017-05-01

    In this paper, the effect in structural and magnetic properties of iron doping with concentration of 20% in hafnium dioxide (HfO2) nanoparticles is investigated. HfO2 is a wide band gap oxide with great potential to be used as high-permittivity gate dielectrics, which can be improved by doping. Nanoparticle samples were prepared by sol-gel chemical method and had their structure, morphology, and magnetic properties, respectively, investigated by X-ray diffraction (XRD), transmission electron microscopy (TEM) and scanning electron microscopy (SEM) with electron back scattering diffraction (EBSD), and magnetization measurements. TEM and SEM results show size distribution of particles in the range from 30 nm to 40 nm with small dispersion. Magnetization measurements show the blocking temperature at around 90 K with a strong paramagnetic contribution. XRD results show a major tetragonal phase (94%).

  5. Stable tetragonal phase and magnetic properties of Fe-doped HfO2 nanoparticles

    Directory of Open Access Journals (Sweden)

    T. S. N. Sales

    2017-05-01

    Full Text Available In this paper, the effect in structural and magnetic properties of iron doping with concentration of 20% in hafnium dioxide (HfO2 nanoparticles is investigated. HfO2 is a wide band gap oxide with great potential to be used as high-permittivity gate dielectrics, which can be improved by doping. Nanoparticle samples were prepared by sol-gel chemical method and had their structure, morphology, and magnetic properties, respectively, investigated by X-ray diffraction (XRD, transmission electron microscopy (TEM and scanning electron microscopy (SEM with electron back scattering diffraction (EBSD, and magnetization measurements. TEM and SEM results show size distribution of particles in the range from 30 nm to 40 nm with small dispersion. Magnetization measurements show the blocking temperature at around 90 K with a strong paramagnetic contribution. XRD results show a major tetragonal phase (94%.

  6. Atomic Origins of Monoclinic-Tetragonal (Rutile) Phase Transition in Doped VO 2 Nanowires

    KAUST Repository

    Asayesh-Ardakani, Hasti

    2015-10-12

    There has been long-standing interest in tuning the metal-insulator phase transition in vanadium dioxide (VO) via the addition of chemical dopants. However, the underlying mechanisms by which doping elements regulate the phase transition in VO are poorly understood. Taking advantage of aberration-corrected scanning transmission electron microscopy, we reveal the atomistic origins by which tungsten (W) dopants influence the phase transition in single crystalline WVO nanowires. Our atomically resolved strain maps clearly show the localized strain normal to the (122¯) lattice planes of the low W-doped monoclinic structure (insulator). These strain maps demonstrate how anisotropic localized stress created by dopants in the monoclinic structure accelerates the phase transition and lead to relaxation of structure in tetragonal form. In contrast, the strain distribution in the high W-doped VO structure is relatively uniform as a result of transition to tetragonal (metallic) phase. The directional strain gradients are furthermore corroborated by density functional theory calculations that show the energetic consequences of distortions to the local structure. These findings pave the roadmap for lattice-stress engineering of the MIT behavior in strongly correlated materials for specific applications such as ultrafast electronic switches and electro-optical sensors.

  7. Atomic Origins of Monoclinic-Tetragonal (Rutile) Phase Transition in Doped VO 2 Nanowires

    KAUST Repository

    Asayesh-Ardakani, Hasti; Nie, Anmin; Marley, Peter M.; Zhu, Yihan; Phillips, Patrick J.; Singh, Sujay; Mashayek, Farzad; Sambandamurthy, Ganapathy; Low, Ke Bin; Klie, Robert F.; Banerjee, Sarbajit; Odegard, Gregory M.; Shahbazian-Yassar, Reza

    2015-01-01

    There has been long-standing interest in tuning the metal-insulator phase transition in vanadium dioxide (VO) via the addition of chemical dopants. However, the underlying mechanisms by which doping elements regulate the phase transition in VO are poorly understood. Taking advantage of aberration-corrected scanning transmission electron microscopy, we reveal the atomistic origins by which tungsten (W) dopants influence the phase transition in single crystalline WVO nanowires. Our atomically resolved strain maps clearly show the localized strain normal to the (122¯) lattice planes of the low W-doped monoclinic structure (insulator). These strain maps demonstrate how anisotropic localized stress created by dopants in the monoclinic structure accelerates the phase transition and lead to relaxation of structure in tetragonal form. In contrast, the strain distribution in the high W-doped VO structure is relatively uniform as a result of transition to tetragonal (metallic) phase. The directional strain gradients are furthermore corroborated by density functional theory calculations that show the energetic consequences of distortions to the local structure. These findings pave the roadmap for lattice-stress engineering of the MIT behavior in strongly correlated materials for specific applications such as ultrafast electronic switches and electro-optical sensors.

  8. /sup 87/Rb NMR study at the cubic to tetragonal phase transition in RbCaF/sub 3/

    Energy Technology Data Exchange (ETDEWEB)

    Bulou, A [Angers Univ., 72 - Le Mans (France). Centre Universitaire; Theveneau, H; Trokiner, A; Papon, P [Ecole Superieure de Physique et Chimie Industrielles, 75 - Paris (France)

    1979-07-01

    The /sup 87/Rb nuclear magnetic resonance spectrum, in perovskite single crystal of RbCaF/sub 3/, is studied above and below the cubic-to-tetragonal phase transition occurring at 198 K. In the high-temperature cubic phase, the temperature dependence of the resonance line amplitude deviates from the Curie law and this can be attributed to the existence of tetragonal domains. In the low temperature tetragonal phase, a second-order quadrupole shift of the central line is observed, from which the CaF/sub 6/ tilt angle (order parameter) is derived. The order parameter temperature dependence is described by a power law with a cross over from exponent 0.5 to exponent 0.32 at 150 K. The tilt angle PHI is compared to the values obtained from X-ray and neutron powder diffraction data.

  9. Thermal stability and phase transformation in fully indium oxide (InO{sub 1.5}) stabilized zirconia

    Energy Technology Data Exchange (ETDEWEB)

    Piva, R.H., E-mail: honorato.piva@ua.pt; Piva, D.H.; Morelli, M.R.

    2017-01-15

    Indium oxide (InO{sub 1.5}) stabilized zirconia (InSZ) is an attractive material as electrolyte, or electrode, in solid oxide fuel cells (SOFCs), and as corrosion resistant top coat in thermal barrier coatings. However, little is known about the phase stability of cubic InSZ at temperatures that simulate the conditions in an operating SOFC or turbine. This article provides an investigation of the phase stability and phase transformations in cubic InSZ after heat treatments at 800, 1000, and 1200 °C for periods up to 2000 h. The results revealed that cubic InSZ is not stable during annealing at 1000 and 1200 °C, owing to a fast destabilization of the initial cubic phase to tetragonal, and eventually to monoclinic (c → t → m). The c → t → m transition in InSZ is intimately associated with the indium volatilization. On the other hand, cubic InSZ remained stable for 2000 h at 800 °C, although the partial formation of the tetragonal phase was observed along with a 0.25% contraction in the unit cell volume of the cubic phase, caused by short-range ordering. These results demonstrate that technological applications of cubic InSZ are restricted to temperatures at which the volatilization of the InO{sub 1.5} stabilizer does not occur. - Highlights: •Phase stability of fully InO{sub 1.5} stabilized zirconia (cubic InSZ) was evaluated. •Cubic InSZ is instable at temperatures ≥ 1000 °C, owing to the cubic-to-tetragonal-to-monoclinic destabilization. •Cubic InSZ undergoes the cubic-to-tetragonal transformation at ~ 800 °C. •Owing to the low phase stability, applications of cubic InSZ in TBCs or SOFCs are restricted.

  10. Atomic Origins of Monoclinic-Tetragonal (Rutile) Phase Transition in Doped VO2 Nanowires.

    Science.gov (United States)

    Asayesh-Ardakani, Hasti; Nie, Anmin; Marley, Peter M; Zhu, Yihan; Phillips, Patrick J; Singh, Sujay; Mashayek, Farzad; Sambandamurthy, Ganapathy; Low, Ke-Bin; Klie, Robert F; Banerjee, Sarbajit; Odegard, Gregory M; Shahbazian-Yassar, Reza

    2015-11-11

    There has been long-standing interest in tuning the metal-insulator phase transition in vanadium dioxide (VO2) via the addition of chemical dopants. However, the underlying mechanisms by which doping elements regulate the phase transition in VO2 are poorly understood. Taking advantage of aberration-corrected scanning transmission electron microscopy, we reveal the atomistic origins by which tungsten (W) dopants influence the phase transition in single crystalline WxV1-xO2 nanowires. Our atomically resolved strain maps clearly show the localized strain normal to the (122̅) lattice planes of the low W-doped monoclinic structure (insulator). These strain maps demonstrate how anisotropic localized stress created by dopants in the monoclinic structure accelerates the phase transition and lead to relaxation of structure in tetragonal form. In contrast, the strain distribution in the high W-doped VO2 structure is relatively uniform as a result of transition to tetragonal (metallic) phase. The directional strain gradients are furthermore corroborated by density functional theory calculations that show the energetic consequences of distortions to the local structure. These findings pave the roadmap for lattice-stress engineering of the MIT behavior in strongly correlated materials for specific applications such as ultrafast electronic switches and electro-optical sensors.

  11. Experimental study of the oxide film structural phase state in the E635 and E110 alloys

    International Nuclear Information System (INIS)

    Shevyakov, A. Yu.; Shishov, V. N.; Novikov, V. V.

    2013-01-01

    The microstructure, phase and element compositions of oxide films of E110 (Zr-1%Nb) and E635 (Zr-1%Nb-0,35%Fe-1,2%Sn) alloys after autoclave tests in pure water had been studied by the method of transmission electron microscopy (TEM) with energy dispersive X-ray spectroscopy (EDS). TEM investigations of oxide film structure were carried on different oxide layers according to their thickness (near interface of “metal-oxide”, in central part of the oxide film and near outer surface) and in cross-section. The results of the tests show that oxide films of the alloys have different microstructure (grain size, fraction of tetragonal phase, content of defects, etc) and the phase compositions. The crystal structure of oxide films is mainly monoclinic, however, at the “metal-oxide” interface there are a significant fraction of the tetragonal phase. Researching of oxides on different stages of oxidation allow us to determine the kinetics of the second phase precipitate structure change: a) in E635 alloy at early oxidation stages of the amorphization process of the Laves phase precipitates begins with decreasing the content of iron and niobium; b) in E110 alloy the amorphization process of β-Nb precipitates begins at a later stage of oxidation. The influence of changes of the crystal structure and the chemical composition of the second phase precipitates on protective properties of the oxides had been determined. Researching of alloying element redistribution in E635 alloy oxide film shows that iron and niobium are concentrated in pores. Increased porosity of the E635 alloy oxide films at a later oxidation stage, in comparison with the E110 alloy, shows the influence of change composition and subsequent dissolution of the Laves phase particles on the pore formation in the oxide. (authors)

  12. Low temperature phase transition of the stoichiometric Ln2NiO4 oxides

    International Nuclear Information System (INIS)

    Fernandez, F.; Saez-Puche, R.; Botto, I.L.; Baran, E.J.

    1991-01-01

    In this paper we will present a comparative study of the structural phase transition in Ln 2 NiO 4 oxides, by means of neutron diffraction and infrared(IR) spectroscopy. In the Ln 2 NiO 4 oxides (Ln=La, Pr and Nd), there is a low temperature structural phase transition from the orthorhombic symmetry to a tetragonal phase, of first order character. The IR spectra show, at low temperature, a splitting of the bands related with the stretching Ni-O, strongly correlated with the phase transformation. From the neutron data, the phase transition can be visualized as a sudden tilt of the nickel octahedra

  13. Tetragonal-cubic phase boundary in nanocrystalline ZrO2-Y2O3 solid solutions synthesized by gel-combustion

    International Nuclear Information System (INIS)

    Fabregas, Ismael O.; Craievich, Aldo F.; Fantini, Marcia C.A.; Millen, Ricardo P.; Temperini, Marcia L.A.; Lamas, Diego G.

    2011-01-01

    Research highlights: → Gel-combustion synthesis yields compositionally homogeneous, single-phased ZrO 2 -Y 2 O 3 nanopowders, that exhibit the presence at room temperature of three different phases depending on Y 2 O 3 content, namely two tetragonal forms (t' and t'') and the cubic phase. → Phase identification can be achieved by synchrotron XPD (SXPD) and Raman spectroscopy since the tetragonal forms and the cubic phase can be distinguished by these techniques. → The crystallographic features of ZrO 2 -Y 2 O 3 nanopowders were determined by SXPD. They are similar to those reported by Yashima and coworkers for compositionally homogeneous materials containing larger (micro)crystals. However, the lattice parameters are slightly different and the axial ratios c/a of our t' samples are smaller than those reported by these authors. → Compositional t'/t'' and t''/cubic phase boundaries are located at (9 ± 1) and (10.5 ± 0.5) mol% Y 2 O 3 , respectively. → For the whole series of nanocrystalline ZrO 2 -Y 2 O 3 solid solutions studied in the present work, no evidences of the presence of a mixture of phases - as reported by Yashima and coworkers for microcrystalline solid solutions - were detected. - Abstract: By means of synchrotron X-ray powder diffraction (SXPD) and Raman spectroscopy, we have detected, in a series of nanocrystalline and compositionally homogeneous ZrO 2 -Y 2 O 3 solid solutions, the presence at room temperature of three different phases depending on Y 2 O 3 content, namely two tetragonal forms and the cubic phase. The studied materials, with average crystallite sizes within the range 7-10 nm, were synthesized by a nitrate-citrate gel-combustion process. The crystal structure of these phases was also investigated by SXPD. The results presented here indicate that the studied nanocrystalline ZrO 2 -Y 2 O 3 solid solutions exhibit the same phases reported in the literature for compositionally homogeneous materials containing larger (micro

  14. Study on effect of cubic- and tetragonal phased BaTiO{sub 3} on the electrical and thermal properties of polymeric nanocomposites

    Energy Technology Data Exchange (ETDEWEB)

    Thanki, A.A.; Goyal, R.K., E-mail: rkgoyal72@yahoo.co.in

    2016-11-01

    Polymer matrix nanocomposites based on polycarbonate (PC) and nanosized-cubic/tetragonal phases of barium titanate (BaTiO{sub 3}) were fabricated using a solution method followed by hot pressing. The content of both cubic- and tetragonal phased BaTiO{sub 3} was varied from 0 to 50 wt%. For a given weight fraction, the dielectric constant of the nanocomposites containing tetragonal BaTiO{sub 3} is more than those of cubic BaTiO{sub 3} filled nanocomposites. Moreover, cubic BaTiO{sub 3}/PC nanocomposites showed significantly lower dissipation factor than those of tetragonal BaTiO{sub 3}/PC nanocomposites. The dielectric constant of the nanocomposites was found to be frequency-independent. The microhardness of the nanocomposites increased with increase in the BaTiO{sub 3} content (both cubic- and tetragonal-phased) compared to the pure matrix. Scanning electron microscopy showed better dispersion and good interaction of the tetragonal BaTiO{sub 3} nanoparticles in the matrix. The addition of cubic BaTiO{sub 3} nanoparticles significantly reduced the thermal stability of the nanocomposites compared to matrix while the addition of tetragonal BaTiO{sub 3} nanoparticles decreased it slightly. The glass transition temperature of the cubic BaTiO{sub 3}/PC nanocomposites decreased significantly, whereas it reduced slightly for the tetragonal BaTiO{sub 3}/PC nanocomposites. - Highlights: • The effect of cubic-BaTiO{sub 3} and tetragonal-BaTiO{sub 3} nanoparticles were studied. • Cubic-BaTiO{sub 3} nanoparticles showed better microhardness. • Tetragonal-BaTiO{sub 3} nanoparticles showed better dielectric and thermal properties. • Frequency independent dielectric constants of the nanocomposites were observed.

  15. Acoustic emission characterization of the tetragonal-monoclinic phase transformation in zirconia

    International Nuclear Information System (INIS)

    Clarke, D.R.; Arora, A.

    1983-01-01

    The processes accompanying the tetragonal-monoclinic phase transformation in zirconia (ZrO 2 ) have been studied using acoustic emission and electron microscopy in an attempt to characterize the different mechanisms by which the transformation can be accommodated in bulk materials. Experiments in which the acoustic emission is detected as specimens are cooled through the transformation, following densification by sintering, are described. For comparison, the acoustic emission from free, nominally unconstrained powders similarly cooled through the transformation is reported. The existence of distinct processes accompanying the phase transformation is established on the basis of postexperiment multiparametric correlation analysis of the acoustic emission

  16. Is there an ordered tetragonal phase in the Ti3Al-Nb system?

    International Nuclear Information System (INIS)

    Banerjee, D.

    1994-01-01

    In a recent series of papers, describing aging transformations in plasma sprayed Ti-24Al-11Nb, Hsiung and co-workers proposed a new ordered tetragonal structure as the first metastable phase to form in a series of transformations from quenched-in B2 to the equilibrium phase. They describe this new phase as a ''DO 3 like tetragonal structure'' with a composition Ti 5 Al 2 Nb, and lattice parameters, a = 0.65 nm and c/a ≅ 1.02. Their unit cell is constituted by 8 bcc unit cells, and the atomic coordinates of their structure are given in Table 1 on this basis. The symmetry of this structure is P4/mm. Though it is not the smallest possible unit cell for the structure, comparison with other bcc binary derivative structures is easily possible on this basis. The atomic coordinates for the latter, for a ternary composition Ti 2 AlNb, are also given. They note that the site occupation for the Hsiung et al. structure is quite distinct from that for a ternary DO 3 phase or any of the other possible bcc derivative structures (neglecting 2 possibilities with 128 or 432 atoms per unit cell(8) and interstitial ordering)

  17. The measurement of stress and phase fraction distributions in pre and post-transition Zircaloy oxides using nano-beam synchrotron X-ray diffraction

    Energy Technology Data Exchange (ETDEWEB)

    Swan, H., E-mail: helen.swan@nnl.co.uk [National Nuclear Laboratory, Building D5, Culham Science Centre, Abingdon, Oxfordshire, OX14 3DB (United Kingdom); Blackmur, M.S., E-mail: matthew.s.blackmur@nnl.co.uk [National Nuclear Laboratory, Building D5, Culham Science Centre, Abingdon, Oxfordshire, OX14 3DB (United Kingdom); Hyde, J.M., E-mail: jonathan.m.hyde@nnl.co.uk [National Nuclear Laboratory, Building D5, Culham Science Centre, Abingdon, Oxfordshire, OX14 3DB (United Kingdom); Laferrere, A., E-mail: alice.laferrere@atkinsglobal.com [W.S.Atkins, The Hub, Aztec West, 500 Park Ave, Almondsbury, Bristol BS32 4RZ (United Kingdom); Ortner, S.R., E-mail: susan.r.ortner@nnl.co.uk [National Nuclear Laboratory, Building D5, Culham Science Centre, Abingdon, Oxfordshire, OX14 3DB (United Kingdom); Styman, P.D., E-mail: paul.d.styman@nnl.co.uk [National Nuclear Laboratory, Building D5, Culham Science Centre, Abingdon, Oxfordshire, OX14 3DB (United Kingdom); Staines, C., E-mail: cassie.staines@nnl.co.uk [National Nuclear Laboratory, 102B, Stonehouse Park, Stonehouse, Gloucestershire, GL10 3UT (United Kingdom); Gass, M., E-mail: mhairi.gass@amecfw.com [Amec Foster Wheeler Clean Energy Europe, Walton House, Birchwood, WA3 6GA (United Kingdom); Hulme, H., E-mail: helen.hulme@amecfw.com [Amec Foster Wheeler Clean Energy Europe, Walton House, Birchwood, WA3 6GA (United Kingdom); Cole-Baker, A., E-mail: aidan.cole-baker@rolls-royce.com [Rolls-Royce plc, PO Box 2000, Derby, DE21 7XX (United Kingdom); Frankel, P., E-mail: philipp.frankel@manchester.ac.uk [Materials Performance Centre, School of Materials, The University of Manchester, Manchester, M13 9PL (United Kingdom)

    2016-10-15

    Zircaloy-4 oxide stress profiles and tetragonal:monoclinic oxide phase fraction distributions were studied using nano-beam transmission X-ray diffraction. Continuous stress relief and phase transformation during the first cycle of oxide growth was observed. The in-plane monoclinic stress was shown to relax strongly up to each transition, whereas in-plane tetragonal stress-relief (near the metal-oxide interface) was only observed post transition. The research demonstrates that plasticity in the metal and the development of a band of in-plane cracking both relax the monoclinic in-plane stress. The observations are consistent with a model of transition in which in-plane cracking becomes interlinked prior to transition. These cracks, combined with the development of cracks with a through-thickness component (driven primarily by plasticity in the metal) and/or a porous network of fine cracks (associated with phase transformation), form a percolation path through the oxide layer. The oxidising species can then percolate from the oxide surface to the metal/oxide interface, at which stage transition then ensues. - Highlights: • Measurement of stress in Zr-4 oxides using nano-beam transmission X-ray diffraction. • In-plane monoclinic stress relaxes strongly up to each transition. • In-plane tetragonal stress relaxation is only observed post transition. • Development of band of cracking is related to monoclinic in-plane stress relaxation. • Linking of in-plane cracking with through-plane crack/porosity leads to transition.

  18. Infrared studies of the monoclinic-tetragonal phase transition in Pb(Zr,Ti)O3 ceramics

    International Nuclear Information System (INIS)

    Guarany, C A; Pelaio, L H Z; Araujo, E B; Yukimitu, K; Moraes, J C S; Eiras, J A

    2003-01-01

    Recently, the observation of a new monoclinic phase in the PbZr 1-x Ti x O 3 (PZT) system in the vicinity of the morphotropic phase boundary was reported. Investigations of this new phase were reported using different techniques such as high-resolution synchrotron x-ray powder diffraction and Raman spectroscopy. In this work, the monoclinic → tetragonal phase transition in PbZr 0.50 Ti 0.50 O 3 ceramics was studied using infrared spectroscopy between 1000 and 400 cm -1 . The four possible ν 1 -stretching modes (Ti-O and Zr-O stretch) in the BO 6 octahedron in the ABO 3 structure of PZT in this region were monitored as a function of temperature. The lower-frequency mode ν 1 -(Zr-O) remains practically unaltered, while both intermediate ν 1 -(Ti-O) modes decrease linearly as temperature increases from 89 to 263 K. In contrast, the higher-frequency ν 1 -(Ti-O) and ν 1 -(Zr-O) modes present anomalous behaviour around 178 K. The singularity observed at this mode was associated with the monoclinic → tetragonal phase transition in PbZr 0.50 Ti 0.50 O 3 ceramics

  19. Tetragonal phase in Al-rich region of U-Fe-Al system

    International Nuclear Information System (INIS)

    Meshi, L.; Zenou, V.; Ezersky, V.; Munitz, A.; Talianker, M.

    2005-01-01

    A new ternary aluminide U 2 FeAl 20 with the approximate composition Al-4.2at% Fe-8.5at% U was observed in the Al-rich corner of the U-Al-Fe system. Transmission electron microscopy and electron microdiffraction technique were used for characterization of the structure of this phase. It has a tetragonal unit cell with the parameters a=12.4A and c=10.3A and can be described by the space group I4-bar 2m

  20. Spall strength, dynamic elastic limit and fracture of ittrya dopped tetragonal zirconia

    Science.gov (United States)

    Milyavskiy, Vladimir; Savinykh, Andrey; Schlothauer, Thomas; Lukin, Evgeny; Akopov, Felix

    2013-06-01

    Specimens of the ceramics based on zirconia partially stabilized by yttrium oxide of the composition of 97 mol % ZrO2 + 3 mol % Y2O3 were prepared. The densities of the specimens were 5.79 and 6.01 g/cc. The ceramics mainly have the tetragonal structure (93-98 wt. % of t-ZrO2) . The mechanical action on the ceramic activates the transformation of the tetragonal phase into the monoclinic one: at the abrasive cutting or at the fracture by hammer shock, the content of the monoclinic phase is increasing. The same trend was observed in the specimens, recovered after stepwise shock compression up to 36, 52 and 99 GPa. It was found that shock compression do not initiates tetragonal-monoclinic phase transition directly, and this transition is caused by the destruction. Recovered specimens do not reveal any traces of the phase change which was observed by Mashimo et al. under the pressures 30-35 GPa (J. Appl. Phys. 1995. V. 77. P. 5069). Recording of the profiles of the free surface velocity of the specimens during single-stage shock compression allowed us to determine the dynamic elastic limit, as well as spall strength of the material versus maximal shock stress. In addition, the ceramics were subjected to the action of low temperatures. There were no significant changes in the specimens recovered after storage in liquid nitrogen and helium. The work was supported by The State Atomic Energy Corporation ROSATOM.

  1. Oxidation of uraninite: does tetragonal U3O7 occur in nature?

    International Nuclear Information System (INIS)

    Janeczek, J.; Ewing, R.C.; Thomas, L.E.

    1993-01-01

    Samples of uraninite and pitchblende annealed at 1200 C in H 2 , and untreated pitchblende were sequentially oxidized in air at 180-190 C, 230 C, and 300 C. Uraninite and untreated pitchblende oxidized to the U 4 O 9 -type oxide, and their X-ray symmetry remained isometric up to 300 C. Reduced pitchblende after oxidation to UO 2+x and U 4 O 9 -type oxides transformed into α-U 3 O 8 at 300 C. Two major mechanisms control uraninite and untreated pitchblende stability during oxidation: (1) Th and/or REE maintain charge balance and block oxygen interstitials near impurity cations; (2) the uraninite structure saturates with respect to excess oxygen and radiation-induced oxygen interstitials. Untreated pitchblende during oxidation behaved similarly to irradiated UO 2 in spent nuclear fuel; whereas, reduced pitchblende resembled nonirradiated UO 2 . An analysis of the data in the literature, as well as our own efforts to identify U 3 O 7 in samples from Cigar Lake, Canada, failed to provide conclusive evidence of the natural occurrence of tetragonal α-U 3 O 7 . Most probably, reported occurrences of U 3 O 7 are mixtures of isometric uraninites of slightly different compositions. (orig.)

  2. Tetragonal-cubic phase boundary in nanocrystalline ZrO{sub 2}-Y{sub 2}O{sub 3} solid solutions synthesized by gel-combustion

    Energy Technology Data Exchange (ETDEWEB)

    Fabregas, Ismael O. [CINSO (Centro de Investigaciones en Solidos), CITEFA-CONICET, J.B. de La Salle 4397, 1603 Villa Martelli, Pcia. de Buenos Aires (Argentina); Craievich, Aldo F.; Fantini, Marcia C.A. [Instituto de Fisica, Universidade de Sao Paulo, Travessa R da Rua do Matao, No. 187, Cidade Universitaria, 05508-900 Sao Paulo (Brazil); Millen, Ricardo P.; Temperini, Marcia L.A. [Instituto de Quimica, Universidade de Sao Paulo, Avenida Prof. Lineu Prestes 748, Cidade Universitaria, 05508-900 Sao Paulo (Brazil); Lamas, Diego G., E-mail: dlamas@uncoma.edu.ar [CINSO (Centro de Investigaciones en Solidos), CITEFA-CONICET, J.B. de La Salle 4397, 1603 Villa Martelli, Pcia. de Buenos Aires (Argentina); Laboratorio de Caracterizacion de Materiales, Facultad de Ingenieria, Universidad Nacional del Comahue, Buenos Aires 1400, (8300) Neuquen Capital, Prov. de Neuquen (Argentina)

    2011-04-21

    Research highlights: > Gel-combustion synthesis yields compositionally homogeneous, single-phased ZrO{sub 2}-Y{sub 2}O{sub 3} nanopowders, that exhibit the presence at room temperature of three different phases depending on Y{sub 2}O{sub 3} content, namely two tetragonal forms (t' and t'') and the cubic phase. > Phase identification can be achieved by synchrotron XPD (SXPD) and Raman spectroscopy since the tetragonal forms and the cubic phase can be distinguished by these techniques. > The crystallographic features of ZrO{sub 2}-Y{sub 2}O{sub 3} nanopowders were determined by SXPD. They are similar to those reported by Yashima and coworkers for compositionally homogeneous materials containing larger (micro)crystals. However, the lattice parameters are slightly different and the axial ratios c/a of our t' samples are smaller than those reported by these authors. > Compositional t'/t'' and t''/cubic phase boundaries are located at (9 {+-} 1) and (10.5 {+-} 0.5) mol% Y{sub 2}O{sub 3}, respectively. > For the whole series of nanocrystalline ZrO{sub 2}-Y{sub 2}O{sub 3} solid solutions studied in the present work, no evidences of the presence of a mixture of phases - as reported by Yashima and coworkers for microcrystalline solid solutions - were detected. - Abstract: By means of synchrotron X-ray powder diffraction (SXPD) and Raman spectroscopy, we have detected, in a series of nanocrystalline and compositionally homogeneous ZrO{sub 2}-Y{sub 2}O{sub 3} solid solutions, the presence at room temperature of three different phases depending on Y{sub 2}O{sub 3} content, namely two tetragonal forms and the cubic phase. The studied materials, with average crystallite sizes within the range 7-10 nm, were synthesized by a nitrate-citrate gel-combustion process. The crystal structure of these phases was also investigated by SXPD. The results presented here indicate that the studied nanocrystalline ZrO{sub 2}-Y{sub 2}O{sub 3} solid

  3. Electric field-induced phase transitions and composition-driven nanodomains in rhombohedral-tetragonal potassium-sodium niobate-based ceramics

    KAUST Repository

    Lv, Xiang

    2017-08-07

    The mechanisms behind the high piezoelectricity of (K,Na)NbO3-based lead-free ceramics were investigated, including electric field-induced phase transitions and composition-driven nanodomains. The construction of a rhombohedral-tetragonal (R-T) phase boundary, confirmed using several advanced techniques, allowed a large piezoelectric constant (d33) of 450 ± 5 pC/N to be obtained in (1-x)K0.4Na0.6Nb0.945Sb0.055O3-xBi0.5Na0.5(Hf1-ySny)O3 (0 ≤ x ≤ 0.06 and 0 ≤ y ≤ 0.5) ceramics possessing an ultralow ΔUT-R of 7.4 meV. More importantly, the existence of an intermediate phase, i.e., the electric-induced phase (EIP), bridging the rhombohedral R [Ps//(111)] and tetragonal T [Ps//(001)] phases during the polarization rotation was demonstrated. Striped nanodomains (∼40 nm) that easily responded to external stimulation were also observed in the ceramics with an R-T phase. Thus, the enhanced piezoelectric properties originated from EIP and the striped nanodomains.

  4. Structural study on cubic-tetragonal transition of CH3NH3PbI3

    International Nuclear Information System (INIS)

    Kawamura, Yukihiko; Mashiyama, Hiroyuki; Hasebe, Katsuhiko

    2002-01-01

    The cubic-tetragonal phase transition of CH 3 NH 3 PbI 3 was investigated by single crystal X-ray diffractometry. The crystal structure was refined at five temperatures in the tetragonal phase. The PbI 6 octahedron rotates around the c-axis alternatively to construct the SrTiO 3 -type tetragonal structure. A methylammonium ion is partially ordered; 24 disordered states in the cubic phase are reduced to 8. With decreasing temperature, the rotation angle of the octahedron increases monotonically, which indicates it is an order parameter of the cubic-tetragonal transition. (author)

  5. Cubic to tetragonal phase transition of Tm3+ doped nanocrystals in oxyfluoride glass ceramics

    International Nuclear Information System (INIS)

    Li, Yiming; Fu, Yuting; Shi, Yahui; Zhang, Xiaoyu; Yu, Hua; Zhao, Lijuan

    2016-01-01

    Tm 3+ ions doped β-PbF 2 nanocrystals in oxyfluoride glass ceramics with different doping concentrations and thermal temperatures are prepared by a traditional melt-quenching and thermal treatment method to investigate the structure and the phase transition of Tm 3+ doped nanocrystals. The structures are characterized by X-ray diffraction Rietveld analysis and confirmed with numerical simulation. The phase transitions are proved further by the emission spectra. Both of the doping concentration and thermal temperature can induce an O h to D 4h site symmetry distortion and a cubic to tetragonal phase transition. The luminescence of Tm 3+ doped nanocrystals at 800 nm was modulated by the phase transition of the surrounding crystal field

  6. Pressure-induced change of the electronic state in the tetragonal phase of CaFe2As2

    International Nuclear Information System (INIS)

    Sakaguchi, Yui; Ikeda, Shugo; Kuse, Tetsuji; Kobayashi, Hisao

    2014-01-01

    We have investigated the electronic states of single-crystal CaFe 2 As 2 under hydrostatic pressure using 57 Fe Mössbauer spectroscopy and magnetization measurements. The center shift and the quadrupole splitting were refined from observed 57 Fe Mössbauer spectra using the single-crystalline sample under pressure at room temperature. A discontinuous decrease in the pressure dependence of the refined center shift was observed at 0.33 GPa without any anomaly in the pressure dependence of the refined quadrupole splitting, indicating a purely electronic state change in CaFe 2 As 2 with a tetragonal structure. Such a change is shown to be reflected in the peak-like anomalies observed in the pressure dependences of the magnetic susceptibility at 0.26 GPa above 150 K. Our results reveal that this pressure-induced electronic state change suppresses the tetragonal-to-orthorhombic structural phase transition accompanied by an antiferromagnetic ordering. We further observed superconductivity in CaFe 2 As 2 below ∼8 K around 0.33 GPa although our sample was not in a single phase at this pressure. These findings suggest that the electronic state change observed in CaFe 2 As 2 with the tetragonal structure is relevant to the appearance of the pressure-induced superconductivity in AFe 2 As 2 . (paper)

  7. Adaptive ferroelectric state at morphotropic phase boundary: Coexisting tetragonal and rhombohedral phases

    International Nuclear Information System (INIS)

    Zhang, Yang; Xue, Dezhen; Wu, Haijun; Ding, Xiangdong; Lookman, Turab; Ren, Xiaobing

    2014-01-01

    With a focus on local symmetry, the microstructural basis for high piezoelectric performance in PbMg 1/3 Nb 2/3 O 3 –xPbTiO 3 (PMN–PT) ceramics at the morphotropic phase boundary (MPB) composition was investigated by means of convergent-beam electron diffraction analysis and twin diffraction pattern analysis. The local structure was found to consist of coexisting (1 0 1)-type tetragonal nanotwins and (0 0 1)-type rhombohedral nanotwins. A phenomenological theory based on crystallography is proposed to show that such nanoscale coexistence can give rise to an average monoclinic structure through strain accommodation. The average monoclinic structures (Ma and Mc) vary with temperature and composition due to the dependence on temperature and composition of the lattice parameters. Based on in situ X-ray diffraction data, we demonstrate how the polarization rotates across the MPB region in PMN–PT ceramics with varying temperatures and compositions

  8. Effect of beta phase composition and surface machining on the oxidation behavior of Zr-2.5Nb pressure tube material

    International Nuclear Information System (INIS)

    Nouduru, S.K.; Kiran Kumar, M.; Kain, V.; Khanna, A.S.

    2015-01-01

    Zr-2.5Nb is commonly used as the pressure tube material in pressurized heavy water reactors. it is also the pressure tube material for Advanced Heavy Water Reactor (AHWR) being developed indigenously in India with light water as coolant and water chemistry similar to Boiling Water Reactors (BWR). Oxidation of the pressure tube depends on various factors like material composition, microstructure, fabrication route, and water chemistry. In the present research, the role of the composition and morphology of second phase β on the high temperature and pressure oxidation behavior of Zr-2.5Nb pressure tube material in steam was systematically studied. The as-received pressure tube material (fabricated through cold worked and stress relieved, CWSR route) was subjected to selective heat treatments to generate microstructures containing predominantly β(Zr) (∼ 20% Nb) and β(Nb) (∼ 80% Nb) phases. The presence of such phases was characterized by X-ray diffraction and transmission electron microscopy-energy dispersive spectroscopy. Subsequently both the heat treated materials were subjected to surface machining. The Zr-2.5Nb material in different microstructural conditions was subjected to accelerated oxidation exposures in steam at 400 C. degrees, and 10 MPa pressure up to 30 days. Raman spectroscopy was carried out on the oxide surfaces to observe the variation in tetragonal versus monoclinic phase fractions with oxidation duration. The microstructure consisting of predominantly β(Nb) showed a relatively improved oxidation resistance as compared to the one with predominantly β(Zr). The tetragonal phase fraction in the oxide film decreased with oxidation time in all microstructural conditions and was found to be the least in the microstructure containing β(Zr) after 10 days of exposures. The explanation for the observed higher oxidation resistance of β(Nb) microstructure lies in the context of depleted matrix Nb content in the case of β(Nb). Surface machining

  9. Tetragonal to orthorhombic transformation in Mg-PSZ

    International Nuclear Information System (INIS)

    Liu, Z.W.; Spargo, A.E.C.; Hannink, R.H.J.; Drennan, J.

    1997-01-01

    The phase transformation from tetragonal to orthorhombic in MgO-partially-stabilized zirconia has been investigated by using high resolution transmission electron microscopy (HRTEM). Evidences are given to show that orthorhombic ZrO 2 frequently observed in transmission electron microscopy (TEM) thin foil studies was induced by dimpling and polishing during the specimen preparation. It was also found that the orthorhombic to monoclinic transformation was less sensitive to stress that the tetragonal to monoclinic transformation. 20 refs., 1 tab., 8 figs

  10. Synthesis and electrical conductivity of nanocrystalline tetragonal FeS

    International Nuclear Information System (INIS)

    Zeng Shu-Lin; Wang Hui-Xian; Dong Cheng

    2014-01-01

    A convenient method for synthesis of tetragonal FeS using iron powder as iron source, is reported. Nanocrystalline tetragonal FeS samples were successfully synthesized by reacting metallic iron powder with sodium sulfide in acetate buffer solution. The obtained sample is single-phase tetragonal FeS with lattice parameters a = 0.3767 nm and c = 0.5037 nm, as revealed by X-ray diffraction. The sample consists of flat nanosheets with lateral dimensions from 20 nm up to 200 nm and average thickness of about 20 nm. We found that tetragonal FeS is a fairly good conductor from the electrical resistivity measurement on a pellet of the nanosheets. The temperature dependence of conductivity of the pellet was well fitted using an empirical equation wherein the effect of different grain boundaries was taken into consideration. This study provides a convenient, economic way to synthesize tetragonal FeS in a large scale and reports the first electrical conductivity data for tetragonal FeS down to liquid helium temperature. (condensed matter: electronic structure, electrical, magnetic, and optical properties)

  11. A preliminary X-ray diffraction study of the tetragonal superconducting oxide LaBa2Cu3O7-δ

    International Nuclear Information System (INIS)

    Hervieu, M.; Nguyen, N.; Michel, C.

    1987-01-01

    X-ray diffraction study of LaBa 2 Cu 3 O 7-δ showed that this tetragonal oxide exhibits an ordered oxygen deficient perovskite structure. It appears that the oxygen vacancy distribution differs from that observed for the orthorhombic superconductor YBa 2 Cu 3 O 7-δ . A structural model is proposed and discussed [fr

  12. Cubic-to-Tetragonal Phase Transitions in Ag-Cu Nano rods

    International Nuclear Information System (INIS)

    Delogu, F.; Mascia, M.

    2012-01-01

    Molecular dynamics simulations have been used to investigate the structural behavior of nano rods with square cross section. The nano rods consist of pure Ag and Cu phases or of three Ag and Cu domains in the sequence Ag-Cu-Ag or Cu-Ag-Cu. Ag and Cu domains are separated by coherent interfaces. Depending on the side length and the size of individual domains, Ag and Cu can undergo a transition from the usual face-centered cubic structure to a body-centered tetragonal one. Such transition can involve the whole nano rod, or only the Ag domains. In the latter case, the transition is accompanied by a loss of coherency at the Ag-Cu interfaces, with a consequent release of elastic energy. The observed behaviors are connected with the stresses developed at the nano rod surfaces.

  13. Ligand mediated synthesis of AgInSe2 nanoparticles with tetragonal/orthorhombic crystal phases

    International Nuclear Information System (INIS)

    Abazović, Nadica D.; Čomor, Mirjana I.; Mitrić, Miodrag N.; Piscopiello, Emanuela; Radetić, Tamara; Janković, Ivana A.; Nedeljković, Jovan M.

    2012-01-01

    Nanosized AgInSe 2 particles (d ∼ 7–25 nm) were synthesized using colloidal chemistry method at 270 °C. As solvents/surface ligands 1-octadecene, trioctylphosphine, and oleylamine were used. It was shown that choice of ligand has crucial impact not only on final crystal phase of nanoparticles, but also at mechanism of crystal growth. X-ray diffraction and TEM/HRTEM techniques were used to identify obtained crystal phases and to measure average size and shape of nanoparticles. UV/Vis data were used to estimate band-gap energies of obtained samples. It was shown that presented routes can provide synthesis of nanoparticles with desired crystal phase (tetragonal and/or orthorhombic), with band-gap energies in the range from 1.25 to 1.53 eV.

  14. First principles study of the structural and electronic properties of double perovskite Ba2YTaO6 in cubic and tetragonal phases

    International Nuclear Information System (INIS)

    Deluque Toro, C.E.; Rodríguez M, Jairo Arbey; Landínez Téllez, D.A.; Moreno Salazar, N.O.; Roa-Rojas, J.

    2014-01-01

    The Ba 2 YTaO 6 double perovskite presents a transition from cubic (Fm−3m) to tetragonal structure (I4/m) at high temperature. In this work, we present a detailed study of the structural and electronic properties of the double perovskite Ba 2 YTaO 6 in space group Fm−3m and I4/m. Calculations were made with the Full-Potential Linear Augmented Plane Wave method (FP-LAPW) within the framework of the Density Functional Theory (DFT) with exchange and correlation effects in the Generalized Gradient (GGA) and Local Density (LDA) approximations. From the minimization of energy as a function of volume and the fitting of the Murnaghan equation some structural characteristics were determined as, for example, total energy, lattice parameter (a=8.50 Å in cubic phase and a=5.985 Å and c=8.576 Å in tetragonal), bulk modulus (135.6 GPa in cubic phase and 134.1 GPa in tetragonal phase) and its derivative. The study of the electronic characteristics was performed from the analysis of the electronic density of states (DOS). We find a non-metallic behavior for this with a direct band gap of approximately 3.5 eV and we found that the Ba 2 YTaO 6 (I4/m) phase is the most stable one. © 2013 Elsevier Science. All rights reserved

  15. Thermodynamic theory of intrinsic finite-size effects in PbTiO3 nanocrystals. I. Nanoparticle size-dependent tetragonal phase stability

    Science.gov (United States)

    Akdogan, E. K.; Safari, A.

    2007-03-01

    We propose a phenomenological intrinsic finite-size effect model for single domain, mechanically free, and surface charge compensated ΔG-P ⃗s-ξ space, which describes the decrease in tetragonal phase stability with decreasing ξ rigorously.

  16. Phase field modelling of precipitate morphologies in systems with tetragonal interfacial free energy anisotropy

    OpenAIRE

    Roy, Arijit; Gururajan, M P

    2017-01-01

    A wide variety of morphologies arise due to the tetragonal anisotropy in interfacial free energy. In this paper, we report on a family of Extended Cahn-Hilliard (ECH) models for incorporating tetragonal anisotropy in interfacial free energy. We list the non-zero and independent parameters that are introduced in our model and list the constraints on them. For appropriate choice of these parameters, our model can produce a many of the morphologies seen in tetragonal systems such as di-pyramids,...

  17. Neutron powder investigation of the tetragonal to monoclinic phase transformation in undoped zirconia

    International Nuclear Information System (INIS)

    Boysen, H.; Frey, F.

    1991-01-01

    The tetragonal (t) to monoclinic (m) transformation in pure ZrO 2 was investigated by neutron powder diffraction at temperatures between 1900 K and room temperature. The results of a Rietveld analysis are compared with a previous investigation of the m → t transformation. The t → m transformation takes place near 1200 K (implaying a hysteresis of 300 K) and in a much smaller interval (about 150 K compared with about 600 K in the m → t case). There are no indications of a two-stage process as found for the m → t transformation. The structural parameters of the m phase depend only on temperature while those of the t phase differ at the same temperatures for the forward and reverse transformation. The temperature dependence of the lattice constants suggests an orientational relationship a t parallela m * and c t parallelb m . There are no macrostrains whereas the overall microstrain behaviour is similar in both cases, viz. the large microstrains present in both phases are released within the transformation regime. An analysis of temperature factors and diffuse background suggest dynamical disorder in the t phase and static disorder in the m phase. (orig.)

  18. Formation of metastable tetragonal zirconia nanoparticles: Competitive influence of the dopants and surface state

    Energy Technology Data Exchange (ETDEWEB)

    Gorban, Oksana, E-mail: matscidep@aim.com [Donetsk Institute for Physics and Engineering named after A.A. Galkin of the NAS of Ukraine, Nauki av. 46, Kyiv 03680 (Ukraine); Synyakina, Susanna; Volkova, Galina; Gorban, Sergey; Konstantiova, Tetyana [Donetsk Institute for Physics and Engineering named after A.A. Galkin of the NAS of Ukraine, Nauki av. 46, Kyiv 03680 (Ukraine); Lyubchik, Svetlana, E-mail: s_lyubchik@yahoo.com [REQUIMTE, Universida de Nova de Lisboa, 2829-516 Caparica (Portugal)

    2015-12-15

    The effect of the surface modification of the nanoparticles of amorphous and crystalline partially stabilized zirconia by fluoride ions on stability of the metastable tetragonal phase was investigated. Based on the DSC, titrimetry and FTIR spectroscopy data it was proven that surface modification of the xerogel resulted from an exchange of the fluoride ions with the basic OH groups. The effect of the powder pre-calcination temperature before modification on the formation of metastable tetragonal phase in partially stabilized zirconia was investigated. It was shown that the main factor of tetragonal zirconia stabilization is the state of nanoparticles surface at pre-crystallization temperatures.

  19. Pressure effects on high temperature steam oxidation of Zircaloy-4

    International Nuclear Information System (INIS)

    Park, Kwangheon; Kim, Kwangpyo; Ryu, Taegeun

    2000-01-01

    The pressure effects on Zircaloy-4 (Zry-4) cladding in high temperature steam have been analyzed. A double layer autoclave was made for the high pressure, high temperature oxidation tests. The experimental test temperature range was 700 - 900 deg C, and pressures were 0.1 - 15 MPa. Steam partial pressure turns out to be an important one rather than total pressure. Steam pressure enhances the oxidation rate of Zry-4 exponentially. The enhancement depends on the temperature, and the maximum exists between 750 - 800 deg C. Pre-existing oxide layer decreases the enhancement about 40 - 60%. The acceleration of oxidation rate by high pressure team seems to be originated from the formation of cracks by abrupt transformation of tetragonal phase in oxide, where the un-stability of tetragonal phase comes from the reduction of surface energy by steam. (author)

  20. Phases and structural characteristics of high Tc superconducting oxide in (Bi, Pb)-Sr-Ca-Cu-O system

    International Nuclear Information System (INIS)

    Chen, Zuyano; Li, Zhengrong; Qian, Yitai; Zhou, Quien; Cheng, Tingzhu

    1989-01-01

    The various phases, which are responsible for variant maximum d-value including 18.5 angstrom, 15.4 angstrom, 12.2 angstrom, 6.2 angstrom, 3.2 angstrom and possible 9.1 angstrom respectively, observed in high Tc superconducting complex oxide of (Bi,Pb)-Sr-Ca-Cu-O system are reported in this paper according to the result of X-ray diffraction on platelike crystals or crystallites synthesized under different preparation conditions. The phase of tetragonal system with c=3.21 angstrom, a=3.86 angstrom is possible parent structural unit and it is of great significance to the structure constitution of various phases with large lattice parameter c and structural characteristics of superconducting oxide. In view of the above a model of two-dimension stack-up which causes a stack in variant styles along c-axis and constitute various phases with different lattice parameter c is proposed and discussed

  1. Thermodynamic analysis of the formation of tetragonal bainite in steels

    Science.gov (United States)

    Mirzayev, D. A.; Mirzoev, A. A.; Buldashev, I. V.; Okishev, K. Yu.

    2017-06-01

    In the articles of Bkhadeshia, a new class of high-strength steels based on the structure of carbidefree bainite with an enhanced carbon content has been developed. According to Bkhadeshia, the main factor responsible for the high solubility of carbon is the occurrence of a tetragonality of the bainite lattice. To check this effect, in this article, the theory of tetragonality of martensite of iron alloys developed by Zener and Khachaturyan was applied to bainite under the assumption that the precipitation of carbides is prohibited. Equations for the chemical potentials of carbon and iron in austenite and in tetragonal ferrite have been derived. The equilibrium of these phases has been considered, and the calculations of the boundary concentrations of carbon and iron at different temperatures (300-1000 K) and at different parameters of the deformation interaction λ0 have been performed. The rigorous calculations confirmed Bkhadeshia's hypothesis that the suppression of the carbide formation during the formation of bainite leads to an increase in the carbon solubility in the bcc phase.

  2. Nucleation in stress-induced tetragonal-monoclinic transformation of constrained zirconia

    International Nuclear Information System (INIS)

    Chan, S.K.

    1992-08-01

    A theory for stress-induced tetragonal→monoclinic transformation of constrained zirconia is presented based on the assumption that when forcibly strained to a regime of absolute instability where the free energy density of the tetragonal phase has a negative curvature, the constrained tetragonal zirconia becomes unstable with respect to the development of a modulated strain pattern that will evolve into a band of twin monoclinic domains. The temperature range for such an instability, the critical size of the inclusion, the corresponding critical strain, and the periodicity of the modulation are derived in terms of parameters that can be related to the elastic stiffness coefficients of various orders of the inclusion and the shear modulus of the host matrix. An entirely different mechanism is suggested for the reverse monoclinic→tetragonal transformation because the monoclinic phase is metastable when the extrinsic stress is removed. Estimates for the parameters are inferred from a variety of experimental data for pure zirconia and the numerical values for the predicted physical quantities are obtained

  3. First principles study of the structural and electronic properties of double perovskite Ba{sub 2}YTaO{sub 6} in cubic and tetragonal phases

    Energy Technology Data Exchange (ETDEWEB)

    Deluque Toro, C.E., E-mail: deluquetoro@gmail.com [Grupo de Nuevos Materiales, Universidad Popular del Cesar, Valledupar (Colombia); Rodríguez M, Jairo Arbey [Grupo de Estudios de Materiales—GEMA, Departamento de Física, Universidad Nacional de Colombia, AA 5997 Bogotá DC (Colombia); Landínez Téllez, D.A. [Grupo de Física de Nuevos Materiales, Departamento de Física, Universidad Nacional de Colombia, AA 5997 Bogotá DC (Colombia); Moreno Salazar, N.O. [Departamento de Física, Universidade Federal de Sergipe (Brazil); Roa-Rojas, J. [Grupo de Física de Nuevos Materiales, Departamento de Física, Universidad Nacional de Colombia, AA 5997 Bogotá DC (Colombia)

    2014-12-15

    The Ba{sub 2}YTaO{sub 6} double perovskite presents a transition from cubic (Fm−3m) to tetragonal structure (I4/m) at high temperature. In this work, we present a detailed study of the structural and electronic properties of the double perovskite Ba{sub 2}YTaO{sub 6} in space group Fm−3m and I4/m. Calculations were made with the Full-Potential Linear Augmented Plane Wave method (FP-LAPW) within the framework of the Density Functional Theory (DFT) with exchange and correlation effects in the Generalized Gradient (GGA) and Local Density (LDA) approximations. From the minimization of energy as a function of volume and the fitting of the Murnaghan equation some structural characteristics were determined as, for example, total energy, lattice parameter (a=8.50 Å in cubic phase and a=5.985 Å and c=8.576 Å in tetragonal), bulk modulus (135.6 GPa in cubic phase and 134.1 GPa in tetragonal phase) and its derivative. The study of the electronic characteristics was performed from the analysis of the electronic density of states (DOS). We find a non-metallic behavior for this with a direct band gap of approximately 3.5 eV and we found that the Ba{sub 2}YTaO{sub 6} (I4/m) phase is the most stable one. {sup ©} 2013 Elsevier Science. All rights reserved.

  4. Fe-Vacancy-Induced Ferromagnetism in Tetragonal FeSe Thin Films

    International Nuclear Information System (INIS)

    Yong-Feng, Li; Gui-Bin, Liu; Li-Jie, Shi; Bang-Gui, Liu

    2009-01-01

    Motivated by recent experiments, we investigate structural, electronic, and magnetic properties of tetragonal FeSe with Fe vacancies using the state-of-the-art first-principles method. We show that Fe vacancies tend to stay in the same one of the two sublattices and thus induce ferromagnetism in the ground-state phase. Our calculated net moment is in good agreement with the experimental data available. Therefore, the ferromagnetism observed in tetragonal FeSe thin films is explained. It could be made controllable soon for spintronic applications

  5. Tetragonal BiFeO3 on yttria-stabilized zirconia

    International Nuclear Information System (INIS)

    Liu, Heng-Jui; Du, Yu-Hao; Gao, Peng; Ikuhara, Yuichi; Huang, Yen-Chin; Chen, Yi-Chun; Chen, Hsiao-Wen; Liu, Hsiang-Lin; He, Qing; Chu, Ying-Hao

    2015-01-01

    High structural susceptibility of multiferroic BiFeO 3 (BFO) makes it a potential replacement of current Pb-based piezoelectrics. In this study, a tetragonal phase is identified based on a combination of x-ray diffraction, scanning transmission electronic microscopy, x-ray absorption spectroscopy, and Raman spectroscopy when BFO is grown on yttria-stabilized zirconia (YSZ) substrates. To distinguish the discrepancy between this tetragonal phase and common cases of monoclinic BFO, piezoelectric force microscopy images and optical property are also performed. It shows a lower electrostatic energy of ferroelectric domains and a large reduction of band gap for BFO grown on YSZ substrate comparing to the well-known one grown on LaAlO 3 substrate. Our findings in this work can provide more insights to understand the structural diversity of multiferroic BFO system for further applications

  6. Collapsed tetragonal phase as a strongly covalent and fully nonmagnetic state: Persistent magnetism with interlayer As-As bond formation in Rh-doped Ca0 .8Sr0 .2Fe2As2

    Science.gov (United States)

    Zhao, K.; Glasbrenner, J. K.; Gretarsson, H.; Schmitz, D.; Bednarcik, J.; Etter, M.; Sun, J. P.; Manna, R. S.; Al-Zein, A.; Lafuerza, S.; Scherer, W.; Cheng, J. G.; Gegenwart, P.

    2018-02-01

    A well-known feature of the CaFe2As2 -based superconductors is the pressure-induced collapsed tetragonal phase that is commonly ascribed to the formation of an interlayer As-As bond. Using detailed x-ray scattering and spectroscopy, we find that Rh-doped Ca0.8Sr0.2Fe2As2 does not undergo a first-order phase transition and that local Fe moments persist despite the formation of interlayer As-As bonds. Our density functional theory calculations reveal that the Fe-As bond geometry is critical for stabilizing magnetism and the pressure-induced drop in the c lattice parameter observed in pure CaFe2As2 is mostly due to a constriction within the FeAs planes. The collapsed tetragonal phase emerges when covalent bonding of strongly hybridized Fe 3 d and As 4 p states completely wins out over their exchange splitting. Thus the collapsed tetragonal phase is properly understood as a strong covalent phase that is fully nonmagnetic with the As-As bond forming as a by-product.

  7. A comprehensive investigation of tetragonal Gd-doped BiVO{sub 4} with enhanced photocatalytic performance under sun-light

    Energy Technology Data Exchange (ETDEWEB)

    Luo, Yangyang; Tan, Guoqiang, E-mail: tan3114@163.com; Dong, Guohua; Ren, Huijun; Xia, Ao

    2016-02-28

    Graphical abstract: - Highlights: • Tetragonal Gd-BiVO{sub 4} with enhanced photocatalytic activity was synthesized. • Gd doping can induce the phase transition from monoclinic to tetragonal BiVO{sub 4}. • GdVO{sub 4} seeds as crystal nucleus dominate the formation of tetragonal Gd-BiVO{sub 4}. • Tetragonal Gd-BiVO{sub 4} exhibits the excellent separation of electrons and holes. • The contribution of high photocatalytic activity under sun-light is from UV-light. - Abstract: Tetragonal Gd-doped BiVO{sub 4} having enhanced photocatalytic activity have been synthesized by a facile microwave hydrothermal method. The structural analysis indicates that Gd doping can induce the phase transition from monoclinic to tetragonal BiVO{sub 4}. The reaction results in precursor solutions imply that tetragonal GdVO{sub 4} seeds as crystal nucleus are the original and determined incentives to force the formation of tetragonal Gd-BiVO{sub 4}. The influences of the surface defect, band structure, and BET surface area on the improved photocatalytic activities of tetragonal Gd-doped BiVO{sub 4} are investigated systematically. The results demonstrate that the more surface oxygen deficiencies as active sites and the excellent mobility and separation of photogenerated electrons and holes are beneficial to the enhancement of the photocatalytic performance of tetragonal Gd-BiVO{sub 4}. The RhB photodegradation experiments indicate that the contribution of high photocatalytic activities under simulated sun-light is mainly from UV-light region due to the tetragonal structure feature. The best photocatalytic performance is obtained for tetragonal 10 at% Gd-BiVO{sub 4}, of which the RhB degradation rate can reach to 96% after 120 min simulated sun-light irradiation. The stable tetragonal Gd-BiVO{sub 4} with efficient mineralization will be a promising photocatalytic material applied in water purification.

  8. Atomistic studies of cation transport in tetragonal ZrO2 during zirconium corrosion

    International Nuclear Information System (INIS)

    Bai, Xian-Ming; Zhang, Yongfeng; Tonks, Michael R.

    2015-01-01

    Zirconium alloys are the major fuel cladding materials in current reactors. The water-side corrosion is a significant degradation mechanism of these alloys. During corrosion, the transport of oxidizing species in zirconium dioxide (ZrO 2 ) determines the corrosion kinetics. Previously, it has been argued that the outward diffusion of cations is important for forming protective oxides. In this work, the migration of Zr defects in tetragonal ZrO 2 is studied with temperature accelerated dynamics and molecular dynamics simulations. The results show that Zr interstitials have anisotropic diffusion and migrate preferentially along the [001] or c direction in tetragonal ZrO 2 . The compressive stresses can increase the Zr interstitial migration barrier significantly. The migration of Zr interstitials at a grain boundary is much slower than in a bulk oxide. The implications of these atomistic simulation results in the Zr corrosion are discussed. (authors)

  9. Phase Behavior and Equations of State of the Actinide Oxides

    Science.gov (United States)

    Chidester, B.; Pardo, O. S.; Panero, W. R.; Fischer, R. A.; Thompson, E. C.; Heinz, D. L.; Prescher, C.; Prakapenka, V. B.; Campbell, A.

    2017-12-01

    The distribution of the long-lived heat-producing actinide elements U and Th in the deep Earth has important implications for the dynamics of the mantle and possibly the energy budget of Earth's core. The low shear velocities of the Large Low-Shear Velocity Provinces (LLSVPs) on the core-mantle boundary suggests that these regions are at least partially molten and may contain concentrated amounts of the radioactive elements, as well as other large cations such as the rare Earth elements. As such, by exploring the phase behavior of actinide-bearing minerals at extreme conditions, some insight into the mineralogy, formation, and geochemical and geodynamical effects of these regions can be gained. We have performed in situ high-pressure, high-temperature synchrotron X-ray diffraction experiments and calculations on two actinide oxide materials, UO2 and ThO2, to determine their phase behavior at the extreme conditions of the lower mantle. Experiments on ThO2 reached 60 GPa and 2500 K, and experiments on UO2 reached 95 GPa and 2500 K. We find that ThO2 exists in the fluorite-type structure to 20 GPa at high temperatures, at which point it transforms to the high-pressure cotunnite-type structure and remains thus up to 60 GPa. At room temperature, an anomalous expansion of the fluorite structure is observed prior to the transition, and may signal anion sub-lattice disorder. Similarly, UO2 exists in the fluorite-type structure at ambient conditions and up to 28 GPa at high temperatures. Above these pressures, we have observed a previously unidentified phase of UO2 with a tetragonal structure as the lower-temperature phase and the cotunnite-type phase at higher temperatures. Above 78 GPa, UO2 undergoes another transition or possible dissociation into two separate oxide phases. These phase diagrams suggest that the actinides could exist as oxides in solid solution with other analogous phases (e.g. ZrO2) in the cotunnite-type structure throughout much of Earth's lower mantle.

  10. Accommodation of tin in tetragonal ZrO{sub 2}

    Energy Technology Data Exchange (ETDEWEB)

    Bell, B. D. C.; Grimes, R. W.; Wenman, M. R., E-mail: m.wenman@imperial.ac.uk [Department of Materials and Centre for Nuclear Engineering, Imperial College, London SW7 2AZ (United Kingdom); Murphy, S. T. [Department of Physics and Astronomy, University College London, Gower Street, London WC1E 6BT (United Kingdom); Burr, P. A. [Department of Materials and Centre for Nuclear Engineering, Imperial College, London SW7 2AZ (United Kingdom); Institute of Materials Engineering, Australian Nuclear Science and Technology Organisation, Menai, New South Wales 2234 (Australia)

    2015-02-28

    Atomic scale computer simulations using density functional theory were used to investigate the behaviour of tin in the tetragonal phase oxide layer on Zr-based alloys. The Sn{sub Zr}{sup ×} defect was shown to be dominant across most oxygen partial pressures, with Sn{sub Zr}{sup ″} charge compensated by V{sub O}{sup ••} occurring at partial pressures below 10{sup −31 }atm. Insertion of additional positive charge into the system was shown to significantly increase the critical partial pressure at which Sn{sub Zr}{sup ″} is stable. Recently developed low-Sn nuclear fuel cladding alloys have demonstrated an improved corrosion resistance and a delayed transition compared to Sn-containing alloys, such as Zircaloy-4. The interaction between the positive charge and the tin defect is discussed in the context of alloying additions, such as niobium and their influence on corrosion of cladding alloys.

  11. Variable-temperature single-crystal X-ray diffraction study of tetragonal and cubic perovskite-type barium titanate phases.

    Science.gov (United States)

    Nakatani, Tomotaka; Yoshiasa, Akira; Nakatsuka, Akihiko; Hiratoko, Tatsuya; Mashimo, Tsutomu; Okube, Maki; Sasaki, Satoshi

    2016-02-01

    A variable-temperature single-crystal X-ray diffraction study of a synthetic BaTiO3 perovskite has been performed over the temperature range 298-778 K. A transition from a tetragonal (P4mm) to a cubic (Pm3m) phase has been revealed near 413 K. In the non-centrosymmetric P4mm symmetry group, both Ti and O atoms are displaced along the c-axis in opposite directions with regard to the Ba position fixed at the origin, so that Ti(4+) and Ba(2+) cations occupy off-center positions in the TiO6 and BaO12 polyhedra, respectively. Smooth temperature-dependent changes of the atomic coordinates become discontinuous with the phase transition. Our observations imply that the cations remain off-center even in the high-temperature cubic phase. The temperature dependence of the mean-square displacements of Ti in the cubic phase includes a significant static component which means that Ti atoms are statistically distributed in the off-center positions.

  12. Investigation of Zirconium Oxide Films in Different Dissolved Hydrogen Concentration

    International Nuclear Information System (INIS)

    Kim, Taeho; Choi, Kyoung Joon; Yoo, Seung Chang; Kim, Ji Hyun

    2016-01-01

    It has been reported that in pre-transition zirconium oxide, the volume fraction of tetragonal zirconium oxide increased near the oxide/metal (O/M) interface, and the sub-stoichiometric zirconium oxide layer was observed. The diffusion of oxygen ion through the oxide layer is the rate-limiting process during the pre-transition oxidation process, and this diffusion mainly occurs in the grain boundaries. The two layered oxide structure is formed in pre-transition oxide for the zirconium alloy in high-temperature water environment. It is known that the corrosion rate is related to the volume fraction of zirconium oxide and the pores in the oxides; therefore, the aim of this paper is to investigate the oxidation behavior in the pre-transition zirconium oxide in high-temperature water chemistry. In this study, in situ Raman and TEM analysis were conducted for investigating the phase transformation of zirconium alloy in primary water. From this study, the following conclusions are drawn: 1. The zirconium alloy was oxidized in primary water chemistry for 100 d, and Raman and TEM were measured after 30, 50, 80, and 100 d from start-up. 2. TEM and FFT analysis showed that the zirconium oxide mostly consisted of the monoclinic phase. The tetragonal zirconium oxide was just found near the O/M interface

  13. Tetragonal BiFeO{sub 3} on yttria-stabilized zirconia

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Heng-Jui [Department of Materials Science Engineering, National Chiao Tung University, Hsinchu 30010, Taiwan (China); Department of Physics, National Taiwan Normal University, Taipei 11677, Taiwan (China); Du, Yu-Hao [Department of Materials Science Engineering, National Chiao Tung University, Hsinchu 30010, Taiwan (China); Gao, Peng; Ikuhara, Yuichi [Institute of Engineering Innovation, The University of Tokyo, Tokyo 113-8656 (Japan); Huang, Yen-Chin; Chen, Yi-Chun [Department of Physics, National Cheng Kung University, Tainan 70101, Taiwan (China); Chen, Hsiao-Wen; Liu, Hsiang-Lin [Department of Physics, National Taiwan Normal University, Taipei 11677, Taiwan (China); He, Qing [Department of Physics, Durham University, Durham DH1 3LE (United Kingdom); Chu, Ying-Hao, E-mail: yhc@nctu.edu.tw [Department of Materials Science Engineering, National Chiao Tung University, Hsinchu 30010, Taiwan (China); Institute of Physics, Academia Sinica, Taipei 11529, Taiwan (China)

    2015-11-01

    High structural susceptibility of multiferroic BiFeO{sub 3} (BFO) makes it a potential replacement of current Pb-based piezoelectrics. In this study, a tetragonal phase is identified based on a combination of x-ray diffraction, scanning transmission electronic microscopy, x-ray absorption spectroscopy, and Raman spectroscopy when BFO is grown on yttria-stabilized zirconia (YSZ) substrates. To distinguish the discrepancy between this tetragonal phase and common cases of monoclinic BFO, piezoelectric force microscopy images and optical property are also performed. It shows a lower electrostatic energy of ferroelectric domains and a large reduction of band gap for BFO grown on YSZ substrate comparing to the well-known one grown on LaAlO{sub 3} substrate. Our findings in this work can provide more insights to understand the structural diversity of multiferroic BFO system for further applications.

  14. In situ Investigation of Oxide Films on Zirconium Alloy in PWR Primary Water Chemistry

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Taeho; Choi, Kyoung Joon; Yoo, Seung Chang; Kim, Ji Hyun [Ulsan National Institute of Science and Technology, Ulsan (Korea, Republic of)

    2015-05-15

    Zirconium alloys are used as fuel cladding materials in nuclear power reactors, because these materials have a very low thermal neutron capture cross section as well as desirable mechanical properties. However, the Fukushima accident shows that the oxidation behavior of zirconium alloy is an important issue because the zirconium alloy functions as a shield of nuclear material (i.e., uranium, fission gas), and the degradation on zirconium cladding directly causes severe accident on nuclear power plant. Therefore, to ensure the safety of nuclear power reactors, the performance and sustainability of nuclear fuel should be understood. Currently, the water-metal interface is regarded as the rate-controlling site governing the rapid oxidation transition in high-burn-up fuels. Zirconium oxide is formed at the water-metal interface, and its structure and phase play an important role in determining its mechanical properties. In the early stage of the oxidation process, zirconium oxide with both tetragonal and monoclinic phases is formed. With an increase in the oxidation time to 150 h, the unstable tetragonal phase disappears and the monoclinic phase is dominant and possibly because of the stress relaxation according to previous and present results.

  15. Nb effect on Zr-alloy oxidation under high pressure steam at high temperatures

    International Nuclear Information System (INIS)

    Park, Kwangheon; Yang, Sungwoo; Kim, Kyutae

    2005-01-01

    The high-pressure steam effects on the oxidation of Zircaloy-4 (Zry-4) and Zirlo (Zry-1%Nb) claddings at high temperature have been analyzed. Test temperature range was 700-900degC, and pressures were 1-150 bars. High pressure-steam enhances oxidation of Zry-4, and the dependency of enhancement looks exponential to steam pressure. The origin of the oxidation enhancement turned out to be the formation of cracks in oxide. The loss of tetragonal phase by high-pressure steam seems related to the crack formation. Addition of Nb as an alloying element to Zr alloy reduces significantly the steam pressure effects on oxidation. The higher compressive stresses and the smaller fraction of tetragonal oxides in Zry-1%Nb seem to be the diminished effect of high-pressure steam on oxidation. (author)

  16. Mechanical properties and dependence with temperature of tetragonal polycrystalline zirconia materials

    International Nuclear Information System (INIS)

    Orange, G.

    1986-01-01

    Polycrystalline zirconia materials with a high content of metastable tetragonal phase have been obtained by pressureless sintering from experimental powders. Mechanical properties have been determined at room temperature and compared with similar materials. The fracture strength (σ /SUB f/ ) and fracture toughness (K /SUB 1c/ ) temperature dependence has been studied, in air environment up to 1000 0 C. Microstructure was studied by SEM examinations of fracture faces and TEM observations. Fracture toughness (of about 10 MPa √m at room temperature) decreases from 200 0 C to 800 0 C. The critical temperature (T /SUB c/ ) is estimated at 600 0 C. We observe an important decreases of fracture strength at 200 0 C. These mechanical properties are discussed on the basis of the stability of the tetragonal phase depending on additive content, grain size and temperature

  17. Tetragonal CuO: End member of the 3d transition metal monoxides

    NARCIS (Netherlands)

    Siemons, W.; Koster, Gertjan; Blank, David H.A.; Hammond, Robert H.; Geballe, Theodore H.; Beasley, Malcolm R.

    2009-01-01

    Monoclinic CuO is anomalous both structurally as well as electronically in the 3d transition metal oxide series. All the others have the cubic rocksalt structure. Here we report the synthesis and electronic property determination of a tetragonal (elongated rocksalt) form of CuO created using an

  18. Stabilisation of late transition metal and noble metal films in hexagonal and body centred tetragonal phases by epitaxial growth

    Energy Technology Data Exchange (ETDEWEB)

    Hueger, E.

    2005-08-26

    In this work ultrathin metallic films with a crystal phase different to their natural bulk structure were produced by hetero-epitaxial growth on metallic substrates. A further aim of this work was to understand the initiation, growth and stability of crystal phase modifications of these films. there exist cases where the films turn beyond the pseudomorphic-growth to a crystal phase different from their natural bulk structure. The present work presents and discusses such a case in addition to the general phenomenon of pseudomorphic-growth. In particular it is shown that metals whose natural phase is face centred cubic (fcc) can be grown in body centred tetragonal (bct) or hexagonal close packed (hcp) phases in the form of thin films on (001) surfaces of appropriate substrates. The growth behavior, electron diffraction analysis, appearance conditions, geometric fit considerations, examples and a discussion of the phase stability of non-covered films and superlattices is given reviewing all epitaxial-systems whose diffraction pattern can be explained by the hexagonal or pseudomorphic bct phase. (orig.)

  19. orbital selective correlation reduce in collapse tetragonal phase of CaFe2(As0.935P0.065)2 and electronic structure reconstruction studied by angel resolved photoemission spectroscopy

    Science.gov (United States)

    Zeng, Lingkun

    We performed an angle-resolved photoemission spectroscopy (ARPES) study of the CaFe2(As0.935P0.065)2 in the collapse tetragonal(CT) phase and uncollapse tetragonal(UCT) phase. We find in the CT phase the electronic correlation dramatically reduces respective to UCT phase. Meanwhile, the reduction of correlation in CT phase show an orbital selective effect: correlation in dxy reduces the most, and then dxz/yz, while the one in dz2-r2 almost keeps the same. In CT phase, almost all bands sink downwards to higher binding energy, leading to the hole like bands around Brillouin zone(BZ) center sink below EF compared with UCT phase. However, the electron pocket around Brillouin Zone(BZ) corner(M) in UCT phase, forms a hole pocket around BZ center(Z point) in CT phase. Moreover, the dxy exhibits larger movement down to higher binding energy, resulting in farther away from dyz/xz and closer to dxy.We propose the electron filling ,namely high spin state in UCT phase to low spin state in CT phase(due to competing between crystal structure field and Hund's coupling), other than the Fermi surface nesting might be responsible for the absent of magnetic ordering.

  20. A novel perovskite oxide chemically designed to show multiferroic phase boundary with room-temperature magnetoelectricity

    Science.gov (United States)

    Fernández-Posada, Carmen M.; Castro, Alicia; Kiat, Jean-Michel; Porcher, Florence; Peña, Octavio; Algueró, Miguel; Amorín, Harvey

    2016-09-01

    There is a growing activity in the search of novel single-phase multiferroics that could finally provide distinctive magnetoelectric responses at room temperature, for they would enable a range of potentially disruptive technologies, making use of the ability of controlling polarization with a magnetic field or magnetism with an electric one (for example, voltage-tunable spintronic devices, uncooled magnetic sensors and the long-searched magnetoelectric memory). A very promising novel material concept could be to make use of phase-change phenomena at structural instabilities of a multiferroic state. Indeed, large phase-change magnetoelectric response has been anticipated by a first-principles investigation of the perovskite BiFeO3-BiCoO3 solid solution, specifically at its morphotropic phase boundary between multiferroic polymorphs of rhombohedral and tetragonal symmetries. Here, we report a novel perovskite oxide that belongs to the BiFeO3-BiMnO3-PbTiO3 ternary system, chemically designed to present such multiferroic phase boundary with enhanced ferroelectricity and canted ferromagnetism, which shows distinctive room-temperature magnetoelectric responses.

  1. Raman and luminescence spectroscopy of zirconium oxide with the use of the MOLE microprobe

    International Nuclear Information System (INIS)

    Doyle, T.E.; Alvarez, J.L.

    1984-01-01

    Raman and luminescence spectroscopy with the use of the MOLE microprobe has been used to characterize ZrO 2 originating from oxidized fuel-rod cladding in nuclear accidents. Micro-Raman analysis of samples from Three Mile Island Unit 2 and the Power Burst Facility identified tetragonal and cubic ZrO 2 . The tetragonal and cubic phases are high-temperature polymorphs of ZrO 2 and provide information about temperatures and hydrogen formation in the TMI-2 core. The data suggest that the tetragonal ZrO 2 in TMI-2 samples was stabilized by a crystallite size effect, whereas cubic ZrO 2 in PBF debris samples was stabilized by impurities. Luminescence was used to differentiate yttria-stabilized ZrO 2 ceramics and oxidized fuel-rod cladding in PBF debris samples. The ZrO 2 ceramics produced strong, sharp luminescence peaks which indicated the presence of titanium and yttria in the ZrO 2 . Oxidized fuel-rod cladding displayed no luminescence

  2. Zircaloy oxidation studies

    International Nuclear Information System (INIS)

    Prater, J.T.; Beauchamp, R.H.; Saenz, N.T.

    1985-06-01

    The oxidation kinetics of Zircaloy-4 in steam have been determined at 1300-2400 0 C. Growth of the ZrO 2 and α-Zr layers display parabolic behavior over the entire temperature range studied. A discontinuity in the oxidation kinetics at 1510 0 C causes rates to increase above those previously established by the Baker-Just relationship. This increase coincides with the tetragonal-to-cubic phase transformation in ZrO/sub 2-x/. No discontinuity in the oxide growth rate is observed upon melting of Zr(0). The effects of temperature gradients have been taken into account and corrected values representative of near-isothermal conditions have been computed

  3. Phenomenological Equations Relating Various Critical Anomalies above a Cubic-to-Tetragonal Phase Transition Point

    Science.gov (United States)

    Hamano, Katsumi; Hirotsu, Shunsuke

    1980-01-01

    Phenomenological equations are derived which interrelate the anomalies in various thermodynamic quantities above the transition point of a cubic-to-tetragonal phase transition caused by an instability of a triply degenerate soft mode. The anomalous part of the Gibbs free energy is assumed to be a simple sum of the three parts which represent the contributions from the three fluctuation components. A cylindrical approximation is adopted to each of the three contributions by taking into account the symmetry of the fluctuations. The theory predicts that the adiabatic elastic compliances, s11s, s12s, and also s11s-s12s should exhibit anomalies proportional to the anomaly in the specific heat at constant pressure. This is in marked contrast with the result of the generalized Pippard equations derived by Garland, and by Janovec. The new equations are successfully tested for KMnF3, CsPbCl3, and CsPbBr3. The β-γ transition of NH4Br is also discussed.

  4. Calculation of lattice sums and electrical field gradients for the rhombic and tetragonal phases of YBa2Cu3Ox

    International Nuclear Information System (INIS)

    Lyubutin, I.S.; Terziev, V.G.; Gor'kov, V.P.

    1989-01-01

    The point charge model is used to calculate the lattice sums and determine the electrical field gradients (EFG) as well as the asymmetry parameters η for all cation sites of the rhombic and tetragonal phases of the superconductor YBa 2 Cu 3 O x . The cases of copper of different valency at the Cu 1 sites are considered separately and EFG and η values are calculated in the vicinity of local defects caused by differences in the number and ordering of the oxygen vacancies at the Cu1 sites

  5. The tetragonal-monoclinic transformations of zirconia studied by small angle neutron scattering and differential thermal analysis

    International Nuclear Information System (INIS)

    Li, Z.; Epperson, J.E.; Fang, Y.; Chan, S.K.

    1992-08-01

    The tetragonal-monoclinic transformations of zirconia have been studied on pristine single crystals and on their cycled crystallites. Two complementary techniques have been used. Small angle neutron scattering experiments were carried out to monitor the degree of completion of a transformation under equilibrium conditions for collections of 20--30 large crystals using the total internal and external surface area as an indicator. Differential thermal analysis experiments were carried out on smaller single-domain crystals of different sizes individually during heating and cooling to measure the rates of latent heat absorption and emission. The investigation establishes the upper limit of stability of the monoclinic phase, the lower limit of stability of the tetragonal phase, and the coexistence temperature between the two phases. The characteristics of the transformations are also inferred from these experiments

  6. First-principles cluster variation calculations of tetragonal-cubic transition in ZrO2

    International Nuclear Information System (INIS)

    Mohri, Tetsuo; Chen, Ying; Kiyokane, Naoya

    2013-01-01

    Highlights: ► Cluster variation method is extended to study displacive transition. ► Electronic structure total energy calculations are performed on ZrO2. ► Tetragonal-cubic transition is studied within the framework of order -disorder transition. -- Abstract: It is attempted to extend the basic idea of continuous displacement cluster variation method (CDCVM) to the study of a displacive phase transition. As a preliminary study, we focus on cubic to tetragonal transition in ZrO 2 in which oxygen atoms on the cubic lattice are displaced alternatively in the opposite direction (upward and downward) along the tetragonal axis. Within the CDCVM, displaced atoms are regarded as different atomic species, and two distinguished atoms, A-oxygen (upward shifting) and B-oxygen (downward shifting), are introduced in the description of the free energy. FLAPW electronic structure total energy calculations are performed to extract effective interaction energies among displaced oxygen atoms, and by combing them with CDCVM, the transition temperature is calculated from the first-principles

  7. Protocol of thermal treatments for the recovery of tetragonal phase in infrastructures of dental prostheses base of ZrO_2 (3-Y_2O_3) mills in CAD / CAM systems or panthories

    International Nuclear Information System (INIS)

    Simba, B.G.; Ferreira, B.; Santos, C.

    2011-01-01

    ZrO_2(3%Y_2O_3) bioceramics are used as dental materials mainly as prosthesis components, because present high mechanical properties and translucence. The use of CAD/CAM machining technique needs final grinding which promotes tetragonal monoclinic transformation reducing the reliability of this ceramic. In this work, ZrO_2(3%Y_2O_3) ceramics were sintered at 1450-0h, 1530-2h or 1600-4h and characterized. Different heat-treatment (400-1200 deg C) are proposed aiming the recuperation of the tetragonal crystalline phase. (author)

  8. On the nature of phase transitions in the tetragonal tungsten bronze GdK2Nb5O15 ceramics

    International Nuclear Information System (INIS)

    Gagou, Y.; Lukyanchuk, I.; El Marssi, M.; Amira, Y.; Mezzane, D.; Courty, M.; Masquelier, C.; Yuzyuk, Yu. I.

    2014-01-01

    Phase transitions in gadolinium potassium niobate GdK 2 Nb 5 O 15 (GKN) ceramics have been investigated by x-ray diffraction, dielectric susceptibility, differential scanning calorimetry, and Raman scattering. The results of our complementary studies show that GKN exhibits two phase transitions at T c1  = 238 °C and T c2  = 375 °C attributed to the ferroelectric-antiferroelectric-paraelectric (FE-AFE-PE) phase transitions. According to the x-ray diffraction analysis, the FE and PE phases were refined in the polar P4bm and centrosymmetric P4/mbm space groups. For the intermediate phase, the structure is refined in the space group P4nc with doubling of the c unit cell parameter, which is compatible with an AFE phase. This result was confirmed by Raman spectroscopy since new low-frequency lines are activated in the AFE phase due to the Brillouin zone-folding effect, typical for the modulated phases. The presence of the AFE phase between the FE and PE phases and the complex nature of tetragonal tungsten bronze crystal structure can explain the large thermal hysteresis observed at the FE-AFE transition between heating and cooling cycle and the strong depression of the Curie-Weiss temperature T 0 . The semi-phenomenological Ising-like model based on the obtained experimental data is proposed to account for the observed FE-AFE-PE transition sequence

  9. Zirconia dispersion as a toughening agent in alumina - Influence of the cerium oxide

    International Nuclear Information System (INIS)

    Gritti, Olivier

    1987-01-01

    The improvement of mechanical properties of alumina can be obtained by fine dispersion of zirconia particles. The addition of cerium oxide as a stabilizer of the tetragonal phase has been examined. Different powder preparations, based on impregnation of the alumina powder by zirconium and cerium precursor salts, have been studied. Parameters, such as properties of alumina powder and cerium oxide content, for the production of reactive powders have been determined by two laboratory processes. The sintering of these powders in air at 1600 deg. C has resulted in dense materials with homogeneous microstructure. The mechanical properties, in particular the biaxial flexure strength and the toughness, have been determined in the temperature range 20 deg. C-900 deg. C. A reinforcement of about 80 pc in comparison with alumina is achieved. The optimal composition is (Al 2 O 3 ) 0.8 (ZrO 2 ) 0.18 (CeO 2 ) 0.02 . In the other hand, powder preparation by spray drying has been chosen for an approach to a larger scale process. The sintered ceramics made with these powders present a double microstructure which does not affect the mechanical properties. The presence of cerium oxide produces the following improvements: - increased mobility of the intergranular zirconia inclusions which results in a faster densification; - stabilization of a tetragonal phase without prohibiting the stress induced transformation; - increase of the critical sizes of the tetragonal → monoclinic transformation; - a large decrease in the transformation kinetic in water at 300 deg. C in comparison with that observed for alumina-zirconia doped with yttrium oxide. (author) [fr

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

    Science.gov (United States)

    Verma, Surbhi; Rani, Saruchi; Kumar, Sushil

    2018-05-01

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

  11. Spatially modulated magnetic structure of EuS due to the tetragonal domain structure of SrTiO3 APS

    CERN Document Server

    Rosenberg, Aaron J.; Kirtley, John R.; Gedik, Nuh; Moodera, Jagadeesh S.; Moler, Kathryn A.

    2017-12-15

    The combination of ferromagnets with topological superconductors or insulators allows for new phases of matter that support excitations such as chiral edge modes and Majorana fermions. EuS, a wide-bandgap ferromagnetic insulator with a Curie temperature around 16 K, and SrTiO3 (STO), an important substrate for engineering heterostructures, may support these phases. We present scanning superconducting quantum interference device measurements of EuS grown epitaxially on STO that reveal micron-scale variations in ferromagnetism and paramagnetism. These variations are oriented along the STO crystal axes and only change their configuration upon thermal cycling above the STO cubic-to-tetragonal structural transition temperature at 105 K, indicating that the observed magnetic features are due to coupling between EuS and the STO tetragonal structure. We speculate that the STO tetragonal distortions may strain the EuS, altering the magnetic anisotropy on a micron scale. This result demonstrates that local variation in...

  12. Toughening of dental porcelain by tetragonal ZrO2 additions

    International Nuclear Information System (INIS)

    Morena, R.; Lockwood, P.E.; Evans, A.L.; Fairhurst, C.W.

    1986-01-01

    The effect of mechanical behavior of ZrO 2 additions to a dental porcelain was investigated. The ZrO 2 was introduced into the glassy matrix phase of the porcelain by refritting the all-glass porcelain constituent. X-ray diffraction indicated that a sizeable fraction of the ZrO 2 was retained in the tetragonal from after the porcelain was fired. Zirconia additions to the porcelain produced substantial improvements in fracture toughness, strength, and thermal shock resistance

  13. Synthesis, microstructure and mechanical properties of ceria stabilized tetragonal zirconia prepared by spray drying technique

    International Nuclear Information System (INIS)

    Sharma, S.C.; Gokhale, N.M.; Dayal, Rajiv; Lazl, Ramji

    2002-01-01

    Ceria stabilized zirconia powders with ceria concentration varying from 6 to 16 mol% were synthesized using spray drying technique. Powders were characterized for their particle size distribution and specific surface area. The dense sintered ceramics fabricated using these powders were characterized for their microstructure, crystallite size and phase composition. The flexural strength, fracture toughness and micro-hardness of sintered ceramics were measured. High fracture toughness and flexural strength were obtained for sintered bodies with 12 mol% of CeO 2 . Flexural strength and fracture toughness were dependent on CeO 2 concentration, crystallite size and phase composition of sintered bodies. Correlation of data has indicated that the transformable tetragonal phase is the key factor in controlling the fracture toughness and strength of ceramics. It has been demonstrated that the synthesis method is effective to prepare nanocrystalline tetragonal ceria stabilized zirconia powders with improved mechanical properties. Ce-ZrO 2 with 20 wt% alumina was also prepared with flexural strength, 1200 MPa and fracture toughness 9.2 MPa√m. (author)

  14. On the phase formation of sputtered hafnium oxide and oxynitride films

    International Nuclear Information System (INIS)

    Sarakinos, K.; Music, D.; Mraz, S.; Baben, M. to; Jiang, K.; Nahif, F.; Braun, A.; Zilkens, C.; Schneider, J. M.; Konstantinidis, S.; Renaux, F.; Cossement, D.; Munnik, F.

    2010-01-01

    Hafnium oxynitride films are deposited from a Hf target employing direct current magnetron sputtering in an Ar-O 2 -N 2 atmosphere. It is shown that the presence of N 2 allows for the stabilization of the transition zone between the metallic and the compound sputtering mode enabling deposition of films at well defined conditions of target coverage by varying the O 2 partial pressure. Plasma analysis reveals that this experimental strategy facilitates control over the flux of the O - ions which are generated on the oxidized target surface and accelerated by the negative target potential toward the growing film. An arrangement that enables film growth without O - ion bombardment is also implemented. Moreover, stabilization of the transition sputtering zone and control of the O - ion flux without N 2 addition is achieved employing high power pulsed magnetron sputtering. Structural characterization of the deposited films unambiguously proves that the phase formation of hafnium oxide and hafnium oxynitride films with the crystal structure of HfO 2 is independent from the O - bombardment conditions. Experimental and theoretical data indicate that the presence of vacancies and/or the substitution of O by N atoms in the nonmetal sublattice favor the formation of the cubic and/or the tetragonal HfO 2 crystal structure at the expense of the monoclinic HfO 2 one.

  15. Ferroelasticity of t'-zirconia. 1: High-voltage electron microscopy studies of the microstructure in polydomain tetragonal zirconia

    International Nuclear Information System (INIS)

    Baither, D.; Baufeld, B.; Messerschmidt, U.; Foitzik, A.H.; Ruehle, M.

    1997-01-01

    The microstructure of polydomain tetragonal zirconia (t'-ZrO 2 ), i.e., a ZrO 2 modification exhibiting ferroelastic behavior, is studied by high-voltage electron microscopy. This material consists of three domain variants of the tetragonal phase with their c-axes nearly orthogonal to each other. Always two variants of these platelike domains are alternately arranged, forming elongated regular colonies. Hence, in both variants the common habit plane of the domains is a {110} twin plane. The colonies are of columnar shape with a longitudinal axis. They are bound by {110} planes, too, which are twin planes for the domains in the contiguous colonies. Owing to their particular structure and the helical arrangement of the adjoining colonies, the material remains coherent and pseudocubic over large macroscopic regions, although it is formed by different tetragonal domains

  16. Unique Optical Properties of Methylammonium Lead Iodide Nanocrystals Below the Bulk Tetragonal-Orthorhombic Phase Transition.

    Science.gov (United States)

    Diroll, Benjamin T; Guo, Peijun; Schaller, Richard D

    2018-02-14

    Methylammonium (MA) and formamidinium (FA) lead halides are widely studied for their potential as low-cost, high-performance optoelectronic materials. Here, we present measurements of visible and IR absorption, steady state, and time-resolved photoluminescence from 300 K to cryogenic temperatures. Whereas FAPbI 3 nanocrystals (NCs) are found to behave in a very similar manner to reported bulk behavior, colloidal nanocrystals of MAPbI 3 show a departure from the low-temperature optical behavior of the bulk material. Using photoluminescence, visible, and infrared absorption measurements, we demonstrate that unlike single crystals and polycrystalline films NCs of MAPbI 3 do not undergo optical changes associated with the bulk tetragonal-to-orthorhombic phase transition, which occurs near 160 K. We find no evidence of frozen organic cation rotation to as low as 80 K or altered exciton binding energy to as low as 3 K in MAPbI 3 NCs. Similar results are obtained in MAPbI 3 NCs ranging from 20 to over 100 nm and in morphologies including cubes and plates. Colloidal MAPbI 3 NCs therefore offer a window into the properties of the solar-relevant, room-temperature phase of MAPbI 3 at temperatures inaccessible with single crystals or polycrystalline samples. Exploiting this phenomenon, these measurements reveal the existence of an optically passive photoexcited state close to the band edge and persistent slow Auger recombination at low temperature.

  17. The mechanical response of tetragonal zirconia polycrystal to conical indentation

    International Nuclear Information System (INIS)

    Asif, S.A.S.; Biswas, S.K.

    1994-01-01

    Blocks of 3Y-TZP were indented with conical diamond indenters. Indentation caused tetragonal to monoclinic phase transformation in a subsurface. Of the cracks generated in the subsurface, radial and lateral cracks can be accounted for by a continuum model of the indented subsurface, built using a combination of the Boussinesq and blister stress fields. Additional ring, median and cone cracks were also observed. It is hypothesized that the latter are motivated by the reduction in blister strength or residual energy brought about by the material damage caused by the phase transformation. This damage reduces the load bearing capacity of the material progressively with increasing normal load. (author). 13 refs., 5 figs., 2 tabs

  18. The oxidation kinetics and the structure of the oxide film on Zircaloy before and after the kinetic transition

    International Nuclear Information System (INIS)

    Arima, T.; Masuzumi, T.; Furuya, H.; Idemitsu, K.; Inagaki, Y.

    2001-01-01

    Oxidation kinetics of Zircaloy-4 have been measured using a micro-balance technique in CO-CO 2 gas mixtures between 450 deg. C and 600 deg. C. Oxidation kinetics of Zircaloy-4 obeyed a cubic rate law with time at 450-600 deg. C up to 24 h. At 600 deg. C, the kinetic transition occurred after about 36 h. After the transition, oxidation kinetics obeyed a linear rate law. X-ray diffraction patterns for the samples oxidized at 600 deg. C showed that the volume fraction of tetragonal phase of zirconia decreased with time until the kinetic transition occurred and was almost constant after that. In addition, stresses in the oxide films were found to be larger for the pre-transition samples than for the post-transition ones. (authors)

  19. Bi1−xNbxO1.5+x (x=0.0625, 0.12) fast ion conductors: Structures, stability and oxide ion migration pathways

    International Nuclear Information System (INIS)

    Tate, Matthew L.; Hack, Jennifer; Kuang, Xiaojun; McIntyre, Garry J.; Withers, Ray L.; Johnson, Mark R.; Radosavljevic Evans, Ivana

    2015-01-01

    A combined experimental and computational study of Bi 1−x Nb x O 1.5+x (x=0.0625 and 0.12) has been carried out using laboratory X-ray, neutron and electron diffraction, impedance measurements and ab-initio molecular dynamics. We demonstrate that Bi 0.9375 Nb 0.0625 O 1.5625 , previously reported to adopt a cubic fluorite-type superstructure, can form two different polymorphs depending on the synthetic method: a metastable cubic phase is produced by quenching; while slower cooling yields a stable material with a tetragonal √2×√2×1 superstructure, which undergoes a reversible phase transition into the cubic form at ~680 °C on subsequent reheating. Neutron diffraction reveals that the tetragonal superstructure arises mainly from ordering in the oxygen sublattice, with Bi and Nb remaining disordered, although structured diffuse scattering observed in the electron diffraction patterns suggests a degree of short-range ordering. Both materials are oxide ion conductors. On thermal cycling, Bi 0.88 Nb 0.12 O 1.62 exhibits a decrease in conductivity of approximately an order of magnitude due to partial transformation into the tetragonal phase, but still exhibits conductivity comparable to yttria-stabilised zirconia (YSZ). Ab-initio molecular dynamics simulations performed on Bi 0.9375 Nb 0.0625 O 1.5625 show that oxide ion diffusion occurs by O 2− jumps between edge- and corner-sharing OM 4 groups (M=Bi, Nb) via tetrahedral □M 4 and octahedral □M 6 vacancies. - Graphical abstract: Oxide ion migration in tetragonal Bi 0.9375 Nb 0.0625 O 1.5625 occurs by O 2− jumps between edge- and corner-sharing OM 4 groups (M=Bi, Nb) via tetrahedral M 4 and octahedral M 6 vacancies. - Highlights: • Bi 0.9375 Nb 0.0625 O 1.5625 adopts a tetragonal √2×√2×1 fluorite superstructure. • Superstructure is due to ordering in the O-sublattice, with Bi/Nb disordered. • Bi 0.9375 Nb 0.0625 O 1.5625 is a good oxide ion conductor. • O 2− jump between OM 4 groups (M

  20. Swift heavy ion induced phase transformation and thermoluminescence properties of zirconium oxide

    Energy Technology Data Exchange (ETDEWEB)

    Lokesha, H.S. [Physics R & D Centre, PES Institute of Technology, BSK 3rd Stage, Bangalore 560085 (India); Nagabhushana, K.R., E-mail: bhushankr@gmail.com [Physics R & D Centre, PES Institute of Technology, BSK 3rd Stage, Bangalore 560085 (India); Department of Physics, PES University, BSK 3rd Stage, Bangalore 560085 (India); Singh, Fouran [Inter University Accelerator Center, Aruna Asaf Ali Marg, New Delhi 110 067 (India)

    2016-07-15

    Zirconium oxide (ZrO{sub 2}) powder is synthesized by combustion technique. XRD pattern of ZrO{sub 2} shows monoclinic phase with average crystallite size 35 nm. Pellets of ZrO{sub 2} are irradiated with 100 MeV swift Si{sup 7+}, Ni{sup 7+} and 120 MeV swift Ag{sup 9+} ions in the fluence range 3 × 10{sup 10}–3 × 10{sup 13} ions cm{sup −2}. XRD pattern show the main diffraction peak correspond to monoclinic and tetragonal phase of ZrO{sub 2} in 2θ range 27–33°. Structural phase transformation is observed for Ni{sup 7+} and Ag{sup 9+} ion irradiated samples at a fluence 1 × 10{sup 13} ions cm{sup −2} and 3 × 10{sup 12} ions cm{sup −2} respectively, since the deposited electronic energy loss exceeds an effective threshold (>12 keV nm{sup −1}). Phase transition induced by Ag{sup 9+} ion is nearly 2.9 times faster than Ni{sup 7+} ion at 1 × 10{sup 13} ions cm{sup −2}. Ag{sup 9+} ion irradiation leads two ion impact processes. Thermoluminescence (TL) glow curves exhibit two glows, a well resolved peak at ∼424 K and unresolved peak at 550 K for all SHI irradiated samples. TL response is decreased with increase of ion fluence. Beyond 3 × 10{sup 12} ions cm{sup −2}, samples don’t exhibit TL due to annihilation of defects.

  1. Joining of yttria-tetragonal zirconia polycrystal with an aluminum-zirconium alloy

    International Nuclear Information System (INIS)

    Rathner, R.C.; Green, D.J.

    1990-01-01

    Specimens of yttria-tetragonal zirconia polycrystal (Y-TZP) have been joined with an Al-5.8 wt% Zr alloy at temperatures of 900 degrees C and above. The braze alloy contained large needlelike precipitates of the intermetallic phase Al 3 Sr. It is shown that these large precipitates can aid in strengthening of the joint, especially if they are close to the interface. With decreasing layer thickness, the strengths increased with values as high as 420 MPa

  2. Superconductivity in an anomalously tetragonal YB2C3O6.62 single crystal: A possible singularity in the structural phase diagram

    DEFF Research Database (Denmark)

    Frello, T.; Andersen, N.H.; Baziljevich, M.

    2003-01-01

    superconducting. This makes the sample highly anomalous in two respects: with a stoichiometry of YBa2Cu3O6.62 the sample should have an orthorhombic symmetry, and a tetragonal undoped sample should not be superconducting at all. Our results corroborate previous findings of Topnikov [JETP Lett. 46, 577 (1987......)] of a tetragonal superconducting YBCO crystal with x=0.62....

  3. Martensitic cubic → tetragonal transition

    International Nuclear Information System (INIS)

    Schumann, H.

    1983-01-01

    Indium-thallium alloys containing 14 to 30% At. Tl have a cubic face-centred beta phase wich changes into a tetragonal face-centred alpha martensite during solidification. The martensite contains twin crystals that are large enough to be seen by means of a light microscope. The phenomenological crystallographic martensite theory was used to calculate Miller's index of the habit plane, the formation of the surface relief, the orientation relations and the critical thickness ratio of the twins. In a beta monocrystal frequently only one of the 24 crystallographic possible habit planes are formed at one end of the sample and migrate through the whole crystal when the temperature drops. Externally applied tension and compression influence in different ways the direction in which the habit plane moves and can even destroy the twinned structure, i.e. they can modify the substructure of the martensite crystal. This induces superelasticity, an effect that has also been described quantitatively. (author)

  4. Kinetics of oxidic phase dissolution in acids

    International Nuclear Information System (INIS)

    Gorichev, I.G.; Kipriyanov, N.A.

    1981-01-01

    The critical analysis of the experimental data on dissolution kinetics of metal oxides (BeO, V 2 O 5 , UO 2 , Nb 2 O 5 , Ta 2 O 5 etc.) in acid media is carried out. Kinetic peculiarities of oxide dissolution are explained on the basis of the notions of electron- proton theory. It is established that the surface nonstoichiometric ccomposition of oxide phase and potential jump, appearing on the interface of the oxide-electrolyte phase are the important factors, determining the dissolution rate of a solid phase. The dissolution rate of metal oxides is limited by the transition of protons into the solid oxide phase. Morphological models of heterogeneous kinetics are used when explaining kinetic regularities of oxide dissolution process [ru

  5. Oxidation behavior of TiC, ZrC, and HfC dispersed in oxide matrices

    International Nuclear Information System (INIS)

    Arun, R.; Subramanian, M.; Mehrotra, G.M.

    1990-01-01

    The oxidation behavior of hot pressed TiC-Al 2 O 3 , TiC-ZrO 2 , ZrC-ZrO 2 , and HfC-HfO 2 composites has been investigated at 1273 K. The oxidation of TiC, ZrC, and HfC in hot-pressed composites containing ZrO 2 and HfO 2 has been found to be extremely rapid. The kinetics of oxidation of TiC and a 90 wt% TiC-Al 2 O 3 composite appear to be faster compared to that of pure TiC. X-ray diffraction results for hot-pressed ZrC-HfO 2 and HfC-HfO 2 composites indicate partial stabilization of tetragonal ZrO 2 and HfO 2 phases in these composites

  6. On the nature of phase transitions in the tetragonal tungsten bronze GdK{sub 2}Nb{sub 5}O{sub 15} ceramics

    Energy Technology Data Exchange (ETDEWEB)

    Gagou, Y.; Lukyanchuk, I.; El Marssi, M., E-mail: mimoun.elmarssi@u-picardie.fr [Laboratoire de Physique de la Matière Condensée, Université de Picardie Jules Verne, 33 rue Saint-Leu, 80039 Amiens Cedex (France); Amira, Y. [Laboratoire de Physique de la Matière Condensée, Université de Picardie Jules Verne, 33 rue Saint-Leu, 80039 Amiens Cedex (France); Laboratoire de la Matière Condensée et Nanostructures, FSTG, Université Cadi Ayyad Marrakech, Maroc (Morocco); Mezzane, D. [Laboratoire de la Matière Condensée et Nanostructures, FSTG, Université Cadi Ayyad Marrakech, Maroc (Morocco); Courty, M.; Masquelier, C. [Laboratoire de Réactivité et Chimie des Solides, UMR 7314, Université de Picardie Jules Verne, Pôle Scientifique, 33 rue Saint-Leu, 80039 Amiens Cedex 1 (France); Yuzyuk, Yu. I. [Faculty of Physics, Southern Federal University, 5, Zorge Str. Rostov-on-Don 344090 (Russian Federation)

    2014-02-14

    Phase transitions in gadolinium potassium niobate GdK{sub 2}Nb{sub 5}O{sub 15} (GKN) ceramics have been investigated by x-ray diffraction, dielectric susceptibility, differential scanning calorimetry, and Raman scattering. The results of our complementary studies show that GKN exhibits two phase transitions at T{sub c1} = 238 °C and T{sub c2} = 375 °C attributed to the ferroelectric-antiferroelectric-paraelectric (FE-AFE-PE) phase transitions. According to the x-ray diffraction analysis, the FE and PE phases were refined in the polar P4bm and centrosymmetric P4/mbm space groups. For the intermediate phase, the structure is refined in the space group P4nc with doubling of the c unit cell parameter, which is compatible with an AFE phase. This result was confirmed by Raman spectroscopy since new low-frequency lines are activated in the AFE phase due to the Brillouin zone-folding effect, typical for the modulated phases. The presence of the AFE phase between the FE and PE phases and the complex nature of tetragonal tungsten bronze crystal structure can explain the large thermal hysteresis observed at the FE-AFE transition between heating and cooling cycle and the strong depression of the Curie-Weiss temperature T{sub 0}. The semi-phenomenological Ising-like model based on the obtained experimental data is proposed to account for the observed FE-AFE-PE transition sequence.

  7. Preparation of macroporous zirconia monoliths from ionic precursors via an epoxide-mediated sol-gel process accompanied by phase separation

    International Nuclear Information System (INIS)

    Guo, Xingzhong; Song, Jie; Lvlin, Yixiu; Yang, Hui; Nakanishi, Kazuki; Kanamori, Kazuyoshi

    2015-01-01

    Monolithic macroporous zirconia (ZrO 2 ) derived from ionic precursors has been successfully fabricated via the epoxide-mediated sol-gel route accompanied by phase separation in the presence of propylene oxide (PO) and poly(ethylene oxide) (PEO). The addition of PO used as an acid scavenger mediates the gelation, whereas PEO enhances the polymerization-induced phase separation. The appropriate choice of the starting compositions allows the production of a macroporous zirconia monolith with a porosity of 52.9% and a Brunauer–Emmett–Teller (BET) surface area of 171.9 m 2 · g −1 . The resultant dried gel is amorphous, whereas tetragonal ZrO 2 and monoclinic ZrO 2 are precipitated at 400 and 600 °C, respectively, without spoiling the macroporous morphology. After solvothermal treatment with an ethanol solution of ammonia, tetragonal ZrO 2 monoliths with smooth skeletons and well-defined mesopores can be obtained, and the BET surface area is enhanced to 583.8 m 2 · g −1 . (paper)

  8. Grain size stabilization of tetragonal phase of zirconia in sputtered Zr-O cermet films

    International Nuclear Information System (INIS)

    Hadavi, M. S.; Keshmiri, H.; Kompany, A.; Zhang, Q. C.

    2005-01-01

    In this research, thin films of Zr/ZrO 2 composites were deposited by reactive magnetron sputtering technique on Si and fused Silica substrates, and their structures were investigated by x-ray diffraction method. During the deposition of the cermet layers, a Zr metallic target was sputtered in a gas mixture of Ar and O 2 . By controlling of O 2 flow rate, the different metal volume fractions in the cermet layers were achieved. The optical response of the samples was studied using spectroscopy methods. Also the effect of vacuum annealing on the structures and the optical properties were studies. x-ray diffraction results indicated that the prepared samples were amorphous and vacuum annealing induced crystallization in the cermet films. This research also show that without doping, the tetragonal phase of Zirconia can be stabilized at a temperature lower than the normal transition temperature. This is g rain size stabilization a nd relates to the small size of the crystallizes. In order to study the electron diffraction in the selected area patterns, the samples were analysed by a high-resolution transmission microscope. The selected area patterns results showed that all of the as prepared samples were amorphous showing evidence of very small Zr crystallites immersed in a dielectric medium. The Sad results are in close agreement with those obtained by x-ray diffraction analysis

  9. Grain size stabilization of tetragonal phase of zirconia in sputtered Zr- O cermet films

    Directory of Open Access Journals (Sweden)

    M. S. Hadavi

    2005-06-01

    Full Text Available  In this research, thin films of Zr/ZrO2 composites were deposited by reactive magnetron sputtering technique on Si and fused Silica substrates, and their structures were investigated by XRD method. During the deposition of the cermet layers, a Zr metallic target was sputtered in a gas mixture of Ar and O2. By controlling of O2 flow rate, the different metal volume fractions in the cermet layers were achieved. The optical response of the samples was studied using spectroscopy methods. Also the effect of vacuum annealing on the structures and the optical properties were studied. XRD results indicated that the prepared samples were amorphous and vacuum annealing induced crystallization in the cermet films. This research also showed that without doping, the tetragonal phase of zirconia can be stabilized at a temperature lower than the normal transition temperature. This is “grain size stabilization” and relates to the small size of the crystallites. In order to study the electron diffraction in the selected area patterns (SAD, the samples were analyzed by a high-resolution transmission microscope. The SAD results showed that all of the as prepared samples were amorphous showing evidence of very small Zr crystallites immersed in a dielectric medium.The SAD results are in close agreement with those obtained by XRD analysis.

  10. Oxidation phase growth diagram of vanadium oxides film fabricated by rapid thermal annealing

    Institute of Scientific and Technical Information of China (English)

    Tamura KOZO; Zheng-cao LI; Yu-quan WANG; Jie NI; Yin HU; Zheng-jun ZHANG

    2009-01-01

    Thermal evaporation deposited vanadium oxide films were annealed in air by rapid thermal annealing (RTP). By adjusting the annealing temperature and time, a series of vanadium oxide films with various oxidation phases and surface morphologies were fabricated, and an oxidation phase growth diagram was established. It was observed that different oxidation phases appear at a limited and continuous annealing condition range, and the morphologic changes are related to the oxidation process.

  11. Phase control of Mn-based spinel films via pulsed laser deposition

    International Nuclear Information System (INIS)

    Feng, Zhenxing; Chen, Xiao; Fister, Timothy T.; Bedzyk, Michael J.; Fenter, Paul

    2016-01-01

    Phase transformations in battery cathode materials during electrochemical-insertion reactions lead to capacity fading and low cycle life. One solution is to keep the same phase of cathode materials during cation insertion-extraction processes. Here, we demonstrate a novel strategy to control the phase and composition of Mn-based spinel oxides for magnesium-ion battery applications through the growth of thin films on lattice-matched substrates using pulsed laser deposition. Materials at two extreme conditions are considered: fully discharged cathode MgMn_2O_4 and fully charged cathode Mn_2O_4. The tetragonal MgMn_2O_4 (MMO) phase is obtained on MgAl_2O_4 substrates, while the cubic MMO phase is obtained on MgO substrates. Similarly, growth of the empty Mn_2O_4 spinel in the cubic phase is obtained on an MgO substrate. These results demonstrate the ability to control separately the phase of spinel thin films (e.g., tetragonal vs. cubic MMO) at nominally fixed composition, and to maintain a fixed (cubic) phase while varying its composition (MgxMn_2O_4, for x = 0, 1). As a result, this capability provides a novel route to gain insights into the operation of battery electrodes for energy storage applications.

  12. Thermal stability of simple tetragonal and hexagonal diamond germanium

    Science.gov (United States)

    Huston, L. Q.; Johnson, B. C.; Haberl, B.; Wong, S.; Williams, J. S.; Bradby, J. E.

    2017-11-01

    Exotic phases of germanium, that form under high pressure but persist under ambient conditions, are of technological interest due to their unique optical and electrical properties. The thermal evolution and stability of two of these exotic Ge phases, the simple tetragonal (st12) and hexagonal diamond (hd) phases, are investigated in detail. These metastable phases, formed by high pressure decompression in either a diamond anvil cell or by nanoindentation, are annealed at temperatures ranging from 280 to 320 °C for st12-Ge and 200 to 550 °C for hd-Ge. In both cases, the exotic phases originated from entirely pure Ge precursor materials. Raman microspectroscopy is used to monitor the phase changes ex situ following annealing. Our results show that hd-Ge synthesized via a pure form of a-Ge first undergoes a subtle change in structure and then an irreversible phase transformation to dc-Ge with an activation energy of (4.3 ± 0.2) eV at higher temperatures. St12-Ge was found to transform to dc-Ge with an activation energy of (1.44 ± 0.08) eV. Taken together with results from previous studies, this study allows for intriguing comparisons with silicon and suggests promising technological applications.

  13. Quantum Mechanical Calculations Of Elastic Properties Of Doped Tetragonal Yttria-Stabilized Zirconium Dioxide

    Directory of Open Access Journals (Sweden)

    Yuriy Natanzon

    2008-01-01

    Full Text Available We report first principles calculations of the electronic and elastic properties of yttriastabilized tetragonal zirconium dioxide doped with metal oxides like: GeO2, TiO2, SiO2,MgO and Al2O3. It is shown that addition of such dopants affects selected elastic propertiesof ZrO2, which is driven by the attraction of electron density by dopant atom and creationof stronger dopant–oxygen bonds. This effect contributes to the increase of superplasticityof doped material.

  14. Stress-induced martensitic transformation and ferroelastic deformation adjacent microhardness indents in tetragonal zirconia single crystals

    International Nuclear Information System (INIS)

    Chien, F.R.; Ubic, F.J.; Prakash, V.; Heuer, A.H.

    1998-01-01

    The stress-induced tetragonal to monoclinic (t → m) martensitic transformation, stress-induced ferroelastic domain switching, and dislocation slip were induced by Vickers microindentation at elevated temperatures in polydomain single crystals of 3 mol%-Y 2 O 3 -stabilized tetragonal ZrO 2 single crystals (3Y-TZS). Chemical etching revealed traces along t directions adjacent to indentations, and Raman spectroscopy and TEM have shown that these traces are caused by products of the martensitic transformation, i.e. the monoclinic product phase forms primarily as thin, long plates with a habit plane approximately on (bar 301) m . This habit plane and the associated shear strain arising from the transformation, visible in TEM micrographs at the intersection of crystallographically equivalent martensite plates, were successfully predicted using the observed lattice correspondence and the phenomenological invariant plane strain theory of martensitic transformations. The extent of the martensitic transformation increased with increasing temperature from room temperature up to 300 C, but then decreased at higher temperatures. Ferroelastic deformation of tetragonal ZrO 2 has been observed at all temperatures up to 1,000 C. At the highest temperature, only ferroelastic domain switching and dislocation slip occurred during indentation-induced deformation

  15. Sm/Ti co-substituted bismuth ferrite multiferroics: reciprocity between tetragonality and piezoelectricity.

    Science.gov (United States)

    Jha, Pardeep K; Jha, Priyanka A; Singh, Prabhakar; Ranjan, Rajeev; Dwivedi, R K

    2017-10-04

    BiFeO 3 (BFO) systems co-modified with Ti, Sm and Sm-Ti have been investigated for piezoelectricity together with dielectric and multiferroic properties. Structural studies revealed the coexistence of orthorhombic and rhombohedral (R3c) phases for x > 0.12. Impurity phases were shown to have hardly any effect on the remanent magnetization, which rather depends on the Fe-O-Fe bond angle. The dielectric loss was reduced considerably by substitution. A correlation between the piezoelectric coefficient and tetragonality was observed in these samples. BFO co-substituted with Sm-Ti exhibited a high piezoelectric coefficient with better ferroic properties, which revealed a unique combination of green piezoelectricity and multiferroicity.

  16. Room Temperature Monoclinic Phase in BaTiO3 Single Crystals

    Science.gov (United States)

    Denev, Sava; Kumar, Amit; Barnes, Andrew; Vlahos, Eftihia; Shepard, Gabriella; Gopalan, Venkatraman

    2010-03-01

    BaTiO3 is a well studied ferroelectric material for the last half century. It is well known to show phase transitions to tetragonal, orthorhombic and rhombohedral phases upon cooling. Yet, some old and some recent studies have argued that all these phases co-exist with a second phase with monoclinic distortion. Using optical second harmonic generation (SHG) at room temperature we directly present evidence for such monoclininc phase co-existing with tetragonal phase at room temperature. We observe domains with the expected tetragonal symmetry exhibiting 90^o and 180^o domain walls. However, at points of higher stress at the tips of the interpenetrating tetragonal domains we observe a well pronounced metastable ``staircase pattern'' with a micron-scale fine structure. Polarization studies show that this phase can be explained only by monoclinic symmetry. This phase is very sensitive to external perturbations such as temperature and fields, hence stabilizing this phase at room temperature could lead to large properties' tunability.

  17. Shape and phase evolution from CsPbBr3 perovskite nanocubes to tetragonal CsPb2Br5 nanosheets with an indirect bandgap.

    Science.gov (United States)

    Li, Guopeng; Wang, Hui; Zhu, Zhifeng; Chang, Yajing; Zhang, Ting; Song, Zihang; Jiang, Yang

    2016-09-13

    Tetragonal CsPb 2 Br 5 nanosheets were obtained by an oriented attachment of orthorhombic CsPbBr 3 nanocubes, involving a lateral shape evolution from octagonal to square. Meanwhile, the experimental results, together with DFT simulation results, indicated that the tetragonal CsPb 2 Br 5 is an indirect bandgap semiconductor that is PL-inactive with a bandgap of 2.979 eV.

  18. Instability of the layered orthorhombic post-perovskite phase of SrTiO3 and other candidate orthorhombic phases under pressure

    Science.gov (United States)

    Bhandari, Churna; Lambrecht, Walter R. L.

    2018-06-01

    While the tetragonal antiferro-electrically distorted (AFD) phase with space group I 4 / mcm is well known for SrTiO3 to occur below 105 K, there are also some hints in the literature of an orthorhombic phase, either at the lower temperature or at high pressure. A previously proposed orthorhombic layered structure of SrTiO3, known as the post-perovskite or CaIrO3 structure with space group Cmcm is shown to have significantly higher energy than the cubic or tetragonal phase and to have its minimum volume at larger volume than cubic perovskite. The Cmcm structure is thus ruled out. We also study an alternative Pnma phase obtained by two octahedral rotations about different axes. This phase is found to have slightly lower energy than the I 4 / mcm phase in spite of the fact that its parent, in-phase tilted P 4 / mbm phase is not found to occur. Our calculated enthalpies of formation show that the I 4 / mcm phase occurs at slightly higher volume than the cubic phase and has a negative transition pressure relative to the cubic phase, which suggests that it does not correspond to the high-pressure tetragonal phase. The enthalpy of the Pnma phase is almost indistinguishable from the I 4 / mcm phase. Alternative ferro-electric tetragonal and orthorhombic structures previously suggested in literature are discussed.

  19. Ferroelastic domain switching in tetragonal zirconia

    International Nuclear Information System (INIS)

    Chan, C.J.; Ruhle, M.; Jue, J.F.; Virkar, A.V.

    1991-01-01

    Ferroelastic domain switching is one of the possible toughening mechanisms in ceramic materials. Microstructural evidence of domain reorientation (switching) in polydomain tetragonal zirconia single crystals is observed upon the application of a unidirectional compressive stress. Dark field imaging of the three (112) tetragonal twin variants in a [111] zone indicates that two sets of twin variants grow at the expense of the third set upon application of uniaxial compression. The diminishing variant is the one with its c axis parallel to the compression axis. Indentation experiments on uniaxially compressed samples show an anisotropy in crack length. Crack propogates more easily along the loading direction. In this paper construction for the orientation relationship of domains and their twin boundaries is presented

  20. Protocol of thermal treatments for the recovery of tetragonal phase in infrastructures of dental prostheses base of ZrO{sub 2} (3-Y{sub 2}O{sub 3}) mills in CAD / CAM systems or panthories; Protocolo de tratamentos termicos visando recuperacao da fase tetragonal em infraestruturas de proteses dentarias a base de ZrO{sub 2}(3-Y{sub 2}O{sub 3}) fresadas em sistemas CAD/CAM ou pantografos

    Energy Technology Data Exchange (ETDEWEB)

    Simba, B.G.; Ferreira, B.; Santos, C. [Universidade de Sao Paulo (EEL/USP), Lorena, SP (Brazil). Escola de Engenharia; Costa, L. [Centro Universitario de Volta Redonda (MeMAT/UNIFOA), RJ (Brazil). Pro-Reitoria de Pesquisa e Extensao; Sa, L.F.C. de, E-mail: brgalvao@yahoo.com.br [PROTMAT Materiais Avancados, Volta Redonda, RJ (Brazil)

    2011-07-01

    ZrO{sub 2}(3%Y{sub 2}O{sub 3}) bioceramics are used as dental materials mainly as prosthesis components, because present high mechanical properties and translucence. The use of CAD/CAM machining technique needs final grinding which promotes tetragonal monoclinic transformation reducing the reliability of this ceramic. In this work, ZrO{sub 2}(3%Y{sub 2}O{sub 3}) ceramics were sintered at 1450-0h, 1530-2h or 1600-4h and characterized. Different heat-treatment (400-1200 deg C) are proposed aiming the recuperation of the tetragonal crystalline phase. (author)

  1. Crystal structure and properties of tetragonal EuAg4In8 grown by metal flux technique

    International Nuclear Information System (INIS)

    Subbarao, Udumula; Sarkar, Sumanta; Peter, Sebastian C.

    2015-01-01

    The compound EuAg 4 In 8 has been obtained as single crystals in high yield from reactions run in liquid indium. X-ray diffraction on single crystals suggests that EuAg 4 In 8 crystallizes in the CeMn 4 Al 8 structure type, tetragonal space group I4/mmm with lattice constants a=b=9.7937(2) Å and c=5.7492(2) Å. Crystal structure of EuAg 4 In 8 is composed of pseudo Frank–Kasper cages occupied by one europium atom in each ring, which are shared through the corner along the ab plane resulting in a three dimensional network. The magnetic susceptibility of EuAg 4 In 8 was measured in the temperature range 2–300 K, which obeyed Curie–Weiss law above 50 K. Magnetic moment value calculated from the fitting indicates the presence of divalent europium, which was confirmed by X-ray absorption near edge spectroscopy. Electrical resistivity measurements suggest that EuAg 4 In 8 is metallic in nature with a probable Fermi liquid behavior at low temperature. - Graphical abstract: The tetragonal EuAg 4 In 8 has been grown as single crystals from reactions run in liquid indium. Magnetic and XANES measurements suggest divalent nature of Eu and resistivity measurements suggest metallic nature. - Highlights: • EuAg 4 In 8 phase having tetragonal phase is grown by metal flux technique. • Magnetic and XANES measurements exhibit divalent nature of Eu in EuAg 4 In 8 . • Resistivity measurement suggests metallic nature and probable Fermi liquid behavior

  2. Oxidation kinetics of zirconium nitride. I. Planar symmetry

    International Nuclear Information System (INIS)

    Desmaison, Jean; Billy, Michel

    1976-01-01

    The oxidation behavior of ZrNsub(0.93) plates was investigated at temperatures in the range 625-800 deg C in oxygen over the pressure range 10-730 torr. The reaction product consists of monoclinic zirconia accompanied with trace amounts of cubic or tetragonal zirconia. Although the kinetic results are well interpreted by a Prout and Tompkins type model. The morphological observations suggest a transformation governed by a phase boundary reaction, this being confirmed by the oxygen pressure dependence on the rate law [fr

  3. The effect of Sn on autoclave corrosion performance and corrosion mechanisms in Zr–Sn–Nb alloys

    International Nuclear Information System (INIS)

    Wei, J.; Frankel, P.; Polatidis, E.; Blat, M.; Ambard, A.; Comstock, R.J.; Hallstadius, L.; Hudson, D.; Smith, G.D.W.; Grovenor, C.R.M.; Klaus, M.; Cottis, R.A.; Lyon, S.; Preuss, M.

    2013-01-01

    The desire to improve the corrosion resistance of Zr cladding material for high burn-up has resulted in a general trend among fuel manufacturers to develop alloys with reduced levels of Sn. While commonly accepted, the reason for the improved corrosion performance observed for low-tin zirconium alloys in high-temperature aqueous environments remains unclear. High-energy synchrotron X-ray diffraction was used to characterize the oxides formed by autoclave exposure on Zr–Sn–Nb alloys with tin concentration ranging from 0.01 to 0.92 wt.%. The alloys studied included the commercial alloy ZIRLO® (ZIRLO® is a registered trademark of Westinghouse Electric Company LLC in the USA and may be registered in other countries throughout the world. All rights reserved. Unauthorized use is strictly prohibited.) and two variants of ZIRLO with significantly lower tin levels, referred to here as A-0.6Sn and A-0.0Sn. The nature of the oxide grown on tube samples from each alloy was investigated via cross-sectional scanning electron microscopy. Atom probe analysis of ZIRLO demonstrated that the tin present in the alloy passes into the oxide as it forms, with no significant difference in the Sn/Zr ratio between the two. Synchrotron X-ray diffraction measurements on the oxides formed on each alloy revealed that the monoclinic and tetragonal oxide phases display highly compressive in-plane residual stresses with the magnitudes dependent on the phase and alloy. The amount of tetragonal phase present and, more importantly, the level of tetragonal-to-monoclinic phase transformation both decrease with decreasing tin levels, suggesting that tin is a tetragonal oxide phase stabilizing element. It is proposed that in Zr–Nb–Sn alloys with low Sn, the tetragonal phase is mainly stabilized by very small grain size and therefore remains stable throughout the corrosion process. In contrast, alloys with higher tin levels can in addition grow larger, stress stabilized, tetragonal grains that

  4. The role of microstructure and phase distribution in the failure mechanisms and life prediction model for PSZ coatings

    Science.gov (United States)

    Sisson, R. D., Jr.; Sone, Ichiro; Biederman, R. R.

    1985-01-01

    Partially Stabilized Zirconia (PSZ) may become widely used for Thermal Barrier Coatings (TBC). Failure of these coatings can occur due to thermal fatigue in oxidizing atmospheres. The failure is due to the strains that develop due to thermal gradients, differences in thermal expansion coefficients, and oxidation of the bond coating. The role of microstructure and the cubic, tetragonal, and monoclinic phase distribution in the strain development and subsequent failure will be discussed. An X-ray diffraction technique for accurate determination of the fraction of each phase in PSZ will be applied to understanding the phase transformations and strain development. These results will be discussed in terms of developing a model for life prediction in PSZ coatings during thermal cycling.

  5. Bi{sub 1−x}Nb{sub x}O{sub 1.5+x} (x=0.0625, 0.12) fast ion conductors: Structures, stability and oxide ion migration pathways

    Energy Technology Data Exchange (ETDEWEB)

    Tate, Matthew L. [Department of Chemistry, Durham University, Science Site, South Road, Durham DH1 3LE (United Kingdom); Australian Nuclear Science and Technology Organisation, Lucas Heights 2234, NSW (Australia); Hack, Jennifer [Department of Chemistry, Durham University, Science Site, South Road, Durham DH1 3LE (United Kingdom); Institut Laue-Langevin, Grenoble (France); Kuang, Xiaojun [Department of Chemistry, Durham University, Science Site, South Road, Durham DH1 3LE (United Kingdom); McIntyre, Garry J. [Australian Nuclear Science and Technology Organisation, Lucas Heights 2234, NSW (Australia); Withers, Ray L. [Research School of Chemistry, Australian National University, Canberra, ACT (Australia); Johnson, Mark R. [Institut Laue-Langevin, Grenoble (France); Radosavljevic Evans, Ivana, E-mail: ivana.radosavljevic@durham.ac.uk [Department of Chemistry, Durham University, Science Site, South Road, Durham DH1 3LE (United Kingdom); Australian Nuclear Science and Technology Organisation, Lucas Heights 2234, NSW (Australia)

    2015-05-15

    A combined experimental and computational study of Bi{sub 1−x}Nb{sub x}O{sub 1.5+x} (x=0.0625 and 0.12) has been carried out using laboratory X-ray, neutron and electron diffraction, impedance measurements and ab-initio molecular dynamics. We demonstrate that Bi{sub 0.9375}Nb{sub 0.0625}O{sub 1.5625}, previously reported to adopt a cubic fluorite-type superstructure, can form two different polymorphs depending on the synthetic method: a metastable cubic phase is produced by quenching; while slower cooling yields a stable material with a tetragonal √2×√2×1 superstructure, which undergoes a reversible phase transition into the cubic form at ~680 °C on subsequent reheating. Neutron diffraction reveals that the tetragonal superstructure arises mainly from ordering in the oxygen sublattice, with Bi and Nb remaining disordered, although structured diffuse scattering observed in the electron diffraction patterns suggests a degree of short-range ordering. Both materials are oxide ion conductors. On thermal cycling, Bi{sub 0.88}Nb{sub 0.12}O{sub 1.62} exhibits a decrease in conductivity of approximately an order of magnitude due to partial transformation into the tetragonal phase, but still exhibits conductivity comparable to yttria-stabilised zirconia (YSZ). Ab-initio molecular dynamics simulations performed on Bi{sub 0.9375}Nb{sub 0.0625}O{sub 1.5625} show that oxide ion diffusion occurs by O{sup 2−} jumps between edge- and corner-sharing OM{sub 4} groups (M=Bi, Nb) via tetrahedral □M{sub 4} and octahedral □M{sub 6} vacancies. - Graphical abstract: Oxide ion migration in tetragonal Bi{sub 0.9375}Nb{sub 0.0625}O{sub 1.5625} occurs by O{sup 2−} jumps between edge- and corner-sharing OM{sub 4} groups (M=Bi, Nb) via tetrahedral M{sub 4} and octahedral M{sub 6} vacancies. - Highlights: • Bi{sub 0.9375}Nb{sub 0.0625}O{sub 1.5625} adopts a tetragonal √2×√2×1 fluorite superstructure. • Superstructure is due to ordering in the O-sublattice, with Bi

  6. Diffusionless phase transitions and related structures in oxides

    International Nuclear Information System (INIS)

    Boulesteix, C.

    1992-01-01

    The relative importance of oxides in the field of materials science has been spectacularly increasing during the last twenty years. First the study of ferroelectrics kept the attention of scientists. Nevertheless this domain is far from being worked out and a lot of new results and of new fields of interest were recently discovered. Other ferroic oxides, especially ferroelastics, have also been the subject of a very great number of new results. In these cases the properties of oxides are at room temperature very tightly related to the phase transition that is generally occurring a few hundred of degrees above this room temperature. In many other cases also properties of oxides can be related to the existence of a phase transition or to a rather similar phenomenon. This book has been specially devoted to the study of the properties of oxides which are in some way related to the existence of a phase transition. The first chapters are focussed on general considerations: the first one is devoted to a general study of phase transitions, the second one to the twinning phenomenon which is of special interest for many oxides. Chapters 3 and 4 are focussed on ferroelectric and ferroelastic materials. These four chapters consitute the first part of the book. Chapters 5 to 8 are devoted to the study of oxides of special interest which have some of their properties related to a phase transition or to a rather similar phenomenon: rare earth oxides, oxides with a diffuse phase transition, zirconia and alumina systems, tungsten oxides and their relatives. These four chapters constitute the second part of the book. (orig.)

  7. Enhanced Hydrothermal Stability and Catalytic Activity of La x Zr y O z Mixed Oxides for the Ketonization of Acetic Acid in the Aqueous Condensed Phase

    Energy Technology Data Exchange (ETDEWEB)

    Lopez-Ruiz, Juan A. [Energy and Environment Directorate, Pacific Northwest National Laboratory, 902 Battelle Boulevard, Richland, Washington 99352, United States; Cooper, Alan R. [Energy and Environment Directorate, Pacific Northwest National Laboratory, 902 Battelle Boulevard, Richland, Washington 99352, United States; Li, Guosheng [Energy and Environment Directorate, Pacific Northwest National Laboratory, 902 Battelle Boulevard, Richland, Washington 99352, United States; Albrecht, Karl O. [Energy and Environment Directorate, Pacific Northwest National Laboratory, 902 Battelle Boulevard, Richland, Washington 99352, United States

    2017-08-24

    Common ketonization catalysts such as ZrO2, CeO2, CexZryOz, and TiO2-based catalysts have been reported to lose surface area, undergo phase-transformation, and lose catalytic activity when utilized in the condensed aqueous phase. In this work, we synthesized and tested a series of LaxZryOz mixed metal oxides with different La:Zr atomic ratios with the goal of enhancing the catalytic activity and stability for the ketonization of acetic acid in condensed aqueous media at 568 K. We synthesized a hydrothermally stable LaxZryOz mixed-metal oxide catalyst with enhanced ketonization activities 360 and 40 times more active than La2O3 and ZrO2, respectively. Catalyst characterization techniques suggest that the formation of a hydrothermally stable catalyst which is isomorphic with tetragonal-ZrO2 under hydrothermal reaction conditions.

  8. First-principles comparison of the cubic and tetragonal phases of Mo3Sb7

    KAUST Repository

    Nazir, Safdar; Auluck, Sushil V.; Pulikkotil, Jiji Thomas Joseph; Singh, Nirpendra; Schwingenschlö gl, Udo

    2011-01-01

    Using ab initio density functional based methods, we study the normal metal state properties of the ∼3 K Mo3Sb7 superconductor, in its high temperature cubic and low temperature tetragonal structures. Although the density of states at the Fermi energy is reasonably high in both structures, our calculations unequivocally show that there exists no long range magnetic ordering in this system. We also address the optical properties of the compound. The magnetism in Mo3Sb7 is studied by fixed spin moment calculations, which yield a shallow non-magnetic minimum, thus inferring propensity to a magnetic instability. © 2011 Elsevier B.V. All rights reserved.

  9. First-principles comparison of the cubic and tetragonal phases of Mo3Sb7

    KAUST Repository

    Nazir, Safdar

    2011-03-01

    Using ab initio density functional based methods, we study the normal metal state properties of the ∼3 K Mo3Sb7 superconductor, in its high temperature cubic and low temperature tetragonal structures. Although the density of states at the Fermi energy is reasonably high in both structures, our calculations unequivocally show that there exists no long range magnetic ordering in this system. We also address the optical properties of the compound. The magnetism in Mo3Sb7 is studied by fixed spin moment calculations, which yield a shallow non-magnetic minimum, thus inferring propensity to a magnetic instability. © 2011 Elsevier B.V. All rights reserved.

  10. Revealing the hidden structural phases of FeRh

    Science.gov (United States)

    Kim, Jinwoong; Ramesh, R.; Kioussis, Nicholas

    2016-11-01

    Ab initio electronic structure calculations reveal that tetragonal distortion has a dramatic effect on the relative stability of the various magnetic structures (C-, A-, G-, A'-AFM, and FM) of FeRh giving rise to a wide range of novel stable/metastable structures and magnetic phase transitions between these states. We predict that the cubic G-AFM structure, which was believed thus far to be the ground state, is metastable and that the tetragonally expanded G-AFM is the stable structure. The low energy barrier separating these states suggests phase coexistence at room temperature. We propose an A'-AFM phase to be the global ground state among all magnetic phases which arises from the strain-induced tuning of the exchange interactions. The results elucidate the underlying mechanism for the recent experimental findings of electric-field control of magnetic phase transition driven via tetragonal strain. The magnetic phase transitions open interesting prospects for exploiting strain engineering for the next-generation memory devices.

  11. Retention at room temperature of the tetragonal t''-form in Sc{sub 2}O{sub 3}-doped ZrO{sub 2} nanopowders

    Energy Technology Data Exchange (ETDEWEB)

    Abdala, Paula M., E-mail: pabdala@citefa.gov.a [CINSO (Centro de Investigaciones en Solidos), CITEFA-CONICET, J.B. de La Salle 4397, 1603 Villa Martelli, Pcia. de Buenos Aires (Argentina); Lamas, Diego G. [CINSO (Centro de Investigaciones en Solidos), CITEFA-CONICET, J.B. de La Salle 4397, 1603 Villa Martelli, Pcia. de Buenos Aires (Argentina); Fantini, Marcia C.A.; Craievich, Aldo F. [Instituto de Fisica, FAP, USP, Travessa R da Rua do Matao, No. 187, Cidade Universitaria, 05508-900 Sao Paulo (Brazil)

    2010-04-16

    Synchrotron X-ray powder diffraction was applied to the study of the effect of crystallite size on the crystal structure of ZrO{sub 2}-10 mol% Sc{sub 2}O{sub 3} nanopowders synthesized by a nitrate-lysine gel-combustion route. Nanopowders with different average crystallite sizes were obtained by calcination at several temperatures, ranging from 650 to 1200 {sup o}C. The metastable t''-form of the tetragonal phase, exhibiting a cubic unit cell and tetragonal P4{sub 2}/nmc spatial symmetry, was retained at room temperature in fine nanocrystalline powders, completely avoiding the presence of the stable rhombohedral {beta} phase. Differently, this phase was identified in samples calcined at high temperatures and its content increased with increasing crystallite size. The critical maximum crystallite size for the retention of the mestastable t''-form resulted of about 35 nm.

  12. Problems of selectivity in liquid-phase oxidation

    Energy Technology Data Exchange (ETDEWEB)

    Emanuel, N M

    1978-07-01

    Based on a kinetic analysis of a generalized scheme for radical-chain process and on published experimental results, factors determining the selectivities of various liquid-phase oxidations of organic compounds are examined, including the kinetic chain length, molecular and chain decomposition of products, and competing routes in the initiated oxidation or autoxidation of hydrocarbons to peroxides. Also discussed are selective inhibition of undesirable routes in chain reactions, e.g., styrene and acetaldehyde co-oxidation; activation of molecular oxygen by variable-valence metal compounds used as homogeneous catalysts; modeling of fermentative processes by oxidation of hydrocarbons in complex catalytic systems, e.g., hydroxylation of alkanes, epoxidation or carbonylation of olefins, or oxidation of alcohols and ketones to acids; and the mechanisms of heterogeneous catalysis in liquid-phase reactions, e.g., oxidation of alkylaromatic hydrocarbons to peroxides and co-oxidation of propylene and acetaldehyde.

  13. Effect of superconductivity on the cubic to tetragonal structural transition due to a two-fold degenerate electronic band

    International Nuclear Information System (INIS)

    Ghatak, S.K.; Khanra, B.C.; Ray, D.K.

    1978-01-01

    The effect of the BCS superconductivity on the cubic to tetragonal structural transition arising from a two-fold degenerate electronic band is investigated within the mean field approximation. The phase diagram of the two transitions is given for a half filled esub(g)-band. Modification of the two transitions when they are close together is also discussed. (author)

  14. CeO2-stabilized tetragonal ZrO2 polycrystals (Ce-TZP ceramics)

    International Nuclear Information System (INIS)

    Andrade Nono, M.C. de.

    1990-12-01

    This work presents the development and the characterization of CeO 2 -stabilized tetragonal ZrO 2 polycrystals (Ce-TZP ceramics), since it is considered candidate material for applications as structural high performance ceramics. Sintered ceramics were fabricated from mixtures of powders containing different CeO 2 content prepared by conventional and nonconventional techniques. These powders and their resultant sintered ceramics were specified by chemical and physical characterization, compactation state and mechanical properties. The chemical characteristics were determined by chemical analysis and the physical characteristics were evaluated by phase content, particle and agglomerate size and aspect, and powder porosity. (author)

  15. Characterization of a Diamond Ground Y-TZP and Reversion of the Tetragonal to Monoclinic Transformation.

    Science.gov (United States)

    Candido, L M; Fais, Lmg; Ferreira, E B; Antonio, S G; Pinelli, Lap

    To characterize the surface of an yttria-stabilized zirconia (Y-TZP) ceramic after diamond grinding in terms of its crystalline phase, morphology, mean roughness (Ra), and wettability as well as to determine a thermal treatment to reverse the resulting tetragonal to monoclinic (t-m) transformation. Y-TZP specimens were distributed into different groups according to the actions (or no action) of grinding and irrigation. Grinding was accomplished using a diamond stone at a low speed. The samples were characterized by x-ray diffraction (XRD), scanning electron microscopy, goniometry, and profilometry. In situ high-temperature XRD was used to determine an annealing temperature to reverse the t-m transformation. Ra was submitted to the Kruskal-Wallis test, followed by the Dunn test (α=0.05). The volume fraction of the monoclinic phase and contact angle were submitted to one-way analysis of variance, followed by the Tukey test (α=0.05). Monoclinic zirconia was observed on the surface of samples after dry and wet grinding with a diamond stone. The volume fraction of the monoclinic phase was smaller on the dry ground samples (3.6%±0.3%) than on the wet ground samples (5.6%±0.3%). High-temperature XRD showed reversion of the t-m phase transformation, which started at 700°C and completed at 800°C in a conventional oven. Grinding with a diamond stone partially transformed the crystalline phase on the surface of a Y-TZP ceramic from tetragonal to monoclinic zirconia while simultaneously increasing the surface roughness and wettability. The t-m transformation could be reversed by heat treatment at 800°C or 900°C for 60 minutes or 1000°C for 30 minutes.

  16. Structural phase transitions in niobium oxide nanocrystals

    Science.gov (United States)

    Yuvakkumar, R.; Hong, Sun Ig

    2015-09-01

    Niobium oxide nanocrystals were successfully synthesized employing the green synthesis method. Phase formation, microstructure and compositional properties of 1, 4 and 7 days incubation treated samples after calcinations at 450 °C were examined using X-ray diffraction, Raman, photoluminescence (PL), infrared, X-ray photoelectron spectra and transmission electron microscopic characterizations. It was observed that phase formation of Nb2O5 nanocrystals was dependent upon the incubation period required to form stable metal oxides. The characteristic results clearly revealed that with increasing incubation and aging, the transformation of cubic, orthorhombic and monoclinic phases were observed. The uniform heating at room temperature (32 °C) and the ligation of niobium atoms due to higher phenolic constituents of utilized rambutan during aging processing plays a vital role in structural phase transitions in niobium oxide nanocrystals. The defects over a period of incubation and the intensities of the PL spectra changing over a period of aging were related to the amount of the defects induced by the phase transition.

  17. In situ Raman Spectroscopy of Oxide Films on Zirconium Alloy in Simulated PWR Primary Water Condition

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Tae Ho; Choi, Kyoung Joon; Yoo, Seung Chang; Kim, Ji Hyun [UNIST, Ulsan (Korea, Republic of)

    2016-05-15

    The two layered oxide structure is formed in pre-transition oxide for the zirconium alloy in high temperature water environment. It is known that the corrosion rate is related to the volume fraction of zirconium oxide and the pores in the oxides; therefore, the aim of this paper is to investigate the oxidation behavior in the pretransition zirconium oxide in high-temperature water chemistry. In this work, Raman spectroscopy was used for in situ investigations for characterizing the phase of zirconium oxide. In situ Raman spectroscopy is a well-suited technique for investigating in detail the characteristics of oxide films in a high-temperature corrosion environment. In previous studies, an in situ Raman system was developed for investigating the oxides on nickel-based alloys and low alloy steels in high-temperature water environment. Also, the early stage oxidation behavior of zirconium alloy with different dissolved hydrogen concentration environments in high temperature water was treated in the authors' previous study. In this study, a specific zirconium alloy was oxidized and investigated with in situ Raman spectroscopy for 100 d oxidation, which is close to the first transition time of the zirconium alloy oxidation. The ex situ investigation methods such as transmission electron microscopy (TEM) and energy dispersive X-ray spectroscopy (EDS) were used to further characterize the zirconium oxide structure. As oxidation time increased, the Raman peaks of tetragonal zirconium oxide were merged or became weaker. However, the monoclinic zirconium oxide peaks became distinct. The tetragonal zirconium oxide was just found near the O/M interface and this could explain the Raman spectra difference between the 30 d result and others.

  18. Defect-induced local variation of crystal phase transition temperature in metal-halide perovskites.

    Science.gov (United States)

    Dobrovolsky, Alexander; Merdasa, Aboma; Unger, Eva L; Yartsev, Arkady; Scheblykin, Ivan G

    2017-06-26

    Solution-processed organometal halide perovskites are hybrid crystalline semiconductors highly interesting for low-cost and efficient optoelectronics. Their properties are dependent on the crystal structure. Literature shows a variety of crystal phase transition temperatures and often a spread of the transition over tens of degrees Kelvin. We explain this inconsistency by demonstrating that the temperature of the tetragonal-to-orthorhombic phase transition in methylammonium lead triiodide depends on the concentration and nature of local defects. Phase transition in individual nanowires was studied by photoluminescence microspectroscopy and super-resolution imaging. We propose that upon cooling from 160 to 140 K, domains of the crystal containing fewer defects stay in the tetragonal phase longer than highly defected domains that readily transform to the high bandgap orthorhombic phase at higher temperatures. The existence of relatively pure tetragonal domains during the phase transition leads to drastic photoluminescence enhancement, which is inhomogeneously distributed across perovskite microcrystals.Understanding crystal phase transition in materials is of fundamental importance. Using luminescence spectroscopy and super-resolution imaging, Dobrovolsky et al. study the transition from the tetragonal to orthorhombic crystal phase in methylammonium lead triiodide nanowires at low temperature.

  19. Synthesis and properties of oxide /beta/-V/sub 2/O/sub 5/

    Energy Technology Data Exchange (ETDEWEB)

    Volkov, V L; Golovkin, B G; Fedyukov, A S; Zajnulin, Yu G

    1988-11-01

    Orthorhombic vanadium (5) oxide crystallizes in tetragonal syngony with elementary cell parameters: a=14.259+-0.006 and c=(12.576+-0.006) A, at 873 K temperature and pressure over 3.5 GPa. /beta/-V/sub 2/O/sub 5/ phase is stable up to 573 K under normal conditions. IR spectra and temperature dependence of /beta/-V/sub 2/O/sub 5/ electric conductivity are investigated. At temperatures over 458 K its electric conductivity is of inactivation character.

  20. Local atomic structure in tetragonal pure ZrO{sub 2} nanopowders

    Energy Technology Data Exchange (ETDEWEB)

    Acuna, Leandro M.; Lamas, Diego G.; Fuentes, Rodolfo O.; Fabregas, Ismael O. [CITEFA-CONICET, Villa Martelli, Provincia de Buenos Aires (AR). CINSO (Centro de Investigaciones en Solidos); Fantini, Marcia C.A.; Craievich, Aldo F. [Universidade de Sao Paulo (Brazil). Inst. de Fisica; Prado, Rogerio J. [Universidade Federal de Mato Grosso (UFMT), Cuiaba (Brazil). Inst. de Fisica

    2010-04-15

    The local atomic structures around the Zr atom of pure (undoped) ZrO{sub 2} nanopowders with different average crystallite sizes, ranging from 7 to 40 nm, have been investigated. The nanopowders were synthesized by different wetchemical routes, but all exhibit the high-temperature tetragonal phase stabilized at room temperature, as established by synchrotron radiation X-ray diffraction. The extended X-ray absorption fine structure (EXAFS) technique was applied to analyze the local structure around the Zr atoms. Several authors have studied this system using the EXAFS technique without obtaining a good agreement between crystallographic and EXAFS data. In this work, it is shown that the local structure of ZrO{sub 2} nanopowders can be described by a model consisting of two oxygen subshells (4+4 atoms) with different Zr-O distances, in agreement with those independently determined by X-ray diffraction. However, the EXAFS study shows that the second oxygen subshell exhibits a Debye-Waller (DW) parameter much higher than that of the first oxygen subshell, a result that cannot be explained by the crystallographic model accepted for the tetragonal phase of zirconia-based materials. However, as proposed by other authors, the difference in the DW parameters between the two oxygen subshells around the Zr atoms can be explained by the existence of oxygen displacements perpendicular to the z direction; these mainly affect the second oxygen subshell because of the directional character of the EXAFS DW parameter, in contradiction to the crystallographic value. It is also established that this model is similar to another model having three oxygen subshells, with a 4+2+2 distribution of atoms, with only one DW parameter for all oxygen subshells. Both models are in good agreement with the crystal structure determined by X-ray diffraction experiments. (orig.)

  1. A microstuctural study on accelerated zirconium alloy oxidation

    International Nuclear Information System (INIS)

    Sohn, Seung Bum; Oh, Seung Jun; Jang, Jung Nam; Kim, Yong Soo; Jung, Yong Hwan; Baek, Jong Hyuk; Park, Jung Yong

    2005-01-01

    It has been reported that the effect of thermal redistribution of hydrides across the zirconium metaloxide interface, coupled with thermal feedback on the metal-oxide interface, is a dominating factor in the accelerated oxidation in zirconium alloys cladding PWR fuel. Basically this influence determines characteristic of oxide layer. Influence estimation for corrosion oxide layer due to hydrogen / hydride carried out because of investigation on the kinetic on accelerated oxidation due to hydride precipitation was preceded. Generally, it is known that ZrO 2 tetragonal layer structures play an important role as a barrier layer. So analysing the ZrO 2 monoclinic and tetragonal structure distribution is our main aim. Especially, this study focused on the hydride effects. In other words, the difference of crystal structure distribution between pre-hydrided and without hydrided specimen is just expected results. Experimental results of microstructure at zirconium metal-oxide interface through TEM and EBSD analysis was confirmed

  2. Direct visualization of phase separation between superconducting and nematic domains in Co-doped CaFe2As2 close to a first-order phase transition

    Science.gov (United States)

    Fente, Antón; Correa-Orellana, Alexandre; Böhmer, Anna E.; Kreyssig, Andreas; Ran, S.; Bud'ko, Sergey L.; Canfield, Paul C.; Mompean, Federico J.; García-Hernández, Mar; Munuera, Carmen; Guillamón, Isabel; Suderow, Hermann

    2018-01-01

    We show that biaxial strain induces alternating tetragonal superconducting and orthorhombic nematic domains in Co-substituted CaFe2As2 . We use atomic force, magnetic force, and scanning tunneling microscopy to identify the domains and characterize their properties, finding in particular that tetragonal superconducting domains are very elongated, more than several tens of micrometers long and about 30 nm wide; have the same Tc as unstrained samples; and hold vortices in a magnetic field. Thus, biaxial strain produces a phase-separated state, where each phase is equivalent to what is found on either side of the first-order phase transition between antiferromagnetic orthorhombic and superconducting tetragonal phases found in unstrained samples when changing Co concentration. Having such alternating superconducting domains separated by normal conducting domains with sizes of the order of the coherence length opens opportunities to build Josephson junction networks or vortex pinning arrays and suggests that first-order quantum phase transitions lead to nanometric-size phase separation under the influence of strain.

  3. Crystal structure relation between tetragonal and orthorhombic CsAlD{sub 4}: DFT and time-of-flight neutron powder diffraction studies

    Energy Technology Data Exchange (ETDEWEB)

    Bernert, Thomas; Krech, Daniel; Felderhoff, Michael; Weidenthaler, Claudia [Department of Heterogeneous Catalysis, Max-Planck-Institut fuer Kohlenforschung, Muelheim/Ruhr (Germany); Kockelmann, Winfried [Rutherford Appleton Laboratory, Harwell Oxford, Didcot (United Kingdom); Frankcombe, Terry J. [Research School of Chemistry, The Australian National University, Canberra, ACT (Australia); School of Physical, Environmental and Mathematic Sciences, The University of New South Wales, Canberra, ACT (Australia)

    2015-11-15

    The crystal structures of orthorhombic and tetragonal CsAlD{sub 4} were refined from time-of-flight neutron powder diffraction data starting from atomic positions predicted from DFT calculations. The earlier proposed crystal structure of orthorhombic CsAlH{sub 4} is confirmed. For tetragonal CsAlH{sub 4}, DFT calculations predicted a crystal structure in I4{sub 1}/amd as potential minimum structure, while from neutron diffraction studies of CsAlD{sub 4} best refinement is obtained for a disordered structure in the space group I4{sub 1}/a, with a = 5.67231(9) Aa, c = 14.2823(5) Aa. While the caesium atoms are located on the Wyckoff position 4b and aluminium at Wyckoff position 4a, there are two distinct deuterium positions at the Wyckoff position 16f with occupancies of 50 % each. From this structure, the previously reported phase transition between the orthorhombic and tetragonal polymorphs could be explained. (Copyright copyright 2015 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  4. High-pressure phase of the cubic spinel NiMn2O4

    DEFF Research Database (Denmark)

    Åsbrink, S.; Waskowska, A.; Olsen, J. Staun

    1998-01-01

    experimental uncertainty, there is no volume change at the transition. The cia ratio of the tetragonal spinel is almost independent of pressure and equal to 0.91. The phase transition is attributed to the Jahn-Teller-type distortion and the ionic configurationcan be assumed as (Mn3+)(tetr)[Ni2+Mn3+](oct......It has been observed that the fee spinel NiMn2O4 transforms to a tetragonal structure at about 12 GPa. The tetragonal phase does not revert to the cubic phase upon decompression and its unit-cell constants at ambient pressure are a(0)=8.65(8) and c(0)=7.88(15) Angstrom (distorted fee). Within thr......). The bulk modulus of the cubic phase is 206(4) GPa....

  5. Structural, magnetic and superconducting phase transitions in CaFe2As2 under ambient and applied pressure

    International Nuclear Information System (INIS)

    Canfield, P.C.; Bud'ko, S.L.; Ni, N.; Kreyssig, A.; Goldman, A.I.; McQueeney, R.J.; Torikachvili, M.S.; Argyriou, D.N.; Luke, G.; Yu, W.

    2009-01-01

    At ambient pressure CaFe 2 As 2 has been found to undergo a first order phase transition from a high temperature, tetragonal phase to a low-temperature orthorhombic/antiferromagnetic phase upon cooling through T ∼ 170 K. With the application of pressure this phase transition is rapidly suppressed and by ∼0.35 GPa it is replaced by a first order phase transition to a low-temperature collapsed tetragonal, non-magnetic phase. Further application of pressure leads to an increase of the tetragonal to collapsed tetragonal phase transition temperature, with it crossing room temperature by ∼1.7 GPa. Given the exceptionally large and anisotropic change in unit cell dimensions associated with the collapsed tetragonal phase, the state of the pressure medium (liquid or solid) at the transition temperature has profound effects on the low-temperature state of the sample. For He-gas cells the pressure is as close to hydrostatic as possible and the transitions are sharp and the sample appears to be single phase at low temperatures. For liquid media cells at temperatures below media freezing, the CaFe 2 As 2 transforms when it is encased by a frozen media and enters into a low-temperature multi-crystallographic-phase state, leading to what appears to be a strain stabilized superconducting state at low temperatures.

  6. Phase transformation in sol-gel prepared zirconia using in-situ high temperature X-ray diffraction

    International Nuclear Information System (INIS)

    Srinivasan, R.; Davis, B.H.; Hubbard, C.R.; Cavin, O.B.; Porter, W.D.

    1991-01-01

    Zirconia was precipitated at a pH of 10.5 by admixing a solution of ZrCl 4 and NH 4 OH both rapidly (∼ 1 min) and slowly (∼ 8 hr). The precipitate was calcined at 500C for 5 hours and then furnace cooled. The former exhibited monoclinic phase while the latter yielded tetragonal phase. The pathway from amorphous to crystalline form was followed by in-situ high temperature X-ray diffraction in flowing air and in He. The data showed the evolution of the tetragonal crystalline phase on heating. On rapid cooling the tetragonal phase is retained at R.T., and on slow cooling the transformation to monoclinic phase occurs in air

  7. Nanosized lead lanthanum titanate (PLT) ceramic powders synthesized by the oxidant peroxo method

    Energy Technology Data Exchange (ETDEWEB)

    Camargo, Emerson R. [LIEC-Laboratorio Interdisciplinar de Eletroquimica e Ceramica, Department of Chemistry, UFSCar-Federal University of Sao Carlos, Rod.Washingtin Luis km 235, CP 676, Sao Carlos SP 13565-9905 (Brazil)], E-mail: camargo@ufscar.br; Barrado, Cristiano M. [LIEC-Laboratorio Interdisciplinar de Eletroquimica e Ceramica, Department of Chemistry, UFSCar-Federal University of Sao Carlos, Rod.Washingtin Luis km 235, CP 676, Sao Carlos SP 13565-9905 (Brazil); Ribeiro, Caue [EMBRAPA Instrumentacao Agropecuaria, Rua XV de Novembro 1452, Sao Carlos SP 13560-970 (Brazil)], E-mail: caue@cnpdia.embrapa.br; Longo, Elson [Department of Biochemistry, Chemistry Institute of Araraquara, UNESP-Sao Paulo State University, Rua Francisco Degni, CP 355, Araraquara SP 14801-907 (Brazil)], E-mail: elson@iq.unesp.br; Leite, Edson R. [LIEC-Laboratorio Interdisciplinar de Eletroquimica e Ceramica, Department of Chemistry, UFSCar-Federal University of Sao Carlos, Rod.Washingtin Luis km 235, CP 676, Sao Carlos SP 13565-9905 (Brazil)], E-mail: derl@power.ufscar.br

    2009-05-05

    For the first time it is reported the synthesis of lead titanate modified with rare earth by the oxidant-peroxo method (OPM). Lanthanum was added up to 20% in mol through the dissolution of lanthanum oxide in nitric acid, followed by the addition of a solution of lead and lanthanum nitrate into an aqueous solution of titanium peroxo complexes. The amorphous precipitate formed was heat-treated at different temperatures in the range from 400 to 900 deg. C for crystallization. Powders were characterized by Raman spectroscopy and X-ray diffraction. Tetragonal perovskite structure was observed for the samples up to 15% of lanthanum substitution and cubic perovskite for sample with 20% of lanthanum. Crystallographic domains calculated by Scherrer equation showing a probable suppression of the crystallite growth in function of lanthanum content. It was observed shifting to lower frequencies of Raman modes in the range between 100 and 400 cm{sup -1} and the vanishing of the A1(2TO) and E(1LO) modes could be attributed to transition phase from tetragonal to cubic. Electronic microscopy image revealed that the powders annealed at height temperature are spherical with sharp size distribution.

  8. Nanosized lead lanthanum titanate (PLT) ceramic powders synthesized by the oxidant peroxo method

    International Nuclear Information System (INIS)

    Camargo, Emerson R.; Barrado, Cristiano M.; Ribeiro, Caue; Longo, Elson; Leite, Edson R.

    2009-01-01

    For the first time it is reported the synthesis of lead titanate modified with rare earth by the oxidant-peroxo method (OPM). Lanthanum was added up to 20% in mol through the dissolution of lanthanum oxide in nitric acid, followed by the addition of a solution of lead and lanthanum nitrate into an aqueous solution of titanium peroxo complexes. The amorphous precipitate formed was heat-treated at different temperatures in the range from 400 to 900 deg. C for crystallization. Powders were characterized by Raman spectroscopy and X-ray diffraction. Tetragonal perovskite structure was observed for the samples up to 15% of lanthanum substitution and cubic perovskite for sample with 20% of lanthanum. Crystallographic domains calculated by Scherrer equation showing a probable suppression of the crystallite growth in function of lanthanum content. It was observed shifting to lower frequencies of Raman modes in the range between 100 and 400 cm -1 and the vanishing of the A1(2TO) and E(1LO) modes could be attributed to transition phase from tetragonal to cubic. Electronic microscopy image revealed that the powders annealed at height temperature are spherical with sharp size distribution.

  9. Phase-field modeling of corrosion kinetics under dual-oxidants

    Science.gov (United States)

    Wen, You-Hai; Chen, Long-Qing; Hawk, Jeffrey A.

    2012-04-01

    A phase-field model is proposed to simulate corrosion kinetics under a dual-oxidant atmosphere. It will be demonstrated that the model can be applied to simulate corrosion kinetics under oxidation, sulfidation and simultaneous oxidation/sulfidation processes. Phase-dependent diffusivities are incorporated in a natural manner and allow more realistic modeling as the diffusivities usually differ by many orders of magnitude in different phases. Simple free energy models are then used for testing the model while calibrated free energy models can be implemented for quantitative modeling.

  10. Effect of grinding and polishing on near-surface phase transformations in zirconia

    International Nuclear Information System (INIS)

    Reed, J.S.; Lejus, A.M.

    1977-01-01

    The transformation of near-surface material on grinding and polishing has been investigated in sintered zirconia of 1 μm grain size and 99 percent density containing 4.5 and 7.0 mole percent Y 2 O 3 . Rough wet and dry grinding transformed about 20 percent cubic phase into 18 percent tetragonal and 2 percent monoclinic in material initially 47 percent cubic and 53 percent tetragonal (4.5 mole percent Y 2 O 3 ) but no change of phase in material that was fully cubic (7.0 mole percent Y 2 O 3 ). Annealing and polishing reduced lattice strain but only polishing reduced the concentration of monoclinic and tetragonal phases. Microhardness studies indicated that lattice strain and the phase transformations increased the penetration hardness to a depth of about 4 μm

  11. Phase Transformation of Hot Dipped Aluminium during High Temperature Oxidation

    International Nuclear Information System (INIS)

    Zaifol Samsu; Muhammad Daud; Hishamuddin Husain; Mohd Saari Ripin; Rusni Rejab; Zaiton Selamat; Mohd Shariff Sattar

    2014-01-01

    Low alloy carbon steel was coated by hot-dipping into a molten aluminum bath. Isothermal oxidations were carried out at 750 degree Celsius in static air to study the oxidation behaviour of the hot-dipped aluminide steel. The phase transformation in the aluminide layer during diffusion at 750 degree Celsius in static air was analyzed by SEM-EDX and XRD. After hot-dip treatment, the coating layers consisted of three phases, where Al, thinner layer of FeAl 3 , and thicker layer of Fe 2 Al 5 were detected from external topcoat to the aluminide/ steel substrate. After oxidation, the Fe 2 Al 5 formed during the immersion process completely transformed to Fe 2 Al 5 , FeAl 2 , FeAl and Al-Fe(Al) phases because of the composition gradient and the chemical diffusion by oxidation. After oxidation, there are some voids were found at the coating/ substrate interface due to the rapid inter-diffusion of iron and aluminium during oxidation. The FeAl phase kept growing with increasing exposure time at 750 degree Celsius, while the Fe 2 Al 5 was consumed during oxidation. After 168 hrs oxidation, the Fe 2 Al 5 phase was going disappeared as the aluminum layer was consumed. (author)

  12. Thermodynamics of the tetragonal to monoclinic phase transformation in constrained zirconia microcrystals

    International Nuclear Information System (INIS)

    Garvie, R.C.; Swain, M.V.

    1985-01-01

    End-point thermodynamic analyses were made of the tetragonal to monoclinic transformation (t -> m) occurring in ZrO 2 precipitates in a Ca-PSZ alloy and particles in Al 2 O 3 -ZrO 2 composites. Calculated plots of the reciprocal critical size for transformation temperature were in excellent agreement with experiment data for both systems. Contributions to the total free energy change included bulk chemical, dilatational and residual shear strain energies and also interfacial energies. The latter term consisted of contributions from the change in the chemical surface free energy, the presence of twin boundaries in the precipitate (particle) - matrix interfacial energy. The major impediment to the transformation was the shear strain energy which could not be reduced sufficiently by twinning alone. The t -> m reaction proceeded spontaneously when the energy barrier was reduced by the response of the particle - matrix interface. The response comprised loss of coherency and grain boundary microcracking for the Ca/PSZ and Al 2 O 3 -ZrO 2 alloys, respectively. These results are in accord with recent suggestions that either a stress-free strain or a free surface is a necessary condition for the initiation of a martensitic transformation. (author)

  13. Corrosion Behavior and Oxide Properties of Zr-Nb-Cu and Zr-Nb-Sn Alloy in High Dissolved Hydrogen Primary Water Chemistry

    Energy Technology Data Exchange (ETDEWEB)

    Lee, Yun Ju; Kim, Tae Ho; Kim, Ji Hyun [UNIST, Ulsan (Korea, Republic of)

    2016-05-15

    The water-metal interface is regarded as rate-controlling site governing the rapid oxidation transition in high burn-up fuel. And the zirconium oxide is made in water-metal interface and its structure and phase do an important role in terms of oxide properties. During oxidation process, the protective tetragonal oxide layer develops at the interface due to accumulated high stress during oxide growth, and it turns into non-protective monoclinic oxide with increasing oxide thickness, thus decreasing the stress. It has been reported that Nb addition was proven to be very beneficial for increasing the corrosion resistance of the zirconium alloys. From a more recent study, Cu addition in Nb containing Zirconium alloy was reported to be effective for increasing corrosion resistance in water containing B and Li. According to the previous research conducted, Zr-Nb-Cu shows better corrosion resistance than Zircaloy-4. The dissolved hydrogen (DH) concentration is the key issue of primary water chemistry, and the effect of DH concentration on the corrosion rate of nickel based alloy has been researched. However, the effect of DH on the zirconium alloy corrosion mechanism was not fully investigated. In this study, the weight gain measurement, FIB-SEM analysis, and Raman spectroscopic measurement were conducted to investigate the effects of dissolved hydrogen concentration and the chemical composition on the corrosion resistance and oxide phase of Zr-Nb-Cu alloy and Zr-Nb-Sn alloy after oxidizing in a primary water environment for 20 d. The corrosion rate of Zr-Nb-Cu alloy is slow, when it is compared to Zr-Nb-Sn alloy. In SEM images, the oxide thickness of Zr-Nb-Cu alloy is measured to be around 1.06 μm it of Zr-Nb-Sn alloy is measured to be 1.15 μm. It is because of the Segregation made by Sn solute element when Sn solute element oxidized. And according to ex situ Raman spectra, Zr-Nb-Cu alloy oxide has more tetragonal zirconium oxide fraction than Zr-Nb-Sn alloy oxide.

  14. Phase characterization of precipitated zirconia

    International Nuclear Information System (INIS)

    Gutzov, S.; Ponahlo, J.; Lengauer, C.L.; Beran, A.

    1994-01-01

    The phase compositions of undoped and europium-doped zirconia samples, obtained by precipitation and thermal treatment from 350 to 1,000 C, have been investigated by powder X-ray diffractometry, infrared spectroscopy, and cathodoluminescence spectroscopy. The low-temperature stabilization of tetragonal zirconia is mainly controlled by the presence of anion additives, such as ammonium chloride. The influences of the crystallite size is less important. Cathodoluminescence spectra show a structural similarity between tetragonal and amorphous zirconia

  15. Order-disorder phase transition in ZrV2Dsub(3.6)

    International Nuclear Information System (INIS)

    Didisheim, J.-J.; Yvon, K.; Tissot, P.

    1981-01-01

    The deuterated C15-type Laves phase ZrV 2 Dsub(3.6) undergoes a structural phase transition near room temperature (T of the order of 325 K). In the cubic high-temperature phase the deuterium atoms are disordered over two types of tetrahedral interstices, the centres of which are 1.3 A apart. In the tetragonal low-temperature phase the D atoms are ordered and occupy only the energetically more favourable interstices. The tetragonal structure is isotypic with the low-temperature phase of HfV 2 D 4 . The shortest D-D distance is 2.1 A. (author)

  16. Co-existence of tetragonal and monoclinic phases and multiferroic properties for x ⩽ 0.30 in the (1 − x)Pb(Zr{sub 0.52}Ti{sub 0.48})O{sub 3}–(x)BiFeO{sub 3} system

    Energy Technology Data Exchange (ETDEWEB)

    Sharma, Subhash; Singh, Vikash [Department of Physics and Materials Science and Engineering, Jaypee Institute of Information Technology, A-10, Sector-62, Noida 201307, Uttar Pradesh (India); Kotnala, R.K. [National Physical Laboratory (CSIR), Dr. K.S. Krishnan Marg, New Delhi 110012 (India); Ranjan, Rajeev [Department of Materials Engineering, Indian Institute of Science, Bangalore 560012 (India); Dwivedi, R.K., E-mail: rk.dwivedi@jiit.ac.in [Department of Physics and Materials Science and Engineering, Jaypee Institute of Information Technology, A-10, Sector-62, Noida 201307, Uttar Pradesh (India)

    2014-11-25

    Highlights: • Synthesis of (1 − x)PbZr{sub 0.52}Ti{sub 0.48}O{sub 3}–(x)BiFeO{sub 3} with x ⩽ 0.30 by sol–gel method. • Structural phase transformation with x has been revealed by Rietveld analysis. • Raman analysis supports structural phase transition. • Occurrence of MC is a strong evidence of magneto-electric coupling. • Enhance magnetization is obtained in the dominant monoclinic phase for x ⩾0.15. - Abstract: Compositions with x ⩽ 0.30 in the system (1 − x)Pb(Zr{sub 0.52}Ti{sub 0.48})O{sub 3}–(x)BiFeO{sub 3} were synthesized by sol–gel method. Rietveld analysis of X-ray diffraction data reveals tetragonal structure (P4mm) for x ⩽ 0.05 and monoclinic (Cm) phase along with the existence of tetragonal phase for 0.10 ⩽ x ⩽ 0.25 and monoclinic phase for x = 0.30. Transformation of E(2TO) and E + B1 vibrational modes in the range 210–250 cm{sup −1} (present for x ⩽ 0.25) into A′ + A″ modes at ∼236 cm{sup −1} for x = 0.30, and occurrence of new vibrational modes A′ and A″ in Raman spectra for x ⩾ 0.10 unambiguously support the presence of monoclinic phase. Occurrence of remnant polarisation and enhanced magnetization with concentration of BiFeO{sub 3} indicates superior multiferroic properties. Variation of magneto-capacitance with applied magnetic field is a strong evidence of magneto-electric multiferroic coupling in these materials.

  17. Liquid phase oxidation chemistry in continuous-flow microreactors.

    Science.gov (United States)

    Gemoets, Hannes P L; Su, Yuanhai; Shang, Minjing; Hessel, Volker; Luque, Rafael; Noël, Timothy

    2016-01-07

    Continuous-flow liquid phase oxidation chemistry in microreactors receives a lot of attention as the reactor provides enhanced heat and mass transfer characteristics, safe use of hazardous oxidants, high interfacial areas, and scale-up potential. In this review, an up-to-date overview of both technological and chemical aspects of liquid phase oxidation chemistry in continuous-flow microreactors is given. A description of mass and heat transfer phenomena is provided and fundamental principles are deduced which can be used to make a judicious choice for a suitable reactor. In addition, the safety aspects of continuous-flow technology are discussed. Next, oxidation chemistry in flow is discussed, including the use of oxygen, hydrogen peroxide, ozone and other oxidants in flow. Finally, the scale-up potential for continuous-flow reactors is described.

  18. From Two-Phase to Three-Phase: The New Electrochemical Interface by Oxide Electrocatalysts

    Science.gov (United States)

    Xu, Zhichuan J.

    2018-03-01

    Electrochemical reactions typically occur at the interface between a solid electrode and a liquid electrolyte. The charge exchange behaviour between these two phases determines the kinetics of electrochemical reactions. In the past few years, significant advances have been made in the development of metal oxide electrocatalysts for fuel cell and electrolyser reactions. However, considerable gaps remain in the fundamental understanding of the charge transfer pathways and the interaction between the metal oxides and the conducting substrate on which they are located. In particular, the electrochemical interfaces of metal oxides are significantly different from the traditional (metal) ones, where only a conductive solid electrode and a liquid electrolyte are considered. Oxides are insulating and have to be combined with carbon as a conductive mediator. This electrode configuration results in a three-phase electrochemical interface, consisting of the insulating oxide, the conductive carbon, and the liquid electrolyte. To date, the mechanistic insights into this kind of non-traditional electrochemical interface remain unclear. Consequently conventional electrochemistry concepts, established on classical electrode materials and their two-phase interfaces, are facing challenges when employed for explaining these new electrode materials. [Figure not available: see fulltext.

  19. Zirconium metal-water oxidation kinetics. III. Oxygen diffusion in oxide and alpha Zircaloy phases

    International Nuclear Information System (INIS)

    Pawel, R.E.

    1976-10-01

    The reaction of Zircaloy in steam at elevated temperature involves the growth of discrete layers of oxide and oxygen-rich alpha Zircaloy from the parent beta phase. The multiphase, moving boundary diffusion problem involved is encountered in a number of important reaction schemes in addition to that of Zircaloy-oxygen and can be completely (albeitly ideally) characterized through an appropriate model in terms of oxygen diffusion coefficients and equilibrium concentrations for the various phases. Conversely, kinetic data for phase growth and total oxygen consumption rates can be used to compute diffusion coefficients. Equations are developed that express the oxygen diffusion coefficients in the oxide and alpha phases in terms of the reaction rate constants and equilibrium solubility values. These equations were applied to recent experimental kinetic data on the steam oxidation of Zircaloy-4 to determine the effective oxygen diffusion coefficients in these phases over the temperature range 1000--1500 0 C

  20. The phase transition and elastic and optical properties of polymorphs of CuI

    International Nuclear Information System (INIS)

    Zhu Jiajie; Pandey, Ravindra; Gu Mu

    2012-01-01

    The high-pressure polymorphs of CuI have attracted much attention due to the somewhat contradictory identification of their structures by means of x-ray diffraction measurements and theoretical calculations. In this paper, we report the results of a theoretical investigation of polymorphs of CuI including zinc-blende, rhombohedral, tetragonal, rocksalt and orthorhombic phases. We find that CuI follows the high-pressure transition path from the zinc-blende phase to the orthorhombic phase via the tetragonal phase, and the rhombohedral phase shows mechanical instability under high pressure. The bulk moduli are almost isotropic but the shear moduli show large anisotropy in these polymorphs. A relatively strong hybridization of I p and Cu d states appears to determine the electronic properties of the CuI polymorphs. The zinc-blende and tetragonal CuI are direct gap semiconductors and their optical properties are similar, whereas the orthorhombic CuI is metallic.

  1. Phase chemistry of the system Nb–Rh–O

    International Nuclear Information System (INIS)

    Jacob, K.T.; Gupta, Preeti; Vinay, M.; Waseda, Y.

    2013-01-01

    Phase relations in the system Nb–Rh–O at 1223 K were investigated by isothermal equilibration of eleven compositions and analysis of quenched samples using OM, XRD, SEM and EDS. The oxide phase in equilibrium with the alloy changes progressively from NbO to NbO 2 , NbO 2.422 and Nb 2 O 5−x with increasing Rh. Only one ternary oxide NbRhO 4 with tetragonal structure (a=0.4708 nm and c=0.3017 nm) was detected. It coexists with Rh and Nb 2 O 5 . The standard Gibbs energy of formation of NbRhO 4 from its component binary oxides measured using a solid-state electrochemical cell can be represented by the equation; ΔG f,ox o (J/mol)=−38,350+5.818×T(±96) Constructed on the basis of thermodynamic information of the various alloy and oxide phases are oxygen potential diagram for the system Nb–Rh–O at 1223 K and temperature–composition diagrams at constant partial pressures of oxygen. - Graphical abstract: Isothermal section of ternary phase diagram for the system Nb–Rh–O at 1223 K. - Highlights: • First complete isothermal section for the system Nb–Rh–O has been established. • An electrochemical cell is used to measure the thermodynamic properties of NbRhO 4 . • Oxygen potential diagram at 1223 K is computed from thermodynamic data. • Temperature–composition diagrams at constant oxygen partial pressures. • A complete thermodynamic characterization of the system Nb–Rh–O is presented

  2. Phase chemistry of the system Nb–Rh–O

    Energy Technology Data Exchange (ETDEWEB)

    Jacob, K.T., E-mail: katob@materials.iisc.ernet.in [Department of Materials Engineering, Indian Institute of Science, Bangalore 560012 (India); Gupta, Preeti; Vinay, M. [Department of Materials Engineering, Indian Institute of Science, Bangalore 560012 (India); Waseda, Y. [Institute of Multidisciplinary Research for Advanced Materials, Tohoku University, Sendai 980-8577 (Japan)

    2013-06-01

    Phase relations in the system Nb–Rh–O at 1223 K were investigated by isothermal equilibration of eleven compositions and analysis of quenched samples using OM, XRD, SEM and EDS. The oxide phase in equilibrium with the alloy changes progressively from NbO to NbO₂, NbO₂.₄₂₂ and Nb₂O5–x with increasing Rh. Only one ternary oxide NbRhO₄ with tetragonal structure (a=0.4708 nm and c=0.3017 nm) was detected. It coexists with Rh and Nb₂O₅. The standard Gibbs energy of formation of NbRhO₄ from its component binary oxides measured using a solid-state electrochemical cell can be represented by the equation; ΔGf,oxo(J/mol)=-38,350+5.818×T(±96) Constructed on the basis of thermodynamic information of the various alloy and oxide phases are oxygen potential diagram for the system Nb–Rh–O at 1223 K and temperature–composition diagrams at constant partial pressures of oxygen. - Graphical abstract: Isothermal section of ternary phase diagram for the system Nb–Rh–O at 1223 K. Highlights: • First complete isothermal section for the system Nb–Rh–O has been established. • An electrochemical cell is used to measure the thermodynamic properties of NbRhO₄. • Oxygen potential diagram at 1223 K is computed from thermodynamic data. • Temperature–composition diagrams at constant oxygen partial pressures. • A complete thermodynamic characterization of the system Nb–Rh–O is presented.

  3. Tetragonal Ce-based Ce-Sm(Fe, Co, Ti){sub 12} alloys for permanent magnets

    Energy Technology Data Exchange (ETDEWEB)

    Martin-Cid, Andres; Salazar, Daniel [BCMaterials, Bizkaia Science and Tecnology Park, 48160 Derio (Spain); Gabay, Aleksandr M.; Hadjipanayis, George C. [Department of Physics and Astronomy, University of Delaware, Newark, DE, 19716 (United States); Barandiaran, Jose Manuel [BCMaterials, Bizkaia Science and Tecnology Park, 48160 Derio (Spain); Department of Electricity and Electronics, University Basque Country (UPV/EHU), 48080 Bilbao (Spain)

    2016-12-15

    Abundance and relatively low cost of Ce provide a great incentive for its use in rare-earth permanent magnets. It has been recently reported that the tetragonal Ce(Fe,Co,Ti)12 compounds may exhibit application-worthy intrinsic magnetic properties. In this work the effect of the α-Fe phase formation due to the evaporation of Sm during alloy fabrication has been studied, as a previous step in the attempt to convert the intrinsic magnetic properties into functional properties of a permanent magnet. Ce{sub 0.5}Sm{sub 0.5}Fe{sub 9}Co{sub 2}Ti alloys based on the ThMn12-type crystal structure have been synthesized via melt-spinning with different Sm content. Coercive fields between 2.8 and 1.4 kOe have been found for α-Fe phase contents between 8 and 46% in volume, showing the influence of the α-Fe phase on the coercivity and exchange coupling between the hard and soft phase. (copyright 2016 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  4. Growth and characterization of oxide layers on zirconium alloys

    International Nuclear Information System (INIS)

    Maroto, A.J.G.; Bordoni, R.; Villegas, M.; Olmedo, A.M.; Blesa, M.A.; Iglesias, A.; Koenig, P.

    1996-01-01

    In the range 265-435 C Zr-2.5Nb corrosion takes place in two stages, as opposed to the cyclic behaviour of Zry-4. The Zry-4 corrosion stages are described by a single equation, in terms of the dense oxide layer thickness that decreases sharply at each transition. Tetragonal zirconia is present in the oxide layers of both alloys. In Zry-4, its volume fraction decreases as the oxide grows; it is barely discernible in Zr-2.5Nb in films below 1 μm, to later increase up to the transition. In both alloys, compressive stresses are developed associated with the oxide growth. Their relaxation at the transition correlates with the transformation of ZrO 2 (t) to ZrO 2 (m) and with the decrease of the dense oxide layer. In Zr-2.5Nb, oxide ridges form on the β-Zr phase filaments, at the very onset of film growth. The cyclic behaviour associated with the periodical breakdown of the dense oxide layer is therefore blurred, although optical microscopy shows that the scale retains the multilayered structure typical of Zry-4. (orig.)

  5. Synthesis of binary bismuth-cadmium oxide nanorods with sensitive electrochemical sensing performance

    International Nuclear Information System (INIS)

    Wen, Yong; Pei, Lizhai; Wei, Tian

    2017-01-01

    Binary bismuth-cadmium oxide nanorods have been synthesized by a simple hydrothermal process without templates and additives. X-ray diffraction and high-resolution transmission electron microscopy reveal that the nanorods possess single crystalline tetragonal Bi 2 CdO 4 phase. Scanning electron microscopy and transmission electron microscopy images show that the length and diameter of the nanorods are 20-300 nm and 5-10 μm, respectively. The formation of the binary bismuth-cadmium oxide nanorods is closely related to the hydrothermal parameters. The electrochemical sensing performance of the binary bismuth-cadmium oxide nanorods has been investigated using the nanorods as glassy carbon electrode modifiers. The detection limit is 0.19 μM with a linear range of 0.0005-2 mM. The nanorod-modified glassy carbon electrode exhibits good electrocatalytic activity toward L-cysteine and great application potential for electrochemical sensors.

  6. Grain size dependent phase stabilities and presence of a monoclinic (Pm) phase in the morphotropic phase boundary region of (1−x)Bi(Mg{sub 1/2}Ti{sub 1/2})O{sub 3}-xPbTiO{sub 3} piezoceramics

    Energy Technology Data Exchange (ETDEWEB)

    Upadhyay, Ashutosh; Singh, Akhilesh Kumar, E-mail: akhilesh-bhu@yahoo.com, E-mail: aksingh.mst@itbhu.ac.in [School of Materials Science and Technology, Indian Institute of Technology (Banaras Hindu University), Varanasi 221005 (India)

    2015-04-14

    Results of the room temperature structural studies on (1−x)Bi(Mg{sub 1/2}Ti{sub 1/2})O{sub 3}-xPbTiO{sub 3} ceramics using Rietveld analysis of the powder x-ray diffraction data in the composition range 0.28 ≤ x ≤ 0.45 are presented. The morphotropic phase boundary region exhibits coexistence of monoclinic (space group Pm) and tetragonal (space group P4 mm) phases in the composition range 0.33 ≤ x ≤ 0.40. The structure is nearly single phase monoclinic (space group Pm) in the composition range 0.28 ≤ x ≤ 0.32. The structure for the compositions with x ≥ 0.45 is found to be predominantly tetragonal with space group P4 mm. Rietveld refinement of the structure rules out the coexistence of rhombohedral and tetragonal phases in the morphotropic phase boundary region reported by earlier authors. The Rietveld structure analysis for the sample x = .35 calcined at various temperatures reveals that phase fraction of the coexisting phases in the morphotropic phase boundary region varies with grain size. The structural parameters of the two coexisting phases also change slightly with changing grain size.

  7. Pressure-induced phase transformations in L-alanine crystals

    DEFF Research Database (Denmark)

    Olsen, J. Staun; Gerward, Leif; Freire, P.T.C.

    2008-01-01

    Raman scattering and synchrotron X-ray diffraction have been used to investigate the high-pressure behavior of L-alanine. This study has confirmed a structural phase transition observed by Raman scattering at 2.3 GPa and identified it as a change from orthorhombic to tetragonal structure. Another...... phase transformation from tetragonal to monoclinic structure has been observed at about 9 GPa. From the equation of state, the zero-pressure bulk modulus and its pressure derivative have been determined as (31.5 +/- 1.4) GPa and 4.4 +/- 0.4, respectively....

  8. Synthesis and crystallization behavior of 3 mol% yttria stabilized tetragonal zirconia polycrystals (3Y-TZP) nanosized powders prepared using a simple co-precipitation process

    Energy Technology Data Exchange (ETDEWEB)

    Hsu, Yu-Wei [Graduate Institute of Applied Science, National Kaohsiung University of Applied Sciences, 415 Chien-Kung Road, Kaohsiung 80782, Taiwan (China); Yang, Ko-Ho, E-mail: yangkoho@cc.kuas.edu.tw [Graduate Institute of Applied Science, National Kaohsiung University of Applied Sciences, 415 Chien-Kung Road, Kaohsiung 80782, Taiwan (China); Department of Mold and Die Engineering, National Kaohsiung University of Applied Sciences, 415 Chien-Kung Road, Kaohsiung 80782, Taiwan (China); Chang, Kuo-Ming [Department of Mechanical Engineering, National Kaohsiung University of Applied Sciences, 415 Chien-Kung Road, Kaohsiung 80782, Taiwan (China); Dental Materials Research Center, National Kaohsiung University of Applied Sciences, 415 Chien-Kung Road, Kaohsiung 80782, Taiwan (China); Yeh, Sung-Wei [Metal Industries Research and Development Centre, 1001 Kaohsiung Highway, Kaohsiung 811, Taiwan (China); Wang, Moo-Chin, E-mail: mcwang@kmu.edu.tw [Department of Fragrance and Cosmetics Science, Kaohsiung Medical University, 100, Shihchuan 1st Road, Kaohsiung 80728, Taiwan (China)

    2011-06-16

    Highlights: > The thermal behavior of 3Y-TZP precursor powders had been investigated. > The crystallization behavior of 3Y-TZP nanopowders had been investigated. > The activation energy for crystallization of tetragonal ZrO{sub 2} was obtained. > The growth morphology parameter n is approximated as 2.0. > The crystallites show a plate-like morphology. - Abstract: The synthesis and crystallization behavior of 3 mol% yttria stabilized tetragonal zirconia polycrystals (3Y-TZP) nanopowders prepared using a simple co-precipitation process at 348 K and pH = 7 were investigated using differential scanning calorimetry/thermogravimetry (DSC/TG), an X-ray diffractometer (XRD), the Raman spectra, transmission electron microscopy (TEM), selected area electron diffraction (SAED), and an energy dispersive spectrometer (EDS). The activation energy of tetragonal ZrO{sub 2} crystallization from 3Y-TZP freeze-dried precursor powders using a non-isothermal method, namely, 169.2 {+-} 21.9 kJ mol{sup -1}, was obtained. The growth morphology parameter n was approximated as 2.0, which indicated that it had a plate-like morphology. The XRD, Raman spectra, and SAED patterns showed that the phase of the tetragonal ZrO{sub 2} was maintained at 1273 K. The crystallite size of 3Y-TZP freeze-dried precursor powders calcined at 1273 K for 5 min was 21.3 nm.

  9. Synthesis and crystallization behavior of 3 mol% yttria stabilized tetragonal zirconia polycrystals (3Y-TZP) nanosized powders prepared using a simple co-precipitation process

    International Nuclear Information System (INIS)

    Hsu, Yu-Wei; Yang, Ko-Ho; Chang, Kuo-Ming; Yeh, Sung-Wei; Wang, Moo-Chin

    2011-01-01

    Highlights: → The thermal behavior of 3Y-TZP precursor powders had been investigated. → The crystallization behavior of 3Y-TZP nanopowders had been investigated. → The activation energy for crystallization of tetragonal ZrO 2 was obtained. → The growth morphology parameter n is approximated as 2.0. → The crystallites show a plate-like morphology. - Abstract: The synthesis and crystallization behavior of 3 mol% yttria stabilized tetragonal zirconia polycrystals (3Y-TZP) nanopowders prepared using a simple co-precipitation process at 348 K and pH = 7 were investigated using differential scanning calorimetry/thermogravimetry (DSC/TG), an X-ray diffractometer (XRD), the Raman spectra, transmission electron microscopy (TEM), selected area electron diffraction (SAED), and an energy dispersive spectrometer (EDS). The activation energy of tetragonal ZrO 2 crystallization from 3Y-TZP freeze-dried precursor powders using a non-isothermal method, namely, 169.2 ± 21.9 kJ mol -1 , was obtained. The growth morphology parameter n was approximated as 2.0, which indicated that it had a plate-like morphology. The XRD, Raman spectra, and SAED patterns showed that the phase of the tetragonal ZrO 2 was maintained at 1273 K. The crystallite size of 3Y-TZP freeze-dried precursor powders calcined at 1273 K for 5 min was 21.3 nm.

  10. Absence of low temperature phase transitions and enhancement of ferroelectric transition temperature in highly strained BaTiO{sub 3} epitaxial films grown on MgO Substrates

    Energy Technology Data Exchange (ETDEWEB)

    Kumar, Satish; Kumar, Dhirendra; Sathe, V. G., E-mail: vasant@csr.res.in [UGC-DAE Consortium for Scientific Research, University Campus, Khandwa Road, Indore 452001 (India); Kumar, Ravi; Sharma, T. K. [Semiconductor Physics and Devices Lab, Raja Ramanna Centre for Advanced Technology, Indore 452013 (India)

    2015-04-07

    Recently, a large enhancement in the ferroelectric transition temperature of several oxides is reported by growing the respective thin films on appropriate substrates. This phenomenon is correlated with high residual strain in thin films often leading to large increase in the tetragonality of their crystal structure. However, such an enhancement of transition temperature is usually limited to very thin films of ∼10 nm thickness. Here, we report growth of fully strained epitaxial thin films of BaTiO{sub 3} of 400 nm thickness, which are coherently grown on MgO substrates by pulsed laser deposition technique. Conventional high resolution x-ray diffraction and also the reciprocal space map measurements confirm that the film is fully strained with in-plane tensile strain of 5.5% that dramatically increases the tetragonality to 1.05. Raman measurements reveal that the tetragonal to cubic structural phase transition is observed at 583 K, which results in an enhancement of ∼200 K. Furthermore, temperature dependent Raman studies on these films corroborate absence of all the low temperature phase transitions. Numerical calculations based on thermodynamical model predict a value of the transition temperature that is greater than 1500 °C. Our experimental results are therefore in clear deviation from the existing strain dependent phase diagrams.

  11. A new liquid-phase-separation glaze containing neodymium oxide

    International Nuclear Information System (INIS)

    Jing, S.; Xianque, C.; Luxing, K.; Pentecost, J.L.

    1986-01-01

    A color-changeable opaque glaze containing neodymium oxide was investigated. Results show that the glaze is a new example of the liquid-phase-separation type. The discrete phase droplets are from 50 to 500 nm in size. They are rich in Nd, Zn, Ca, and Mg and the continuous phase is rich in Si, Al, and K. The concentration of the discrete phase is approx. =45%. The large number of discrete droplets and the zinc oxide in the glaze increase its opacity to cover the selective light absorption and scattering of the neodymium ion and reduce the opalescence effect

  12. Mechanisms Responsible for the Large Piezoelectricity at the Tetragonal-Orthorhombic Phase Boundary of (1-x)BaZr0.2Ti0.8O3-xBa0.7Ca0.3TiO3 System.

    Science.gov (United States)

    Yang, Tao; Ke, Xiaoqin; Wang, Yunzhi

    2016-09-16

    Recently it was found that in the lead-free (1-x)BaZr0.2Ti0.8O3-xBa0.7Ca0.3TiO3 (BZT-xBCT) system, the highest piezoelectric d33 coefficient appears at the tetragonal (T) - orthorhombic (O) phase boundary rather than the O - rhombohedral (R) phase boundary, but the physical origin of it is still unclear. In this work we construct the phase diagram of the BZT-xBCT system using a generic sixth-order Landau free energy polynomial and calculate the energy barrier (EB) for direct domain switching between two variants of the stable low-symmetry ferroelectric phase. We find that the EB at the T-O phase boundary is lower than that at the O-R phase boundary and EB may serve as a rigorous quantitative measure of the degree of polarization anisotropy through Landau potential. The calculations may shed some light on the physical origin of the highest piezoelectric coefficients as well as the softest elastic compliance at the T-O phase boundary observed in experiments.

  13. Composition-induced structural phase transitions in the (Ba1-xLax)2In2O5+x (0=

    International Nuclear Information System (INIS)

    Tenailleau, C.; Pring, A.; Moussa, S.M.; Liu, Y.; Withers, R.L.; Tarantino, S.; Zhang, M.; Carpenter, M.A.

    2005-01-01

    Composition-induced structural phase changes across the high temperature, fast oxide ion conducting (Ba 1-x La x ) 2 In 2 O 5+x , 0= orthorhombic transition, while the cubic->tetragonal transition could be continuous. Differences between the variation with composition of spectral parameters and of macroscopic strain parameters are consistent with a substantial order/disorder component for the transitions. There is also evidence for precursor effects within the cubic structure before symmetry is broken

  14. Mechanism of the transition from orthorhombic to tetragonal YBa 2Cu 3O 7- x. Investigation of a reversible topotactic reaction in the electron microscope

    Science.gov (United States)

    Müller, J.-H.; Gruehn, R.

    The phase transition from orthorhombic to tetragonal could be observed (in situ) with High-Resolution Transmission Electron Microscopy (HRTEM). In superconducting samples of YBa 2Cu 3O 7- x ( x=0.09) twinned areas were found which changed from orthorhombic to tetragonal symmetry upon electron irradiation parallel to the long c axis. In opposition to annealing experiments the length of the c-axis remained unchanged. The transition was reversible in the high vacuum of the electron microscope. Therefore we surmise that this reaction has no reductive character (no perceptible loss of oxygen). Within the tetragonal structure one can assume a statistical sharing (“disorder”) of oxygen by the metal atoms. The transition could also be explained by a migration of oxygen to the surface. After finishing the irradiation experiment and waiting for several minutes, the oxygen seems to occupy partially ordered positions resulting again in an orthorhombic symmetry. In some cases we could observed transition states of the structural transformation. A schematic model of the mechanism is depicted.

  15. Electro-optical properties of tetragonal KNbO 3

    Indian Academy of Sciences (India)

    Linear electro-optical tensor coefficients and optical susceptibility of tetragonal KNbO3 are calculated using a formalism based on bond charge theory. Results are in close agreement with the experimental data. The covalent Nb–O bonding network comprising the distorted NbO6 octahedral groups in the structure is found to ...

  16. Long-term oxidization and phase transition of InN nanotextures

    Directory of Open Access Journals (Sweden)

    Dražic Goran

    2011-01-01

    Full Text Available Abstract The long-term (6 months oxidization of hcp-InN (wurtzite, InN-w nanostructures (crystalline/amorphous synthesized on Si [100] substrates is analyzed. The densely packed layers of InN-w nanostructures (5-40 nm are shown to be oxidized by atmospheric oxygen via the formation of an intermediate amorphous In-O x -N y (indium oxynitride phase to a final bi-phase hcp-InN/bcc-In2O3 nanotexture. High-resolution transmission electron microscopy, energy-dispersive X-ray spectroscopy, electron energy loss spectroscopy and selected area electron diffraction are used to identify amorphous In-O x -N y oxynitride phase. When the oxidized area exceeds the critical size of 5 nm, the amorphous In-O x -N y phase eventually undergoes phase transition via a slow chemical reaction of atomic oxygen with the indium atoms, forming a single bcc In2O3 phase.

  17. Kinetics, Mechanism, and Secondary Organic Aerosol Yield of Aqueous Phase Photo-oxidation of α-Pinene Oxidation Products.

    Science.gov (United States)

    Aljawhary, Dana; Zhao, Ran; Lee, Alex K Y; Wang, Chen; Abbatt, Jonathan P D

    2016-03-10

    Formation of secondary organic aerosol (SOA) involves atmospheric oxidation of volatile organic compounds (VOCs), the majority of which are emitted from biogenic sources. Oxidation can occur not only in the gas-phase but also in atmospheric aqueous phases such as cloudwater and aerosol liquid water. This study explores for the first time the aqueous-phase OH oxidation chemistry of oxidation products of α-pinene, a major biogenic VOC species emitted to the atmosphere. The kinetics, reaction mechanisms, and formation of SOA compounds in the aqueous phase of two model compounds, cis-pinonic acid (PIN) and tricarballylic acid (TCA), were investigated in the laboratory; TCA was used as a surrogate for 3-methyl-1,2,3-butanetricarboxylic acid (MBTCA), a known α-pinene oxidation product. Aerosol time-of-flight chemical ionization mass spectrometry (Aerosol-ToF-CIMS) was used to follow the kinetics and reaction mechanisms at the molecular level. Room-temperature second-order rate constants of PIN and TCA were determined to be 3.3 (± 0.5) × 10(9) and 3.1 (± 0.2) × 10(8) M(-1) s(-1), respectively, from which were estimated their condensed-phase atmospheric lifetimes. Aerosol-ToF-CIMS detected a large number of products leading to detailed reaction mechanisms for PIN and MBTCA. By monitoring the particle size distribution after drying, the amount of SOA material remaining in the particle phase was determined. An aqueous SOA yield of 40 to 60% was determined for PIN OH oxidation. Although recent laboratory studies have focused primarily on aqueous-phase processing of isoprene-related compounds, we demonstrate that aqueous formation of SOA materials also occurs from monoterpene oxidation products, thus representing an additional source of biogenically driven aerosol formation.

  18. Synthesis of binary bismuth-cadmium oxide nanorods with sensitive electrochemical sensing performance

    Energy Technology Data Exchange (ETDEWEB)

    Wen, Yong [Xinjiang Univ., Xinjiang (China). School of Civil Engineering and Architecture; Pei, Lizhai; Wei, Tian [Anhui Univ. of Technology, Anhui (China). School of Materials Science and Engineering

    2017-07-15

    Binary bismuth-cadmium oxide nanorods have been synthesized by a simple hydrothermal process without templates and additives. X-ray diffraction and high-resolution transmission electron microscopy reveal that the nanorods possess single crystalline tetragonal Bi{sub 2}CdO{sub 4} phase. Scanning electron microscopy and transmission electron microscopy images show that the length and diameter of the nanorods are 20-300 nm and 5-10 μm, respectively. The formation of the binary bismuth-cadmium oxide nanorods is closely related to the hydrothermal parameters. The electrochemical sensing performance of the binary bismuth-cadmium oxide nanorods has been investigated using the nanorods as glassy carbon electrode modifiers. The detection limit is 0.19 μM with a linear range of 0.0005-2 mM. The nanorod-modified glassy carbon electrode exhibits good electrocatalytic activity toward L-cysteine and great application potential for electrochemical sensors.

  19. Evaluation of oxides formed at high temperatures in Zr-2.5Nb pressure tubing

    Energy Technology Data Exchange (ETDEWEB)

    Kiran Kumar, N.A.P.; Szpunar, J.A., E-mail: kiraniitkgp@yahoo.com [Univ. of Saskatchewan, Saskatoon, Saskatchewan (Canada)

    2012-07-01

    The oxidation behavior of Zr-2.5Nb pressure tube samples has been studied at four different temperatures, i.e., 400°, 600°, 800°, and 1000°C. The amount of tetragonal phase is found to decrease with increase of temperature. The oxide texture of (002){sub m} and (111){sub m} type increased with the temperature from 400°C to 600°C, however at temperatures above 600°C the texture strength seems to diminish and the oxide layer becomes structurally unstable. Further, the impedance response is found to be dependent on the microstructure of the oxide film. For the sample oxidized at 400°C, Electrochemical Impedance Spectroscopy (EIS) spectra exhibited a two-time constant behavior, showing the formation of two-layer oxide film on the Zr-2.5Nb alloy, which correspond to a porous outer oxide and a barrier inner oxide, respectively. In addition, the samples were oxidized at constant temperature of 600°C with varying oxidation time. The observation shows that the oxide is more protective in the early stage of oxide growth. However, further growth of oxide film has resulted in degeneration of its protective character. (author)

  20. Mercury Oxidation via Catalytic Barrier Filters Phase II

    Energy Technology Data Exchange (ETDEWEB)

    Wayne Seames; Michael Mann; Darrin Muggli; Jason Hrdlicka; Carol Horabik

    2007-09-30

    In 2004, the Department of Energy National Energy Technology Laboratory awarded the University of North Dakota a Phase II University Coal Research grant to explore the feasibility of using barrier filters coated with a catalyst to oxidize elemental mercury in coal combustion flue gas streams. Oxidized mercury is substantially easier to remove than elemental mercury. If successful, this technique has the potential to substantially reduce mercury control costs for those installations that already utilize baghouse barrier filters for particulate removal. Completed in 2004, Phase I of this project successfully met its objectives of screening and assessing the possible feasibility of using catalyst coated barrier filters for the oxidation of vapor phase elemental mercury in coal combustion generated flue gas streams. Completed in September 2007, Phase II of this project successfully met its three objectives. First, an effective coating method for a catalytic barrier filter was found. Second, the effects of a simulated flue gas on the catalysts in a bench-scale reactor were determined. Finally, the performance of the best catalyst was assessed using real flue gas generated by a 19 kW research combustor firing each of three separate coal types.

  1. Rapid synthesis of tin oxide nanostructures by microwave-assisted thermal oxidation for sensor applications

    Science.gov (United States)

    Phadungdhitidhada, S.; Ruankham, P.; Gardchareon, A.; Wongratanaphisan, D.; Choopun, S.

    2017-09-01

    In the present work nanostructures of tin oxides were synthesized by a microwave-assisted thermal oxidation. Tin precursor powder was loaded into a cylindrical quartz tube and further radiated in a microwave oven. The as-synthesized products were characterized by scanning electron microscope, transmission electron microscope, and x-ray diffractometer. The results showed that two different morphologies of SnO2 microwires (MWs) and nanoparticles (NPs) were obtained in one minute of microwave radiation under atmospheric ambient. A few tens of the SnO2 MWs with the length of 10-50 µm were found. Some parts of the MWs were decorated with the SnO2 NPs. However, most of the products were SnO2 NPs with the diameter ranging from 30-200 nm. Preparation under loosely closed system lead to mixed phase SnO-SnO2 NPs with diameter of 30-200 nm. The single-phase of SnO2 could be obtained by mixing the Sn precursor powders with CuO2. The products were mostly found to be SnO2 nanowires (NWs) and MWs. The diameter of SnO2 NWs was less than 50 nm. The SnO2 NPs, MWs, and NWs were in the cassiterite rutile structure phase. The SnO NPs was in the tetragonal structure phase. The growth direction of the SnO2 NWs was observed in (1 1 0) and (2 2 1) direction. The ethanol sensor performance of these tin oxide nanostructures showed that the SnO-SnO2 NPs exhibited extremely high sensitivity. Invited talk at 5th Thailand International Nanotechnology Conference (Nano Thailand-2016), 27-29 November 2016, Nakhon Ratchasima, Thailand.

  2. Plasma oxidation of the high T/sub c/ superconducting perovskites

    International Nuclear Information System (INIS)

    Bagley, B.G.; Greene, L.H.; Tarascon, J.; Hull, G.W.

    1987-01-01

    A near room-temperature plasma oxidation process is shown to restore superconductivity and metalliclike behavior in oxygen deficient La/sub 2-//sub x/ Sr/sub x/ CuO/sub 4-//sub y/ and YBa 2 Cu 3 O/sub 7-//sub x/ compounds. In the YBa 2 Cu 3 O/sub 7-//sub x/ compound the conversion from an oxygen deficient n-type tetragonal to the p-type orthorhombic phase with a concomitant factor of 5 x 10 5 increase in room-temperature conductivity is also accomplished. This process is of technological importance because oxygen can be restored in these materials at temperatures compatible with device processing. Of scientific interest, the process allows us to carefully control the oxidation state and thereby systematically study the 90 and 55 K superconducting transitions in YBa 2 Cu 3 O/sub 7-//sub x/

  3. Heterogeneous Oxidation of Atmospheric Organic Aerosol: Kinetics of Changes to the Amount and Oxidation State of Particle-Phase Organic Carbon.

    Science.gov (United States)

    Kroll, Jesse H; Lim, Christopher Y; Kessler, Sean H; Wilson, Kevin R

    2015-11-05

    Atmospheric oxidation reactions are known to affect the chemical composition of organic aerosol (OA) particles over timescales of several days, but the details of such oxidative aging reactions are poorly understood. In this study we examine the rates and products of a key class of aging reaction, the heterogeneous oxidation of particle-phase organic species by the gas-phase hydroxyl radical (OH). We compile and reanalyze a number of previous studies from our laboratories involving the oxidation of single-component organic particles. All kinetic and product data are described on a common basis, enabling a straightforward comparison among different chemical systems and experimental conditions. Oxidation chemistry is described in terms of changes to key ensemble properties of the OA, rather than to its detailed molecular composition, focusing on two quantities in particular, the amount and the oxidation state of the particle-phase carbon. Heterogeneous oxidation increases the oxidation state of particulate carbon, with the rate of increase determined by the detailed chemical mechanism. At the same time, the amount of particle-phase carbon decreases with oxidation, due to fragmentation (C-C scission) reactions that form small, volatile products that escape to the gas phase. In contrast to the oxidation state increase, the rate of carbon loss is nearly uniform among most systems studied. Extrapolation of these results to atmospheric conditions indicates that heterogeneous oxidation can have a substantial effect on the amount and composition of atmospheric OA over timescales of several days, a prediction that is broadly in line with available measurements of OA evolution over such long timescales. In particular, 3-13% of particle-phase carbon is lost to the gas phase after one week of heterogeneous oxidation. Our results indicate that oxidative aging represents an important sink for particulate organic carbon, and more generally that fragmentation reactions play a major

  4. Order parameters for symmetry-breaking structural transitions: The tetragonal-monoclinic transition in ZrO2

    Science.gov (United States)

    Thomas, John C.; Van der Ven, Anton

    2017-10-01

    Group/subgroup structural phase transitions are exploited in a wide variety of technologies, including those that rely on shape-memory behavior and on transformation toughening. Here, we introduce an approach to identify symmetry-adapted strain and shuffle order parameters for any group/subgroup structural transition between a high-symmetry parent phase and its symmetrically equivalent low-symmetry product phases. We show that symmetry-adapted atomic shuffle order parameters can be determined by the diagonalization of an orbital covariance matrix, formed by taking the covariance among the atomic displacement vectors of all symmetrically equivalent product phase variants. We use this approach to analyze the technologically important tetragonal to monoclinic structural phase transformation of ZrO2. We explore the energy landscapes, as calculated with density functional theory, along distinct paths that connect m ZrO2 to t ZrO2 and to other m ZrO2 variants. The calculations indicate favorable pairs of variants and reveal intermediate structures likely to exist at coherent twin boundaries and having relatively low deformation energy. We identify crystallographic features of the monoclinic ZrO2 variant that make it very sensitive to shape changing strains.

  5. Grain size dependent phase stabilities and presence of a monoclinic (Pm) phase in the MPB region of (1-x)Bi(Mg_1_/_2Ti_1_/_2)O_3_-_xPbTiO_3

    International Nuclear Information System (INIS)

    Upadhyay, A.; Singh, A.K.

    2016-01-01

    The results of the room temperature structural studies on (1-x)Bi(Mg_1_/_2Ti_1_/_2)O_3_-_xPbTiO_3 ceramics using Rietveld analysis of the powder X-ray diffraction data in the composition range 0.28≤x≤0.45 are presented. The morphotropic phase boundary region exhibits coexistence of monoclinic (space group Pm) and tetragonal (space group P4mm) phases in the composition range 0.33≤x≤0.40. The structure is nearly single phase monoclinic (space group Pm) in the composition range 0.28≤x≤0.32. The structure for the compositions with x≥0.45 is found to be predominantly tetragonal with space group P4mm. Rietveld refinement of the structure rules out the coexistence of rhombohedral and tetragonal phases in the morphotropic phase boundary region reported by earlier authors. The Rietveld structure analysis for the sample x=0.35 calcined at various temperatures reveals that phase fraction of the coexisting phases in the morphotropic phase boundary region varies with grain size. The structural parameters of the two coexisting phases also change slightly with changing grain size. (author)

  6. Intermediate phases in the hydrogen disproportionated state of NdFeB-type powders

    International Nuclear Information System (INIS)

    Yi, G.; Chapman, J. N.; Brown, D. N.; Harris, I. R.

    2001-01-01

    Transmission electron microscopy studies have been carried out on partially disproportionated NdFeB-type alloys. A new intermediate magnetic (NIM) phase has been identified. Moreover, the lamella structure which subsequently develops from the tetragonal NIM phase comprises a tetragonal NdFe-containing (IL) phase and α-Fe. The experimental data show strong evidence of a well-defined crystallographic relation between both the NIM and lamella phases and between the IL phase and α-Fe. These observations give insight into how crystallographic texture, and hence anisotropy, can be developed in NdFeB-type powders processed by the hydrogenation, disproportionation, desorption, and recombination route. copyright 2001 American Institute of Physics

  7. Phase Transformation and Lattice Parameter Changes of Non-trivalent Rare Earth-Doped YSZ as a Function of Temperature

    Science.gov (United States)

    Jiang, Shengli; Huang, Xiao; He, Zhang; Buyers, Andrew

    2018-05-01

    To examine the effect of doping/co-doping on high-temperature phase compositions of YSZ, stand-alone YSZ and CeO2 and Nb2O5 co-doped YSZ samples were prepared using mechanical alloy and high-temperature sintering. XRD analysis was performed on these samples from room temperature to 1100 °C. The results show that the structure for the co-doped samples tends to be thermally stable when the test temperature is higher than a critical value. Monoclinic phase was dominant in Nb2O5 co-doped YSZ at temperatures lower than 600 °C, while for the YSZ and CeO2 co-doped YSZ, cubic/tetragonal phase was dominant in the whole test temperature range. The lattice parameters for all the samples increase with increasing test temperature generally. The lattice parameters for the two non-trivalent rare earth oxides co-doped YSZ show that the lattice parameter a for the cubic phase of the Ce4+ co-doped YSZ is consistently greater than that of 7YSZ which is related to the presence of larger radius of Ce4+ in the matrix. The lattice parameters a, b, c for the monoclinic phase of Ce4+ co-doped YSZ are much closer to each other than that of the Nb5+ co-doped YSZ, indicating the former has better tendency to form cubic/tetragonal phase, which is desired for vast engineering applications.

  8. Ternary ceramic alloys of Zr-Ce-Hf oxides

    Science.gov (United States)

    Becher, P.F.; Funkenbusch, E.F.

    1990-11-20

    A ternary ceramic alloy is described which produces toughening of zirconia and zirconia composites through the stress transformation from tetragonal phase to monoclinic phase. This alloy, having the general formula Ce[sub x]Hf[sub y]Zr[sub 1[minus]x[minus]y]O[sub 2], is produced through the addition of appropriate amounts of ceria and hafnia to the zirconia. Typically, improved toughness is achieved with about 5 to about 15 mol % ceria and up to about 40 mol % hafnia. The preparation of alloys of these compositions are given together with data as to the densities, tetragonal phase content, hardness and fracture toughness. The alloys are useful in preparing zirconia bodies as well as reinforcing ceramic composites. 1 fig.

  9. Phase stability of oxide dispersion-strengthened ferritic steels in neutron irradiation

    International Nuclear Information System (INIS)

    Yamashita, S.; Oka, K.; Ohnuki, S.; Akasaka, N.; Ukai, S.

    2002-01-01

    Oxide dispersion-strengthened ferritic steels were irradiated by neutrons up to 21 dpa and studied by microstructural observation and microchemical analysis. The original high dislocation density did not change after neutron irradiation, indicating that the dispersed oxide particles have high stability under neutron irradiation. However, there is potential for recoil resolution of the oxide particles due to ballistic ejection at high dose. From the microchemical analysis, it was implied that some of the complex oxides have a double-layer structure, such that TiO 2 occupied the core region and Y 2 O 3 the outer layer. Such a structure may be more stable than the simple mono-oxides. Under high-temperature irradiation, Laves phase was the predominant precipitate occurring at grain boundaries α phase and χ phase were not observed in this study

  10. A study of the formation processes of the 2212 phase in the Bi-based superconductor systems. [BiSrCaCuO

    Energy Technology Data Exchange (ETDEWEB)

    Wai, Lo; Glowacki, B A [Interdisciplinary Research Centre in Superconductivity, Univ. of Cambridge (United Kingdom)

    1992-04-15

    A study towards the identification of the reactions contributing to and accompanying the formation of the 2212 phase from oxides and carbonates by solid state reaction processes was conducted. The formation processes were investigated by thermal analysis, powder X-ray diffractometry and AC magnetic susceptometry. The 2212 phase was found to form from reactions between the 2201 phases (the non-superconducting pseudo-tetragonal and the superconducting monoclinic phases), Bi{sub 6}Ca{sub 7}O{sub 16}, CuO and SrCO{sub 3}. The 2201 phases were produced by the reactions of Bi-Sr-Cu-O or Bi-Sr-O compounds with SrCO{sub 3} or CuO. The 2201 phases could also be formed through the direct reaction between Bi{sub 2}CuO{sub 4} and SrCO{sub 3}. (orig.).

  11. Catalysts with Cu base supported in mixed oxides to generate H2: reformed of methanol in oxidant atmosphere

    International Nuclear Information System (INIS)

    Aguila M, M.M.; Perez H, R.; Rodriguez L, V.

    2006-01-01

    In this work, the characterization of Cu supported in CeO 2 -ZrO 2 , for to generate H 2 starting from the one reformed of methanol with water vapor and oxygen is presented. The sol-gel technique and classic impregnation for the obtaining of the supports and catalysts respectively were used. The materials were characterized by XRD, SEM, adsorption- desorption of N 2 and TPR. The catalytic materials presented crystalline phases associated with the zircon (tetragonal and monoclinic phase) and the ceria (cubic phase) depending on the CeO 2 /ZrO 2 relationship. The morphology of the catalysts was analyzed by SEM being observed semispheric particles for the rich materials in ZrO 2 and added planars in the rich materials in CeO 2 . The ceria addition to the zircon favors the specific area of the mixed oxides CeO 2 -ZrO 2 and it promotes the reducibility of the copper oxide at low temperatures. The rich catalysts in ceria also showed high activity in the methanol transformation and bigger selectivity toward the production of H 2 . This result is associated with the presence of copper species that decrease to low temperature present in the rich catalysts in ceria and that they are not present in the rich catalysts in zircon. (Author)

  12. Crystallographic and oxidation kinetic study of uranium dioxide by high temperature X-ray diffractometry

    International Nuclear Information System (INIS)

    Teixeira, S.R.

    1981-01-01

    The structural behavior of UO 2 sintered plates was studied as a function of temperature by X-ray diffractometry. All the experiments were carried out under an inert atmosphere with low oxygen content (approximated 140 ppm). The thermal expansion coefficient of UO 2 05 was found to be 10,5 x 10 - 6 0 C - 1 for temperatures above 165 0 C. Structural transformations during oxidation were observed at 170,235 and 275 0 C. The isothermal oxidation of UO 2 to U 3 O 7 follows a parabolic form and the diffusion of oxygen through the product layer U 4 O 9 is the mechanism controlling the oxidation rate. The phases observed were UO 2 (cubic) - U 4 O 9 (cubic) - U 3 O 7 (tetragonal). Activation energies of oxidation were found for different crystallographic planes (hkl). From this one can conclude that there is a preferential occupation of interstitial oxygen within the UO 2 structure. (Author) [pt

  13. The accelerated oxidation of zircaloy-4 at 700∼900 .deg. C in high pressure steam

    International Nuclear Information System (INIS)

    Kim, K. P.; Park, K. H.

    1999-01-01

    To find the effect of pressure on the high temperature oxidation of zircaloy-4, an autoclave capable of measuring the degree of oxidation at high temperatures and high pressure was manufactured. The specimens used in experiments are commercially available Zircaloy-4 used in Kori nuclear power plants. All the measurements were done at 700∼900 .deg. C in steam. Pressure effects were noticed. The oxide thickness was much thicker in high pressure steam, comparing to that in the 1 atm steam. And, the higher is the steam pressure, the thicker becomes the oxide. The enhancement of oxide growth rate at 700∼900 .deg. C in high pressure steam is approximately propotion to the power of 1.0∼1.6 of the ratio of experimental steam pressure to critical steam pressure. There is a critical steam pressure above that the oxidation rate enhances. The critical steam pressure was measured as 30∼40 bar. The enhanced oxidation seems from the oxide cracking due to the tetragonal to monoclinic phase transformation at high pressure steam

  14. Microstructural evolution and stability of tetragonal precipitates in Y2O3 partially-stabilized ZrO2 single crystals

    International Nuclear Information System (INIS)

    Martinez-Fernandez, J.; Jimenez-Melendo, M.; Dominguez-Rodriguez, A.

    1995-01-01

    The microstructure and morphology of tetragonal precipitates (t-ZrO 2 ) in yttria partially-stabilized zirconia single crystals containing various amounts of Y 2 O 3 (3, 4, 4.7 and 5.8 mol%) have been studied as a function of aging time at 1,600 C in air. The precipitate size and volume fraction of t-ZrO 2 phase were determined using transmission electron microscopy. The evolution of the precipitate volume fraction with aging time indicated that the precipitation reaction was completed after 24 h of annealing, in agreement with the values of the Y 2 O 3 composition in the matrix measured by analytical electron microscopy. Further aging coarsened the precipitates which joined together forming fiber-like particles of several micrometers in length and remaining untransformed despite their large size. The stability of the t-ZrO 2 precipitates against the tetragonal to monoclinic transformation in the ZrO 2 -Y 2 O 3 system seems to be related to interactions between precipitates due to coherency stresses rather than with their morphological characteristics

  15. Effects of deposition and annealing atmospheres on phase transition of tungsten oxide films grown by ultra-high-vacuum reactive sputtering

    International Nuclear Information System (INIS)

    Ghen, G.S.; Liao, W.L.; Chen, S.T.; Su, W.C.; Lin, C.K.

    2005-01-01

    A series of oxygen-contained tungsten films were grown on Si(100) substrates without intentional heating by ultra-high-vacuum reactive magnetron sputtering at a constant argon pressure (P Ar ) of 1.33 x 10 -1 Pa mixed with a wide range of O 2 partial pressures (P O ) from 1.33 x 10 -4 to 4 x 10 -1 Pa, equivalent to P O -to-P Ar ratios (P O/Ar ) from 1 x 10 -3 to 3. The effect of varying P O/Ar on phase evolution was evaluated by annealing the films in a controlled atmosphere (argon or oxygen) at 500 or 700 deg. C for 1 h. Grazing incident X-ray diffraction and transmission electron microscopy, together with the data of electrical resistivity and deposition rate, reveal that gradually increasing P O/Ar induces a sequence of phase transitions from nanocrystalline β-W(O) (P O/Ar ≤ 0.1), amorphous WO 2 (P O/Ar = 0.6) to amorphous WO 3 (P O/Ar ≥ 2). When annealed in argon atmosphere, the amorphous WO 2 and WO 3 exhibit a very different magnitude of crystallization temperature (T c ) and can be transformed, respectively, into monoclinic WO 2 (T c = 500 deg. C) and tetragonal WO 3 (T c = 700 deg. C). However, the oxidizing atmosphere plays a role to accelerate significantly the crystallization of the amorphous WO 2 into a completely different phase (monoclinic WO 3 ) at a significantly reduced T c of 500 deg. C

  16. X-Ray Photoelectron Spectroscopic Characterization of Iron Oxide Nanoparticles

    Energy Technology Data Exchange (ETDEWEB)

    Radu, T., E-mail: Teodora.Radu@itim-cj.ro [National Institute for Research and Development of Isotopic and Molecular Technologies, 67-103 Donat Street, 400293, Cluj Napoca (Romania); Iacovita, C. [Department of Pharmaceutical Physics-Biophysics, Faculty of Pharmacy, “Iuliu Hatieganu” University of Medicine and Pharmacy, 400349, Cluj-Napoca (Romania); Benea, D. [Faculty of Physics, Babes Bolyai University, 400271, Cluj-Napoca (Romania); Turcu, R. [National Institute for Research and Development of Isotopic and Molecular Technologies, 67-103 Donat Street, 400293, Cluj Napoca (Romania)

    2017-05-31

    Highlights: • Characterization of three types of iron oxides magnetic nanoparticles. • A correlation between valence band XPS and the degree of iron oxidation is proposed. • Theoretical contributions of Fe in tetragonal and octahedral environment are shown. - Abstract: We report X-ray photoelectron spectroscopy (XPS) results on iron oxide magnetic nanoparticle (Fe{sub 3}O{sub 4}) synthesized using solvothermal reduction in the presence of polyethylene glycol. The magnetite obtained was employed as precursor for the synthesis of γ-Fe{sub 2}O{sub 3} (by oxygen dissociation) which in turn was transformed into α-Fe{sub 2}O{sub 3}. We confirmed the magnetite, maghemite and hematite structure by Fourier Transformed Spectroscopy (FTIR) and X-ray diffraction (XRD). The analysis of the XPS core level and valence band (VB) photoemission spectra for all investigated samples is discussed in terms of the degree of iron oxidation. This is of fundamental importance to better understand the electronic structure of the obtained iron oxide nanoparticles in order to control and improve their quality for specific biomedical applications. Moreover, theoretical band structure calculations are performed for magnetite and the separate contributions of Fe in tetragonal and octahedral environment are shown.

  17. Production of ultrafine particles of high-temperature tetragonal WO3 by dc arc discharge in Ar-O2 gases

    International Nuclear Information System (INIS)

    Guo Yumei; Murata, Norihiko; Ono, Kazuya; Okazaki, Tsugio

    2005-01-01

    Ultrafine particles of WO 3 are successfully produced by dc arc discharge in Ar-O 2 gases. Particle sizes are distributed from 10 nm to 1 μm depending on production conditions: gas pressure, collection position and discharge current. Observations of the cooled particles by electron microscopy indicate that the WO 3 particles are tetragonal, a phase that is usually only stable above 725 deg. C. The octahedral crystals are bounded by eight {1 0 1} faces and occasionally truncated by {1 0 0} and/or {0 0 1} faces. This method of producing WO 3 by dc arc discharge therefore affords a high-temperature phase that is preserved upon cooling to room temperature

  18. Novel antimony doped tin oxide/carbon aerogel as efficient electrocatalytic filtration membrane

    Directory of Open Access Journals (Sweden)

    Zhimeng Liu

    2016-05-01

    Full Text Available A facile method was developed to prepare antimony doped tin oxide (Sb-SnO2/carbon aerogel (CA for use as an electrocatalytic filtration membrane. The preparation process included synthesis of a precursor sol, impregnation, and thermal decomposition. The Sb-SnO2, which was tetragonal in phase with an average crystallite size of 10.8 nm, was uniformly distributed on the CA surface and firmly attached via carbon-oxygen-tin chemical bonds. Preliminary filtration tests indicated that the Sb-SnO2/CA membrane had a high rate of total organic carbon removal for aqueous tetracycline owing to its high current efficiency and electrode stability.

  19. High-temperature steam-oxidation behavior of Zr-1Nb-1Sn-0.1Fe cladding tube at temperatures of 800-1000

    International Nuclear Information System (INIS)

    Lee, Cheol Min; Cho, Tae Won; Jeong, Gwan Yoon; Kim, Mi Jin; Kim, Ji Hyeon; Lee, Hee Jae; Sohn, Dong Seong; Mok, Yong Kyoon

    2016-01-01

    To prevent cladding failure, NRC issued a regulation Title 10 § 50.46, which specifies cladding temperature of 1204 .deg. C and 17% ECR should not be exceeded. The fundamental reason of the mechanical degradation of cladding is the formation of the oxide which is brittle. Theoretically, the oxide layer is formed following parabolic rate. However, from many experiments, sub-parabolic rates are often observed. There have been many suggestions so far; chemical and stress gradient across the oxide layer could initiate the sub-parabolic rate, the phase transformation of Zirconium dioxide from tetragonal to monoclinic could be the reason, change of the grain size of Zirconium dioxide could cause the cubic oxidation rate, and there is a suggestion that if electron migration is the major mechanism of the oxide growth, then the subparabolic rate can show up. However, the reason why the sub-parabolic rate appears is still not certain. Another important degradation mechanism is breakaway oxidation. A clear explanation that why the breakaway oxidation appears is still not clear. Most of the people believe the phase transformation of Zirconium dioxide cause instability within the oxide, which causes breakaway oxidation to appear. However, how much effect is caused from the phase transformation is not so sure. In this study, detailed analysis about the oxidation kinetics and the breakaway oxidation of Zr-1Nb-1Sn- 0.1Fe were carried out at temperatures between 800 - 1000 .deg. C.

  20. Reaction pathways for catalytic gas-phase oxidation of glycerol over mixed metal oxides

    Energy Technology Data Exchange (ETDEWEB)

    Suprun, W.; Glaeser, R.; Papp, H. [Leipzig Univ. (Germany). Inst. of Chemical Technology

    2011-07-01

    Glycerol as a main by-product from bio-diesel manufacture is a cheap raw material with large potential for chemical or biochemical transformations to value-added C3-chemicals. One possible way of glycerol utilization involves its catalytic oxidation to acrylic acid as an alternative to petrochemical routes. However, this catalytic conversion exhibits various problems such as harsh reaction conditions, severe catalyst coking and large amounts of undesired by-products. In this study, the reaction pathways for gas-phase conversion of glycerol over transition metal oxides (Mo, V und W) supported on TiO{sub 2} and SiO{sub 2} were investigated by two methods: (i) steady state experiments of glycerol oxidation and possible reactions intermediates, i.e., acrolein, 3-hydroxy propionaldehyde and acetaldehyde, and (ii) temperature-programmed surface reaction (TPSR) studies of glycerol conversion in the presence and in the absence of gas-phase oxygen. It is shown that the supported W-, V and Mo-oxides possess an ability to catalyze the oxidation of glycerol to acrylic acid. These investigations allowed us to gain a deeper insight into the reaction mechanism. Thus, based on the obtained results, three possible reactions pathways for the selective oxidation of glycerol to acrylic acid on the transition metal-containing catalysts are proposed. The major pathways in presence of molecular oxygen are a fast successive destructive oxidation of glycerol to CO{sub x} and the dehydration of glycerol to acrolein which is a rate-limiting step. (orig.)

  1. Formation of tungsten blue oxide and its phase constitution

    International Nuclear Information System (INIS)

    Zou, Z.; Wu, E.; Tan, A.; Qian, C.

    1984-01-01

    By means of X-ray diffraction structure analysis, SEM observation, chemical analysis and particle specific surface analysis etc., an investigation was made in order to determine the regularity of tungsten blue oxide formation during reductional calcine process of APT. It was found that the oxygen index (OI) decreased continuously with increasing calcine temperature. The decrease rate of OI variated as the calcine atmosphere being changed, the stronger the reductivity of the atmosphere is, the more OI decreases. The deammonia-dewater process and the phase constitution variation during calcine was studied, some idea for description of phase transformation path was suggested. It was found that the most important parameter affecting phase constitution and transformation is calcine temperature. At the temperature lower than 450 0 C, the main formed phase was ATB, while at higher temperature, the different phase like W/sub 20/O/sub 58/, WO/sub 3/ etc., could be formed by different ways depending on the atmosphere reductivity. The composition and the OI of ATB are changeable. An experiment for some blue oxides reduction at low temperature was carried out. It was found that OI and the constitution of blue oxide strongly affected the particle size of the formed W-powder

  2. Low temperature electron microscopy on the cubic-tetragonal transformation of V3Si

    Science.gov (United States)

    Onozuka, T.; Ohnishi, N.; Hirabayashi, M.

    1988-04-01

    The cubic-tetragonal martensitic transition of V3Si and its precursor have been investigated in the temperature range from 13 K to 80 K using a 1 MV electron microscope with a double-tilting cold stage. Below the transition temperature Tm = 19 K, fine twin lamellae appear parallel to {110} plane traces, being connected continuously with mottled striations having the same orientation. Fine striations along {110} traces or so-called tweeds are observed below 50 K at the precursor of the structural phase transition. The image contrast of mottled striations and tweed patterns is attributed to the presence of lattice distortion owing to the softening of the shear modulus. Reversible changes of the patterns recorded with a TV-VTR system during cooling and heating processes were discussed briefly.

  3. Nematic phase formation in suspensions of graphene oxide

    Science.gov (United States)

    Fresneau, Nathalie; Campidelli, Stéphane

    The last decade has seen the rise of graphene. Graphene is a single layer of graphite; it can be obtained by direct liquid phase exfoliation of the latter through harsh sonication. This technique presents the disadvantage to produce small graphene flakes (typically in the 0.05 to 0.4 μm2 range for the monolayers) and multilayer graphene with uncontrolled thickness distributions. In order to improve the exfoliation process, one has to counter the strong van der Waals interactions between the carbon planes of graphite. This implies to increase the distance between two planes and it can be done, for example, by oxidizing graphite to introduce oxygen species in the graphenic planes. The fabrication of graphite oxide is known for almost 150 years, and it became popular again these last ten years. Generally, the oxidation of graphite is performed following a method described by Hummers in the 1950's and the material produced by this technique exfoliates quasi-spontaneously into monolayer species called graphene oxide (GO). The highly anisotropic shape of GO (several μm in length and width for a thickness of ca. 1 nm) combined with the presence of oxygenated functions on the sp2 carbon structure of graphene lead to the formation of a lyotropic liquid crystalline phase in water. Above a certain concentration of graphene flakes the gain in translational entropy for a long-range ordered phase outweighs the loss in rotational entropy, and the liquid crystal phase then forms. The value of the threshold is affected by the aspect ratio of the graphene flakes but other factors such as the interactions also play a strong role.

  4. Comparison of the air oxidation behaviors of Zircaloy-4 implanted with yttrium and cerium ions at 500 deg. C

    International Nuclear Information System (INIS)

    Chen, X.W.; Bai, X.D.; Xu, J.; Zhou, Q.G.; Chen, B.S.

    2002-01-01

    As a valuable process for surface modification of materials, ion implantation is eminent to improve mechanical properties, electrochemical corrosion resistance and oxidation behaviors of varieties of materials. To investigate and compare the oxidation behaviors of Zircaloy-4, implantation of yttrium ion and cerium ion were respectively employed by using an MEVVA source at the energy of 40 keV with a dose ranging from 1x10 16 to 1x10 17 ions/cm 2 . Subsequently, weight gain curves of the different specimens including as-received Zircaloy-4 and Zircaloy-4 specimens implanted with the different ions were measured after oxidation in air at 500 deg. C for 100 min. It was obviously found that a significant improvement was achieved in the oxidation behaviors of implanted Zircaloy-4 compared with that of the as-received Zircaloy-4, and the oxidation behavior of cerium-implanted Zircaloy-4 was somewhat better than that of yttrium-implanted specimen. To obtain the valence and the composition of the oxides in the scale, X-ray photoemission spectroscopy was used in the present study. Glancing angle X-ray diffraction, employed to analyze the phase transformation in the oxide films, showed that the addition of yttrium transformed the phase from monoclinic zirconia to tetragonal zirconia, yet the addition of cerium transformed the phase from monoclinic zirconia to hexagonal zirconia. In the end, the mechanism of the improvement of the oxidation behavior was discussed

  5. Laser-induced partial oxidation of cyclohexane in liquid phase

    International Nuclear Information System (INIS)

    Oshima, Y.; Wu, X.W.; Koda, S.

    1995-01-01

    A laser-induced partial oxidation of cyclohexane was studied in the liquid phase. With KrF excimer laser (248 nm) irradiation to neat liquid cyclohexane in which O 2 was dissolved, cyclohexanol and cyclohexanone were obtained with very high selectivities, together with cyclohexane as a minor product. Radical recombination reactions to produce dicyclohexyl ether and bicyclohexyl also took place, while these products were not observed in the gas phase reaction. These experimental results were considered to be due not only to higher concentration of cyclohexane but to the cage effect in the liquid phase oxidation. To clarify the reaction progress including the photoabsorption process, the effects of laser intensity and O 2 pressure on product distribution were studied. (author)

  6. Thin-foil phase transformations of tetragonal ZrO/sub 2/ in a ZrO/sub 2/-8 wt% Y/sub 2/O/sub 3/ alloy

    International Nuclear Information System (INIS)

    Bestgen, H.; Chaim, R.; Heuer, A.H.

    1988-01-01

    Tetragonal zirconia (t-ZrO/sub 2/) grains in an annealed ZrO/sub 2/-8 wt% Y/sub 2/O/sub 3/ alloy transformed to orthorhombic (o) or mono-clinic (m) symmetry by stresses induced by localized electron beam heating in the transmission electron microscope. Different transformation mechanisms were observed, depending on foil thickness and orientation of individual grains. In thicker grains (≥150 nm), the transformation proceeded by a burst-like growth of m laths, and this is believed to approximate bulk behavior. In thinner grains near the edge of the foil, usually those with a [100]/sub t/ orientation perpendicular to the thin-foil surface, continuous growth of an o or m phase with an antiphase-boundary-containing microstructure was observed. The o phase is believed to be a high-pressure polymorph of ZrO/sub 2/, which forms (paradoxically) as a thin-foil artifact because it is less dense than t-ZrO/sub 2/, but more dense than m-ZrO/sub 2/. In some very thin grains, the t → m transformation was thermoelastic. Furthermore, a mottled structure often occurred just before the t → m or t → o transformation, which is attributed to surface transformation. Aside from the lath formation, the observed transformation modes are a result of the reduced constraints in thin foils

  7. The Structural Phase Transition in Solid DCN

    DEFF Research Database (Denmark)

    Dietrich, O. W.; Mackenzie, Gordon A.; Pawley, G. S.

    1975-01-01

    Neutron scattering measurements on deuterated hydrogen cyanide have shown that the structural phase change from a tetragonal to an orthorhombic form at 160K is a first-order transition. A transverse acoustic phonon mode, which has the symmetry of the phase change, was observed at very low energies...

  8. Growth kinetics of tetragonal and monoclinic ZrO2 crystallites in 3 mol% yttria partially stabilized ZrO2 (3Y-PSZ) precursor powder

    International Nuclear Information System (INIS)

    Kuo, Chih-Wei; Lee, Kuen-Chan; Yen, Feng-Lin; Shen, Yun-Hwei; Lee, Huey-Er; Wen, Shaw-Bing; Wang, Moo-Chin; Stack, Margaret Mary

    2014-01-01

    Highlights: • The crystalline structures were composed of tetragonal and monoclinic ZrO 2 . • Growth kinetics of t-ZrO 2 in the 3Y-PSZ precursor powder is described as: D te 2 =(4.57±0.55)t 0.12±0.02 exp(-((24.79±0.38)×10 3 )/(RT) ). • Growth kinetics of m-ZrO 2 in the 3Y-PSZ precursor powder is described as: D m 2 =(4.40±1.63)t 0.17±0.08 exp(-((66.47±3.97)×10 3 )/(RT) ). - Abstract: The growth kinetics of tetragonal and monoclinic ZrO 2 crystallites in 3 mol% yttria partially stabilized ZrO 2 (3Y-PSZ) precursor powder has been investigated using X-ray diffraction (XRD), Brunauer–Emmett–Teller (BET) specific surface area analysis, transmission electron microscopy (TEM) and high resolution TEM (HRTEM). After calcination of the 3Y-PSZ precursor powder between 773 and 1073 K for 2 h, the crystalline structures were composed of tetragonal and monoclinic ZrO 2 as the primary and secondary phases, respectively. When the 3Y-PSZ precursor powder was calcined at 773 K for 2 h, the BET specific surface area was 97.13 m 2 /g, which is equivalent to a particle size of 10.30 nm. The crystallite sizes determined via XRD and BET agreed well, indicating that the powder was virtually non-agglomerated. The growth kinetics of tetragonal and monoclinic ZrO 2 crystallite isothermal growth in the 3Y-PSZ precursor powder are described by: D te 2 =(4.57±0.55)t 0.12±0.02 exp(-((24.79±0.38)×10 3 )/(RT) ) and D m 2 =(4.40±1.63)t 0.17±0.08 exp(-((66.47±3.97)×10 3 )/(RT) ), respectively, for 773K≤T≤1073K. D te and D m denote the crystallite size of tetragonal and monoclinic ZrO 2 at time t and temperature T, respectively

  9. Synthesis of new perovskite and ''tetragonal bronze'' materials with thorium

    International Nuclear Information System (INIS)

    Launay, Suzanne; Erb, Alfred; Freundlich, William

    1982-01-01

    Disclosure and crystal chemistry study of the solid solutions Th(NbO 3 ) 4 , NaNbO 3 or AgNbO 3 with perovskite structure and Th(Nb, TaO 3 ) 4 , K(Nb,Ta)O 3 with ''tetragonal tungstene bronze'' structure, ''Banana'' type [fr

  10. The analysis of magnesium oxide hydration in three-phase reaction system

    Energy Technology Data Exchange (ETDEWEB)

    Tang, Xiaojia; Guo, Lin; Chen, Chen; Liu, Quan; Li, Tie; Zhu, Yimin, E-mail: ntp@dlmu.edu.cn

    2014-05-01

    In order to investigate the magnesium oxide hydration process in gas–liquid–solid (three-phase) reaction system, magnesium hydroxide was prepared by magnesium oxide hydration in liquid–solid (two-phase) and three-phase reaction systems. A semi-empirical model and the classical shrinking core model were used to fit the experimental data. The fitting result shows that both models describe well the hydration process of three-phase system, while only the semi-empirical model right for the hydration process of two-phase system. The characterization of the hydration product using X-Ray diffraction (XRD) and scanning electron microscope (SEM) was performed. The XRD and SEM show hydration process in the two-phase system follows common dissolution/precipitation mechanism. While in the three-phase system, the hydration process undergo MgO dissolution, Mg(OH){sub 2} precipitation, Mg(OH){sub 2} peeling off from MgO particle and leaving behind fresh MgO surface. - Graphical abstract: There was existence of a peeling-off process in the gas–liquid–solid (three-phase) MgO hydration system. - Highlights: • Magnesium oxide hydration in gas–liquid–solid system was investigated. • The experimental data in three-phase system could be fitted well by two models. • The morphology analysis suggested that there was existence of a peel-off process.

  11. Crystal structure and phase transitions of sodium potassium niobate perovskites

    Science.gov (United States)

    Tellier, J.; Malic, B.; Dkhil, B.; Jenko, D.; Cilensek, J.; Kosec, M.

    2009-02-01

    This paper presents the crystal structure and the phase transitions of K xNa 1- xNbO 3 (0.4 ≤ x ≤ 0.6). X-ray diffraction measurements were used to follow the change of the unit-cell parameters and the symmetry in the temperature range 100-800 K. At room temperature all the compositions exhibited a monoclinic metric of the unit cell with a small monoclinic distortion (90.32° ≤ β ≤ 90.34°). No major change of symmetry was evidenced in the investigated compositional range, which should be characteristic of the morphotropic phase-boundary region. With increasing temperature, the samples underwent first-order monoclinic-tetragonal and tetragonal-cubic transitions. Only the potassium-rich phases were rhombohedral at 100 K.

  12. Various magnetic behaviors of the hydrides deriving from the tetragonal CeFeSi-type compounds

    International Nuclear Information System (INIS)

    Chevalier, B.; Tence, S.; Gaudin, E.; Matar, S.F.; Bobet, J.-L.

    2009-01-01

    The hydrides RETXH (RE = rare earth, T = transition metal and X = Si, Ge) crystallizing in the tetragonal ZrSiCuAs-type are obtained by hydrogen absorption of the intermetallics adopting the tetragonal CeFeSi-type. The H-insertion induces interesting magnetic transitions governed by two effects: the increase of the unit cell volume linked to the H-absorption and the occurrence of the RE-H chemical bonding. Some typical examples are reported in this present brief review.

  13. The magnetic Curie temperature and exchange coupling between cations in tetragonal spinel oxide Mn{sub 2.5}M{sub 0.5}O{sub 4} (M = Co, Ni, Mn, Cr, and Mg) films

    Energy Technology Data Exchange (ETDEWEB)

    Kuo, K.; Cheng, C. W.; Chern, G. [Physics Department and SPIN Research Center, National Chung Cheng University, Chia-Yi, Taiwan, 621 (China)

    2012-04-01

    Mn{sub 3}O{sub 4} is a Jahn-Taller tetragonal ferrite that has a relatively low Curie temperature (T{sub c}) of {approx}43 K due to weak coupling between the canting spins. In this study, we fabricated a series of 100-nm-thick Mn{sub 2.5}M{sub 0.5}O{sub 4} (M = Co, Ni, Mn, Cr, and Mg) films via oxygen-plasma-assisted molecular beam epitaxy and measured the structural and magnetic properties of these films. These films show single phase quality, and the c-axis lattice parameter of pure Mn{sub 3}O{sub 4} is 0.944 nm, with a c/a ratio {approx}1.16, consistent with the bulk values. The replacement of Mn by M (M = Co, Ni, Cr, and Mg) changes the lattice parameters, and the c/a ratio varies between 1.16 and 1.06 depending upon the cation distribution of the films. The magnetic Curie temperatures of these films also vary in the range of 25-66 K in that Ni and Co enhance the T{sub c} whereas Mg reduces the T{sub c} (Cr shows no effect on the T{sub c}). These changes to the T{sub c} are related to both the element electronic state and the cation distributions in these compounds. As a non-collinear spin configuration can induce electrical polarization, the present study provides a systematic way to enhance the magnetic transition temperature in tetragonal spinel ferrites.

  14. Phase transitions and optical characterization of lead-free piezoelectric (K0.5Na0.5)0.96Li0.04(Nb 0.8Ta0.2)O3 thin films

    KAUST Repository

    Yao, Yingbang; Chan, H. T.; Mak, C. L.; Wong, Kinhung

    2013-01-01

    . The phase transitions of the films were studied by Raman spectroscopy. Two distinct anomalies originating from the cubic-to-tetragonal (TC-T ~ 300 C) and tetragonal-to-orthorhombic (TT-O ~ 120 C) phase transitions were observed. Our results show that Raman

  15. [In vitro evaluation of low-temperature aging effects of Y2O3 stabilized tetragonal zirconia polycrystals dental ceramics].

    Science.gov (United States)

    Yi, Yuan-fu; Liu, Hong-chen; Wang, Chen; Tian, Jie-mo; Wen, Ning

    2008-03-01

    To investigate the influence of in vitro low-temperature degradation (LTD) treatment on the structural stability of 5 kinds of Y2O3 stabilized tetragonal zirconia polycrystals (Y-TZP) dental ceramics. TZ-3YS powder was compacted at 200 MPa using cold isostatic pressure and pre-sintered at 1050 degrees C for 2 h forming presintered blocks. Specimens were sectioned into 15 mm x 15 mm x 1.5 mm slices from blocks of TZ-3YS, Vita In-Ceram YZ, Ivoclar, Cercon Smart, and Kavo Y-TZP presintered blocks, 18 slices for each brand, and then densely sintered. Specimens were divided into 6 groups and subjected to an accelerated aging test carried out in an autoclave in steam at 134 degrees C, 0.2 MPa, for 0, 1, 2, 3, 4, and 5 h. X-ray diffraction (XRD) was used to identify crystal phases and relative content of monoclinic phase was calculated. Specimens for three-point bending test were fabricated using TZ-3YS ceramics according to the ISO 6872 standard and bending strength was tested before and after aging. The polished and aging specimens of TZ-3YS and Cercon Smart zirconia ceramics were observed by atomic force microscopy (AFM) to evaluate surface microstructure. Tetragonal-to-monoclinic phase transformation was detected for specimens of TZ-3YS, Vita In-Ceram YZ, Ivoclar, and Kavo zirconia ceramics except for Cercon Smart ceramics after aging, and the relative content of monoclinic phase was increasing with the prolonged aging time. TZ-3YS was the most affected material, Kavo took the second, and Vita and Ivoclar were similar. Aging had no significant negative effects on flexural strength of TZ-3YS with average bending strength being over 1100 MPa. The nucleation and growth of monoclinic phase were detected by AFM in surface of Cercon Smart zirconia in which monoclinic phase was not detected by XRD. The results suggest that LTD of dental Y-TZP is time dependent, but the aging test does not reduce the flexural strength of TZ-3YS. The long-term clinical serviceability of dental

  16. Phase stability of TiH{sub 2} under high pressure and temperatures

    Energy Technology Data Exchange (ETDEWEB)

    Selva Vennila, R.; Durygin, A.; Saxena, S.K. [Center for Study of Matter at Extreme Conditions (CeSMEC), Florida International University, VH-150, University Park, Miami, FL 33199 (United States); Merlini, Marco [European Synchrotron Radiation Facility (ESRF), Grenoble 38043 (France); Wang, Zhongwu [Cornell High Energy Synchrotron Source (CHESS), Wilson Laboratory, Cornell University, Ithaca, NY 14853 (United States)

    2008-11-15

    Phase stability of titanium hydride (TiH{sub 2}) was studied at high pressure-high temperature conditions using synchrotron radiation under non-hydrostatic conditions. Resistive heating method was used to heat the sample to a maximum temperature of 873 K in a diamond anvil cell (DAC) under pressure up to 12 GPa. Pressure-temperature behavior was studied by varying the temperature upto 823 K in steps of 50 K with pressure variations within 3 GPa. Structural phase transformation from tetragonal (I4/mmm) to cubic (Fm-3 m) was observed with increase in temperature. Tetragonal phase was found to be stabilized when the sample was subjected to pressure and temperature cycle. (author)

  17. Structure of tetragonal martensite in the In95.42Cd4.58 cast alloy

    Science.gov (United States)

    Khlebnikova, Yu. V.; Egorova, L. Yu.; Rodionov, D. P.; Kazantsev, V. A.

    2017-11-01

    The structure of martensite in the In95.42Cd4.58 alloy has been studied by metallography, X-ray diffraction, dilatometry, and transmission electron microscopy. It has been shown that a massive structure built of colonies of tetragonal lamellar plates divided by a twin boundary {101}FCT is formed in the alloy under cooling below the martensite FCC → FCT transition temperature. The alloy recrystallizes after a cycle of FCT → FCC → FCT transitions with a decrease in the grain size by several times compared with the initial structure such fashion that the size of massifs and individual martensite lamella in the massif correlates with the change in the size of the alloy grain. Using thermal cycling, it has been revealed that the alloy tends to stabilize the high-temperature phase.

  18. Phase formation and stability in TiO{sub x} and ZrO{sub x} thin films. Extremely sub-stoichiometric functional oxides for electrical and TCO applications

    Energy Technology Data Exchange (ETDEWEB)

    Henning, Ralph A.; Leichtweiss, Thomas; Decker, Yannic; Janek, Juergen [Giessen Univ. (Germany). Inst. of Physical Chemistry; Dorow-Gerspach, Daniel; Schmidt, Ruediger; Wuttig, Matthias [RWTH Aachen Univ. (Germany). Inst. of Physics; Wolff, Niklas; Schuermann, Ulrich; Kienle, Lorenz [Kiel Univ. (Germany). Faculty of Engineering

    2017-03-01

    Most functional materials are thermodynamic equilibrium phases representing minima in the thermodynamic phase space. However, it is expected that many metastable phases with highly interesting properties also exist. Here, we report on a systematic approach to prepare thin-films of such non-equilibrium phases based on the gas phase deposition methods sputtering and pulsed laser deposition (PLD). Our synthetic strategy is to deposit a ''precursor phase'' which is amorphous or already a crystalline non-equilibrium phase. Subsequent heat treatment leads to the nucleation of crystalline phases which again may be metastable or stable compounds. In the present paper we focus on the binary systems Ti-O and Zr-O, both systems being widely applied and technologically relevant. Highly oxygen-deficient titanium oxide (TiO{sub 1.6}) and zirconium oxide (ZrO) films prepared by pulsed laser deposition at room temperature are optically absorbing and possess electronic conductivities in the range of 10 S/cm. Both materials are metastable in respect to both composition and structure. For TiO{sub 1.6} we find an amorphous matrix with embedded grains of cubic titanium monoxide (γ-TiO) directly after deposition. Upon annealing nanocrystalline grains of metallic Ti are formed in the amorphous matrix due to an internal solid-state disproportionation whereas the electrical conductivity of the films increases and comes close to metal-like conductivity (1000 S/cm) at about 450 C. Congruently, room temperature deposited ZrO films with an average composition of Zr:O= 1:1 contain small ZrO nanocrystals within an amorphous matrix. Heat treatment again leads to an internal disproportionation reaction whereas small crystals of Zr{sub 2}O and ZrO{sub 2} precipitate at temperatures as low as 75 C. Increasing the temperature then results in the crystallization of metastable tetragonal ZrO{sub 2} at about 400 C. Sputter deposition allows a subtler control of the oxygen partial

  19. HRTEM investigation of orthorhombic phase in Mg-PSZ

    International Nuclear Information System (INIS)

    Liu, Z.W.; Spargo, A.E.C.; Hannink, R.H.J.

    1997-01-01

    Tetragonal, orthorhombic and monoclinic phases are only slight distortions of the cubic structure. Due to minor differences in unit cell parameters it is difficult to distinguish these phases only by high resolution images. However, using high resolution transmission electron microscopy (HRTEM) observation in combination with image simulation and digital Fourier transformation of HRTEM images, it was found that one tetragonal precipitate can be transformed to several orthorhombic domains with different orientations in MgO-partially-stabilized zirconia (Mg-PSZ). The lattice correspondence between two adjacent orthorhombic domains is such that their b axes are parallel, while their a axes are perpendicular to each other. Also it was found that cubic ZrO 2 could be transformed to orthorhombic ZrO 2 . 8 refs., 1 tab., 4 figs

  20. Role of sintering time, crystalline phases and symmetry in the piezoelectric properties of lead-free KNN-modified ceramics

    International Nuclear Information System (INIS)

    Rubio-Marcos, F.; Marchet, P.; Merle-Mejean, T.; Fernandez, J.F.

    2010-01-01

    Lead-free KNN-modified piezoceramics of the system (Li,Na,K)(Nb,Ta,Sb)O 3 were prepared by conventional solid-state sintering. The X-ray diffraction patterns revealed a perovskite phase, together with some minor secondary phase, which was assigned to K 3 LiNb 6 O 17 , tetragonal tungsten-bronze (TTB). A structural evolution toward a pure tetragonal structure with the increasing sintering time was observed, associated with the decrease of TTB phase. A correlation between higher tetragonality and higher piezoelectric response was clearly evidenced. Contrary to the case of the LiTaO 3 modified KNN, very large abnormal grains with TTB structure were not detected. As a consequence, the simultaneous modification by tantalum and antimony seems to induce during sintering a different behaviour from the one of LiTaO 3 modified KNN.

  1. Role of sintering time, crystalline phases and symmetry in the piezoelectric properties of lead-free KNN-modified ceramics

    Energy Technology Data Exchange (ETDEWEB)

    Rubio-Marcos, F., E-mail: frmarcos@icv.csic.es [Electroceramic Department, Instituto de Ceramica y Vidrio, CSIC, Kelsen 5, 28049 Madrid (Spain); Marchet, P.; Merle-Mejean, T. [SPCTS, UMR 6638 CNRS, Universite de Limoges, 123, Av. A. Thomas, 87060 Limoges (France); Fernandez, J.F. [Electroceramic Department, Instituto de Ceramica y Vidrio, CSIC, Kelsen 5, 28049 Madrid (Spain)

    2010-09-01

    Lead-free KNN-modified piezoceramics of the system (Li,Na,K)(Nb,Ta,Sb)O{sub 3} were prepared by conventional solid-state sintering. The X-ray diffraction patterns revealed a perovskite phase, together with some minor secondary phase, which was assigned to K{sub 3}LiNb{sub 6}O{sub 17}, tetragonal tungsten-bronze (TTB). A structural evolution toward a pure tetragonal structure with the increasing sintering time was observed, associated with the decrease of TTB phase. A correlation between higher tetragonality and higher piezoelectric response was clearly evidenced. Contrary to the case of the LiTaO{sub 3} modified KNN, very large abnormal grains with TTB structure were not detected. As a consequence, the simultaneous modification by tantalum and antimony seems to induce during sintering a different behaviour from the one of LiTaO{sub 3} modified KNN.

  2. Linear electro-optical properties of tetragonal BaTiO 3

    Indian Academy of Sciences (India)

    Linear optical susceptibility and clamped linear electro-optical tensor coefficients of tetragonal BaTiO3 are calculated using a formalism based on bond charge theory. Calculated values are in close agreement with experimental data. The covalent Ti–O bonds constituting distorted TiO6 octahedral groups are found to be ...

  3. Synthesis of new perovskite and ''tetragonal bronze'' materials with thorium

    Energy Technology Data Exchange (ETDEWEB)

    Launay, S; Erb, A; Freundlich, W [Universite Paris-VI (France)

    1982-03-22

    Disclosure and crystal chemistry study of the solid solutions Th(NbO/sub 3/)/sub 4/, NaNbO/sub 3/ or AgNbO/sub 3/ with perovskite structure and Th(Nb, TaO/sub 3/)/sub 4/, K(Nb,Ta)O/sub 3/ with ''tetragonal tungstene bronze'' structure, ''Banana'' type.

  4. Effects of iron content on electrical resistivity of oxide films on Zr-base alloys

    International Nuclear Information System (INIS)

    Kubo, Toshio; Uno, Masayoshi

    1991-01-01

    Measurements of electrical resistivity were made for oxide films formed by anodic oxidation and steam oxidation (400degC/12 h) on Zr plates with different Fe contents. When the Fe content was higher than about 1,000 ppm the electrical resistivity of the steam oxide films was almost equivalent to that of the anodic oxide films, while at lower Fe content the former exhibited lower electrical resistivity than the latter by about 1∼3 orders of magnitude. The anodic oxide film was an almost homogeneous single oxide layer. The steam oxide films, on the other hand, were composed of duplex oxide layers. The oxide layer formed in the vicinity of the oxide/metal interface had higher electrical resistivity than the near-surface oxide layer by about 1∼4 orders of magnitude. The oxide layer in the vicinity of the interface could act as a protective film against corrosion and its electrical resistivity is one important factor controlling the layer protectiveness. The electrical resistivity of the oxide/metal interfacial layer was strongly dependent on the Fe content. One possible reason for Fe to improve the corrosion resistance is that Fe ions would tend to stabilize the tetragonal (or cubic) phase and consequently suppress the formation of open pores and cracks in the interfacial layer. (author)

  5. Ferroelastic phase transitions in (NH4)2TaF7

    Science.gov (United States)

    Pogorel'tsev, E. I.; Mel'nikova, S. V.; Kartashev, A. V.; Molokeev, M. S.; Gorev, M. V.; Flerov, I. N.; Laptash, N. M.

    2013-03-01

    The heat capacity, unit cell parameters, permittivity, optical properties, and thermal expansion of the (NH4)2TaF7 compound with a seven-coordinated anion polyhedron have been measured. It has been found that the compound undergoes two successive phase transitions with the symmetry change: tetragonal → ( T 1 = 174 K) orthorhombic → ( T 2 = 156 K) tetragonal. The ferroelastic nature of structural transformations has been established, and their entropy and susceptibility to hydrostatic pressure have been determined.

  6. Excited State Dynamics and Semiconductor-to-Metallic Phase Transition of VO2 Thin Film

    National Research Council Canada - National Science Library

    Liu, Huimin

    2004-01-01

    .... Vanadium dioxide shows an ultrafast, passive phase transition (PT) from a monoclinic semiconductor phase to a metallic tetragonal rutile structure when the sample temperature is above 68 degrees C...

  7. Phase equilibria, crystal structure and properties of complex oxides in the Nd{sub 2}O{sub 3}–SrO–CoO system

    Energy Technology Data Exchange (ETDEWEB)

    Aksenova, T.V.; Efimova, T.G. [Department of Physical and Inorganic Chemistry, Institute of Natural Science and Mathematics, Ural Federal University, Lenin av., 51, Yekaterinburg 620000 (Russian Federation); Lebedev, O.I. [Laboratoire CRISMAT, ENSICAEN UMR6508, 6 Bd Maréchal Juin, Cedex 4, Caen 14050 (France); Elkalashy, Sh.I.; Urusova, A.S. [Department of Physical and Inorganic Chemistry, Institute of Natural Science and Mathematics, Ural Federal University, Lenin av., 51, Yekaterinburg 620000 (Russian Federation); Cherepanov, V.A., E-mail: v.a.cherepanov@urfu.ru [Department of Physical and Inorganic Chemistry, Institute of Natural Science and Mathematics, Ural Federal University, Lenin av., 51, Yekaterinburg 620000 (Russian Federation)

    2017-04-15

    The phase equilibria in the ½Nd{sub 2}O{sub 3}–SrO–CoO system were systematically studied at 1373 K in air. The intermediate phases formed in the ½Nd{sub 2}O{sub 3}–SrO–CoO system at 1373 K in air are: Nd{sub 1-x}Sr{sub x}CoO{sub 3-δ} (0.0≤x≤0.5 with orthorhombic structure, sp. gr. Pbnm and 0.6≤x≤0.95 whose structure was detected as cubic according to XRD sp. gr. Pm3m, but shown to be tetragonal by TEM due to the oxygen vacancy ordering), Nd{sub 2-y}Sr{sub y}CoO{sub 4-δ} (0.6≤y≤1.1 with tetragonal K{sub 2}NiF{sub 4}-type structure, sp. gr. I4/mmm) and Nd{sub 2-z}Sr{sub z}O{sub 3} (0.0≤z≤0.15 with hexagonal structure, sp. gr. P-3m1). The unit cell parameters for the single phase samples were refined by the Rietveld analysis. The changes of oxygen content in Nd{sub 1-x}Sr{sub x}CoO{sub 3-δ} (0.6≤x≤0.95) and Ruddlesden-Popper oxide Nd{sub 2-y}Sr{sub y}CoO{sub 4-δ} were examined by TGA. All were found to be oxygen deficient phases. High-temperature dilatometry allows calculating the thermal expansion coefficient and evaluating the chemical expansion coefficient at high temperature. The projection of isothermal-isobaric phase diagram for the Nd–Sr–Co–O system at 1373 K in air to the compositional triangle of metallic components has been constructed. The phase equilibria in the studied Nd–Sr–Co–O system were compared to La–Sr–Co–O and Nd–M–Co–O (M=Ca and Ba). - Graphical abstract: Crystal structure of vacancy ordered supercell for Nd{sub 0.2}Sr{sub 0.8}CoO{sub 3-δ} and projection of phase diagram for the Nd–Sr–Co–O system onto the triangle edge of metallic components at 1373 K in air. - Highlights: • The diagram for the Nd–Sr–Co–O system at 1373 K in air has been constructed. • The crystal structure of Nd{sub 1-x}Sr{sub x}CoO{sub 3-δ} and Nd{sub 2-y}Sr{sub y}CoO{sub 4±δ} was refined. • The formation of superstructure due to the oxygen vacancy ordering was proved. • The changes of oxygen

  8. The phase stability and toughening effect of 3Y-TZP dispersed in the lanthanum zirconate ceramics

    International Nuclear Information System (INIS)

    Wang, Yanfei; Xiao, Ping

    2014-01-01

    The low fracture toughness of lanthanum zirconate (La 2 Zr 2 O 7 , LZ) greatly impedes its wide application as thermal barrier coatings (TBC). The 3 mol% Y 2 O 3 -stabilized tetragonal zirconia polycrystals (3Y-TZP) have been introduced to toughen the brittle LZ ceramics. The dispersive 3Y-TZP undergoes a simultaneous t–m transformation upon cooling below a critical volume fraction x of 3Y-TZP, above which its tetragonal phases can however be preserved. The different stabilities of 3Y-TZP second phases arise from a variation of residual tensile stress within them. The fracture toughness has been greatly improved by dispersing the tetragonal particulates (t-3YSZ) in the LZ matrix and the primary toughening mechanisms are phase transformations of the dispersive second phases and the residual compressive stress within the matrix. An anticipated increase of fracture toughness from the ferroelastic toughening and the residual compressive stress toughening highlights the great potentials to improve coating durability by depositing t′-3YSZ/LZ composite TBCs by the industrial non-equilibrium route

  9. Oxidation kinetics of zircaloy-4 in the temperature range correspondent to alpha phase

    International Nuclear Information System (INIS)

    Medeiros, L.F.

    1975-12-01

    Oxidation kinetics of Zry-4 in the alpha phase is isothermally studied in the temperature range from 600 0 C to 800 0 C, by continuous and discontinuous gravimetric methods. The total mass gain during the oxidation takes place by two distinct ways: oxide formation and solid solution formation. The first one has been studied by microscopy: the latter by microhardness. The oxygen diffusion coefficients in the zirconium are experimentally determined by microhardness measurements and are compared with those obtained by the oxide layer thickness and by oxygen mass in the oxide. The oxygen diffusion coefficients in the oxide are obtained too by oxide layer thickness and by oxygen diffusivities in the alpha phase and compared with literature. (author)

  10. Phase coexistence in ferroelectric solid solutions: Formation of monoclinic phase with enhanced piezoelectricity

    Directory of Open Access Journals (Sweden)

    Xiaoyan Lu

    2016-10-01

    Full Text Available Phase morphology and corresponding piezoelectricity in ferroelectric solid solutions were studied by using a phenomenological theory with the consideration of phase coexistence. Results have shown that phases with similar energy potentials can coexist, thus induce interfacial stresses which lead to the formation of adaptive monoclinic phases. A new tetragonal-like monoclinic to rhombohedral-like monoclinic phase transition was predicted in a shear stress state. Enhanced piezoelectricity can be achieved by manipulating the stress state close to a critical stress field. Phase coexistence is universal in ferroelectric solid solutions and may provide a way to optimize ultra-fine structures and proper stress states to achieve ultrahigh piezoelectricity.

  11. Off-center Jahn-Teller ion: coupled polar and tetragonal deformations

    International Nuclear Information System (INIS)

    Vikhnin, V.S.; Sochava, L.S.

    1979-01-01

    Models of the off-center Jahn-Teller ions are considered, i.e. Ni + in SrO and Cu 27 in SrO studied earlier. Models of the off-center Jahn-Teller ion are proposed, in which mutual effect of dipole-active deformations conditioning off-centering and the Jahn-Teller tetragonal deformations takes place. Manifestations of a new type of multipit potential XY 24 of an off-center ion are considered. The Jahn-Teller effect (JTE) is studied for a duplicate in cubic environment, unharmonism of the fourth order being taken into account. In such a model of Exe of JTE, the position and quantity of minima of adiabatic potential are changed as compared with Exe of JTE taking account of unharmonism of the third order or the square Jahn-Teller interaction. While using models of the off-center Jahn-Teller ion which take account of the effect of two tetragonal Jahn-Teller deformations occurring in the Exe problem considering unharmonism of the fourth order produced on dipole-active deformations, it becomes possible to explain the experiment for SrO:Ni +

  12. Iron Oxide Doped Alumina-Zirconia Nanoparticle Synthesis by Liquid Flame Spray from Metal Organic Precursors

    Directory of Open Access Journals (Sweden)

    Juha-Pekka Nikkanen

    2008-01-01

    Full Text Available The liquid flame spray (LFS method was used to make iron oxide doped alumina-zirconia nanoparticles. Nanoparticles were generated using a turbulent, high-temperature (Tmax⁡∼3000 K H2-O2 flame. The precursors were aluminium-isopropoxide, zirconium-n-propoxide, and ferrocene in xylene solution. The solution was atomized into micron-sized droplets by high velocity H2 flow and introduced into the flame where nanoparticles were formed. The particle morphology, size, phase, and chemical composition were determined by TEM, XRD, XPS, and N2-adsorption measurements. The collected particulate material consists of micron-sized aggregates with nanosized primary particles. In both doped and undoped samples, tetragonal phase of zirconia was detected in room temperature while alumina was found to be noncrystalline. In the doped powder, Fe was oxidized to Fe2O3. The primary particle size of collected sample was approximately from 6 nm to 40 nm. Doping was observed to increase the specific surface area of the powder from 39 m2/g to 47 m2/g.

  13. Composition-dependent properties and phase stability of Fe-Pd ferromagnetic shape memory alloys: A first-principles study

    Science.gov (United States)

    Li, Chun-Mei; Hu, Yan-Fei

    2017-12-01

    The composition-dependent properties and their correlation with the phase stability of Fe75+xPd25-x (- 10.0 ≤x ≤10.0 ) alloys are systematically investigated by using first-principles exact muffin-tin orbitals (EMTO)-coherent potential approximation (CPA) calculations. It is shown that the martensitic transformation (MT) from L 12 to body-centered-tetragonal (bct) occurs in the ordered alloys with about -5.0 ≤x ≤10.0 . In both the L 12 and bct phases, the evaluated a and c/a agree well with the available experimental data; the average magnetic moment per atom increases whereas the local magnetic moments of Fe atoms, dependent on both their positions and the structure of the alloy, decrease with increasing x. The tetragonal shear elastic constant of the L 12 phase ( C ' ) decreases whereas that of the bct phase (Cs) increases with x. The tetragonality of the martensite ( |1 -c /a | ) increases whereas its energy relative to the austenite with a negative value decreases with Fe addition. All these effects account for the increase of MT temperature (TM) with x. The MT from L 12 to bct is finally confirmed originating from the splitting of Fe 3d Eg and T2 g bands upon tetragonal distortion due to the Jahn-Teller effect.

  14. The crystal structure and the phase transitions of pyridinium trifluoromethanesulfonate

    International Nuclear Information System (INIS)

    Jesariew, Dominik; Ilczyszyn, Maria M; Pietraszko, Adam

    2014-01-01

    The calorimetric and optical studies and the structural properties of pyridinium trifluoromethanesulfonate (abbreviated as PyHOTf) are reported. A sequence of four fully reversible solid–solid phase transitions, at 223.0, 309.0, 359.9 and 394.3 K, has been discovered. The phase transition sequence was confirmed by x-ray diffraction data. The crystal structures of three phases (V, IV and III) have been determined from the single crystal x-ray diffraction data. Structural properties of the high temperature phases are characterized using powder x-ray diffraction data measured in the 290–425 K temperature range. The structural changes triggered by the temperature change are discussed in relation to the phase transitions. Two low temperature phases (V and IV) belong to the P4 3 2 1 2 space group of the tetragonal system. The intermediate phases (III and II) are monoclinic and the prototype high temperature phase (I) is a pseudo-cubic (tetragonal) one. The low temperature phases (V and IV) are well ordered. The crystal structure of intermediate (III and II) and prototype (I) phases are characterized by high disorder of the pyridinium cations and triflate anions. (papers)

  15. Phase transitions and electrical characterizations of (K 0.5Na 0.5) 2x(Sr 0.6Ba 0.4) 5-xNb 10O 30 (KNSBN) ceramics with 'unfilled' and 'filled' tetragonal tungsten-bronze (TTB) crystal structure

    KAUST Repository

    Yao, Yingbang

    2012-12-01

    Alkali-doped strontium barium niobate (K 0.5Na 0.5) 2x(Sr 0.6Ba 0.4) 5-xNb 10O 30 (KNSBN) ceramics has been prepared by a conventional solid-state reaction method. The alkali-dopant concentration x has been varied from 0.24 to 1.15 so that the crystal structure was transformed from \\'unfilled\\' to \\'filled\\' tetragonal tungsten-bronze (TTB) structure. Apart from the change in the structural properties, the effects of the alkali-dopants on the phase transition as well as ferroelectric, piezoelectric and pyroelectric properties have also been investigated. Phase transitions have been studied in the temperature range of -200°C to 350°C. The origins of these phase transitions are discussed. The addition of the alkali-dopants enhances the ferroelectric, piezoelectric and pyroelectric properties of the KNSBN ceramics. Alkali-doping also favors abnormal grain growth and thus results in a porous microstructure, which might contribute to the enhancement of the pyroelectric performance. © 2012 Elsevier Ltd.

  16. Phase transitions and electrical characterizations of (K 0.5Na 0.5) 2x(Sr 0.6Ba 0.4) 5-xNb 10O 30 (KNSBN) ceramics with 'unfilled' and 'filled' tetragonal tungsten-bronze (TTB) crystal structure

    KAUST Repository

    Yao, Yingbang; Mak, C. L.; Ploss, Bernd

    2012-01-01

    Alkali-doped strontium barium niobate (K 0.5Na 0.5) 2x(Sr 0.6Ba 0.4) 5-xNb 10O 30 (KNSBN) ceramics has been prepared by a conventional solid-state reaction method. The alkali-dopant concentration x has been varied from 0.24 to 1.15 so that the crystal structure was transformed from 'unfilled' to 'filled' tetragonal tungsten-bronze (TTB) structure. Apart from the change in the structural properties, the effects of the alkali-dopants on the phase transition as well as ferroelectric, piezoelectric and pyroelectric properties have also been investigated. Phase transitions have been studied in the temperature range of -200°C to 350°C. The origins of these phase transitions are discussed. The addition of the alkali-dopants enhances the ferroelectric, piezoelectric and pyroelectric properties of the KNSBN ceramics. Alkali-doping also favors abnormal grain growth and thus results in a porous microstructure, which might contribute to the enhancement of the pyroelectric performance. © 2012 Elsevier Ltd.

  17. Crystalline oxides on semiconductors: A structural transition of the interface phase

    Science.gov (United States)

    Walker, F. J.; Buongiorno-Nardelli, Marco; Billman, C. A.; McKee, R. A.

    2004-03-01

    The growth of crystalline oxides on silicon is facilitated by the preparation of a surface phase of alkaline earth silicide. We describe how the surface phase serves as a precursor of the final interface phase using reflection high energy electron diffraction (RHEED) and density functional theory (DFT). RHEED intensity oscillations of the growth of BaSrO show layer-by-layer build up of the oxide on the interface. The 2x1 symmetry of the surface precursor persists up to 3 ML BaSrO coverage at which point a 1x1 pattern characteristic of the rock-salt structure of BaSrO is observed. Prior to 3 ML growth of alkaline earth oxide, DFT calculations and RHEED show that the surface precursor persists as the interface phase and induces large displacements in the growing oxide layer away from the rock-salt structure and having a 2x1 symmetry. These distortions of the rock-salt structure are energetically unfavorable and become more unfavorable as the oxide thickness increases. At 3 ML, the stability of the rock-salt structure drives a structural transformation of the film and the interface phase to a structure that is distinct from the surface precursor. Research sponsored jointly by the Division of Materials Sciences and Engineering, Office of Basic Energy Sciences, U.S. Department of Energy at Oak Ridge National Laboratory under contract DE-AC05-00OR22725 with UT-Battelle, LLC and at the University of Tennessee under contract DE-FG02-01ER45937. Calculations have been performed on CCS supercomputers at Oak Ridge National Laboratory.

  18. Use of neutron diffraction in determining strains in high-temperaure superconducting composites

    International Nuclear Information System (INIS)

    Hitterman, R.L.; Faber, J. Jr.; Kupperman, D.S.; Singh, J.P.; Majumdar, S.

    1990-01-01

    The Argonne Intense Pulsed Neutron Source and General Purpose Powder Diffractometer have been used to study high T c metal oxide composites composed of yttrium barium copper oxide and silver. Neutron diffraction techniques were applied to composites with 15, 20 and 30% silver content by volume. The authors have observed that after hot pressing, the 30% Ag specimens contained both orthorhombic high T c and tetragonal, non-superconducting phases near the center of the specimens but only tetragonal near the surface. The relationship of shifts in Bragg peaks to strains of the constituents is discussed

  19. The covalent effect on the energy levels of d3 ions in tetragonal compounds

    International Nuclear Information System (INIS)

    Li, Dong-Yang; Du, Mao-Lu

    2015-01-01

    For d 3 ions in covalent compounds with tetragonal symmetry, this paper presents a complete energy matrix, in which the different covalence of t 2 and e orbitals is considered not only in the electrostatic repulsions part of energy matrix elements but also in the crystal-field potential part of energy matrix elements. With taking and no taking the crystal field parameter B 00 0 into account, the effect of covalence on the energy levels of d 3 ions system were investigated, respectively. The investigation shows that it is very necessary for considering the different covalence of t 2 and e orbitals in both electrostatic repulsions part and crystal-field potential part when the optical properties of d 3 ions in strong covalent compounds with tetragonal symmetry is investigated. On the other hand, the crystal field parameter B 00 0 has a significant effect on the energy levels, and should be considered in investigations of d 3 ions in strong covalent compounds with tetragonal symmetry. Application to calculating the energy levels for Co 2+ in CdGa 2 Se 4 , the calculated results are in agreement with the experiment data

  20. Process for forming a homogeneous oxide solid phase of catalytically active material

    Science.gov (United States)

    Perry, Dale L.; Russo, Richard E.; Mao, Xianglei

    1995-01-01

    A process is disclosed for forming a homogeneous oxide solid phase reaction product of catalytically active material comprising one or more alkali metals, one or more alkaline earth metals, and one or more Group VIII transition metals. The process comprises reacting together one or more alkali metal oxides and/or salts, one or more alkaline earth metal oxides and/or salts, one or more Group VIII transition metal oxides and/or salts, capable of forming a catalytically active reaction product, in the optional presence of an additional source of oxygen, using a laser beam to ablate from a target such metal compound reactants in the form of a vapor in a deposition chamber, resulting in the deposition, on a heated substrate in the chamber, of the desired oxide phase reaction product. The resulting product may be formed in variable, but reproducible, stoichiometric ratios. The homogeneous oxide solid phase product is useful as a catalyst, and can be produced in many physical forms, including thin films, particulate forms, coatings on catalyst support structures, and coatings on structures used in reaction apparatus in which the reaction product of the invention will serve as a catalyst.

  1. Internal friction and elastic modulus of NdxY1-xBa2Cu3Oy (x 0.0-1.0) at 200 kHz near the orthorhombic-to-tetragonal phase transition

    International Nuclear Information System (INIS)

    Inagaki, M.

    2000-01-01

    The internal friction and Young's modulus of a series of superconductors Nd x Y 1-x Ba 2 Cu 3 O y (x = 0.0-1.0) were measured over the temperature range from 300 to 1050 K using a 200 kHz LiNbO3 piezoelectric composite oscillator. Anelastic relaxation peaks due to oxygen migration were observed at about 850 K. The minimum Young's modulus, which is related to the orthorhombic-to-tetragonal phase transition, was also observed near this temperature. The temperature at the minimum Young's modulus decreased with an increase in the neodymium composition. In contrast, the internal friction peak temperature showed an unsystematic shift with an increase in x, while changes of the average cell structure exhibited a linear relationship when plotted versus the average ionic radius for trivalent rare-earth ions with the coordination number eight. (author)

  2. Understanding Strain-Induced Phase Transformations in BiFeO3 Thin Films.

    Science.gov (United States)

    Dixit, Hemant; Beekman, Christianne; Schlepütz, Christian M; Siemons, Wolter; Yang, Yongsoo; Senabulya, Nancy; Clarke, Roy; Chi, Miaofang; Christen, Hans M; Cooper, Valentino R

    2015-08-01

    Experiments demonstrate that under large epitaxial strain a coexisting striped phase emerges in BiFeO 3 thin films, which comprises a tetragonal-like ( T ') and an intermediate S ' polymorph. It exhibits a relatively large piezoelectric response when switching between the coexisting phase and a uniform T ' phase. This strain-induced phase transformation is investigated through a synergistic combination of first-principles theory and experiments. The results show that the S ' phase is energetically very close to the T ' phase, but is structurally similar to the bulk rhombohedral ( R ) phase. By fully characterizing the intermediate S ' polymorph, it is demonstrated that the flat energy landscape resulting in the absence of an energy barrier between the T ' and S ' phases fosters the above-mentioned reversible phase transformation. This ability to readily transform between the S ' and T ' polymorphs, which have very different octahedral rotation patterns and c / a ratios, is crucial to the enhanced piezoelectricity in strained BiFeO 3 films. Additionally, a blueshift in the band gap when moving from R to S ' to T ' is observed. These results emphasize the importance of strain engineering for tuning electromechanical responses or, creating unique energy harvesting photonic structures, in oxide thin film architectures.

  3. Bio-active synthesis of tin oxide nanoparticles using eggshell membrane for energy storage application

    Science.gov (United States)

    Celina Selvakumari, J.; Nishanthi, S. T.; Dhanalakshmi, J.; Ahila, M.; Pathinettam Padiyan, D.

    2018-05-01

    Nano-sized tin oxide (SnO2) particles were synthesized using eggshell membrane (ESM), a natural bio-waste from the chicken eggshell. The crystallization of SnO2 into the tetragonal structure was confirmed from powder X-ray diffraction and the crystallite size ranged from 13 to 40 nm. Various shapes including rod, hexagonal and spherical SnO2 nanoparticles were observed from the morphological studies. The electrochemical impedance study revealed a lower charge transfer resistance (Rct) of 8.565 Ω and the presence of a constant phase element which arised due to surface roughness and porosity. Capacitive behavior seen in the cyclic voltammetry curve of the prepared SnO2 nanoparticles, find future applications in supercapacitors.

  4. Liquid phase oxidation via heterogeneous catalysis organic synthesis and industrial applications

    CERN Document Server

    Clerici, Mario G

    2013-01-01

    Sets the stage for environmentally friendly industrial organic syntheses From basic principles to new and emerging industrial applications, this book offers comprehensive coverage of heterogeneous liquid-phase selective oxidation catalysis. It fully examines the synthesis, characterization, and application of catalytic materials for environmentally friendly organic syntheses. Readers will find coverage of all the important classes of catalysts, with an emphasis on their stability and reusability. Liquid Phase Oxidation via Heterogeneous Catalysis features contributions from an internation

  5. Structural and physical properties of the tetragonal superconductors lanthanum barium alkaline earth copper oxides LaBaACu3O7-d (A = calcium and strontium)

    NARCIS (Netherlands)

    Fu, W.T.; Zandbergen, H.W.; Beek, van der C.J.; Verheijen, A.A.; Jongh, de L.J.; Brabers, V.A.M.

    1989-01-01

    The compounds LaBaACu3O7-d (A = Ca and Sr) have been prepared and characterized by X-ray diffraction and electron microscopy. Their structure is similar to that of YBa2Cu3O7, except that they are tetragonal. Electron diffraction of LaCaBaCu3O7-d reveals the presence of a weak superstructure having

  6. Structural, optical and electrochemical properties of F-doped vanadium oxide transparent semiconducting thin films

    Energy Technology Data Exchange (ETDEWEB)

    Mousavi, M.; Khorrami, G.H. [University of Bojnord, Department of Physics, Faculty of Basic Science, Bojnord (Iran, Islamic Republic of); Kompany, A. [Ferdowsi University of Mashhad, Department of Physics, Mashhad (Iran, Islamic Republic of); Yazdi, S.T. [Payame Noor University (PNU), Department of Physics, Tehran (Iran, Islamic Republic of)

    2017-12-15

    In this study, F-doped vanadium oxide thin films with doping levels up to 60 at % were prepared by spray pyrolysis method on glass substrates. To measure the electrochemical properties, some films were deposited on fluorine-tin oxide coated glass substrates. The effect of F-doping on the structural, electrical, optical and electrochemical properties of vanadium oxide samples was investigated. The X-ray diffractographs analysis has shown that all the samples grow in tetragonal β-V{sub 2}O{sub 5} phase structure with the preferred orientation of [200]. The intensity of (200) peak belonging to β-V{sub 2}O{sub 5} phase was strongest in the undoped vanadium oxide film. The scanning electron microscopy images show that the samples have nanorod- and nanobelt-shaped structure. The size of the nanobelts in the F-doped vanadium oxide films is smaller than that in the pure sample and the width of the nanobelts increases from 30 to 70 nm with F concentration. With increasing F-doping level from 10 to 60 at %, the resistivity, the transparency and the optical band gap decrease from 111 to 20 Ω cm, 70 to 50% and 2.4 to 2.36 eV, respectively. The cyclic voltammogram (CV) results show that the undoped sample has the most extensive CV and by increasing F-doping level from 20 to 60 at %, the area of the CV is expanded. The anodic and cathodic peaks in F-doped samples are stronger. (orig.)

  7. Phases quantification in titanium oxides by means of X-ray diffraction

    International Nuclear Information System (INIS)

    Macias B, L.R.; Garcia C, R.M.; Ita T, A. de; Chavez R, A.

    2001-01-01

    In this work two phases of titanium oxides are quantified which belong to the same crystalline system and by means of a computer program named Quanto created by the first author, contains the information for calculating the absorption coefficients, it can be quantified phases having one of the pure phases and the problem samples. In order to perform this work different mixtures of different titanium oxides were prepared measuring by means of the X-ray diffraction technique in the Siemens X-ray diffractometer of ININ which were processed with the Peakfit package and also they were evaluated by means of the computer program with the necessary information finding acceptable results. (Author)

  8. X-ray diffraction and dielectric studies across morphotropic phase boundary in (1 - x) [Pb(Mg0.5W0.5)O3]-xPbTiO3 ceramics

    International Nuclear Information System (INIS)

    Singh, A.K.; Singh, Akhilesh Kumar

    2011-01-01

    Research highlights: → Structural studies reveal pseudocubic structure of PMW-xPT for the x ≤ 0.42, tetragonal for the x ≥ 0.72 and the coexistences of the two phases for intermediate compositions (0.46 ≤ x 0.68). → Temperature dependent dielectric constant for compositions in the two phase region shows two dielectric anomalies above room temperature and not just one as reported by earlier workers. → Rietveld structural analysis of PMW-xPT ceramics is presented for the first time to determine the fraction of the coexisting phases in MPB region. - Abstract: We present here the results of comprehensive X-ray diffraction and dielectric studies on several compositions of (1 - x)[Pb(Mg 0.5 W 0.5 )O 3 ]-xPbTiO 3 (PMW-xPT) solid solution across the morphotropic phase boundary. Rietveld analysis of the powder X-ray diffraction data reveals cubic (space group Fm3m) structure of PMW-xPT ceramics for the compositions with x ≤ 0.42, tetragonal (space group P4mm) structure for the compositions with x ≥ 0.72 and coexistence of the tetragonal and cubic phases for the intermediate compositions (0.46 ≤ x ≤ 0.68). Temperature dependence of the dielectric permittivity above room temperature exhibits diffuse nature of phase transitions for the compositions in the cubic and two phase region while the compositions with tetragonal structure at room temperature exhibit sharp ferroelectric to paraelectric phase transition. The PMW-xPT compositions with coexistence of tetragonal and cubic phases at room temperature exhibit two anomalies in the temperature dependence of the dielectric permittivity above room temperature. Using results of structural and dielectric studies a partial phase diagram of PMW-xPT ceramics is also presented.

  9. Study of optical characteristics of tin oxide thin film prepared by sol ...

    Indian Academy of Sciences (India)

    wear-resistant coating on glass containers (Nakagawa et al. 1997), Infrared reflectors for ... Tin oxide is a tetragonal n-type semiconductor having high bandgap energy ... (IV) chloride due to the cost factor and availability. The main purpose of ...

  10. Hydrothermal degradation of tetragonal ZrO2 ceramic components used in dental applications

    International Nuclear Information System (INIS)

    Mukaeda, L.E.; Robin, A.; Taguchi, S.P.

    2009-01-01

    With the evolution of the dental restoration techniques, a considerable growth in the demand of ceramic products occurred. These materials present good strength associated to reliability. In this work, micrometric and nanometric scale tetragonal ZrO 2 blocks were sintered at 1500 deg C-2h and 1350 deg C-2h, respectively, ground and polished. Ceramics with relative density higher than 98% were obtained. The specimens were immersed in hot water (150 deg C), for times ranging from 10h to 30h. The mass variation of the samples was measured and the crystalline phases present before and after the degradation tests were identified by X-ray diffractometry, in order to evaluate the capacity of these ceramics in resisting to aqueous medium exposure. Materials with nanometric structure present higher resistance to degradation than those with micrometric scale, and this interferes in structural stability after the test, and reduces the martensitic transformation. (author)

  11. Solid-phase vibrational redox reactions in coordinated oxides

    International Nuclear Information System (INIS)

    Kostikova, G.P.; Korol'kov, D.V.; Kostikov, Yu.P.

    1996-01-01

    The properties of multicomponent oxides (YBa 2 Cu 3 O 7-x , etc.), incorporating different valency forms of each of two (or more) different elements have been compared with the properties of the known chemical systems, where vibrational (periodic) redox-reactions are realized a fortiori. The essence of the new theoretical concept suggested consists in the following: high-T c superconductivity of the complex oxides and similar compounds originates from vibrational redox reaction proceeding in solid phase and involving different valency atoms of every element

  12. Stability of nanoscale secondary phases in an oxide dispersion strengthened Fe-12Cr alloy

    International Nuclear Information System (INIS)

    Castro, V. de; Marquis, E.A.; Lozano-Perez, S.; Pareja, R.; Jenkins, M.L.

    2011-01-01

    Transmission electron microscopy and atom-probe tomography were used to characterize on a near-atomic scale the microstructure and oxide and carbide phases that form during thermo-mechanical treatments of a model oxide dispersion strengthened Fe-12 wt.% Cr-0.4 wt.% Y 2 O 3 alloy. It was found that some of the Y-rich nanoparticles retained their initial crystallographic structure but developed a Cr-enriched shell, while others evolved into ternary oxide phases during the initial processing. The Y- and Cr-rich oxide phases formed remained stable after annealing at 1023 K for 96 h. However, the number of Cr-rich carbides appeared to increase, inducing Cr depletion in the matrix.

  13. Stability of nanoscale secondary phases in an oxide dispersion strengthened Fe-12Cr alloy

    Energy Technology Data Exchange (ETDEWEB)

    Castro, V. de, E-mail: vanessa.decastro@uc3m.es [Department of Materials, University of Oxford, Oxford OX1 3PH (United Kingdom); Marquis, E.A.; Lozano-Perez, S. [Department of Materials, University of Oxford, Oxford OX1 3PH (United Kingdom); Pareja, R. [Departamento de Fisica, Universidad Carlos III de Madrid, Avda. de la Universidad 30, 28911 Leganes, Madrid (Spain); Jenkins, M.L. [Department of Materials, University of Oxford, Oxford OX1 3PH (United Kingdom)

    2011-06-15

    Transmission electron microscopy and atom-probe tomography were used to characterize on a near-atomic scale the microstructure and oxide and carbide phases that form during thermo-mechanical treatments of a model oxide dispersion strengthened Fe-12 wt.% Cr-0.4 wt.% Y{sub 2}O{sub 3} alloy. It was found that some of the Y-rich nanoparticles retained their initial crystallographic structure but developed a Cr-enriched shell, while others evolved into ternary oxide phases during the initial processing. The Y- and Cr-rich oxide phases formed remained stable after annealing at 1023 K for 96 h. However, the number of Cr-rich carbides appeared to increase, inducing Cr depletion in the matrix.

  14. High-pressure phases of CuI studied by 129I-Moessbauer spectroscopy

    International Nuclear Information System (INIS)

    Kaindl, G.; Nowik, I.; Frank, K.H.

    1992-01-01

    The results of an 129 I-Moessbauer study of the high-pressure phases of CuI at 4.2 K and for external pressures up to 71 kbar are reported. The isomer shift S and the electric quadrupole interaction E q are found to undergo large discontinuities at the crystallographic phase-transition pressures of ≅18 kbar from zinc-blende to rhombohedral structure and at ≅46 kbar from rhombohedral to tetragonal. The pressure coefficients of these hyperfine parameters are significantly different for the three phases (zinc-blende; rhombohedral; tetragonal): dS/dP=-3.3; =+1.5; =+2.5x10 -3 mm/s/kbar. These results cannot be explained in terms of a simple molecular-orbital picture; instead, they reflect pressure-induced variations of the halogen-p/metal-d hybridization in the valence bands of the various phases of CuI. (orig.)

  15. Room temperature ferromagnetism of tin oxide nanocrystal based on synthesis methods

    Energy Technology Data Exchange (ETDEWEB)

    Sakthiraj, K.; Hema, M. [Department of Physics, Kamaraj College of Engineering and Technology, Virudhunagar 626001, Tamil Nadu (India); Balachandrakumar, K. [Department of Physics, Raja Doraisingam Government Arts College, Sivagangai 630561, Tamil Nadu (India)

    2016-04-15

    The experimental conditions used in the preparation of nanocrystalline oxide materials play an important role in the room temperature ferromagnetism of the product. In the present work, a comparison was made between sol–gel, microwave assisted sol–gel and hydrothermal methods for preparing tin oxide nanocrystal. X-ray diffraction analysis indicates the formation of tetragonal rutile phase structure for all the samples. The crystallite size was estimated from the HRTEM images and it is around 6–12 nm. Using optical absorbance measurement, the band gap energy value of the samples has been calculated. It reveals the existence of quantum confinement effect in all the prepared samples. Photoluminescence (PL) spectra confirms that the luminescence process originates from the structural defects such as oxygen vacancies present in the samples. Room temperature hysteresis loop was clearly observed in M–H curve of all the samples. But the sol–gel derived sample shows the higher values of saturation magnetization (M{sub s}) and remanence (M{sub r}) than other two samples. This study reveals that the sol–gel method is superior to the other two methods for producing room temperature ferromagnetism in tin oxide nanocrystal.

  16. Phase development and dielectric properties of (1-x)Pb(Zr0.52Ti0.48)O3-xBaTiO3 ceramics

    International Nuclear Information System (INIS)

    Chaisan, Wanwilai; Yimnirun, Rattikorn; Ananta, Supon; Cann, David P.

    2006-01-01

    (1-x)Pb(Zr 0.52 Ti 0.48 )O 3 -xBaTiO 3 ceramics were prepared by a modified mixed-oxide method. The phase formation was studied by XRD analysis. All compositions exhibit complete solid solutions of perovskite-like phase in the (1-x)PZT-xBT system. The (2 0 0)/(0 0 2) peak was found to split at the composition x = 0.6 and the co-existence of tetragonal-rhombohedral phases occurs with x ≤ 0.6. The possible range of compositions which correspond to a phase transition is 0.6 < x < 0.7. While pure BT ceramics exhibited a sharp phase transformation expected for normal ferroelectrics, phase transformation behavior of the (1-x)PZT-xBT solid solutions became more diffuse with increasing BT contents. This was primarily evidenced by an increased broadness in the dielectric peak, with a maximum peak width occurring at x = 0.5

  17. Phase-Field Simulations of Topological Structures and Topological Phase Transitions in Ferroelectric Oxide Heterostructures

    Science.gov (United States)

    Zijian Hong

    Ferroelectrics are materials that exhibit spontaneous electric polarization which can be switched between energy-degenerated states by external stimuli (e.g., mechanical force and electric field) that exceeds a critical value. They have wide potential applications in memories, capacitors, piezoelectric and pyroelectric sensors, and nanomechanical systems. Topological structures and topological phase transitions have been introduced to the condensed matter physics in the past few decades and have attracted broad attentions in various disciplines due to the rich physical insights and broad potential applications. Ferromagnetic topological structures such as vortex and skyrmion are known to be stabilized by the antisymmetric chiral interaction (e.g., Dzyaloshinskii-Moriya interaction). Without such interaction, ferroelectric topological structures (i.e., vortex, flux-closure, skyrmions, and merons) have been studied only recently with other designing strategies, such as reducing the dimension of the ferroelectrics. The overarching goal of this dissertation is to investigate the topological structures in ferroelectric oxide perovskites as well as the topological phase transitions under external applied forces. Pb(Zr,Ti)O3 (PZT) with morphotropic phase boundary is widely explored for high piezoelectric and dielectric properties. The domain structure of PZT tetragonal/rhombohedral (T/R) bilayer is investigated. Strong interfacial coupling is shown, with large polarization rotation to a lower symmetry phase near the T/R interface. Interlayer domain growth can also be captured, with T-domains in the R layer and R-domains in the T layer. For thin PZT bilayer with 5nm of T-layer and 20 nm of R-layer, the a1/a 2 twin domain structure is formed in the top T layer, which could be fully switched to R domains under applied bias. While a unique flux-closure pattern is observed both theoretically and experimentally in the thick bilayer film with 50 nm of thickness for both T and R

  18. Growth kinetics of tetragonal and monoclinic ZrO{sub 2} crystallites in 3 mol% yttria partially stabilized ZrO{sub 2} (3Y-PSZ) precursor powder

    Energy Technology Data Exchange (ETDEWEB)

    Kuo, Chih-Wei [Department of Resources Engineering, National Cheng Kung University, 1 Ta-Hsueh Road, Tainan 70101, Taiwan (China); Lee, Kuen-Chan [Department of Fragrance and Cosmetic Science, Kaohsiung Medical University, 100 Shih-Chuan 1st Road, Kaohsiung 807, Taiwan (China); Yen, Feng-Lin, E-mail: flyen@kmu.edu.tw [Department of Fragrance and Cosmetic Science, Kaohsiung Medical University, 100 Shih-Chuan 1st Road, Kaohsiung 807, Taiwan (China); Shen, Yun-Hwei [Department of Resources Engineering, National Cheng Kung University, 1 Ta-Hsueh Road, Tainan 70101, Taiwan (China); Lee, Huey-Er [Department of Dentistry, Kaohsiung Medical University, 100 Shih-Chuan 1st Road, Kaohsiung 807, Taiwan (China); Department of Dentistry, Kaohsiung Medical University, Chung Ho Memorial Hospital, 100 Tzyou 1st Road, Kaohsiung 807, Taiwan (China); Wen, Shaw-Bing [General Education Center, Meiho Institute of Technology, 23 Pingguang Road, Neipu, Pingtung 91202, Taiwan (China); Wang, Moo-Chin, E-mail: mcwang@kmu.edu.tw [Department of Fragrance and Cosmetic Science, Kaohsiung Medical University, 100 Shih-Chuan 1st Road, Kaohsiung 807, Taiwan (China); Stack, Margaret Mary [Department of Mechanical and Aerospace Engineering, University of Strathclyde, 75 Montrose Street, Glasgow (United Kingdom)

    2014-04-01

    Highlights: • The crystalline structures were composed of tetragonal and monoclinic ZrO{sub 2}. • Growth kinetics of t-ZrO{sub 2} in the 3Y-PSZ precursor powder is described as: D{sub te}{sup 2}=(4.57±0.55)t{sup 0.12±0.02}exp(-((24.79±0.38)×10{sup 3})/(RT) ). • Growth kinetics of m-ZrO{sub 2} in the 3Y-PSZ precursor powder is described as: D{sub m}{sup 2}=(4.40±1.63)t{sup 0.17±0.08}exp(-((66.47±3.97)×10{sup 3})/(RT) ). - Abstract: The growth kinetics of tetragonal and monoclinic ZrO{sub 2} crystallites in 3 mol% yttria partially stabilized ZrO{sub 2} (3Y-PSZ) precursor powder has been investigated using X-ray diffraction (XRD), Brunauer–Emmett–Teller (BET) specific surface area analysis, transmission electron microscopy (TEM) and high resolution TEM (HRTEM). After calcination of the 3Y-PSZ precursor powder between 773 and 1073 K for 2 h, the crystalline structures were composed of tetragonal and monoclinic ZrO{sub 2} as the primary and secondary phases, respectively. When the 3Y-PSZ precursor powder was calcined at 773 K for 2 h, the BET specific surface area was 97.13 m{sup 2}/g, which is equivalent to a particle size of 10.30 nm. The crystallite sizes determined via XRD and BET agreed well, indicating that the powder was virtually non-agglomerated. The growth kinetics of tetragonal and monoclinic ZrO{sub 2} crystallite isothermal growth in the 3Y-PSZ precursor powder are described by: D{sub te}{sup 2}=(4.57±0.55)t{sup 0.12±0.02}exp(-((24.79±0.38)×10{sup 3})/(RT) ) and D{sub m}{sup 2}=(4.40±1.63)t{sup 0.17±0.08}exp(-((66.47±3.97)×10{sup 3})/(RT) ), respectively, for 773K≤T≤1073K. D{sub te} and D{sub m} denote the crystallite size of tetragonal and monoclinic ZrO{sub 2} at time t and temperature T, respectively.

  19. Oxidation studies of β-sialon ceramics containing amorphous and / or crystalline intergranular phases

    International Nuclear Information System (INIS)

    Persson, J.; Kall, P.O.; Jansson, K.; Nygren, M.

    1992-01-01

    β-sialon ceramics of equal overall compositions but containing amorphous, partly crystalline and almost completely crystalline intergranular phase(s) have been oxidized in oxygen at 1350 deg C for 20 hours. The obtained weight gain curves do not follow the parabolic rate law (ΔW/A 0 ) 2 = k p t + β. To the extent that crystallization occurs in the oxide scale during the oxidation experiment, the amorphous cross section area through which oxygen most easily diffuses will decrease with time. A brief description of this new rate law is given, and the obtained oxidation curves will be discussed within that framework. 4 refs., 2 tabs., 2 figs

  20. Effect of strain on the martensitic phase transition in superconducting Nb3Sn

    International Nuclear Information System (INIS)

    Hoard, R.W.; Scanlan, R.M.; Smith, G.S.; Farrell, C.L.

    1980-01-01

    The connection between the cubic-to-tetragonal martensitic phase transformation and the phenomenon of superconductivity in A15 compounds is being investigated. The degradation of the critical parameters, such as T/sub c/, H/sub c2/, and J/sub c/, with mechanical straining is of particular interest. Low-temperature x-ray diffraction experiments are performed on Nb 3 Sn ribbons (with the bronze layers etched off) mounted on copper and indium sample stages. The cryostat used is unique in that it has a vacuum mechanical insert which allows the superconductor to be placed under both compressive and tensile strains while at low temperatures. Preliminary results indicate that the martensitic phase transition temperature, T/sub m/, increases with compressive strains. Other effects of strain on tetragonal phase production are also discussed

  1. On the crystal structure of Z-phase Cr(V,Nb)N

    DEFF Research Database (Denmark)

    Danielsen, Hilmar Kjartansson; Hald, John; Grumsen, Flemming Bjerg

    2006-01-01

    The Z-phase Cr(YNb)N particles in various 9 to 12 pct Cr creep-resistant steels were investigated with electron diffraction, energy dispersive spectroscopy (EDS), and electron energy loss spectroscopy(EELS). In addition to the well-known tetragonal crystal structure for Z phase, a cubic crystal s...

  2. Opto-electronic properties of bismuth oxide films presenting different crystallographic phases

    Energy Technology Data Exchange (ETDEWEB)

    Gomez, Celia L. [Instituto de Investigaciones en Materiales, UNAM, Circuito Exterior s/n CU, México D.F. 04510 (Mexico); Posgrado en Ciencia e Ingeniería de Materiales, UNAM, Unidad de Posgrado, Edificio C, Piso 1, Zona Cultural de CU, México, D.F. 04510 (Mexico); Depablos-Rivera, Osmary, E-mail: osmarydep@yahoo.com [Instituto de Investigaciones en Materiales, UNAM, Circuito Exterior s/n CU, México D.F. 04510 (Mexico); Posgrado en Ciencia e Ingeniería de Materiales, UNAM, Unidad de Posgrado, Edificio C, Piso 1, Zona Cultural de CU, México, D.F. 04510 (Mexico); Silva-Bermudez, Phaedra [Instituto de Investigaciones en Materiales, UNAM, Circuito Exterior s/n CU, México D.F. 04510 (Mexico); Instituto Nacional de Rehabilitación, Calz. México Xochimilco No. 289 Col. Arenal de Guadalupe, C.P.14389, Ciudad de México, D.F. (Mexico); Muhl, Stephen [Instituto de Investigaciones en Materiales, UNAM, Circuito Exterior s/n CU, México D.F. 04510 (Mexico); Zeinert, Andreas; Lejeune, Michael; Charvet, Stephane; Barroy, Pierre [Laboratoire de Physique de la Matière Condensée, Université de Picardie Jules Verne, 33 rue Saint Leu, 80039 Amiens Cedex 1 (France); Camps, Enrique [Instituto Nacional de Investigaciones Nucleares, Carretera México-Toluca S/N, kilómetro 36.5. La Marquesa, Municipio de Ocoyoacac, CP 52750, Estado de México (Mexico); Rodil, Sandra E. [Instituto de Investigaciones en Materiales, UNAM, Circuito Exterior s/n CU, México D.F. 04510 (Mexico)

    2015-03-02

    The optical, electrical and structural properties of bismuth oxide thin films deposited by radio frequency reactive magnetron sputtering were studied. The Bi{sub 2}O{sub 3} thin films were grown on Si and glass substrates under different power and substrate temperatures in an oxygen-enriched plasma leading to films with different crystalline phase as evidenced by X-ray diffraction and Raman spectroscopy. The optical properties of the films were measured using ellipsometric spectroscopy and optical transmission spectra. In order to parameterize the optical dispersion functions (n, k) of the films, the Tauc–Lorentz dispersion model was used. The optical bandgap was then assessed by different methods and the results are compared to the thermal variations of the electrical resistivity of the films. It was found that the refractive index, extinction coefficient and optical gap strongly depend on the deposition conditions and the crystalline phase; the fluorite defect cubic δ-Bi{sub 2}O{sub 3} phase showed the lowest optical gap and lower resistivity. - Highlights: • Different bismuth oxide phases were obtained by sputtering. • The power and substrate temperature were the two key parameters. • Room temperature delta-Bi{sub 2}O{sub 3} thin films were obtained. • The optical bandgap was around 1.5 and 2.2 eV, depending on the phase. • The bismuth oxide films presented activation energies around 1 eV.

  3. Opto-electronic properties of bismuth oxide films presenting different crystallographic phases

    International Nuclear Information System (INIS)

    Gomez, Celia L.; Depablos-Rivera, Osmary; Silva-Bermudez, Phaedra; Muhl, Stephen; Zeinert, Andreas; Lejeune, Michael; Charvet, Stephane; Barroy, Pierre; Camps, Enrique; Rodil, Sandra E.

    2015-01-01

    The optical, electrical and structural properties of bismuth oxide thin films deposited by radio frequency reactive magnetron sputtering were studied. The Bi 2 O 3 thin films were grown on Si and glass substrates under different power and substrate temperatures in an oxygen-enriched plasma leading to films with different crystalline phase as evidenced by X-ray diffraction and Raman spectroscopy. The optical properties of the films were measured using ellipsometric spectroscopy and optical transmission spectra. In order to parameterize the optical dispersion functions (n, k) of the films, the Tauc–Lorentz dispersion model was used. The optical bandgap was then assessed by different methods and the results are compared to the thermal variations of the electrical resistivity of the films. It was found that the refractive index, extinction coefficient and optical gap strongly depend on the deposition conditions and the crystalline phase; the fluorite defect cubic δ-Bi 2 O 3 phase showed the lowest optical gap and lower resistivity. - Highlights: • Different bismuth oxide phases were obtained by sputtering. • The power and substrate temperature were the two key parameters. • Room temperature delta-Bi 2 O 3 thin films were obtained. • The optical bandgap was around 1.5 and 2.2 eV, depending on the phase. • The bismuth oxide films presented activation energies around 1 eV

  4. Phase transition of a cobalt-free perovskite as a high-performance cathode for intermediate-temperature solid oxide fuel cells.

    Science.gov (United States)

    Jiang, Shanshan; Zhou, Wei; Niu, Yingjie; Zhu, Zhonghua; Shao, Zongping

    2012-10-01

    It is generally recognized that the phase transition of a perovskite may be detrimental to the connection between cathode and electrolyte. Moreover, certain phase transitions may induce the formation of poor electronic and ionic conducting phase(s), thereby lowering the electrochemical performance of the cathode. Here, we present a study on the phase transition of a cobalt-free perovskite (SrNb(0.1)Fe(0.9)O(3-δ), SNF) and evaluate its effect on the electrochemical performance of the fuel cell. SNF exists as a primitive perovskite structure with space group P4mm (99) at room temperature. As evidenced by in situ high-temperature X-ray diffraction measurements over the temperature range of 600 to 1000 °C, SNF undergoes a transformation to a tetragonal structure with a space group I4/m (87). This phase transition is accompanied by a moderate change in the volume, allowing a good cathode/electrolyte interface on thermal cycling. According to the electrochemical impedance spectroscopy evaluation, the I4/m phase exhibits positive effects on the cathode's performance, showing the highest oxygen reduction reaction activity of cobalt-free cathodes reported so far. This activity improvement is attributed to enhanced oxygen surface processes. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. Atomic-Scale Structure of Al2O3-ZrO2 Mixed Oxides Prepared by Laser Ablation

    International Nuclear Information System (INIS)

    Yang Xiuchun; Dubiel, M.; Hofmeister, H.; Riehemann, W.

    2007-01-01

    By means of x-ray diffractometry (XRD) and X-ray absorption fine structure spectroscopy, the phase composition and atomic structure of laser evaporated ZrO2 and ZrO2-Al2O3 nanopowders have been studied. The results indicate that pure ZrO2 exists in the form of tetragonal structure, Al2O3 doped ZrO2 nanoparticles, however, have cubic structure. Compared to bulk tetragonal ZrO2, pure tetragonal ZrO2 nanoparticles have a shorter Zr-O- and Zr-Zr shell, indicating that the lattice contracts with decreasing particle size. For Al2O3 doped ZrO2 solid solution, the distances of first Zr-O and Zr-Zr (Al) coordination decrease with increasing solid solubility. The disorder degree of the ZrO2 lattice increases with increasing solid solubility. The coevaporated ZrO2-Al2O3 is quickly solidified into amorphous phase when it is ablated in a higher pressure. The amorphous phase contains Zr-O-Zr (Al) clusters and has shorter Zr-O distance and tower Zr-O coordination number

  6. Oxidation behaviour of a Ti2AlN MAX-phase coating

    International Nuclear Information System (INIS)

    Wang Qimin; Kim, Kwangho; Garkas, W; Renteria, A Flores; Leyens, C; Sun Chao

    2011-01-01

    In this paper, we reported the oxidation behaviour of Ti 2 AlN coatings on a -TiAl substrate. The coatings composed mainly of Ti 2 AlN MAX phase were obtained by magnetron sputtering and subsequent vacuum annealing. Isothermal oxidation tests at 700-900 deg. C were performed in air. The results indicated that the oxidation resistance of the -TiAl alloy can be improved by depositing a Ti 2 AlN layer on the alloy surface, especially at high temperatures. An Al-rich oxide scale formed on the coating surfaces during oxidation. This scale acts as diffusion barrier blocking the ingress of oxidation, and effectively protects the coated alloys from further oxidation attack.

  7. The influence of zirconia precursor/binding polymer mass ratio in the intermediate electrospun composite fibers on the phase transformation of final zirconia nanofibers

    Energy Technology Data Exchange (ETDEWEB)

    Rodaev, Vyacheslav V.; Zhigachev, Andrey O.; Korenkov, Viktor V.; Golovin, Yuri I. [Institute for Nanotechnology and Nanomaterials, Tambov State University, Internatsionalnaya Str. 33, 392000, Tambov (Russian Federation)

    2016-09-15

    Nanofibrous zirconia was fabricated by calcination of electrospun zirconium oxychloride/polyethylene oxide (PEO) composite fibers with different mass fraction of the components. ZrO{sub 2} nanofibers were characterized by scanning electron microscopy (SEM), nitrogen adsorption at 77 K, and X-ray diffractometry (XRD). It was revealed that increase in ZrOCl{sub 2}/PEO mass ratio above the threshold value significantly decreases tetragonal phase (t-ZrO{sub 2}) content and increases monoclinic phase (m-ZrO{sub 2}) content in final ceramic nanofibers. Distinct t-ZrO{sub 2} → m-ZrO{sub 2} transformation takes place when average ZrO{sub 2} grain size approaches to 30 nm. (copyright 2016 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  8. Comparative analysis of oxide phase formation and its effects on electrical properties of SiO{sub 2}/InSb metal-oxide-semiconductor structures

    Energy Technology Data Exchange (ETDEWEB)

    Lee, Jaeyel [Department of Materials Science and Engineering, Seoul National University, Seoul 151-744 (Korea, Republic of); Park, Sehun [Department of Materials Science and Engineering, Seoul National University, Seoul 151-744 (Korea, Republic of); WCU Hybrid Materials Program, Department of Materials Science and Engineering, Seoul National University, Seoul 151-744 (Korea, Republic of); Kim, Jungsub; Yang, Changjae; Kim, Sujin; Seok, Chulkyun [Department of Materials Science and Engineering, Seoul National University, Seoul 151-744 (Korea, Republic of); Park, Jinsub [Department of Electronic Engineering, Hanyang University, Seoul 133-791 (Korea, Republic of); Yoon, Euijoon, E-mail: eyoon@snu.ac.kr [Department of Materials Science and Engineering, Seoul National University, Seoul 151-744 (Korea, Republic of); WCU Hybrid Materials Program, Department of Materials Science and Engineering, Seoul National University, Seoul 151-744 (Korea, Republic of); Department of Nano Science and Technology, Graduate School of Convergence Science and Technology, Seoul National University, Suwon 443-270 (Korea, Republic of); Energy Semiconductor Research Center, Advanced Institutes of Convergence Technology, Seoul National University, Suwon 443-270 (Korea, Republic of)

    2012-06-01

    We report on the changes in the interfacial phases between SiO{sub 2} and InSb caused by various deposition temperatures and heat treatments. X-ray photoelectron spectroscopy (XPS) and Raman spectroscopy were used to evaluate the relative amount of each phase present at the interface. The effect of interfacial phases on the electrical properties of SiO{sub 2}/InSb metal-oxide-semiconductor (MOS) structures was investigated by capacitance-voltage (C-V) measurements. The amount of both In and Sb oxides increased with the deposition temperature. The amount of interfacial In oxide was larger for all samples, regardless of the deposition and annealing temperatures and times. In particular, the annealed samples contained less than half the amount of Sb oxide compared with the as-deposited samples, indicating a strong interfacial reaction between Sb oxide and the InSb substrate during annealing. The interface trap density sharply increased for deposition temperatures above 240 Degree-Sign C. The C-V measurements and Raman spectroscopy indicated that elemental Sb accumulation due to the interfacial reaction of Sb oxide with InSb substrate was responsible for the increased interfacial trap densities in these SiO{sub 2}/InSb MOS structures. - Highlights: Black-Right-Pointing-Pointer We report the quantitative analysis of interfacial oxides at the SiO{sub 2}/InSb interface. Black-Right-Pointing-Pointer Interfacial oxides were measured quantitatively by X-ray Photoelectron Spectroscopy. Black-Right-Pointing-Pointer As-grown and annealed samples showed different compositions of oxide phases. Black-Right-Pointing-Pointer Considerable reduction of antimony oxide phases was observed during annealing. Black-Right-Pointing-Pointer Interface trap densities at the SiO{sub 2}/InSb interface were calculated.

  9. Monoterpene oxidation in an oxidative flow reactor: SOA yields and the relationship between bulk gas-phase properties and organic aerosol growth

    Science.gov (United States)

    Friedman, B.; Link, M.; Farmer, D.

    2016-12-01

    We use an oxidative flow reactor (OFR) to determine the secondary organic aerosol (SOA) yields of five monoterpenes (alpha-pinene, beta-pinene, limonene, sabinene, and terpinolene) at a range of OH exposures. These OH exposures correspond to aging timescales of a few hours to seven days. We further determine how SOA yields of beta-pinene and alpha-pinene vary as a function of seed particle type (organic vs. inorganic) and seed particle mass concentration. We hypothesize that the monoterpene structure largely accounts for the observed variance in SOA yields for the different monoterpenes. We also use high-resolution time-of-flight chemical ionization mass spectrometry to calculate the bulk gas-phase properties (O:C and H:C) of the monoterpene oxidation systems as a function of oxidant concentrations. Bulk gas-phase properties can be compared to the SOA yields to assess the capability of the precursor gas-phase species to inform the SOA yields of each monoterpene oxidation system. We find that the extent of oxygenated precursor gas-phase species corresponds to SOA yield.

  10. Functional Properties of Polydomain Ferroelectric Oxide Thin Films

    NARCIS (Netherlands)

    Houwman, Evert Pieter; Vergeer, Kurt; Koster, Gertjan; Rijnders, Augustinus J.H.M.; Nishikawa, H.; Iwata, N.; Endo, T.; Takamura, Y.; Lee, G-H.; Mele, P.

    2017-01-01

    The properties of a ferroelectric, (001)-oriented, thin film clamped to a substrate are investigated analytically and numerically. The emphasis is on the tetragonal, polydomain, ferroelectric phase, using a three domain structure, as is observed experimentally, instead of the two-domain structure

  11. Reaction kinetics of oxygen on single-phase alloys, oxidation of nickel and niobium alloys

    International Nuclear Information System (INIS)

    Lalauze, Rene

    1973-01-01

    This research thesis first addresses the reaction kinetics of oxygen on alloys. It presents some generalities on heterogeneous reactions (conventional theory, theory of jumps), discusses the core reaction (with the influence of pressure), discusses the influence of metal self-diffusion on metal oxidation kinetics (equilibrium conditions at the interface, hybrid diffusion regime), reports the application of the hybrid diffusion model to the study of selective oxidation of alloys (Wagner model, hybrid diffusion model) and the study of the oxidation kinetics of an alloy forming a solid solution of two oxides. The second part reports the investigation of the oxidation of single phase nickel and niobium alloys (phase α, β and γ)

  12. UV-visible spectroscopic estimation of photodegradation of rhodamine-B dye using tin(IV) oxide nanoparticles.

    Science.gov (United States)

    Sangami, G; Dharmaraj, N

    2012-11-01

    Nanocrystalline, tin(IV) oxide (SnO(2)) particles has been prepared by thermal decomposition of tin oxalate precursor obtained from the reactions of tin(IV) chloride and sodium oxalate using eggshell membrane (ESM). The as-prepared SnO(2) nanoparticles were characterized by thermal studies, transmission electron microscopy (TEM), powder X-ray diffraction (XRD), Raman, FT-IR and UV-visible studies and used as a photocatalyst for the degradation of rhodamine-B (Rh-B) dye. The size of the prepared nanoparticles was in the range of 5-12nm as identified from the TEM images. Powder XRD data revealed the presence of a tetragonal, rutile crystalline phase of the tin(IV) oxide nanoparticles. Thermal analysis showed that the decomposition of tin oxalate precursor to yield the titled tin(IV) oxide nanoparticles was completed below 500°C. The extent of degradation of Rh-B in the presence of SnO(2) monitored by absorption spectral measurements demonstrated that 94.48% of the selected dye was degraded upon irradiation with UV light for 60 min. Copyright © 2012 Elsevier B.V. All rights reserved.

  13. Syntrophic acetate oxidation in two-phase (acid-methane) anaerobic digesters.

    Science.gov (United States)

    Shimada, T; Morgenroth, E; Tandukar, M; Pavlostathis, S G; Smith, A; Raskin, L; Kilian, R E

    2011-01-01

    The microbial processes involved in two-phase anaerobic digestion were investigated by operating a laboratory-scale acid-phase (AP) reactor and analyzing two full-scale, two-phase anaerobic digesters operated under mesophilic (35 °C) conditions. The digesters received a blend of primary sludge and waste activated sludge (WAS). Methane levels of 20% in the laboratory-scale reactor indicated the presence of methanogenic activity in the AP. A phylogenetic analysis of an archaeal 16S rRNA gene clone library of one of the full-scale AP digesters showed that 82% and 5% of the clones were affiliated with the orders Methanobacteriales and Methanosarcinales, respectively. These results indicate that substantial levels of aceticlastic methanogens (order Methanosarcinales) were not maintained at the low solids retention times and acidic conditions (pH 5.2-5.5) of the AP, and that methanogenesis was carried out by hydrogen-utilizing methanogens of the order Methanobacteriales. Approximately 43, 31, and 9% of the archaeal clones from the methanogenic phase (MP) digester were affiliated with the orders Methanosarcinales, Methanomicrobiales, and Methanobacteriales, respectively. A phylogenetic analysis of a bacterial 16S rRNA gene clone library suggested the presence of acetate-oxidizing bacteria (close relatives of Thermacetogenium phaeum, 'Syntrophaceticus schinkii,' and Clostridium ultunense). The high abundance of hydrogen consuming methanogens and the presence of known acetate-oxidizing bacteria suggest that acetate utilization by acetate oxidizing bacteria in syntrophic interaction with hydrogen-utilizing methanogens was an important pathway in the second-stage of the two-phase digestion, which was operated at high ammonium-N concentrations (1.0 and 1.4 g/L). A modified version of the IWA Anaerobic Digestion Model No. 1 (ADM1) with extensions for syntrophic acetate oxidation and weak-acid inhibition adequately described the dynamic profiles of volatile acid production

  14. Quantitative determination of phases in ZrO2 (MgO) (Y2O3) using the Rietveld method

    International Nuclear Information System (INIS)

    Castro, Antonio Carlos de

    2007-01-01

    The key objective of this work is the crystallographic characterization of the zircon co-doped with Yttria and magnesium with the application of the Rietveld method for quantitative phase analysis of zircon polymorph (zircon monoclinic, tetragonal, and cubic). Samples of zircon polymorph were obtained from zircon doped with Yttria and magnesium at defined molar concentrations. The zircon polymorph stability during subeutetoid aging at 1350 deg C were investigated to determine ZrO 2 - MgO - Y 2 0 3 phases degradation and to define the solid solutions stability environment. ZrO 2 powders doped with 8 mol por cent of MgO and 1 mol por cent of Y 2 O 3 , and 9 mol por cent of MgO and 0 mol por cent of Y 2 O 3 have been prepared by chemical route using the co-precipitation method. These samples have been calcinate at 550 deg C, sintered at 1500 deg C and characterized by the Rietveld method using the X-ray diffraction data. The variation of the lattice parameter, changes in the phase composition and their microstructures are discussed. The application of the Rietveld method for quantitative phase analysis of zircon polymorph (zircon tetragonal and cubic) reveals no formation of tetragonal phase and indicating that the matrix is the cubic phase with low concentration of monoclinic phase.(author)

  15. ALTERATION OF U(VI)-PHASES UNDER OXIDIZING CONDITIONS

    Energy Technology Data Exchange (ETDEWEB)

    A.P. Deditius; S. Utsunomiya; R.C. Ewing

    2006-02-21

    Uranium-(VI) phases are the primary alteration products of the UO{sub 2} in spent nuclear fuel and the UO{sub 2+x}, in natural uranium deposits. The U(VI)-phases generally form sheet structures of edge-sharing UO{sub 2}{sup 2+} polyhedra. The complexity of these structures offers numerous possibilities for coupled-substitutions of trace metals and radionuclides. The incorporation of radionuclides into U(VI)-structures provides a potential barrier to their release and transport in a geologic repository that experiences oxidizing conditions. In this study, we have used natural samples of UO{sub 2+x}, to study the U(VI)-phases that form during alteration and to determine the fate of the associated trace elements.

  16. ALTERATION OF U(VI)-PHASES UNDER OXIDIZING CONDITIONS

    International Nuclear Information System (INIS)

    A.P. Deditius; S. Utsunomiya; R.C. Ewing

    2006-01-01

    Uranium-(VI) phases are the primary alteration products of the UO 2 in spent nuclear fuel and the UO 2+x , in natural uranium deposits. The U(VI)-phases generally form sheet structures of edge-sharing UO 2 2+ polyhedra. The complexity of these structures offers numerous possibilities for coupled-substitutions of trace metals and radionuclides. The incorporation of radionuclides into U(VI)-structures provides a potential barrier to their release and transport in a geologic repository that experiences oxidizing conditions. In this study, we have used natural samples of UO 2+x , to study the U(VI)-phases that form during alteration and to determine the fate of the associated trace elements

  17. Characterization of dense lead lanthanum titanate ceramics prepared from powders synthesized by the oxidant peroxo method

    Energy Technology Data Exchange (ETDEWEB)

    Pinto, Alexandre H. [LIEC-Laboratorio Interdisciplinar de Eletroquimica e Ceramica, Departamento de Quimica, UFSCar-Universidade Federal de Sao Carlos, Rod.Washington Luis km 235, CP 676 Sao Carlos, SP 13565-905 (Brazil); Souza, Flavio L., E-mail: flavio.souza@ufabc.edu.br [Centro de Ciencias Naturais e Humanas, Universidade Federal do ABC, Rua Santa Adelia 166, Bangu, Santo Andre, SP 09210-170 (Brazil); Chiquito, Adenilson J., E-mail: chiquito@df.ufscar.br [Departamento de Fisica, UFSCar-Federal University of Sao Carlos, Rod.Washington Luis km 235, CP 676 Sao Carlos, SP 13565-905 (Brazil); Longo, Elson, E-mail: elson@iq.unesp.br [Instituto de Quimica de Araraquara, UNESP-Universidade Estadual Paulista, Rua Francisco Degni, CP 355 Araraquara, SP 14801-907 (Brazil); Leite, Edson R., E-mail: derl@power.ufscar.br [LIEC-Laboratorio Interdisciplinar de Eletroquimica e Ceramica, Departamento de Quimica, UFSCar-Universidade Federal de Sao Carlos, Rod.Washington Luis km 235, CP 676 Sao Carlos, SP 13565-905 (Brazil); Camargo, Emerson R., E-mail: camargo@ufscar.br [LIEC-Laboratorio Interdisciplinar de Eletroquimica e Ceramica, Departamento de Quimica, UFSCar-Universidade Federal de Sao Carlos, Rod.Washington Luis km 235, CP 676 Sao Carlos, SP 13565-905 (Brazil)

    2010-12-01

    Nanosized powders of lead lanthanum titanate (Pb{sub 1-x}La{sub x}TiO{sub 3}) were synthesized by means of the oxidant-peroxo method (OPM). Lanthanum was added from 5 to 30% in mol through the dissolution of lanthanum oxide in nitric acid, followed by the addition of lead nitrate to prepare a solution of lead and lanthanum nitrates, which was dripped into an aqueous solution of titanium peroxo complexes, forming a reactive amorphous precipitate that could be crystallized by heat treatment. Crystallized powders were characterized by FT-Raman spectroscopy and X-ray powder diffraction, showing that tetragonal perovskite structure is obtained for samples up to 25% of lanthanum and cubic perovskite for samples with 30% of lanthanum. Powders containing 25 and 30% in mol of lanthanum were calcined at 700 deg. C for 2 h, and in order to determine the relative dielectric permittivity and the phase transition behaviour from ferroelectric-to-paraelectric, ceramic pellets were prepared and sintered at 1100 or 1150 deg. C for 2 h and subjected to electrical characterization. It was possible to observe that sample containing 25% in mol of La presented a normal behaviour for the phase transition, whereas the sample containing 30% in mol of La presented a diffuse phase transition and relaxor behaviour.

  18. Characterization of dense lead lanthanum titanate ceramics prepared from powders synthesized by the oxidant peroxo method

    International Nuclear Information System (INIS)

    Pinto, Alexandre H.; Souza, Flavio L.; Chiquito, Adenilson J.; Longo, Elson; Leite, Edson R.; Camargo, Emerson R.

    2010-01-01

    Nanosized powders of lead lanthanum titanate (Pb 1-x La x TiO 3 ) were synthesized by means of the oxidant-peroxo method (OPM). Lanthanum was added from 5 to 30% in mol through the dissolution of lanthanum oxide in nitric acid, followed by the addition of lead nitrate to prepare a solution of lead and lanthanum nitrates, which was dripped into an aqueous solution of titanium peroxo complexes, forming a reactive amorphous precipitate that could be crystallized by heat treatment. Crystallized powders were characterized by FT-Raman spectroscopy and X-ray powder diffraction, showing that tetragonal perovskite structure is obtained for samples up to 25% of lanthanum and cubic perovskite for samples with 30% of lanthanum. Powders containing 25 and 30% in mol of lanthanum were calcined at 700 deg. C for 2 h, and in order to determine the relative dielectric permittivity and the phase transition behaviour from ferroelectric-to-paraelectric, ceramic pellets were prepared and sintered at 1100 or 1150 deg. C for 2 h and subjected to electrical characterization. It was possible to observe that sample containing 25% in mol of La presented a normal behaviour for the phase transition, whereas the sample containing 30% in mol of La presented a diffuse phase transition and relaxor behaviour.

  19. Theory of structural phase transition in MgTi{sub 2}O{sub 4}

    Energy Technology Data Exchange (ETDEWEB)

    Talanov, V. M., E-mail: valtalanov@mail.ru [South Russian State Polytechnical University (Russian Federation); Shirokov, V. B. [Russian Academy of Sciences, South Science Centre (Russian Federation); Ivanov, V. V. [South Russian State Polytechnical University (Russian Federation); Talanov, M. V. [South Federal University (Russian Federation)

    2015-01-15

    A theory of phase transition in MgTi{sub 2}O{sub 4} is proposed based on a study of the order-parameter symmetry, thermodynamics, and mechanisms of formation of the atomic and orbital structure of the low-symmetry MgTi{sub 2}O{sub 4} phase. The critical order parameter (which induces a phase transition) is determined. It is shown that the calculated MgTi{sub 2}O{sub 4} tetragonal structure is a result of displacements of magnesium, titanium, and oxygen atoms; ordering of oxygen atoms; and the participation of d{sub xy}, d{sub xz}, and d{sub yz} orbitals. The contribution of noncritical representations to ion displacements is proven to be insignificant. The existence of various metal clusters in the tetragonal phase has been established by calculation in correspondence with experimental data. It is shown (within the Landau theory of phase transitions) that phase states can be changed as a result of both first- and second-order phase transitions: the high-symmetry phase borders two low-symmetry phases by second-order transition lines, while the border between low-symmetry phases is a first-order transition line.

  20. Sol-gel preparation of cobalt manganese mixed oxides for their use as electrode materials in lithium cells

    International Nuclear Information System (INIS)

    Lavela, P.; Tirado, J.L.; Vidal-Abarca, C.

    2007-01-01

    An ethanol dehydration procedure has been used to precipitate gel-like citrate precursors containing cobalt and manganese transition metal ions. Further annealing led to the Mn x Co 3-x O 4 spinel oxide series (x: 1, 1.5, 2, 3). Annealing temperature and treatment time were also evaluated to optimize the performance of the oxides as active electrode materials in lithium cells. The manganese-cobalt mixed oxides obtained by this procedure were cubic or tetragonal phases depending on the cobalt content. SEM images showed spherical macroporous aggregates for MnCo 2 O 4 and hollow spheres for manganese oxides. The galvanostatic cycling of lithium cells assembled with these materials demonstrated a simultaneous reduction of cobalt and manganese during the first discharge and separation of cobalt- and manganese-based products on further cycling. As compared with binary manganese oxides, a notorious electrochemical improvement was observed in the mixed oxides. This behavior is a consequence of the synergistic effect of both transition metal elements, associated with the in-situ formation of a nanocomposite electrode material when cobalt is introduced in the manganese oxide composition. Values higher than 400 mAh/g were sustained after 50 cycles for MnCo 2 O 4

  1. Initial Bacterial Adhesion on Different Yttria-Stabilized Tetragonal Zirconia Implant Surfaces in Vitro

    Directory of Open Access Journals (Sweden)

    Lamprini Karygianni

    2013-12-01

    Full Text Available Bacterial adhesion to implant biomaterials constitutes a virulence factor leading to biofilm formation, infection and treatment failure. The aim of this study was to examine the initial bacterial adhesion on different implant materials in vitro. Four implant biomaterials were incubated with Enterococcus faecalis, Staphylococcus aureus and Candida albicans for 2 h: 3 mol % yttria-stabilized tetragonal zirconia polycrystal surface (B1a, B1a with zirconium oxide (ZrO2 coating (B2a, B1a with zirconia-based composite coating (B1b and B1a with zirconia-based composite and ZrO2 coatings (B2b. Bovine enamel slabs (BES served as control. The adherent microorganisms were quantified and visualized using scanning electron microscopy (SEM; DAPI and live/dead staining. The lowest bacterial count of E. faecalis was detected on BES and the highest on B1a. The fewest vital C. albicans strains (42.22% were detected on B2a surfaces, while most E. faecalis and S. aureus strains (approximately 80% were vital overall. Compared to BES; coated and uncoated zirconia substrata exhibited no anti-adhesive properties. Further improvement of the material surface characteristics is essential.

  2. Experimental study of stress-induced localized transformation plastic zones in tetragonal zirconia polycrystalline ceramics

    International Nuclear Information System (INIS)

    Sun, Q.; Zhao, Z.; Chen, W.; Qing, X.; Xu, X.; Dai, F.

    1994-01-01

    Stress-induced martensitic transformation plastic zones in ceria-stabilized tetragonal zirconia polycrystalline ceramics (Ce-TZP), under loading conditions of uniaxial tension, compression, and three-point bending, are studied by experiments. The transformed monoclinic phase volume fraction distribution and the corresponding plastic strain distribution and the surface morphology (surface uplift) are measured by means of moire interferometry, Raman microprobe spectroscopy, and the surface measurement system. The experimental results from the above three kinds of specimens and methods consistently show that the stress-induced transformation at room temperature of the above specimen is not uniform within the transformation zone and that the plastic deformation is concentrated in some narrow band; i.e., macroscopic plastic flow localization proceeds during the initial stage of plastic deformation. Flow localization phenomena are all observed in uniaxial tension, compression, and three-point bending specimens. Some implications of the flow localization to the constitutive modeling and toughening of transforming thermoelastic polycrystalline ceramics are explored

  3. Effect of boron oxide on the cubic-to-monoclinic phase transition in yttria-stabilized zirconia

    International Nuclear Information System (INIS)

    Florio, D.Z. de; Muccillo, R.

    2004-01-01

    Specimens of yttria fully stabilized zirconia with different amounts of boron oxide have been studied by X-ray diffraction at room temperature and at higher temperatures up to 1250 deg. C. A boron oxide-assisted cubic-to-monoclinic phase transformation was determined in the temperature range 800-1250 deg. C. In situ high temperature X-ray diffraction experiments gave evidences of the dependence of the phase transformation on the heating rate. The possibility of tuning the cubic-monoclinic phase ratio by suitable addition of boron oxide before pressing and sintering is proposed

  4. Method of forming an oxide superconducting thin film having an R1A2C3 crystalline phase over an R2A1C1 crystalline phase

    International Nuclear Information System (INIS)

    Lelental, M.; Romanofsky, H.J.

    1992-01-01

    This patent describes a process which comprises forming a mixed rare earth alkaline earth copper oxide layer on a substrate and converting the mixed rare earth alkaline earth copper oxide layer to an electrically conductive layer. It comprises crystalline R 1 A 2 C 3 oxide phase by heating in the presence of oxygen, wherein rare earth and R is in each instance chosen from among yttrium, lanthanum, samarium, europium, gadolinium, dysprosium, holmium, erbium, thulium, ytterbium, and lutetium and alkaline earth and A is in each instance chosen from among calcium, strontium and barium, characterized in that a crystalline R 2 A 1 C 1 oxide phase is first formed as a layer on the substrate and the crystalline R 1 A 2 C 3 oxide phase is formed over the crystalline R 2 A 1 C 1 oxide phase by coating a mixed rare earth alkaline earth copper oxide on the crystalline R 2 A 1 C 1 oxide phase and heating the mixed rare earth alkaline earth copper oxide to a temperature of at least 1000 degrees C

  5. Presence of a monoclinic (Pm) phase in the morphotropic phase boundary region of multiferroic (1 − x)Bi(Ni{sub 1/2}Ti{sub 1/2})O{sub 3}-xPbTiO{sub 3} solid solution: A Rietveld study

    Energy Technology Data Exchange (ETDEWEB)

    Pandey, Rishikesh, E-mail: akhilesh-bhu@yahoo.com, E-mail: aksingh.mst@itbhu.ac.in; Singh, Akhilesh Kumar, E-mail: akhilesh-bhu@yahoo.com, E-mail: aksingh.mst@itbhu.ac.in [School of Materials Science and Technology, Indian Institute of Technology (Banaras Hindu University), Varanasi 221005 (India)

    2014-07-28

    We present here the results of structural studies on multiferroic (1 − x)Bi(Ni{sub 1/2}Ti{sub 1/2})O{sub 3}-xPbTiO{sub 3} solid solution using Rietveld analysis on powder x-ray diffraction data in the composition range 0.35 ≤ x ≤ 0.55. The stability region of various crystallographic phases at room temperature for (1 − x)Bi(Ni{sub 1/2}Ti{sub 1/2})O{sub 3}-xPbTiO{sub 3} is determined precisely. Structural transformation from pseudo-cubic (x ≤ 0.40) to tetragonal (x ≥ 0.50) phase is observed via phase coexistence region demarcating the morphotropic phase boundary. The morphotropic phase boundary region consists of coexisting tetragonal and monoclinic structures with space group P4mm and Pm, respectively, stable in composition range 0.41 ≤ x ≤ 0.49 as confirmed by Rietveld analysis. The results of Rietveld analysis completely rule out the coexistence of rhombohedral and tetragonal phases in the morphotropic phase boundary region reported by earlier workers. A comparison between the bond lengths for “B-site cations-oxygen anions” obtained after Rietveld refinement, with the bond length calculated using Shannon-Prewitt ionic radii, reveals the ionic nature of B-O (Ni/Ti-O) bonds for the cubic phase and partial covalent character for the other crystallographic phases.

  6. Efecto de la nitruración en la degradación hidrotérmica de circona tetragonal policristalina estabilizada con Y2O3

    Directory of Open Access Journals (Sweden)

    Anglada, M.

    2004-02-01

    Full Text Available The effect of nitridation at 1650 ºC during 2 hours on hydrothermal aging of Y-TZP stabilized with 2.5 % moles of yttria has been studied. It has been shown that the superficial layer of nitrided samples was resistant to t→m phase transformation in water at 100 ºC during the investigated time period (850 hours. Conversely, the non-nitrided material transformed at the surface but no significant reduction in biaxial strength was observed. However, the biaxial strength of nitrided samples diminishes with hydrothermal aging time, which is thought to be due to the presence of an important amount of monoclinic phase inside the sample which is due to the high transformability of tetragonal grains. It appears that water does not play any important role in degradation of nitrided samples. The observations has been associated to changes in crystalline structure of a surface layer and to the high transformability of the tetragonal phase to monoclinic one inside the nitrided samples.Se ha estudiado el efecto de la nitruración a 1650 ºC durante 2 horas en la degradación hidrotérmica de una cerámica policristalina (YTZP estabilizada con 2.5% molar de itria. Se ha observado que la microestructura superficial de la cerámica nitrurada es resistente a la transformación de fase t→m en presencia de agua a 100 ºC durante el período de tiempo investigado (850 horas, mientras que el material de partida se transforma en la superficie, pero no sufre ninguna reducción significativa en la resistencia. Sin embargo, en las muestras nitruradas se observa una disminución de la resistencia a flexión biaxial con el tiempo de ataque hidrotérmico, la cual se atribuye a la presencia de una cantidad importante de fase monoclínica en el interior de la muestra. Es decir, los granos situados en esta zona son más transformables en las probetas nitruradas, sin que el agua desempeñe aparentemente ningún papel en la degradación de la resistencia de estas muestras

  7. Phase Identification and Internal Stress Analysis of Steamside Oxides on Plant Exposed Superheater Tubes

    DEFF Research Database (Denmark)

    Pantleon, Karen; Montgomery, Melanie

    2012-01-01

    During long-term, high-temperature exposure of superheater tubes in thermal power plants, various oxides are formed on the inner side (steamside) of the tubes, and oxide spallation is a serious problem for the power plant industry. Most often, oxidation in a steam atmosphere is investigated...... in laboratory experiments just mimicking the actual conditions in the power plant for simplified samples. On real plant-exposed superheater tubes, the steamside oxides are solely investigated microscopically. The feasibility of X-ray diffraction for the characterization of steamside oxidation on real plant......-exposed superheater tubes was proven in the current work; the challenges for depth-resolved phase analysis and phase-specific residual stress analysis at the inner side of the tubes with concave surface curvature are discussed. Essential differences between the steamside oxides formed on two different steels...

  8. Magnetic ordering induced giant optical property change in tetragonal BiFeO3

    Science.gov (United States)

    Tong, Wen-Yi; Ding, Hang-Chen; Gong, Shi Jing; Wan, Xiangang; Duan, Chun-Gang

    2015-12-01

    Magnetic ordering could have significant influence on band structures, spin-dependent transport, and other important properties of materials. Its measurement, especially for the case of antiferromagnetic (AFM) ordering, however, is generally difficult to be achieved. Here we demonstrate the feasibility of magnetic ordering detection using a noncontact and nondestructive optical method. Taking the tetragonal BiFeO3 (BFO) as an example and combining density functional theory calculations with tight-binding models, we find that when BFO changes from C1-type to G-type AFM phase, the top of valance band shifts from the Z point to Γ point, which makes the original direct band gap become indirect. This can be explained by Slater-Koster parameters using the Harrison approach. The impact of magnetic ordering on band dispersion dramatically changes the optical properties. For the linear ones, the energy shift of the optical band gap could be as large as 0.4 eV. As for the nonlinear ones, the change is even larger. The second-harmonic generation coefficient d33 of G-AFM becomes more than 13 times smaller than that of C1-AFM case. Finally, we propose a practical way to distinguish the two AFM phases of BFO using the optical method, which is of great importance in next-generation information storage technologies.

  9. On the Tetragonal Forms of KMo 4O 6

    Science.gov (United States)

    McCarroll, W. H.; Ramanujachary, K. V.; Greenblatt, M.; Marsh, Richard E.

    1995-06-01

    A reexamination of the X-ray diffraction data for the tetragonal form of KMo4O6 prepared by fused salt electrolysis leads to the conclusion that the crystal structure is better described by using space group P 4/mbm and not P4¯ as previously reported. However, refinement in the new space group does not result in any significant changes in the atomic arrangement. Possible reasons for the significant difference between the c lattice parameter of this form of KMo4O6 and that prepared at high pressures are also discussed.

  10. Influence of cobalt oxide on structure and phase composition of zirconium-containing materials

    International Nuclear Information System (INIS)

    Vladimirova, O.S.; Gruzdev, A.I.; Koposova, Z.L.; Lyutsareva, L.A.

    1986-01-01

    Effect of Co 3 O 4 addition in a quantity from 10 to 90% on microstructure, phase content, lattice parameter and structure of ZrO 2 ceramics spallings stabilized with yttrium oxide, is studied. It is found out that in the process of ceramics synthesis the formation of three-phased heterogeneous system of matrix type occurs. At cobalt oxide content within the range of 10-30% a matrix consist of ZrO 2 base solid solution, at cobalt oxide content from 50 to 90% it is a matrix base, at 40% Co 3 O 4 the regions with both type matrixes exist. Cobalt oxide introduction decreases the sintering temperature without loss in operation indices of heat sensitive ceramics for resistance transducers

  11. X-ray diffraction analysis of the phase transition orthorhombic-tetragonal in Y(1-x)Ca(x)Ba2Cu3O(7) superconductors dependent on the oxygen pressure at 500 and 600deg C. Etude de la transition orthorhombique-tetragonale dans les supraconducteurs Y sub 1-x Ca sub x Ba sub 2 Cu sub 3 O sub z par diffraction des rayons X en fonction de la pression d'oxygene a 500 et 600deg C

    Energy Technology Data Exchange (ETDEWEB)

    Touzelin, B [Lab. C.N.S., Chimie Generale, Univ. Paris 11, 91 - Orsay (France)

    1991-04-15

    The oxygen partial pressures and the oxygen composition z dependence of the lattice parameters of Y{sub 1-x}Ca{sub x}Ba{sub 2}Cu{sub 3}O{sub z} have been investigated by X-ray diffraction at 500 and 600deg C for 10%, 20% and 30% calcium content. The coexistence of the orthorhombic and tetragonal phases is observed in an oxygen composition range which decreases with increasing calcium content. The tetragonal phase occurs alone at the same oxygen content: z=6.745 in a temperature range of approximately 100deg C whatever the calcium content. Its structural transition will be first order with no second order at all, as undoped 1-2-3. Lastly it is noticed that the superconductivity is independent of the structural O-T transition. (orig.).

  12. Oxygen-Rich Lithium Oxide Phases Formed at High Pressure for Potential Lithium-Air Battery Electrode.

    Science.gov (United States)

    Yang, Wenge; Kim, Duck Young; Yang, Liuxiang; Li, Nana; Tang, Lingyun; Amine, Khalil; Mao, Ho-Kwang

    2017-09-01

    The lithium-air battery has great potential of achieving specific energy density comparable to that of gasoline. Several lithium oxide phases involved in the charge-discharge process greatly affect the overall performance of lithium-air batteries. One of the key issues is linked to the environmental oxygen-rich conditions during battery cycling. Here, the theoretical prediction and experimental confirmation of new stable oxygen-rich lithium oxides under high pressure conditions are reported. Three new high pressure oxide phases that form at high temperature and pressure are identified: Li 2 O 3 , LiO 2 , and LiO 4 . The LiO 2 and LiO 4 consist of a lithium layer sandwiched by an oxygen ring structure inherited from high pressure ε-O 8 phase, while Li 2 O 3 inherits the local arrangements from ambient LiO 2 and Li 2 O 2 phases. These novel lithium oxides beyond the ambient Li 2 O, Li 2 O 2 , and LiO 2 phases show great potential in improving battery design and performance in large battery applications under extreme conditions.

  13. The structure of ZrO2 phases and deviltrification processes in a Ca-Zr-Si-O-based glass ceramic: a combined a-XRD and XAS study

    International Nuclear Information System (INIS)

    Meneghini, C.; Mobilio, S.

    2004-01-01

    The structure of Zr atomic environment in a CaO-ZrO 2 -Si 2 glass ceramic as a function of thermal treatments has been studied, combining X-ray absorption spectroscopy (XAS), X-ray diffraction (XRD) and anomalous XRD (a-XRD) techniques. The analysis of XRD patterns demonstrates that the devitrification process proceeds through the partial segregation of Zr-depleted phases (wollastonite-like) and Zr-rich phases (Zr oxides). The XAS and a-XRD measurements at the Zr K-edge have been exploited in order to obtain a closer insight into the atomic structure around the Zr atoms. In the as-quenched glass the Zr atom is sixfold coordinated to O atoms in an amorphous environment rich in Ca and Si. Thermal treatment firstly (T=1273-1323 K) causes partial segragation of Zr in the form of an oxide with a tetragonal zirconia (t-ZrO 2 ) crystalline structure. Raising the temperature (T=1373 K) causes the formation of ZrO 2 crystallites in the monoclinic crystallographic phase (baddeleyite, m-ZrO 2 ). Analysis of the XAS data shows that a considerable amount of Zr remains in an amorphous calcium silicate phase. (orig.)

  14. Domain wall and interphase boundary motion in (1−x)Bi(Mg{sub 0.5}Ti{sub 0.5})O{sub 3}–xPbTiO{sub 3} near the morphotropic phase boundary

    Energy Technology Data Exchange (ETDEWEB)

    Tutuncu, Goknur [Department of Materials Science and Engineering, University of Florida, Gainesville, Florida 32611 (United States); Chen, Jun; Fan, Longlong [Department of Physical Chemistry, University of Science and Technology Beijing, Beijing 100083 (China); Fancher, Chris M.; Zhao, Jianwei [Department of Materials Science and Engineering, North Carolina State University, Raleigh, North Carolina 27695 (United States); Forrester, Jennifer S.; Jones, Jacob L., E-mail: JacobJones@ncsu.edu [Department of Materials Science and Engineering, University of Florida, Gainesville, Florida 32611 (United States); Department of Materials Science and Engineering, North Carolina State University, Raleigh, North Carolina 27695 (United States)

    2016-07-28

    Electric field-induced changes in the domain wall motion of (1−x)Bi(Mg{sub 0.5}Ti{sub 0.5})O{sub 3}–xPbTiO{sub 3} (BMT-xPT) near the morphotropic phase boundary (MPB) where x = 0.37 (BMT-37PT) and x = 0.38 (BMT-38PT), are studied by means of synchrotron x-ray diffraction. Through Rietveld analysis and profile fitting, a mixture of coexisting monoclinic (Cm) and tetragonal (P4mm) phases is identified at room temperature. Extrinsic contributions to the property coefficients are evident from electric-field-induced domain wall motion in both the tetragonal and monoclinic phases, as well as through the interphase boundary motion between the two phases. Domain wall motion in the tetragonal and monoclinic phases for BMT-37PT is larger than that of BMT-38PT, possibly due to this composition's closer proximity to the MPB. Increased interphase boundary motion was also observed in BMT-37PT. Lattice strain, which is a function of both intrinsic piezoelectric strain and elastic interactions of the grains (the latter originating from domain wall and interphase boundary motion), is similar for the respective tetragonal and monoclinic phases.

  15. Gas phase reactions of nitrogen oxides with olefins

    Energy Technology Data Exchange (ETDEWEB)

    Altshuller, A P; Cohen, I

    1961-01-01

    The nature of the condensation products formed in the gas phase reactions of nitrogen dioxide and nitric oxide with pentene-1, 2-methylbutene-2, and 2-methylbutadiene-1,3 was investigated. The reactants were combined at partial pressures in the range of 0.1 to 2.5 mm with the total pressure at one atmosphere. The products were determined by infrared and ultraviolet spectroscopy and colorimetry. The condensates included primary and secondary nitro compounds and alkyl nitrates. Strong hydroxyl and single bond carbon to oxygen stretching vibrations indicate the presence of either nitroalcohols or simple aliphatic alcohols formed through oxidation reactions. Carbonyl stretching frequencies observable in some of the reactions support the conclusion that a portion of the reactants disappear by oxidation rather than by nitration processes. The available results do not indicate the presence of appreciable amounts of tert.-nitro compounds, conjugated nitro-olefins, or gem-dinitro-alkanes. The reactivities of the olefins with the nitrogen oxides are in the decreasing order: 2-methyl-butadiene-1,3, 2-methylbutene-2, pentene-1. 20 references.

  16. Proton and O sup(2-) ion diffusion studied by γ-γ angular correlation and by impedance spectroscopy

    International Nuclear Information System (INIS)

    Oliveira Damasceno, O. de.

    1988-01-01

    The interaction of sup(181) Ta quadrupole momentum with electric field gradient was measured by perturbed angular correlation spectroscopy in polycrystalline samples of hafnium hydride and hafnium oxide. The measurements were done as function of the temperature, in cubic and tetragonal phases of hafnium hydride. In the cubic phase, spin relaxation effects related to proton diffusion with activation energy of 0.43 ± 0.05eV were observed, and in the tetragonal phase, the interaction was purely static. The hafnium oxide was studied in cubic phase stabilized by addition of calcium oxide or magnesium oxide. Relaxation effects probably due to O sup(2-) ion diffusion were verified. The protonic conduction in K H sub(2) PO sub(4) was studied by impedance spectroscopy, in pellets prepared by melting or powder compression using silver and platinum electrodes. In the case of silver electrodes, in the low frequency region, the impedance spectrum tends to a 45 sup(0) typical line of the diffusion process. It was attributed to hydrogen injection in the electrode. Heating k H sub(2) PO sub(4) at about 230 sup(0)C modifies significantly the electric properties. Two relaxation annealing reduced conductivities to constant values independently of preparation method. (author)

  17. Hydrothermal degradation of tetragonal ZrO{sub 2} ceramic components used in dental applications; Efeito da degradacao em meio aquoso de componentes ceramicos a base de ZrO{sub 2} tetragonal para uso odontologico

    Energy Technology Data Exchange (ETDEWEB)

    Mukaeda, L.E.; Robin, A.; Taguchi, S.P. [Universidade de Sao Paulo (DEMAR/EEL/USP), Lorena, SP (Brazil). Escola de Engenharia de Lorena. Dept. de Engenharia de Materiais; Santos, C. [ProtMat Materiais Avancados, Guaratingueta, SP (Brazil)

    2009-07-01

    With the evolution of the dental restoration techniques, a considerable growth in the demand of ceramic products occurred. These materials present good strength associated to reliability. In this work, micrometric and nanometric scale tetragonal ZrO{sub 2} blocks were sintered at 1500 deg C-2h and 1350 deg C-2h, respectively, ground and polished. Ceramics with relative density higher than 98% were obtained. The specimens were immersed in hot water (150 deg C), for times ranging from 10h to 30h. The mass variation of the samples was measured and the crystalline phases present before and after the degradation tests were identified by X-ray diffractometry, in order to evaluate the capacity of these ceramics in resisting to aqueous medium exposure. Materials with nanometric structure present higher resistance to degradation than those with micrometric scale, and this interferes in structural stability after the test, and reduces the martensitic transformation. (author)

  18. Aqueous phase oxidation techniques as an alternative to incineration

    International Nuclear Information System (INIS)

    Gray, L.W.; Adamson, M.G.; Hickman, R.G.; Farmer, J.C.; Chiba, Z.; Gregg, D.W.; Wang, F.T.

    1992-03-01

    The Lawrence Livermore National Laboratory (LLNL) has three aqueous phase techniques under development for oxidation of high value or high risk waste steams. One is direct electrochemical oxidation and one is mediated electrochemical oxidation utilizing regenerable, strongly oxidizing cations such as Ag(II), Co (III), Ce(IV), etc. These cations can either attack oxidizable materials directly and/or indirectly via first reacting with water to generate OH radicals which then attack the oxidizable materials. The third system utilizes H 2 O 2 and UV light to generate OH radicals directly which in turn attack the oxidizable materials. All systems have the advantage of a chemical off-switch in that when the power is turned off, the reaction quickly subsides. All systems operate with low concentrations (typically <5 wt %) of oxidizable materials, therefore, the stored energy for possible run-away reactions is very low. 15 figures, 22 references

  19. Oxidation behaviour of a Ti{sub 2}AlN MAX-phase coating

    Energy Technology Data Exchange (ETDEWEB)

    Wang Qimin; Kim, Kwangho [National Core Research Center for Hybrid Materials Solution, Pusan National University, Busan 609-735 (Korea, Republic of); Garkas, W; Renteria, A Flores [Chair of Physical Metallurgy and Materials Technology, Technical University of Brandenburg at Cottbus, 03046 Cottbus (Germany); Leyens, C [Institute of Materials Science, Technical University of Dresden, Helmholtzstrasse 7, 01069 Dresden (Germany); Sun Chao, E-mail: qmwang@pusan.ac.kr, E-mail: kwhokim@pusan.ac.kr [Division of Surface Engineering of Materials, Institute of Metal Research, Chinese Academy of Sciences, Shenyang 110016 (China)

    2011-10-29

    In this paper, we reported the oxidation behaviour of Ti{sub 2}AlN coatings on a -TiAl substrate. The coatings composed mainly of Ti{sub 2}AlN MAX phase were obtained by magnetron sputtering and subsequent vacuum annealing. Isothermal oxidation tests at 700-900 deg. C were performed in air. The results indicated that the oxidation resistance of the -TiAl alloy can be improved by depositing a Ti{sub 2}AlN layer on the alloy surface, especially at high temperatures. An Al-rich oxide scale formed on the coating surfaces during oxidation. This scale acts as diffusion barrier blocking the ingress of oxidation, and effectively protects the coated alloys from further oxidation attack.

  20. Oxidation of uraninite

    International Nuclear Information System (INIS)

    Janeczek, J.; Ewing, R.C.

    1993-06-01

    Samples of uraninite and pitchblende annealed at 1200 degrees C in H 2 , and untreated pitchblende were sequentially oxidized in air at 180-190 degrees C, 230 degrees C, and 300 degrees C. Uraninite and untreated pitchblende oxidized to the U 4 O 9 -type oxide, and their x-ray symmetry remained isometric up to 300 degrees C. Reduced pitchblende, after oxidation to UO 2+x and U 4 O 9 -type oxides, transformed into α-U 3 O 8 at 300 degrees C. Two major mechanisms control uraninite and untreated pitchblende stability during oxidation: 1. Th and/or lanthanide elements maintain charge balance and block oxygen interstitials near impurity cations; 2. the uraninite structure saturates with respect to excess and radiation-induced oxygen interstitials. Untreated pitchblende during oxidation behaved similarly to irradiated UO 2 in spent nuclear fuel; whereas, reduced pitchblende resembled non-irradiated UO 2 . An analysis of the data in the literature, as well as our own efforts (XRD, EMPA, SEM, AEM) to identify U 3 O 7 in samples form Cigar Lake, Canada, failed to provide conclusive evidence of the natural occurrence of tetragonal αU 3 O 7 . Most probably, reported occurrences of U 3 O 7 are mixtures of isometric uraninites of slightly different compositions, 45 refs

  1. Yttria-Ceria stabilized tetragonal zirconia polycrystals: Sintering, grain growth and grain boundary segregation

    NARCIS (Netherlands)

    Boutz, M.M.R.; Boutz, M.M.R.; Winnubst, Aloysius J.A.; Burggraaf, Anthonie; Burggraaf, A.J.

    1994-01-01

    An analysis is presented of grain growth and densification of yttria-ceria stabilized tetragonal zirconia polycrystals (Y, Ce-TZPs) using both isothermal and non-isothermal techniques. The characteristics of Y, Ce-TZPs are compared to those of Y-TZP and Ce-TZP and the effect of increasing ceria

  2. Oxidation kinetics of some zirconium alloys in flowing carbon dioxide at high temperatures

    International Nuclear Information System (INIS)

    Kohli, R.

    1980-01-01

    The oxidation kinetics of three zirconium alloys (Zr-2.2 wt% Hf, Zr-2.5 wt% Nb, and Zr-3 wt% Nb-1 wt% Sn) have been measured in flowing carbon dioxide in the temperature range from 873 to 1173 K to 120 ks (2000 min). At all oxidation temperatures, Zr-2.5 Nb and Zr-3 Nb-1 Sn showed a transition to rapid linear kinetics after initial parabolic oxidation. The Zr-2.2 Hf showed this transition at temperatures in the range from 973 to 1173 K; at 873 K, no transition was observed within the oxidation times reported. The Zr-2.2 Hf showed the smallest weight gains, followed in order by Zr-2.5 Nb and Zr-3 Nb-1 Sn. Increased oxidation rates and shorter times-to-rate-transition of Zr-2.2 Nb and Zr-1 Sn as compared with Zr-2.2 Hf can be attributed to the presence of niobium, tin, and hafnium in the alloys. This is considered in terms of the Nomura-Akutsu model, according to which hafnium should delay the rate transition, while niobium and tin lead to shorter times-to-rate-transition. The scale on Zr-2.2 Hf was identified as monoclinic zirconia, while the tetragonal phase, 6ZrO 2 .Nb 2 O 5 , was contained in the monoclinic zirconia scales on both other alloys

  3. Protection of yttria-stabilized zirconia for dental applications by oxidic PVD coating.

    Science.gov (United States)

    Hübsch, C; Dellinger, P; Maier, H J; Stemme, F; Bruns, M; Stiesch, M; Borchers, L

    2015-01-01

    In this study, the application of transparent physical vapor deposition (PVD) coatings on zirconia ceramics was examined as an approach to retard the low-temperature degradation of zirconia for dental applications. Transparent monolayers of titanium oxide (TixOy) and multilayers consisting of titanium oxide-alumina-titanium oxide (TixOy-AlxOy-TixOy) were deposited onto standardized discs of 3Y-TZP using magnetron sputtering. Using X-ray photospectroscopy and time-of-flight secondary-ion mass spectrometry, the compositions of the coatings were verified, and an approximate thickness of 50 nm for each type of coating was ascertained. After aging the coated and uncoated samples in water vapor at 134°C and 3 bar for 4, 8, 16, 32, 64 and 128 h, the monoclinic phase content was determined using X-ray diffraction, and its impact on mechanical properties was assessed in biaxial flexural strength tests. In addition, the depth of the transformation zone was measured from scanning electron microscopy images of the fracture surfaces of hydrothermally aged samples. The results revealed that the tetragonal-to-monoclinic phase transformation of the zirconia ceramic was retarded by the application of PVD coatings. During the first stages of aging, the coated samples exhibited a significantly lower monoclinic phase content than the uncoated samples and, after 128 h of aging, showed a transformation zone which was only ∼12-15 μm thick compared to ∼30 μm in the control group. Biaxial flexural strength decreased by ∼10% during aging and was not influenced by the application of a PVD coating. Copyright © 2014 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

  4. Electronic structure and high pressure phase transition in LaSb and CeSb

    International Nuclear Information System (INIS)

    Mathi Jaya, S.; Sanyal, S.P.

    1992-09-01

    The electronic structure and high pressure structural phase transition in cerium and lanthanum antimonides have been investigated using the tight binding LMTO method. The calculation of total energy reveals that the simple tetragonal structure is found to be stable at high pressures for both the compounds. In the case of LaSb, the calculated value of the equilibrium cell volume and the cell volume at which phase transition occurs are found to have a fairly good agreement with the experimental results. However, in the case of CeSb, the agreement is not as good as in LaSb. We also predicted the most favoured c/a value in the high pressure phase (simple tetragonal) for these compounds. Further we present the calculated results on the electronic structure of these systems at the equilibrium as well as at the reduced cell volumes. (author). 8 refs, 11 figs, 1 tab

  5. Electric field-induced phase transitions in Li-modified Na{sub 0.5}K{sub 0.5}NbO{sub 3} at the polymorphic phase boundary

    Energy Technology Data Exchange (ETDEWEB)

    Iamsasri, Thanakorn; Jones, Jacob L., E-mail: jacobjones@ncsu.edu [Department of Materials Science and Engineering, North Carolina State University, Raleigh, North Carolina 27695 (United States); Department of Materials Science and Engineering, University of Florida, Gainesville, Florida 32611 (United States); Tutuncu, Goknur [Department of Materials Science and Engineering, University of Florida, Gainesville, Florida 32611 (United States); Uthaisar, Chunmanus; Pojprapai, Soodkhet [School of Ceramic Engineering, Institute of Engineering, Suranaree University of Technology, Nakorn Ratchasima 30000 (Thailand); Wongsaenmai, Supattra [Program in Materials Science, Faculty of Science, Maejo University, Chiang Mai 50290 (Thailand)

    2015-01-14

    The electric field-induced phase transitions in Li-modified Na{sub 0.5}K{sub 0.5}NbO{sub 3} at the polymorphic phase boundary (PPB) were observed using in situ X-ray diffraction. The ratio of monoclinic to tetragonal phase fraction was used as an indicator of the extent and reversibility of the phase transitions. The reversibility of the phase transition was greater in compositions further from the PPB. These results demonstrate that the field-induced phase transition is one of the origins of high piezoelectric properties in lead-free ferroelectric materials.

  6. Structural Evolution of the R-T Phase Boundary in KNN-Based Ceramics

    KAUST Repository

    Lv, Xiang

    2017-10-04

    Although a rhombohedral-tetragonal (R-T) phase boundary is known to substantially enhance the piezoelectric properties of potassium-sodium niobate ceramics, the structural evolution of the R-T phase boundary itself is still unclear. In this work, the structural evolution of R-T phase boundary from -150 °C to 200 °C is investigated in (0.99-x)K0.5Na0.5Nb1-ySbyO3-0.01CaSnO3-xBi0.5K0.5HfO3 (where x=0~0.05 with y=0.035, and y=0~0.07 with x=0.03) ceramics. Through temperature-dependent powder X-ray diffraction (XRD) patterns and Raman spectra, the structural evolution was determined to be Rhombohedral (R, <-125 °C) → Rhombohedral+Orthorhombic (R+O, -125 °C to 0 °C) → Rhombohedral+Tetragonal (R+T, 0 °C to 150 °C) → dominating Tetragonal (T, 200 °C to Curie temperature (TC)) → Cubic (C, >TC). In addition, the enhanced electrical properties (e.g., a direct piezoelectric coefficient (d33) of ~450±5 pC/N, a conversion piezoelectric coefficient (d33*) of ~580±5 pm/V, an electromechanical coupling factor (kp) of ~0.50±0.02, and TC~250 °C), fatigue-free behavior, and good thermal stability were exhibited by the ceramics possessing the R-T phase boundary. This work improves understanding of the physical mechanism behind the R-T phase boundary in KNN-based ceramics and is an important step towards their adoption in practical applications. This article is protected by copyright. All rights reserved.

  7. Closed-cage tungsten oxide clusters in the gas phase.

    Science.gov (United States)

    Singh, D M David Jeba; Pradeep, T; Thirumoorthy, Krishnan; Balasubramanian, Krishnan

    2010-05-06

    During the course of a study on the clustering of W-Se and W-S mixtures in the gas phase using laser desorption ionization (LDI) mass spectrometry, we observed several anionic W-O clusters. Three distinct species, W(6)O(19)(-), W(13)O(29)(-), and W(14)O(32)(-), stand out as intense peaks in the regular mass spectral pattern of tungsten oxide clusters suggesting unusual stabilities for them. Moreover, these clusters do not fragment in the postsource decay analysis. While trying to understand the precursor material, which produced these clusters, we found the presence of nanoscale forms of tungsten oxide. The structure and thermodynamic parameters of tungsten clusters have been explored using relativistic quantum chemical methods. Our computed results of atomization energy are consistent with the observed LDI mass spectra. The computational results suggest that the clusters observed have closed-cage structure. These distinct W(13) and W(14) clusters were observed for the first time in the gas phase.

  8. Kinematics and thermodynamics of non-stoichiometric oxidation phase transitions in spent fuel

    International Nuclear Information System (INIS)

    Stout, R.B.; Kansa, E.J.; Wijesinghe, A.M.

    1993-01-01

    At low temperatures ( 2 lattice to a U 4 O 9 lattice but with an oxygen-to-uranium (O/U) ratio of ∼2.4. Also, the weight gain time response has a plateau as the O/U approaches 2.4. Part of this response results from a geometrical dependency as a U 4 O 9 oxidation front propagates into grain volumes Of UO 2 It may also be indicative of a metastable, non-stoichiometric U 4 O 9 phase whose existence may inhibit the transition kinetics to the next expected phase Of U 3 O 8 . To gain a mechanistic understanding and to plan future oxidation tests, lattice kinematic and thermodynamic models are developed for lattice deformations and energetics of lattice phase changes (UO 2 → U 4 O 9 → U 3 0 7 → U 3 O 8) that include zeroth order influences on oxidation kinetics due to interstitial oxygen atoms and vacancies plus interstitial and substitutional actinides and fission decay products in spent fuel

  9. Gas-Phase Photocatalytic Oxidation of Dimethylamine: The Reaction Pathway and Kinetics

    Directory of Open Access Journals (Sweden)

    Anna Kachina

    2007-01-01

    Full Text Available Gas-phase photocatalytic oxidation (PCO and thermal catalytic oxidation (TCO of dimethylamine (DMA on titanium dioxide was studied in a continuous flow simple tubular reactor. Volatile PCO products of DMA included ammonia, formamide, carbon dioxide, and water. Ammonia was further oxidized in minor amounts to nitrous oxide and nitrogen dioxide. Effective at 573 K, TCO resulted in the formation of ammonia, hydrogen cyanide, carbon monoxide, carbon dioxide, and water. The PCO kinetic data fit well to the monomolecular Langmuir-Hinshelwood model, whereas TCO kinetic behaviour matched the first-order process. No deactivation of the photocatalyst during the multiple long-run experiments was observed.

  10. A self-ordered, body-centered tetragonal superlattice of SiGe nanodot growth by reduced pressure CVD

    Science.gov (United States)

    Yamamoto, Yuji; Zaumseil, Peter; Capellini, Giovanni; Schubert, Markus Andreas; Hesse, Anne; Albani, Marco; Bergamaschini, Roberto; Montalenti, Francesco; Schroeder, Thomas; Tillack, Bernd

    2017-12-01

    Self-ordered three-dimensional body-centered tetragonal (BCT) SiGe nanodot structures are fabricated by depositing SiGe/Si superlattice layer stacks using reduced pressure chemical vapor deposition. For high enough Ge content in the island (>30%) and deposition temperature of the Si spacer layers (T > 700 °C), we observe the formation of an ordered array with islands arranged in staggered position in adjacent layers. The in plane periodicity of the islands can be selected by a suitable choice of the annealing temperature before the Si spacer layer growth and of the SiGe dot volume, while only a weak influence of the Ge concentration is observed. Phase-field simulations are used to clarify the driving force determining the observed BCT ordering, shedding light on the competition between heteroepitaxial strain and surface-energy minimization in the presence of a non-negligible surface roughness.

  11. Study of the phase composition of nanostructures produced by the local anodic oxidation of titanium films

    International Nuclear Information System (INIS)

    Avilov, V. I.; Ageev, O. A.; Konoplev, B. G.; Smirnov, V. A.; Solodovnik, M. S.; Tsukanova, O. G.

    2016-01-01

    The results of experimental studies of the phase composition of oxide nanostructures formed by the local anodic oxidation of a titanium thin film are reported. The data of the phase analysis of titanium-oxide nanostructures are obtained by X-ray photoelectron spectroscopy in the ion profiling mode of measurements. It is established that the surface of titanium-oxide nanostructures 4.5 ± 0.2 nm in height possesses a binding energy of core levels characteristic of TiO_2 (458.4 eV). By analyzing the titanium-oxide nanostructures in depth by X-ray photoelectron spectroscopy, the formation of phases with binding energies of core levels characteristic of Ti_2O_3 (456.6 eV) and TiO (454.8 eV) is established. The results can be used in developing the technological processes of the formation of a future electronic-component base for nanoelectronics on the basis of titanium-oxide nanostructures and probe nanotechnologies.

  12. Ab-initio study of the hyperfine parameters in P21/c, P42nmc and Fm3m zirconia phases doped with Tazr and the vacancy-Tazr complex

    International Nuclear Information System (INIS)

    Casali, R.A.; Caravaca, M.A.

    2007-01-01

    In this work we develop selfconsistent calculations by means of the all-electron method NFP-LMTO. The electronic structure, quadrupolar frequencies and asymmetry parameters of ZrO 2 polymorphs doped with Ta placed at substitutional site to Zr (Ta Zr ), with and without vacancies are studied in the monoclinic, tetragonal and cubic phases. The calculated hyperfine parameters in neutral Ta Zr in the monoclinic phase are in agreement with hypine parameters measured with PAC and assigned to substitutional site in a wide range of temperatures. However, in the case of Ta Zr in the tetragonal P42nmc phase, the electric field gradient (EFG) is in large disagreement with the experimental assignment. Therefore we explored the incorporation of a near neighbor oxygen vacancy in several charged states. We found that the TaV 0 and TaV +1 pairs in the tetragonal symmetry with axis length ratio c/a=1.02 gives electric field gradients V zz and η in agreement with low-temperature values of the experimentally assigned pure tetragonal, called t-form. Further, the pair Ta-V with a ratio c/a=1 gives EFG in close agreement with reported high-temperature values

  13. Superconductivity in the Sr-Ca-Cu-O system and the phase with infinite-layer structure

    International Nuclear Information System (INIS)

    Shaked, H.; Shimakawa, Y.; Hunter, B.A.; Hitterman, R.L.; Jorgensen, J.D.; Han, P.D.; Payne, D.A.

    1995-01-01

    Superconductivity and structure in samples of (Sr,Ca)CuO 2 with the infinite-layer structure, prepared by high-pressure synthesis, have been studied using magnetic susceptibility measurements, small angle x-ray diffraction, and neutron diffraction. It is found that the superconducting (T c ∼100 K) samples in this system are phase impure and contain, in addition to the infinite-layer phase, members of the two homologous series Sr n-1 Cu n+1 O 2n (n=3,5,...; orthorhombic), and Sr n+1 Cu n O 2n+1+δ (n=1,2,...; tetragonal), as minor phases. Samples with larger phase fractions of the Sr n+1 Cu n O 2n+1+δ compounds showed higher superconducting fractions. Phase-pure infinite-layer samples are not superconducting. Based on these results, and results previously published in the literature, it is proposed that the superconductivity in these infinite-layer samples comes from the tetragonal Sr n+1 Cu n O 2n+1+δ compounds, not from the phase with the infinite-layer structure

  14. The effect of adding magnesium oxide on the mechanical properties of the tricalcium phosphate-zirconia composites

    Energy Technology Data Exchange (ETDEWEB)

    Sallemi, Imen, E-mail: imen.sallemi@hotmail.com; Bouaziz, Jamel; Ben Ayed, Foued

    2015-02-01

    The effect of magnesium oxide on the mechanical properties of the tricalcium phosphate – 50 wt.% zirconia composites was investigated during a sintering process between 1300 °C and 1400 °C. The characteristics of the samples before and after the sintering process were realized by using the differential thermal analysis, dilatometry, X-ray diffraction, the {sup 31}P magic angle scanning nuclear magnetic resonance, the scanning electron microscope and by considering such mechanical properties as the rupture strength and Vickers hardness. The mechanical performances of the tricalcium phosphate-50 wt.% zirconia composites increased with both the percentage of magnesium oxide and the sintering temperature. At 1400 °C, the mechanical properties of the composites sintered with 10 wt.% magnesium oxide reached their maximum value. Thus, Vickers hardness increased from 554 to 6350 MPa and the rupture strength of the corresponding composites varied from 5.2 to 25 MPa. The increase of the mechanical properties of the samples is due to the formation of both the tetragonal zirconia phase and the liquid phase which helps to fill the pores. The microstructure of needle form is most probably phosphate precipitates which are formed from this liquid phase. Furthermore, the presence of magnesium oxide in the composites prevented the inverse allotropic transformation of zirconia. - Highlights: • We measure the rupture strength and Vickers hardness of bioceramics. • We characterize the effect of MgO on the mechanical properties of the tricalcium phosphate – 50 wt% zirconia composites. • MgO increase the mechanical properties of the composites.

  15. Effect of titanium and calcium oxide additions on Zr2O2 polymorphism during Al2O3+Zr2O2 mixture fusion

    International Nuclear Information System (INIS)

    Gladkov, V.E.; Zhekhanova, N.B.; Fotiev, A.A.; Viktorov, V.V.; Ivashinnikov, V.T.; Zubov, A.S.

    1985-01-01

    The effect of titanium and calcium containing additions introduced into the Al 2 O 3 +ZrO 2 melt on the phase composition and temperature ranges of ZrO 2 polymorphous transformation in the material is investigated. It is shown that introducing sponge titanium into the 70Al 2 O 3 +30ZrO 2 prepared composition melt (mass. %) with its subsequent intensive cooling one can conserve upto room temperatures 50-70% of ZrO 2 metastable tetragonal modification and therefore reduce the volume changes causing metal cracking. Calcium oxide doping stabilizes the ZrO 2 cubic modification and reduces α-Al 2 O 3 content due to formation of aluminates

  16. Metal Oxide-Carbon Nanocomposites for Aqueous and Nonaqueous Supercapacitors, Phase I

    Data.gov (United States)

    National Aeronautics and Space Administration — This Small Business Innovation Research Phase I effort focuses on development of novel metal-oxide-carbon nanocomposites for application in pseudocapacitive...

  17. Thermal synthesis of oxide molecular sieve and Mn (K-OMS-2) from K-birnessite obtained from Sol-gel method

    International Nuclear Information System (INIS)

    Rezende, D.S.; Figueira, B.A.M.; Moraes, M.C. de; Silva, L.N. da; Mercury, J.M.R.; Figueiredo, G.P. de

    2016-01-01

    This study presents the thermal synthesis of molecular sieve with K-OMS2 structure from K-birnessite tunneling process, one Mn oxide with structure in layer. According X-Ray diffraction data it was possible to monitoring the conversion of the layered structure around 550 deg C for (K-OMS-2) tunnel with tetragonal system and I2/m space group. The FTIR main spectrum bands of K-OMS-2 was observed in 700, 525 e 470 cm-1 region and are related to elongation Mn 3+ -O e Mn 4+ -O in the tunnel structure. The product morphology identified by Scanning Electron Microscopy it was verified as pseudo tetragonal, reflecting externally the crystallographic system of cryptomelane structure. The results reveal one simple route for the Mn oxide molecular sieve with K-OMS-2 structure

  18. Characterization of Schottky barrier diodes fabricated from electrochemical oxidation of {alpha} phase brass

    Energy Technology Data Exchange (ETDEWEB)

    Bond, John W., E-mail: jwb13@le.ac.u [Forensic Research Centre, University of Leicester, Leicester LE1 7 EA (United Kingdom)

    2011-04-01

    By careful selection of chloride ion concentration in aqueous sodium chloride, electrochemical oxidation of {alpha} phase brass is shown to permit fabrication of either p-type copper (I) oxide/metal or n-type zinc oxide/metal Schottky barrier diodes. X-ray photoelectron and Auger electron spectroscopies provide evidence that barrier formation and rectifying qualities depend on the relative surface abundance of copper (I) oxide and zinc oxide. X-ray diffraction of the resulting diodes shows polycrystalline oxides embedded in amorphous oxidation products that have a lower relative abundance than the diode forming oxide. Conventional I/V characteristics of these diodes show good rectifying qualities. When neither of the oxides dominate, the semiconductor/metal junction displays an absence of rectification.

  19. Heavy haze in winter Beijing driven by fast gas phase oxidation

    Science.gov (United States)

    Lu, K.; Tan, Z.; Wang, H.; Li, X.; Wu, Z.; Chen, Q.; Wu, Y.; Ma, X.; Liu, Y.; Chen, X.; Shang, D.; Dong, H.; Zeng, L.; Shao, M.; Hu, M.; Fuchs, H.; Novelli, A.; Broch, S.; Hofzumahaus, A.; Holland, F.; Rohrer, F.; Bohn, B.; Georgios, G.; Schmitt, S. H.; Schlag, P.; Kiendler-Scharr, A.; Wahner, A.; Zhang, Y.

    2017-12-01

    Heavy haze conditions were frequently presented in the airsheds of Beijing and surrounding areas, especially during winter time. To explore the trace gas oxidation and the subsequent formation of aerosols, a comprehensive field campaign was performed at a regional site (in the campus of University of Chinese Academy of Science, UCAS) in Beijing winter 2016. Serious haze pollution processes were often observed with the fast increase of inorganic salt (especially nitrate) and these pollutions were always associated with enhanced humidity and the concentrations of PAN (PeroxyAcyl Nitrates) which is normally a marker of gas phase oxidations from NOx and VOCs. Moreover, based on the measurements of OH, HO2, RO2, total OH reactivity, N2O5, NO, NO2, SO2, particle concentrations/distributions/chemical compositions, and meteorological parameters, the gas phase oxidation rates that leads to the formation of sulfate, nitrate and secondary organic aerosols were estimated. These determined formation rates were clearly enhanced by several folds during pollution episodes compared to that of the clean air masses. Preliminary analysis result showed that the gas phase formation potential of nitrate and secondary organic aerosols were larger than the observed concentrations of nitrate and SOA of which the excess production may be explained by deposition and dilution.

  20. Crystalline mesoporous zirconia catalysts having stable tetragonal pore wall structure

    Science.gov (United States)

    Sachtler, W.M.H.; Huang, Y.Y.

    1998-07-28

    Methods are disclosed for the preparation of new sulfated mesoporous zirconia materials/catalysts with crystalline pore walls of predominantly tetragonal crystal structure, characterized by nitrogen physical sorption measurement, X-ray diffraction, transmission electron microscopy and catalytic tests using n-butane isomerization to iso-butane and alkylation of 1-naphthol with 4-tert-butylstyrene as probe reactions. Sulfate deposition is preferred for the transformation of a mesoporous precursor with amorphous pore walls into a material with crystalline pore walls maintaining the mesoporous characteristics. 17 figs.

  1. High pressure structural phase transition of neodymium mono pnictides

    International Nuclear Information System (INIS)

    Pagare, Gitanjali; Ojha, P.; Sanyal, S.P.; Aynyas, Mahendra

    2007-01-01

    We have investigated theoretically the high-pressure structural phase transition of two neodymium mono NdX (X=As, Sb) using an interionic potential theory with necessary modification to include the effect of Coulomb screening by the delocalized f electrons of Nd ion. These compounds exhibits first order crystallographic phase transition from their NaCl (B 1 ) phase to body centered tetragonal (BCT) at 27 GPa and 15.3 GPa respectively. We also calculated the Nd-Nd distance as a function of pressure. (author)

  2. Electric-field-induced paraelectric to ferroelectric phase transformation in prototypical polycrystalline BaTiO3

    International Nuclear Information System (INIS)

    Wang, Zhiyang; Hinterstein, Manuel; Daniels, John E.; Webber, Kyle G.; Hudspeth, Jessica M.

    2014-01-01

    An electric-field-induced paraelectric cubic to ferroelectric tetragonal phase transformation has been directly observed in prototypical polycrystalline BaTiO 3 at temperatures above the Curie point (T C ) using in situ high-energy synchrotron X-ray diffraction. The transformation persisted to a maximum temperature of 4 °C above T C . The nature of the observed field-induced transformation and the resulting development of domain texture within the induced phase were dependent on the proximity to the transition temperature, corresponding well to previous macroscopic measurements. The transition electric field increased with increasing temperature above T C , while the magnitude of the resultant tetragonal domain texture at the maximum electric field (4 kV mm −1 ) decreased at higher temperatures. These results provide insights into the phase transformation behavior of a prototypical ferroelectric and have important implications for the development of future large-strain phase-change actuator materials.

  3. In-situ structural investigations of ferroelasticity in soft and hard rhombohedral and tetragonal PZT

    Energy Technology Data Exchange (ETDEWEB)

    Morozov, Maxim I., E-mail: maximm@alumni.ntnu.no; Einarsrud, Mari-Ann; Tolchard, Julian R.; Grande, Tor [Department of Materials Science and Engineering, Norwegian University of Science and Technology, NO-7491 Trondheim (Norway); Geiger, Philipp T.; Webber, Kyle G. [Department of Materials Science, Friedrich-Alexander-Universität Erlangen-Nürnberg, 91058 Erlangen (Germany); Damjanovic, Dragan [Ceramics Laboratory, Swiss Federal Institute of Technology in Lausanne-EPFL, 1015 Lausanne (Switzerland)

    2015-10-28

    Despite the technological importance of hard and soft PZT, Pb(Zr,Ti)O{sub 3}, ceramics, the mechanisms of ferroelectric hardening and softening remain widely discussed in the literature. The hardening and softening phenomena have traditionally been investigated in relation with dielectric manifestations such as aging of the dielectric susceptibility and constriction of the polarization-electric field hysteresis loop. Here, we present a systematic investigation of the ferroelectric and ferroelastic properties of soft and hard PZT in both the tetragonal and rhombohedral phases. A particular focus has been devoted to ferroelastic domain switching by characterizing the macroscopic mechanical constitutive behavior and in-situ synchrotron X-ray diffraction during compression. It is demonstrated that variation of the ordering state of point defects in PZT ceramics affects the switching behavior of both ferroelectric and ferroelastic domains under mechanical or electrical fields. Softening of the mechanical and electrical properties of originally hard PZT ceramics was conferred by quenching the materials from above the Curie temperature. The present findings are discussed with respect to the current understanding of hardening-softening transitions in ferroelectric materials.

  4. Biaxial stress driven tetragonal symmetry breaking and high-temperature ferromagnetic semiconductor from half-metallic CrO2

    Science.gov (United States)

    Xiao, Xiang-Bo; Liu, Bang-Gui

    2018-03-01

    It is highly desirable to combine the full spin polarization of carriers with modern semiconductor technology for spintronic applications. For this purpose, one needs good crystalline ferromagnetic (or ferrimagnetic) semiconductors with high Curie temperatures. Rutile CrO2 is a half-metallic spintronic material with Curie temperature 394 K and can have nearly full spin polarization at room temperature. Here, we find through first-principles investigation that when a biaxial compressive stress is applied on rutile CrO2, the density of states at the Fermi level decreases with the in-plane compressive strain, there is a structural phase transition to an orthorhombic phase at the strain of -5.6 % , and then appears an electronic phase transition to a semiconductor phase at -6.1 % . Further analysis shows that this structural transition, accompanying the tetragonal symmetry breaking, is induced by the stress-driven distortion and rotation of the oxygen octahedron of Cr, and the half-metal-semiconductor transition originates from the enhancement of the crystal field splitting due to the structural change. Importantly, our systematic total-energy comparison indicates the ferromagnetic Curie temperature remains almost independent of the strain, near 400 K. This biaxial stress can be realized by applying biaxial pressure or growing the CrO2 epitaxially on appropriate substrates. These results should be useful for realizing full (100%) spin polarization of controllable carriers as one uses in modern semiconductor technology.

  5. Phase transformations, heat evolution, and atomic diffusion during slow heating of Al-rich Al/Zr multilayered foils

    Energy Technology Data Exchange (ETDEWEB)

    Fisher, Kaitlynn; Barron, S. C.; Knepper, R.; Weihs, T. P., E-mail: weihs@jhu.edu [Department of Materials Science and Engineering, Johns Hopkins University, Baltimore, Maryland 21218-2689 (United States); Bonds, M. A.; Browning, N. D. [Department of Chemical Engineering and Materials Science, University of California, Davis, California 95616 (United States); Condensed Matter and Materials Division, Lawrence Livermore National Laboratory, Livermore, California 94550 (United States); Livi, K. J. T. [High-Resolution Analytical Electron Microbeam Facility, Integrated Imaging Center, Johns Hopkins University, Baltimore, Maryland 21218 (United States); Campbell, G. H. [Condensed Matter and Materials Division, Lawrence Livermore National Laboratory, Livermore, California 94550 (United States)

    2013-12-28

    We describe the energy and sequence of phase transformations in multilayered Al/Zr foils with atomic ratios of 3 Al:1 Zr during low temperature (<350 °C) heat treatments in a differential scanning calorimeter. The initial phase formed is an Al-rich amorphous phase that appears to grow by Zr diffusion through the amorphous phase. The subsequent nucleation and growth of tetragonal Al{sub 3}Zr along the Al/amorphous layer interface is mediated by Al diffusion through the crystalline intermetallic phase. Diffusion coefficients associated with these processes are higher than expected from reports of diffusivities measured at higher temperatures. The inferred heat of formation of the tetragonal Al{sub 3}Zr phase is 1240 ± 40 J/g (53 ± 2 kJ/mol atom). No anomalous variation in the energy or sequence of phase transformations is found with bilayer thickness for samples with bilayer thickness in the range of 17 nm to 90 nm despite anomalies in the bilayer dependence of self-propagating reaction velocities in the same foils.

  6. Oxidation of Alumina-Forming MAX Phases in Turbine Environments

    Science.gov (United States)

    Smialek, James; Garg, Anita; Harder, Bryan; Nesbitt, James; Gabb, Timothy; Gray, SImon

    2017-01-01

    Protective coatings for high temperature turbine components are based on YSZ thermal barriers and oxidation resistant, alumina-forming NiAl or NiCoCrAlY bond coats. Ti2AlC and Cr2AlC MAX phases are thus of special interest because of good oxidation resistance and CTE that can match Al2O3 and YSZ. Their alumina scales grow according to cubic kinetics due to grain growth in the scale, with initial heating dominated by fast TiO2 growth. Protective cubic kinetics are also found in high pressure burner rig tests of MAXthal 211 Ti2AlC, but with reduced rates due to volatile TiO(OH)2 formation in water vapor. YSZ-coatings on bulk Ti2AlC exhibit remarkable durability up to 1300C in furnace tests and at least a 25x life advantage compared to superalloys. At another extreme, Cr2AlC is resistant to low temperature Na2SO4 hot corrosion and exhibits thermal cycling stability bonded to a superalloy disk material. Accordingly, sputtered Cr2AlC coatings on disk specimens prevented hot corrosion detriments on LCF. Breakaway oxidation (Ti2AlC), scale spallation (Cr2AlC), interdiffusion, and processing as coatings still present serious challenges. However the basic properties of MAX phases provide some unusual opportunities for use in high temperature turbines.

  7. Oxidation behaviour of Zr-based bulk metallic glasses

    International Nuclear Information System (INIS)

    Wang, Bin

    2011-01-01

    The Zr-based bulk metallic glasses, developed since the late 1980's, have very interesting mechanical properties, which can be considered for many applications including working under oxidizing atmosphere conditions at high temperatures. It is therefore interesting to study their oxidation resistance and to characterize the oxide scale formed on alloys surface. The fundamental objective of this thesis is to enhance the understanding of the role of various thermodynamic and chemistry parameters on the oxidation behaviour of the Zr-based bulk metallic glasses at high temperature under dry air, to determine the residual stresses in the oxide layer, in comparison with their crystalline alloys with the same chemical composition after an annealing treatment. The oxidation kinetics of these glasses and the crystalline structure of oxide scale ZrO 2 depend on the temperature and the oxidation duration: for short periods of oxidation or at a temperature below Tg, the kinetics follows a parabolic law, whereas, if the sample is oxidized at T ≥ Tg, the kinetics can be divided into two parts. The crystalline counterparts are oxidized by a parabolic rule whatever the temperature; for long oxidation duration at a temperature close to Tg, the kinetics becomes more complex because of the crystallisation of the glasses during the oxidation tests. Also the crystalline structure of the oxide layers depends on the oxidation temperature: the oxide layer consists only in tetragonal Zirconia at T ≤ Tg, while monoclinic Zirconia was formed at higher temperature. The mechanism of the formation of the oxide scale is due to both the interior diffusion of Oxygen ions and the external diffusion of Zirconium ions. However the diffusion of Zirconium ions slows gradually during the crystallisation process of the glass matrix. When the crystallisation is completed, the formation of Zirconia is controlled by only the internal diffusion of oxygen ions. The corresponding residual stresses

  8. Thermal behavior and phase transformation of ZrO2–10%SiO2 precursor powder prepared by a co-precipitation route without adding stability agent

    International Nuclear Information System (INIS)

    Chu, Hsueh-Liang; Hwang, Weng-Sing; Wang, Cheng-Li; Wang, Moo-Chin; Lee, Kuen-Chan; Huang, Hong-Hsin; Lee, Huey-Er

    2014-01-01

    Highlights: • The precursor powders contained about 68.3 wt% ZrO 2 , which corresponds to ZrO 2 ·1/8 H 2 O. • The exothermic peak temperature of tetragonal ZrO 2 formation occurred at 1014 K. • The activation energy of ZrO 2 –10%SiO 2 precursors crystallization is 993.7 kJ/mol. • Only the tetragonal ZrO 2 formed when the precursor calcined at 1173–1373 K for 2 h. • As calcined at 1473 K for 2 h, tetragonal ZrO 2 fully converted to monoclinic ZrO 2 . - Abstract: Thermal behavior and phase transformation of ZrO 2 –10%SiO 2 precursor powder prepared by a co-precipitation route without adding stability agent has been studied using different thermal analysis/thermogravimetry (DTA/TG), X-ray diffraction (XRD), transmission electron microscopy (TEM), selected area electron diffraction (SAED), nano beam electron diffraction (NBED), high-resolution TEM (HRTEM) and energy-dispersive X-ray spectrometer (EDS). The TG results show that four weight loss regions were from 298 to 443 K, 443 to 743 K, 743 to 793 K and 793 to 1400 K. The DTA result shows that the ZrO 2 freeze-dried precursor powders crystallization at 1014 K. The activation energy of 993.7 kJ/mol was obtained for tetragonal ZrO 2 crystallization using a non-isothermal process. The XRD result shows that only a single phase of tetragonal ZrO 2 appears when the freeze-dried precursor powders after calcination between 1173 and 1373 K for 2 h. Moreover, when calcined at 1473 K for 2 h, the phase transformation from tetragonal ZrO 2 fully converted to monoclinic ZrO 2 occurred

  9. Phase stability in yttria-stabilized zirconia from first principles

    Energy Technology Data Exchange (ETDEWEB)

    Carbogno, Christian; Scheffler, Matthias [Materials Department, University of California, Santa Barbara, CA (United States); Fritz-Haber-Institut der Max-Planck-Gesellschaft, Berlin (Germany); Levi, Carlos G.; Van de Walle, Chris G. [Materials Department, University of California, Santa Barbara, CA (United States)

    2012-07-01

    Zirconia based ceramics are of pivotal importance for a variety of industrial technologies, e.g., for thermal barrier coatings in gas and airplane turbines. Naturally, the stability of such coatings at elevated temperatures plays a critical role in these applications. It is well known that an aliovalent doping of tetragonal ZrO{sub 2} with yttria, which induces oxygen vacancies due to charge conservation, increases its thermodynamic stability. However, the atomistic mechanisms that determine the phase stability of such yttria-stabilized Zirconia (YSZ) coatings are not yet fully understood. In this work, we use density functional theory calculations to assess the electronic structure of the different YSZ polymorphs at various levels of doping. With the help of population analysis schemes, we are able to unravel the intrinsic mechanisms that govern the interaction in YSZ and that can so explain the relative stabilities of the various polymorphs. We critically compare our results to experimental measurements and discuss the implications of our findings with respect to other oxides.

  10. Fracture toughness for copper oxide superconductors

    Science.gov (United States)

    Goretta, Kenneth C.; Kullberg, Marc L.

    1993-01-01

    An oxide-based strengthening and toughening agent, such as tetragonal Zro.sub.2 particles, has been added to copper oxide superconductors, such as superconducting YBa.sub.2 Cu.sub.3 O.sub.x (123) to improve its fracture toughness (K.sub.IC). A sol-gel coating which is non-reactive with the superconductor, such as Y.sub.2 BaCuO.sub.5 (211) on the ZrO.sub.2 particles minimized the deleterious reactions between the superconductor and the toughening agent dispersed therethrough. Addition of 20 mole percent ZrO.sub.2 coated with 211 yielded a 123 composite with a K.sub.IC of 4.5 MPa(m).sup.0.5.

  11. Fracture toughness for copper oxide superconductors

    Science.gov (United States)

    Goretta, K.C.; Kullberg, M.L.

    1993-04-13

    An oxide-based strengthening and toughening agent, such as tetragonal ZrO[sub 2] particles, has been added to copper oxide superconductors, such as superconducting YBa[sub 2]Cu[sub 3]O[sub x] (123) to improve its fracture toughness (K[sub IC]). A sol-gel coating which is non-reactive with the superconductor, such as Y[sub 2]BaCuO[sub 5] (211) on the ZrO[sub 2] particles minimized the deleterious reactions between the superconductor and the toughening agent dispersed therethrough. Addition of 20 mole percent ZrO[sub 2] coated with 211 yielded a 123 composite with a K[sub IC] of 4.5 MPa(m)[sup 0.5].

  12. Phase transformations im smart materials

    International Nuclear Information System (INIS)

    Newnham, R.E.

    1998-01-01

    One of the qualities that distinguishes living systems from inanimate matter is the ability to adapt to changes in the environment. Smart materials have the ability to perform both sensing and actuating functions and are, therefore, capable of imitating this rudimentary aspect of life. Four of the most widely used smart materials are piezoelectric Pb(Zr, Ti)O 3 , electrostrictive Pb(Mg, Nb)O 3 , magnetostrictive (Tb, Dy)Fe 2 and the shape-memory alloy NiTi. All four are ferroic with active domain walls and two phase transformations, which help to tune the properties of these actuator materials. Pb(Zr, Ti)O 3 is a ferroelectric ceramic which is cubic at high temperature and becomes ferroelectric on cooling through the Curie temperature. At room temperature, it is poised on a rhombohedral-tetragonal phase boundary which enhances the piezoelectric coefficients. Terfenol, (Tb, Dy)Fe 2 , is also cubic at high temperature and then becomes magnetic on cooling through its Curie temperature. At room temperature, it too is poised on a rhombohedral-tetragonal transition which enhances its magnetostriction coefficients. Pb(Mg, Nb)O 3 and nitinol (NiTi) are also cubic at high temperatures and on annealing transform to a partially ordered state. On further cooling, Pb(Mg, Nb)O 3 passes through a diffuse phase transformation at room temperature where it exhibits very large dielectric and electrostrictive coefficients. Just below room temperature, it transforms to a ferroelectric rhombohedral phase. The partially ordered shape-memory alloy NiTi undergoes an austenitic (cubic) to martensitic (mono-clinic) phase change just above room temperature. It is easily deformed in the martensitic state but recovers its original shape when reheated to austenite

  13. Oxidation kinetics of a Pb-64 at.% In single-phase alloy

    International Nuclear Information System (INIS)

    Zhang, M.X.; Chang, Y.A.; Marcotte, V.C.

    1991-01-01

    The solid-state oxidation kinetics of a Pb-64 at.% IN(50 wt.%) single-phase alloy were studied from room temperature to 150C using AES (Auger Electron Spectroscopy) depth profiling technique. The general oxidation behavior of this alloy is different from that of a Pb-3 at.% In alloy but similar to that of a Pb-30 at.% In alloy. The oxide formed on this alloy is almost pure In oxide (In 2 O 3 ) with the possible existence of some In suboxide near the oxide/alloy interface. At room temperature, oxidation of the alloy follows a direct logarithmic law, and the results can be described by the model proposed previously by Zhang, Chang, and Marcotte. At temperatures higher than 75C, rapid oxidation occurred initially followed by a slower parabolic oxidation at longer time. These data were described quantitatively by the model which assumes the existence of short-circuit diffusion in addition to lattice diffusion in the oxide as proposed by Smeltzer, Haering, and Kirkaldy. The effects of alloy composition in the oxidation kinetics of (pb, In) alloy are also examined by comparing the data for Pb-3, 30, and 64 at.% In alloys

  14. Identification of intermetallic phases in a eutectic Al-Si casting alloy using electron backscatter diffraction pattern analysis

    International Nuclear Information System (INIS)

    Kral, M.V.; McIntyre, H.R.; Smillie, M.J.

    2004-01-01

    Intermetallic phases in sand cast eutectic Al-Si alloys were characterized using a combination of SEM, EDS and EBSD pattern analysis. Chinese script α-phase particles were consistent with cubic Al 19 (Fe,Mn) 5 Si 2 . Plate-shaped β-phase particles were consistent with tetragonal Al 3 (Fe,Mn)Si 2

  15. Hysteresis phenomena at metal-semiconductor phase transformation in vanadium oxides

    International Nuclear Information System (INIS)

    Lanskaya, T.G.; Merkulov, I.A.; Chudnovski , F.A.

    1978-01-01

    The hysteresis phenomena during the metal-semiconductor phase transformation (MSPT) in vanadium oxides are investigated. It is shown experimentally that the hysteresis effects during MSPT in vanadium oxides are associated not only with the martensite nature of the transformation, but also with activation processes. It is shown that the hysteresis phenomena during MSPT may be described by the distribution function of microregions of the crystal in the phase transformation temperature T 0 and the coercive temperature Tsub(c). An experimental method for constructing this distribution function was worked out. An analysis of the experimental data shows that finely dispersed films are characterized by a wide range of values of T 0 and Tsub(c) (55 deg C 0 <65 deg C, 6 deg C< Tsub(c)<12 deg C). The peculiarities of the optical recording of information on monocrystal and finely dispersed films are considered

  16. Strain-induced topological quantum phase transition in phosphorene oxide

    Science.gov (United States)

    Kang, Seoung-Hun; Park, Jejune; Woo, Sungjong; Kwon, Young-Kyun

    Using ab initio density functional theory, we investigate the structural stability and electronic properties of phosphorene oxides (POx) with different oxygen compositions x. A variety of configurations are modeled and optimized geometrically to search for the equilibrium structure for each x value. Our electronic structure calculations on the equilibrium configuration obtained for each x reveal that the band gap tends to increase with the oxygen composition of x 0.5. We further explore the strain effect on the electronic structure of the fully oxidized phosphorene, PO, with x = 1. At a particular strain without spin-orbit coupling (SOC) is observed a band gap closure near the Γ point in the k space. We further find the strain in tandem with SOC induces an interesting band inversion with a reopened very small band gap (5 meV), and thus gives rise to a topological quantum phase transition from a normal insulator to a topological insulator. Such a topological phase transition is confirmed by the wave function analysis and the band topology identified by the Z2 invariant calculation.

  17. How Pt nanoparticles affect TiO2-induced gas-phase photocatalytic oxidation reactions

    NARCIS (Netherlands)

    Fraters, B.D.; Amrollahi Buky, Rezvaneh; Mul, Guido

    2015-01-01

    The effect of Pt nanoparticles on the gas-phase photocatalytic oxidation activity of TiO2 is shown to be largely dependent on the molecular functionality of the substrate. We demonstrate that Pt nanoparticles decrease rates in photocatalytic oxidation of propane, whereas a strong beneficial effect

  18. Gas-phase advanced oxidation as an integrated air pollution control technique

    Directory of Open Access Journals (Sweden)

    Getachew A. Adnew

    2016-03-01

    Full Text Available Gas-phase advanced oxidation (GPAO is an emerging air cleaning technology based on the natural self-cleaning processes that occur in the Earth’s atmosphere. The technology uses ozone, UV-C lamps and water vapor to generate gas-phase hydroxyl radicals that initiate oxidation of a wide range of pollutants. In this study four types of GPAO systems are presented: a laboratory scale prototype, a shipping container prototype, a modular prototype, and commercial scale GPAO installations. The GPAO systems treat volatile organic compounds, reduced sulfur compounds, amines, ozone, nitrogen oxides, particles and odor. While the method covers a wide range of pollutants, effective treatment becomes difficult when temperature is outside the range of 0 to 80 °C, for anoxic gas streams and for pollution loads exceeding ca. 1000 ppm. Air residence time in the system and the rate of reaction of a given pollutant with hydroxyl radicals determine the removal efficiency of GPAO. For gas phase compounds and odors including VOCs (e.g. C6H6 and C3H8 and reduced sulfur compounds (e.g. H2S and CH3SH, removal efficiencies exceed 80%. The method is energy efficient relative to many established technologies and is applicable to pollutants emitted from diverse sources including food processing, foundries, water treatment, biofuel generation, and petrochemical industries.

  19. Treatment of reduced sulphur compounds and SO2 by Gas Phase Advanced Oxidation

    DEFF Research Database (Denmark)

    Meusinger, Carl; Bluhme, Anders Brostrøm; Ingemar, Jonas L.

    2017-01-01

    Reduced sulphur compounds (RSCs) emitted from pig farms are a major problem for agriculture, due to their health and environmental impacts and foul odour. This study investigates the removal of RSCs, including H2S, and their oxidation product SO2 using Gas Phase Advanced Oxidation (GPAO). GPAO...... is a novel air cleaning technique which utilises accelerated atmospheric chemistry to oxidise pollutants before removing their oxidation products as particles. Removal efficiencies of 24.5% and 3.9% were found for 461 ppb of H2S and 714 ppb of SO2 in a laboratory system (volumetric flow Q = 75 m3/h......). A numerical model of the reactor system was developed to explore the basic features of the system; its output was in fair agreement with the experiment. The model verified the role of OH radicals in initiating the oxidation chemistry. All sulphur removed from the gas phase was detected as particulate matter...

  20. Catalysts with Cu base supported in mixed oxides to generate H{sub 2}: reformed of methanol in oxidant atmosphere; Catalizadores a base de Cu soportado en oxidos mixtos para generar H{sub 2}: Reformado de metanol en atmosfera oxidante

    Energy Technology Data Exchange (ETDEWEB)

    Aguila M, M M; Perez H, R [ININ, Carr. Mexico-Toluca S/N LaMarquesa, Ocoyoacac, Edo. de Mexico C. P. 52750 (Mexico); Rodriguez L, V [Centro Universitario de Vinculacion-BUAP, Puebla (Mexico)

    2006-07-01

    In this work, the characterization of Cu supported in CeO{sub 2}-ZrO{sub 2}, for to generate H{sub 2} starting from the one reformed of methanol with water vapor and oxygen is presented. The sol-gel technique and classic impregnation for the obtaining of the supports and catalysts respectively were used. The materials were characterized by XRD, SEM, adsorption- desorption of N{sub 2} and TPR. The catalytic materials presented crystalline phases associated with the zircon (tetragonal and monoclinic phase) and the ceria (cubic phase) depending on the CeO{sub 2}/ZrO{sub 2} relationship. The morphology of the catalysts was analyzed by SEM being observed semispheric particles for the rich materials in ZrO{sub 2} and added planars in the rich materials in CeO{sub 2}. The ceria addition to the zircon favors the specific area of the mixed oxides CeO{sub 2}-ZrO{sub 2} and it promotes the reducibility of the copper oxide at low temperatures. The rich catalysts in ceria also showed high activity in the methanol transformation and bigger selectivity toward the production of H{sub 2}. This result is associated with the presence of copper species that decrease to low temperature present in the rich catalysts in ceria and that they are not present in the rich catalysts in zircon. (Author)

  1. The detailed orbital-decomposed electronic structures of tetragonal ZrO2

    International Nuclear Information System (INIS)

    Zhang, Yan; Ji, Vincent; Xu, Ke-Wei

    2013-01-01

    The detailed orbital-decomposed electronic structures of the tetragonal zirconia have been investigated by using the first-principles projector augmented wave (PAW) potential within the generalized gradient approximation (GGA) as well as taking into account the on-site Coulomb repulsive interaction (GGA+U). The deviation of the minimization energy from d z =0 to d z =±0.032 for experimental lattice constants (a=3.605 Å and c=5.180 Å) confirms the alternating displacement of the oxygen atoms, which causes half of the Zr---O bonds stronger and the other half weaker compared with the bonds in symmetric (d z =0) zirconia. The distorted tetragonal environment of the eight oxygen anions around Zr site splits the five-fold degenerate d states of a free Zr atom into triply degenerate t 2g (d xy , d yz and d zx ) states and doubly degenerate e g (d z 2 and d x 2 -y 2 ) states. The additional covalent character upon Zr-O ionic bonds are resulted from the hybridization between the O(2s), O(2p) and Zr(5s), triply degenerate t 2g (d xy , d yz and d zx ) states of Zr(4d). The O(2s) and O(2p) states are clearly separated and no hybrid bonding states are formed

  2. Aqueous-phase oxidation of green leaf volatiles by hydroxyl radical as a source of SOA: Product identification from methyl jasmonate and methyl salicylate oxidation

    Science.gov (United States)

    Hansel, Amie K.; Ehrenhauser, Franz S.; Richards-Henderson, Nicole K.; Anastasio, Cort; Valsaraj, Kalliat T.

    2015-02-01

    Green leaf volatiles (GLVs) are a group of biogenic volatile organic compounds (BVOCs) released into the atmosphere by vegetation. BVOCs produce secondary organic aerosol (SOA) via gas-phase reactions, but little is known of their aqueous-phase oxidation as a source of SOA. GLVs can partition into atmospheric water phases, e.g., fog, mist, dew or rain, and be oxidized by hydroxyl radicals (˙OH). These reactions in the liquid phase also lead to products that have higher molecular weights, increased polarity, and lower vapor pressures, ultimately forming SOA after evaporation of the droplet. To examine this process, we investigated the aqueous, ˙OH-mediated oxidation of methyl jasmonate (MeJa) and methyl salicylate (MeSa), two GLVs that produce aqueous-phase SOA. High performance liquid chromatography/electrospray ionization mass spectrometry (HPLC-ESI-MS) was used to monitor product formation. The oxidation products identified exhibit higher molecular mass than their parent GLV due to either dimerization or the addition of oxygen and hydroxyl functional groups. The proposed structures of potential products are based on mechanistic considerations combined with the HPLC/ESI-MS data. Based on the structures, the vapor pressure and the Henry's law constant were estimated with multiple methods (SPARC, SIMPOL, MPBPVP, Bond and Group Estimations). The estimated vapor pressures of the products identified are significantly (up to 7 orders of magnitude) lower than those of the associated parent compounds, and therefore, the GLV oxidation products may remain as SOA after evaporation of the water droplet. The contribution of the identified oxidation products to SOA formation is estimated based on measured HPLC-ESI/MS responses relative to previous aqueous SOA mass yield measurements.

  3. Tetragonal zirconia ceramics in Zr O2-Ce O2 system (Ce-TZP): preparation, characterization and mechanical properties

    International Nuclear Information System (INIS)

    Andrade Nono, M.C. de.

    1992-01-01

    This paper describes and discusses the results achieved in a study about Ce-TZP ceramics prepared from conventional powder mixtures of Zr O 2 and Ce O 2 (with composition in the range of 8 to 16 mol% Ce O 2 ). Physical and chemical characteristics were related with the powder compaction behavior and with the sintering state. The sintered ceramics showed a level of high porosity (≅ 4%), mainly due to the fairly adequate powder characteristics and compaction. The crystalline phases were analysed from X-rays diffraction data and showed that these ceramics can present tetragonal-to-monoclinic stress induced transformation. The bending strength, fracture toughness and Vickers hardness results were influenced by Ce O 2 content microstructure and sintering temperature. These Ce-TZP ceramics showed mechanical strength results comparable to those published in the international literature. (author)

  4. The effect of microstructure and temperature on the oxidation behavior of two-phase Cr-Cr2X (X=Nb,Ta) alloys

    International Nuclear Information System (INIS)

    Brady, M.P.; Tortorelli, P.F.

    1998-01-01

    The oxidation behavior of Cr(X) solid solution (Cr ss ) and Cr 2 X Laves phases (X = Nb, Ta) was studied individually and in combination at 950--1,100 C in air. The Cr ss phase was significantly more oxidation resistant than the Cr 2 X Laves phase. At 950 C, two-phase alloys of Cr-Cr 2 Nb and Cr-Cr 2 Ta exhibited in-situ internal oxidation, in which remnants of the Cr 2 X Laves phase were incorporated into a growing chromia scale. At 1,100 C, the Cr-Cr 2 Nb alloys continued to exhibit in-situ internal oxidation, which resulted in extensive O/N penetration into the alloy ahead of the alloy-scale interface and catastrophic failure during cyclic oxidation. IN contrast, the Cr-Cr 2 Ta alloys exhibited a transition to selective Cr oxidation and the formation of a continuous chromia scale. The oxidation mechanism is interpreted in terms of multiphase oxidation theory

  5. Characterization of the oxide grown on Zr-20 Nb with different heat treatments in water at high temperature

    International Nuclear Information System (INIS)

    Olmedo, Ana M.; Bordoni, Roberto; Koenig, Patricia

    2003-01-01

    This work presents the corrosion behaviour of Zr-20 Nb alloy with different heat treatments. All the samples were annealed at 850 C degrees for one hour and cooled in air. After this heat treatment the sample coupons were aged at different temperatures and times. The corrosion kinetic of the different coupon samples were determined in water at 315 C degrees. The microstructure of the oxides were analysed using X-ray diffraction. The oxides grown in water steam at 400 C degrees, in coupons with a β Zr microstructure and in coupons aged in order to obtain a α Zr· + β Nb microstructure were also analysed. The oxides grown at the different temperatures and for all the microstructures were very adherent and black for all the times studied. The corrosion kinetics showed that the aging treatments decrease the corrosion rate of this material in degassed water at 315 C degrees and also in water steam at 400 C degrees. The greatest corrosion resistance is achieved for the equilibrium or near equilibrium microstructure of the samples and the presence of the · phase does not decrease the corrosion resistance of the material. The microstructure analysis of the oxides indicated that oxides grown on samples with β Zr microstructure are composed mainly by a Zr-Nb oxide of the type Nb 2 O 5· 6ZrO 2 , together with a small fraction of monoclinic ZrO 2 . Aging treatments produce an increase of the monoclinic phase and diminish the proportion of the mixed oxide. When the aging treatment gives the equilibrium or near equilibrium microstructure of α Zr· + β Nb , the oxide is composed mainly of monoclinic ZrO 2 , a small proportion of tetragonal component and also Nb 2 O 5 . (author)

  6. Thermal behavior and phase transformation of ZrO{sub 2}–10%SiO{sub 2} precursor powder prepared by a co-precipitation route without adding stability agent

    Energy Technology Data Exchange (ETDEWEB)

    Chu, Hsueh-Liang [Department of Materials Science and Engineering, National Cheng Kung University, 1 Ta-Hsueh Road, Tainan 70101, Taiwan (China); Hwang, Weng-Sing [Department of Materials Science and Engineering, National Cheng Kung University, 1 Ta-Hsueh Road, Tainan 70101, Taiwan (China); Institute of Nanotechnology and Microsystems Engineering, National Cheng Kung University, 1 Ta-Hsueh Road, Tainan 70101, Taiwan (China); Wang, Cheng-Li [Department of Materials Science and Engineering, National Cheng Kung University, 1 Ta-Hsueh Road, Tainan 70101, Taiwan (China); Wang, Moo-Chin, E-mail: mcwang@kmu.edu.tw [Department of Fragrance and Cosmetic Science, Kaohsiung Medical University, 100 Shih-Chuan 1st Road, Kaohsiung 80708, Taiwan (China); Lee, Kuen-Chan [Department of Fragrance and Cosmetic Science, Kaohsiung Medical University, 100 Shih-Chuan 1st Road, Kaohsiung 80708, Taiwan (China); Huang, Hong-Hsin [Department of Electrical Engineering, Cheng Shiu University, 840 Cheng Ching Road, Niaosong, Kaohsiung 83347, Taiwan (China); Lee, Huey-Er, E-mail: huerle@kmu.edu.tw [School of Dentistry, College of Dental Medicine, Kaohsiung Medical University, 100 Shih-Chuan 1st Road, Kaohsiung 807, Taiwan (China); Department of Dentistry, Kaohsiung Medical University, 100 Tzyou 1st Road, Kaohsiung 807, Taiwan (China)

    2014-12-15

    Highlights: • The precursor powders contained about 68.3 wt% ZrO{sub 2}, which corresponds to ZrO{sub 2}·1/8 H{sub 2}O. • The exothermic peak temperature of tetragonal ZrO{sub 2} formation occurred at 1014 K. • The activation energy of ZrO{sub 2}–10%SiO{sub 2} precursors crystallization is 993.7 kJ/mol. • Only the tetragonal ZrO{sub 2} formed when the precursor calcined at 1173–1373 K for 2 h. • As calcined at 1473 K for 2 h, tetragonal ZrO{sub 2} fully converted to monoclinic ZrO{sub 2}. - Abstract: Thermal behavior and phase transformation of ZrO{sub 2}–10%SiO{sub 2} precursor powder prepared by a co-precipitation route without adding stability agent has been studied using different thermal analysis/thermogravimetry (DTA/TG), X-ray diffraction (XRD), transmission electron microscopy (TEM), selected area electron diffraction (SAED), nano beam electron diffraction (NBED), high-resolution TEM (HRTEM) and energy-dispersive X-ray spectrometer (EDS). The TG results show that four weight loss regions were from 298 to 443 K, 443 to 743 K, 743 to 793 K and 793 to 1400 K. The DTA result shows that the ZrO{sub 2} freeze-dried precursor powders crystallization at 1014 K. The activation energy of 993.7 kJ/mol was obtained for tetragonal ZrO{sub 2} crystallization using a non-isothermal process. The XRD result shows that only a single phase of tetragonal ZrO{sub 2} appears when the freeze-dried precursor powders after calcination between 1173 and 1373 K for 2 h. Moreover, when calcined at 1473 K for 2 h, the phase transformation from tetragonal ZrO{sub 2} fully converted to monoclinic ZrO{sub 2} occurred.

  7. Development of an elevated temperature aluminum alloy containing Al3X-type dispersed phases

    International Nuclear Information System (INIS)

    Zedalis, M.S.

    1985-01-01

    The extents of solid solubility in the equilibrium, tetragonal Al 3 X-type dispersed phases (X represents binary and ternary combinations of Hf, Ti, V, and Zr) were examined using powder x-ray diffraction methods. Minimum lattice disregistry (delta) with the Al(ss) matrix was achieved by maximizing the amount of Ti or V added to the Al 3 Hf and/or Al 3 Zr phases without forming a co-intermetallic compound exhibiting a DO 22 crystal structure. In comparison to Al 3 Zr, with a (delta) equal to 2.88%, the addition of V to Al 3 Zr in the ratio 7:1, i.e., Al 3 (v/sub 0.875/Zr/sub 0.125/), results in a decrease in (delta) by approximately 17%. Electron diffraction revealed that the addition of V to the metastable cubic (L1 2 ) Al 3 Zr phase also resulted in a reduction in the lattice disregistry across the precipitate/matrix boundary. In comparison with the cubic Al 3 Zr phase, with a (delta) of approximately 1.0%, the Al 3 (V/sub 0.875/Zr/sub 0.125/) phase exhibits a mismatch of approximately -0.14%. The cubic Al 3 (V/sub 0.875/Zr/sub 0.125/) phase was observed by TEM to be substantially more stable, i.e., resist transformation to the equilibrium tetragonal phase, when compared to the cubic Al 3 Zr phase. It is proposed that a reduction in lattice disregistry results in a decrease in the strain energy component of the system's total free energy. A systematic decrease in the coarsening rate with a reduction in the lattice disregistry for the cubic Al 3 Zr, Al 3 (V/sub 0.725/Zr/sub 0.275/) and Al 3 (V/sub 0.875/Zr/sub 0.125/) and tetragonal Al 3 Zr and Al 3 (V/sub 0.875/Zr/sub 0.125/) phases is proposed to be representative of a decrease in the interfacial energy across the precipitate/matrix boundary

  8. Theoretical consideration on phase behaviors of poly(ethylene oxide-block-propylene oxide)/LiCF3SO3 systems in lithium battery

    International Nuclear Information System (INIS)

    Ko, Sung Jin; Kim, Sun Joon; Kong, Sung Ho; Bae, Young Chan

    2004-01-01

    A new thermodynamic model is developed based on the extended perturbed hard sphere chain (PHSC) model and melting point depression theory to describe the phase behaviors of copolymer electrolyte/salt systems. The phase behaviors of poly(ethylene oxide-block-propylene oxide)/LiCF 3 SO 3 systems are investigated by thermo-optical analysis (TOA) technique. Quantitative descriptions according to the proposed model are in good agreement with experimental data. The obtained results show that monomer ratio and sequence type of copolymers play a great role in determining eutectic points of the given systems

  9. A New Method to Improve the Electrical Properties of KNN-based Ceramics: Tailoring Phase Fraction

    KAUST Repository

    Lv, Xiang; Wu, Jiagang; Zhu, Jianguo; Xiao, Dingquan; Zhang, Xixiang

    2017-01-01

    Although both the phase type and fraction of multi-phase coexistence can affect the electrical properties of (K,Na)NbO3 (KNN)-based ceramics, effects of phase fraction on their electrical properties were few concerned. In this work, through changing the calcination temperature of CaZrO3 powders, we successfully developed the 0.96K0.5Na0.5Nb0.96Sb0.04O3-0.01CaZrO3-0.03Bi0.5Na0.5HfO3 ceramics containing a wide rhombohedral-tetragonal (R-T) phase coexistence with the variations of T (or R) phase fractions. It was found that higher T phase fraction can warrant a larger piezoelectric constant (d33) and d33 also showed a linear variation with respect to tetragonality ratio (c/a). More importantly, a number of domain patterns were observed due to high T phase fraction and large c/a ratio, greatly benefiting the piezoelectricity. In addition, the improved ferroelectric fatigue behavior and thermal stability were also shown in the ceramics containing high T phase fraction. Therefore, this work can bring a new viewpoint into the physical mechanism of KNN-based ceramics behind R-T phase coexistence.

  10. A New Method to Improve the Electrical Properties of KNN-based Ceramics: Tailoring Phase Fraction

    KAUST Repository

    Lv, Xiang

    2017-08-18

    Although both the phase type and fraction of multi-phase coexistence can affect the electrical properties of (K,Na)NbO3 (KNN)-based ceramics, effects of phase fraction on their electrical properties were few concerned. In this work, through changing the calcination temperature of CaZrO3 powders, we successfully developed the 0.96K0.5Na0.5Nb0.96Sb0.04O3-0.01CaZrO3-0.03Bi0.5Na0.5HfO3 ceramics containing a wide rhombohedral-tetragonal (R-T) phase coexistence with the variations of T (or R) phase fractions. It was found that higher T phase fraction can warrant a larger piezoelectric constant (d33) and d33 also showed a linear variation with respect to tetragonality ratio (c/a). More importantly, a number of domain patterns were observed due to high T phase fraction and large c/a ratio, greatly benefiting the piezoelectricity. In addition, the improved ferroelectric fatigue behavior and thermal stability were also shown in the ceramics containing high T phase fraction. Therefore, this work can bring a new viewpoint into the physical mechanism of KNN-based ceramics behind R-T phase coexistence.

  11. Synthesis, crystal structure, and ionic conductivity of novel Ruddlesden-Popper related phases, Li4Sr3Nb5.77Fe0.23O19.77 and Li4Sr3Nb6O20

    International Nuclear Information System (INIS)

    Bhuvanesh, N.S.P.; Crosnier-Lopez, M.P.; Bohnke, O.; Emery, J.; Fourquet, J.L.

    1999-01-01

    The authors have synthesized two new lithium-containing oxides which are related to Ruddlesden-Popper phases, Li 4 Sr 3 Nb 5.77 Fe 0.23 O 19.77 and Li 4 Sr 3 Nb 6 O 20 , with partial occupancy of the 12-coordinated sites by Sr, for the first time by direct solid-state reaction. While the single crystal and powder X-ray diffraction data indicate that these oxides crystallize in tetragonal cells (space group I4/mmm; a = 3.9585(2) angstrom, c = 25.915(3) angstrom and a = 3.953(2) angstrom, c = 26.041(5) angstrom for the respective oxides), the electron diffraction of some of the crystallites shows supercell reflections with a ∼ √2a p , c ∼ 25.9 angstrom, probably indicating a twisting of the NbO 6 octahedra in the ab-plane. Although, these oxides show no significant lithium ionic conduction at room temperature, they show distinct conductivity values at elevated temperatures

  12. Polymorphic phase transition and morphotropic phase boundary in Ba{sub 1-x}Ca{sub x}Ti{sub 1-y}Zr{sub y}O{sub 3} ceramics

    Energy Technology Data Exchange (ETDEWEB)

    Abdessalem, M. Ben; Aydi, S.; Aydi, A.; Abdelmoula, N.; Khemakhem, H. [Universite de Sfax, Faculte des Sciences de Sfax (FSS), Laboratoire des Materiaux Multifonctionnels et Applications (LaMMA) LR16ES18, B.P.1171, Sfax (Tunisia); Sassi, Z. [Laboratoire de Genie Electrique et Ferroelectricite (LGEF) de L' INSA de Lyon, Lyon (France)

    2017-09-15

    This paper deals with Ca and Zr co-doped BaTiO{sub 3} (BCTZ{sub (x,} {sub y)}) (x = 0.1, 0.13, 0.2 and y = 0.05, 0.1, 0.15). These ceramics were prepared using the conventional solid state method. The symmetry, dielectric properties, Raman spectroscopy, ferroelectric behavior and piezoelectric effect were examined. X-ray diffraction (XRD) results display that morphotropic boundary occurs from tetragonal to orthorhombic region of BCZT{sub (x=0.1,} {sub 0.2,} {sub y=0.05,} {sub 0.1)} and polymorphic phase transitions from tetragonal to orthorhombic, orthorhombic to rhombohedral regions of BCZT{sub (x=0.13,} {sub y=0.1)}. The evolution of the Raman spectra was investigated as a function of compositions at room temperature, in correlation with XRD analysis and dielectric measurements. We note that the substitution of Ca in Ba site and Zr ions in Ti site slightly decreased the cubic-tetragonal temperature transition (T{sub C}) and increased the orthorhombic-tetragonal (T{sub 1}) and rhombohedral-orthorhombic (T{sub 2}) temperatures transitions. The ferroelectric properties were examined by a P-E hysteresis loop. The two parameters ΔT{sub 1} and ΔT{sub 2} are defined as ΔT{sub 1} = T{sub C} - T{sub 1} and ΔT{sub 2} = T{sub C} - T{sub 2}, they come close to T{sub C} for x = 0.13, y = 0.1, which reveals that this composition is around the polymorphic phase. The excellent piezoelectric coefficient of d{sub 33} = 288 pC N{sup -1}, the electromechanical coupling factor k{sub p} = 40%, high constant dielectric 9105, coercive field E{sub c} = 0.32 (KV mm{sup -1}) and remanent polarization P{sub r} = 0.1 (μc mm{sup -2}) were obtained for composition x = 0.13, y = 0.1. (orig.)

  13. Preparation and properties of yttria doped tetragonal zirconia polycrystal/Sr-doped barium hexaferrite ceramic composites

    International Nuclear Information System (INIS)

    Wang, Shanshan; Zhang, Chao; Guo, Ruisong; Liu, Lan; Yang, Yuexia; Li, Kehang

    2015-01-01

    Highlights: • The 3Y-TZP/Sr-doped barium ferrite composites were prepared. • The saturation magnetization was improved by 15% with Sr-doping. • The dispersion coefficient p could reflect the microscopic lattice variation. • The composite with x = 0.5 had the maximum fracture toughness of 8.3 MPa m 1/2 . - Abstract: The effects of substitution of Ba 2+ by Sr 2+ on the magnetic property of barium ferrite and addition barium ferrite secondary phase to the 3 mol% yttria-doped tetragonal zirconia polycrystal (3Y-TZP) matrix on the mechanical property of composites were investigated. The Sr-doped barium ferrite (Ba 1−x Sr x Fe 12 O 19 , x = 0, 0.25, 0.50 and 0.75) was synthesized by solid-state reaction in advance. Then 3Y-TZP/20 wt% Sr-doped barium ferrite composites were prepared by means of conventional ceramic method. It was found that a moderate amount of Sr added to barium ferrite could boost the saturation magnetization by 15% compared with the composites without Sr-doping. Besides, the composite with x = 0.50 possessed the best mechanical properties, such as 11.5 GPa for Vickers hardness and 8.3 MPa m 1/2 for fracture toughness, respectively. It was demonstrated that magnetic and mechanical properties of the composites could be harmonized by the incorporation of barium ferrite secondary phase

  14. Transmission electron microscopy characterization of Zircaloy-4 and ZIRLO™ oxide layers

    International Nuclear Information System (INIS)

    Gabory, Benoit de; Motta, Arthur T.; Wang, Ke

    2015-01-01

    Waterside corrosion of zirconium alloy nuclear fuel cladding varies markedly from one alloy to another. In addition, for a given alloy, the corrosion rate evolves during the corrosion process, most notably when the oxide loses its stability at the oxide transition. In an effort to understand the mechanism resulting in the variations of corrosion rate observed at the oxide transition, oxide layers formed on Zircaloy-4 and ZIRLO™ in high temperature water autoclave environments, and archived before and after the transition, are characterized using transmission electron microscopy. The study characterizes and compares the oxide morphology in both alloys at different times during the corrosion process, in an effort to understand the oxide growth mechanism for these alloys. Results show that the oxide is mainly composed of monoclinic ZrO 2 , with a preponderance of columnar oxide grains which extend to the oxide/metal interface. The oxide formed right after the transition has occurred, exhibits a 150 nm-wide layer of small equiaxed grains with high tetragonal oxide fraction. This layer has a similar morphology and structure as the first oxide layer formed (observed near the oxide/water interface). A study of the oxygen-rich region near the oxide/metal interface reveals a complex structure of different phases at different stages of corrosion. The interface exhibits an intermediate layer, identified as ZrO, a discontinuous layer of “blocky” Zr 3 O grains embedded in the ZrO layer, and a suboxide layer corresponding to an oxygen saturated solid solution in the metal matrix side. The thickness of this interfacial layer decreased markedly at the transition. Hydrides are also observed in that region, with a definite orientation relationship with the matrix. The observations of the oxide/metal interface are qualitatively similar for the two alloys but quantitatively different. The incorporation of intermetallic precipitates into the oxide layer is also studied, and

  15. Crystal phase transition in LixNa1-xGdF4 solid solution nanocrystals - Tuning of optical properties

    KAUST Repository

    Bański, Mateusz

    2014-01-01

    The influence of precursor composition on the crystallization of LixNa1-xGdF4 is investigated and discussed. Nanocrystals are prepared from the thermal decomposition of trifluoroacetates in the presence of trioctylphosphine oxide to provide control over particle size. A crystal phase transition from hexagonal to cubic and to tetragonal is observed by increasing lithium trifluoroacetate (Li-TFA) in the solution. Controlling the composition of LixNa1-xGdF4 nanocrystals results in modified crystal field symmetry and emission properties from doped europium (Eu3+) ions. We report that for lithium (Li+) substitution <15%, the hexagonal crystal field is preferred, while the Eu3+ emission is already tuned, whereas at higher Li+ substitution, a phase change takes place and the number of crystalline matrix defects increases which is reflected in the optical properties of Eu3+. From Eu3+ emission properties, the optimum Li+ content is determined to be ∼6.2% in the prepared LixNa1-xGdF4 nanocrystals.

  16. Selective oxidation of dual phase steel after annealing at different dew points

    Science.gov (United States)

    Lins, Vanessa de Freitas Cunha; Madeira, Laureanny; Vilela, Jose Mario Carneiro; Andrade, Margareth Spangler; Buono, Vicente Tadeu Lopes; Guimarães, Juliana Porto; Alvarenga, Evandro de Azevedo

    2011-04-01

    Hot galvanized steels have been extensively used in the automotive industry. Selective oxidation on the steel surface affects the wettability of zinc on steel and the grain orientation of inhibition layer (Fe-Al-Zn alloy) and reduces the iron diffusion to the zinc layer. The aim of this work is to identify and quantify selective oxidation on the surface of a dual phase steel, and an experimental steel with a lower content of manganese, annealed at different dew points. The techniques employed were atomic force microscopy, X-ray photoelectron spectroscopy, and glow discharge optical emission spectroscopy. External selective oxidation was observed for phosphorus on steel surface annealed at 0 °C dp, and for manganese, silicon, and aluminum at a lower dew point. The concentration of manganese was higher on the dual phase steel surface than on the surface of the experimental steel. The concentration of molybdenum on the surface of both steels increased as the depth increased.

  17. Exchange anisotropy as a probe of antiferromagnetism in expanded face-centered-tetragonal Mn(001) layers

    NARCIS (Netherlands)

    Kohlhepp, J.T.; Wieldraaijer, H.; Jonge, de W.J.M.

    2006-01-01

    Manganese (Mn) grows coherent and with an expanded metastable face-centered-tetragonal (e-fct) structure on ultrathin fct Co(001)/Cu(001) template layers. From the temp. dependence of the obsd. unidirectional Mn/Co interface exchange anisotropy, an antiferromagnetic state with a blocking temp.

  18. Immobilization of Radioactive Rare Earth oxide Waste by Solid Phase Sintering

    International Nuclear Information System (INIS)

    Ahn, Byung Gil; Park, Hwan Seo; Kim, Hwan Young; Lee, Han Soo; Kim, In Tae

    2010-01-01

    In the pyroprocessing of spent nuclear fuels, LiCl-KCl waste salt containing radioactive rare earth chlorides are generated. The radioactive rare earth oxides are recovered by co-oxidative precipitation of rare earth elements. The powder phase of rare earth oxide waste must be immobilized to produce a monolithic wasteform suitable for storage and ultimate disposal. The immobilization of these waste developed in this study involves a solid state sintering of the waste with host borosilicate glass and zinc titanate based ceramic matrix (ZIT). And the rare-earth monazite which synthesised by reaction of ammonium di-hydrogen phosphate with the rare earth oxides waste, were immobilized with the borosilicate glass. It is shown that the developed ZIT ceramic wasteform is highly resistant the leaching process, high density and thermal conductivity.

  19. Designing magnetic compensated states in tetragonal Mn{sub 3}Ge-based Heusler alloys

    Energy Technology Data Exchange (ETDEWEB)

    You, Yurong; Xu, Guizhou, E-mail: gzxu@njust.edu.cn; Hu, Fang; Gong, Yuanyuan; Liu, Er; Peng, Guo; Xu, Feng, E-mail: xufeng@njust.edu.cn

    2017-05-01

    Magnetic compensated materials attracted much interests due to the observed large exchange bias and large coercivity, and also their potential applications in the antiferromagnetic spintronics with merit of no stray field. In this work, by using ab-initio studies, we designed several Ni (Pd, Pt) doped Mn{sub 3}Ge-based D0{sub 22}-type tetragonal Heusler alloys with fully compensated states. Theoretically, we find the total moment change is asymmetric across the compensation point (at ~x=0.3) in Mn{sub 3-x}Y{sub x}Ge (Y=Ni, Pd, Pt). In addition, an uncommon discontinuous jump is observed across the critical zero-moment point, indicating that some non-trivial properties may emerge at this point. Further electronic analyses of these compensated alloys reveal high spin polarizations at the Fermi level, which is advantageous for spin transfer torque applications. - Highlights: • Several new fully compensated magnetic states are identified in Mn{sub 3}Ge-based tetragonal alloys. • The magnetic moment changes are asymmetric upon Ni, Pd and Pt substitution. • Discontinuous jumps exist across the compensated points. • The three compensated alloys possess large spin polarizations.

  20. Persistent Fe moments in the normal-state collapsed-tetragonal phase of the pressure-induced superconductor Ca0.67Sr0.33Fe2As2

    Science.gov (United States)

    Jeffries, J. R.; Butch, N. P.; Lipp, M. J.; Bradley, J. A.; Kirshenbaum, K.; Saha, S. R.; Paglione, J.; Kenney-Benson, C.; Xiao, Y.; Chow, P.; Evans, W. J.

    2014-10-01

    Using nonresonant Fe Kβ x-ray emission spectroscopy, we reveal that Sr substitution into CaFe2As2 decouples the Fe moment from the volume collapse transition, yielding a collapsed-tetragonal, paramagnetic normal state out of which superconductivity develops. X-ray diffraction measurements implicate the c-axis lattice parameter as the controlling criterion for the Fe moment, promoting a generic description for the appearance of pressure-induced superconductivity in the alkaline-earth-based 122 ferropnictides (AFe2As2). The evolution of Tc with pressure lends support to theories for superconductivity involving unconventional pairing mediated by magnetic fluctuations.

  1. Phase relations and conductivity of Sr-zirconates and La-zirconates

    DEFF Research Database (Denmark)

    Poulsen, F.W.; Vanderpuil, N.

    1992-01-01

    phase orthorhombic SrZrO3 and somewhat impure, tetragonal Sr2ZrO4 were observed, whereas the formation of ordered Ruddlesden-Popper phases, SrnZrn-1O3n-2, where n = 4 and 3, could not be verified. The conductivity of La2Zr2O7 was 3.7 X 10(-6) S/cm at 750-degrees-C and 3.8 x 10(-5) S/cm at 1000-degrees...

  2. Role of multiorbital effects in the magnetic phase diagram of iron pnictides

    Science.gov (United States)

    Christensen, Morten H.; Scherer, Daniel D.; Kotetes, Panagiotis; Andersen, Brian M.

    2017-07-01

    We elucidate the pivotal role of the band structure's orbital content in deciding the type of commensurate magnetic order stabilized within the itinerant scenario of iron pnictides. Recent experimental findings in the tetragonal magnetic phase attest to the existence of the so-called charge and spin ordered density wave over the spin-vortex crystal phase, the latter of which tends to be favored in simplified band models of itinerant magnetism. Here we show that employing a multiorbital itinerant Landau approach based on realistic band structures can account for the experimentally observed magnetic phase, and thus shed light on the importance of the orbital content in deciding the magnetic order. In addition, we remark that the presence of a hole pocket centered at the Brillouin zone's M point favors a magnetic stripe rather than a tetragonal magnetic phase. For inferring the symmetry properties of the different magnetic phases, we formulate our theory in terms of magnetic order parameters transforming according to irreducible representations of the ensuing D4 h point group. The latter method not only provides transparent understanding of the symmetry-breaking schemes but also reveals that the leading instabilities always belong to the {A1 g,B1 g} subset of irreducible representations, independently of their C2 or C4 nature.

  3. Composition-Driven Phase Boundary and Piezoelectricity in Potassium-Sodium Niobate-Based Ceramics.

    Science.gov (United States)

    Zheng, Ting; Wu, Jiagang; Xiao, Dingquan; Zhu, Jianguo; Wang, Xiangjian; Lou, Xiaojie

    2015-09-16

    The piezoelectricity of (K,Na)NbO3 ceramics strongly depends on the phase boundary types as well as the doped compositions. Here, we systematically studied the relationships between the compositions and phase boundary types in (K,Na) (Nb,Sb)O3-Bi0.5Na0.5AO3 (KNNS-BNA, A=Hf, Zr, Ti, Sn) ceramics; then their piezoelectricity can be readily modified. Their phase boundary types are determined by the doped elements. A rhombohedral-tetragonal (R-T) phase boundary can be driven in the compositions range of 0.035≤BNH≤0.040 and 0.035≤BNZ≤0.045; an orthorhombic-tetragonal (O-T) phase boundary is formed in the composition range of 0.005≤BNT≤0.02; and a pure O phase can be only observed regardless of BNS content (≤0.01). In addition, the phase boundary types strongly affect their corresponding piezoelectricities. A larger d33 (∼440-450 pC/N) and a higher d33* (∼742-834 pm/V) can be attained in KNNS-BNA (A=Zr and Hf) ceramics due to the involvement of R-T phase boundary, and unfortunately KNNS-BNA (A=Sn and Ti) ceramics possess a relatively poor piezoelectricity (d33≤200 and d33*piezoelectricity and phase boundary types were also discussed. We believe that comprehensive research can design more excellent ceramic systems concerning potassium-sodium niobate.

  4. Theoretical and experimental evaluation of piezo-optic parameters and photoelastic constant in tetragonal PWO.

    Science.gov (United States)

    Natali, Pier Paolo; Montalto, Luigi; Daví, Fabrizio; Mengucci, Paolo; Ciriaco, Andrea; Paone, Nicola; Rinaldi, Daniele

    2018-02-01

    The tetragonal PbWO 4 (PWO) is one of the most important scintillating crystals, being used both in the Compact Muon Solenoid (CMS) experiment at the European Organization for Nuclear Research (CERN) and in the PANDA project at the Facility for Antiproton and Ion Research (FAIR). Light yield and other relevant scintillation properties depend, among many factors, also on the crystal mechanical quality. Accordingly, a detailed knowledge of crystal piezo-optic properties is a mandatory step toward understanding elasto-optic behavior and performing crystal quality control. In this paper, we evaluate for the first time, to the best of our knowledge, by means of both photoelastic and x-ray measurements, some components of the piezo-optic tensor; moreover, when the crystal is acted upon by a uniaxial stress, we obtain an evaluation for the rotation angle of the optic plane under stress as well as the photoelastic constant. These parameters are necessary to detect the residual stresses within the crystal, if any, and to give an overall quality measure. Such a methodology is in general suitable for any tetragonal crystals.

  5. Three-phase boundary length in solid-oxide fuel cells: A mathematical model

    Energy Technology Data Exchange (ETDEWEB)

    Janardhanan, Vinod M. [Institutefor Chemical Technology and Polymer Chemistry, University of Karlsruhe (TH), Kaiserstr. 12, D-76128 Karlsruhe (Germany); Heuveline, Vincent; Deutschmann, Olaf [Institute for Applied and Numerical Mathematics, University of Karlsruhe (TH), Kaiserstr. 12, D-76128 Karlsruhe (Germany)

    2008-03-15

    A mathematical model to calculate the volume specific three-phase boundary length in the porous composite electrodes of solid-oxide fuel cell is presented. The model is exclusively based on geometrical considerations accounting for porosity, particle diameter, particle size distribution, and solids phase distribution. Results are presented for uniform particle size distribution as well as for non-uniform particle size distribution. (author)

  6. Three-phase boundary length in solid-oxide fuel cells: A mathematical model

    Science.gov (United States)

    Janardhanan, Vinod M.; Heuveline, Vincent; Deutschmann, Olaf

    A mathematical model to calculate the volume specific three-phase boundary length in the porous composite electrodes of solid-oxide fuel cell is presented. The model is exclusively based on geometrical considerations accounting for porosity, particle diameter, particle size distribution, and solids phase distribution. Results are presented for uniform particle size distribution as well as for non-uniform particle size distribution.

  7. Synthesis and crystal structure of Mg2B24C, a new boron-rich boride related to 'tetragonal boron I'

    International Nuclear Information System (INIS)

    Adasch, Volker; Hess, Kai-Uwe; Ludwig, Thilo; Vojteer, Natascha; Hillebrecht, Harald

    2006-01-01

    Single crystals of Mg 2 B 24 C, a new boron-rich boridecarbide of magnesium, were synthesized as black needles and columns by reaction of the elements in Ta ampoules and BN crucibles at 1300 deg. C. The crystal structure was determined by X-ray diffraction (P-4n2, a=8.9391(13)A, c=5.0745(10)A, Z=2, 713 reflections, 64 variables, R 1 (F)=0.0235, wR 2 (I)=0.0591). It is closely related to 'tetragonal boron I' and can be described as a tetragonal rod packing of corner-linked B 12 icosahedra with C and Mg atoms in the voids. Each B 12 icosahedron has 2 B-C bonds and 10 exohedral bonds to other icosahedra, 2 within the rod and 4x2 to neighbouring rods. The isolated C atoms are 4-fold coordinated forming distorted tetrahedra. Mg is placed on two crystallographically independent positions within the three-dimensional B 12 C network. Mg 2 B 24 C is the first example for a compound related to 'tetragonal boron I' with a stoichiometric composition

  8. Synthesis and characterization of hafnium oxide for luminescent applications

    International Nuclear Information System (INIS)

    Guzman Mendoza, J.; Aguilar Frutis, M.A.; Flores, G. Alarcon; Garcia Hipolito, M.; Azorin Nieto, J.; Rivera Montalvo, T.; Falcony, C.

    2008-01-01

    Full text: Hafnium oxide (HfO 2 ) is a material with a wide range of possible technological applications because it's chemical and physical properties such as high melting point, high chemical stability, high refraction index, high dielectric constant and hardness near to diamond in the tetragonal phase. The large energy gap and low phonon frequencies of the HfO 2 makes it appropriate as a host matrix for been doped with rare earth activators. Efficient luminescent materials find wide application in electroluminescent flat panel displays; color plasma displays panels, scintillators, cathode ray tubes, fluorescent lamps, lasers, etc. In recent years the study of luminescent materials based on HfO 2 has been intensified. Some groups have studied the optical properties of doped and undoped HfO 2 . In this contribution, Hafnium Oxide (HfO 2 ) films were prepared using the spray pyrolysis deposition technique. The material was synthesized using chlorides as raw materials in deionised water as solvent and deposited on Corning glass substrates at temperatures from 300 deg C to 600 deg C. For substrate temperatures lower than 400 deg C, the deposited films are amorphous, while for substrate temperatures higher than 450 deg C, the monoclinic phase of HfO 2 appears. Scanning electron microscopy with microprobe analysis was use to observe the microstructure and obtain the chemical composition of the films; rough surfaces with spherical particles were appreciated. UV and low energy X Ray radiations were used in order to achieve the thermoluminescent characterization of the films as a function of the deposition temperature

  9. Electrically Controllable Spontaneous Magnetism in Nanoscale Mixed Phase Multiferroics

    Energy Technology Data Exchange (ETDEWEB)

    He, Q.; Chu, Y. H.; Heron, J. T.; Yang, S. Y.; Wang, C. H.; Kuo, C. Y.; Lin, H. J.; Yu, P.; Liang, C. W.; Zeches, R. J.; Chen, C. T.; Arenholz, E.; Scholl, A.; Ramesh, R.

    2010-08-02

    The emergence of enhanced spontaneous magnetic moments in self-assembled, epitaxial nanostructures of tetragonal (T-phase) and rhombohedral phases (R-phase) of the multiferroic BiFeO{sub 3} system is demonstrated. X-ray magnetic circular dichroism based photoemission electron microscopy (PEEM) was applied to investigate the local nature of this magnetism. We find that the spontaneous magnetization of the R-phase is significantly enhanced above the canted antiferromagnetic moment in the bulk phase, as a consequence of a piezomagnetic coupling to the adjacent T-phase and the epitaxial constraint. Reversible electric field control and manipulation of this magnetic moment at room temperature is shown using a combination of piezoresponse force microscopy and PEEM studies.

  10. Full Electroresistance Modulation in a Mixed-Phase Metallic Alloy

    Science.gov (United States)

    Liu, Z. Q.; Li, L.; Gai, Z.; Clarkson, J. D.; Hsu, S. L.; Wong, A. T.; Fan, L. S.; Lin, M.-W.; Rouleau, C. M.; Ward, T. Z.; Lee, H. N.; Sefat, A. S.; Christen, H. M.; Ramesh, R.

    2016-03-01

    We report a giant, ˜22 %, electroresistance modulation for a metallic alloy above room temperature. It is achieved by a small electric field of 2 kV /cm via piezoelectric strain-mediated magnetoelectric coupling and the resulting magnetic phase transition in epitaxial FeRh /BaTiO3 heterostructures. This work presents detailed experimental evidence for an isothermal magnetic phase transition driven by tetragonality modulation in FeRh thin films, which is in contrast to the large volume expansion in the conventional temperature-driven magnetic phase transition in FeRh. Moreover, all the experimental results in this work illustrate FeRh as a mixed-phase model system well similar to phase-separated colossal magnetoresistance systems with phase instability therein.

  11. High pressure phase transition in Pr-monopnictides

    Energy Technology Data Exchange (ETDEWEB)

    Raypuria, Gajendra Singh, E-mail: sosfizix@gmail.com, E-mail: gsraypuria@gmail.com; Gupta, Dinesh Chandra [Condensed Matter Theory Group, School of Studies in Physics, Jiwaji University, Gwalior - 474011 (India); Department of Physics, Govt. K.R.G. P.G. Autonomous College, Gwalior - 474001 (India)

    2015-06-24

    The Praseodymium-monopnictides compounds have been found to undergo transition from their initial NaCl-type structure to high pressure body centered tetragonal (BCT) structure (distorted CsCl-type P4/mmm) using CTIP model. The calculated values of cohesive energy, lattice constant, phase transition pressure, relative volume collapse agree well with the available measured data and better than those computed by earlier workers.

  12. Influence of Ar-ion implantation on the structural and mechanical properties of zirconia as studied by Raman spectroscopy and nanoindentation techniques

    Science.gov (United States)

    Kurpaska, L.; Jasinski, J.; Wyszkowska, E.; Nowakowska-Langier, K.; Sitarz, M.

    2018-04-01

    In this study, structural and nanomechanical properties of zirconia polymorphs induced by ion irradiation were investigated by means of Raman spectroscopy and nanoindentation techniques. The zirconia layer have been produced by high temperature oxidation of pure zirconium at 600 °C for 5 h at normal atmospheric pressure. In order to distinguish between the internal and external parts of zirconia, the spherical metallographic sections have been prepared. The samples were irradiated at room temperature with 150 keV Ar+ ions at fluences ranging from 1 × 1015 to 1 × 1017 ions/cm2. The main objective of this study was to distinguish and confirm different structural and mechanical properties between the interface layer and fully developed scale in the internal/external part of the oxide. Conducted studies suggest that increasing ion fluence impacts Raman bands positions (especially characteristic for tetragonal phase) and increases the nanohardness and Young's modulus of individual phases. This phenomenon has been examined from the point of view of stress-induced hardening effect and classical monoclinic → tetragonal (m → t) martensitic phase transformation.

  13. Influence of surface treatment of yttria-stabilized tetragonal zirconia polycrystal with hot isostatic pressing on cyclic fatigue strength.

    Science.gov (United States)

    Iijima, Toshihiko; Homma, Shinya; Sekine, Hideshi; Sasaki, Hodaka; Yajima, Yasutomo; Yoshinari, Masao

    2013-01-01

    Hot isostatic pressing processed yttria-stabilized tetragonal zirconia polycrystal (HIP Y-TZP) has the potential for application to implants due to its high mechanical performance. The aim of this study was to investigate the influence of surface treatment of HIP Y-TZP on cyclic fatigue strength. HIP Y-TZP specimens were subjected to different surface treatments. Biaxial flexural strength was determined by both static and cyclic fatigue testing. In the cyclic fatigue test, the load was applied at a frequency of 10 Hz for 10(6) cycles in distilled water at 37°C. The surface morphology, roughness, and crystal phase of the surfaces were also evaluated. The cyclic fatigue strength (888 MPa) of HIP Y-TZP with sandblasting and acid-etching was more than twice that of Y-TZP as specified in ISO 13356 for surgical implants (320 MPa), indicating the clinical potential of this material.

  14. Universal phase diagram for high-piezoelectric perovskite systems

    NARCIS (Netherlands)

    Cox, D.E.; Noheda, B.; Shirane, G.; Uesu, Y.; Fujishiro, K.; Yamada, Y.

    2001-01-01

    Strong piezoelectricity in perovskite-type PbZn1-xTixO3 (PZT) and Pb(Zn1/3Nb2/3)O3–PbTiO3 (PZN–PT) systems is generally associated with the existence of a morphotropic phase boundary (MPB) separating regions with rhombohedral and tetragonal symmetry. An x-ray study of PZN–9% PT has revealed the

  15. Phase transition of La- chalcogenides under high pressure

    Energy Technology Data Exchange (ETDEWEB)

    Gupta, Dinesh Chandra [Condensed Matter Theory Group, School of Studies in Physics, Jiwaji University, Gwalior - 474 011 (India); Raypuria, Gajendra Singh, E-mail: gsraypuria@gmail.com [Department of Physics, Govt. K.R.G. P.G. Autonomous College, Gwalior - 474 001 (India)

    2014-04-24

    The lanthanum compounds have been found to undergo transition from their initial NaCl-type structure to high pressure body centered tetragonal (BCT) structure (distorted CsCl-type P4/mmm) using CTIP model. The calculated values of cohesive energy, lattice constant, phase transition pressure, relative volume collapse agree well with the available measured data and better than those computed by earlier workers.

  16. Ceramic superconductors II

    International Nuclear Information System (INIS)

    Yan, M.F.

    1988-01-01

    This volume compiles papers on ceramic superconductors. Topics include: structural patterns in High-Tc superconductors, phase equilibria of barium oxide superconductors, localized electrons in tetragonal YBa/sub 2/Cu/sub 3/O/sub 7-δ/, lattice and defect structure and properties of rare earth/alkaline earth-copper-oxide superconductors, alternate candidates for High-Tc superconductors, perovskite-structure superconductors; superconductive thin film fabrication, and superconductor/polymer composites

  17. Phase transformations in the Cu.6 Pd.4 alloy

    International Nuclear Information System (INIS)

    Imakuma, K.

    1977-01-01

    Order-disorder and structural transformations in the Cu-Pd 60-40% (Cu. 6 Pd. 4 ) alloy by means of a temperature and time dependent treatment are studied. The structural transformations by x-rays diffraction are also studied, where the bcc, fcc and tetragonal phases were observed. A qualitative analyze of the resistivity kinetics are made [pt

  18. Toughening behavior in ceramics associated with the transformation of tetragonal ZrO/sub 2/

    International Nuclear Information System (INIS)

    Becher, P.F.

    1986-01-01

    The contribution of the stress-induced phase transformation ZrO/sub 2/ to the fracture toughness of ceramics is described in terms of the zone size, the critical transformation stress and the influence of these parameters on the tetragonal to monoclinic transformation. For example in partially stabilized zirconia (PSZ), the ΔK/sub lC//sup T/ is shown to depend upon the martensite start (M/sub s/) temperature, which can be altered by the solute content and the particle or precipitate size. This behavior is consistent with the thermodynamics of the transformation. Experimental data correspond to the behavior predicted for various systems toughened by the addition of tetragonal ZrO/sub 2/ [e.g. PSZ and Al/sub 2/O/sub 3/-Z/sub 4/O/sub 2/(Y/sub 2/O/sub 3/). The stress required to transform the ZrO/sub 2/ is also modified by residual stresses due to the mismatch in matrix and particle (esp. thermal expansion) properties in the composite systems. The total residual stress acting on a particle is the sum of the particle's internal stress and the stress field of neighboring particles, and as a result, the total residual stress increases with volume fraction of ZrO/sub 2/ (V/sub f/). In the case of the Al/sub 2/O/sub 3/-ZrO/sub 2/ composites the pertinent stresses are tensile in character and thus promote the ZrO/sub 2/ transformation as V/sub f/ increases] For each level of Y/sub 2/O/sub 3/ in the ZrO/sub 2/, ΔK/sub lc//sup T/ then goes through a maximum with increase in V/sub f/ at a value of V/sub f/ where σ/sub R//sup T/ - σ/sub C//sup T/. The critical transformation stress is thus described for different levels of solute (e.g. Y/sub 2/O/sub 3/) in the ZrO/sub 2/. The dependence of ΔK/sub lc//sup T/ upon (σ/sub C//sup T/ - σ/sub R//sup T/) obtained is found to agree with the predicted behavior

  19. 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 theory.

    Science.gov (United States)

    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 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.

  20. Phase Transformation Behavior of Oxide Particles Formed in Mechanically Alloyed Fe-5Y{sub 2}O{sub 3} Powder

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Ga Eon; Choi, Jung-Sun; Noh, Sanghoon; Kang, Suk Hoon; Choi, Byoung Kwon; Kim, Tae Kyu [Korea Atomic Energy Research Institute, Deajeon (Korea, Republic of); Kim, Young Do [Hanyang University, Seoul (Korea, Republic of)

    2017-05-15

    The phase transformation behavior of the oxides formed in mechanically alloyed Fe-5Y{sub 2}O{sub 3} powder is investigated. Non-stoichiometric Y-rich and Fe-rich oxides with sizes of less than 300 nm are observed in the mechanically alloyed powder. The diffusion and redistribution reactions of the elements in these oxides during heating of the powder above 800 ℃ were observed, and these reactions result in the formation of a Y{sub 3}Fe{sub 5}O{sub 12} phase after heating at 1050 ℃. Thus, it is considered that the Y{sub 2}O{sub 3} powder and some Fe powder are formed from the non-stoichiometric Y-rich and Fe-rich oxides after the mechanical alloying process, and a considerable energy accumulated during the mechanical alloying process leads to a phase transformation of the Y-rich and Fe-rich oxides to Y{sub α}Fe{sub β}O{sub γ}-type phase during heating.

  1. Online Measurements of Highly Oxidized Organics in the Gas and Particle phase during SOAS and SENEX

    Science.gov (United States)

    Lopez-Hilfiker, F.; Lee, B. H.; Mohr, C.; Ehn, M.; Rubach, F.; Mentel, T. F.; Kleist, E.; Thornton, J. A.

    2014-12-01

    We present measurements of a large suite of gas and particle phase organic compounds made with a Filter Inlet for Gas and AEROsol (FIGAERO) coupled to a high resolution time of flight chemical ionization mass spectrometer (HR-ToF-CIMS) developed at the University of Washington and with airborne HR-ToF-CIMS measurements. The FIGAERO instrument was deployed on the Jülich Plant Atmosphere Chamber to study α-pinene oxidation, and subsequently at the SMEAR II forest station in Hyytiälä, Finland and the SOAS ground site, in Brent Alabama. During the Southern Atmosphere Study, a gas-phase only version of the HR-ToF-CIMS was deployed on the NOAA WP-3 aircraft as part of SENEX. We focus here on highly oxygenated organic compounds derived from monoterpene oxidation detected both aloft during SENEX and at the ground-based site during SOAS. In both chamber and the atmosphere, many highly oxidized, low volatility compounds were observed in the gas and particles and many of the same compositions detected in the gas-phase were detected in the particles upon temperature programmed thermal desorption. The fraction of a given compound measured in the particle phase follows expected trends with elemental composition such as O/C ratios, but many compounds would not be well described by an absorptive partitioning model assuming unity activity coefficients. The detailed structure in the thermograms reveals a significant contribution from large molecular weight organics and/or oligomers in both chamber and ambient aerosol samples. Approximately 50% of the measured organics in the particle phase are associated with compounds having effective vapour pressures 4 or more orders of magnitude lower than commonly measured monoterpene oxidation products. We discuss the implications of these findings for measurements of gas-particle partitioning and for evaluating the contribution of monoterpene oxidation to organic aerosol formation and growth. We also use the aircraft measurements and a

  2. PHASE CHANGES ON 4H AND 6H SIC AT HIGH TEMPERATURE OXIDATION

    Directory of Open Access Journals (Sweden)

    Jan Setiawan

    2016-10-01

    Full Text Available ABSTRACT PHASE CHANGES ON 4H AND 6H SIC AT HIGH TEMPERATURE OXIDATION. The oxidation on two silicon carbide contain 6H phase and contains 6H and 4H phases has been done.  Silicon carbide is ceramic non-oxide with excellent properties that potentially used in industry.  Silicon carbide is used in nuclear industry as structure material that developed as light water reactor (LWR fuel cladding and as a coating layer in the high temperature gas-cooled reactor (HTGR fuel.  In this study silicon carbide oxidation simulation take place in case the accident in primary cooling pipe is ruptured.  Sample silicon carbide made of powder that pressed into pellet with diameter 12.7 mm and thickness 1.0 mm, then oxidized at temperature 1000 oC, 1200 oC dan 1400 oC for 1 hour.  The samples were weighted before and after oxidized.  X-ray diffraction con-ducted to the samples using Panalytical Empyrean diffractometer with Cu as X-ray source.  Diffraction pattern analysis has been done using General Structure Analysis System (GSAS software. This software was resulting the lattice parameter changes and content of SiC phases.  The result showed all of the oxidation samples undergoes weight gain.  The 6S samples showed the highest weight change at oxidation temperature 1200 oC, for the 46S samples showed increasing tendency with the oxidation temperature.  X-ray diffraction pattern analysis showed the 6S samples contain dominan phase 6H-SiC that matched to ICSD 98-001-5325 card.  Diffraction pattern on 6S showed lattice parameter, composition and crystallite size changes.  Lattice parameters changes had smaller tendency from the model and before oxidation.  However, the lowest silicon carbide composition or the highest converted into other phases up to 66.85 %, occurred at oxidation temperature 1200 oC.  The 46S samples contains two polytypes silicon car-bide.  The 6H-SiC phases matched by ICSD 98-016-4972 card and 4H-SiC phase matched by ICSD 98

  3. Pre-sintered Y-TZP sandblasting: effect on surface roughness, phase transformation, and Y-TZP/veneer bond strength

    Directory of Open Access Journals (Sweden)

    Carla Müller Ramos-Tonello

    Full Text Available Abstract Sandblasting is a common method to try to improve the Y-TZP/veneer bond strength of dental prostheses, however, it may put stress on zirconia surfaces and could accelerate the t→m phase transformation. Y-TZP sandblasting before sintering could be an alternative to improve surface roughness and bonding strength of veneering ceramic. Objectives. The aim of this study was to analyze the effect of Y-TZP pre-sintering sandblasting on surface roughness, phase transformation, and the Y-TZP/veneer shear bond strength. Material and Methods. The Y-TZP specimen surface underwent sandblasting with aluminum oxide (50 μm pre-sintering (Z-PRE and post-sintering (Z-POS. Z-CTR was not subjected to surface treatment. After ceramic veneer application, the specimens were subjected to shear bond testing. Surface roughness was analyzed by confocal microscopy. Y-TZP monoclinic and tetragonal phases were evaluated by micro-Raman spectroscopy. Shear bond strength and surface roughness data were analyzed by One-way ANOVA and Tukey tests (α=0.05. Differences in the wave numbers and the broadening bands of the Raman spectra were compared among groups. Results. Z-POS (9.73±5.36 MPa and Z-PRE (7.94±2.52 MPa showed the highest bond strength, significantly higher than that of Z-CTR (5.54±2.14 MPa. The Ra of Z-PRE (1.59±0.23 µm was much greater and significantly different from that of Z-CTR (0.29±0.05 µm and Z-POS (0.77±0.13 µm. All groups showed bands typical of the tetragonal (T and monoclinic (M phases. Y-TZP sandblasting before sintering resulted in rougher surfaces but did not increase the shear bond strength compared to post-sintering and increased surface defects. Conclusions. Surface treatment with Al3O2, regardless of the moment and application, improves the results of Y-TZP/veneer bonding and is not a specific cause of t→m transformation.

  4. The liquid phase oxidation of n-butane: a search for plausible mechanisms

    Energy Technology Data Exchange (ETDEWEB)

    Hobbs, C.C. [Celanese Ltd., TX (United States). Corpus Christi Technical Center

    1998-12-31

    This articles deals with an approach that has given some key information about the mechanisms of the liquid phase oxidation of butane to acetic acid. This procedure has been developed over the last 34 years; however, much of what will be discussed represents a synthesis of previous insights. Many of the observations are relatively recent and have not been previously published. In principle, this approach should be applicable to many oxidation processes. (orig.)

  5. Subsurface characterization of an oxidation-induced phase transformation and twinning in nickel-based superalloy exposed to oxy-combustion environments

    International Nuclear Information System (INIS)

    Zhu Jingxi; Holcomb, Gordon R.; Jablonski, Paul D.; Wise, Adam; Li Jia; Laughlin, David E.; Sridhar, Seetharaman

    2012-01-01

    Highlights: ►Oxidation products of Ni-based superalloy were studied in oxy-fuel combustion conditions. ► An oxidation-induced phase transformation occurred in the subsurface region. ► One of the two product phases was not in the Ni database of Thermo-Calc. ► This unknown phase is an ordered derivative of FCC structure of Ni–Ti(–Ta) system. ► This phase is likely detrimental to the mechanical integrity of the alloy in use. - Abstract: In the integration of oxy-fuel combustion to turbine power generation system, turbine alloys are exposed to high temperature and an atmosphere comprised of steam, CO 2 and O 2 . While surface and internal oxidation of the alloy takes place, the microstructure in the subsurface region also changes due to oxidation. In this study, bare metal coupons of Ni-base superalloys were exposed in oxy-fuel combustion environment for up to 1000 h and the oxidation-related microstructures were examined. Phase transformation occurred in the subsurface region in Ni-based superalloy and led to twinning. The transformation product phases were analyzed through thermodynamic equilibrium calculations and various electron microscopy techniques, including scanning electron microscopy (SEM), orientation imaging microscopy (OIM) and transmission electron microscopy (TEM). The mechanism by which the phase transformation and the formation of the microstructure occurred was also discussed. The possible effects of the product phases on the performance of the alloy in service were discussed.

  6. Oxidative desulfurization of benzothiophene and thiophene with WOx/ZrO2 catalysts: Effect of calcination temperature of catalysts

    International Nuclear Information System (INIS)

    Hasan, Zubair; Jeon, Jaewoo; Jhung, Sung Hwa

    2012-01-01

    Highlights: ► Oxidative desulfurization was studied with WO x /ZrO 2 calcined at different temp. ► The importance of the phases of zirconia and tungsten oxide was suggested. ► The catalyst was analyzed thoroughly with Raman and XRD techniques. ► The importance of electron density on S was confirmed with the kinetics of oxidation. - Abstract: Oxidative desulfurization (ODS) of model fuel containing benzothiophene (BT) or thiophene (Th) has been carried out with WO x /ZrO 2 catalyst, which was calcined at various temperatures. Based on the conversion of BT in the model fuel, it can be shown that the optimum calcination temperature of WO x /ZrO 2 catalyst is around 700 °C. The most active catalyst is composed of tetragonal zirconia (ZrO 2 ) with well dispersed polyoxotungstate species and it is necessary to minimize the contents of the crystalline WO 3 and monoclinic ZrO 2 for a high BT conversion. The oxidation rate was interpreted with the first-order kinetics, and it demonstrated the importance of electron density since the kinetic constant for BT was higher than that for Th even though the BT is larger than Th in size. A WO x /ZrO 2 catalyst, treated suitably, can be used as a reusable active catalyst in the ODS.

  7. Investigation of phase stability in the scandia-zirconia

    International Nuclear Information System (INIS)

    Grosso, Robson Lopes

    2016-01-01

    In this work, the phase stability of scandia-zirconia (ScSZ) system was investigated by the thermodynamic study of nanoparticles, within the range of 0 to 20 mol% Sc 2 O 3 , and by codoping of ZrO 2 -10 mol% Sc 2 O 3 (10ScSZ) with Dy 2 O 3 and Nb 2 O 5 . The phase stability of ScSZ was evaluated based on thermodynamic data collected by water adsorption microcalorimetry and high temperature oxide melt solution. Nanostructured zirconia-scandia solid solutions were synthesized by coprecipitation method. Thermodynamic data were determined for ScSZ polymorph (monoclinic, tetragonal, cubic, rhombohedral β and γ) found by X-ray diffraction. This systemic work resulted in an unprecedented phase diagram at the nanoscale of particle size-composition. The effects of additives on 10ScSZ were investigated aiming to stabilize the cubic (c) structure at room temperature and to suppress the characteristic cubic-rhombohedral β phase transformation. Compositions were prepared by coprecipitation and solid state reaction. Materials were sintered by conventional and spark plasma sintering. Full stabilization of the cubic phase was attained by 1 mol% Dy 2 O 3 and 0.5 mol% Nb 2 O 5 additions. The smallest Nb 2 O 5 content required for cubic phase stabilization was attributed to liquid phase formation during sintering and to small ionic radius of Nb 5+ . Results of high temperature X-ray diffraction and thermal analysis show suppression of the c-β transformation. Samples containing 0.5 mol% Nb 2 O 5 show total ionic conductivity similar to 10ScSZ without additives within a broad temperature range with high stability during 170 h at 600 °C. (author)

  8. Synthesis of high-oxidation Y-Ba-Cu-O phases in superoxygenated thin films

    Science.gov (United States)

    Zhang, H.; Gauquelin, N.; McMahon, C.; Hawthorn, D. G.; Botton, G. A.; Wei, J. Y. T.

    2018-03-01

    It is known that solid-state reaction in high-pressure oxygen can stabilize high-oxidation phases of Y-Ba-Cu-O superconductors in powder form. We extend this superoxygenation concept of synthesis to thin films which, due to their large surface-to-volume ratio, are more reactive thermodynamically. Epitaxial thin films of YBa2Cu3O7 -δ grown by pulsed laser deposition are annealed at up to 700 atm O2 and 900 ∘C , in conjunction with Cu enrichment by solid-state diffusion. The films show the clear formation of Y2Ba4Cu7O15 -δ and Y2Ba4Cu8O16 as well as regions of YBa2Cu5O9 -δ and YBa2Cu6O10 -δ phases, according to scanning transmission electron microscopy, x-ray diffraction, and x-ray absorption spectroscopy. Similarly annealed YBa2Cu3O7 -δ powders show no phase conversion. Our results demonstrate a route of synthesis towards discovering more complex phases of cuprates and other superconducting oxides.

  9. Spectroscopic and luminescent properties of Co2+ doped tin oxide thin films by spray pyrolysis

    Directory of Open Access Journals (Sweden)

    K. Durga Venkata Prasad

    2016-07-01

    Full Text Available The wide variety of electronic and chemical properties of metal oxides makes them exciting materials for basic research and for technological applications alike. Oxides span a wide range of electrical properties from wide band-gap insulators to metallic and superconducting. Tin oxide belongs to a class of materials called Transparent Conducting Oxides (TCO which constitutes an important component for optoelectronic applications. Co2+ doped tin oxide thin films were prepared by chemical spray pyrolysis synthesis and characterized by powder X-ray diffraction, SEM, TEM, FT-IR, optical, EPR and PL techniques to collect the information about the crystal structure, coordination/local site symmetry of doped Co2+ ions in the host lattice and the luminescent properties of the prepared sample. Powder XRD data revealed that the crystal structure belongs to tetragonal rutile phase and its lattice cell parameters are evaluated. The average crystallite size was estimated to be 26 nm. The morphology of prepared sample was analyzed by using SEM and TEM studies. Functional groups of the prepared sample were observed in the FT-IR spectrum. Optical absorption and EPR studies have shown that on doping, Co2+ ions enter in the host lattice as octahedral site symmetry. PL studies of Co2+ doped SnO2 thin films exhibit blue and yellow emission bands. CIE chromaticity coordinates were also calculated from emission spectrum of Co2+ doped SnO2 thin films.

  10. Ion irradiation-induced diffusion in bixbyite-fluorite related oxides: Dislocations and phase transformation

    Energy Technology Data Exchange (ETDEWEB)

    Rolly, Gaboriaud, E-mail: Rolly.gaboriaud@univ-poitiers.fr [Institut Pprime, CNRS-University of Poitiers, SP2MI-BP 30179, 86962 Chasseneuil-Futuroscope (France); Fabien, Paumier [Institut Pprime, CNRS-University of Poitiers, SP2MI-BP 30179, 86962 Chasseneuil-Futuroscope (France); Bertrand, Lacroix [CSIC – University of Sevilla, Avenida Américo Vespucio, 49, 41092 Sevilla (Spain)

    2014-05-01

    Ion-irradiation induced diffusion and the phase transformation of a bixbyite-fluorite related rare earth oxide thin films are studied. This work is focused on yttrium sesquioxide, Y{sub 2}O{sub 3}, thin films deposited on Si (1 0 0) substrates using the ion beam sputtering technique (IBS). As-deposited samples were annealed ant then irradiated at cryogenic temperature (80 K) with 260 keV Xe{sup 2+} at different fluences. The irradiated thin oxide films are characterized by X-ray diffraction. A cubic to monoclinic phase transformation was observed. Analysis of this phenomenon is done in terms of residual stresses. Stress measurements as a function of irradiation fluences were realised using the XRD-sin{sup 2}ψ method. Stress evolution and kinetic of the phase transformation are compared and leads to the role-played by the nucleation of point and extended defects.

  11. Catalytic oxidation of cyanides in an aqueous phase over individual and manganese-modified cobalt oxide systems

    International Nuclear Information System (INIS)

    Christoskova, St.; Stoyanova, M.

    2009-01-01

    The possibility for purification of wastewaters containing free cyanides by applying of a new method based on cyanides catalytic oxidation with air to CO 2 and N 2 at low temperature and atmospheric pressure was investigated. On this purpose, individual and modified with manganese Co-oxide systems as active phase of environmental catalysts were synthesized. The applied method of synthesis favours the preparation of oxide catalytic systems with high active oxygen content (total-O* and surface-O* s ) possessing high mobility, and the metal ions being in a high oxidation state and in an octahedral coordination-factors determining high activity in reactions of complete oxidation. The catalysts employed were characterized by powder X-ray diffraction, Infrared spectroscopy, and chemical analysis. The effect of pH of the medium and catalyst loading on the effectiveness of the cyanide oxidation process, expressed by the degree of conversion (α, %), by the rate constant (k, min -1 ), and COD was studied. The results obtained reveal that using catalysts investigated a high cyanide removal efficiency could be achieved even in strong alkaline medium. The higher activity of the manganese promoted catalytic sample could be explained on the basis of higher total active oxygen content and its higher mobility both depending on the conditions, under which the synthesis of catalyst is being carried out.

  12. Liquid Phase Plasma Synthesis of Iron Oxide/Carbon Composite as Dielectric Material for Capacitor

    Directory of Open Access Journals (Sweden)

    Heon Lee

    2014-01-01

    Full Text Available Iron oxide/carbon composite was synthesized using a liquid phase plasma process to be used as the electrode of supercapacitor. Spherical iron oxide nanoparticles with the size of 5~10 nm were dispersed uniformly on carbon powder surface. The specific capacitance of the composite increased with increasing quantity of iron oxide precipitate on the carbon powder up to a certain quantity. When the quantity of the iron oxide precipitate exceeds the threshold, however, the specific capacitance was rather reduced by the addition of precipitate. The iron oxide/carbon composite containing an optimum quantity (0.33 atomic % of iron oxide precipitate exhibited the smallest resistance and the largest initial resistance slope.

  13. Competing magnetic interactions and low temperature magnetic phase transitions in composite multiferroics

    International Nuclear Information System (INIS)

    Borkar, Hitesh; Singh, V N; Kumar, Ashok; Choudhary, R J; Tomar, M; Gupta, Vinay

    2015-01-01

    Novel magnetic properties and magnetic interactions in composite multiferroic oxides Pb[(Zr 0.52 Ti 0.48 ) 0.60 (Fe 0.67 W 0.33 ) .40 ]O 3 ] 0.80 –[CoFe 2 O 4 ] 0.20 (PZTFW–CFO) have been studied from 50 to 1000 Oe field cooled (FC) and zero field cooled (ZFC) probing conditions, and over a wide range of temperatures (4–350 K). Crystal structure analysis, surface morphology, and high resolution transmission electron microscopy images revealed the presence of two distinct phases, where micro- and nano-size spinel CFO were embedded in tetragonal PZTFW matrix and applied a significant built-in compressive strain (∼0.4–0.8%). Three distinct magnetic phase transitions were observed with the subtle effect of CFO magnetic phase on PZTFW magnetic phase transitions below the blocking temperature (T B ). Temperature dependence magnetic property m(T) shows a clear evidence of spin freezing in magnetic order with lowering in thermal vibration. Chemical inhomogeneity and confinement of nanoscale ferrimagnetic phase in paramagnetic/antiferromagnetic matrix restrict the long range interaction of spin which in turn develop a giant spin frustration. A large divergence in the FC and ZFC data and broad hump in ZFC data near 200 (±10) K were observed which suggests that large magnetic anisotropy and short range order magnetic dipoles lead to the development of superparamagnetic states in composite. (paper)

  14. Evaluation of microstructure and phase relations in a powder processed Ti-44Al-12Nb alloy

    International Nuclear Information System (INIS)

    Kumar, S.G.; Reddy, R.G.; Wu, J.; Holthus, J.

    1995-01-01

    Titanium aluminides based on the ordered face-centered tetragonal γTiAl phase possess attractive properties, such as low density, high melting point, good elevated temperature strength, modulus retention, and oxidation resistance, making these alloys potential high-temperature structural materials. These alloys can be processed by both ingot metallurgy and powder metallurgy routes. In the present study, three variations of the powder metallurgy route were studied to process a Ti-44Al-12Nb (at.%) alloy: (a) cold pressing followed by reaction sintering (CP process); (b) cold pressing, vacuum hot pressing, and then sintering (HP process); and (c) arc melting, hydride-dehydride process to make the alloy powder, cold isostatic pressing, and then sintering (AM process). Microstructural and phase relations were studied by x-ray diffraction (XRD) analysis, optical microscopy, scanning electron microscopy with an energy-dispersive spectrometer (SEM-EDS), and electron probe microanalysis (EPMA). The phases identified were Ti 3 Al and TiAl; an additional Nb 2 Al phase was observed in the HP sample. The microstructures of CP and HP processed samples are porous and chemically inhomogeneous whereas the AM processed sample revealed fine equiaxed microstructure. This refinement of the microstructure is attributed to the fine, homogeneous powder produced by the hydride-dehydride process and the high compaction pressures

  15. Intra-well relaxation process in magnetic fluids subjected to strong polarising fields

    Energy Technology Data Exchange (ETDEWEB)

    Marin, C.N., E-mail: cmarin@physics.uvt.ro [West University of Timisoara, Faculty of Physics, B-dul V. Parvan, No. 4, Timisoara 300223 (Romania); Fannin, P.C. [Department of Electronic and Electrical Engineering, Trinity College, Dublin 2 (Ireland); Malaescu, I.; Barvinschi, P.; Ercuta, A. [West University of Timisoara, Faculty of Physics, B-dul V. Parvan, No. 4, Timisoara 300223 (Romania)

    2012-02-15

    We report on the frequency and field dependent complex magnetic susceptibility measurements of a kerosene-based magnetic fluid with iron oxide nanoparticles, stabilized with oleic acid, in the frequency range 0.1-6 GHz and over the polarising field range of 0-168.4 kA/m. By increasing polarising field, H, a subsidiary loss-peak clearly occurs in the vicinity of the ferromagnetic resonance peak, from which it remains distinct even in strong polarising fields of 168.4 kA/m. This is in contrast to other reported cases in which the intra-well relaxation process is manifested only as a shoulder of the resonance peak, which vanishes in polarising fields larger than that of 100 kA/m. The results of the XRD analysis connected to the anisotropy field results confirm that the investigated sample contains particles of magnetite and of the tetragonal phase of maghemite. Taking into account the characteristics of our sample, the theoretical analysis revealed that the intra-well relaxation process of the small particles of the tetragonal phase of maghemite may be responsible for the subsidiary loss peak of the investigated magnetic fluid. - Highlights: > Intra-well relaxation process in a magnetic fluid is studied. > Sample consists of the tetragonal phase of maghemite and magnetite particles. > A subsidiary relaxation peak is observed in the vicinity of the resonance peak. > Relaxation peak is correlated to the intra-well relaxation process. > It is assigned to the tetragonal phase of maghemite particles.

  16. Ab-initio study of the hyperfine parameters in P2{sub 1}/c, P42nmc and Fm3m zirconia phases doped with Ta{sub zr} and the vacancy-Ta{sub zr} complex

    Energy Technology Data Exchange (ETDEWEB)

    Casali, R.A. [Facultad de Ciencias Exactas, y Nat. y Agr.-UNNE-Avenue Libertad 5600, Corrientes (Argentina)]. E-mail: rac@exa.unne.edu.ar; Caravaca, M.A. [Facultad de Ingenieria-UNNE, Avenue Las Heras 727, Resistencia (Argentina)

    2007-02-01

    In this work we develop selfconsistent calculations by means of the all-electron method NFP-LMTO. The electronic structure, quadrupolar frequencies and asymmetry parameters of ZrO{sub 2} polymorphs doped with Ta placed at substitutional site to Zr (Ta{sub Zr}), with and without vacancies are studied in the monoclinic, tetragonal and cubic phases. The calculated hyperfine parameters in neutral Ta{sub Zr} in the monoclinic phase are in agreement with hypine parameters measured with PAC and assigned to substitutional site in a wide range of temperatures. However, in the case of Ta{sub Zr} in the tetragonal P42nmc phase, the electric field gradient (EFG) is in large disagreement with the experimental assignment. Therefore we explored the incorporation of a near neighbor oxygen vacancy in several charged states. We found that the TaV{sup 0} and TaV{sup +1} pairs in the tetragonal symmetry with axis length ratio c/a=1.02 gives electric field gradients V{sub zz} and {eta} in agreement with low-temperature values of the experimentally assigned pure tetragonal, called t-form. Further, the pair Ta-V with a ratio c/a=1 gives EFG in close agreement with reported high-temperature values.

  17. Phase and structural transformations in annealed copper coatings in relation to oxide whisker growth

    Energy Technology Data Exchange (ETDEWEB)

    Dorogov, M.V.; Priezzheva, A.N. [Togliatti State University, Belorusskaya 14, 445667 Togliatti (Russian Federation); Vlassov, S., E-mail: vlassovs@ut.ee [Institute of Solid State Physics, University of Latvia, Kengaraga 8, LV-1063 Riga (Latvia); Kink, I.; Shulga, E. [Institute of Physics, University of Tartu, Ravila 14c, 50411 Tartu (Estonia); Dorogin, L.M. [Togliatti State University, Belorusskaya 14, 445667 Togliatti (Russian Federation); Institute of Physics, University of Tartu, Ravila 14c, 50411 Tartu (Estonia); ITMO University, Kronverkskiy 49, 197101 Saint Petersburg (Russian Federation); Lõhmus, R. [Institute of Physics, University of Tartu, Ravila 14c, 50411 Tartu (Estonia); Tyurkov, M.N.; Vikarchuk, A.A. [Togliatti State University, Belorusskaya 14, 445667 Togliatti (Russian Federation); Romanov, A.E. [Togliatti State University, Belorusskaya 14, 445667 Togliatti (Russian Federation); Institute of Physics, University of Tartu, Ravila 14c, 50411 Tartu (Estonia); ITMO University, Kronverkskiy 49, 197101 Saint Petersburg (Russian Federation); Ioffe Physical Technical Institute, RAS, Polytechnicheskaya 26, 194021 Saint Petersburg (Russian Federation)

    2015-08-15

    Highlights: • Coatings prepared by Cu microparticle electrodeposition. • Structural and phase transformation in Cu coatings annealed at 400 °C. • Annealing is accompanied by intensive growth of CuO whiskers. • Layered oxide phases (Cu{sub 2}O and CuO) in the coating are characterized. • Formation of volumetric defects in the coating is demonstrated. - Abstract: We describe structural and phase transformation in copper coatings made of microparticles during heating and annealing in air in the temperature range up to 400 °C. Such thermal treatment is accompanied by intensive CuO nanowhisker growth on the coating surface and the formation of the layered oxide phases (Cu{sub 2}O and CuO) in the coating interior. X-ray diffraction and focused ion beam (FIB) are employed to characterize the multilayer structure of annealed copper coatings. Formation of volumetric defects such as voids and cracks in the coating is demonstrated.

  18. Formation of high oxide ion conductive phases in the sintered oxides of the system Bi2O3-Ln2O3 (Ln = La-Yb)

    International Nuclear Information System (INIS)

    Iwahara, H.; Esaka, T.; Sato, T.; Takahashi, T.

    1981-01-01

    The electrical conduction in various phases of the system Bi 2 O 3 -Ln 2 O 3 (Ln = La, Nd, Sm, Dy, Er, or Yb) was investigated by measuring ac conductivity and the emf of the oxygen gas concentration cell. High-oxide-ion conduction was observed in the rhombohedral and face-centered cubic (fcc) phase in these systems. The fcc phase could be stabilized over a wide range of temperature by adding a certain amount of Ln 2 O 3 . In these cases, the larger the atomic number of Ln, the lower the content of Ln 2 O 3 required to form the fcc solid solution, except in the case of Yb 2 O 3 . The oxide ion conductivity of this phase decreased with increasing content of Ln 2 O 3 . Maximum conductivity was obtained at the lower limit of the fcc solid solution formation range in each system, which was more than one order of magnitude higher than those of conventional stabilized zirconias. Lattice parameters of the fcc phase were calculated from the x-ray diffraction patterns. The relationship between the oxide ion conductivity and the lattice parameter was also discussed

  19. Significance of internal stresses for the martensitic transformation in yttria-stabilized tetragonal zirconia polycrystals during degradation

    International Nuclear Information System (INIS)

    Schmauder, S.; Schubert, H.

    1986-01-01

    Various aspects of the tetragonal (t) to monoclinic (m) transformation during degradation have been studied experimentally and theoretically in yttria-stabilized tetragonal zirconia polycrystals (Y-TZP), i.e., polycrystalline t-ZrO/sub 2/ containing Y/sub 2/O/sub 3/ in solution. Transmission electron microscopy (TEM) revealed that protruding grains at the surface of Y-TZP specimens do not transform under corrosive conditions (250 0 C, humid atmosphere) even after n annealing time of 168 h.) Eigenstresses due to anistropic thermal expansion in and around protruding and bulk grains have been calculated for Y-TZP containing 2 and 3 mol% Y/sub 2/O/sub 3/. The prominent role of these stresses on subsequent transformation nucleation during degradation is shown to agree qualitatively with an established free energy concept. The lack of complete transformation of m-ZrO/sub 2/ is attributed to characteristics of the nucleation - and growth- controlled transformation process

  20. Oxygen 1s excitation and tetragonal distortion from core-hole effect in BaTiO3

    Science.gov (United States)

    Bugnet, Matthieu; Radtke, Guillaume; Botton, Gianluigi A.

    2013-11-01

    The accurate description of the O 1s excitation in BaTiO3 has been elusive so far. In this Rapid Communication, the electronic structure and the high-resolution electron energy-loss near-edge structures of the O K edge in tetragonal BaTiO3 are investigated using first-principles calculations. The results demonstrate a clear correlation between the broadening of the lower energy fine structure and the anisotropic effects induced by the core-hole potential, which are directly related to the structural distortion occurring in tetragonal BaTiO3. Moreover, we show that a significant improvement of the description of higher-lying structures can be obtained when correcting the energy position of the Ba 4f states. This demonstrates that the O 1s spectrum can be a very effective probe of the distortion and changes in the local electronic structure, and be used as a sensitive tool for studying new materials and ferroelectric transitions.

  1. Heterogeneous inhibition of the liquid phase oxidation of hydrocarbons by molybdenum compounds

    Energy Technology Data Exchange (ETDEWEB)

    Tavadyan, L.A.; Karapetyan, A.P.; Madatovyan, V.M.

    1988-05-01

    The heterogeneous action of molybdenum compounds: MoB, MoSe/sub 2/, MoSi/sub 2/, Mo/sub 2/C, MoO/sub 3/, Mo on the oxidation of n-decane, ethylbenzene, and nonene-1 has been investigated. A parameter representing the inhibiting effect of the heterogeneous catalyst was calculated theoretically. It was found that NoB, MoSe/sub 2/, and MoSi/sub 2/ inhibited the oxidation of n-decane at 408 K while the remaining heterogeneous contacts catalyzed it. A critical phenomenon was detected in the inhibition by MoSi/sub 2/. All the molybdenum compounds investigated inhibited the oxidation of ethylbenzene at 393 K owing to the formation of phenol by catalytic decomposition of the hydroperoxide. The liquid phase oxidation autoinhibited by phenol is described theoretically.

  2. Formation Mechanism and Dispersion of Pseudo-Tetragonal BaTiO3-PVP Nanoparticles from Different Titanium Precursors: TiCl4 and TiO2

    Directory of Open Access Journals (Sweden)

    Jinhui Li

    2017-12-01

    Full Text Available Nano-sized tetragonal BaTiO3 (BT particles that are well dispersed in solution are essential for the dielectric layer in multilayer ceramic capacitor technology. A hydrothermal process using TiCl4 and BaCl2, as source of Ti and Ba, respectively, or the precursor TiO2 as seed for the formation of BT, and poly(vinylpyrrolidone (PVP as a surfactant, was employed in this study to enhance both the dispersibility and tetragonality (c/a simultaneously in a single reaction process. The process parameters, i.e., the ratio of TiO2 substitution of TiCl4, the reaction time, and PVP content were systematically studied, and the growth mechanism and relation between the tetragonality and the particle size are discussed. Dynamic light scattering (DLS analysis was used to show that truncated pseudo-tetragonal BT-PVP particles with an average size of 100 nm, having a narrow size distribution and a coefficient of variation (CV as low as 20% and being mono-dispersed in water, were produced. The narrow particle size distribution is attributed to the ability of PVP to inhibit the growth of BT particles, and the high c/a of BT-PVP to heterogeneous particle growth using TiO2 seeds.

  3. Optical properties of body-centered tetragonal C4: Insights from many-body perturbation and time-dependent density functional theories

    Science.gov (United States)

    Tarighi Ahmadpour, Mahdi; Rostamnejadi, Ali; Hashemifar, S. Javad

    2018-04-01

    We study the electronic structure and optical properties of a body-centered tetragonal phase of carbon (bct-C4) within the framework of time-dependent density functional theory and Bethe-Salpeter equation. The results indicate that the optical properties of bct-C4 are strongly affected by the electron-hole interaction. It is demonstrated that the long-range corrected exchange-correlation kernels could fairly reproduce the Bethe-Salpeter equation results. The effective carrier number reveals that at energies above 30 eV, the excitonic effects are not dominant any more and that the optical transitions originate mainly from electronic excitations. The emerged peaks in the calculated electron energy loss spectra are discussed in terms of plasmon excitations and interband transitions. The results of the research indicate that bct-C4 is an indirect wide-band-gap semiconductor, which is transparent in the visible region and opaque in the ultraviolet spectral range.

  4. Investigation of the effects of phase transformations in micro and nano aluminum powders on kinetics of oxidation using thermogravimetric analysis.

    Science.gov (United States)

    Saceleanu, Florin; Atashin, Sanam; Wen, John Z

    2017-07-26

    Aluminum micro and nanoparticles are key ingredients in the synthesis of nano energetic materials. Hence it is important to characterize the kinetics and the rate controlling process of their oxidation. The literature shows that the mass diffusion and phase transformation within the aluminum oxide shell are important. However, the description of physical processes regarding simultaneous oxidation and phase transformation is lacking. In this paper, the controlled thermogravimetric (TGA) oxidation of 40-60 nm and 1 µm Al powders is investigated at constant heating rates and under isothermal conditions, respectively, upon varying the partial pressure of oxygen. It is found that the core-shell model of homogenous oxidation is applicable to explain the TGA results when the shell does not undergo phase transformation, which predicts the apparent activation energy in good agreement with the literature data. On the other hand, the simultaneous oxidation and phase transformation is able to be addressed using the JMAK model which reveals key parameters of the rate controlling processes. Mass diffusion is indeed rate determining during the oxidation of Al micro and nanopowders while the kinetics of the reaction is fast. Unlike the micron powders, the particle size distribution has a significant effect on the shape of the oxidation curves of the nanopowders.

  5. Raman studies of lanthanum cuprate superconductors

    International Nuclear Information System (INIS)

    Weber, W.H.; Peters, C.R.; Logothetis, E.M.

    1989-01-01

    Raman-scattering studies of the high-T/sub c/ superconductor La/sub 2-//sub x/(Sr, Ba)/sub x/CuO 4 are briefly reviewed. A detailed analysis of the phonon-mode symmetries is given along with a discussion of the effects expected from the orthorhombic-to-tetragonal phase transition, which is known to occur in these materials. Survey spectra are given for powders, ceramics, and single crystals, and an oxide of Cu is identified as the primary impurity phase. Extensive spectra are given from oriented single crystals of La 2 CuO 4 and La/sub 1.85/Sr/sub 0.15/CuO 4 , and several mode assignments are made. Spectra for the high-temperature tetragonal phase and the low-temperature orthorhombic phase are given for each material. The soft phonon associated with the phase transition is seen in La 2 CuO 4 as is a broad peak arising from two-magnon scattering. Neither of these features is seen in the Sr-doped sample

  6. Shape memory lifetime of CeO2-stabilized tetragonal zirconia polycrystals

    International Nuclear Information System (INIS)

    Zhe Xiaoli; Li Bo; Meng Man

    1993-01-01

    Lifetime of shape memory effect (SME) of CeO 2 -stabilized tetragonal zirconia polycrystals was studied by means of both tests of constraint stress and constraint strain mode during reverse martensite transformation. Up to 8th cycling of SME, the shape of sample entirely recovered except microcracks in the constraint stress mode and the accumulated strain reached 4.6% in the constraint strain mode. It was found that the yield stress decreased, however, the reverse transformation temperature of stress-induced martensite increased with times of the cycling. The reason of these phenomena are discussed in terms of microcracking and strain energy relaxation

  7. Thermal oxidation of cesium loaded Prussian blue as a precaution for exothermic phase change in extreme conditions

    International Nuclear Information System (INIS)

    Parajuli, Durga; Tanaka, Hisashi; Takahashi, Akira; Kawamoto, Tohru

    2013-01-01

    Cesium adsorbed Prussian blue is studied for the thermal oxidation. The TG-DTA shows exothermic phase change of micro aggregates of nano-PB at above 270°C. For this reason, Cs loaded PB was heated between 180 to 260°C. Heating at 180 removed only the water. Neither the oxidation of Iron nor the removal of cyanide is observed at this temperature. Oxidation of cyanide is observed upon heating above 200°C while loaded Cs is released after heating at >250°C followed by washing with water. Thermal oxidation between 200 to 220°C for more than 2 h showed control on exothermic phase change and loaded Cs is also not solubilized. (author)

  8. The calculation of phase equilibria of oxide core-concrete systems

    International Nuclear Information System (INIS)

    Ball, R.G.J.; Mignanelli, M.A.; Barry, T.I.; Gisby, J.A.

    1993-01-01

    Thermodynamic models have been developed to describe the phase equilibria of oxide solutions appropriate for the understanding of the chemical interactions between nuclear reactor core debris and concrete. For this purpose, the Gibbs energy of the liquid phase is described by the inclusion of associate species and nonideal interactions between the components and associate species. Assessments of the thermodynamic and phase equilibrium data for the subsystems of the CaO-Al 2 O 3 -SiO 2 -UO 2 -ZrO 2 system have been used to obtain a thermodynamic description of the crystalline and liquid phases in good agreement with published data. The data for the subsystems have then been combined, using well established principles, to predict the phase relationships in the ternary and quaternary sytsems and in the overall quinary system. The results show that he overall system cannot properly be treated as a pseudo-ideal liquid and solid solution, as used in some computer codes which attempt to model the physics and chemistry of core-concrete interactions. The limitations of the current model are discussed. (orig.)

  9. In situ growth of capping-free magnetic iron oxide nanoparticles on liquid-phase exfoliated graphene

    NARCIS (Netherlands)

    Tsoufis, T.; Syrgiannis, Z.; Akhtar, N.; Prato, M.; Katsaros, F.; Sideratou, Z.; Kouloumpis, A.; Gournis, D.; Rudolf, P.

    2015-01-01

    We report a facile approach for the in situ synthesis of very small iron oxide nanoparticles on the surface of high-quality graphene sheets. Our synthetic strategy involved the direct, liquid-phase exfoliation of highly crystalline graphite (avoiding any oxidation treatment) and the subsequent

  10. Phase transformations during machining and properties of surface layers in zirconium dioxide ceramics

    International Nuclear Information System (INIS)

    Grigor'ev, O.N.; Krivoshej, G.S.; Stel'mashenko, N.A.; Trefilov, V.I.; Shevchenko, A.V.

    1991-01-01

    The methods of X-ray allow studying phase composition and inner stresses in the surface layers of partially stabilized zirconium dioxide after mashining. It is shown that under conditions of abrasive treatment transitions from tetragonal into rhomboedric and monoclinic phases initiate. As a result of phase transitions fields of compressible stresses achieving 900 MPa under grinding with ACM abrasive are created on the surface. An essential increase of hardness due to growth of the brittle fauilure resistance and deformation hardening is revealed

  11. Martensitic phase transformations in Ni–Ti-based shape memory alloys: The Landau theory

    International Nuclear Information System (INIS)

    Shchyglo, Oleg; Salman, Umut; Finel, Alphonse

    2012-01-01

    We present a simple Landau free energy functional for cubic-to-orthorhombic and cubic-to-monoclinic martensitic phase transformations. The functional is derived following group–subgroup relations between different martensitic phasestetragonal, trigonal, orthorhombic and monoclinic – in order to fully capture the symmetry properties of the free energy of the austenite and martensite phases. The derived free energy functional is fitted to the elastic and thermodynamic properties of NiTi and NiTiCu shape memory alloys which exhibit cubic-to-monoclinic and cubic-to-orthorhombic martensitic phase transformations, respectively.

  12. Zinc oxide crystal whiskers as a novel sorbent for solid-phase extraction of flavonoids.

    Science.gov (United States)

    Wang, Licheng; Shangguan, Yangnan; Hou, Xiudan; Jia, Yong; Liu, Shujuan; Sun, Yingxin; Guo, Yong

    2017-08-15

    As a novel solid-phase extraction material, zinc oxide crystal whiskers were used to extract flavonoid compounds and showed good extraction abilities. X-ray diffraction, scanning electron microscopy with energy dispersive X-ray spectroscopy and surface area/pore volume characterized the sorbent. The zinc oxide was packed into a solid-phase extraction micro-column and its extraction ability was evaluated by four model flavonoid compounds. The sample loading and elution parameters were optimized and the zinc oxide based analytical method for flavonoids was established. It showed that the method has wide linearities from 1 to 150μg/L and low limits of detection at 0.25μg/L. The relative standard deviations of a single column repeatability and column to column reproducibility were less than 6.8% and 10.6%. Several real samples were analyzed by the established method and satisfactory results were obtained. The interactions between flavonoids and zinc oxide were calculated and proved to be from the Van der Waals' forces between the 4p and 5d orbitals from zinc atom and the neighboring π orbitals from flavonoid phenyl groups. Moreover, the zinc oxide crystal whiskers showed good stability and could be reused more than 50 times under the operation conditions. This work proves that the zinc oxide crystal whiskers are a good candidate for flavonoids enrichment. Copyright © 2017. Published by Elsevier B.V.

  13. Novel synthesis of manganese and vanadium mixed oxide (V2O5/OMS-2) as an efficient and selective catalyst for the oxidation of alcohols in liquid phase

    International Nuclear Information System (INIS)

    Mahdavi, Vahid; Soleimani, Shima

    2014-01-01

    Graphical abstract: Oxidation of various alcohols is studied in the liquid phase over new composite mixed oxide (V 2 O 5 /OMS-2) catalyst using tert-butyl hydroperoxide (TBHP). The activity of V 2 O 5 /OMS-2 samples was considerably increased with respect to OMS-2 catalyst and these samples are found to be suitable for the selective oxidation of alcohols. - Highlights: • V 2 O 5 /K-OMS-2 with different V/Mn molar ratios prepared by the impregnation method. • Oxidation of alcohols was studied in the liquid phase over V 2 O 5 /K-OMS-2 catalyst. • V 2 O 5 /K-OMS-2 catalyst had excellent activity for alcohol oxidation. • Benzyl alcohol oxidation using excess TBHP followed a pseudo-first order kinetic. • The selected catalyst was reused without significant loss of activity. - Abstract: This work reports the synthesis and characterization of mixed oxide vanadium–manganese V 2 O 5 /K-OMS-2 at various V/Mn molar ratios and prepared by the impregnation method. Characterization of these new composite materials was made by elemental analysis, BET, XRD, FT-IR, SEM and TEM techniques. Results of these analyses showed that vanadium impregnated samples contained mixed phases of cryptomelane and crystalline V 2 O 5 species. Oxidation of various alcohols was studied in the liquid phase over the V 2 O 5 /K-OMS-2 catalyst using tert-butyl hydroperoxide (TBHP) and H 2 O 2 as the oxidant. Activity of the V 2 O 5 /K-OMS-2 samples was increased considerably with respect to K-OMS-2 catalyst due to the interaction of manganese oxide and V 2 O 5 . The kinetic of benzyl alcohol oxidation using excess TBHP over V 2 O 5 /K-OMS-2 catalyst was investigated at different temperatures and a pseudo-first order reaction was determined with respect to benzyl alcohol. The effects of reaction time, oxidant/alcohol molar ratio, reaction temperature, solvents, catalyst recycling potential and leaching were investigated

  14. Phase identification and internal stress analysis of steamside oxides on superheater tubes by means of X-ray diffraction

    DEFF Research Database (Denmark)

    Pantleon, Karen; Montgomery, Melanie

    Steamside oxides formed on plant exposed superheated tubes were investigated using X-ray diffraction. Phase identification and stress analysis revealed that on ferritic X20CrMoV12-1 pure Hematite and pure Magnetite formed and both phases are under tensile stress. IN contrast, on austenitic TP347H...... Mn-, Cr- and/or Ni-containing oxides are observed, instead of pure Magnetite, underneath a pure Hematite surface layer. Oxides on the austenitic steel are under compressive stress or even stress-free....

  15. Electronic properties and structural phase transition in A4 [M4O4] (A=Li, Na, K and Rb; M=Ag and Cu): A first principles study

    Science.gov (United States)

    Umamaheswari, R.; Yogeswari, M.; Kalpana, G.

    2013-02-01

    Self-consistent scalar relativistic band structure calculations for AMO (A=Li, Na, K and Rb; M=Ag and Cu) compounds have been performed using the tight-binding linear muffin-tin orbital (TB-LMTO) method within the local density approximation (LDA). At ambient conditions, these compounds are found to crystallize in tetragonal KAgO-type structure with two different space group I-4m2 and I4/mmm. Nowadays, hypothetical structures are being considered to look for new functional materials. AMO compounds have stoichiometry similar to eight-electron half-Heusler materials of type I-I-VI which crystallizes in cubic (C1b) MgAgAs-type structure with space group F-43m. For all these compounds, by interchanging the positions of atoms in the hypothetical cubic structure, three phases (α, β and γ) are formed. The energy-volume relation for these compounds in tetragonal KAgO-type structure and cubic α, β and γ phases of related structure have been obtained. Under ambient conditions these compounds are more stable in tetragonal KAgO-type (I4/mmm) structure. The total energies calculated within the atomic sphere approximation (ASA) were used to determine the ground state properties such as equilibrium lattice parameters, c/a ratio, bulk modulus, cohesive energy and are compared with the available experimental results. The results of the electronic band structure calculations at ambient condition show that LiCuO and NaMO are indirect band gap semiconductors whereas KMO and RbMO are direct band gap semiconductors. At high pressure the band gap decreases and the phenomenon of band overlap metallization occur. Also these compounds undergo structural phase transition from tetragonal I-4m2 phase to cubic α-phase and transition pressures were calculated.

  16. Oxidation of ammonium sulfite by a multi-needle-to-plate gas phase pulsed corona discharge reactor

    Science.gov (United States)

    Ren, Hua; Lu, Na; Shang, Kefeng; Li, Jie; Wu, Yan

    2013-03-01

    The oxidation of ammonium sulfite in the ammonia-based flue gas desulfurization (FGD) process was investigated in a multi-needle-to-plate gas phase pulsed corona discharge reactor in this paper. The effect of several parameters, including capacitance and peak pulse voltage of discharge system, electrode gap and bubbling gas flow rate on the oxidation rate of ammonium sulfite was reviewed. The oxidation rate of ammonium sulfite could reach 47.2% at the capacitance, the peak pulse voltage, electrode gap and bubbling gas flow rate equal to 2 nF, -24.6 k V, 35 mm and 4 L min-1 within treatment time of 40 min The experimental results indicate that the gas phase pulsed discharge system with a multi-needle-to-plate electrode can oxide the ammonium sulfite. The oxidation rate increased with the applied capacitance and peak pulse voltage and decreased with the electrode gap. As the bubbling gas flow rate increased, the oxidation rate increased first and then tended to reach a stationary value. These results would be important for the process optimization of the (NH4)2SO3 to (NH4)2SO4 oxidation.

  17. Assessment of antibacterial and cytotoxic effects of orthodontic stainless steel brackets coated with different phases of titanium oxide: An in-vitro study.

    Science.gov (United States)

    Baby, Roshen Daniel; Subramaniam, Siva; Arumugam, Ilakkiya; Padmanabhan, Sridevi

    2017-04-01

    Our objective was to assess the antibacterial and cytotoxic effects of orthodontic stainless steel brackets coated with different phases of photocatalytic titanium oxide. From a total sample of 115 brackets, 68 orthodontic stainless steel brackets were coated with titanium oxide using a radiofrequency magnetron sputtering machine. The coated brackets were then converted into 34 each of the anatase and rutile phases of titanium oxide. These brackets were subdivided into 4 groups for antibacterial study and 3 groups for cytotoxicity study. Brackets for the antibacterial study were assessed against the Streptococcus mutans species using microbiologic tests. Three groups for the cytotoxicity study were assessed using the thiazolyl tetrazolium bromide assay. The antibacterial study showed that both phases were effective, but the rutile phase of photocatalytic titanium oxide had a greater bactericidal effect than did the anatase phase. The cytotoxicity study showed that the rutile phase had a greater decrease in viability of cells compared with the anatase phase. It is recommended that orthodontic brackets be coated with the anatase phase of titanium oxide since they exhibited a significant antibacterial property and were only slightly cytotoxic. Copyright © 2016 American Association of Orthodontists. Published by Elsevier Inc. All rights reserved.

  18. Comprehensive Analysis of the Gas- and Particle-Phase Products of VOC Oxidation

    Science.gov (United States)

    Bakker-Arkema, J.; Ziemann, P. J.

    2017-12-01

    Controlled environmental chamber studies are important for determining atmospheric reaction mechanisms and gas and aerosol products formed in the oxidation of volatile organic compounds (VOCs). Such information is necessary for developing detailed chemical models for use in predicting the atmospheric fate of VOCs and also secondary organic aerosol (SOA) formation. However, complete characterization of atmospheric oxidation reactions, including gas- and particle-phase product yields, and reaction branching ratios, are difficult to achieve. In this work, we investigated the reactions of terminal and internal alkenes with OH radicals in the presence of NOx in an attempt to fully characterize the chemistry of these systems while minimizing and accounting for the inherent uncertainties associated with environmental chamber experiments. Gas-phase products (aldehydes formed by alkoxy radical decomposition) and particle-phase products (alkyl nitrates, β-hydroxynitrates, dihydroxynitrates, 1,4-hydroxynitrates, 1,4-hydroxycarbonyls, and dihydroxycarbonyls) formed through pathways involving addition of OH to the C=C double bond as well as H-atom abstraction were identified and quantified using a suite of analytical techniques. Particle-phase products were analyzed in real time with a thermal desorption particle beam mass spectrometer; and off-line by collection onto filters, extraction, and subsequent analysis of functional groups by derivatization-spectrophotometric methods developed in our lab. Derivatized products were also separated by liquid chromatography for molecular quantitation by UV absorbance and identification using chemical ionization-ion trap mass spectrometry. Gas phase aldehydes were analyzed off-line by collection onto Tenax and a 5-channel denuder with subsequent analysis by gas chromatography, or by collection onto DNPH-coated cartridges and subsequent analysis by liquid chromatography. The full product identification and quantitation, with careful

  19. Gas-Phase Oxidation of Aqueous Ethanol by Nanoparticle Vanadia/Anatase Catalysts

    DEFF Research Database (Denmark)

    Jørgensen, Betina; Kristensen, Steffen Buus; Kunov-Kruse, Andreas Jonas

    2009-01-01

    The gas-phase oxidation of aqueous ethanol with dioxygen has been examined with a new nanoparticle V2O5/TiO2 catalyst. Product selectivity could to a large extent be controlled by small alterations of reaction parameters, allowing production of acetaldehyde at a selectivity higher than 90%, near...

  20. Phase identification and internal stress analysis of steamside oxides on superheater tubes by means of X-ray diffraction

    Energy Technology Data Exchange (ETDEWEB)

    Pantleon, Karen; Montgomery, Melanie [Technical Univ. of Denmark, Lyngby (Denmark). Inst. of Manufacturing Engineering and Management

    2005-05-01

    For superheater tubes, the adherence of the inner steamside oxide is especially important as spallation of this oxide results in a) blockage of loops which cause insufficient steam flow through the superheaters and subsequently overheating and tube failure and b) spalled oxide can cause erosion of turbine blades. Oxide spallation is a serious problem for austenitic steels where the significant differences of the thermal expansion coefficients of steel and oxide cause relatively high thermal stresses. Usually, various oxides layered within the scale are suggested from microscopical observations of the morphology and/or topography of the oxide scale accompanied by the analysis of chemical elements present. Reports about the application of X-ray diffraction on the study of steamside oxide formation are very scarce in literature. If applied at all, XRD-studies are restricted to ideally flat samples oxidized under laboratory conditions, but relation to real operating conditions and the effect of the real sample geometry is missing. Within the frame of the project, steamside oxides on plant exposed components of ferritic/ martensitic X20CrMoV12-1 as well as fine- and coarse-grained austenitic TP347H were studied by means of X-ray diffraction. Depth dependent phase analysis on sample segments cut from the tubes was carried out by means of grazing incidence diffraction and, in order to obtain information from a larger depth, conventional XRD was combination with stepwise mechanical removal of the steamside oxides. After each removal step phase analysis was performed both on the segments and on the removed powders. Phase specific stress analysis was carried out on rings cut from the tube. Results show that steamside oxides on X20CrMoV12-1 consist of pure Hematite at the surface followed by a relatively thick layer of pure Magnetite. Both phases are under relatively high tensile stresses. While the phase composition of the Hematite layer appears to be the same for all

  1. Gas-phase advanced oxidation for effective, efficient in situ control of pollution

    DEFF Research Database (Denmark)

    Johnson, Matthew Stanley; Nilsson, Elna Johanna Kristina; Svensson, Erik Anders

    2014-01-01

    In this article, gas-phase advanced oxidation, a new method for pollution control building on the photo-oxidation and particle formation chemistry occurring in the atmosphere, is introduced and characterized. The process uses ozone and UV-C light to produce in situ radicals to oxidize pollution......, generating particles that are removed by a filter; ozone is removed using a MnO2 honeycomb catalyst. This combination of in situ processes removes a wide range of pollutants with a comparatively low specific energy input. Two proof-of-concept devices were built to test and optimize the process...... particulate mass. Secondary pollution including formaldehyde and ultrafine particles might be generated, depending on the composition of the primary pollution....

  2. Phase diagrams of Ca(Fe,Ru){sub 2}As{sub 2} system

    Energy Technology Data Exchange (ETDEWEB)

    Zhao, Kan; Gegenwart, Philipp [Experimentalphysik VI, Elektronische Korrelationen und Magnetismus, Institut fuer Physik, Universitaet Augsburg, D-86135 Augsburg (Germany)

    2015-07-01

    Single crystalline Ca(Fe,Ru){sub 2}As{sub 2} series have been grown and characterized by structural, magnetic, and transport measurements. These measurement shows Ca(Fe,Ru){sub 2}As{sub 2} undergoes successive phase transitions with increasing Ru element doping. The antiferromagnetic phase with orthorhombic structure at x<0.023 (x means the doping concentration of Ru element) is directly driven to a Fermi-liquid type collapsed tetragonal (cT) phase at 0.023phase, consistent with the conclusion of CaFe{sub 2}As{sub 2} under hydrostatic pressure.

  3. Structural phase transitions in Iron - based superconductors BaFe2-xCrxAs2 under high pressure

    International Nuclear Information System (INIS)

    Uhoya, W.O.; Montgomery, J.M.; Samudrala, G.K.; Tsoi, G.M.; Vohra, Y.K.; Sefar, A.S.

    2011-01-01

    Pure BaFe 2 As 2 with the ThCr 2 Si 2 -type crystal structure under ambient conditions is known to superconduct under high pressure and undergo an isostructural phase transition from tetragonal to collapsed tetragonal phase which is accompanied by anomalous compressibility effects. Presently, there is no reported work on the crystal structure on any of the chemically doped 122- iron based superconductors under high pressure. We have carried out the electrical resistance measurements and high pressure X-ray diffraction studies on Chromium doped samples of BaFe 2-x Cr x As 2 (x = 0, 0.05, 0.15, 0.4, 0.61) to a pressure of 75 GPa and a temperature of 10K using a synchrotron source and designer diamond anvils, so as to investigate the influence of chemical doping and high pressure on crystal structure and superconductivity

  4. US-UK Phase 3 Task 1 Oxidation in Supercritical Fluids

    Energy Technology Data Exchange (ETDEWEB)

    Holcomb, Gordon R. [National Energy Technology Lab. (NETL), Albany, OR (United States)

    2017-03-20

    A presentation of the US-UK Phase 3 Task 1 Oxidation in Supercritical Fluids. Includes slides on Supercritical Steam, sCO2 Power Cycles – Indirect, sCO2 Power Cycles – Direct, Experimental Exposures, Alloys, Why Si, Results—Ni-xCr Alloys (5-24Cr), Fatigue Crack Growth$-$Experiment, and Alloys and Samples, Fatigue Crack Growth—Results (H282).

  5. Low Friction in CuO-Doped Yttria-Stabilized Tetragonal Zirconia Ceramics: A Complementary Macro- and Nanotribology Study

    NARCIS (Netherlands)

    Tocha, E.; Pasaribu, H.R.; Schipper, Dirk J.; Schönherr, Holger; Vancso, Gyula J.

    2008-01-01

    The tribological behavior of CuO-doped yttria-stabilized tetragonal zirconia (3Y-TZP) ceramics in the absence of additional lubricants was characterized by macroscale pin-on-disk measurements and nanoscale atomic force microscopy (AFM) for a broad range of velocities. The previously observed low

  6. Nanoscale Phase Stability Reversal During the Nucleation and Growth of Titanium Oxide Minerals

    Science.gov (United States)

    Hummmer, D. R.; Heaney, P. J.; Kubicki, J. D.; Kent, P. R.; Post, J. E.

    2008-12-01

    Fine-grained titanium oxide minerals are important in soils, where they affect a variety of geochemical processes. They are also industrially important as catalysts, pigments, food additives, and dielectrics. Recent research has indicated an apparent reversal of thermodynamic stability between TiO2 phases at the nanoscale thought to be caused by an increased contribution of surface energy to the total free energy. Time-resolved X-ray diffraction (XRD) experiments in which titanium oxides crystallize from aqueous TiCl4 solutions confirm that anatase, a metastable phase, is always the first phase to nucleate under our range of initial conditions. Rutile peaks are observed only minutes after the first appearance of anatase, after which anatase abundance slowly decreases while rutile continues to form. Whole pattern refinement of diffraction data reveals that lattice constants of both phases increase throughout the crystallization process. In addition, transmission electron microscope (TEM) observations and kinetic modeling indicate that anatase does not undergo a solid-state transformation to the rutile structure as once thought. Instead, anatase appears to re-dissolve and then feed the growth of already nucleated rutile nanocrystals. Density functional theory (DFT) calculations were employed to model 1, 2, and 3 nm particles of both mineral phases. The total surface energies calculated from these models did yield lower values for anatase than for rutile by 8-13 kJ/mol depending on particle size, indicating that surface free energy is sufficient to account for stability reversal. However, these whole-particle surface energies were much higher than the sum of energies of each particle's constituent crystallographic surfaces. We attribute the excess energy to defects associated with the edges and corners of nanoparticles, which are not present on a 2-D periodic surface. This previously unreported edge and corner energy may play a dominant role in the stability reversal

  7. Titanium dioxide-coated fluorine-doped tin oxide thin films for improving overall photoelectric property

    International Nuclear Information System (INIS)

    Li, Bao-jia; Huang, Li-jing; Ren, Nai-fei; Zhou, Ming

    2014-01-01

    Titanium (Ti) layers were deposited by direct current (DC) magnetron sputtering on commercial fluorine-doped tin oxide (FTO) glasses, followed by simultaneous oxidation and annealing treatment in a tubular furnace to prepare titanium dioxide (TiO 2 )/FTO bilayer films. Large and densely arranged grains were observed on all TiO 2 /FTO bilayer films. The presence of TiO 2 tetragonal rutile phase in the TiO 2 /FTO bilayer films was confirmed by X-ray diffraction (XRD) analysis. The results of parameter optimization indicated that the TiO 2 /FTO bilayer film, which was formed by adopting a temperature of 400 °C and an oxygen flow rate of 15 sccm, had the optimal overall photoelectric property with a figure of merit of 2.30 × 10 −2 Ω −1 , higher than 1.78 × 10 −2 Ω −1 for the FTO single-layer film. After coating a 500 nm-thick AZO layer by DC magnetron sputtering on this TiO 2 /FTO bilayer film, the figure of merit of the trilayer film achieved to a higher figure of merit of 3.12 × 10 −2 Ω −1 , indicating further improvement of the overall photoelectric property. This work may provide a scientific basis and reference for improving overall photoelectric property of transparent conducting oxide (TCO) films.

  8. Solid-state phase transitions in CuCl under hydrostatic pressures to 12.8 GPa

    International Nuclear Information System (INIS)

    Liebenberg, D.H.; Mills, R.L.; Huang, C.Y.; Olsen, C.; Schmidt, L.C.

    1981-01-01

    The phase transitions in solid CuCl under hydrostatic conditions at pressures to 12.8 GPa are examined. The transition at 4.4 GPa from zinc-blende to tetragonal is observed. Our negative observations for the upper transition at 8.2 GPa and for the formation of an opaque phase due to the disproportionation reaction support the contention that pressure gradients are important in affecting the behavior of pure CuCl

  9. Powder-metallurgy superalloy strengthened by a secondary gamma phase.

    Science.gov (United States)

    Kotval, P. S.

    1971-01-01

    Description of experiments in which prealloyed powders of superalloy compositions were consolidated by extrusion after the strengthening by precipitation of a body-centered tetragonal gamma secondary Ni3 Ta phase. Thin foil electron microscopy showed that the mechanical properties of the resultant powder-metallurgy product were correlated with its microstructure. The product exhibited high strength at 1200 F without loss of ductility, after thermomechanical treatment and aging.

  10. Spray deposited gallium doped tin oxide thinfilm for acetone sensor application

    Science.gov (United States)

    Preethi, M. S.; Bharath, S. P.; Bangera, Kasturi V.

    2018-04-01

    Undoped and gallium doped (1 at.%, 2 at.% and 3 at.%) tin oxide thin films were prepared using spray pyrolysis technique by optimising the deposition conditions such as precursor concentration, substrate temperature and spraying rate. X-ray diffraction analysis revealed formation of tetragonally structured polycrystalline films. The SEM micrographs of Ga doped films showed microstructures. The electrical resistivity of the doped films was found to be more than that of the undoped films. The Ga-doped tin oxide thin films were characterised for gas sensors. 1 at.% Ga doped thin films were found to be better acetone gas sensor, showed 68% sensitivity at 350°C temperature.

  11. Electrochemical Energy Storage Applications of CVD Grown Niobium Oxide Thin Films.

    Science.gov (United States)

    Fiz, Raquel; Appel, Linus; Gutiérrez-Pardo, Antonio; Ramírez-Rico, Joaquín; Mathur, Sanjay

    2016-08-24

    We report here on the controlled synthesis, characterization, and electrochemical properties of different polymorphs of niobium pentoxide grown by CVD of new single-source precursors. Nb2O5 films deposited at different temperatures showed systematic phase evolution from low-temperature tetragonal (TT-Nb2O5, T-Nb2O5) to high temperature monoclinic modifications (H-Nb2O5). Optimization of the precursor flux and substrate temperature enabled phase-selective growth of Nb2O5 nanorods and films on conductive mesoporous biomorphic carbon matrices (BioC). Nb2O5 thin films deposited on monolithic BioC scaffolds produced composite materials integrating the high surface area and conductivity of the carbonaceous matrix with the intrinsically high capacitance of nanostructured niobium oxide. Heterojunctions in Nb2O5/BioC composites were found to be beneficial in electrochemical capacitance. Electrochemical characterization of Nb2O5/BioC composites showed that small amounts of Nb2O5 (as low as 5%) in conjunction with BioCarbon resulted in a 7-fold increase in the electrode capacitance, from 15 to 104 F g(-1), while imparting good cycling stability, making these materials ideally suited for electrochemical energy storage applications.

  12. TEMPERATURE TRENDS OF THE PERMITTIVITY IN COMPLEX OXIDES OF RARE-EARTH ELEMENTS WITH PEROVSKITE-TYPE STRUCTURE

    Directory of Open Access Journals (Sweden)

    A.G.Belous

    2003-01-01

    Full Text Available Ceramic materials based on complex oxides with both the perovskite structure (Ln2/3Nb2O6 and the structure of tetragonal tungsten bronze (Ba6-xLn8+2x/3Ti18O54 have been investigated over a wide frequency and temperature ranges. The results obtained for certain structures denote the presence of the temperature anomalies of dielectric parameters (ε, tanδ. These anomalies occur over the wide frequency range including submilimeter (SMM wavelength range, and are related neither with the processing peculiarities nor with the presence of the phase transitions. Temperature behavior of the permittivity has been considered in terms of the polarization mechanism based on the elastic-strain lattice oscillations. It has been assumed that the observed anomalies could be ascribed to a superposition of harmonic and anharmonic contribution to lattice oscillations that determines τε sign and magnitude.

  13. Kinetics and mechanism of the selective oxidation of primary aliphatic alcohols under phase transfer catalysis

    Directory of Open Access Journals (Sweden)

    K. Bijudas

    2014-03-01

    Full Text Available Kinetics of the oxidation of primary aliphatic alcohols has been carried out using phase transferred monochromate in benzene. Tetrabutylammonium bromide (TBAB and tetrabutylphosphonium bromide (TBPB are used as phase transfer catalysts (PT catalyst. The reaction shows first order dependence on both [alcohol] and [monochromate ion]. The oxidation leads to the formation of corresponding aldehyde and no traces of carboxylic acid has been detected. The reaction mixture failed to induce the polymerization of added acrylonitrile which rules out the presence radical intermediates in the reaction. Various thermodynamic parameters have been evaluated and a suitable mechanism has been proposed.

  14. Deep desulfurization of diesel via peroxide oxidation using phosphotungstic acid as phase transfer catalyst

    Energy Technology Data Exchange (ETDEWEB)

    Sachdeva, T.O.; Pant, K.K. [Department of Chemical Engineering, Indian Institute of Technology, Delhi, New Delhi, 110016 (India)

    2010-09-15

    High sulfur level in diesel fuel has been identified as a major contributor to air pollutant in term of sulfur dioxide (SO{sub x}) through diesel fueled vehicles. The main aim of the present work is to develop a promising methodology for ultra deep desulfurization of diesel fuel using oxidation followed by phase transfer of oxidized sulfur. Experiments were carried out in a batch reactor using n-decane as the model diesel compound and also using commercial diesel feedstock. To remove sulfur tetraoctylammonium bromide, phosphotungstic acid, and hydrogen peroxide were used as phase transfer agent, catalyst and oxidant respectively. The percent sulfur removal increases with increasing the initial concentration of sulfur in fuel and with increasing the reaction temperature. Similar trends were observed when commercial diesel was used to carry out desulfurization studies. The amphiphilic catalyst serves as a catalyst and also as an emulsifying agent to stabilize the emulsion droplets. The effects of temperature, agitation speed, quantity of catalyst and the phase transfer agent were studied to estimate the optimal conditions for the reactions. The sulfur removal from a commercial diesel by phase transfer catalysis has been found effective and removal efficiency was more than 98%. Kinetic experiments carried out for the desulfurization revealed that the sulfur removal results are best fitted to a pseudo first order kinetics and the apparent activation energy of desulfurization was 30.6 kJ/mol. (author)

  15. Deep desulfurization of diesel via peroxide oxidation using phosphotungstic acid as phase transfer catalyst

    International Nuclear Information System (INIS)

    Sachdeva, T.O.; Pant, K.K.

    2010-01-01

    High sulfur level in diesel fuel has been identified as a major contributor to air pollutant in term of sulfur dioxide (SO x ) through diesel fueled vehicles. The main aim of the present work is to develop a promising methodology for ultra deep desulfurization of diesel fuel using oxidation followed by phase transfer of oxidized sulfur. Experiments were carried out in a batch reactor using n-decane as the model diesel compound and also using commercial diesel feedstock. To remove sulfur tetraoctylammonium bromide, phosphotungstic acid, and hydrogen peroxide were used as phase transfer agent, catalyst and oxidant respectively. The percent sulfur removal increases with increasing the initial concentration of sulfur in fuel and with increasing the reaction temperature. Similar trends were observed when commercial diesel was used to carry out desulfurization studies. The amphiphilic catalyst serves as a catalyst and also as an emulsifying agent to stabilize the emulsion droplets. The effects of temperature, agitation speed, quantity of catalyst and the phase transfer agent were studied to estimate the optimal conditions for the reactions. The sulfur removal from a commercial diesel by phase transfer catalysis has been found effective and removal efficiency was more than 98%. Kinetic experiments carried out for the desulfurization revealed that the sulfur removal results are best fitted to a pseudo first order kinetics and the apparent activation energy of desulfurization was 30.6 kJ/mol. (author)

  16. Investigation of phase stability and oxide ion performance in new perovskite-type bismuth vanadate

    International Nuclear Information System (INIS)

    Al-Alas, Ahlam; Beg, Saba; Al-Areqi, Niyazi A.S.

    2012-01-01

    Samples of the BICDVOX system, formulated as Bi 4 Cd x V 2−x O 11−(3x/2)−δ in the Cd substitution range 0 ≤ x ≤ 0.25 were synthesized using the standard solid state reaction.The correlation between phase stability and oxide ion performance were investigated by variable temperature XRPD, DSC and AC impedance spectroscopy. The substitution of V 5+ by Cd 2+ exhibited different phase transitions upon varying composition. For compositions with x ≤ 0.05, two successive transitions; α↔β↔γ are evident, while the β↔γ transition exists in the composition range 0.05 4+ → V 5+ re–oxidation results in increased defect trapping effects in the system at higher temperatures. -- Highlights: ► γ-Stabilized BICDVOX at lower dopant concentrations. ► Good oxide-ion conductivity at lower temperatures. ► High temperature-vanadium reduction with lower dopant concentrations.

  17. Evidence of an Intermediate Phase in bulk alloy oxide glass sysem

    Science.gov (United States)

    Chakraborty, S.; Boolchand, P.

    2011-03-01

    Reversibility windows have been observed in modified oxides (alkali-silicates and -germanates) and identified with Intermediate Phases(IPs). Here we find preliminary evidence of an IP in a ternary oxide glass, (B2 O3)5 (Te O2)95-x (V2O5)x , which is composed of network formers. Bulk glasses are synthesized across the 18% x 35 % composition range, and examined in Raman scattering, modulated DSC and molar volume experiments. Glass transition temperatures Tg (x) steadily decrease with V2O5 content x, and reveal the enthalpy of relaxation at Tg to show a global minimum in the 24% x < 27 range, the reversibility window (IP). Molar volumes reveal a minimum in this window. Raman scattering reveals a Boson mode, and at least six other vibrational bands in the 100cm-1 < ν < 1700cm-1 range. Compositional trends in vibrational mode strengths and frequency are established. These results will be presented in relation to glass structure evolution with vanadia content and the underlying elastic phases. Supported by NSF grant DMR 08-53957.

  18. Structural phase transition of BaZrO3 under high pressure

    International Nuclear Information System (INIS)

    Yang, Xue; Li, Quanjun; Liu, Ran; Liu, Bo; Zhang, Huafang; Jiang, Shuqing; Zou, Bo; Cui, Tian; Liu, Bingbing; Liu, Jing

    2014-01-01

    We studied the phase transition behavior of cubic BaZrO 3 perovskite by in situ high pressure synchrotron X-ray diffraction experiments up to 46.4 GPa at room temperature. The phase transition from cubic phase to tetragonal phase was observed in BaZrO 3 for the first time, which takes place at 17.2 GPa. A bulk modulus 189 (26) GPa for cubic BaZrO 3 is derived from the pressure–volume data. Upon decompression, the high pressure phase transforms into the initial cubic phase. It is suggested that the unstable phonon mode caused by the rotation of oxygen octahedra plays a crucial role in the high pressure phase transition behavior of BaZrO 3

  19. Ionoluminscence of partially-stabilized zirconia for thermal barrier coatings

    International Nuclear Information System (INIS)

    Rebollo, N.R.; Ruvalcaba-Sil, J.L.; Miranda, J.

    2007-01-01

    Ionoluminescence is explored as an alternative technique to study the high temperature phase stability of zirconia-based oxides. The evolution of an initially metastable single tetragonal phase towards de-stabilization is investigated for three single-doped zirconia compositions with Y, Yb and Gd. The differences in de-stabilization paths are identified using X-ray diffraction and ionoluminescence; elemental analysis is also performed using particle-induced X-ray emission. X-ray diffraction studies reveal a different scenario for each of the compositions selected; the differences are strongly influenced by the thermodynamic driving forces associated to the fluorite-to-tetragonal displacive transformation. Ionoluminescence studies indicate a significant increment on the signal intensity for de-stabilized samples, relative to previous annealing stages. There are also more subtle differences in the luminescent response from the samples at intermediate annealing stages also related to phase changes. This study provides a basis to characterize phase evolution in single-doped zirconia compositions for thermal insulation applications using luminescence

  20. In situ X-ray diffraction study of the electrochemical reaction on lead electrodes in sulphate electrolytes

    International Nuclear Information System (INIS)

    Angerer, P.; Mann, R.; Gavrilovic, A.; Nauer, G.E.

    2009-01-01

    The anodic oxidation of pure lead in two acidic sulphate electrolytes with identical ionic strength (pH ∼ 0 and pH ∼ -0.1) was studied by in situ grazing incidence X-ray diffraction method (GIXD). Crystalline products such as lead sulphate (anglesite, PbSO 4 , orthorhombic), α- and β-lead dioxide (α-PbO 2 , orthorhombic, and β-PbO 2 , tetragonal), and tribasic lead sulphate hydrate with the stoichiometric composition 3PbO.PbSO 4 .H 2 O (triclinic) were detected at defined potentials. A method for the semi-quantitative determination of the thickness of the deposited layer from diffraction data is described. After the in situ measurement, the washed and dried working electrodes were additionally characterized ex situ by GIXD measurements at different angles of incidence. The phase litharge (lead oxide, t-PbO, tetragonal) and lead sulphate were observed at the surface of the lead substrate. The quantitative evaluation of the diffraction intensity of this measurement series enables the modelling of a qualitative depth profile of the layer generated during the electrochemical treatment. The anglesite phase is located in the uppermost layer, while the litharge phase was detected closer to the lead substrate

  1. Synthesis and structural and thermodynamical characterization of hollandite type material intended for the specific containment of cesium; Synthese et caracterisation de ceramiques de type hollandite destinees au conditionnement specifique du cecium

    Energy Technology Data Exchange (ETDEWEB)

    Leinekugel-Le-Cocq-Errien, A.Y

    2005-09-15

    This thesis deals with the characterization of the Ba{sub 1}Cs{sub 0.28}Fe{sub 0.82}Al{sub 1.46}Ti{sub 5.72}O{sub 16} hollandite envisaged for Cs containment. Techniques used are essentially classical powder XRD or synchrotron radiation at the absorption threshold of Ba and Cs, TEM and high-temperature calorimetry. Two syntheses have been studied: an alcoxide route and a dry route. After sintering, both routes lead to an incommensurate modulated tetragonal hollandite structure (space group: I4/m(00{gamma})00) with a modulation vector distribution. Before sintering, the material obtained by the alcoxide route is composed of three phases: a tetragonal hollandite like above, a monoclinic Ba-free hollandite and a weak-coherence-length phase containing only Ba. On contrary, the dry route already leads to the tetragonal hollandite at this step of the synthesis. High temperature oxide melt solution calorimetry was used to derive standard enthalpy of formation of hollandite to deduce its free enthalpy of formation. (author)

  2. Reverse martensitic transformation in alumina-15 vol% zirconia nanostructured powder synthesized by high energy ball milling

    Energy Technology Data Exchange (ETDEWEB)

    Maneshian, M.H. [Department of Materials Science and Engineering, Sharif University of Technology, Azadi Avenue, P.O. Box 11365-9466, Tehran (Iran, Islamic Republic of)], E-mail: mh_maneshian@yahoo.com; Banerjee, M.K. [National Institute of Foundry and Forge Technology, Hatia, Ranchi 834003 (India)

    2008-07-14

    In the present work, three alumina-15 vol% zirconia composites with Y{sub 2}O{sub 3}, MgO as dopants and without oxide as dopant have been investigated. High energy ball milling (HEBM) provides the positive thermodynamic driving force for monoclinic to tetragonal transformation and it reduces starting temperature for the reverse martensitic transformation, meanwhile mobility of zirconium cations and oxygen anions are enhanced in zirconia by HEBM. The general, albeit heuristic, reasoning is corroborated by nanocrystallity, particle size and also the retained monoclinic seem to play an important role. After 10 h HEBM, approximately 28% zirconia tetragonal phase is achieved. Non-stoichiometric tetragonal zirconia phase; Zr{sub 0.95}O{sub 2} is seen to have been achieved by high energy ball milling (HEBM). The structural and compositional evolutions during HEBM have been investigated using X-ray diffraction method (XRD) and scanning electron microscopy (SEM). High resolution transmission electron microscope (TEM) is also used for further understanding about the phenomenological changes taking place during high energy ball milling.

  3. Phase transformation, oxidation and shape memory properties of Ti–50Au–10Zr alloy for high temperature applications

    International Nuclear Information System (INIS)

    Wadood, A.; Hosoda, H.; Yamabe-Mitarai, Y.

    2014-01-01

    Highlights: • Ti–50Au–10Zr exhibited better thermo-mechanical and shape memory properties than Ti–50Au. • Improvement was related to solid solution and precipitation strengthening. • No oxidation problem as oxidation was observed at 100 K higher than A f . • TMA was used not only for thermo-mechanical but also for shape memory and oxidation. - Abstract: In this study, we investigated the phase transformation, oxidation and high temperature mechanical and shape memory properties of Ti–50Au–10Zr (all compositions in atomic%) alloy. Thermo-mechanical analyzer (TMA) was used not only for phase transformation but also for the measurement of shape memory effect and oxidation behavior in air environment. Ti–50Au–10Zr exhibited lower martensitic transformation temperature of 758 K than TiAu stoichiometric alloy exhibiting 870 K since Zr addition stabilizes B2 parent phase. Oxidation was initiated at 873 K that was about 100 K higher than the austenite finish temperature, indicating no such oxidation problems for practical use. Shape memory effect was improved by partial substitution of Ti with Zr in Ti–50Au–10Zr alloy. Compression test of Ti–50Au–10Zr revealed high compressive strength of 1239 MPa of martensite at 691 K (=M f − 50 K) and 924 MPa of B2 parent phase at 834 K (=A f + 50 K) in comparison with Ti–50Au. It is concluded that Zr is effective to improve the mechanical and shape memory properties of TiAu alloy, and that Ti–50Au–10Zr shape memory alloy has potential for high temperature (∼650–850 K) practical applications

  4. Pulsed cathodoluminescence of nanoscale aluminum oxide with different phase compositions

    International Nuclear Information System (INIS)

    Kortov, V.S.; Zvonarev, S.V.; Medvedev, A.I.

    2011-01-01

    The methods of pulsed cathodoluminescence have been used to study compacted powders and ceramics containing different phases of aluminum oxide. An intensive luminescence of the samples under study in the visible, NIR, and UV regions of the spectrum has been found. The luminescence bands are very broad and include a few components. The number of the bands depends on the phase composition of the samples. The oxygen vacancies, which capture one or two electrons, produce luminescence centers in the near UV region. The most probable in the visible region is the luminescence of aggregate defects, impurities, and surface centers. - Highlights: → We investigate pulsed cathodoluminescence spectra of nanoscale alumina. → We found the intensive luminescence in the visible, NIR, and UV regions. → The transformation of R-line structure depends on phase composition of alumina. → We substantiate the relation of luminescence bands with concrete centers.

  5. Anomalous magnetoelastic behaviour near morphotropic phase boundary in ferromagnetic Tb{sub 1-x}Nd{sub x}Co{sub 2} system

    Energy Technology Data Exchange (ETDEWEB)

    Murtaza, Adil; Yang, Sen, E-mail: yang.sen@mail.xjtu.edu.cn; Zhou, Chao; Chang, Tieyan; Chen, Kaiyun; Tian, Fanghua; Song, Xiaoping [School of Science, MOE Key Laboratory for Nonequilibrium Synthesis and Modulation of Condensed Matter, State Key Laboratory for Mechanical Behaviour of Materials, Xi' an Jiaotong University, Xi' an 710049 (China); Suchomel, Matthrew R.; Ren, Y. [X-Ray Science Division, Argonne National Laboratory, Argonne, Illinois 60439 (United States)

    2016-08-01

    In this work, we report a morphotropic phase boundary (MPB) involved ferromagnetic system Tb{sub 1-x}Nd{sub x}Co{sub 2} and reveal the corresponding structural and magnetoelastic properties of this system. With high resolution synchrotron X-ray diffractometry, the crystal structure of the TbCo{sub 2}-rich side is detected to be rhombohedral and that of NdCo{sub 2}-rich side is tetragonal below their respective Curie temperatures T{sub C}. The MPB composition Tb{sub 0.35}Nd{sub 0.65}Co{sub 2} corresponds to the coexistence of the rhombohedral phase (R-phase) and tetragonal phase (T-phase). Contrary to previously reported MPB involved ferromagnetic systems, the MPB composition of Tb{sub 0.35}Nd{sub 0.65}Co{sub 2} shows minimum magnetization which can be understood as compensation of sublattice moments between the R-phase and the T-phase. Furthermore, magnetostriction of Tb{sub 1-x}Nd{sub x}Co{sub 2} decreases with increasing Nd concentration until x = 0.8 and then increases in the negative direction with further increasing Nd concentration; the optimum point for magnetoelastic properties lies towards the rhombohedral phase. Our work not only shows an anomalous type of ferromagnetic MPB but also provides an effective way to design functional materials.

  6. Photodegradation of polycyclic aromatic hydrocarbon pyrene by iron oxide in solid phase

    International Nuclear Information System (INIS)

    Wang, Y.; Liu, C.S.; Li, F.B.; Liu, C.P.; Liang, J.B.

    2009-01-01

    To better understand the photodegradation of polycyclic aromatic hydrocarbons (PAH) in solid phase in natural environment, laboratory experiments were conducted to study the influencing factors, kinetics and intermediate compound of pyrene photodegradation by iron oxides. The results showed that the pyrene photodegradation rate followed the order of α-FeOOH > α-Fe 2 O 3 > γ-Fe 2 O 3 > γ-FeOOH at the same reaction conditions. Lower dosage of α-FeOOH and higher light intensity increased the photodegradation rate of pyrene. Iron oxides and oxalic acid can set up a photo-Fenton-like system without additional H 2 O 2 in solid phase to enhance the photodegradation of pyrene under UV irradiation. All reaction followed the first-order reaction kinetics. The half-life (t 1/2 ) of pyrene in the system showed the higher efficiencies of using iron oxide as photocatalyst to degrade pyrene. Intermediate compound pyreno was found during photodegradation reactions by gas chromatography-mass spectrometry (GC-MS). The photodegradation efficiency for PAHs in this photo-Fenton-like system was also confirmed by using the contaminated soil samples. This work provides some useful information to understand the remediation of PAHs contaminated soils by photochemical techniques under practical condition

  7. Phase equilibria, crystal structure and oxygen content of intermediate phases in the Y-Ba-Co-O system

    OpenAIRE

    Urusova, A. S.; Cherepanov, V. A.; Aksenova, T. V.; Gavrilova, L. Y.; Kiselev, E. A.

    2013-01-01

    The phase equilibria in the Y-Ba-Co-O system were systematically studied at 1373 K in air. The intermediate phases formed in the Y-Ba-Co-O system at 1373 K in air were: YBaCo2O5+δ, YBaCo4O 7 and BaCo1-yYyO3-δ (0.09≤y≤0.42). It was shown that YBaCo2O5+δ possesses tetragonal structure with the 3ap×3a p×2ap superstructure (sp. gr. P4/mmm). High-temperature X-ray diffraction analysis of the YBaCo2O 5+δ in the temperature range from 298 K up to 1073 K under Po2=0.21 atm has not shown any phase tra...

  8. Study of glass-nanocomposite and glass-ceramic containing ferroelectric phase

    Energy Technology Data Exchange (ETDEWEB)

    Abdel-Khalek, E.K., E-mail: Eid_khalaf0@yahoo.com [Department of Physics, Faculty of Science, Al Azhar University, Nasr City 11884, Cairo (Egypt); Mohamed, E.A. [Department of Physics, Faculty of Science (Girl' s Branch), Al Azhar University, Nasr City, Cairo (Egypt); Salem, Shaaban M.; Ebrahim, F.M.; Kashif, I. [Department of Physics, Faculty of Science, Al Azhar University, Nasr City 11884, Cairo (Egypt)

    2012-03-15

    Highlights: Black-Right-Pointing-Pointer Glass nanocomposites was synthesized. Black-Right-Pointing-Pointer Glass nanocomposites exhibit both optical transmission bands at 598 and 660 nm and broad dielectric anomalies. Black-Right-Pointing-Pointer The ferroelectricity in pure single-phase oxide glass has not yet been discovered. - Abstract: Transparent glass nanocomposite in the pseudo binary system (100 - x) Li{sub 2}B{sub 4}O{sub 7}-xBaTiO{sub 3} with x = 0 and 60 (in mol%) were prepared. Amorphous and glassy characteristics of the as-prepared samples were established via X-ray powder diffraction (XRD) and differential scanning calorimetry (DSC) respectively. The precipitated BaTiO{sub 3} nanocrystal phase embedded in the glass sample at x = 60 mol% was identified by transmission electron microscopic (TEM). The optical transmission bands at 598 and 660 nm were assigned to Ti{sup 3+} ions in tetragonal distorted octahedral sites. The precipitated Li{sub 2}B{sub 4}O{sub 7}, BaTi(BO{sub 3}){sub 2} and BaTiO{sub 3} nanocrystallites phases with heat-treatment at 923 K for 6 h (HT923) in glass-ceramic were identified by XRD, TEM and infrared absorption spectroscopy. The as-prepared at x = 60 mol% and the HT923 samples exhibit broad dielectric anomalies in the vicinity of the ferroelectric-to-paraelectric transition temperature. The results demonstrate that the method presented may be an effective way to fabricate ferroelectric host and development of multifunctional ferroelectrics.

  9. Pressure-induced structural phase transition and elastic properties in rare earth CeBi and LaBi

    International Nuclear Information System (INIS)

    Mankad, Venu; Gupta, Sanjay D.; Gupta, Sanjeev K.; Jha, Prafulla

    2011-01-01

    Pressure is one of the external parameters by which the interplay of the f-electrons with the normal conduction electrons may be varied. At ambient conditions the rare-earth compounds are characterized by a fixed f n configuration of atomic-like f-electrons, but the decreased lattice spacing resulting from the application of pressure eventually leads to the destabilization of the f-shell. The theoretical description of this electronic transition remains a challenge. The present study reports a comprehensive study on structural, electronic band structures, elastic and lattice dynamical properties of rare earth monopnictides CeBi and LaBi using first principles density functional calculations within the pseudopotential approximation. Both compounds possess NaCI (B1) structure at ambient pressure and transform either to CsCI or body centered tetragonal (BCT) structure. Our results concerning equilibrium lattice parameter and bulk modulus agree well with the available experimental and previous theoretical data. The volume change at the crystallographic transition is attributed to a decrease of the cerium valence or a lowering of the p-f hybridization due to the larger interatomic distances in both high pressure phases. The equation of state for rare earth bismuth compounds are calculated and compared with available experimental results. From the total energy and relative volume one can clearly see the relative stabilities of the high pressure phases of both compounds. As the primitive tetragonal phase of both compounds. As the primitive tetragonal phase can be viewed as a CsCl structure, one may think of a transition from B1 to B2. We have also calculated band structure for both phase and here we have presented for B1 case. The narrow bands originating above the Fermi level are mainly due to Ce 'f'-like states, and the major contribution to the density of states is mainly from Ce 'd'-like states. Furthermore, in high-pressure CsCI phase, there is an appreciable

  10. Use of gas-phase ethanol to mitigate extreme UV/water oxidation of extreme UV optics

    Science.gov (United States)

    Klebanoff, L. E.; Malinowski, M. E.; Clift, W. M.; Steinhaus, C.; Grunow, P.

    2004-03-01

    A technique is described that uses a gas-phase species to mitigate the oxidation of a Mo/Si multilayer optic caused by either extreme UV (EUV) or electron-induced dissociation of adsorbed water vapor. It is found that introduction of ethanol (EtOH) into a water-rich gas-phase environment inhibits oxidation of the outermost Si layer of the Mo/Si EUV reflective coating. Auger electron spectroscopy, sputter Auger depth profiling, EUV reflectivity, and photocurrent measurements are presented that reveal the EUV/water- and electron/water-derived optic oxidation can be suppressed at the water partial pressures used in the tests (~2×10-7-2×10-5 Torr). The ethanol appears to function differently in two time regimes. At early times, ethanol decomposes on the optic surface, providing reactive carbon atoms that scavenge reactive oxygen atoms before they can oxidize the outermost Si layer. At later times, the reactive carbon atoms form a thin (~5 Å), possibly self-limited, graphitic layer that inhibits water adsorption on the optic surface. .

  11. Room temperature chemically oxidized La2CuO4+y: Phase separation induced by thermal treatment

    DEFF Research Database (Denmark)

    Rial,C.; Moran, E.; Alario-Franco, M.A.

    1997-01-01

    The structure of roam temperature chemically oxidized La2CuO4+y [y = 0.103(4)] has been refined from powder neutron diffraction data using the space group Bmab. The modifications induced in the CuO2 and the LaO planes by the insertion of oxygen are consistent with the high T-c measured for this m......The structure of roam temperature chemically oxidized La2CuO4+y [y = 0.103(4)] has been refined from powder neutron diffraction data using the space group Bmab. The modifications induced in the CuO2 and the LaO planes by the insertion of oxygen are consistent with the high T-c measured...... a short treatment at 433 K, La2CuO4.103(4) undergoes a phase separation into two phases: phase 1, with estimated y(1) = 0.086(4) and T-cl = 30 K, and phase 2, with estimated y(2) = 0.12(1) and T-c2 = 17 K. By increasing the annealing times, phase 2 transforms to phase I and finally disappears. Therefore...

  12. First-principles study on the phase transition, elastic properties and electronic structure of Pt3Al alloys under high pressure

    International Nuclear Information System (INIS)

    Liu, Yanjun; Huang, Huawei; Pan, Yong; Zhao, Guanghui; Liang, Zheng

    2014-01-01

    Highlights: • The phase transition of Pt 3 Al alloys occurs at 60 GPa. • The elastic modulus of Pt 3 Al alloys increase with increasing pressure. • The cubic structure has good resistance to volume deformation under high pressure. • The pressure enhances the hybridization between Pt atom and Al atom. - Abstract: The phase transition, formation enthalpies, elastic properties and electronic structure of Pt 3 Al alloys are studied using first-principle approach. The calculated results show that the pressure leads to phase transition from tetragonal structure to cubic structure at 60 GPa. With increasing pressure, the elastic constants, bulk modulus and shear modulus of these Pt 3 Al alloys increase linearly and the bond lengths of Pt–Al metallic bonds and the peak at E F decrease. The cubic Pt 3 Al alloy has excellent resistance to volume deformation under high pressure. We suggest that the phase transition is derived from the hybridization between Pt and Al atoms for cubic structure is stronger than that of tetragonal structure and forms the strong Pt–Al metallic bonds under high pressure

  13. Enhanced Cr(VI) reduction and As(III) oxidation in ice phase: Important role of dissolved organic matter from biochar

    Energy Technology Data Exchange (ETDEWEB)

    Dong, Xiaoling [Department of Soil and Water Science, University of Florida, Gainesville, FL 32611 (United States); Ma, Lena Q., E-mail: lqma@ufl.edu [State Key Laboratory of Pollution Control and Resource Reuse, School of the Environment, Nanjing University, Jiangsu 210046 (China); Department of Soil and Water Science, University of Florida, Gainesville, FL 32611 (United States); Gress, Julia; Harris, Willie [Department of Soil and Water Science, University of Florida, Gainesville, FL 32611 (United States); Li, Yuncong [Soil and Water Science Department, Tropical Research and Education Center, University of Florida, Homestead, FL 33031-3314 (United States)

    2014-02-01

    Graphical abstract: - Highlights: • Biochar-derived dissolved organic matter (DOM) effectively reduced Cr(VI) and oxidized As(III). • Cr(VI) and As(III) could serve as a redox couple. • Cr(VI) and As(III) redox conversion was more effective in the ice phase than aqueous phase. • FTIR and ESR showed that biochar DOM served as both electron donor and acceptor. - Abstract: This study evaluated the impact of DOM from two biochars (sugar beet tailing and Brazilian pepper) on Cr(VI) reduction and As(III) oxidation in both ice and aqueous phases with a soil DOM as control. Increasing DOM concentration from 3 to 300 mg C L{sup −1} enhanced Cr(VI) reduction from 20% to 100% and As(III) oxidation from 6.2% to 25%; however, Cr(VI) reduction decreased from 80–86% to negligible while As(III) oxidation increased from negligible to 18–19% with increasing pH from 2 to 10. Electron spin resonance study suggested semiquinone radicals in DOM were involved in As(III) oxidation while Fourier transform infrared analysis suggested that carboxylic groups in DOM participated in both Cr(VI) reduction and As(III) oxidation. During Cr(VI) reduction, part of DOM (∼10%) was oxidized to CO{sub 2}. The enhanced conversion of Cr(VI) and As(III) in the ice phase was due to the freeze concentration effect with elevated concentrations of electron donors and electron acceptors in the grain boundary. Though DOM enhanced both Cr(VI) reduction and As(III)oxidation, Cr(VI) reduction coupled with As(III) oxidation occurred in absence of DOM. The role of DOM, Cr(VI) and/or As(III) in Cr and As transformation may provide new insights into their speciation and toxicity in cold regions.

  14. Role of temperature and energy density in the pulsed laser deposition of zirconium oxide thin film

    International Nuclear Information System (INIS)

    Mittra, Joy; Abraham, G.J.; Viswanadham, C.S.; Kulkarni, U.D.; Dey, G.K.

    2011-01-01

    Present work brings out the effects of energy density and substrate temperature on pulsed laser deposition of zirconium oxide thin film on Zr-base alloy substrates. The ablation of sintered zirconia has been carried out using a KrF excimer laser having 30 ns pulse width and 600 mJ energy at source at 10 Hz repetition rate. To comprehend effects of these parameters on the synthesized thin film, pure zirconia substrate has been ablated at two different energy densities, 2 J.cm -2 and 5 J.cm -2 , keeping the substrate at 300 K, 573 K and 873 K, respectively. After visual observation, deposited thin films have been examined using Raman Spectroscopy (RS) and X-ray Photo-electron Spectroscopy (XPS). It has been found that the oxide deposited at 300 K temperature does not show good adherence with the substrate and deteriorates further with the reduction in energy density of the incident laser. The oxide films, deposited at 573 K and 873 K, have been found to be adherent with the substrate and appear lustrous black. These indicate that the threshold for adherence of the zirconia film on the Zr-base alloy substrate lies in between 300 K and 573 K. Analysis of Raman spectra has indicated that thin films of zirconia, deposited using pulsed laser, on the Zr-base metallic substrate are initially in amorphous state. Experimental evidence has indicated a strong link among the degree of crystallinity of the deposited oxide film, the substrate temperature and the energy density. It also has shown that the crystallization of the oxide film is dependent on the substrate temperature and the duration of holding at high temperature. The O:Zr ratios of the films, analyzed from the XPS data, have been found to be close to but less than 2. This appears to explain the reason for the transformation of amorphous oxide into monoclinic and tetragonal phases, below 573 K, and not into cubic phase, which is reported to be more oxygen deficient. (author)

  15. The Phase Transitions between H 0.27V 0.27W 0.73O 3· {1}/{3} H 2O and V 0.27W 0.73O 2.865: An X-Ray, Thermal Analysis, and HREM Study

    Science.gov (United States)

    Dupont, L.; Sundberg, M.

    1998-03-01

    A mixed vanadium-tungsten oxide hydrate (H 0.27V 0.27W 0.73O 3· {1}/{3}H 2O) has been synthesized by a soft chemistry method, and the phase transitions from the hydrate (precursor) to the final product V 0.27W 0.73O 2.865have been studied by thermal analysis, X-ray powder diffraction, and high-resolution electron microscopy (HREM) techniques. Supermetastable, metastable, and stable oxides have been observed. H 0.27V 0.27W 0.73O 3· {1}/{3}H 2O possesses a structure related to WO 3· {1}/{3}H 2O. Dehydration of the precursor leads to a supermetastable phase, H 0.27V 0.27W 0.73O 3, with a structure similar to that of the hydrate. At 350°C this phase transforms to the metastable H 0.27V 0.27W 0.73O 3, with a structure isotypic with WO 3(hex). The phase transition between the hydrate and H 0.27V 0.27W 0.73O 3is both pseudomorphous and topotactic. Removal of hydrogen and oxygen from the metastable oxide induces a second phase transition at 500°C to a more stable phase, V 0.27W 0.73O 2.865, with an oxygen-deficient WO 3-type structure. The monoclinic symmetry of the latter oxide increases at higher temperature, first to orthorhombic and then to tetragonal. This transition is not pseudomorphous but of a topotactic nature. The obtained results suggest that the hydrogen content stabilizes the WO 3(hex)-related structure of the metastable phase. A hypothetical model based on HREM observations is proposed for the structural transformation H 0.27V 0.27W 0.73O 3→V 0.27W 0.73O 2.865.

  16. Synthesis and characterization of a novel stationary phase, Si-Zr/Ti(PMTDS), based upon ternary oxide support for high performance liquid chromatography

    Energy Technology Data Exchange (ETDEWEB)

    Amparo, Maura R.; Marques, Fabiana A.; Faria, Anizio M., E-mail: anizio@pontal.ufu.br [Universidade Federal de Uberlandia (FACIP/UFU), Ituiutaba, MG (Brazil). Faculdade de Ciencias Integradas do Pontal

    2013-09-15

    A new stationary phase based on the thermal immobilization of poly(methyltetradecylsiloxane) (PMTDS) on silica particles coated with a mixture of zirconia and titania was prepared and evaluated for the chromatographic separation of test mixtures. The spherical particles were characterized by elemental analysis, SEM, FTIR and {sup 29}Si NMR. The physicochemical properties of PMTDS phase supported on Si-Zr/Ti were intermediate between PMTDS phases supported on titanized silica and zirconized silica. The chromatographic performance of Si-Zr/Ti(PMTDS) phase was similar to PMTDS phases based on metal oxide coated silica having only one metal oxide and the preparation of a Si-Zr/Ti(PMTDS) phase allowed evaluation of the effect of each oxide, zirconia and titania, on the separation process and on the stability of the immobilized polymer phase. The hydrolytic stability of Si-Zr/Ti(PMTDS) stationary phase was similar to the Si-Ti(PMTDS) phase, improving the chemical stability of the silica-based PMTDS phase by about 100%. (author)

  17. Direct gas-phase epoxidation of propylene to propylene oxide through radical reactions: A theoretical study

    Science.gov (United States)

    Kizilkaya, Ali Can; Fellah, Mehmet Ferdi; Onal, Isik

    2010-03-01

    The gas-phase radical chain reactions which utilize O 2 as the oxidant to produce propylene oxide (PO) are investigated through theoretical calculations. The transition states and energy profiles were obtained for each path. The rate constants were also calculated. The energetics for the competing pathways indicate that PO can be formed selectively due to its relatively low activation barrier (9.3 kcal/mol) which is in a good agreement with the experimental value (11 kcal/mol) of gas-phase propylene epoxidation. The formation of the acrolein and combustion products have relatively high activation barriers and are not favored. These results also support the recent experimental findings.

  18. Optical second harmonic generation phase measurement at interfaces of some organic layers with indium tin oxide

    Science.gov (United States)

    Ngah Demon, Siti Zulaikha; Miyauchi, Yoshihiro; Mizutani, Goro; Matsushima, Toshinori; Murata, Hideyuki

    2014-08-01

    We observed phase shift in optical second harmonic generation (SHG) from interfaces of indium tin oxide (ITO)/copper phthalocyanine (CuPc) and ITO/pentacene. Phase correction due to Fresnel factors of the sample was taken into account. The phase of SHG electric field at the ITO/pentacene interface, ϕinterface with respect to the phase of SHG of bare substrate ITO was 160°, while the interface of ITO/CuPc had a phase of 140°.

  19. Optical second harmonic generation phase measurement at interfaces of some organic layers with indium tin oxide

    OpenAIRE

    Ngah Demon, Siti Zulaikha; Miyauchi, Yoshihiro; Mizutani, Goro; Matsushima, Toshinori; Murata, Hideyuki

    2014-01-01

    We observed phase shift in optical second harmonic generation (SHG) from interfaces of indium tin oxide (ITO)/copper phthalocyanine (CuPc) and ITO/pentacene. Phase correction due to Fresnel factors of the sample was taken into account. The phase of SHG electric field at the ITO/pentacene interface, ϕ_ with respect to the phase of SHG of bare substrate ITO was 160°, while the interface of ITO/CuPc had a phase of 140°.

  20. Sulfur isotope fractionation during oxidation of sulfur dioxide: gas-phase oxidation by OH radicals and aqueous oxidation by H2O2, O3 and iron catalysis

    Directory of Open Access Journals (Sweden)

    J. N. Crowley

    2012-01-01

    Full Text Available The oxidation of SO2 to sulfate is a key reaction in determining the role of sulfate in the environment through its effect on aerosol size distribution and composition. Sulfur isotope analysis has been used to investigate sources and chemical processes of sulfur dioxide and sulfate in the atmosphere, however interpretation of measured sulfur isotope ratios is challenging due to a lack of reliable information on the isotopic fractionation involved in major transformation pathways. This paper presents laboratory measurements of the fractionation factors for the major atmospheric oxidation reactions for SO2: Gas-phase oxidation by OH radicals, and aqueous oxidation by H2O2, O3 and a radical chain reaction initiated by iron. The measured fractionation factor for 34S/32S during the gas-phase reaction is αOH = (1.0089±0.0007−((4±5×10−5 T(°C. The measured fractionation factor for 34S/32S during aqueous oxidation by H2O2 or O3 is αaq = (1.0167±0.0019−((8.7±3.5 ×10−5T(°C. The observed fractionation during oxidation by H2O2 and O3 appeared to be controlled primarily by protonation and acid-base equilibria of S(IV in solution, which is the reason that there is no significant difference between the fractionation produced by the two oxidants within the experimental error. The isotopic fractionation factor from a radical chain reaction in solution catalysed by iron is αFe = (0.9894±0.0043 at 19 °C for 34S/32S. Fractionation was mass-dependent with regards to 33S/32S for all the reactions investigated. The radical chain reaction mechanism was the only measured reaction that had a faster rate for the light isotopes. The results presented in this study will be particularly useful to determine the importance of the transition metal-catalysed oxidation pathway compared to other oxidation pathways, but other main oxidation pathways can not be distinguished based on stable sulfur isotope measurements alone.

  1. Continuous-flow ultrasound assisted oxidative desulfurization (UAOD) process: An efficient diesel treatment by injection of the aqueous phase.

    Science.gov (United States)

    Rahimi, Masoud; Shahhosseini, Shahrokh; Movahedirad, Salman

    2017-11-01

    A new continuous-flow ultrasound assisted oxidative desulfurization (UAOD) process was developed in order to decrease energy and aqueous phase consumption. In this process the aqueous phase is injected below the horn tip leading to enhanced mixing of the phases. Diesel fuel as the oil phase with sulfur content of 1550ppmw and an appropriate mixture of hydrogen peroxide and formic acid as the aqueous phase were used. At the first step, the optimized condition for the sulfur removal has been obtained in the batch mode operation. Hence, the effect of more important oxidation parameters; oxidant-to-sulfur molar ratio, acid-to-sulfur molar ratio and sonication time were investigated. Then the optimized conditions were obtained using Response Surface Methodology (RSM) technique. Afterwards, some experiments corresponding to the best batch condition and also with objective of minimizing the residence time and aqueous phase to fuel volume ratio have been conducted in a newly designed double-compartment reactor with injection of the aqueous phase to evaluate the process in a continuous flow operation. In addition, the effect of nozzle diameter has been examined. Significant improvement on the sulfur removal was observed specially in lower sonication time in the case of dispersion method in comparison with the conventional contact between two phases. Ultimately, the flow pattern induced by ultrasonic device, and also injection of the aqueous phase were analyzed quantitatively and qualitatively by capturing the sequential images. Copyright © 2017 Elsevier B.V. All rights reserved.

  2. Critical behavior of the spontaneous polarization and the dielectric susceptibility close to the cubic-tetragonal transition in BaTiO3

    Directory of Open Access Journals (Sweden)

    H. Yurtseven

    2015-09-01

    Full Text Available Using Landau mean field model, the spontaneous polarization and the dielectric susceptibility are analyzed as functions of temperature and pressure close to the cubic–tetragonal (ferroelectric–paraelectric transition in BaTiO3. From the analysis of the dielectric susceptibility and the spontaneous polarization, the critical exponents are deduced in the classical and quantum limits for BaTiO3. From the critical behavior of the dielectric susceptibility, the spontaneous polarization can be described for the ferroelectric–paraelectric (cubic to tetragonal transition between 4 and 8 GPa at constant temperatures of 0 to 200 K in BaTiO3 within the Landau mean field model given here.

  3. X-ray analysis of phase coexistence and electric poling processing in alkaline niobate-based compositions

    International Nuclear Information System (INIS)

    Fu Jian; Zuo Ruzhong; Liu Yi

    2010-01-01

    The characteristic and origin of two-phase coexistence and the content of each phase in typical alkaline niobate-based lead-free compositions were investigated through the refinement of X-ray diffraction peaks and the measurement of dielectric constant versus temperature curves. The diffuse nature of polymorphic phase transition has resulted in the coexistence of two ferroelectric phases within a wide composition and temperature range. As a result, the optimum piezoelectric properties appear in the composition rich in tetragonal phases and there is a remarkable poling temperature effect. Discussions on the difference between morphotropic phase boundary and polymorphic phase boundary were made in combination with the variation of electrical properties.

  4. Determination of the crystallographic parameters of cubic-to-tetragonal martensitic transformation using the infinitesimal deformation approach and wechsler, lieberman, and read theory

    Science.gov (United States)

    Navruz, N.

    2001-02-01

    The aim of the present study is to discuss the infinitesimal deformation (ID) approach’s application and practical applicability. Therefore, ID theory was reformulated and applied to the face centered cubic (fcc) to body centered tetragonal (bct) martensitic transformation for the case of the (110) [bar 110] slip system as the lattice invariant shear (LIS). The analytical solutions for the habit plane orientation, the magnitude of the lattice invariant shear, the orientation relation between parent and product phases, etc. were derived for fcc to bct martensitic transformation in an Fe-7 pct Al-2 pct C alloy. In order to compare with phenomenological theory’s results, crystallographic parameters were also calculated by using Wechsler, Lieberman, and Read (W-L-R) phenomenological theory. Agreement between the two results obtained from ID approach and W-L-R theory was found to be excellent.

  5. Perovskite phases in the systems Asup(II)O-UO/sub 3/. 1. Tetragonal perovskite Ba/sub 2/Basub(7/8)vacantsub(1/8)UO/sub 5/sub(7/8)

    Energy Technology Data Exchange (ETDEWEB)

    Griffiths, A J; Kemmler-Sack, S [Tuebingen Univ. (Germany, F.R.)

    1979-10-01

    The new tetragonal compound Ba/sub 2/Basub(7/8)vacantsub(1/8)UO/sub 5/sub(7/8) (a = 2 x 6.31/sub 2/ A; c = 2 x 8.76/sub 7/ A) has been found besides Ba/sub 3/UO/sub 6/ (triclinic) in the BaO-UO/sub 3/ system. It crystallizes with a superstructure of perovskite type. The differences in properties between Ba/sub 3/UO/sub 6/ and Ba/sub 2/Basub(7/8)vacantsub(1/8) UO/sub 5/sub(7/8) are discussed.

  6. Synthesis, characterization and photoluminescence properties of Dy{sup 3+}-doped nano-crystalline SnO{sub 2}

    Energy Technology Data Exchange (ETDEWEB)

    Pillai, Sreejarani K.; Sikhwivhilu, Lucky M. [National Centre for Nano-Structured Materials, CSIR, PO Box 395, Pretoria 0001 (South Africa); Hillie, Thembela K., E-mail: thillie@csir.co.za [National Centre for Nano-Structured Materials, CSIR, PO Box 395, Pretoria 0001 (South Africa); Physics Department, University of the Free State, P.O. Box 339, Bloemfontein 9300 (South Africa)

    2010-04-15

    Nano-crystalline of tin oxide doped with varying wt% of Dy{sup 3+} was prepared using chemical co-precipitation method and characterised by various advanced techniques such as BET-surface area, Fourier transform infrared spectroscopy, X-ray diffraction, Raman spectroscopy and photoluminescence measurements. Analytical results demonstrated that the nanocrystalline tin oxide is in tetragonal crystalline phase and doping with Dy{sup 3+} could inhibit the phase transformation, increases surface area and decreases the crystallite size. The experimental result on photoluminescence characteristics originating from Dy{sup 3+}-doping in nanocrystalline SnO{sub 2} reveals the dependence of the luminescent intensity on dopant concentration.

  7. An eigenstrain approach to predict phase transformation and self-accommodation in partially stabilized zirconia

    International Nuclear Information System (INIS)

    Hensl, Th.; Mühlich, U.; Budnitzki, M.; Kuna, M.

    2015-01-01

    Highlights: • Analytical model to predict phase transformation in PSZ is developed. • Analytical model to predict number of twins in monoclinic inclusions in PSZ. • Models consider inclusions size, shape, temperature, remote loading and surface energy. - Abstract: This work focuses on micromechanical modeling of the tetragonal to monoclinic phase transformation (t–m transformation) in partially stabilized zirconia (PSZ). Tetragonal particles dispersed in a cubic matrix may transform into the monoclinic phase under sufficiently high mechanical loading or if the material is cooled down below a critical temperature. This phase transformation is supposed to be responsible for the so called transformation toughening effect of PSZ. The transformation is usually accompanied by a self-accommodation process, which reduces the occurring eigenstresses in the surrounding matrix. The influences of particle size and geometry, chemical driving force, temperature, surface energy and remote loading on the t–m transformation are estimated by a thermostatic approach. We assume, that transformations occur, once the Gibbs free energy of the transformed equilibrium state is lower than that of the untransformed reference state. To obtain an analytical solution, the microstructure is modeled as an inclusion of rectangular cross section, restrained by an infinite elastic matrix, under plane strain conditions. The developed model for phase transformation captures the well-known size and temperature dependencies. Furthermore, it indicates a significant influence of the particle geometry, that large aspect ratios of the inclusion’s cross section lower the trigger stress for phase transformation

  8. High pressure study of the zinc phosphide semiconductor compound in two different phases

    International Nuclear Information System (INIS)

    Mokhtari, Ali

    2009-01-01

    Electronic and structural properties of the zinc phosphide semiconductor compound are calculated at hydrostatic pressure using the full-potential all-electron linearized augmented plane wave plus local orbital (FP-LAPW+lo) method in both cubic and tetragonal phases. The exchange-correlation potential is treated by the generalized gradient approximation within the scheme of Perdew, Burke and Ernzerhof, GGA96 (1996 Phys. Rev. Lett. 77 3865). Also, the Engel and Vosko GGA formalism, EV-GGA (Engel and Vosko 1993 Phys. Rev. B 47 13164), is used to improve the band-gap results. Internal parameters are optimized by relaxing the atomic positions in the force directions using the Hellman-Feynman approach. The lattice constants, internal parameters, bulk modulus, cohesive energy and band structures have been calculated and compared to the available experimental and theoretical results. The structural calculations predict that the stable phase is tetragonal. The effects of hydrostatic pressure on the behavior of band parameters such as band-gap, valence bandwidths and internal gaps (the energy gap between different parts of the valence bands) are studied using both GGA96 and EV-GGA.

  9. High pressure study of the zinc phosphide semiconductor compound in two different phases

    Energy Technology Data Exchange (ETDEWEB)

    Mokhtari, Ali [Simulation Laboratory, Department of Physics, Faculty of Science, Shahrekord University, PB 115, Shahrekord (Iran, Islamic Republic of)], E-mail: mokhtari@sci.sku.ac.ir

    2009-07-08

    Electronic and structural properties of the zinc phosphide semiconductor compound are calculated at hydrostatic pressure using the full-potential all-electron linearized augmented plane wave plus local orbital (FP-LAPW+lo) method in both cubic and tetragonal phases. The exchange-correlation potential is treated by the generalized gradient approximation within the scheme of Perdew, Burke and Ernzerhof, GGA96 (1996 Phys. Rev. Lett. 77 3865). Also, the Engel and Vosko GGA formalism, EV-GGA (Engel and Vosko 1993 Phys. Rev. B 47 13164), is used to improve the band-gap results. Internal parameters are optimized by relaxing the atomic positions in the force directions using the Hellman-Feynman approach. The lattice constants, internal parameters, bulk modulus, cohesive energy and band structures have been calculated and compared to the available experimental and theoretical results. The structural calculations predict that the stable phase is tetragonal. The effects of hydrostatic pressure on the behavior of band parameters such as band-gap, valence bandwidths and internal gaps (the energy gap between different parts of the valence bands) are studied using both GGA96 and EV-GGA.

  10. Review of high pressure phases of calcium by first-principles calculations

    Science.gov (United States)

    Ishikawa, T.; Nagara, H.; Suzuki, N.; Tsuchiya, J.; Tsuchiya, T.

    2010-03-01

    We review high pressure phases of calcium which have obtained by recent experimental and first-principles studies. In this study, we investigated the face-centered cubic (fcc) structure, the body-centered cubic (bcc) structure, the simple cubic (sc) structure, a tetragonal P43212 [Ishikawa T et al. 2008 Phys. Rev. B 77 020101(R)], an orthorhombic Cmca [Ishikawa T et al. 2008 Phys. Rev. B 77 020101(R)], an orthorhombic Cmcm [Teweldeberhan A M and Bonev S A 2008 Phys. Rev. B 78 140101(R)], an orthorhombic Pnma [Yao Y et al. 2008 Phys. Rev. B 78 054506] and a tetragonal I4/mcm(00) [Arapan S et al. 2008 Proc. Natl. Acad. Sci. USA 105 20627]. We compared the enthalpies among the structures up to 200 GPa and theoretically determined the phase diagram of calcium. The sequence of the structural transitions is fcc (0- 3.5 GPa) → bcc (3.5 - 35.7 GPa) → Cmcm (35.7- 52GPa) → P43212 (52-109 GPa) → Cmca (109-117.4GPa) → Pnma (117.4-134.6GPa) → I4/mcm(00) (134.6 GPa -). The sc phase is experimentally observed in the pressure range from 32 to 113 GPa but, in our calculation, there is no pressure region where the sc phase is the most stable. In addition, we found that the enthalpy of the hexagonal close-packed (hcp) structure is lower than that of I4/mcm(00) above 495 GPa.

  11. Metastable phases in yttrium oxide plasma spray deposits and their effect on coating properties

    International Nuclear Information System (INIS)

    Gourlaouen, V.; Schnedecker, G.; Boncoeur, M.; Lejus, A.M.; Collongues, R.

    1993-01-01

    Yttrium oxide coatings were obtained by plasma spray. Structural investigations on these deposits show that, due to the drastic conditions of this technique, a minor monoclinic B phase is formed in the neighborhood of the major cubic C form. The authors discuss here the influence of different plasma spray parameters on the amount of the B phase formed. They describe also the main properties of Y 2 O 3 B and C phases in these deposits such as structural characteristics, thermal stability and mechanical behavior

  12. Method of encapsulating a phase change material with a metal oxide

    Science.gov (United States)

    Ram, Manoj Kumar; Jotshi, Chand K.; Stefanakos, Elias K.; Goswami, Dharendra Yogi

    2016-11-15

    Storage systems based on latent heat storage have high-energy storage density, which reduces the footprint of the system and the cost. However, phase change materials (PCMs), such as NaNO.sub.3, NaCl, KNO.sub.3, have very low thermal conductivities. To enhave the storage of PCMs, macroencapsulation of PCMs was performed using a metal oxide, such as SiO.sub.2 or a graphene-SiO.sub.2, over polyimide-coated or nickel-embedded, polyimide-coated pellets The macro encapsulation provides a self-supporting structure, enhances the heat transfer rate, and provides a cost effective and reliable solution for thermal energy storage for use in solar thermal power plants. NaNO.sub.3 was selected for thermal storage in a temperature range of 300.degree. C. to 500.degree. C. The PCM was encapsulated in a metal oxide cell using self-assembly reactions, hydrolysis, and simultaneous chemical oxidation at various temperatures.

  13. Tin-antimony oxide oxidation catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Berry, Frank J. [Open University, Department of Chemistry (United Kingdom)

    1998-12-15

    Tin-antimony oxide catalysts for the selective oxidation of hydrocarbons have been made by precipitation techniques. The dehydration of the amorphous dried precipitate by calcination at increasingly higher temperatures induces the crystallisation of a rutile-related tin dioxide-type phase and the segregation of antimony oxides which volatilise at elevated temperatures. The rutile-related tin dioxide-type phase contains antimony(V) in the bulk and antimony(III) in the surface. Specific catalytic activity for the oxidative dehydrogenation of butene to butadiene is associated with materials with large concentrations of antimony(III) in the surface.

  14. Effective oxidation of benzylic and alkane C-H bonds catalyzed by sodium o-iodobenzenesulfonate with Oxone as a terminal oxidant under phase-transfer conditions.

    Science.gov (United States)

    Cui, Li-Qian; Liu, Kai; Zhang, Chi

    2011-04-07

    Catalytic oxidation of benzylic C-H bonds could be efficiently realized using IBS as a catalyst which was generated in situ from the oxidation of sodium 2-iodobenzenesulfonate (1b) by Oxone in the presence of a phase-transfer catalyst, tetra-n-butylammonium hydrogen sulfate, in anhydrous acetonitrile at 60 °C. Various alkylbenzenes, including toluenes and ethylbenzenes, several oxygen-containing functionalities substituted alkylbenzenes, and a cyclic benzyl ether could be efficiently oxidized. And, the same reagent system of cat. 1b/Oxone/cat. n-Bu(4)NHSO(4) could be applied to the effective oxidation of alkanes as well.

  15. Synthesis and characterization of new oxides and oxynitrides of niobium; Synthese und Charakterisierung neuer Oxide und Oxidnitride des Niobs

    Energy Technology Data Exchange (ETDEWEB)

    Orthmann, Steven

    2017-11-02

    By different synthesis routes the first oxide nitrides in the series scandium-niobium-oxygen-nitrogen could be synthesized and characterized. ScNb{sub 4}O{sub 7}N{sub 3}, which crystallizes in the rutile-type structure, exhibit a band gap of 2.62 eV after a short oxidation. Furthermore anion-deficit NbSc{sub 2}(O,N,□){sub 6} with fluorite-type structure could be synthesized. UV-Vis measurements point to a band gap of 3.36 eV after a short oxidation of the product. In the series zirconium-niobium-oxygen-nitrogen new oxides and oxide nitrides could be synthesized. By replacing zirconium with hafnium isotopical compounds with comparable composition could be obtained. The crystal structure of these new compounds is discussed respecting magnetism and the results of electron microscopy and neutron diffraction. By partially substitution of niobium with magnesium or zinc three additional oxide nitrides with the compositions Mg{sub 2}Nb{sub 4}O{sub 2}N{sub 5}, Zn{sub 2}NbO{sub 0,3}N{sub 2,8}, and ZnNb{sub 3}O{sub 0,1}N{sub 4,5}, showing a tetragonal Nb{sub 4}N{sub 5}-type structure, could be synthesized.

  16. Anelastic anomalies and negative Poisson's ratio in tetragonal BaTiO3 ceramics

    International Nuclear Information System (INIS)

    Dong Liang; Stone, Donald S.; Lakes, Roderic S.

    2010-01-01

    Anelastic anomalies (sharp variations in modulus and damping with temperature) were observed in tetragonal BaTiO 3 via broadband viscoelastic spectroscopy after aging at 50 deg. C for 15 h. The effect was most pronounced under electrical short circuit condition, at low frequency and under small excitation strain (10 -6 ). Softening in bulk modulus and negative Poisson's ratio were observed near 60 deg. C. Effects are attributed to an oxygen vacancy mechanism. A relaxational model cannot account for sharp response at smaller strains. Heterogeneity of negative stiffness is considered as a cause.

  17. Characterization of pH dependent Mn(II) oxidation strategies and formation of a bixbyite-like phase by Mesorhizobium australicum T-G1

    Science.gov (United States)

    Bohu, Tsing; Santelli, Cara M; Akob, Denise M.; Neu, Thomas R; Ciobota, Valerian; Rösch, Petra; Popp, Jürgen; Nietzsche, Sándor; Küsel, Kirsten

    2015-01-01

    Despite the ubiquity of Mn oxides in natural environments, there are only a few observations of biological Mn(II) oxidation at pH MOB) isolates limits our understanding of how pH influences biological Mn(II) oxidation in extreme environments. Here, we report that a novel MOB isolate, Mesorhizobium australicum strain T-G1, isolated from an acidic and metalliferous uranium mining area, can oxidize Mn(II) at both acidic and neutral pH using different enzymatic pathways. X-ray diffraction, Raman spectroscopy, and scanning electron microscopy with energy dispersive X-ray spectroscopy revealed that T-G1 initiated bixbyite-like Mn oxide formation at pH 5.5 which coincided with multi-copper oxidase expression from early exponential phase to late stationary phase. In contrast, reactive oxygen species (ROS), particularly superoxide, appeared to be more important for T-G1 mediated Mn(II) oxidation at neutral pH. ROS was produced in parallel with the occurrence of Mn(II) oxidation at pH 7.2 from early stationary phase. Solid phase Mn oxides did not precipitate, which is consistent with the presence of a high amount of H2O2 and lower activity of catalase in the liquid culture at pH 7.2. Our results show that M. australicum T-G1, an acid tolerant MOB, can initiate Mn(II) oxidation by varying its oxidation mechanisms depending on the pH and may play an important role in low pH manganese biogeochemical cycling.

  18. X-ray diffraction study of elastic strains for modelling γ/γ' two-phase behavior

    International Nuclear Information System (INIS)

    Durand, L.; Massaoudi, M.; Lavelle, B.

    2005-01-01

    To describe the two-phase monocrystals behavior, we used has X-rays diffraction method. Our study is based on the mechanics of the continuous media framework in elasticity. We extend to the quadratic structure the study by X-rays developed at the laboratory on cubic materials with coarse grains. We show that the two phases γ and γ' undergo a tetragonal distortion and that the strains are not constant in each phase. Our results are in agreement with a study by the finite element method developed in addition

  19. Dimorphism in La{sub 5}Ge{sub 3} and Ce{sub 5}Ge{sub 3}? How exploratory syntheses led to surprising new finds in the La-Ge and Ce-Ge binary phase diagrams

    Energy Technology Data Exchange (ETDEWEB)

    Suen, Nian-Tzu; Bobev, Svilen [Department of Chemistry and Biochemistry, University of Delaware, Newark, DE (United States)

    2014-04-15

    Reported are the synthesis, the crystal structures, and the electronic structures of two new tetragonal phases, La{sub 5}Ge{sub 3} and Ce{sub 5}Ge{sub 3}. Both title compounds crystallize in the Pu{sub 5}Rh{sub 3} (P4/ncc) structure type, which has close structural relationship with the W{sub 5}Si{sub 3} (I4/mcm) structure type. The synthetic results, supported by thermal analysis suggest that this tetragonal phase is only stable at relatively low temperature and it transforms to the hexagonal form (Mn{sub 5}Si{sub 3} structure type, P6{sub 3}/mcm) at above 850 C. The structural relationship between La{sub 5}Ge{sub 3} (Pu{sub 5}Rh{sub 3} type) and La{sub 5}Sn{sub 3} (W{sub 5}Si{sub 3} type) is discussed as well. Temperature dependent DC magnetization and resistivity measurements indicate that the tetragonal phase La{sub 5}Ge{sub 3} exhibits Pauli-like paramagnetism and is a good metallic conductor. For the tetragonal phase Ce{sub 5}Ge{sub 3}, the magnetic behavior obeys the Curie-Weiss law in the high-temperature regime, while it deviates from the Curie-Weiss law at low temperature. No long-range magnetic ordering was observed down to 5 K, although short-range correlations can be inferred below ca. 50 K. The resistivity measurements of Ce{sub 5}Ge{sub 3} also show metallic-like temperature dependence, although the low-temperature behavior resembling a T{sup 2} law could signify anomalous electron-scattering (e.g., Kondo-like effect). The electronic structures of multiple phases with the same nominal compositions, computed by the TB-LMTO-ASA method, are compared and discussed. (Copyright copyright 2014 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  20. Dynamic\tmodelling of catalytic three-phase reactors for hydrogenation and oxidation processes

    Directory of Open Access Journals (Sweden)

    Salmi T.

    2000-01-01

    Full Text Available The dynamic modelling principles for typical catalytic three-phase reactors, batch autoclaves and fixed (trickle beds were described. The models consist of balance equations for the catalyst particles as well as for the bulk phases of gas and liquid. Rate equations, transport models and mass balances were coupled to generalized heterogeneous models which were solved with respect to time and space with algorithms suitable for stiff differential equations. The aspects of numerical solution strategies were discussed and the procedure was illustrated with three case studies: hydrogenation of aromatics, hydrogenation of aldehydes and oxidation of ferrosulphate. The case studies revealed the importance of mass transfer resistance inside the catalyst pallets as well as the dynamics of the different phases being present in the reactor. Reliable three-phase reactor simulation and scale-up should be based on dynamic heterogeneous models.

  1. CdWO4 polymorphs: Selective preparation, electronic structures, and photocatalytic activities

    International Nuclear Information System (INIS)

    Yan, Tingjiang; Li, Liping; Tong, Wenming; Zheng, Jing; Wang, Yunjian; Li, Guangshe

    2011-01-01

    This work explored the selective synthesis of polymorphs of CdWO 4 in either tetragonal or monoclinic phase by optimizing the experimental parameters. Systematic characterization indicated that both polymorphs possessed similar spherical morphologies but different structural building blocks. Electronic structures calculations for both polymorphs demonstrated the same constructions of conduction band or valence band, while the conduction band widths of both polymorphs were quite different. Both CdWO 4 polymorphs exhibited good photocatalytic activity for degradation of methyl orange under UV light irradiation. When comparing to some other well-known tungstate oxide materials, the photocatalytic activity was found to follow such a consequence, monoclinic CdWO 4 ∼monoclinic ZnWO 4 >tetragonal CdWO 4 >tetragonal CaWO 4 . The specific photocatalytic activity of monoclinic CdWO 4 was even higher than that of commercial TiO 2 photocatalyst (Degussa P25). The increased activity from the tetragonal CdWO 4 to the monoclinic was consistent with the trend of the decreased symmetry, and this could be explained in terms of the geometric structures and electronic structures for both polymorphs. -- Graphical abstract: Monoclinic CdWO 4 exhibited a much higher photocatalytic activity than the tetragonal form owing to the lower symmetry, more distorted geometric structure, and the dispersive band configuration. Display Omitted Research highlights: → Polymorphs of CdWO 4 in either tetragonal or monoclinic phase were selectively synthesized. → Both polymorphs possessed similar spherical morphologies, while the relevant structural building blocks were different. → Photocatalytic activities of CdWO 4 polymorphs depended strongly on the symmetry, geometric structure, as well as band configuration.

  2. Potential Impacts of two SO2 oxidation pathways on regional sulfate concentrations: acqueous-hase oxidation by NO2 and gas-phase oxidation by Stabilized Criegee Intermediates

    Science.gov (United States)

    We examine the potential impacts of two additional sulfate production pathways using the Community Multiscale Air Quality modeling system. First we evaluate the impact of the aqueous-phase oxidation of S(IV) by nitrogen dioxide using two published rate constants, differing by 1-2...

  3. Characterization of pH dependent Mn(II) oxidation strategies and formation of a bixbyite-like phase by Mesorhizobium australicum T-G1

    Science.gov (United States)

    Bohu, Tsing; Santelli, Cara M; Akob, Denise M.; Neu, Thomas R; Ciobota, Valerian; Rösch, Petra; Popp, Jürgen; Nietzsche, Sándor; Küsel, Kirsten

    2015-01-01

    Despite the ubiquity of Mn oxides in natural environments, there are only a few observations of biological Mn(II) oxidation at pH < 6. The lack of low pH Mn-oxidizing bacteria (MOB) isolates limits our understanding of how pH influences biological Mn(II) oxidation in extreme environments. Here, we report that a novel MOB isolate, Mesorhizobium australicum strain T-G1, isolated from an acidic and metalliferous uranium mining area, can oxidize Mn(II) at both acidic and neutral pH using different enzymatic pathways. X-ray diffraction, Raman spectroscopy, and scanning electron microscopy with energy dispersive X-ray spectroscopy revealed that T-G1 initiated bixbyite-like Mn oxide formation at pH 5.5 which coincided with multi-copper oxidase expression from early exponential phase to late stationary phase. In contrast, reactive oxygen species (ROS), particularly superoxide, appeared to be more important for T-G1 mediated Mn(II) oxidation at neutral pH. ROS was produced in parallel with the occurrence of Mn(II) oxidation at pH 7.2 from early stationary phase. Solid phase Mn oxides did not precipitate, which is consistent with the presence of a high amount of H2O2 and lower activity of catalase in the liquid culture at pH 7.2. Our results show that M. australicum T-G1, an acid tolerant MOB, can initiate Mn(II) oxidation by varying its oxidation mechanisms depending on the pH and may play an important role in low pH manganese biogeochemical cycling.

  4. Oxidation-induced phase transformations and lifetime limits of chromia-forming nickel-base alloy 625

    Energy Technology Data Exchange (ETDEWEB)

    Chyrkin, Anton

    2011-12-05

    For its high creep resistance the commercial nickel-base alloy 625 relies on solid solution strengthening in combination with precipitation hardening by formation of δ-Ni{sub 3}Nb and (Ni,Mo,Si){sub 6}C precipitates during high-temperature service. In oxidizing environments the alloy forms a slow growing, continuous chromia layer on the material surface which protects the alloy against rapid oxidation attack. The growth of the chromia base oxide scale results during exposure at 900-1000 C in oxidation-induced chromium depletion in the subsurface zone of the alloy. Microstructural analyses of the cross-sectioned specimens revealed that this process results in formation of a wide subsurface zone in which the mentioned strengthening phases are dissolved, in spite of the fact that both phases do not contain substantial amounts of the scale-forming element chromium. The cross-sectional analyses revealed that, in parallel to the formation of a precipitate depleted zone, a thin, continuous layer of niobium-rich intermetallic precipitates formed in the immediate vicinity of the scale/alloy interface. The Subsurface Phase Enrichment (abbreviated as SPE) was shown to be the result of an uphill-diffusion of niobium, i.e. the element stabilizing the strengthening precipitates δ-Ni{sub 3}Nb, in the chromium activity gradient and is thus a natural consequence of the oxidation-induced chromium depletion beneath the chromia scale. The thermodynamic calculations carried out using the Thermo-Calc/DICTRA software packages revealed that in alloy 625 the chemical activity of niobium decreases with decreasing chromium content. As chromium is being continuously removed from the alloy as the result of the chromia scale growth, the zone of lowest Nb-activity is formed in the location with the lowest chromium concentration, i.e. the scale/alloy interface. This creates a driving force for Nb to diffuse towards the scale/alloy interface against its own concentration gradient, which is known

  5. Cooperative properties of single phases of complex oxide catalyst for oxidation of propylene to acrolein

    International Nuclear Information System (INIS)

    Orel, L.I.; Udalova, O.V.; Korchak, V.N.; Isaev, O.V.; Krylov, O.V.; Gershenzon, Yu.M.; Aptekar', E.L.

    1992-01-01

    Synergetic effect of increase of acrolein yield during propylene oxidation on mechanical mixture of (α + β)CoMoO 4 and MoO 3 , as well as CO and CO 2 yield on mixture of CoMoO 4 and Bi 2 O 3 ·2MoO 3 was revealed. It is shown that CoMoO 4 generates allyl radicals, desorption of these radicals to gaseous phase is not practically observed with MoO 3 , bismuth molybdates and Fe 2 O 3 · Fe 2 O 3 ·3MoO 3

  6. Effects of whitening dentifrice on yttria-stabilized tetragonal zirconia polycrystal surfaces after simulating brushing.

    Science.gov (United States)

    Pinelli, Lígia Antunes Pereira; Gimenes Olbera, Amanda Caroline; Candido, Lucas Miguel; Miotto, Larissa Natiele; Antonio, Selma Gutierrez; Fais, Laiza Maria Grassi

    2017-01-01

    The changes that occur after brushing yttria-stabilized tetragonal zirconia polycrystal (Y-TZP) are unknown. These changes may favor the retention of microorganisms and chemisorption of water, impairing its longevity. The purpose of this in vitro study was to evaluate the effects of a whitening dentifrice on Y-TZP surfaces after simulating 10 years of brushing. Seventy-two bar-shaped specimens (20×4×1.2 mm) were divided into 4 groups: storage in distilled water (SW, control), brushing with distilled water (BW), brushing with dentifrice (BD), and brushing with whitening dentifrice (BWD). Brushing was conducted using a linear brushing machine (878400 cycles, 0.98 N, soft toothbrush). The mean roughness (Ra) was analyzed with a profilometer and the superficial topography with scanning electron microscopy (SEM) at baseline and after treatment. Crystalline phases were characterized using x-ray diffraction. Baseline and posttreatment Ra were analyzed using the 1-way ANOVA and Tukey HSD multiple comparison test; the paired t test was used for intragroup comparison (all α=.05). The Ra (μm) means (before/after treatment) were SW 0.28/0.28; BW 0.32/0.31; BD 0.28/0.36; BWD 0.30/0.20. No statistically significant difference was found for Ra at baseline (P=.108) than for posttreatment results (P<.001); the BD group had higher Ra values when compared with baseline (P=.019); the BWD group had the lowest values (P<.001). The BD surfaces showed pronounced scratches and detachment of the surface, while BWD showed smoother surfaces; similar crystallographic results among groups were observed. Brushing Y-TZP with conventional dentifrice increased roughness, while brushing with whitening dentifrice reduced roughness. Neither dentifrice changed the crystallographic phases after brushing. Copyright © 2016 Editorial Council for the Journal of Prosthetic Dentistry. Published by Elsevier Inc. All rights reserved.

  7. Phase transition in Sr8[Al12O24](MoO4)2 aluminate sodalite (SAM)

    International Nuclear Information System (INIS)

    Depmeier, W.; Melzer, R.; Hu, X.

    1993-01-01

    The cubic-tetragonal phase transition at 571 K of the aluminate sodalite Sr 8 [Al 12 O 24 ](MoO 4 ) 2 (SAM) has ben studied by following the position of the (pseudo-)cubic {400} reflections as a function of temperature. The high resolution of the synchrotron powder diffraction experiment allowed the temperature dependencies to be followed with good precision. The tetragonal a lattice parameter appears to be a linear extrapolation of the cubic one, with only a small upward shift at the transition, whereas the c parameter decreases strongly below 571 K. These observations can be explained by a model which assumes the superposition of a ferroelastic strain component, and a volume strain component. The volume strain can be rationalized as being the result of a 'shearing' of the sodalite framework. Causes and consequences of the 'shearing' in relation to the sodalite framework are discussed. The weakly first-order transition is nearly tricritical; power-law exponents seem to be influenced by defects. The thermal expansion of the cubic lattice parameter, as well as of the tetragonal a axis, is nearly linear. The linear thermal-expansion coefficient α is 8.6(4)x10 -6 K -1 . The tetragonal c axis also expands linearly between room temperature and about Tc-100 K with practically the same coefficient, but behaves non-linearly nearer to the transition temperature. (orig.)

  8. A new method of residual stress distribution analysis for corroded Zircaloy-4 cladding

    International Nuclear Information System (INIS)

    Godlewski, J.; Cadalbert, R.

    1992-01-01

    An X-ray diffraction method of residual stress measurement is developed to determine the stress level in the metal near the metal/oxide interface of Zircaloy-4 cladding samples oxidized in steam water at 400degC under a pressure of 10.3 MPa. The stress gradient is obtained and the evolution of the average stress is determined as function of the oxidation time. The presence of tetragonal zirconia phase in quite large quantity near the metal/oxide interface could be correlated to the high stress level in the base metal, adjacent to the interface. (author)

  9. A new method for residual stress distribution - analysis of corroded zircaloy-4 cladding

    International Nuclear Information System (INIS)

    Godlewski, J.; Cadalbert, R.

    1992-01-01

    An X-ray diffraction method for residual stress measurement is developed to determine the stress level in the metal near the metal/oxide interface of Zircaloy-4 cladding samples oxidized in steam water at 400 deg C under a pressure of 10.3 MPa. The stress gradient is obtained and the evolution of the average stress is determined as a function of the oxidation time. The presence of tetragonal zirconia phase in quite large quantity near the metal/oxide interface could be correlated to the high stress level in the base metal, adjacent to the interface. 12 refs., 5 figs., 1 tab

  10. Evolution from successive phase transitions to "morphotropic phase boundary" in BaTiO3-based ferroelectrics

    Science.gov (United States)

    Zhou, Chao; Ke, Xiaoqin; Yao, Yonggang; Yang, Sen; Ji, Yuanchao; Liu, Wenfeng; Yang, Yaodong; Zhang, Lixue; Hao, Yanshuang; Ren, Shuai; Zhang, Le; Ren, Xiaobing

    2018-04-01

    Obtaining superior physical properties for ferroic materials by manipulating the phase transitions is a key concern in solid state physics. Here, we investigated the dielectric permittivity, piezoelectric coefficient d33, storage modulus, and crystal symmetry of (1-x)Ba(Ti0.8Zr0.2)O3-x(Ba1-yCay)TiO3 (BZT-xBCyT) systems to demonstrate the gradual evolution process from successive phase transitions in BaTiO3 to the morphotropic phase boundary (MPB) regime in BZT-xBC0.3T. Furthermore, we analysed with a Landau-type theoretical model to show that the high field-sensitive response (dielectric permittivity) originates from a small polarization anisotropy and low energy barrier at the quadruple point. Together, the intermediate orthorhombic phase regime and the tetragonal-orthorhombic and orthorhombic-rhombohedral phase boundaries constitute the MPB. Our work not only reconciles the arguments regarding whether the structural state around the MPB corresponds to a single-phase regime or a multiple-phase-coexistence regime but also suggests an effective method to design high-performance functional ferroic materials by tailoring the successive phase transitions.

  11. Symmetry-induced deformation and reconstructive phase transformation in metal-oxide interface: the Fe (001) example

    International Nuclear Information System (INIS)

    Lahoche, L.; Universite de Technologie de Compiegne; Lorman, V.; Roelandt, J.M.; Rochal, S.B.

    1996-01-01

    A model is proposed for the structural transformation and corresponding induced deformation in physical three-dimensional interface of the metal-oxide system. The thermodynamical and elastic state of the system is described by the Landau-Ginzbourg free energy. Calculated theoretical phase diagram shows several different types of isothermal growth processes. The model is applied to the case of the oxidation of the (001) Fe surface. (orig.)

  12. Structural phase transitions in CsPbCl/sub 3/ and RbCdCl/sub 3/

    Energy Technology Data Exchange (ETDEWEB)

    Plesko, S; Kind, R; Roos, J [Swiss Federal Inst. of Technology, Zuerich. Lab. of Solid State Physics

    1978-08-01

    Structural phase transitions in CsPbCl/sub 3/ have been investigated by /sup 133/Cs and /sup 87/Rb nuclear magnetic resonance. The space groups of the room temperature phase in CsPbCl/sub 3/ and of two unknown phases in RbCdCl/sub 3/ could be clarified. Thus both perovskites show the same phase sequence from cubic Pm3m-O sub(h)sup(1) to tetragonal P4/mbm-D sub(4h)sup(5), orthorhombic Cmcm-D sub(2h)sup(17) and further orthorhombic Pnma-D sub(2h)sup(16).

  13. Density-functional theory study of the pressure-induced phase transition in hydronitrogen compound N{sub 4}H{sub 4}

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Qi-Jun, E-mail: qijunliu@home.swjtu.edu.cn [Bond and Band Engineering Group, Sichuan Provincial Key Laboratory (for Universities) of High Pressure Science and Technology, School of Physical Science and Technology, Southwest Jiaotong University, Chengdu, Sichuan 610031 (China); Zhang, Ning-Chao; Sun, Yan-Yun; Zhang, Ming-Jian; Liu, Fu-Sheng [Bond and Band Engineering Group, Sichuan Provincial Key Laboratory (for Universities) of High Pressure Science and Technology, School of Physical Science and Technology, Southwest Jiaotong University, Chengdu, Sichuan 610031 (China); Liu, Zheng-Tang [State Key Laboratory of Solidification Processing, School of Materials Science and Engineering, Northwestern Polytechnical University, Xi' an, Shaanxi 710072 (China)

    2014-03-01

    Using first-principles density-functional theory, we have investigated the pressure-induced phase transition in hydronitrogen compound N{sub 4}H{sub 4} and discussed the potential tetragonal structure. We find that tetragonal structure with P4{sub 2}/n space group is mechanically stable and ductile. The thermodynamic stability of Pmna>P1{sup ¯}>P4{sub 2}/n>P2{sub 1}/m has been obtained. With increasing pressure, the phase transition pressures of T{sub Pmna→P4{sub 2/n}}, T{sub P4{sub 2/n→Pmna}}, T{sub Pmna→P1{sup ¯}} and T{sub P1{sup ¯}→P2{sub 1/m}} are 5.6, 15.0, 30.0 and 69.2 GPa, respectively, which are in agreement with the available data. Moreover, the mechanical stability of four structures under pressure has been analyzed.

  14. On the effective mass in tetragonal semiconductors in the presence of an arbitrarily oriented quantizing magnetic field

    International Nuclear Information System (INIS)

    Mondal, M.; Ghatak, K.P.

    1984-01-01

    A generalized expression of the effective mass of charge carriers in tetragonal semiconductors (taking n-Cd 3 As 2 as an example) in the presence of arbitrary magnetic quantization has been derived considering the generalized dispersion relation of the conduction electrons and taking into account only the effective mass of the electrons at the Fermi surface

  15. First-principles study of lattice dynamics, structural phase transition, and thermodynamic properties of barium titanate

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Huai-Yong; Zhao, Ying-Qin; Lu, Qing [Sichuan Univ., Chengdu (China). Inst. of Atomic and Molecular Physics; Zeng, Zhao-Yi [Chongqing Normal Univ. (China). College of Physics and Electronic Engineering; Chinese Academy of Engineering Physics, Mianyang (China). National Key Laboratory for Shock Wave and Detonation Physics Research; Cheng, Yan [Sichuan Univ., Chengdu (China). Inst. of Atomic and Molecular Physics; Sichuan Univ., Chengdu (China). Key Laboratory of High Energy Density Physics and Technology of Ministry of Education

    2016-11-01

    Lattice dynamics, structural phase transition, and the thermodynamic properties of barium titanate (BaTiO{sub 3}) are investigated by using first-principles calculations within the density functional theory (DFT). It is found that the GGA-WC exchange-correlation functional can produce better results. The imaginary frequencies that indicate structural instability are observed for the cubic, tetragonal, and orthorhombic phases of BaTiO{sub 3} and no imaginary frequencies emerge in the rhombohedral phase. By examining the partial phonon density of states (PDOSs), we find that the main contribution to the imaginary frequencies is the distortions of the perovskite cage (Ti-O). On the basis of the site-symmetry consideration and group theory, we give the comparative phonon symmetry analysis in four phases, which is useful to analyze the role of different atomic displacements in the vibrational modes of different symmetry. The calculated optical phonon frequencies at Γ point for the four phases are in good agreement with other theoretical and experimental data. The pressure-induced phase transition of BaTiO{sub 3} among four phases and the thermodynamic properties of BaTiO{sub 3} in rhombohedral phase have been investigated within the quasi-harmonic approximation (QHA). The sequence of the pressure-induced phase transition is rhombohedral → ort