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Sample records for monoclinic zirconia nanocrystals

  1. Phonon anharmonicity of monoclinic zirconia and yttrium-stabilized zirconia

    DOE PAGES

    Li, Chen W.; Smith, Hillary L.; Lan, Tian; ...

    2015-04-13

    Inelastic neutron scattering measurements on monoclinic zirconia (ZrO2) and 8 mol% yttrium-stabilized zirconia were performed at temperatures from 300 to 1373 ωK. We reported temperature-dependent phonon densities of states (DOS) and Raman spectra obtained at elevated temperatures. First-principles lattice dynamics calculations with density functional theory gave total and partial phonon DOS curves and mode Grüneisen parameters. These mode Grüneisen parameters were used to predict the experimental temperature dependence of the phonon DOS with partial success. However, substantial anharmonicity was found at elevated temperatures, especially for phonon modes dominated by the motions of oxygen atoms. Yttrium-stabilized zirconia (YSZ) was somewhat moremore » anharmonic and had a broader phonon spectrum at low temperatures, owing in part to defects in its structure. YSZ also has a larger vibrational entropy than monoclinic zirconia.« less

  2. Phonon anharmonicity of monoclinic zirconia and yttrium-stabilized zirconia

    SciTech Connect

    Li, Chen W.; Smith, Hillary L.; Lan, Tian; Niedziela, Jennifer L.; Munoz, Jorge A.; Keith, J. Brian; Mauger, L.; Abernathy, Douglas L; Fultz, B.

    2015-04-13

    Inelastic neutron scattering measurements on monoclinic zirconia (ZrO2) and 8 mol% yttrium-stabilized zirconia were performed at temperatures from 300 to 1373 ωK. We reported temperature-dependent phonon densities of states (DOS) and Raman spectra obtained at elevated temperatures. First-principles lattice dynamics calculations with density functional theory gave total and partial phonon DOS curves and mode Grüneisen parameters. These mode Grüneisen parameters were used to predict the experimental temperature dependence of the phonon DOS with partial success. However, substantial anharmonicity was found at elevated temperatures, especially for phonon modes dominated by the motions of oxygen atoms. Yttrium-stabilized zirconia (YSZ) was somewhat more anharmonic and had a broader phonon spectrum at low temperatures, owing in part to defects in its structure. YSZ also has a larger vibrational entropy than monoclinic zirconia.

  3. Protonated Forms of Monoclinic Zirconia: A Theoretical Study

    SciTech Connect

    Mantz, Yves A.; Gemmen, Randall S.

    2010-05-06

    In various materials applications of zirconia, protonated forms of monoclinic zirconia may be formed, motivating their study within the framework of density-functional theory. Using the HCTH/120 exchange-correlation functional, the equations of state of yttria and of the three low-pressure zirconia polymorphs are computed, to verify our approach. Next, the favored charge state of a hydrogen atom in monoclinic zirconia is shown to be positive for all Fermilevel energies in the band gap, by the computation of defect formation energies.This result is consistent with a single previous theoretical prediction at midgap as well as muonium spectroscopy experiments. For the formally positively (+1e) charged system of a proton in monoclinic zirconia (with a homogeneous neutralizing background charge densityimplicitly included), modeled using up to a 3 x 3 x 3 arrangement of unit cells, different stable and metastable structures are identified. They are similar to those structures previously proposed for the neutral system of hydrogen-doedmonoclinic zirconia, at a similar level of theory. As predicted using the HCTH/120 functional, the lowest energy structure of the proton bonded to one of the two available oxygen atom types, O1, is favored by 0.39 eV compared to that of the proton bonded to O2. The rate of proton transfer between O1 ions is slower than that for hydrogen-dopedmonoclinic zirconia, whose transition-state structures may be lowered in energy by the extra electron.

  4. Near coincidence site lattice misorientations in monoclinic zirconia

    SciTech Connect

    Gertsman, V.Y. |; Zhilyaev, A.P. |; Szpunar, J.

    1996-12-01

    Zirconium dioxide, ZrO{sub 2}, exists in three crystalline phases: monoclinic, tetragonal, and cubic. Calculations of the coincidence site lattice (CSL) misorientations for the last two lattices and for hexagonal ones using the methods developed represent little difficulty. However, no procedure for the determination of the CSL misorientations in the monoclinic system has been reported so far. Monoclinic zirconia has the crystallographic space group P2{sub 1}/c and the following parameters of the unit cell (e.g., 5, 6): a = 5.1490 {angstrom}, b = 5.2133 {angstrom}, c = 5.3161 {angstrom}, and {beta} = 99.228{degree}. Before discussing possible CSL misorientations in zirconia, consider a simple example based on geometric considerations. In any monoclinic crystal (with any lattice parameters) the two symmetrical boundaries along the (001) and (100) planes must have highly ordered atomic structure. The misorientation of the first boundary is descried as a rotation of either 180{degree} around the [100] direction or 180{degree} around the normal to the (001) plane. The misorientation of the second boundary is 180{degree} [001] or 180{degree} around the normal to the (100) plane. It can be shown that three-dimensional CSLs will exist in both cases if (c/a)cos{beta} is a rational number. This example justifies the following approximation of the unit cell in the monoclinic zirconia: a = b = c and cos{beta} = {minus}1/6 (i.e., {beta} = 99.594{degree}). Consider the following prismatic cell in the monoclinic crystal structure: ([1 0 1], [{bar 1} 0 1], [0 1 0]). With the above approximation, this cell is orthogonal with the ratios of the squares of the edge lengths expressed as 5:7:3. Therefore, one can apply the algorithm for calculations of the CSL misorientations in orthorhombic lattices with rational ratios of squares of the lattice periods, which is based on the general vector-quaternion method of misorientation representation.

  5. Phase field modeling of tetragonal to monoclinic phase transformation in zirconia

    NASA Astrophysics Data System (ADS)

    Mamivand, Mahmood

    Zirconia based ceramics are strong, hard, inert, and smooth, with low thermal conductivity and good biocompatibility. Such properties made zirconia ceramics an ideal material for different applications form thermal barrier coatings (TBCs) to biomedicine applications like femoral implants and dental bridges. However, this unusual versatility of excellent properties would be mediated by the metastable tetragonal (or cubic) transformation to the stable monoclinic phase after a certain exposure at service temperatures. This transformation from tetragonal to monoclinic, known as LTD (low temperature degradation) in biomedical application, proceeds by propagation of martensite, which corresponds to transformation twinning. As such, tetragonal to monoclinic transformation is highly sensitive to mechanical and chemomechanical stresses. It is known in fact that this transformation is the source of the fracture toughening in stabilized zirconia as it occurs at the stress concentration regions ahead of the crack tip. This dissertation is an attempt to provide a kinetic-based model for tetragonal to monoclinic transformation in zirconia. We used the phase field technique to capture the temporal and spatial evolution of monoclinic phase. In addition to morphological patterns, we were able to calculate the developed internal stresses during tetragonal to monoclinic transformation. The model was started form the two dimensional single crystal then was expanded to the two dimensional polycrystalline and finally to the three dimensional single crystal. The model is able to predict the most physical properties associated with tetragonal to monoclinic transformation in zirconia including: morphological patterns, transformation toughening, shape memory effect, pseudoelasticity, surface uplift, and variants impingement. The model was benched marked with several experimental works. The good agreements between simulation results and experimental data, make the model a reliable tool for

  6. Microstructure, bioactivity and osteoblast behavior of monoclinic zirconia coating with nanostructured surface.

    PubMed

    Wang, Guocheng; Meng, Fanhao; Ding, Chuanxian; Chu, Paul K; Liu, Xuanyong

    2010-03-01

    A monoclinic zirconia coating with a nanostructural surface was prepared on the Ti-6Al-4V substrate by an atmospheric plasma-spraying technique, and its microstructure and composition, as well as mechanical and biological properties, were investigated to explore potential application as a bioactive coating on bone implants. X-ray diffraction, transmission electron microscopy, scanning electron microscopy and Raman spectroscopy revealed that the zirconia coating was composed of monoclinic zirconia which was stable at low temperature, and its surface consists of nano-size grains 30-50 nm in size. The bond strength between the coating and the Ti-6Al-4V substrate was 48.4 + or - 6.1 MPa, which is higher than that of plasma-sprayed HA coatings. Hydrothermal experiments indicated that the coating was stable in a water environment and the phase composition and Vickers hardness were independent of the hydrothermal treatment time. Bone-like apatite is observed to precipitate on the surface of the coating after soaking in simulated body fluid for 6 days, indicating excellent bioactivity in vitro. The nanostructured surface composed of monoclinic zirconia is believed to be crucial to its bioactivity. Morphological observation and the cell proliferation test demonstrated that osteoblast-like MG63 cells could attach to, adhere to and proliferate well on the surface of the monoclinic zirconia coating, suggesting possible applications in hard tissue replacements.

  7. Influence of the monoclinic and tetragonal zirconia phases on the water gas shift reaction. A theoretical study.

    PubMed

    Cerón, María Luisa; Herrera, Barbara; Araya, Paulo; Gracia, Francisco; Toro-Labbé, Alejandro

    2013-07-01

    We present a theoretical study of the water gas shift reaction taking place on zirconia surfaces modeled by monoclinic and tetragonal clusters. In order to understand the charge transfer between the active species, in this work we analyze the influence of the geometry of monoclinic and tetragonal zirconia using reactivity descriptors such as electronic chemical potential (μ), charge transfer (ΔN) and molecular hardness (η). We have found that the most preferred surface is tetragonal zirconia (tZrO2) indicating also that low charge transfer systems will generate less stable intermediates, that will allow to facilitate desorption process.

  8. Zirconia nanocrystals as submicron level biological label

    NASA Astrophysics Data System (ADS)

    Smits, K.; Liepins, J.; Gavare, M.; Patmalnieks, A.; Gruduls, A.; Jankovica, D.

    2012-08-01

    Inorganic nanocrystals are of increasing interest for their usage in biology and pharmacology research. Our interest was to justify ZrO2 nanocrystal usage as submicron level biological label in baker's yeast Saccharomyces cerevisia culture. For the first time (to our knowledge) images with sub micro up-conversion luminescent particles in biologic media were made. A set of undoped as well as Er and Yb doped ZrO2 samples at different concentrations were prepared by sol-gel method. The up-conversion luminescence for free standing and for nanocrystals with baker's yeast cells was studied and the differences in up-conversion luminescence spectra were analyzed. In vivo toxic effects of ZrO2 nanocrystals were tested by co-cultivation with baker's yeast.

  9. Analysis of tetragonal to monoclinic phase transformation caused by accelerated artificial aging and the effects of microstructure in stabilized zirconia

    NASA Astrophysics Data System (ADS)

    Lucas, Thomas J.

    This investigation addresses the issue that yttria stabilized zirconia is being used as a dental biomaterial without substantial evidence of its long-term viability. Furthermore, stabilized zirconia (SZ) undergoes low temperature degradation (LTD), which can lead to roughening of the surface. A rougher exterior can lead to increased wear of the antagonist in the oral environment. Despite the LTD concerns, SZ is now widely used in restorative dentistry, including full contour crowns. A comparison of aging methods to determine the role of artificial aging on inducing the transformation has not been extensively studied. Therefore, simulations of the transformation process were investigated by comparing different methods of accelerated aging. The rejected null hypothesis is that the temperature of aging treatment will not affect the time required to cause measurable monoclinic transformation of yttria stabilized zirconia. The transformation of SZ starts at the surface and progresses inward; however, it is unclear whether the progression is constant for different aging conditions. This investigation analyzed the depth of transformation as a function of aging conditions for stabilized zirconia in the top 5-6 mum from the surface. The rejected null hypothesis is that the transformation amount is constant throughout the first six micrometers from the surface. The effects of grain size on the amount of monoclinic transformation were also investigated. This study aimed to determine if the grain size of partially stabilized zirconia affects the amount of monoclinic transformation, surface roughness, and property degradation due to aging. The rejected null hypothesis is that the grain size will not affect the amount of monoclinic transformation, thus have no effect on surface roughening or property degradation. The final part of this study addresses the wear of enamel when opposing zirconia by observing how grain size and aging affected the wear rate of an enamel antagonist

  10. Microstructural characterization and optical properties of green emitting hexagonal and monoclinic CePO4:Tb3+ nanocrystals

    NASA Astrophysics Data System (ADS)

    Sisira, S.; Alexander, Dinu; Thomas, Kukku; Vimal, G.; Mani, Kamal P.; Biju, P. R.; Unnikrishnan, N. V.; Joseph, Cyriac

    2017-02-01

    Green emitting CePO4:Tb3+ nanocrystals with hexagonal and monoclinic structures were successfully synthesized through microwave assisted sol gel method. The variation observed in the powder XRD pattern from that of bulk is explained using HRTEM analysis in relation with the preferential growth in distinct directions to form nanorods. The results obtained from the microstructural characterization of the hexagonal and monoclinic CePO4:Tb3+nanocrystals are successfully correlated with the single crystal data of CePO4 for the first time in accordance with the single crystal growth theory. FTIR spectrum of the CePO4 nanocrystals evidenced the splitting of fundamental vibrations of phosphate group in the nine fold coordination of lanthanide atoms and confirmed the low symmetry of monoclinic structure than the hexagonal system. The diminishing intensity of terbium emission in the hexagonal structure than the monoclinic structured CePO4:Tb3+ nanocrystals is explained in relation with the lattice symmetry. The high intensity green emission due to the strong 5D4–7F5 transition in monoclinic CePO4:Tb3+ nanocrystals make it as a potential candidate for optoelectronic applications.

  11. On the kinetics and impact of tetragonal to monoclinic transformation in an alumina/zirconia composite for arthroplasty applications.

    PubMed

    Chevalier, Jérôme; Grandjean, Sylvie; Kuntz, Meinhard; Pezzotti, Giuseppe

    2009-10-01

    Latest trends in load-bearing materials for arthroplastic applications involve the development of highly fracture resistant alumina/zirconia composites, as an alternative choice to alumina and zirconia monolithic ceramics. Composite materials are designed from both chemical and microstructural viewpoints in order to prevent environmental degradation and fracture events in vivo, whose shadow yet hampers the full exploitation of ceramic materials in the field of arthroplasty. The aim of this paper is to evaluate the resistance to environmental degradation in an alumina/zirconia composite (Biolox Delta), which represents a primary candidate for hip and knee joint applications. Our approach consists first in the experimental determination of an activation energy value for environmentally driven tetragonal to monoclinic (t-m, henceforth) polymorphic transformation in the zirconia phase of the material; then, based on such an experimental value, a prediction is given for the long-term in vivo environmental resistance of prostheses made of the composite material. The present evaluation clarifies the in vivo performance of this new composite for orthopedic applications.

  12. Direct Single-Enzyme Biomineralization of Catalytically Active Ceria and Ceria-Zirconia Nanocrystals.

    PubMed

    Curran, Christopher D; Lu, Li; Jia, Yue; Kiely, Christopher J; Berger, Bryan W; McIntosh, Steven

    2017-02-21

    Biomineralization is an intriguing approach to the synthesis of functional inorganic materials for energy applications whereby biological systems are engineered to mineralize inorganic materials and control their structure over multiple length scales under mild reaction conditions. Herein we demonstrate a single-enzyme-mediated biomineralization route to synthesize crystalline, catalytically active, quantum-confined ceria (CeO2-x) and ceria-zirconia (Ce1-yZryO2-x) nanocrystals for application as environmental catalysts. In contrast to typical anthropogenic synthesis routes, the crystalline oxide nanoparticles are formed at room temperature from an otherwise inert aqueous solution without the addition of a precipitant or additional reactant. An engineered form of silicatein, rCeSi, as a single enzyme not only catalyzes the direct biomineralization of the nanocrystalline oxides but also serves as a templating agent to control their morphological structure. The biomineralized nanocrystals of less than 3 nm in diameter are catalytically active toward carbon monoxide oxidation following an oxidative annealing step to remove carbonaceous residue. The introduction of zirconia into the nanocrystals leads to an increase in Ce(III) concentration, associated catalytic activity, and the thermal stability of the nanocrystals.

  13. Hansen solubility parameter analysis on the dispersion of zirconia nanocrystals.

    PubMed

    Wang, Sho-Hsun; Liu, Jia-Hong; Pai, Chin-Tung; Chen, Chien-Wei; Chung, Pao-Tang; Chiang, Anthony Shiaw-Tseh; Chang, Shinn-Jen

    2013-10-01

    Nanoparticle dispersible in a broad range of solvents is desirable when preparing an organic/inorganic nanocomposite. In this report, the dispersion behavior of carboxylate-grafted zirconia nanoparticle in 25 solvents covering a wide range of polarity was analyzed based on their Hansen solubility parameters (HSP). Particles grafted with alkyl-chain longer than four carbons could only be dispersed in non-polar solvents, while that grafted with acetic acid was dispersible in polar ones. However, particle modified with methacrylic acid (MA) was compatible with both types of solvents, which was rather unexpected. Further NMR analysis showed that the carboxylate-grafted samples contained a trace amount of triethanolamine (TEA) due to the particular ZrO2 synthesis process employed. The combination of the hydrophilic TEA ligand with the short hydrophobic tail of methacrylate broadened the range of compatible solvents from benzene to methanol. Such an extended solvent compatibility was observed previously only for nanoparticles covered with large polymer surfactants having both hydrophilic and hydrophobic groups. Achieving this with two small molecules having separate functional groups is crucial when one needs to maximize the inorganic content in a composite.

  14. Luminescent nanocrystals in the rare-earth niobate–zirconia system formed via hydrothermal method

    SciTech Connect

    Hirano, Masanori Dozono, Hayato

    2013-08-15

    Luminescent nanocrystals based on the rare-earth niobates (Ln{sub 3}NbO{sub 7}, Ln=Y, Eu) and zirconia (ZrO{sub 2}) that were composed of 50 mol% Ln{sub 3}NbO{sub 7} and 50 mol% ZrO{sub 2}, were hydrothermally formed as cubic phase under weakly basic conditions at 240 °C. The lattice parameter of the as-prepared nanoparticles corresponding to the composition of Y{sub 3−x}Eu{sub x}NbO{sub 7}–4ZrO{sub 2} that was estimated as a single phase of cubic gradually increased as the content of europium x increased. The existence of small absorbance peaks at 395 and 466 nm corresponding to the Eu{sup 3+7}F{sub 0}→{sup 5}L{sub 6}, and {sup 7}F{sub 0}→{sup 5}D{sub 2} excitation transition, respectively, was clearly observed in the diffuse reflectance spectra of the as-prepared samples containing europium. The optical band gap of the as-prepared samples was in the range from 3.5 to 3.7 eV. The photoluminescence spectra of the as-prepared nanocrystals containing europium showed orange and red luminescences with main peaks at 590 and 610 nm, corresponding to {sup 5}D{sub 0}→{sup 7}F{sub 1} and {sup 5}D{sub 0}→{sup 7}F{sub 2} transitions of Eu{sup 3+}, respectively, under excitation at 395 nm Xe lamp. The emission intensity corresponding to {sup 5}D{sub 0}→{sup 7}F{sub 2} transition increased as heat-treatment temperature rose from 800 to 1200 °C. - Graphical abstract: This graphical abstract shows the excitation and emission spectra and a transmission electron microscopy image of nanocrystals (with composition based on the rare-earth niobates (Ln{sub 3}NbO{sub 7}, Ln=Y, Eu) and zirconia (ZrO{sub 2}) that were composed of 50 mol% Ln{sub 3}NbO{sub 7} and 50 mol% ZrO{sub 2}) formed via hydrothermal route. Display Omitted - Highlights: • Nanocrystals composed of 50 mol% Y{sub 3−x}Eu{sub x}NbO{sub 7} and 50 mol% ZrO{sub 2} was directly formed. • The nanocrystals were hydrothermally formed under weakly basic conditions at 240 °C. • The Y{sub 3}NbO{sub 7} showed

  15. The radiation response of mesoporous nanocrystalline zirconia thin films

    NASA Astrophysics Data System (ADS)

    Manzini, Ayelén M.; Alurralde, Martin A.; Giménez, Gustavo; Luca, Vittorio

    2016-12-01

    The next generation of nuclear systems will require materials capable of withstanding hostile chemical, physical and radiation environments over long time-frames. Aside from its chemical and physical stability, crystalline zirconia is one of the most radiation tolerant materials known. Here we report the first ever study of the radiation response of nanocrystalline and mesoporous zirconia and Ce3+-stabilized nanocrystalline zirconia (Ce0.1Zr0.9O2) thin films supported on silicon wafers. Zirconia films prepared using the block copolymer Brij-58 as the template had a thickness of around 60-80 nm. In the absence of a stabilizing trivalent cation they consisted of monoclinic and tetragonal zirconia nanocrystals with diameters in the range 8-10 nm. Films stabilized with Ce3+ contained only the tetragonal phase. The thin films were irradiated with iodine ions of energies of 70 MeV and 132 keV at low fluences (1013 - 1014 cm-2) corresponding to doses of 0.002 and 1.73 dpa respectively, and at 180 keV and high fluences (2 × 1016 cm-2) corresponding to 82.4 dpa. The influence of heavy ion irradiation on the nanocrystalline structure was monitored through Rietveld analysis of grazing incidence X-ray diffraction (GIXRD) patterns recorded at angles close to the critical angle to ensure minimum contribution to the diffraction pattern from the substrate. Irradiation of the mesoporous nanocrystalline zirconia thin films with 70 MeV iodine ions, for which electronic energy loss is dominant, resulted in slight changes in phase composition and virtually no change in crystallographic parameters as determined by Rietveld analysis. Iodine ion bombardment in the nuclear energy loss regime (132-180 keV) at low fluences did not provoke significant changes in phase composition or crystallographic parameters. However, at 180 keV and high fluences the monoclinic phase was totally eliminated from the GIXRD pattern of films prepared at both 350 and 500 °C implying either a monoclinic

  16. Luminescence and energy transfer mechanism in Eu3+/Tb3+-co-doped ZrO2 nanocrystal rods

    NASA Astrophysics Data System (ADS)

    Ahemen, I.; Dejene, F. B.

    2017-01-01

    Nanocrystal rods of Eu3+/Tb3+-co-doped ZrO2 were synthesized using a simple chemical precipitation technique. Both ions were successfully doped into the Zr4+ ion site in a mixed structure containing both monoclinic and tetragonal phases. The Eu3+ or Tb3+ singly doped zirconia produced red and green luminescence which are characteristics of Eu3+ and Tb3+ ions, respectively. The co-doped zirconia samples produced blue emission from defect states transitions in the host ZrO2, red and green luminescence from dopant ions giving cool to warm white light emissions. The phosphors were efficiently excited by ultraviolet and near-ultraviolet/blue radiations giving white and red light, respectively. The decay lifetime was found to increase with increasing donor ion concentration contrary to conventional observations reported by previous researchers. Weak quadrupole-quatdrupole multipolar process was responsible for energy transfer from Tb3+ (donor) ion to Eu3+ ion. No energy back-transfer from Eu3+ to Tb3+ ion was observed from the excitation spectra. Temperature-dependent photoluminescence shows the presence of defects at low temperature, but these defects vanished at room temperature and beyond. The Eu3+/Tb3+-co-doped ZrO2 nanocrystal rod is a potential phosphor for white light application using UV as an excitation source. Thermoluminescence measurements show that the inclusion of Tb3+ ion increases trap depths in the host zirconia.

  17. Phase stability of zirconia at nanoscale.

    NASA Astrophysics Data System (ADS)

    Sabiryanov, Renat; Mei, W. N.

    2004-03-01

    There are three phases of ZrO2, namely cubic, tetragonal and monoclinic. Cubic phase of zirconia is usually stabilized by various dopants such as yttria and magnesia. However, it has been observed that these stablizers are indeed the source failure of doped ZrO2 in both orthopaedics and in ZrO2 used in high temperature applications. Recently, the cubic zirconia was fabricated as granular media with the grain sizes less than 17nm. We examine the phase stability in zirconia nanoparticles using first principle electronic structure method. We observe considerable relaxation of lattice in the monoclinic phase near the surface. This effect combined with surface tension and possibly vacancies in nanostructures are sources of stability of cubic zirconia at nanoscale. We performed calculation of the surface tension calculations for the pure (001) surface. The uniform compressive strain is applied in the plane of the slab to find the elastic response of the system. The slab is allowed to relax in the perpendicular direction. Uniform compressive strain in the plane of the slab causes increase in the distance between Zr and O layers for (001) surface (as a solid tends to preserve the volume). For cubic it gives -0.65N/m, while for monoclinic -0.48N/m. Furthermore, the solid-gas surface tension is a fundamental physical/chemical property of a solid, which affects its wetting properties. Therefore, cubic zirconia is more suitable to design the material combining wettability, ductility and hardness.

  18. (Hyperfine experimental investigation of zirconia ceramics)

    SciTech Connect

    Not Available

    1992-01-01

    This research program has encompassed a broad investigation of microscopic structure and point defect properties in insulating materials and some recent exploratory work on semiconductors. The major experimental technique is perturbed angular correlation (PAC) spectroscopy. Our research provides information about the microscopic structure, nucleation, and equilibrium of structural phases in materials under investigation. We have studied phase equilibria in monoclinic, tetragonal, and cubic zirconia in the past and have recently begun more detailed investigation of high-temperature anomalies in monoclinic zirconia and tetragonal stabilized zirconia. We also have found a number of instances where the indium PAC probe has detected subtle phase changes, small precipitate formation, and other phase behavior that are difficult to detect by conventional diffraction methods. The PAC experimental technique is described briefly in section 2, and recent research is reviewed in section 3.

  19. [Hyperfine experimental investigation of zirconia ceramics]. [Annual progress report 20

    SciTech Connect

    Not Available

    1992-09-01

    This research program has encompassed a broad investigation of microscopic structure and point defect properties in insulating materials and some recent exploratory work on semiconductors. The major experimental technique is perturbed angular correlation (PAC) spectroscopy. Our research provides information about the microscopic structure, nucleation, and equilibrium of structural phases in materials under investigation. We have studied phase equilibria in monoclinic, tetragonal, and cubic zirconia in the past and have recently begun more detailed investigation of high-temperature anomalies in monoclinic zirconia and tetragonal stabilized zirconia. We also have found a number of instances where the indium PAC probe has detected subtle phase changes, small precipitate formation, and other phase behavior that are difficult to detect by conventional diffraction methods. The PAC experimental technique is described briefly in section 2, and recent research is reviewed in section 3.

  20. Phase transformation of zirconia ceramics by hydrothermal degradation.

    PubMed

    Kawai, Yohei; Uo, Motohiro; Wang, Yongming; Kono, Sayaka; Ohnuki, Somei; Watari, Fumio

    2011-01-01

    Zirconia has found wide application in dentistry because of its high mechanical strength and superior esthetic properties. However, zirconia degradation caused by phase transformation occurring in a hydrothermal environment is of concern. In the present study, phase transformation and microstructure of tetragonal zirconia polycrystal partially stabilized with yttrium oxide (Y-TZP) and alumina-toughened zirconia (ATZ) sintered at different temperatures were estimated. On grazing angle X-ray diffraction analysis, ATZ showed less phase transformation to the monoclinic phase during hydrothermal treatment and this transformation appeared to occur within a few micrometers below the surface. At a higher sintering temperature the monoclinic phase content of ATZ was found to be lesser than that of Y-TZP, indicating that the alumina in ATZ was effective in suppressing hydrothermal degradation. Examination by transmission electron microscopy and studying of electron backscatter diffraction patterns indicated that grain growth in ATZ was slightly suppressed compared with that in Y-TZP at higher sintering temperatures. The present study demonstrated the effect of adding alumina to zirconia for suppressing hydrothermal degradation and studied the effect of this addition on grain growth in zirconia.

  1. Structural and Chemical Analysis of the Zirconia-Veneering Ceramic Interface.

    PubMed

    Inokoshi, M; Yoshihara, K; Nagaoka, N; Nakanishi, M; De Munck, J; Minakuchi, S; Vanmeensel, K; Zhang, F; Yoshida, Y; Vleugels, J; Naert, I; Van Meerbeek, B

    2016-01-01

    The interfacial interaction of veneering ceramic with zirconia is still not fully understood. This study aimed to characterize morphologically and chemically the zirconia-veneering ceramic interface. Three zirconia-veneering conditions were investigated: 1) zirconia-veneering ceramic fired on sandblasted zirconia, 2) zirconia-veneering ceramic on as-sintered zirconia, and 3) alumina-veneering ceramic (lower coefficient of thermal expansion [CTE]) on as-sintered zirconia. Polished cross-sectioned ceramic-veneered zirconia specimens were examined using field emission gun scanning electron microscopy (Feg-SEM). In addition, argon-ion thinned zirconia-veneering ceramic interface cross sections were examined using scanning transmission electron microscopy (STEM)-energy dispersive X-ray spectrometry (EDS) at high resolution. Finally, the zirconia-veneering ceramic interface was quantitatively analyzed for tetragonal-to-monoclinic phase transformation and residual stress using micro-Raman spectroscopy (µRaman). Feg-SEM revealed tight interfaces for all 3 veneering conditions. High-resolution transmission electron microscopy (HRTEM) disclosed an approximately 1.0-µm transformed zone at sandblasted zirconia, in which distinct zirconia grains were no longer observable. Straight grain boundaries and angular grain corners were detected up to the interface of zirconia- and alumina-veneering ceramic with as-sintered zirconia. EDS mapping disclosed within the zirconia-veneering ceramic a few nanometers thick calcium/aluminum-rich layer, touching the as-sintered zirconia base, with an equally thick silicon-rich/aluminum-poor layer on top. µRaman revealed t-ZrO2-to-m-ZrO2 phase transformation and residual compressive stress at the sandblasted zirconia surface. The difference in CTE between zirconia- and the alumina-veneering ceramic resulted in residual tensile stress within the zirconia immediately adjacent to its interface with the veneering ceramic. The rather minor chemical

  2. Nanocrystal structures

    DOEpatents

    Eisler, Hans J.; Sundar, Vikram C.; Walsh, Michael E.; Klimov, Victor I.; Bawendi, Moungi G.; Smith, Henry I.

    2006-12-19

    A structure including a grating and a semiconductor nanocrystal layer on the grating, can be a laser. The semiconductor nanocrystal layer can include a plurality of semiconductor nanocrystals including a Group II–VI compound, the nanocrystals being distributed in a metal oxide matrix. The grating can have a periodicity from 200 nm to 500 nm.

  3. Synthesis and characterization of mesoporous zirconia and aluminated mesoporous zirconia

    NASA Astrophysics Data System (ADS)

    Zhao, Elizabeth Sun

    Synthesis of mesoporous zirconia has been performed by slowly hydrolyzing zirconium propoxide in the presence of anionic surfactants: namely, dodecyl phosphate or sulfate (P12 and Sf12) and hexadecyl sulfonate (So16) The zirconia. outgassed at 140--150°C has T-plot surface areas higher than 400 M2/g. This outgassing does not remove the surfactant. After calcination in air at 500°C and combustion of the surfactant, the mesoporous volume is reduced by a factor of about 2, whereas the pore wall material crystallizes in the tetragonal phase. The high-resolution electron microscopic study reveals the presence of a disorganized network of polygonal pores structure. It is suggested that the chemistry of the hydrolysis solution is instrumental in determining the pore structure. A schematic model in which the surfactant is a scaffold component is suggested in order to explain these results and the fixation of PO4, or SO4 in the walls may help to preserve the porous structure. It is very different from the templating mechanism. From the density obtained from phase transition temperature, and from the mesoporous volume (N2 adsorption), the thickness of the wall can be calculated as well as the pseudo-length of the pores. From the thickness, the T-plot area can be recalculated and agrees well with the measured T-plot surface area for the sample calcined at 500°C. Around 900°C, the walls become thicker and crystallizes into monoclinic zirconia without pore structure. In order to try to modify, the acidity of the mesoporous sulfated and oxo-phosphated zirconia, they were doped with aluminum. The sulfated zirconia only has a coating layer of amorphous alumina, while the phosphated zirconia has aluminum in the lattice and the alumina coat. A maximum ratio of Al/Zr ˜ 0.04 can be reached in the lattice. The introduction of aluminum into the lattice prevents the crystallization of the oxo-phosphate at 900°C, and helps to preserve the surface area and porosity of the sulfated

  4. Glass ceramic toughened with tetragonal zirconia

    DOEpatents

    Keefer, K.D.

    1984-02-10

    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. Nuclearing 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 to 1700/sup 0/C and is then heat-treated at a temperature within the range of 800 to 1200/sup 0/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.

  5. Silicon carbide whisker-zirconia reinforced mullite and alumina ceramics

    DOEpatents

    Becher, Paul F.; Tiegs, Terry N.

    1987-01-01

    The flexural strength and/or fracture toughness of SiC whisker-reinforced composites utilizing mullite or alumina as the matrix material for the composite are increased by the addition of zirconia in a monoclinic or tetragonal phase to the matrix. The zirconia addition also provides for a lower hot-pressing temperature and increases the flexural strength and/or fracture toughness of the SiC whisker-reinforced composites over SiC whisker-reinforced composites of the similar matrix materials reinforced with similar concentrations of SiC whiskers.

  6. Tailoring the Microstructure of Sol–Gel Derived Hydroxyapatite/Zirconia Nanocrystalline Composites

    PubMed Central

    2011-01-01

    In this study, we tailor the microstructure of hydroxyapatite/zirconia nanocrystalline composites by optimizing processing parameters, namely, introducing an atmosphere of water vapor during sintering in order to control the thermal stability of hydroxyapatite, and a modified sol–gel process that yields to an excellent intergranular distribution of zirconia phase dispersed intergranularly within the hydroxyapatite matrix. In terms of mechanical behavior, SEM images of fissure deflection and the presence of monoclinic ZrO2 content on cracked surface indicate that both toughening mechanisms, stress-induced tetragonal to monoclinic phase transformation and deflection, are active for toughness enhancement. PMID:24764458

  7. Superhard monoclinic polymorph of carbon.

    PubMed

    Li, Quan; Ma, Yanming; Oganov, Artem R; Wang, Hongbo; Wang, Hui; Xu, Ying; Cui, Tian; Mao, Ho-Kwang; Zou, Guangtian

    2009-05-01

    We report a novel phase of carbon possessing a monoclinic C2/m structure (8 atoms/cell) identified using an ab initio evolutionary structural search. This polymorph, which we call M-carbon, is related to the (2x1) reconstruction of the (111) surface of diamond and can also be viewed as a distorted (through sliding and buckling of the sheets) form of graphite. It is stable over cold-compressed graphite above 13.4 GPa. The simulated x-ray diffraction pattern and near K-edge spectroscopy are in satisfactory agreement with the experimental data [W. L. Mao, Science 302, 425 (2003)10.1126/science.1089713] on overcompressed graphite. The hardness and bulk modulus of this new carbon polymorph are calculated to be 83.1 and 431.2 GPa, respectively, which are comparable to those of diamond.

  8. Superhard Monoclinic Polymorph of Carbon

    SciTech Connect

    Li, Quan; Ma, Yanming; Oganov, Artem R.; Wang, Hongbo; Wang, Hui; Xu, Ying; Cui, Tian; Mao, Ho-Kwang; Zou, Guangtian; Jilin; SBU; CIW

    2009-05-08

    We report a novel phase of carbon possessing a monoclinic C2/m structure (8 atoms/cell) identified using an ab initio evolutionary structural search. This polymorph, which we call M-carbon, is related to the (2x1) reconstruction of the (111) surface of diamond and can also be viewed as a distorted (through sliding and buckling of the sheets) form of graphite. It is stable over cold-compressed graphite above 13.4 GPa. The simulated x-ray diffraction pattern and near K-edge spectroscopy are in satisfactory agreement with the experimental data [W.L. Mao et al., Science 302, 425 (2003)] on overcompressed graphite. The hardness and bulk modulus of this new carbon polymorph are calculated to be 83.1 and 431.2 GPa, respectively, which are comparable to those of diamond.

  9. Phase analysis of plasma-sprayed zirconia-yttria coatings

    NASA Technical Reports Server (NTRS)

    Shankar, N. R.; Berndt, C. C.; Herman, H.

    1983-01-01

    Phase analysis of plasma-sprayed 8 wt pct-yttria-stabilized zirconia (YSZ) thermal barrier coatings and powders was carried out by X-ray diffraction. Step scanning was used for increased peak resolution. Plasma spraying of the YSZ powder into water or onto a steel substrate to form a coating reduced the cubic and monoclinic phases with a simultaneous increase in the tetragonal phase. Heat treatment of the coating at 1150 C for 10 h in an Ar atmosphere increased the amount of cubic and monoclinic phases. The implications of these transformations on coating performance and integrity are discussed.

  10. Conduction band topology and optical properties of monoclinic ZrO_2

    NASA Astrophysics Data System (ADS)

    Freeman, A. J.; Medvedeva, J. E.; Geller, C. B.

    2004-03-01

    Zirconia is an attractive base material for a wide variety of optical applications, on account of its high refractive index, large band gap and low optical loss. We report highly precise density functional theory calculations on pure, monoclinic zirconia employing the self-consistent screened exchange local-density approximation(R. Asahi, W. Mannstadt, A. J. Freeman, Phys. Rev. B) 59, 7486 (1999) (sX-LDA) with the full-potential linearized augmented plane wave (FLAPW) method(E. Wimmer, H. Krakauer, M. Weinert, A.J. Freeman, Phys. Rev. B) 24, 864 (1981). The sX-LDA substantially reduces the overbinding error in the LDA resulting in a more accurate description of the band gap and excited states in semiconductors(C.B. Geller er al), Appl. Phys. Lett. 79, 368 (2001) and insulators (this work). The predicted sX-LDA indirect band gap of monoclinic ZrO2 is 5.7 eV, in agreement with experiment. The effects of carrier concentration on the effective masses and optical properties of zirconia are discussed.

  11. Phase distributions in plasma-sprayed zirconia-yttria

    NASA Technical Reports Server (NTRS)

    Miller, R. A.; Garlick, R. G.; Smialek, J. L.

    1983-01-01

    The distribution of phases in plasma-sprayed zirconia-yttria has been determined over a range of yttria levels from 0 to 26.1 molpct YO(1.5) using room temperature X-ray diffractometry. Pure, plasma-sprayed zirconia is composed almost entirely of the monoclinic phase. At levels of yttria between 4 and 10 percent, a quenched-in tetragonal phase predominates, and at higher levels the cubic phase predominates. The phase distributions are compared with previously reported test lives of thermal barrier coatings formed from these materials. Regions of optimal lives were found to correlate with regions having high amounts of the tetragonal phase, small but nonzero amounts of the monoclinic phase, and little or none of the cubic phase. Possible relationships between phase composition and coating performance are discussed.

  12. A sol-powder coating technique for fabrication of yttria stabilised zirconia

    SciTech Connect

    Wattanasiriwech, Darunee . E-mail: darunee@mfu.ac.th; Wattanasiriwech, Suthee; Stevens, Ron

    2006-08-10

    Yttria stabilised zirconia has been prepared using a simple sol-powder coating technique. The polymeric yttria sol, which was prepared using 1,3 propanediol as a network modifier, was homogeneously mixed with nanocrystalline zirconia powder and it showed a dual function: as a binder which promoted densification and a phase modifier which stabilised zirconia in the tetragonal and cubic phases. Thermal analysis and X-ray diffraction revealed that the polymeric yttria sol which decomposed at low temperature into yttrium oxide could change the m {sup {yields}} t phase transformation behaviour of the zirconia, possibly due to the small particle size and very high surface area of both yttria and zirconia particles allowing rapid alloying. The sintered samples exhibited three crystalline phases: monoclinic, tetragonal and cubic, in which cubic and tetragonal are the major phases. The weight fractions of the individual phases present in the selected specimens were determined using quantitative Rietveld analysis.

  13. Contamination of dental zirconia before final firing: effects on mechanical properties.

    PubMed

    Ban, Seiji; Okuda, Yuji; Noda, Makoto; Tsuruki, Jiro; Kawai, Tatsushi; Kono, Hiroshi

    2013-01-01

    Plate-like specimens were prepared, using a diamond saw, from Cercon -a pre-sintered yttria-stabilized tetragonal zirconia polycrystal (Y-TZP) block. These specimens were treated with 10 kinds of dental materials which acted as contaminants, and then sintered at 1,350°C or 1,450°C. After the final firing, specimens were subjected to a three-point flexural test and Vickers hardness test. Their surfaces were also characterized by scanning electron microscopy and X-ray diffractometry. Phosphorus-containing contaminants reduced the three-point flexural strength and hardness of final sintered zirconia due to the formation of YPO4 and phase transformation from tetragonal to monoclinic zirconia. Gypsum also reduced both mechanical properties due to the formation of CaZrO3 and phase transformation from tetragonal to cubic zirconia. Other contaminants showed no adverse effects on the mechanical properties of final sintered zirconia.

  14. From Zirconium Nanograins to Zirconia Nanoneedles

    PubMed Central

    Zalnezhad, E.; Hamouda, A. M. S.; Jaworski, J.; Do Kim, Young

    2016-01-01

    Combinations of three simple techniques were utilized to gradually form zirconia nanoneedles from zirconium nanograins. First, a physical vapor deposition magnetron sputtering technique was used to deposit pure zirconium nanograins on top of a substrate. Second, an anodic oxidation was applied to fabricate zirconia nanotubular arrays. Finally, heat treatment was used at different annealing temperatures in order to change the structure and morphology from nanotubes to nanowires and subsequently to nanoneedles in the presence of argon gas. The size of the pure zirconium nanograins was estimated to be approximately 200–300 nm. ZrO2 nanotubular arrays with diameters of 70–120 nm were obtained. Both tetragonal and monoclinic ZrO2 were observed after annealing at 450 °C and 650 °C. Only a few tetragonal peaks appeared at 850 °C, while monoclinic ZrO2 was obtained at 900 °C and 950 °C. In assessing the biocompatibility of the ZrO2 surface, the human cell line MDA-MB-231 was found to attach and proliferate well on surfaces annealed at 850 °C and 450 °C; however, the amorphous ZrO2 surface, which was not heat treated, did not permit extensive cell growth, presumably due to remaining fluoride. PMID:27623486

  15. Zirconia supported catalysts for bioethanol steam reforming: Effect of active phase and zirconia structure

    NASA Astrophysics Data System (ADS)

    Benito, M.; Padilla, R.; Rodríguez, L.; Sanz, J. L.; Daza, L.

    Three new catalysts have been prepared in order to study the active phase influence in ethanol steam reforming reaction. Nickel, cobalt and copper were the active phases selected and were supported on zirconia with monoclinic and tetragonal structure, respectively. To characterize the behaviour of the catalysts in reaction conditions a study of catalytic activity with temperature was performed. The highest activity values were obtained at 973 K where nickel and cobalt based catalysts achieved an ethanol conversion of 100% and a selectivity to hydrogen close to 70%. Nickel supported on tetragonal zirconia exhibited the highest hydrogen production efficiency, higher than 4.5 mol H 2/mol EtOH fed. The influence of steam/carbon (S/C) ratio on product distribution was another parameter studied between the range 3.2-6.5. Nickel supported on tetragonal zirconia at S/C = 3.2 operated at 973 K without by-product production such as ethylene or acetaldehyde. In order to consider a further application in an ethanol processor, a long-term reaction experiment was performed at 973 K, S/C = 3.2 and atmospheric pressure. After 60 h, nickel supported on tetragonal zirconia exhibited high stability and selectivity to hydrogen production.

  16. Synthesis of zirconia (ZrO2) nanowires via chemical vapor deposition

    NASA Astrophysics Data System (ADS)

    Baek, M. K.; Park, S. J.; Choi, D. J.

    2017-02-01

    Monoclinic zirconia nanowires were synthesized by chemical vapor deposition using ZrCl4 powder as a starting material at 1200 °C and 760 Torr. Graphite was employed as a substrate, and an Au thin film was pre-deposited on the graphite as a catalyst. The zirconia nanostructure morphology was observed through scanning electron microscopy and transmission electron microscopy. Based on X-ray diffraction, selected area electron diffraction, and Raman spectroscopy data, the resulting crystal structure was found to be single crystalline monoclinic zirconia. The homogeneous distributions of Zr, O and Au were studied by scanning transmission electron microscopy with energy dispersive X-ray spectroscopy mapping, and there was no metal droplet at the nanowire tips despite the use of an Au metal catalyst. This result is apart from that of conventional metal catalyzed nanowires.

  17. Stress analysis of zirconia studied by Raman spectroscopy at low temperatures.

    PubMed

    Kurpaska, L; Kozanecki, M; Jasinski, J J; Sitarz, M

    2014-10-15

    The paper presents effect of low temperature upon location of selected Raman bands. The structural properties of pure zirconium pre-oxidized at 773K and 873K have been studied during cooling in the range of temperatures 273K and 93K by Raman spectroscopy. Analysis of the Raman band positions for the monoclinic phase of zirconia oxide was performed. Raman spectroscopy has shown that monoclinic phase of zirconia oxide undergoes a continuous band displacement, individual for each studied Raman mode. Registered shift is aimed towards the high frequency direction. Recorded Raman band displacement was employed to study stress state in zirconia oxide films grown on pure zirconium developed during control cooling. Presented results showed a good correlation between different thicknesses of the oxide scale.

  18. An X-Ray Diffraction Investigation of alpha-Al2O2 Addition to Yttria Stabilized Zirconia (YSZ) Thermal Barrier Coatings Subject to Destabilizing Vanadium Pentoxide (V2O5) Exposure

    DTIC Science & Technology

    1993-09-01

    Stabilized Zirconia TZP - Tetragonal Stabilized Zirconia 6 The effect of ’alloying’ ceramic particles or fibers are clearly evident. The fracture toughness...TA!RL OF CONIMn3S I. INTRO.DUCTION . .. . . . 1 11. BACMWrJD .................... 2 A. CRYSTALLOGRAPHY OF ZIRCONIA .... ............ 2 1. Cubic ...7 1. ZrO2 -Y203 Phase Diagram ......... .......... 7 a. Monoclinic - Tetragonal Transformation 9 b. Cubic

  19. Mechanical properties of zirconia after different surface treatments and repeated firings

    PubMed Central

    Demir, Necla; Kara, Özlem; Ozturk, A. Nilgun; Özel, Faruk

    2014-01-01

    PURPOSE This study investigated the influence of surface conditioning procedures and repeated firings on monoclinic content and strength of zirconia before cementation. MATERIALS AND METHODS Sintered bar-shaped zirconia specimens were subjected to no surface treatment (control), air abrasion, or grinding (n=21). Their roughness was evaluated using a profilometer, and microscope analysis was performed on one specimen of each group. Then, 2 or 10 repeated firings (n=10) were executed, the monoclinic content of specimens was analyzed by X-ray diffraction, and a three-point flexural strength test was performed. Surface roughness values were compared using one-way analysis of variance (ANOVA) and Tukey honestly significant difference (HSD) tests, the monoclinic content values were tested using Kruskal-Wallis and Mann-Whitney U tests, and the flexural strength values were tested using two-way ANOVA and Tukey HSD tests (P=.05). Spearman's correlation test was performed to define relationships among measured parameters. RESULTS Surface-treated specimens were rougher than untreated specimens and had a higher monoclinic content (P<.005), and the relationship between roughness and monoclinic content was significant (P<.000). Neither surface treatment nor firing significantly affected the flexural strength, but Weibull analysis showed that for the air-abraded samples the characteristic strength was significantly lower after the 10th firing than after the 2nd firing. CONCLUSION After firing, a negligible amount of monoclinic content remained on the zirconia surfaces, and rougher surfaces had higher monoclinic contents than untreated surfaces. Multiple firings could be performed if necessary, but the fracture probability could increase after multiple firings for rougher surfaces. PMID:25551006

  20. Contact damage in an yttria stabilized zirconia: implications.

    PubMed

    Zhou, J; Mah, J; Shrotriya, P; Mercer, C; Soboyejo, W O

    2007-01-01

    This paper presents the results of a combined experimental and computational study of contact damage in a 3 mole% yttria partially stabilized zirconia (3-YSZ) that is relevant to hip implants and dental restorations. Contact-induced loading in real applications is idealized using Hertzian contact model to explain plasticity phenomena and failure mechanisms observed under monotonic and cyclic loading. Under monotonic loading, the elastic moduli increase with increasing loading levels. Under cyclic loading, the ceramic specimens fail with progressive cone cracking. X-ray analyses reveal that stress-induced phase transformation (from tetragonal to monoclinic phases) occurs under cyclic contact loading above the critical load levels (approximately 8.5 kN). Furthermore, when the cyclic loading level (5.0 kN) is less than a critical load levels (7.5 kN) that is required to induce surface cone cracks, significant plastic damage is observed in the subsurface zone underneath the contact area. These suggest that the cyclic contact loading induce both plastic damage and tetragonalto-monoclinic phase transformation in the 3-YSZ, leading to significant degradation in long-term strength. The implications of the results are discussed for the design of zirconia femoral heads in total hip replacements and zirconia crowns in dental restoration.

  1. Nanocrystal synthesis

    SciTech Connect

    Tisdale, William; Prins, Ferry; Weidman, Mark; Beck, Megan

    2016-11-01

    A method of preparing monodisperse MX semiconductor nanocrystals can include contacting an M-containing precursor with an X donor to form a mixture, where the molar ratio between the M containing precursor and the X donor is large. Alternatively, if additional X donor is added during the reaction, a smaller ratio between the M containing precursor and the X donor can be used to prepare monodisperse MX semiconductor nanocrystals.

  2. Scandia-and-Yttria-Stabilized Zirconia for Thermal Barriers

    NASA Technical Reports Server (NTRS)

    Mess, Derek

    2003-01-01

    yttria in suitable proportions has shown promise of being a superior thermal- barrier coating (TBC) material, relative to zirconia stabilized with yttria only. More specifically, a range of compositions in the zirconia/scandia/yttria material system has been found to afford increased resistance to deleterious phase transformations at temperatures high enough to cause deterioration of yttria-stabilized zirconia. Yttria-stabilized zirconia TBCs have been applied to metallic substrates in gas turbine and jet engines to protect the substrates against high operating temperatures. These coatings have porous and microcracked structures, which can accommodate strains induced by thermal-expansion mismatch and thermal shock. The longevity of such a coating depends upon yttria as a stabilizing additive that helps to maintain the zirconia in an yttria-rich, socalled non-transformable tetragonal crystallographic phase, thus preventing transformation to the monoclinic phase with an associated deleterious volume change. However, at a temperature greater than about 1,200 C, there is sufficient atomic mobility that the equilibrium, transformable zirconia phase is formed. Upon subsequent cooling, this phase transforms to the monoclinic phase, with an associated volume change that adversely affects the integrity of the coating. Recently, scandia was identified as a stabilizer that could be used instead of, or in addition to, yttria. Of particular interest are scandia-and-yttria-stabilized zirconia (SYSZ) compositions of about 6 mole percent scandia and 1 mole percent yttria, which have been found to exhibit remarkable phase stability at a temperature of 1,400 C in simple aging tests. Unfortunately, scandia is expensive, so that the problem becomes one of determining whether there are compositions with smaller proportions of scandia that afford the required high-temperature stability. In an attempt to solve this problem, experiments were performed on specimens made with reduced

  3. Ion beam-induced amorphous-to-tetragonal phase transformation and grain growth of nanocrystalline zirconia.

    PubMed

    Lian, Jie; Zhang, Jiaming; Namavar, Fereydoon; Zhang, Yanwen; Lu, Fengyuan; Haider, Hani; Garvin, Kevin; Weber, W J; Ewing, Rodney C

    2009-06-17

    Nanocrystalline zirconia has recently attracted extensive research interest due to its unique mechanical, thermal and electrical properties as compared with bulk zirconia counterparts, and it is of particular importance for controlling the phase stability of different polymorphs (amorphous, cubic, tetragonal and monoclinic phases) in different size regimes. In this work, we performed ion beam bombardments on bilayers (amorphous and cubic) of nano-zirconia using 1 MeV Kr2+ irradiation. Transmission electron microscopy (TEM) analysis reveals that amorphous zirconia transforms to a tetragonal structure under irradiation at room temperature, suggesting that the tetragonal phase is more energetically favorable under these conditions. The final grain size of the tetragonal zirconia can be controlled by irradiation conditions. A slower kinetics in the grain growth from cubic nanocrystalline zirconia was found as compared with that for the tetragonal grains recrystallized from the amorphous layer. The radiation-induced nanograins of tetragonal ZrO2 are stable at ambient conditions and maintain their physical integrity over a long period of time after irradiation. These results demonstrated that ion beam methods provide the means to control the phase stability and structure of zirconia polymorphs.

  4. Evaluation of zirconia-porcelain interface using X-ray diffraction.

    PubMed

    Alghazzawi, Tariq F; Janowski, Gregg M

    2015-09-14

    The aim of this study was to determine if accelerated aging of porcelain veneering had an effect on the surface properties specific to a tetragonal-to-monoclinic transformation (TMT) of zirconia restorations. Thirty-six zirconia samples were milled and sintered to simulate core fabrication followed by exposure to various combinations of surface treatments including as-received (control), hydrofluoric acid (HF), application of liner plus firings, application of porcelain by manual layering and pressing with firing, plus accelerated aging. The quantity of transformed tetragonal to monoclinic phases was analyzed utilized an X-ray diffractometer and one-way analysis of variance was used to analyze data. The control samples as provided from the dental laboratory after milling and sintering process had no TMT (Xm = 0). There was an effect on zirconia samples of HF application with TMT (Xm = 0.8%) and liner plus HF application with TMT (Xm = 8.7%). There was an effect of aging on zirconia samples (no veneering) with significant TMT (Xm = 70.25%). Both manual and pressing techniques of porcelain applications reduced the TMT (manual, Xm = 4.41%, pressing, Xm = 11.57%), although there was no statistical difference between them. It can be concluded that simulated applications of porcelain demonstrated the ability to protect zirconia from TMT after aging with no effect of a liner between different porcelain applications. The HF treatment also caused TMT.

  5. Glass ceramic toughened with tetragonal zirconia

    DOEpatents

    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.

  6. Role of Y{sub 2}O{sub 3}, CaO, MgO additives on structural and microstructural behavior of zirconia/mullite aggregates

    SciTech Connect

    Mishra, D. K.; Prusty, Sasmita; Mohapatra, B. K.; Singh, S. K.; Behera, S. N.

    2012-07-23

    Zirconia mullite (MUZ), Y{sub 2}O{sub 3}-MUZ, CaO-MUZ and MgO-MUZ composites, synthesized through plasma fusion technique, are becoming important due to their commercial scale of production within five minutes of plasma treatment from sillimanite, zircon and alumina mixture. The X-ray diffraction studies reveal the monoclinic zirconia phase in MUZ composite whereas mixed monoclinic, tetragonal and cubic phases of zirconia have been observed in Y{sub 2}O{sub 3}, CaO, MgO added MUZ composites. The Y{sub 2}O{sub 3}, CaO and MgO additives act as sintering aids to favour the transformation and stabilisation of tetragonal and cubic zirconia phases at room temperature. These additives also play a key role in the development of various forms of microstructure to achieve dense MUZ composites.

  7. Current status of zirconia restoration.

    PubMed

    Miyazaki, Takashi; Nakamura, Takashi; Matsumura, Hideo; Ban, Seiji; Kobayashi, Taira

    2013-10-01

    During the past decade, zirconia-based ceramics have been successfully introduced into the clinic to fabricate fixed dental prostheses (FDPs), along with a dental computer-aided/computer-aided manufacturing (CAD/CAM) system. In this article (1) development of dental ceramics, (2) the current status of dental CAD/CAM systems, (3) CAD/CAM and zirconia restoration, (4) bond between zirconia and veneering ceramics, (5) bond of zirconia with resin-based luting agents, (6) surface finish of zirconia restoration and antagonist enamel wear, and (7) clinical evaluation of zirconia restoration are reviewed. Yttria partially stabilized tetragonal zirconia polycrystalline (Y-TZP) showed better mechanical properties and superior resistance to fracture than other conventional dental ceramics. Furthermore, ceria-stabilized tetragonal zirconia polycrystalline and alumina nanocomposites (Ce-TZP/A) had the highest fracture toughness and had resistance to low-temperature aging degradation. Both zirconia-based ceramics have been clinically available as an alternative to the metal framework for fixed dental prostheses (FDPs). Marginal adaptation of zirconia-based FDPs is acceptable for clinical application. The most frequent clinical complication with zirconia-based FDPs was chipping of the veneering porcelain that was affected by many factors. The mechanism for the bonding between zirconia and veneering ceramics remains unknown. There was no clear evidence of chemical bonding and the bond strength between zirconia and porcelain was lower than that between metal and porcelain. There were two alternatives proposed that might avoid chipping of veneering porcelains. One was hybrid-structured FDPs comprising CAD/CAM-fabricated porcelain parts adhering to a CAD/CAM fabricated zirconia framework. Another option was full-contour zirconia FDPs using high translucent zirconia. Combined application of silica coating and/or silane coupler, and 10-methacryloyloxydecyl dihydrogen phosphate is

  8. Microstructural aspects of zirconia thermal barrier coatings

    NASA Technical Reports Server (NTRS)

    Mitchell, T. E.; Suhr, D. S.; Keller, R. J.; Lanteri, V.; Heuer, A. H.

    1985-01-01

    Various combination of plasma-sprayed bond coatings and zirconia ceramic coatings on a nickel-based superalloy substrate were tested by static thermal exposure at 1200 C and cyclic thermal exposure to 1000 C. The bond coats were based on Ni-Cr-Al alloys with additions of rare earth elements and Si. The ceramic coats were various ZrO2-Y2O3 compositions, of which the optimum was found to be ZrO2-8.9 wt percent Y2O3. Microstructural analysis showed that resistance to cracking during thermal exposure is strongly related to deleterious phase changes. Zones depleted of Al formed at the bond coat/ceramic coat interface due to oxidation and at the bond coat/substrate interface due to interdiffusion, leading eventually to breakdown of the bond coat. The 8.9 percent Y2O3 coating performed best because the as-sprayed metastable tetragonal phase converted slowly into the low-Y2O3 tetragonal plus high-Y2O3 cubic-phase mixture, so that the deleterious monoclinic phase was inhibited from forming. Failure appeared to start with the formation of circumferential cracks in the zirconia, probably due to compressive stresses during cooling, followed by the formation of radial cracks due to tensile stresses during heating. Cracks appeared to initiate at the Al2O3 scale/bond coat interface and propagate through the zirconia coating. Comparisons were made with the behavior of bulk ZrO2-Y2O3 and the relationship between the microstructure of the tetragonal phase and the phase diagram. A separate investigation was also made of the ZrO2-Al2O3 interface.

  9. Effective property of tooth enamel: monoclinic behavior.

    PubMed

    Lu, Cunyou; Nakamura, Toshio; Korach, Chad S

    2012-05-11

    Human tooth enamel possesses a unique morphology characterized by a repeated cell arrangement, which is composed of varying orientations of hydroxyapatite crystals. In the past, various investigators have reported diverse mechanical properties based on isotropic or orthotropic mechanical models in their experimental and numerical studies. However, these models are insufficient to capture the accurate microstructural effects on the enamel mechanical response. In this paper, a monoclinic anisotropic model, which offers correct descriptions of enamel deformation behaviors, is introduced. The model takes into account the 3D orientation changes of the hydroxyapatite crystals and their spatial elastic property variations. The proposed approach is based on a unit-cell and periodic boundary conditions, and it utilizes the collective deformation characteristics of many rods to determine 13 independent material constants required for the monoclinic model. These constants are necessary to utilize the effective property model to study various mechanical conditions such as abrasion, erosion, wear and fracture of whole tooth enamel.

  10. Monoclinal bending of strata over laccolithic intrusions

    USGS Publications Warehouse

    Koch, F.G.; Johnson, A.M.; Pollard, D.D.

    1981-01-01

    Sedimentary strata on top of some laccolithic intrusions are nearly horizontal and little deformed, but are bent into steeply dipping monoclinal flexures over the peripheries of these intrusions. This form of bending is not explained by previous theories of laccolithic intrusion, which predict either horizontal undeformed strata over the center and faulted strata around the periphery, or strata bent continuously into a dome. However, a slight generalization of these theories accomodates the observed form and contains the previous forms as special cases. A critical assumption is that the strength of contacts within a multilayered overburden is overcome locally by layer-parallel shear. If this strength is less than the strength of the layers themselves, then layers over the center remain bonded together and display negligible bending, whereas layers over the periphery slip over one another and are readily bent into a monoclinal flexure. ?? 1981.

  11. Impact of radiation defects on the structural stability of pure zirconia

    SciTech Connect

    Simeone, D.; Baldinozzi, G.; Gosset, D.

    2004-10-01

    Optical spectroscopy and x-ray diffraction were used to study the behavior of polycrystalline samples of pure monoclinic zirconia irradiated by low energy ions. A microscopic model based on these experiments is proposed to explain the displacive phase transition observed in this material after irradiation. Defects, produced in the oxygen sublattice, induce important strain fields on a nanometric scale. This strain field can be handled as a secondary order parameter within the Landau theory approach, leading to a decrease of the phase transition temperature and thus quenching the high temperature tetragonal phase. The model also explains the consequences of the thermal annealing for restoring the ground state monoclinic structure.

  12. The influence of low-temperature degradation and cyclic loading on the fracture resistance of monolithic zirconia molar crowns.

    PubMed

    Nakamura, K; Harada, A; Kanno, T; Inagaki, R; Niwano, Y; Milleding, P; Örtengren, U

    2015-07-01

    The present study analyzed the kinetics of low-temperature degradation (LTD) in zirconia, and evaluated the influence of LTD and cyclic loading on the fracture resistance of monolithic zirconia molar crowns. Bar-shaped zirconia specimens were divided into nine groups and autoclaved at 134°C for 0-200h to induce LTD. The surface fraction and penetration depth of the monoclinic phase were examined using X-ray diffraction and scanning electron microscopy. Monolithic zirconia molar crowns were prepared for crown fracture testing. The crowns were autoclaved for 0-100h (n=6) and cemented to dies. Six crown-die samples that were not autoclaved and six samples that were autoclaved for 100h were subjected to cyclic loading with a load of 300N for 240,000 cycles. All samples were tested in a load-to-failure test. The monoclinic fraction on the surface increased with autoclaving time and reached a plateau after 50h. The depth of the monoclinic phase increased without reaching a plateau. The fracture load of the crowns significantly decreased from 5683N (SD: 342) to 3975N (SD: 194) after 100h of autoclaving. Cyclic loading did not significantly affect the fracture resistance of the crowns in all cases. Kinetic analysis showed no linear correlation between the surface fraction and depth of the monoclinic phase after 50h of autoclaving. Even though LTD increased the monoclinic phase, resulting in lower strength, the fracture resistance of the monolithic zirconia crowns was still sufficient to withstand the loading conditions in the molar regions.

  13. Probing Local Structures in ZrO2 Nanocrystals Using EXAFS

    NASA Astrophysics Data System (ADS)

    Soo, Y. L.; Chen, P. J.; Huang, S. H.; Shiu, T. J.; Tsai, T. Y.; Chow, Y. H.; Lin, Y. C.; Weng, S. C.; Chang, S. L.; Lee, J. F.; Cheung, C. L.; Sabirianov, R. F.; Namavar, F.; Mei, W. N.

    2008-03-01

    Extended x-ray absorption fine structure (EXAFS) has been employed to investigate the local structures surrounding Zr in cubic zirconia thin films prepared by an ion beam assisted deposition technique. These materials have demonstrated promising mechanical properties such as improved hardness and lubricant wettability compared to yttria-stabilized zirconia. To verify the cubic structure of zirconia in films prepared under different growth conditions and to fully understand the mechanism leading to their unique physical properties, the structural information is a required prerequisite. Since zirconia is in the form of nanosized crystallets, conventional x-ray diffraction method is not useful for this purpose. Our x-ray results reveal cubic-like structure with O vacancies around Zr in several nanocrystal samples. Powders of cubic zirconia prepared using chemical methods were also measured for comparison.

  14. Electrochemically Induced Transformations of Vanadium Dioxide Nanocrystals.

    PubMed

    Dahlman, Clayton J; LeBlanc, Gabriel; Bergerud, Amy; Staller, Corey; Adair, Jacob; Milliron, Delia J

    2016-10-12

    Vanadium dioxide (VO2) undergoes significant optical, electronic, and structural changes as it transforms between the low-temperature monoclinic and high-temperature rutile phases. Recently, alternative stimuli have been utilized to trigger insulator-to-metal transformations in VO2, including electrochemical gating. Here, we prepare and electrochemically reduce mesoporous films of VO2 nanocrystals, prepared from colloidally synthesized V2O3 nanocrystals that have been oxidatively annealed, in a three-electrode electrochemical cell. We observe a reversible transition between infrared transparent insulating phases and a darkened metallic phase by in situ visible-near-infrared spectroelectrochemistry and correlate these observations with structural and electronic changes monitored by X-ray absorption spectroscopy, X-ray diffraction, Raman spectroscopy, and conductivity measurements. An unexpected reversible transition from conductive, reduced monoclinic VO2 to an infrared-transparent insulating phase upon progressive electrochemical reduction is observed. This insulator-metal-insulator transition has not been reported in previous studies of electrochemically gated epitaxial VO2 films and is attributed to improved oxygen vacancy formation kinetics and diffusion due to the mesoporous nanocrystal film structure.

  15. Ion beam-induced amorphous-to-tetragonal phase transformation and grain growth of nanocrystalline zirconia

    SciTech Connect

    Lian, Jie; Zhang, Jiaming; Namavar, Fereydoon; Zhang, Yanwen; Lu, Fengyuan; Haider, Hani; Garvin, Kevin; Weber, William J.; Ewing, Rodney C.

    2009-05-26

    Nanocrystalline zirconia has recently attracted extensive research interest due to its unique mechanical, thermal and electrical properties as compared to bulk zirconia counterparts, and it is of particular importance to control the phase stability of different polymorphs (amorphous, cubic, tetragonal and monoclinic phases) at different size regimes. In this paper, we performed ion beam bombardments on bilayers (amorphous and cubic) of pure nano-zirconia using 1 MeV Kr2+ irradiation. Transmission electron microscopy (TEM) analysis reveals that amorphous zirconia transforms to a tetragonal structure under irradiation at room temperature, suggesting that the tetragonal phase is more energetically favorable under these conditions. The final grain size of the tetragonal zirconia can be controlled by irradiation conditions. The irradiation-induced nanograins of tetragonal ZrO2 are stable at ambient conditions and maintain their physical integrity over a long period of time after irradiation. These results demonstrated that ion-beam modification methods provide the means to control the phase stability and structure of zirconia polymorphs.

  16. Reactions of yttria-stabilized zirconia with oxides and sulfates of various elements

    NASA Technical Reports Server (NTRS)

    Zaplatynsky, I.

    1978-01-01

    The reactions between partially stabilized zirconia, containing 8 weight-percent yttria, and oxides and sulfates of various elements were studied at 1200, 1300, and 1400 C for times to 800, 400, and 200 hours, respectively. These oxides and sulfates represent impurities and additives potentially present in gas turbine fuels or impurities in the turbine combustion air as well as the elements of the substrate alloys in contact with zirconia. Based on the results, these compounds can be classified in four groups: (1) compounds which did not react with zirconia (Na2SO4, K2SO4, Cr2O3, Al2O3 and NiO); (2) compounds that reached completely with both zirconia phases (CaO, BaO, and BaSO4); (3) compounds that reacted preferentially with monoclinic zirconia (Na2O, K2O, CoO, Fe2O3, MgO, SiO2, and ZnO); and (4) compounds that reacted preferentially with cubic zirconia (V2O5, P2O5).

  17. Evaluation of translucency of monolithic zirconia and framework zirconia materials

    PubMed Central

    Tuncel, İlkin; Üşümez, Aslıhan

    2016-01-01

    PURPOSE The opacity of zirconia is an esthetic disadvantage that hinders achieving natural and shade-matched restorations. The aim of this study was to evaluate the translucency of non-colored and colored framework zirconia and monolithic zirconia. MATERIALS AND METHODS The three groups tested were: non-colored framework zirconia, colored framework zirconia with the A3 shade according to Vita Classic Scale, and monolithic zirconia (n=5). The specimens were fabricated in the dimensions of 15×12×0.5 mm. A spectrophotometer was used to measure the contrast ratio, which is indicative of translucency. Three measurements were made to obtain the contrast ratios of the materials over a white background (L*w) and a black background (L*b). The data were analyzed using the one-way analysis of variance and Tukey HSD tests. One specimen from each group was chosen for scanning electron microscope analysis. The determined areas of the SEM images were divided by the number of grains in order to calculate the mean grain size. RESULTS Statistically significant differences were observed among all groups (P<.05). Non-colored zirconia had the highest translucency with a contrast ratio of 0.75, while monolithic zirconia had the lowest translucency with a contrast ratio of 0.8. The mean grain sizes of the non-colored, colored, and monolithic zirconia were 233, 256, and 361 nm, respectively. CONCLUSION The translucency of the zirconia was affected by the coloring procedure and the grain size. Although monolithic zirconia may not be the best esthetic material for the anterior region, it may serve as an alternative in the posterior region for the bilayered zirconia restorations. PMID:27350851

  18. Transition temperature of martensitic transformations in hafnia and zirconia

    NASA Astrophysics Data System (ADS)

    Luo, Xuhui; Demkov, A. A.

    2008-03-01

    Transition metal oxides find applications in ceramics, catalysis and semiconductor technology. In particular, hafnium dioxide or hafnia will succeed silica as a gate dielectric in advanced transistors. However, thermodynamic properties of thin hafnia films are not well understood, despite their technological importance. We use density functional theory to investigate the tetragonal to monoclinic phase transition in hafnia and zirconia. We find that unlike the case of the cubic to tetragonal transition, this phase transition is not driven by a soft mode. We use transition state theory to identify the minimum energy path (MEP) employing first principle calculations for hafnia and zirconia, sow that both transformations are martensitic, and obtain the transition barriers. Martensitic transformations include both the internal coordinate transformation and deformation of the cell lattice vectors (``strain and shuffle''), therefore the potential energy surface and MEP are function not only of the internal atomic coordinates but also of the unit cell lattice vectors. Considering the simplest case of uniform strain the transition temperatures we then relate the barrier height to the transition temperature. As a self-consistency check, assuming the equality of thermodynamics potentials of the tetragonal and monoclinic phases during the transition, and using the difference in the internal energy calculated from first principles we estimate the entropy change associated with the transition which is found in good agreement with that calculated form the phonon spectra.

  19. Nondestructive inspection of phase transformation in zirconia-containing hip joints by confocal Raman spectroscopy

    NASA Astrophysics Data System (ADS)

    Zhu, Wenliang; Sugano, Nobuhiko; Pezzotti, Giuseppe

    2013-12-01

    Environmental metastability of zirconia (ZrO2) ceramic in the human body [represented by a tetragonal-to-monoclinic (t→m) phase transformation] takes place on the surface of the artificial joint and proceeds with time toward its interior. Its quantitative characterization is mandatory for the safety of joint implants and consists of the assessment of the in-depth monoclinic profile fraction as compared to that of the initially untransformed material. We attempt to fully establish a characterization protocol and present two different nondestructive approaches for resolving highly graded phase-transformation profiles along the hip-joint subsurface by confocal Raman microprobe technique. A series of partially transformed tetragonal zirconia polycrystal and zirconia-toughened alumina ceramics are used as screening samples. Probe biases could be eliminated and the real transformation profiles retrieved through a deconvolution procedure of Raman experimental data collected as a function of pinhole aperture and focal depth, respectively. Confirmation of the confocal assessments was made by a destructive cross-sectional inspection by both laser optical microscope and Raman spectral line scans. This study unveils for the first time the real quantitative amount of surface phase-transformation fractions and the related subsurface profiles in zirconia-based retrieved medical samples.

  20. Influence of starting precursors and synthesis methods on the physiochemical properties of zirconia

    SciTech Connect

    Gaydhankar, T.R.; Jha, R.K.; Nikalje, M.D.; Waghmare, K.J.

    2014-07-01

    Graphical abstract: Crystallite size of tetragonal phase of the zirconia samples prepared using different synthesis parameters and precursors as a function of calcination temperature. Surface area values of the zirconia samples calcined at 500 and 700 °C are in given brackets. - Highlights: • Zirconia prepared with modified sol–gel method is less stable compared with zirconia prepared by precipitation method. • Optimized synthesis conditions shifted the glow exotherm to higher temperature range indicating better thermal stability. • Tetragonal-zirconia could be synthesized in cost-effective manner using zirconium oxy-nitrate. • In our studies no co-relation between the surface area and crystallite size was observed. - Abstract: Under identical and judiciously pre-optimized synthesis conditions, the influence of different combinations of zirconium sources and/or post treatment conditions on structural properties, thermal stability, phase composition and morphology of zirconia has been investigated. High surface area tetragonal zirconia could be synthesized in a cost-effective manner from 1 M solution of zirconium oxy-nitrate at pH 11 using aqueous ammonia solution as a precipitant when calcined at 400 °C for 3 h. Irrespective of the preparation method, pH and starting precursor, zirconia samples prepared without digestion contained dominant monoclinic phase with some traces of tetragonal phase when calcined at 700 °C. Even though there is linear decrease in surface area with increase in the crystallite size for each sample as a function of calcination temperature, no co-relation between the surface area and crystallite size could be achieved. SEM images show agglomerated and irregular shape particles between 10 to 20 μm.

  1. Doped zirconia phase and luminescence dependence on the nature of charge compensation

    NASA Astrophysics Data System (ADS)

    Smits, Krisjanis; Olsteins, Dags; Zolotarjovs, Aleksejs; Laganovska, Katrina; Millers, Donats; Ignatans, Reinis; Grabis, Janis

    2017-03-01

    Zirconia is a relatively new material with many promising practical applications in medical imaging, biolabeling, sensors, and other fields. In this study we have investigated lanthanide and niobium doped zirconia by luminescence and XRD methods. It was proven that charge compensation in different zirconia phases determines the incorporation of intrinsic defects and activators. Thus, the structure of zirconia does not affect the Er luminescence directly; however, it strongly affects the defect distribution around lanthanide ions and the way in which activator ions are incorporated in the lattice. Our results demonstrate the correlation between the crystalline phase of zirconia and charge compensation, as well as the contribution of different nanocrystal grain sizes. In addition, our experimental results verify the theoretical studies of metastable (tetragonal, cubic) phase stabilization determined using only oxygen vacancies. Moreover, it was found that adding niobium drastically increases activator luminescence intensity, which makes Ln3+ doped zirconia even more attractive for various practical applications. Although this study was based on the luminescence of the Er ion, the phase stabilization, charge compensation, and luminescence properties described in our results are expected to be similar for other lanthanide elements. Our results suggest that the luminescence intensity of other oxide matrices where lanthanides incorporate in place of tetravalent cations could be increased by addition of Nb ions.

  2. Doped zirconia phase and luminescence dependence on the nature of charge compensation

    PubMed Central

    Smits, Krisjanis; Olsteins, Dags; Zolotarjovs, Aleksejs; Laganovska, Katrina; Millers, Donats; Ignatans, Reinis; Grabis, Janis

    2017-01-01

    Zirconia is a relatively new material with many promising practical applications in medical imaging, biolabeling, sensors, and other fields. In this study we have investigated lanthanide and niobium doped zirconia by luminescence and XRD methods. It was proven that charge compensation in different zirconia phases determines the incorporation of intrinsic defects and activators. Thus, the structure of zirconia does not affect the Er luminescence directly; however, it strongly affects the defect distribution around lanthanide ions and the way in which activator ions are incorporated in the lattice. Our results demonstrate the correlation between the crystalline phase of zirconia and charge compensation, as well as the contribution of different nanocrystal grain sizes. In addition, our experimental results verify the theoretical studies of metastable (tetragonal, cubic) phase stabilization determined using only oxygen vacancies. Moreover, it was found that adding niobium drastically increases activator luminescence intensity, which makes Ln3+ doped zirconia even more attractive for various practical applications. Although this study was based on the luminescence of the Er ion, the phase stabilization, charge compensation, and luminescence properties described in our results are expected to be similar for other lanthanide elements. Our results suggest that the luminescence intensity of other oxide matrices where lanthanides incorporate in place of tetravalent cations could be increased by addition of Nb ions. PMID:28287623

  3. Hole Trapping at Surfaces of m-ZrO2 and m-HfO2 Nanocrystals

    SciTech Connect

    Wolf, Matthew J.; Mckenna, Keith P.; Shlyuger, Alexander L.

    2012-12-03

    We investigate hole trapping at the most prevalent facets of monoclinic zirconia (m-ZrO2) and hafnia (m-HfO2) nanocrystals using first-principles methods. The localization of holes at surface oxygen ions is more favorable than in the bulk crystal by up to ~1 eV. This is caused mainly by the reduction of the absolute value of the electrostatic potential at the surface ions with respect to the bulk and by the significant surface distortion caused by the hole localization. The mobility of holes at surfaces is much lower than that found in the bulk and is fairly isotropic. Unlike in cubic oxides, such as MgO and CaO, we do not find a significant driving force for preferential trapping of holes at steps on the m-ZrO2 surface. These fundamental results are relevant to mechanisms of water oxidation, photocatalysis, contact charging, and photodesorption.

  4. Influence of thermal treatment on the formation of zirconia nanostructured powder by thermal decomposition of different precursors

    NASA Astrophysics Data System (ADS)

    Stoia, Marcela; Barvinschi, Paul; Barbu-Tudoran, Lucian; Negrea, Adina; Barvinschi, Floricica

    2013-10-01

    The paper presents some results concerning the preparation of zirconia powders starting from ZrOCl2·8H2O by using two synthesis methods: (a) precipitation with NH3, at 90 °C, and (b) thermal decomposition of carboxylate precursors, obtained in the reaction of zirconium nitrate and two different alcohols, 1,3-propanediol (PD) and poly(vinyl alcohol) (PVA), at 150 °C. The precursors obtained at different temperatures have been characterized by thermal analysis (TG, DTA) and FT-IR spectroscopy. DTA analysis evidenced very clearly the transition temperatures between zirconia crystalline phases. The precursors have been annealed at different temperatures in order to obtain zirconia powders and the as obtained powders have been characterized by means of X-Ray Diffraction (XRD), Fourier Transform Infrared Spectroscopy (FTIR), and Scanning Electron Microscopy (SEM). In case of precipitation method the presence of the tetragonal phase was observed at 400 °C, while the monoclinic phase appears at temperatures higher than 400 °C, becoming major crystalline phase starting with 700 °C. In case of the powders prepared by thermal decomposition of carboxylate precursors, the tetragonal phase was formed at temperatures below 700 °C, when the monoclinic phase begin to crystallize as secondary phase, in a higher proportion for the samples synthesized with 1,3-propanediol. All powders annealed at 1200 °C are pure monoclinic zirconia. SEM images have evidenced for the zirconia powders annealed at 1000 °C particles with diameters up to 150 nm, agglomerated in micrometer-sized aggregates, more individualized and homogenous than that obtained in the case of zirconia powder synthesized with poly(vinyl alcohol).

  5. Nitrogen-doped zirconia: A comparison with cation stabilized zirconia

    SciTech Connect

    Lee, Jong-Sook . E-mail: jong-sook.lee@fkf.mpg.de; Lerch, Martin; Maier, Joachim

    2006-01-15

    The conductivity behavior of nitrogen-doped zirconia is compared with that of zirconia doped with lower-valent cations and discussed in the framework of defect-defect interactions. While nominally introducing the same number of vacancies as yttrium, nitrogen dopants introduced in the anion sublattice of zirconia lead to substantially different defect kinetics and energetics. Compared to the equivalent yttrium doping nitrogen doping in the Y-Zr-O-N system substantially increases the activation energy and correspondingly decreases the conductivity at temperatures below 500{sup -}bar C in the vacancy range below 4mol%. The comparison of N-doped zirconia and zirconia systems doped with size-matched cation stabilizers, such as Sc, Yb and Y, shows that elastically driven vacancy-vacancy ordering interactions can phenomenologically account for the temperature- and composition-dependence. It is striking that materials with superior high-temperature conductivities due to weak dopant-vacancy interactions undergo severe deterioration at low temperature due to the strong vacancy-ordering. The analysis also explains qualitatively similar effects of Y co-doping in Yb-, Sc-, and N-doped zirconia. Small amount of Y in N-doped zirconia as well as in Sc-doped zirconia appears to hinder the formation of the long-range ordered phase and thus enhance the conductivity substantially.

  6. Sintering additives for zirconia ceramics

    SciTech Connect

    Wu, S.

    1986-01-01

    This book is an overview of sintering science and its application to zirconia materials including CaO, MgO, and Y/sub 2/O/sub 3/-CeO/sub 2/ doped materials. This book is a reference for first-time exposure to zirconia materials technology, particularly densification.

  7. Effect of grinding and heat treatment on the mechanical behavior of zirconia ceramic.

    PubMed

    Ramos, Gabriela Freitas; Pereira, Gabriel Kalil Rocha; Amaral, Marina; Valandro, Luiz Felipe; Bottino, Marco Antonio

    2016-01-01

    The present study investigated the effect of grinding on roughness, flexural strength, and reliability of a zirconia ceramic before and after heat treatment. Seven groups were tested (n = 15): a control group (labeled CG, untreated), and six groups of samples ground with diamond discs, simulating diamond burs, with grits of 200 µm (G80); 160 µm (G120), and 25 µm (G600), either untreated or heat-treated at 1200°C for 2 h (labeled A). Yttria tetragonal zirconia polycrystal discs were manufactured, ground, and submitted to roughness and crystalline phase analyses before the biaxial flexural strength test. There was no correlation between roughness (Ra and Rz) and flexural strength. The reliability of the materials was not affected by grinding or heat treatment, but the characteristic strength was higher after abrasion with diamond discs, irrespective of grit size. The X-ray diffraction data showed that grinding leads to a higher monoclinic (m) phase content, whereas heat treatment produces reverse transformation, leading to a fraction of m-phase in ground samples similar to that observed in the control group. However, after heat treatment, only the G80A samples presented strength similar to that of the control group, while the other groups showed higher strength values. When zirconia pieces must be adjusted for clinical use, a smoother surface can be obtained by employing finer-grit diamond burs. Moreover, when the amount of monoclinic phase is related to the degradation of zirconia, the laboratory heat treatment of ground pieces is indicated for the reverse transformation of zirconia crystals.

  8. Physico-mechanical and morphological features of zirconia substituted hydroxyapatite nano crystals

    NASA Astrophysics Data System (ADS)

    Mansour, S. F.; El-Dek, S. I.; Ahmed, M. K.

    2017-03-01

    Zirconia doped Hydroxyapatite (HAP) nanocrystals [Ca10(PO4)6‑x(ZrO2)x(OH)2] (0 ≤ x ≤ 1 step 0.2) were synthesized using simple low cost facile method. The crystalline phases were examined by X-ray diffraction (XRD). The crystallinity percentage decreased with increasing zirconia content for the as-synthesized samples. The existence of zirconia as secondary phase on the grain boundaries; as observed from scanning electron micrographs (FESEM); resulted in negative values of microstrain. The crystallite size was computed and the results showed that it increased with increasing annealing temperature. Thermo-gravimetric analysis (TGA) assured the thermal stability of the nano crystals over the temperature from room up to 1200 °C depending on the zirconia content. The corrosion rate was found to decrease around 25 times with increasing zirconia content from x = 0.0 to 1.0. Microhardness displayed both compositional and temperature dependence. For the sample (x = 0.6), annealed at 1200 °C, the former increased up to 1.2 times its original value (x = 0.0).

  9. Physico-mechanical and morphological features of zirconia substituted hydroxyapatite nano crystals

    PubMed Central

    Mansour, S. F.; El-dek, S. I.; Ahmed, M. K.

    2017-01-01

    Zirconia doped Hydroxyapatite (HAP) nanocrystals [Ca10(PO4)6−x(ZrO2)x(OH)2]; (0 ≤ x ≤ 1 step 0.2) were synthesized using simple low cost facile method. The crystalline phases were examined by X-ray diffraction (XRD). The crystallinity percentage decreased with increasing zirconia content for the as-synthesized samples. The existence of zirconia as secondary phase on the grain boundaries; as observed from scanning electron micrographs (FESEM); resulted in negative values of microstrain. The crystallite size was computed and the results showed that it increased with increasing annealing temperature. Thermo-gravimetric analysis (TGA) assured the thermal stability of the nano crystals over the temperature from room up to 1200 °C depending on the zirconia content. The corrosion rate was found to decrease around 25 times with increasing zirconia content from x = 0.0 to 1.0. Microhardness displayed both compositional and temperature dependence. For the sample (x = 0.6), annealed at 1200 °C, the former increased up to 1.2 times its original value (x = 0.0). PMID:28256557

  10. EFFECT OF (Bi2O3)0.75(Y2O3)0.25 ADDITION ON MICROSTRUCTURES AND IONIC CONDUCTIVITIES OF CODOPED ZIRCONIA

    NASA Astrophysics Data System (ADS)

    Chou, Chen Chia; Huang, Chun Feng; Yeh, Tsung Her

    2012-09-01

    Variation of microstructures and ionic conductivities in (Bi2O3)0.75(Y2O3)0.25 (YSB) modified electrolyte of 8 mol% Y2O3 stabilized zirconia (8YSZ) and YSB modified codoped zirconia (ZrO2)0.92(Y2O3)0.075(MgO)0.005 (YSZM) is investigated in this work. The results demonstrated that a small amount of δ-YSB addition is effective in reducing the sintering temperature of 8YSZ from 1500 to 1200°C and promoting the densification rate of ceramics. Compared to 8YSZ electrolyte, it is interesting that a very limited amount of monoclinic ZrO2 was observed due to the MgO stabilizer in YSB modified codoped zirconia electrolyte. Besides, enhancement of ionic conductivity in δ-YSB modified codoped zirconia is evidently increased by 67% in comparison to the specimen of 8YSZ electrolyte.

  11. Development of a novel zirconia dental post resistant to hydrothermal degradation

    NASA Astrophysics Data System (ADS)

    Camposilvan, E.; Marro, F. G.; Mestra, A.; Anglada, M. J.

    2012-02-01

    Tetragonal Zirconia Polycrystals stabilized with 3% mol. content of yttria (3Y-TZP) has excellent properties in terms of strength and fracture toughness. These properties are mostly imputable to the transformation toughening mechanism, by which the doped metastable tetragonal phase of zirconia transforms to monoclinic under applied stress ahead of a crack. This phenomenon is accompanied by a volume expansion of 5%, and increases the resistance to crack growth, thus leading to higher toughness and strength. An important drawback of this material is represented by the Low Temperature Degradation (LTD or aging), which consists in the progressive tetragonal-to-monoclinic phase transformation by the influence of water. This work focuses on the improvement of 3Y-TZP aging behavior in order to develop a novel dental post, by means of the addition of ceria from the surface. This was achieved through the impregnation of the pre-sintered samples with a solution containing Cerium, followed by sintering. Various pre-sintering temperatures were studied in terms of microstructure, mechanical properties and aging resistance. The novel zirconia dental posts developed in this work are much more resistant to LTD as compared to the base material with no loss in mechanical properties.

  12. Synthesis of nanocrystalline zirconia by amorphous citrate route: structural and thermal (HTXRD) studies

    SciTech Connect

    Bhagwat, Mahesh; Ramaswamy, Veda

    2004-09-01

    Nanocrystalline zirconia powder with a fairly narrow particle size distribution has been synthesized by the amorphous citrate route. The sample obtained has a high BET surface area of 89 m{sup 2} g{sup -1}. Rietveld refinement of the powder X-ray diffraction (XRD) profile of the zirconia sample confirms stabilization of zirconia in the tetragonal phase with around 8% monoclinic impurity. The data show the presence of both anionic as well as cationic vacancies in the lattice. Crystallite size determined from XRD is 8 nm and is in close agreement with the particle size determined by TEM. The in situ high temperature-X-ray diffraction (HTXRD) study revealed high thermal stability of the mixture till around 1023 K after which the transformation of tetragonal phase into the monoclinic phase has been seen as a function of temperature till 1473 K. This transformation is accompanied by an increase in the crystallite size of the sample from 8 to 55 nm. The thermal expansion coefficients are 9.14 x 10{sup -6} K{sup -1} along 'a'- and 15.8 x 10{sup -6} K{sup -1} along 'c'-axis. The lattice thermal expansion coefficient in the temperature range 298-1623 K is 34.6 x 10{sup -6} K{sup -1}.

  13. Gelcast zirconia-alumina composites

    SciTech Connect

    Omatete, O.O.; Bleier, A.; Westmoreland, C.G.; Young, A.C.

    1991-01-01

    Near net-shaped parts of zirconia-alumina composites have been successfully formed by gelcasting, a technique which utilizes in situ polymerization of acrylamide monomers. The high solids loading required for gelcasting ({approximately}50 vol %) was obtained by controlling the pH-dependent stability of the aqueous zirconia-alumina suspensions. A strong correspondence was found among the surface charges on the particles, colloidal stability, and the maximum solids loading. 14 refs., 3 figs., 2 tabs.

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

    SciTech Connect

    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.

  15. Surface chemical modification of nanocrystals

    DOEpatents

    Helms, Brett Anthony; Milliron, Delia Jane; Rosen, Evelyn Louise; Buonsanti, Raffaella; Llordes, Anna

    2017-03-14

    Nanocrystals comprising organic ligands at surfaces of the plurality of nanocrystals are provided. The organic ligands are removed from the surfaces of the nanocrystals using a solution comprising a trialkyloxonium salt in a polar aprotic solvent. The removal of the organic ligands causes the nanocrystals to become naked nanocrystals with cationic surfaces.

  16. A comparative study of the surface structure, acidity, and catalytic performance of tungstated zirconia prepared from crystalline zirconia or amorphous zirconium oxyhydroxide.

    PubMed

    Lebarbier, Vanessa; Clet, Guillaume; Houalla, Marwan

    2006-07-20

    Tungstated zirconias prepared from W deposition on zirconium oxyhydroxide are reportedly active for alkane isomerization, whereas solids synthesized by impregnation of zirconia are inactive. The origin of the differences between the two preparations is not fully understood. The present paper examines the influence of W surface density and the nature of the support on the surface structure, development of the acidity, and catalytic performance of WO(x)()/ ZrO(2) catalysts. Two series of catalysts containing W surface densities up to 5.2 at. W/nm(2) were prepared by pore volume impregnation of two different supports: zirconium oxyhydroxide and predominantly tetragonal zirconia (65% tetragonal, 35% monoclinic). The texture and structure of the catalysts were investigated by BET measurements, X-ray diffraction, Raman and infrared spectroscopy. The catalytic activity was tested for 2-propanol dehydration and n-hexane isomerization. For catalysts obtained by impregnation of Zr oxyhydroxide, Raman results showed that W was present as a surface phase. Infrared spectra indicated an increase in the degree of polymerization of W species with increasing W surface density. The development of the acidity was monitored by lutidine adsorption and desorption at 523 K, followed by infrared spectroscopy. The results indicated the presence of a threshold of W surface density at 1.3 at. W/ nm(2) for the detection of these acid sites, followed by a progressive increase in their abundance with increasing W surface density. The development of Brønsted acidity correlated with the evolution of the infrared bands attributed to "extensively" polymerized W species. A direct relationship was observed between the abundance of Brønsted acid sites and the catalytic activity for 2-propanol dehydration. For n-hexane isomerization, compared to 2-propanol dehydration, a higher threshold of W surface densities (3.4 at. W/ nm(2)) for the development of activity was observed. The difference was

  17. Rate-dependent phase transitions in Li2FeSiO4 cathode nanocrystals

    PubMed Central

    Lu, Xia; Wei, Huijing; Chiu, Hsien-Chieh; Gauvin, Raynald; Hovington, Pierre; Guerfi, Abdelbast; Zaghib, Karim; Demopoulos, George P.

    2015-01-01

    Nanostructured lithium metal orthosilicate materials hold a lot of promise as next generation cathodes but their full potential realization is hampered by complex crystal and electrochemical behavior. In this work Li2FeSiO4 crystals are synthesized using organic-assisted precipitation method. By varying the annealing temperature different structures are obtained, namely the monoclinic phase at 400°C, the orthorhombic phase at 900°C, and a mixed phase at 700°C. The three Li2FeSiO4 crystal phases exhibit totally different charge/discharge profiles upon delithiation/lithiation. Thus the 400°C monoclinic nanocrystals exhibit initially one Li extraction via typical solid solution reaction, while the 900°C orthorhombic crystals are characterized by unacceptably high cell polarization. In the meantime the mixed phase Li2FeSiO4 crystals reveal a mixed cycling profile. We have found that the monoclinic nanocrystals undergo phase transition to orthorhombic structure resulting in significant progressive deterioration of the material's Li storage capability. By contrast, we discovered when the monoclinic nanocrystals are cycled initially at higher rate (C/20) and subsequently subjected to low rate (C/50) cycling the material's intercalation performance is stabilized. The discovered rate-dependent electrochemically-induced phase transition and stabilization of lithium metal silicate structure provides a novel and potentially rewarding avenue towards the development of high capacity Li-ion cathodes. PMID:25715655

  18. Synthesis of nano-crystalline multifibrous zirconia needle

    SciTech Connect

    Biswas, Mridula; Bandyopadhyay, Siddhartha

    2013-06-01

    Graphical abstract: - Highlights: • Zirconia needles have been successfully prepared by simple inorganic sol–gel route. • The shape of the needles was retained after firing with aspect ratio > 400. • Needles are composed of multiple fibres. • Fibres are composed of nano crystals. - Abstract: Zirconia needles have been successfully synthesized using a simple inorganic sol–gel process without using any template. The method employs mixture of zirconium oxychloride octahydrate and sulphuric acid in aqueous medium. This process requires heat treatment at 40 °C for 2 h in an oven for nucleus formation. Complete formation of needle occurs after 17 days. The green needle retained its original shape after calcination at 1200 °C. Fired needles were of 1–2 cm in length and 5–50 μm in diameter and possess monoclinic phase. Needles are composed of multiple fibres. Depending on the heat treatment temperature, crystallite size varies in the range of 8 to around 300 nm.

  19. Translucency of monolithic and core zirconia after hydrothermal aging

    PubMed Central

    Fathy, Salma M.; El-Fallal, Abeer A.; El-Negoly, Salwa A.; El Bedawy, Abu Baker

    2015-01-01

    Abstract Objective: To evaluate the hydrothermal aging effect on the translucency of partially stabilized tetragonal zirconia with yttria (Y-TZP) used as monolithic or fully milled zirconia and of core type. Methods: Twenty disc-shaped specimens (1 and 10 mm) for each type of monolithic and core Y-TZP materials were milled and sintered according to the manufacturer’s instruction. The final specimens were divided into two groups according to the type of Y-TZP used. Translucency parameter (TP) was measured over white and black backgrounds with the diffuse reflectance method; X-ray diffraction (XRD) and scanning electron microscope (SEM) were used to analyze the microstructure of both Y-TZP types before and after aging. Data for TP values was statistically analyzed using Student’s t-test. Results: Monolithic Y-TZP showed the highest TP mean value (16.4 ± 0.316) before aging while core Y-TZP showed the lowest TP mean value (7.05 ± 0.261) after aging. There was a significant difference between the two Y-TZP types before and after hydrothermal aging. XRD analysis showed increases in monoclinic content in both Y-TZP surfaces after aging. Conclusion: Monolithic Y-TZP has a higher chance to low-temperature degradation than core type, which may significantly affect the esthetic appearance and translucency hence durability of translucent Y-TZP. PMID:27335897

  20. The Zirconia Ceramic: Strengths and Weaknesses

    PubMed Central

    Daou, Elie E.

    2014-01-01

    Metal ceramic restorations were considered the gold standard as reliable materials. Increasing demand for esthetics supported the commercialization of new metal free restorations. A growing demand is rising for zirconia prostheses. Peer-reviewed articles published till July 2013 were identified through a Medline (Pubmed and Elsevier). Emphasizing was made on zirconia properties and applications. Zirconia materials are able to withstand posterior physiologic loads. Although zirconia cores are considered as reliable materials, these restorations are not problem free. PMID:24851138

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

    PubMed

    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.

  2. Optical, structural and morphological properties of zirconia nanoparticles prepared by laser ablation in liquids

    SciTech Connect

    Borodina, T I; Val'yano, G E; Gololobova, O A; Karpukhin, V T; Malikov, M M; Strikanov, D A

    2014-09-30

    Absorption, fluorescence and Raman spectra, the structural composition and morphology of zirconia nanoparticles synthesised via the laser ablation of a metal in water and aqueous solutions of the sodium dodecyl sulphate (SDS) surfactant have been studied using absorption spectroscopy, Raman spectroscopy, X-ray diffraction and scanning electron microscopy. The results demonstrate that, exposing zirconium to intense nanosecond laser pulses at a high repetition rate in these liquids, one can obtain stable cubic, tetragonal and monoclinic crystalline phases of nanozirconia with a particle size in the range 40 – 100 nm and a Zr – SDS organic – inorganic composite. The absorption and fluorescence of the synthesised zirconia strongly depend on the SDS concentration in the starting solution. The gas – vapour bubbles forming during ablation are shown to serve as templates for the formation of hollow nanoand microstructures. (nanostructures)

  3. Zirconia dental implants degradation by confocal Raman microspectroscopy: analytical simulation and experiments

    PubMed Central

    Djaker, Nadia; Wulfman, Claudine; Sadoun, Michaël; Lamy de la Chapelle, Marc

    2013-01-01

    Subsurface hydrothermal degradation of yttria stabilized tetragonal zirconia polycrystals (3Y-TZP) is presented. Evaluation of low temperature degradation (LTD) phase transformation induced by aging in 3Y-TZP is experimentally studied by Raman confocal microspectroscopy. A non-linear distribution of monoclinic volume fraction is determined in depth by using different pinhole sizes. A theoretical simulation is proposed based on the convolution of the excitation intensity profile and the Beer-Lambert law (optical properties of zirconia) to compare between experiment and theory. The calculated theoretical degradation curves matche closely to the experimental ones. Surface transformation (V0) and transformation factor in depth (T) are obtained by comparing simulation and experience for each sample with nondestructive optical sectioning. PMID:23667788

  4. Shift in low-frequency vibrational spectra measured in-situ at 600 °C by Raman spectroscopy of zirconia developed on pure zirconium and Zr-1%Nb alloy

    NASA Astrophysics Data System (ADS)

    Kurpaska, L.; Lesniak, M.; Jadach, R.; Sitarz, M.; Jasinski, J. J.; Grosseau-Poussard, J.-L.

    2016-12-01

    In this study displacement of monoclinic bands of zirconia were investigated in the function of oxidation time using the Raman spectroscopy technique. Oxidations were performed on pure zirconium and zirconium alloy in-situ at 600 °C for 6 h. Analysis of the absolute intensities as well as the positions of the characteristic for monoclinic and tetragonal phase Raman bands were performed. Reported results has highlighted that monoclinic phase of zirconia undergoes a continuous band displacement, individual for each Raman mode. Recorded shift of low frequency vibrational spectra of monoclinic phase was employed to study stress developed in zirconia during high temperature oxidation - herein called as growing stress. In addition, based on the Raman band intensity we discuss observed transition of the metastable tetragonal phase to stable monoclinic phase. Reported results, for the first time showed that studied metals (pure zirconium and its alloy) behave similarly in terms of band shift. However the resulting value of growing stress associated to the band displacement is slightly different in regards of individual band and studied sample.

  5. Shear bond strength of veneering porcelain to porous zirconia.

    PubMed

    Nakamura, Takashi; Sugano, Tsuyoshi; Usami, Hirofumi; Wakabayashi, Kazumichi; Ohnishi, Hiroshi; Sekino, Tohru; Yatani, Hirofumi

    2014-01-01

    In this study, two types of porous zirconia and dense zirconia were used. The flexural strength of non-layered zirconia specimens and those of the layered zirconia specimens with veneering porcelain were examined. Furthermore, the shear bond strength of veneering porcelain to zirconia was examined. The flexural strength of the non-layered specimens was 1,220 MPa for dense zirconia and 220 to 306 MPa for porous zirconia. The flexural strength of the layered specimens was 360 MPa for dense zirconia and 132 to 156 MPa for porous zirconia, when a load was applied to the porcelain side. The shear bond strength of porcelain veneered to dense zirconia was 27.4 MPa and that of porcelain veneered to porous zirconia was 33.6 to 35.1 MPa. This suggests that the veneering porcelain bonded strongly to porous zirconia although porous zirconia has a lower flexural strength than dense zirconia.

  6. Low temperature environmental degradation of zirconia ceramics

    NASA Astrophysics Data System (ADS)

    Zhao, Zhenbo

    2005-11-01

    The low temperature environmental degradation (LTED) of yttria-stabilized tetragonal zirconia polycrystal (Y-TZP) has been prevented, or at least retarded, by using both bulk doping and surface doping methods with either cation, or anion, stabilizers. The introduction of both mullite and alumina into 3Y-TZP by a bulk-doping method was found to be effective in suppressing the tetragonal-->monoclinic transformation induced by water during hydrothermal treatment thus giving rise to better mechanical properties. The beneficial effects of alumina on the phase stability of the 3Y-TZP ceramic are considered to be due to the increase in the elastic modulus of the constraining matrix, as well as to the segregation of A12O3 at grain boundaries. The LTED transformation kinetics as determined by x-ray diffraction (XRD) and White Light Interferometer (WLI) analysis showed that the isothermal tetragonal-to-monoclinic transformation starts from the surface and has an incubation-nucleation-growth mechanism which can be described by the Johnson-Mehl-Avrami equation. The degradation of Y-TZP ceramic after hydrothermal treatment can be effectively overcome by surface doping by a solid diffusion method with tetravalent dopants: CeO2 and GeO2; with trivalent dopants: La2O 3 and Fe2O3; and with divalent dopants: CuO and MgO. For surface CeO2-, GeO2- and Fe2O 3-doping, this degradation inhibition behaviour is attributed to a localized increase in cation stabilizer content which satisfies the requirements for stabilization of the tetragonal phase. However, in each case, the stability mechanisms are different. For surface La2O3doping, surface doping overcomes the formation of La2O3 and La 2Zr2O7 since the extra La2O3 can further diffuse to the center of the 3Y-TZP ceramic. For CuO-doping, small amounts of CuO form a liquid that can act as a conduit for the re-distribution of yttria. In the case of surface MgO modification, the stabilization results from the isolated nature of the

  7. Nanocrystal doped matrixes

    DOEpatents

    Parce, J. Wallace; Bernatis, Paul; Dubrow, Robert; Freeman, William P.; Gamoras, Joel; Kan, Shihai; Meisel, Andreas; Qian, Baixin; Whiteford, Jeffery A.; Ziebarth, Jonathan

    2010-01-12

    Matrixes doped with semiconductor nanocrystals are provided. In certain embodiments, the semiconductor nanocrystals have a size and composition such that they absorb or emit light at particular wavelengths. The nanocrystals can comprise ligands that allow for mixing with various matrix materials, including polymers, such that a minimal portion of light is scattered by the matrixes. The matrixes of the present invention can also be utilized in refractive index matching applications. In other embodiments, semiconductor nanocrystals are embedded within matrixes to form a nanocrystal density gradient, thereby creating an effective refractive index gradient. The matrixes of the present invention can also be used as filters and antireflective coatings on optical devices and as down-converting layers. Processes for producing matrixes comprising semiconductor nanocrystals are also provided. Nanostructures having high quantum efficiency, small size, and/or a narrow size distribution are also described, as are methods of producing indium phosphide nanostructures and core-shell nanostructures with Group II-VI shells.

  8. Metal Adatoms and Clusters on Ultrathin Zirconia Films

    PubMed Central

    2016-01-01

    Nucleation and growth of transition metals on zirconia has been studied by scanning tunneling microscopy (STM) and density functional theory (DFT) calculations. Since STM requires electrical conductivity, ultrathin ZrO2 films grown by oxidation of Pt3Zr(0001) and Pd3Zr(0001) were used as model systems. DFT studies were performed for single metal adatoms on supported ZrO2 films as well as the (1̅11) surface of monoclinic ZrO2. STM shows decreasing cluster size, indicative of increasing metal–oxide interaction, in the sequence Ag < Pd ≈ Au < Ni ≈ Fe. Ag and Pd nucleate mostly at steps and domain boundaries of ZrO2/Pt3Zr(0001) and form three-dimensional clusters. Deposition of low coverages of Ni and Fe at room temperature leads to a high density of few-atom clusters on the oxide terraces. Weak bonding of Ag to the oxide is demonstrated by removing Ag clusters with the STM tip. DFT calculations for single adatoms show that the metal–oxide interaction strength increases in the sequence Ag < Au < Pd < Ni on monoclinic ZrO2, and Ag ≈ Au < Pd < Ni on the supported ultrathin ZrO2 film. With the exception of Au, metal nucleation and growth on ultrathin zirconia films follow the usual rules: More reactive (more electropositive) metals result in a higher cluster density and wet the surface more strongly than more noble metals. These bind mainly to the oxygen anions of the oxide. Au is an exception because it can bind strongly to the Zr cations. Au diffusion may be impeded by changing its charge state between −1 and +1. We discuss differences between the supported ultrathin zirconia films and the surfaces of bulk ZrO2, such as the possibility of charge transfer to the substrate of the films. Due to their large in-plane lattice constant and the variety of adsorption sites, ZrO2{111} surfaces are more reactive than many other oxygen-terminated oxide surfaces. PMID:27213024

  9. Low temperature synthesis of high purity monoclinic celsian using topaz

    SciTech Connect

    Talmy, I.G.; Haught, D.A.

    1991-02-19

    This patent describes a process for preparing monoclinic BaO {center dot} Al{sub 2}O{sub 3} {center dot} 2SiO{sub 2}. It comprises: forming an intimate reaction mixture of powders of topaz and BaCO{sub 3} wherein the molar ratio of topaz to BaCO{sub 3} is from 2:1 to 4:1; and heating the reaction mixture to initiate a celsian formation reaction, in an atmosphere of gases generated by the celsian formation reaction, at a temperature in the range of from 900{degrees} C. to less than 1590{degrees} C. until the monoclinic celsian is produced.

  10. Effect of Time and Temperature on Transformation Toughened Zirconias.

    DTIC Science & Technology

    1987-06-01

    TTZ) and tetragonal airconia polycrystal ( TZP ), as well as sirconla toughened alumina (ZTA), among others. Zirconia based materials are of interest due... zirconia case, two ftctors that affect the analysis are the difficulty in resolving the tetragonal (101) and cubic (111) peaks when copper radiation is...The materials were magnesia stabilized transforma- tion toughened zirconia , yttria stabilized tetragonal zirconia polycrystal, and zirconia toughened

  11. Biomineralization: Nanocrystals by design

    NASA Astrophysics Data System (ADS)

    Shang, Li; Nienhaus, Gerd Ulrich

    2015-10-01

    Nanocrystals with precisely defined structures offer promise as components of advanced materials yet they are challenging to create. Now, a nanocrystal made up of seven cadmium and twelve chloride ions has been synthesized via a biotemplating approach that uses a de novo designed protein.

  12. Fracture resistance of zirconia-composite veneered crowns in comparison with zirconia-porcelain crowns.

    PubMed

    Alsadon, Omar; Patrick, David; Johnson, Anthony; Pollington, Sarah; Wood, Duncan

    2017-02-11

    The objectives were to evaluate the fracture resistance and stress concentration in zirconia/composite veneered crowns in comparison to zirconia/porcelain crowns using occlusal fracture resistance and by stress analysis using finite element analysis method. Zirconia substructures were divided into two groups based on the veneering material. A static load was applied occlusally using a ball indenter and the load to fracture was recorded in Newtons (N). The same crown design was used to create 3D crown models and evaluated using FEA. The zirconia/composite crowns subjected to static occlusal load showed comparable results to the zirconia/porcelain crowns. Zirconia/composite crowns showed higher stress on the zirconia substructure at 63.6 and 50.9 MPa on the zirconia substructure veneered with porcelain. In conclusion, zirconia/composite crowns withstood high occlusal loads similar to zirconia/porcelain crowns with no significant difference. However, the zirconia/composite crowns showed higher stress values than the zirconia/porcelain crowns at the zirconia substructure.

  13. Silicon Nanocrystal Laser

    SciTech Connect

    Yu, J

    2005-03-09

    The purpose of this feasibility study project was to attempt to demonstrate the silicon-nanocrystal-based laser. Such a silicon laser (made using conventional silicon-manufacturing technologies) would provide the crucial missing link that would enable a completely-silicon-based photonic system. We prepared thin layers of silicon nanocrystal material by ion-implanting Si in fused silica substrates, followed by a high temperature anneal process. These Si nanocrystals produced intense photoluminescence when optically pumped with ultraviolet light. Laser structures based on Fabry-Perot cavity and distributed feedback (DFB) designs were fabricated using the Si nanocrystals as the ''lasing'' medium. We optically pumped the samples with CW lasers at 413nm wavelength to quickly assess the feasibility of making lasers out of the Nanocrystal Si material and to verify the gain coefficients reported by other research groups.

  14. Hot Corrosion of Yttria-Stabilized Zirconia Coating, in a Mixture of Sodium Sulfate and Vanadium Oxide at 950 °C

    NASA Astrophysics Data System (ADS)

    Qureshi, Imran Nazir; Shahid, Muhammad; Nusair Khan, A.

    2016-02-01

    Yttria-stabilized zirconia thermal barrier coating along with CoNiCrAlY bondcoat was deposited using air plasma spray on Inconel-X750 superalloy. The coated samples were exposed at 950 °C in a mixture of Na2SO4 and V2O5. The exposed specimens were investigated using XRD and SEM. The formation of spinel and perovskite structures was revealed at the interface of topcoat and the bondcoat. Further, the chemical composition profile of all samples helped to analyze the diffusion behavior of different constituent elements of bondcoat and substrate. XRD analyses of the samples confirmed the phase transformation of the tetragonal zirconia into monoclinic zirconia and yttrium vanadate. The shift of high angle peaks indicated lattice distortion, which was directly related to the stresses in the coating.

  15. Nanocrystal diffusion doping.

    PubMed

    Vlaskin, Vladimir A; Barrows, Charles J; Erickson, Christian S; Gamelin, Daniel R

    2013-09-25

    A diffusion-based synthesis of doped colloidal semiconductor nanocrystals is demonstrated. This approach involves thermodynamically controlled addition of both impurity cations and host anions to preformed seed nanocrystals under equilibrium conditions, rather than kinetically controlled doping during growth. This chemistry allows thermodynamic crystal compositions to be prepared without sacrificing other kinetically trapped properties such as shape, size, or crystallographic phase. This doping chemistry thus shares some similarities with cation-exchange reactions, but proceeds without the loss of host cations and excels at the introduction of relatively unreactive impurity ions that have not been previously accessible using cation exchange. Specifically, we demonstrate the preparation of Cd(1-x)Mn(x)Se (0 ≤ x ≤ ∼0.2) nanocrystals with narrow size distribution, unprecedentedly high Mn(2+) content, and very large magneto-optical effects by diffusion of Mn(2+) into seed CdSe nanocrystals grown by hot injection. Controlling the solution and lattice chemical potentials of Cd(2+) and Mn(2+) allows Mn(2+) diffusion into the internal volumes of the CdSe nanocrystals with negligible Ostwald ripening, while retaining the crystallographic phase (wurtzite or zinc blende), shape anisotropy, and ensemble size uniformity of the seed nanocrystals. Experimental results for diffusion doping of other nanocrystals with other cations are also presented that indicate this method may be generalized, providing access to a variety of new doped semiconductor nanostructures not previously attainable by kinetic routes or cation exchange.

  16. On Ultrasmall Nanocrystals

    PubMed Central

    McBride, James R.; Dukes, Albert D.; Schreuder, Michael A.; Rosenthal, Sandra J.

    2010-01-01

    Ultrasmall nanocrystals are a growing sub-class of traditional nanocrystals that exhibit new properties at diameters typically below 2 nm. In this review, we define what constitutes an ultrasmall nanoparticle while distinguishing between ultrasmall and magic-size nanoparticles. After a brief overview of ultrasmall nanoparticles, including ultrasmall gold clusters, our recent work is presented covering the optical properties, structure, and application of ultrasmall CdSe nanocrystals. This unique material has potential application in solid state lighting due to its balanced white emission. This section is followed by a discussion on the blurring boundary between what can be considered a nanoparticle and a molecule. PMID:21132106

  17. Alumina-Reinforced Zirconia Composites

    NASA Technical Reports Server (NTRS)

    Choi, Sung R.; Bansal, Narottam P.

    2003-01-01

    Alumina-reinforced zirconia composites, used as electrolyte materials for solid oxide fuel cells, were fabricated by hot pressing 10 mol percent yttria-stabilized zirconia (10-YSZ) reinforced with two different forms of alumina particulates and platelets each containing 0 to 30 mol percent alumina. Major mechanical and physical properties of both particulate and platelet composites including flexure strength, fracture toughness, slow crack growth, elastic modulus, density, Vickers microhardness, thermal conductivity, and microstructures were determined as a function of alumina content either at 25 C or at both 25 and 1000 C. Flexure strength and fracture toughness at 1000 C were maximized with 30 particulate and 30 mol percent platelet composites, respectively, while resistance to slow crack growth at 1000 C in air was greater for 30 mol percent platelet composite than for 30 mol percent particulate composites.

  18. Zirconia-molybdenum disilicide composites

    DOEpatents

    Petrovic, John J.; Honnell, Richard E.

    1991-01-01

    Compositions of matter comprised of molybdenum disilicide and zirconium oxide in one of three forms: pure, partially stabilized, or fully stabilized and methods of making the compositions. The stabilized zirconia is crystallographically stabilized by mixing it with yttrium oxide, calcium oxide, cerium oxide, or magnesium oxide and it may be partially stabilized or fully stabilized depending on the amount of stabilizing agent in the mixture.

  19. Cubic zirconia as a high-quality facet coating for semiconductor lasers

    NASA Astrophysics Data System (ADS)

    Chin, A. K.; Satyanarayan, A.; Zarrabi, J. H.; Vetterling, W.

    1988-08-01

    In this paper we describe the properties of high-quality, semiconductor laser facet coatings based on yttria-stabilizied cubic zirconia (90-m% ZrO2/10-m% Y2O3). We have found that cubic zirconia films can be reproducibly deposited by electron-beam evaporation with an index of refraction of 1.98 at 6328 Å, almost ideal for use as a single-layer antireflection coating for GaAs/GaAlAs-based lasers. ZrO2 has a monoclinic crystal structure at room temperature, but changes to tetragonal, hexagonal, and cubic phases upon heating to higher temperatures. However, the addition of the Y2O3 stabilizes ZrO2 in the cubic form, thus allowing electron-beam deposition of thin films of this material to be more controllable and reproducible without the usual addition of oxygen into the vacuum chamber during deposition. Preliminary aging tests of high-power GaAs/GaAlAs lasers show that cubic zirconia films suppress the photo-enhanced oxidation of laser facets that degrades device performance.

  20. Processing of Transparent Rare Earth Doped Zirconia for High Temperature Light Emission Applications

    NASA Astrophysics Data System (ADS)

    Hardin, Corey Lee

    The high fracture toughness of stabilized zirconia makes it one of the most widely applicable high temperature structural materials. However, it is not typicality considered for optical applications since the microstructure achieved by traditional processing makes it opaque. The aim of this dissertation is to develop processing methods for the introducing new functionalities of light transparency and light emission (photoluminescence) and to understand the nanostructure-property relationships that make these functionalities possible. A processing study of rare-earth (RE) doped Zirconium Oxide (ZrO2, zirconia) via Current Activated Pressure Assisted Densification (CAPAD) is presented. The role of processing temperature and dopant concentration on the crystal structure, microstructure and properties of the RE: ZrO2 is studied. Microstructural shows sub-100 nm grain size and homogeneous dopant distribution. X-ray diffraction and Raman analysis show that with increased dopant concentration the material changes from monoclinic to tetragonal. Structural analysis shows the material shows high hardness and toughness values 30% greater than similarly processed yttria-stabilized zirconia. Despite birefringence in the tetragonal phase, optical characterization is presented showing the samples are both highly transparent and photo-luminescent. Special attention is paid to analyzing structural and photoluminescence development during densification, as well as the role of oxygen vacancies on the optical properties of the densified material. This material is shown to be a promising candidate for a number of applications including luminescence thermometry and high temperature light emission.

  1. Different structures of monoclinic martensitic phases in titanium nickelide

    NASA Astrophysics Data System (ADS)

    Voronin, V. I.; Naish, V. E.; Novoselova, T. V.; Pushin, V. G.; Sagaradze, I. V.

    2000-03-01

    The detailed theoretical and experimental analysis has been undertaken to bring to light the true structure of the monoclinic phase in titanium nickelide (NiTi). Theoretical models for such a phase have been proposed to describe the experimental data. In addition to the well-known B19‧ phase two more structures - new monoclinic M phase with Cm space group and triclinic phase with P1 space group - have been produced and analyzed in detail. Diffraction patterns have been obtained from different NiTi samples by using the neutron diffractometer IVV2 at different temperatures. From the refinement by DBWS-9411 program all these neutron patterns have been decoded successfully. The proposed new structures and stereotype B19‧ one agree with correspondent experimental data and the agreement is quite good.

  2. Alpha decay self-damage in cubic and monoclinic zirconolite

    SciTech Connect

    Clinard, F.W. Jr.; Land, C.C.; Peterson, D.E.; Rohr, D.L.; Roof, R.B.

    1981-01-01

    Samples of primarily-monoclinic /sup 238/Pu-doped zirconolite were stored at ambient temperature to allow accumulation of alpha decay self-damage to a dose of 1 x 10/sup 24/ ..cap alpha../m/sup 3/ (equivalent to a SYNROC age of approx. 10/sup 3/y). Bulk swelling reached 2.3 vol% with no tendency toward saturation, a damage response similar to that observed for cubic Pu-doped zirconolite. X-ray volumetric swelling at 4 x 10/sup 24/ ..cap alpha../m/sup 3/ was 1 vol%, considerably less than that for the cubic material. Changes in cell dimensions differed significantly from those reported by others for a monoclinic natural mineral. Extensive microcracking was observed, and is attributed at least partially to swelling differences between the matrix and minor phases.

  3. Synthetic smythite and monoclinic Fe3S4

    NASA Astrophysics Data System (ADS)

    Fleet, Michael E.

    1982-11-01

    Smythite and monoclinic Fe3S4 have been identified by X-ray diffraction procedures in quenched ironsulfide compositions. Both phases appear to be metastable under the conditions of the experiments and their development is structurally induced. Smythite occurs as a coherent twinned intergrowth with hexagonal 3C pyrrhotite. Individual single crystals contain about 50% smythite. Reciprocal lattice rows with h-k ≠ 3n show continuous diffraction streaks. The available data suggest that smythite forms via a “polytypic” displacive transformation, by the introduction of stacking faults in the hexagonal close-packed layers of S atoms in high-temperature 1C pyrrhotite. This is analogous to the transformation of 2H wurtzite to intermediate ordered and disordered ZnS layer sequences. The ideal formula of smythite appears to be Fe13S16. Monoclinic Fe3S4 ( a=5.93, b=3.42, c=10.64 Å, β=91.9°) is present in amounts up to 25% of total sulfides. It has a derivative NiAs-type structure, and is isomorphous with monoclinic Cr3S4 and Fe3Se4. It occurs as small lenticular lamellae within grains of 3C pyrrhotite, and apparently corresponds to the unidentified lamellar phase of Arnold (1962). The lamellae have a rhombohedral morphology, with a habit plane close to {1011}. In single crystal grains of pyrrhotite, monoclinic Fe3S4 in twinned in a manner consistent with transformation from high-temperature 1C pyrrhotite. Although Fe3S4 lamellae have the general appearance of plate martensite, they do not represent a diffusionless transformation.

  4. Nanocrystal-Powered Nanomotor

    SciTech Connect

    Regan, B.C.; Aloni, S.; Jensen, K.; Ritchie, R.O.; Zettl, A.

    2005-07-05

    We have constructed and operated a nanoscale linear motorpowered by a single metal nanocrystal ram sandwiched between mechanicallever arms. Low-level electrical voltages applied to the carbon nanotubelever arms cause the nanocrystal to grow or shrink in a controlledmanner. The length of the ram is adjustable from 0 to more than 150 nm,with extension speeds exceeding 1900 nm/s. The thermodynamic principlesgoverning motor operation resemble those driving frost heave, a naturalsolid-state linear motor.

  5. Nanocrystal dispersed amorphous alloys

    NASA Technical Reports Server (NTRS)

    Perepezko, John H. (Inventor); Allen, Donald R. (Inventor); Foley, James C. (Inventor)

    2001-01-01

    Compositions and methods for obtaining nanocrystal dispersed amorphous alloys are described. A composition includes an amorphous matrix forming element (e.g., Al or Fe); at least one transition metal element; and at least one crystallizing agent that is insoluble in the resulting amorphous matrix. During devitrification, the crystallizing agent causes the formation of a high density nanocrystal dispersion. The compositions and methods provide advantages in that materials with superior properties are provided.

  6. Nanocrystals for electronics.

    PubMed

    Panthani, Matthew G; Korgel, Brian A

    2012-01-01

    Semiconductor nanocrystals are promising materials for low-cost large-area electronic device fabrication. They can be synthesized with a wide variety of chemical compositions and size-tunable optical and electronic properties as well as dispersed in solvents for room-temperature deposition using various types of printing processes. This review addresses research progress in large-area electronic device applications using nanocrystal-based electrically active thin films, including thin-film transistors, light-emitting diodes, photovoltaics, and thermoelectrics.

  7. Assignments of the Raman modes of monoclinic erbium oxide

    SciTech Connect

    Yan, D.; Wu, P. Zhang, S. P.; Liang, L.; Yang, F.; Pei, Y. L.; Chen, S.

    2013-11-21

    As a heavy rare earth oxide, erbium oxide (Er{sub 2}O{sub 3}) has many attractive properties. Monoclinic Er{sub 2}O{sub 3} has useful properties not found in stable cubic Er{sub 2}O{sub 3}, such as unique optical properties and high radiation damage tolerance. In this study, cubic Er{sub 2}O{sub 3} coating and Er{sub 2}O{sub 3} coating with mixed phases were prepared. The Raman scattering spectra of these coatings were investigated by using a confocal micro-Raman spectrometer equipped with 325, 473, 514, 532, 633, and 784 nm lasers. A total of 17 first-order Raman modes of monoclinic Er{sub 2}O{sub 3} were identified and assigned. The modes at 83, 112, 152, 170, 278, 290, 409, 446, 478, 521, 603, and 622 cm{sup −1} are of A{sub g} symmetry, whereas modes at 71, 98, 333, 409, 446, and 468 cm{sup −1} are of B{sub g} symmetry. This research provides basic data necessary for the characterization of monoclinic Er{sub 2}O{sub 3} by Raman spectroscopy.

  8. Solid State Synthesis and Properties of Monoclinic Celsian

    NASA Technical Reports Server (NTRS)

    Bansal, Narottam P.

    1996-01-01

    Monoclinic celsian of Ba(0.75)Sr(0.25)Al2Si2O8 (BSAS-1) and B(0.85)Sr(O.15)Al2Si2O8 (BSAS-2) compositions have been synthesized from metal carbonates and oxides by solid state reaction. A mixture of BaCO3, SrCO3, Al2O3, and SiO2 powders was precalcined at approx. 900-940 C to decompose the carbonates followed by hot pressing at approx. 1300 C. The hot pressed BSAS-1 material was almost fully dense and contained the monoclinic celsian phase, with complete absence of the undesirable hexacelsian as indicated by x-ray diffraction. In contrast, a small fraction of hexacelsian was still present in hot pressed BSAS-2. However, on further heat treatment at 1200 C for 24 h, the hexacelsian phase was completely eliminated. The average linear thermal expansion coefficients of BSAS-1 and BSAS-2 compositions, having the monoclinic celsian phase, were measured to be 5.28 x 10(exp -6)/deg C and 5.15 x 10(exp -6)/deg C, respectively from room temperature to 1200 C. The hot pressed BSAS-1 celsian showed room temperature flexural strength of 131 MPa, elastic modulus of 96 GPa and was stable in air up to temperatures as high as approx. 1500 C.

  9. Zoledronic acid: monoclinic and triclinic polymorphs from powder diffraction data.

    PubMed

    Chernyshev, Vladimir V; Shkavrov, Sergey V; Paseshnichenko, Ksenia A; Puryaeva, Tamara P; Velikodny, Yurii A

    2013-03-01

    The crystal structures of the monoclinic and triclinic polymorphs of zoledronic acid, C5H10N2O7P2, have been established from laboratory powder X-ray diffraction data. The molecules in both polymorphs are described as zwitterions, namely 1-(2-hydroxy-2-phosphonato-2-phosphonoethyl)-1H-imidazol-3-ium. Strong intermolecular hydrogen bonds (with donor-acceptor distances of 2.60 Å or less) link the molecules into layers, parallel to the (100) plane in the monoclinic polymorph and to the (1-10) plane in the triclinic polymorph. The phosphonic acid groups form the inner side of each layer, while the imidazolium groups lie to the outside of the layer, protruding in opposite directions. In both polymorphs, layers related by translation along [100] interact through weak hydrogen bonds (with donor-acceptor distances greater than 2.70 Å), forming three-dimensional layered structures. In the monoclinic polymorph, there are hydrogen-bonded centrosymmetric dimers linked by four strong O-H...O hydrogen bonds, which are not present in the triclinic polymorph.

  10. Silica coating of zirconia by silicon nitride hydrolysis on adhesion promotion of resin to zirconia.

    PubMed

    Lung, Christie Ying Kei; Liu, Dan; Matinlinna, Jukka Pekka

    2015-01-01

    In this study, the effect of silica coating on zirconia by silicon nitride hydrolysis in resin zirconia bonding was investigated. The silica coated zirconia samples were prepared in silicon nitride dispersion at 90 °C under different immersion times followed by a thermal treatment at 1400 °C. Four test groups were prepared: 1) zirconia samples treated by sandblasting, 2) zirconia samples treated by immersion in silicon nitride dispersion for 6 h, 3) zirconia samples treated by immersion in silicon nitride dispersion for 24 h and 4) zirconia samples treated by immersion in silicon nitride dispersion for 48 h. The coatings were characterized by SEM, EDX, XRD and Raman. The resin zirconia bond strengths of the four test groups were evaluated under three storage conditions: dry storage, water storage in deionized water at 37 °C for 30 days and thermo-cycling for 6000 cycles between 5.0 and 55.0 °C. Surface morphology and composition of zirconia were changed after surface treatments. Phase transformation was observed for zirconia surface by sandblasting treatment but was not observed for zirconia surface treated with silicon nitride hydrolysis. Significant differences in bond strengths were found under different surface treatments (p<0.001) and under three storage conditions (p<0.005). The highest bond strength values were obtained by sandblasting treatment.

  11. Neutron and X-ray diffraction of plasma-sprayed zirconia-yttria thermal barrier coatings

    NASA Technical Reports Server (NTRS)

    Shankar, N. R.; Herman, H.; Singhal, S. P.; Berndt, C. C.

    1984-01-01

    ZrO2-7.8mol. pct. YO1.5, a fused powder, and ZrO2-8.7mol. pct. YO1.5, a prereacted powder, were plasma-sprayed onto steel substrates. Neutron diffraction and X-ray diffraction of the as-received powder, the powder plasma sprayed into water, as-sprayed coatings, and coatings heat-treated for 10 and 100 h were carried out to study phase transformations and ordering of the oxygen ions on the oxygen sublattice. The as-received fused powder has a much lower monoclinic percentage than does the pre-reacted powder, this resulting in a much lower monoclinic percentage in the coating. Heat treatment increases the percentages of the cubic and monoclinic phases, while decreasing the tetragonal content. An ordered tetragonal phase is detected by the presence of extra neutron diffraction peaks. These phase transformations and ordering will result in volume changes. The implications of these transformations on the performance of partially stabilized zirconia thermal barrier coatings is discussed.

  12. Zirconia in fixed prosthesis. A literature review

    PubMed Central

    Román-Rodríguez, Juan L.; Ferreiroa, Alberto; Solá-Ruíz, María F.; Fons-Font, Antonio

    2014-01-01

    Statement of problem: Evidence is limited on the efficacy of zirconia-based fixed dental prostheses. Objective: To carry out a literature review of the behavior of zirconium oxide dental restorations. Material and Methods: This literature review searched the Pubmed, Scopus, Medline and Cochrane Library databases using key search words “zirconium oxide,” “zirconia,” “non-metal restorations,” “ceramic oxides,” “veneering ceramic,” “zirconia-based fixed dental prostheses”. Both in vivo and in vitro studies into zirconia-based prosthodontic restoration behavior were included. Results: Clinical studies have revealed a high rate of fracture for porcelain-veneered zirconia-based restorations that varies between 6% and 15% over a 3- to 5-year period, while for ceramo-metallic restorations the fracture rate ranges between 4 and 10% over ten years. These results provoke uncertainty as to the long-term prognosis for this material in the oral medium. The cause of veneering porcelain fractures is unknown but hypothetically they could be associated with bond failure between the veneer material and the zirconia sub-structure. Key words:Veneering ceramic, zirconia-based ceramic restoration, crown, zirconia, tooth-supported fixed prosthesis. PMID:24596638

  13. Enamel wear opposing polished and aged zirconia.

    PubMed

    Burgess, J O; Janyavula, S; Lawson, N C; Lucas, T J; Cakir, D

    2014-01-01

    Aging of dental zirconia roughens its surface through low temperature degradation. We hypothesized that age-related roughening of zirconia crowns may cause detrimental wear to the enamel of an opposing tooth. To test our hypothesis, we subjected artificially aged zirconia and reference specimens to simulated mastication in a wear device and measured the wear of an opposing enamel cusp. Additionally, the roughness of the pretest surfaces was measured. The zirconia specimens, artificially aged by autoclave, showed no significant increase in roughness compared to the nonaged specimens. Furthermore, no significant difference in material or opposing enamel wear between the aged and nonaged zirconia was seen. All zirconia specimens showed less material and opposing enamel wear than the enamel to enamel control or veneering porcelain specimens. Scanning electron micrographs showed relatively smooth surfaces of aged and nonaged zirconia following wear testing. The micrographs of the veneering ceramic showed sharp fractured edges and fragments of wear debris. Zirconia may be considered a wear-friendly material for restorations opposing enamel, even after simulated aging.

  14. Effect of different grinding burs on the physical properties of zirconia

    PubMed Central

    2016-01-01

    PURPOSE Grinding with less stress on 3Y-TZP through proper selection of methods and instruments can lead to a long-term success of prosthesis. The purpose of this study was to compare the phase transformation and physical properties after zirconia surface grinding with 3 different grinding burs. MATERIALS AND METHODS Forty disc-shaped zirconia specimens were fabricated. Each Ten specimens were ground with AllCeramic SuperMax (NTI, Kahla, Germany), Dura-Green DIA (Shofu Inc., Kyoto, Japan), and Dura-Green (Shofu Inc., Kyoto, Japan). Ten specimens were not ground and used as a control group. After the specimen grinding, XRD analysis, surface roughness test, FE-SEM imaging, and biaxial flexural strength test were performed. RESULTS After surface grinding, small amount of monoclinic phase in all experimental groups was observed. The phase change was higher in specimens, which were ground with Dura-Green DIA and AllCeramic SuperMax burs. The roughness of surfaces increased in specimens, which were ground with Dura-Green DIA and AllCeramic SuperMax burs than control groups and ground with Dura-Green. All experimental groups showed lower flexural strength than control group, but there was no statistically significant difference between control group and ground with Dura-Green DIA and AllCeramic SuperMax burs. The specimens, which were ground with Dura- Green showed the lowest strength. CONCLUSION The use of dedicated zirconia-specific grinding burs such as Dura-Green DIA and AllCeramic SuperMax burs decreases the grinding time and did not significantly affect the flexural strength of zirconia, and therefore, they may be recommended. However, a fine polishing process should be accompanied to reduce the surface roughness after grinding. PMID:27141258

  15. Zirconia solubility in boroaluminosilicate glass

    SciTech Connect

    Raman, S.V.; Bopp, R.; Batcheller, T.A.; Yan, Q.

    1995-12-31

    In the Idaho Chemical Processing Plant (ICPP) waste streams, zirconia is often the waste load limiting species. It modifies the glass network, enhances durability, increases viscosity and induces crystallization. The limits of its dissolution in boroaluminosilicate glass, with magnesia and soda additions were experimentally determined. A ternary compositional surface is evolved to present the isothermal regimes of liquid, liquid + zircon, liquid + forsterite, and liquid phase sintered ceramic. The potential of partitioning the transuranics, transition elements and solutes in these regimes is discussed. The visible Raman spectroscopic results are presented to elucidate the dependence among glass composition, structure and chemical durability.

  16. Nanocrystal Solar Cells

    SciTech Connect

    Gur, Ilan

    2006-01-01

    This dissertation presents the results of a research agenda aimed at improving integration and stability in nanocrystal-based solar cells through advances in active materials and device architectures. The introduction of 3-dimensional nanocrystals illustrates the potential for improving transport and percolation in hybrid solar cells and enables novel fabrication methods for optimizing integration in these systems. Fabricating cells by sequential deposition allows for solution-based assembly of hybrid composites with controlled and well-characterized dispersion and electrode contact. Hyperbranched nanocrystals emerge as a nearly ideal building block for hybrid cells, allowing the controlled morphologies targeted by templated approaches to be achieved in an easily fabricated solution-cast device. In addition to offering practical benefits to device processing, these approaches offer fundamental insight into the operation of hybrid solar cells, shedding light on key phenomena such as the roles of electrode-contact and percolation behavior in these cells. Finally, all-inorganic nanocrystal solar cells are presented as a wholly new cell concept, illustrating that donor-acceptor charge transfer and directed carrier diffusion can be utilized in a system with no organic components, and that nanocrystals may act as building blocks for efficient, stable, and low-cost thin-film solar cells.

  17. Absence of ferromagnetism in Mn-doped tetragonal zirconia

    NASA Astrophysics Data System (ADS)

    Srivastava, S. K.; Lejay, P.; Barbara, B.; Boisron, O.; Pailhès, S.; Bouzerar, G.

    2011-08-01

    In a recent letter, it has been predicted within first principle studies that Mn-doped ZrO2 compounds could be good candidates for spintronics application because expected to exhibit ferromagnetism far beyond room temperature. Our purpose is to address this issue experimentally for Mn-doped tetragonal zirconia. We have prepared polycrystalline samples of Y0.15(Zr0.85-yMny)O2 (y = 0, 0.05, 0.10, 0.15, 0.20) by using standard solid state method at equilibrium. The obtained samples were carefully characterized by using x-ray diffraction, scanning electron microscopy, elemental color mapping, x-ray photoemission spectroscopy, and magnetization measurements. From the detailed structural analyses, we have observed that the 5% Mn doped compound crystallized into two symmetries (dominating tetragonal and monoclinic), whereas higher Mn doped compounds are found to be in the tetragonal symmetry only. The spectral splitting of the Mn 3s core-level x-ray photoelectron spectra confirms that Mn ions are in the Mn3+ oxidation state and indicate a local magnetic moment of about 4.5 μB/Mn. Magnetic measurements showed that compounds up to 10% of Mn doping are paramagnetic with antiferromagnetic interactions. However, higher Mn doped compound exhibits local ferrimagnetic ordering. Thus, no ferromagnetism has been observed for all Mn-doped tetragonal ZrO2 samples.

  18. Fitting accuracy and fracture resistance of crowns using a hybrid zirconia frame made of both porous and dense zirconia.

    PubMed

    Nakamura, Takashi; Sugano, Tsuyoshi; Usami, Hirofumi; Wakabayashi, Kazumichi; Ohnishi, Hiroshi; Sekino, Tohru; Yatani, Hirofumi

    2015-01-01

    The purpose of this study is to evaluate the fitting accuracy and fracture resistance of crowns using a hybrid zirconia frame made of both porous and dense zirconia. Commercial semi-sintered zirconia, sintered dense zirconia and sintered hybrid zirconia were used. Sintered zirconia was milled using the CAD/CAM system, and semi-sintered zirconia was milled and sintered to fabricate molar crown frames. Completed frames were veneered with tooth-colored porcelain. The marginal and internal gaps between frames/crowns and abutments were measured. Each crown specimen was subjected to a fracture test. There were no significant differences in marginal and internal gap among all the frames and crowns. The crown with the hybrid zirconia frame had a 31-35% greater fracture load than that with the commercial or dense zirconia frame (p<0.01). This suggests that the all-ceramic crowns with a hybrid zirconia frame have a high fracture resistance.

  19. Catastrophic failure of a monolithic zirconia prosthesis.

    PubMed

    Chang, Jae-Seung; Ji, Woon; Choi, Chang-Hoon; Kim, Sunjai

    2015-02-01

    Recently, monolithic zirconia restorations have received attention as an alternative to zirconia veneered with feldspathic porcelain to eliminate chipping failures of veneer ceramics. In this clinical report, a patient with mandibular edentulism received 4 dental implants in the interforaminal area, and a screw-retained monolithic zirconia prosthesis was fabricated. The patient also received a maxillary complete removable dental prosthesis over 4 anterior roots. At the 18-month follow-up, all of the zirconia cylinders were seen to be fractured, and the contacting abutment surfaces had lost structural integrity. The damaged abutments were replaced with new abutments, and a new prosthesis was delivered with a computer-assisted design and computer-assisted manufacturing fabricated titanium framework with denture teeth and denture base resins. At the 6-month recall, the patient did not have any problems. Dental zirconia has excellent physical properties; however, care should be taken to prevent excessive stresses on the zirconia cylinders when a screw-retained zirconia restoration is planned as a definitive prosthesis.

  20. A Raman study of the nanocrystallite size effect on the pressure temperature phase diagram of zirconia grown by zirconium-based alloys oxidation

    NASA Astrophysics Data System (ADS)

    Bouvier, P.; Godlewski, J.; Lucazeau, G.

    2002-02-01

    The pressure-temperature phase diagrams of different zirconia samples prepared by oxidation of Zircaloy-4 and Zr-1%Nb-0.12O alloys were monitored by Raman spectrometry from 0.1 MPa to 12 GPa and from 300 to 640 K. These new diagrams show that the monoclinic-tetragonal equilibrium line is strongly downshifted in temperature compared to literature measurements performed on usual polycrystalline zirconia. In addition, the monoclinic-orthorhombic equilibrium line is slightly shifted to higher pressure (i.e. 6 GPa). The crystallite sizes smaller than 30 nm, are thought to be responsible for these equilibrium line displacements. The tetragonal phase obtained in temperature under high pressure can be quenched at room temperature, if the pressure is maintained, and it is destabilised and transforms completely into monoclinic phase if the pressure is released. These results confirm that coupled effects of stress, temperature and nanosized grain are responsible for the formation of the tetragonal phase near the metal/oxide interface during the oxidation of zirconium-based alloys.

  1. Substitutional doping in nanocrystal superlattices

    NASA Astrophysics Data System (ADS)

    Cargnello, Matteo; Johnston-Peck, Aaron C.; Diroll, Benjamin T.; Wong, Eric; Datta, Bianca; Damodhar, Divij; Doan-Nguyen, Vicky V. T.; Herzing, Andrew A.; Kagan, Cherie R.; Murray, Christopher B.

    2015-08-01

    Doping is a process in which atomic impurities are intentionally added to a host material to modify its properties. It has had a revolutionary impact in altering or introducing electronic, magnetic, luminescent, and catalytic properties for several applications, for example in semiconductors. Here we explore and demonstrate the extension of the concept of substitutional atomic doping to nanometre-scale crystal doping, in which one nanocrystal is used to replace another to form doped self-assembled superlattices. Towards this goal, we show that gold nanocrystals act as substitutional dopants in superlattices of cadmium selenide or lead selenide nanocrystals when the size of the gold nanocrystal is very close to that of the host. The gold nanocrystals occupy random positions in the superlattice and their density is readily and widely controllable, analogous to the case of atomic doping, but here through nanocrystal self-assembly. We also show that the electronic properties of the superlattices are highly tunable and strongly affected by the presence and density of the gold nanocrystal dopants. The conductivity of lead selenide films, for example, can be manipulated over at least six orders of magnitude by the addition of gold nanocrystals and is explained by a percolation model. As this process relies on the self-assembly of uniform nanocrystals, it can be generally applied to assemble a wide variety of nanocrystal-doped structures for electronic, optical, magnetic, and catalytic materials.

  2. On the interfacial fracture resistance of resin-bonded zirconia and glass-infiltrated graded zirconia

    PubMed Central

    Chai, Herzl; Kaizer, Marina; Chughtai, Asima; Tong, Hui; Tanaka, Carina; Zhang, Yu

    2015-01-01

    Objective A major limiting factor for the widespread use of zirconia in prosthetic dentistry is its poor resin-cement bonding capabilities. We show that this deficiency can be overcome by infiltrating the zirconia cementation surface with glass. Current methods for assessing the fracture resistance of resin-ceramic bonds are marred by uneven stress distribution at the interface, which may result in erroneous interfacial fracture resistance values. We have applied a wedge-loaded double-cantilever-beam testing approach to accurately measure the interfacial fracture resistance of adhesively bonded zirconia-based restorative materials. Methods The interfacial fracture energy GC was determined for adhesively bonded zirconia, graded zirconia and feldspathic ceramic bars. The bonding surfaces were subjected to sandblasting or acid etching treatments. Baseline GC was measured for bonded specimens subjected to 7 days hydration at 37 °C. Long-term GC was determined for specimens exposed to 20,000 thermal cycles between 5 and 55 °C followed by 2-month aging at 37 °C in water. The test data were interpreted with the aid of a 2D finite element fracture analysis. Results The baseline and long-term GC for graded zirconia was 2–3 and 8 times that for zirconia, respectively. More significantly, both the baseline and long-term GC of graded zirconia were similar to those for feldspathic ceramic. Significance The interfacial fracture energy of feldspathic ceramic and graded zirconia was controlled by the fracture energy of the resin cement while that of zirconia by the interface. GC for the graded zirconia was as large as for feldspathic ceramic, making it an attractive material for use in dentistry. PMID:26365987

  3. Oxide Nanocrystal Model Catalysts.

    PubMed

    Huang, Weixin

    2016-03-15

    Model catalysts with uniform and well-defined surface structures have been extensively employed to explore structure-property relationships of powder catalysts. Traditional oxide model catalysts are based on oxide single crystals and single crystal thin films, and the surface chemistry and catalysis are studied under ultrahigh-vacuum conditions. However, the acquired fundamental understandings often suffer from the "materials gap" and "pressure gap" when they are extended to the real world of powder catalysts working at atmospheric or higher pressures. Recent advances in colloidal synthesis have realized controlled synthesis of catalytic oxide nanocrystals with uniform and well-defined morphologies. These oxide nanocrystals consist of a novel type of oxide model catalyst whose surface chemistry and catalysis can be studied under the same conditions as working oxide catalysts. In this Account, the emerging concept of oxide nanocrystal model catalysts is demonstrated using our investigations of surface chemistry and catalysis of uniform and well-defined cuprous oxide nanocrystals and ceria nanocrystals. Cu2O cubes enclosed with the {100} crystal planes, Cu2O octahedra enclosed with the {111} crystal planes, and Cu2O rhombic dodecahedra enclosed with the {110} crystal planes exhibit distinct morphology-dependent surface reactivities and catalytic properties that can be well correlated with the surface compositions and structures of exposed crystal planes. Among these types of Cu2O nanocrystals, the octahedra are most reactive and catalytically active due to the presence of coordination-unsaturated (1-fold-coordinated) Cu on the exposed {111} crystal planes. The crystal-plane-controlled surface restructuring and catalytic activity of Cu2O nanocrystals were observed in CO oxidation with excess oxygen. In the propylene oxidation reaction with O2, 1-fold-coordinated Cu on Cu2O(111), 3-fold-coordinated O on Cu2O(110), and 2-fold-coordinated O on Cu2O(100) were identified

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

    SciTech Connect

    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

    2015-11-01

    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.

  5. Zirconia in dental implantology: A review

    PubMed Central

    Apratim, Abhishek; Eachempati, Prashanti; Krishnappa Salian, Kiran Kumar; Singh, Vijendra; Chhabra, Saurabh; Shah, Sanket

    2015-01-01

    Background: Titanium has been the most popular material of choice for dental implantology over the past few decades. Its properties have been found to be most suitable for the success of implant treatment. But recently, zirconia is slowly emerging as one of the materials which might replace the gold standard of dental implant, i.e., titanium. Materials and Methods: Literature was searched to retrieve information about zirconia dental implant and studies were critically analyzed. PubMed database was searched for information about zirconia dental implant regarding mechanical properties, osseointegration, surface roughness, biocompatibility, and soft tissue health around it. The literature search was limited to English language articles published from 1975 to 2015. Results: A total of 45 papers met the inclusion criteria for this review, among the relevant search in the database. Conclusion: Literature search showed that some of the properties of zirconia seem to be suitable for making it an ideal dental implant, such as biocompatibility, osseointegration, favourable soft tissue response and aesthetics due to light transmission and its color. At the same time, some studies also point out its drawbacks. It was also found that most of the studies on zirconia dental implants are short-term studies and there is a need for more long-term clinical trials to prove that zirconia is worth enough to replace titanium as a biomaterial in dental implantology. PMID:26236672

  6. Nanosilica coating for bonding improvements to zirconia

    PubMed Central

    Chen, Chen; Chen, Gang; Xie, Haifeng; Dai, Wenyong; Zhang, Feimin

    2013-01-01

    Resin bonding to zirconia cannot be established from standard methods that are currently utilized in conventional silica-based dental ceramics. The solution–gelatin (sol–gel) process is a well developed silica-coating technique used to modify the surface of nonsilica-based ceramics. Here, we use this technique to improve resin bonding to zirconia, which we compared to zirconia surfaces treated with alumina sandblasting and tribochemical silica coating. We used the shear bond strength test to examine the effect of the various coatings on the short-term resin bonding of zirconia. Furthermore, we employed field emission scanning electron microscopy, energy-dispersive X-ray spectroscopy, atomic force microscopy, and Fourier transform infrared spectroscopy to characterize the zirconia surfaces. Water–mist spraying was used to evaluate the durability of the coatings. To evaluate the biological safety of the experimental sol–gel silica coating, we conducted an in vitro Salmonella typhimurium reverse mutation assay (Ames mutagenicity test), cytotoxicity tests, and in vivo oral mucous membrane irritation tests. When compared to the conventional tribochemical silica coating, the experimental sol–gel silica coating provided the same shear bond strength, higher silicon contents, and better durability. Moreover, we observed no apparent mutagenicity, cytotoxicity, or irritation in this study. Therefore, the sol–gel technique represents a promising method for producing silica coatings on zirconia. PMID:24179333

  7. Hydroxyapatite: Vibrational spectra and monoclinic to hexagonal phase transition

    NASA Astrophysics Data System (ADS)

    Slepko, Alexander; Demkov, Alexander A.

    2015-02-01

    Fundamental studies of biomaterials are necessary to deepen our understanding of their degradation and to develop cure for related illnesses. Biomineral hydroxyapatite Ca10(PO4)6(OH)2 is the main mineral constituent of mammal bone, and its synthetic analogues are used in biomedical applications. The mineral can be found in either hexagonal or monoclinic form. The transformation between these two phases is poorly understood, but knowing its mechanism may be critical to reversing processes in bone related to aging. Using density functional theory, we investigate the mechanisms of the phase transformation and estimate the transition temperature to be 680 K in fair agreement with the experimental temperature of 470 K. We also report the heat capacity of hydroxyapatite and a peculiarity in its phonon dispersion that might allow for non-destructive measurements of the crystal composition with applications in preventive medical screening for bone mineral loss.

  8. Paired, facing monoclines in the Sanpete-Sevier Valley area, central Utah

    USGS Publications Warehouse

    Witkind, I.J.

    1992-01-01

    Several major monoclines that trend northward through the Sanpete-Sevier Valley area of central Utah are paired and face one another. This pairing of monoclines may have occurred when near-horizontal sedimentary and volcanic strata subsided into voids created as salt was removed from a salt diapir concealed beneath valley fill. Removal was mostly by dissolution or extrusion during Neogene time. The paired monoclines, thus, are viewed as collapse features rather than as normal synclinal folds. -from Author

  9. Ferroelasticity, mechanical behavior, and phase stability of t prime zirconia ceramics

    SciTech Connect

    Jue Janfong.

    1991-01-01

    Large-grained (100-200 {mu}m), yttria doped, polycrystalline t{prime}-zirconia ceramics were fabricated by heating presintered samples at 2100C. Two point four and 3 mol% yttria-doped single crystals obtained from a commercial source were oriented by the Laue back-reflection method and cut along {l angle}100{r angle}, {l angle}110{r angle}, and {l angle}111{r angle} directions. They were also heat treated at 2100C. Ferroelastic domain structure was predicted by group theory and examined by transmission optical microscopy under polarized light and transmission electron microscopy. Orientations of domain boundaries were in accordance with predictions of group theory. X-ray diffraction showed that no monoclinic phase was detected on as-polished, ground, fracture surfaces, and on surfaces under tensile stresses as high as 400 MPa. Relative changes in the tetragonal peak intensities occurred and were attributed to ferroelastic domain switching. Higher toughness of 3 mol% Y{sub 2}O{sub 3} doped t{prime} samples (7.7MPam{sup 1/2}) compared to that of zirconia in the cubic phase (8 mol% Y{sub 2}O{sub 3}, 2.4MPam{sup 1/2}) was attributed in part to ferroelastic domain switching. Polished surfaces of polycrystalline t{prime}-materials showed no mono-clinic phase even after 1,000 hours at 275C in air, whereas conventional Y-TZP ceramics of a grain size larger than 0.5 {mu}m showed substantial transformation.

  10. Effects of Acid Treatment on Dental Zirconia: An In Vitro Study

    PubMed Central

    Xie, Haifeng; Shen, Shuping; Qian, Mengke; Zhang, Feimin; Chen, Chen; Tay, Franklin R.

    2015-01-01

    The aim of this study was to evaluate the effects of hydrofluoric (HF) acid, acetic acid, and citric acid treatments on the physical properties and structure of yttria-stabilized tetragonal zirconia polycrystal (Y-TZP) at ambient temperature. In total, 110 bar-shaped zirconia specimens were randomly assigned to 11 groups. The specimens in the control group (C) received no surface treatment, while those in the Cage group were hydrothermally aged at 134°C and 0.2 MPa for 20 h. Ten specimens each were immersed at ambient temperature in 5% and 40% HF acid for 2 h (40HF0), 1 day (5HF1, 40HF1), and 5 days (5HF5, 40HF5), while 10 each were immersed at ambient temperature in 10% acetic acid and 20% citric acid for 7 (AC7, CI7) and 14 days (AC14, CI14). X-ray diffraction (XRD) was used to quantitatively estimate the monoclinic phase. Furthermore, flexural strength, surface roughness, and surface Vickers hardness were measured after treatment. Scanning electron microscopy (SEM) was used to characterize the surface morphology. The Cage group specimens exhibited an increased monoclinic phase and flexural strength. Furthermore, 40% HF acid immersion decreased the flexural strength and surface hardness and deteriorated the surface finish, while 5% HF acid immersion only decreased the surface hardness. All the HF acid-immersed specimens showed an etched surface texture on SEM observations, while the other groups did not. These findings suggest that the treatment of Y-TZP with 40% HF acid at ambient temperature causes potential damage, while treatment with 5% HF acid, acetic acid, and citric acid is safe. PMID:26301413

  11. Sorting fluorescent nanocrystals with DNA

    SciTech Connect

    Gerion, Daniele; Parak, Wolfgang J.; Williams, Shara C.; Zanchet, Daniela; Micheel, Christine M.; Alivisatos, A. Paul

    2001-12-10

    Semiconductor nanocrystals with narrow and tunable fluorescence are covalently linked to oligonucleotides. These biocompounds retain the properties of both nanocrystals and DNA. Therefore, different sequences of DNA can be coded with nanocrystals and still preserve their ability to hybridize to their complements. We report the case where four different sequences of DNA are linked to four nanocrystal samples having different colors of emission in the range of 530-640 nm. When the DNA-nanocrystal conjugates are mixed together, it is possible to sort each type of nanoparticle using hybridization on a defined micrometer -size surface containing the complementary oligonucleotide. Detection of sorting requires only a single excitation source and an epifluorescence microscope. The possibility of directing fluorescent nanocrystals towards specific biological targets and detecting them, combined with their superior photo-stability compared to organic dyes, opens the way to improved biolabeling experiments, such as gene mapping on a nanometer scale or multicolor microarray analysis.

  12. Chemical design of nanocrystal solids.

    PubMed

    Kovalenko, Maksym V

    2013-01-01

    This account highlights our recent and present activities dedicated to chemical synthesis and applications of inorganic nanostructures. In particular, we discuss the potential of metal amides as precursors in the synthesis of metallic and semiconductor nanocrystals. We show the importance of surface chemical functionalization for the emergence of collective electronic properties in nanocrystal solids. We also demonstrate a new kind of long-range ordered, crystalline matter comprising colloidal nanocrystals and atomically defined inorganic clusters. Finally, we point the reader's attention to the high potential benefits of size- and shape-tunability of nanocrystals for achieving higher performance of rechargeable Li-ion battery electrodes.

  13. Ultrasound assisted synthesis of monoclinic structured spindle BiVO4 particles with hollow structure and its photocatalytic property.

    PubMed

    Liu, Wei; Cao, Lixin; Su, Ge; Liu, Haisong; Wang, Xiangfei; Zhang, Lan

    2010-04-01

    Bismuth vanadate (BiVO(4)) spindle particles with monoclinic scheelite structure have been successfully synthesized via a facile sonochemical method. The as-prepared BiVO(4) photocatalyst exhibited a hollow interior structure constructed from the self-assembly of cone shape primary nanocrystals. A possible oriented attachment growth mechanism has been proposed based on the results of time-dependent experiments, which indicates the formation of spindle particles is mainly attributed to the phase transformation procedure induced by ultrasound irradiation. A series of morphology evolutions of BiVO(4) from compact microspheres, to hollow microspheres, and then to spindle particles have been arrested in the process of sonochemical treatment. Optical absorption experiments revealed the BiVO(4) spindle had strong absorption in the visible light region. A much higher photocatalytic activity of these spindle particles was found in comparison with the SSR-BiVO(4) material for degradation of rhodamine-B under visible light irradiation, which may be ascribed to its special single-crystalline nanostructure.

  14. Electronic and magnetic properties of iron doped zirconia: Theory and experiment

    SciTech Connect

    Debernardi, A. Sangalli, D.; Lamperti, A.; Cianci, E.; Lupo, P.; Casoli, F.; Albertini, F.; Nasi, L.

    2014-05-07

    We systematically investigated, both theoretically and experimentally, Zr{sub 1−x}Fe{sub x}O{sub 2−y} ranging from diluted (x ≈ 0.05) up to large (x ≈ 0.25) Fe concentration. By atomic layer deposition, we grew thin films of high-κ zirconia in cubic phase with Fe uniformly distributed in the film, as proven by time of flight secondary ion mass spectrometry and transmission electron microscopy measurements. Iron is in Fe{sup 3+} oxidation state suggesting the formation of oxygen vacancies with y concentration close to x/2. By ab-initio simulations, we studied the phase diagram relating the stability of monoclinic vs. tetragonal phase as a function of Fe doping and film thickness: the critical thickness at which the pure zirconia is stabilized in the tetragonal phase is estimated ranging from 2 to 6 nm according to film morphology. Preliminary results by X-ray magnetic circular dichroism and alternating gradient force magnetometry are discussed in comparison to ab initio data enlightening the role of oxygen vacancies in the magnetic properties of the system.

  15. Electronic and magnetic properties of iron doped zirconia: Theory and experiment

    NASA Astrophysics Data System (ADS)

    Debernardi, A.; Sangalli, D.; Lamperti, A.; Cianci, E.; Lupo, P.; Casoli, F.; Albertini, F.; Nasi, L.; Ciprian, R.; Torelli, P.

    2014-05-01

    We systematically investigated, both theoretically and experimentally, Zr1-xFexO2-y ranging from diluted (x ≈ 0.05) up to large (x ≈ 0.25) Fe concentration. By atomic layer deposition, we grew thin films of high-κ zirconia in cubic phase with Fe uniformly distributed in the film, as proven by time of flight secondary ion mass spectrometry and transmission electron microscopy measurements. Iron is in Fe3+ oxidation state suggesting the formation of oxygen vacancies with y concentration close to x/2. By ab-initio simulations, we studied the phase diagram relating the stability of monoclinic vs. tetragonal phase as a function of Fe doping and film thickness: the critical thickness at which the pure zirconia is stabilized in the tetragonal phase is estimated ranging from 2 to 6 nm according to film morphology. Preliminary results by X-ray magnetic circular dichroism and alternating gradient force magnetometry are discussed in comparison to ab initio data enlightening the role of oxygen vacancies in the magnetic properties of the system.

  16. Nanocrystal waveguide (NOW) laser

    DOEpatents

    Simpson, John T.; Simpson, Marcus L.; Withrow, Stephen P.; White, Clark W.; Jaiswal, Supriya L.

    2005-02-08

    A solid state laser includes an optical waveguide and a laser cavity including at least one subwavelength mirror disposed in or on the optical waveguide. A plurality of photoluminescent nanocrystals are disposed in the laser cavity. The reflective subwavelength mirror can be a pair of subwavelength resonant gratings (SWG), a pair of photonic crystal structures (PC), or a distributed feedback structure. In the case of a pair of mirrors, a PC which is substantially transmissive at an operating wavelength of the laser can be disposed in the laser cavity between the subwavelength mirrors to improve the mode structure, coherence and overall efficiency of the laser. A method for forming a solid state laser includes the steps of providing an optical waveguide, creating a laser cavity in the optical waveguide by disposing at least one subwavelength mirror on or in the waveguide, and positioning a plurality of photoluminescent nanocrystals in the laser cavity.

  17. Microstructure and mechanical properties of bulk and plasma-sprayed y2O3-partially stabilized zirconia

    NASA Technical Reports Server (NTRS)

    Valentine, P. G.; Maier, R. D.

    1980-01-01

    Bulk 8.0 weight percent yttria partially stabilied zirconia (PSZ) was studied by light microscopy, transmission electron microscopy, X-ray analysis, microhardness testing, and fracture toughness testing. The as received PSZ contained spheroidal and grain boundary precipitates up to 4 micrometers in size. Spheroids up to 1.26 micrometers were metastable tetragonal; large spheroids were monoclinic. Grinding the PSZ into powder did not cause a significant amount of tetragonal to transform to monoclinic. This indicates that transformation toughness is not a significant mechanism in PSZ. Aging the PSZ at 1500 C caused the fine tetragonal precipitates to grow from 0.06 to 0.12 micrometers, in 250 minutes. A peak hardness of 1400 kg/sq mm was attained after 50 minutes. Solution annealing and quenching the as received PSZ eliminated the large precipitates, but fine tetragonal precipitates reformed on quenching. Aging at 1500 C caused the fine 0.02 micrometers tetragonal precipitates to grow into plates about 0.10 by 0.50 micrometers. A peak hardness of 1517 kg/sq mm was obtained after 250 minutes. On further aging, monoclinic percipitates formed along grain boundaries. The fracture toughness of the aged and unaged solution annealed and quenched PSZ was found to be between 2 and 3 MN /square root of m cubed. This range of fracture toughness is consistent with PSZ's that do not undergo transformation toughening.

  18. Preparation and characterization of TiO2 and Si-doped octacalcium phosphate composite coatings on zirconia ceramics (Y-TZP) for dental implant applications

    NASA Astrophysics Data System (ADS)

    Bao, Lei; Liu, Jingxiao; Shi, Fei; Jiang, Yanyan; Liu, Guishan

    2014-01-01

    In order to prevent the low temperature degradation and improve the bioactivity of zirconia ceramic implants, TiO2 and Si-doped octacalcium phosphate composite coating was prepared on zirconia substrate. The preventive effect on low temperature degradation and surface morphology of the TiO2 layer were studied. Meanwhile, the structure and property changes of the bioactive coating after doping Si were discussed. The results indicate that the dense TiO2 layer, in spite of some microcracks, inhibited the direct contact of the water vapor with the sample's surface and thus prevented the low temperature degradation of zirconia substrates. The acceleration aging test shows that the ratio of the monoclinic phase transition decreased from 10% for the original zirconia substrate to 4% for the TiO2-coated substrate. As to the Si-doped octacalcium phosphate coating prepared by biomimetic method, the main phase composition of the coating was octacalcium phosphate. The morphology of the coating was lamellar-like, and the surface was uniform and continuous with no cracks being observed. It is suggested that Si was added into the coating both through substituting for PO43- and doping as NaSiO3.

  19. Oxygen separation from air using zirconia solid electrolyte membranes

    NASA Technical Reports Server (NTRS)

    Suitor, J. W.; Marner, W. J.; Schroeder, J. E.; Losey, R. W.; Ferrall, J. F.

    1988-01-01

    Air separation using a zirconia solid electrolyte membrane is a possible alternative source of oxygen. The process of zirconia oxygen separation is reviewed, and an oxygen plant concept using such separation is described. Potential cell designs, stack designs, and testing procedures are examined. Fabrication of the materials used in a zirconia module as well as distribution plate design and fabrication are examined.

  20. Molybdenum disilicide composites reinforced with zirconia and silicon carbide

    SciTech Connect

    Petrovic, J.J.

    1992-12-31

    This patent pertains to compositions consisting essentially of molybdenum disilicide, silicon carbide, and a zirconium oxide component. The silicon carbide used in the compositions is in whisker or powder form. The zirconium oxide component is pure zirconia or partially stabilized zirconia or fully stabilized zirconia. Fabrication, fracture toughness, and bend strength are covered.

  1. Molybdenum disilicide composites reinforced with zirconia and silicon carbide

    DOEpatents

    Petrovic, John J.

    1995-01-01

    Compositions consisting essentially of molybdenum disilicide, silicon carbide, and a zirconium oxide component. The silicon carbide used in the compositions is in whisker or powder form. The zirconium oxide component is pure zirconia or partially stabilized zirconia or fully stabilized zirconia.

  2. Molybdenum disilicide composites reinforced with zirconia and silicon carbide

    DOEpatents

    Petrovic, J.J.

    1995-01-17

    Compositions are disclosed consisting essentially of molybdenum disilicide, silicon carbide, and a zirconium oxide component. The silicon carbide used in the compositions is in whisker or powder form. The zirconium oxide component is pure zirconia or partially stabilized zirconia or fully stabilized zirconia.

  3. Ceramic fiber-reinforced monoclinic celsian phase glass-ceramic matrix composite material

    NASA Technical Reports Server (NTRS)

    Bansal, Narottam P. (Inventor); Dicarlo, James A. (Inventor)

    1994-01-01

    A hyridopolysilazane-derived ceramic fiber reinforced monoclinic celsian phase barium aluminum silicate glass-ceramic matrix composite material is prepared by ball-milling an aqueous slurry of BAS glass powder and fine monoclinic celsian seeds. The fibers improve the mechanical strength and fracture toughness and with the matrix provide superior dielectric properties.

  4. Encapsulated monoclinic sulfur for stable cycling of li-s rechargeable batteries.

    PubMed

    Moon, San; Jung, Young Hwa; Jung, Wook Ki; Jung, Dae Soo; Choi, Jang Wook; Kim, Do Kyung

    2013-12-03

    Monoclinic S8 , an uncommon allotrope of sulfur at room temperature, can be formed when common orthorhombic S8 is heat-treated under enclosed environments in nanometer dimensions. Monoclinic S8 prevents the formation of soluble polysulfides during battery operation, resulting in unprecedented cycling performance over 1000 cycles under the highest sulfur content to date.

  5. Patterning nanocrystals using DNA

    NASA Astrophysics Data System (ADS)

    Williams, Shara Carol

    One of the goals of nanotechnology is to enable programmed self-assembly of patterns made of various materials with nanometer-sized control. This dissertation describes the results of experiments templating arrangements of gold and semiconductor nanocrystals using 2'-deoxyribonucleic acid (DNA). Previously, simple DNA-templated linear arrangements of two and three nanocrystals structures have been made. Here, we have sought to assemble larger and more complex nanostructures. Cold-DNA conjugates with 50 to 100 bases self-assembled into planned arrangements using strands of DNA containing complementary base sequences. We used two methods to increase the complexity of the arrangements: using branched synthetic doublers within the DNA covalent backbone to create discrete nanocrystal groupings, and incorporating the nanocrystals into a previously developed DNA lattice structure that self-assembles from tiles made of DNA double-crossover molecules to create ordered nanoparticle arrays. In the first project, the introduction of a covalently-branched synthetic doubler reagent into the backbone of DNA strands created a branched DNA "trimer." This DNA trimer templated various structures that contained groupings of three and four gold nanoparticles, giving promising, but inconclusive transmission electron microscopy (TEM) results. Due to the presence of a variety of possible structures in the reaction mixtures, and due to the difficulty of isolating the desired structures, the TEM and gel electrophoresis results for larger structures having four particles, and for structures containing both 5 and 10 nm gold nanoparticles were inconclusive. Better results may come from using optical detection methods, or from improved sample preparation. In the second project, we worked toward making two-dimensional ordered arrays of nanocrystals. We replicated and improved upon previous results for making DNA lattices, increasing the size of the lattices to a length greater than 20 mum, and

  6. Patterning nanocrystals using DNA

    SciTech Connect

    Williams, Shara Carol

    2003-01-01

    One of the goals of nanotechnology is to enable programmed self-assembly of patterns made of various materials with nanometer-sized control. This dissertation describes the results of experiments templating arrangements of gold and semiconductor nanocrystals using 2'-deoxyribonucleic acid (DNA). Previously, simple DNA-templated linear arrangements of two and three nanocrystals structures have been made.[1] Here, we have sought to assemble larger and more complex nanostructures. Gold-DNA conjugates with 50 to 100 bases self-assembled into planned arrangements using strands of DNA containing complementary base sequences. We used two methods to increase the complexity of the arrangements: using branched synthetic doublers within the DNA covalent backbone to create discrete nanocrystal groupings, and incorporating the nanocrystals into a previously developed DNA lattice structure [2][3] that self-assembles from tiles made of DNA double-crossover molecules to create ordered nanoparticle arrays. In the first project, the introduction of a covalently-branched synthetic doubler reagent into the backbone of DNA strands created a branched DNA ''trimer.'' This DNA trimer templated various structures that contained groupings of three and four gold nanoparticles, giving promising, but inconclusive transmission electron microscopy (TEM) results. Due to the presence of a variety of possible structures in the reaction mixtures, and due to the difficulty of isolating the desired structures, the TEM and gel electrophoresis results for larger structures having four particles, and for structures containing both 5 and 10 nm gold nanoparticles were inconclusive. Better results may come from using optical detection methods, or from improved sample preparation. In the second project, we worked toward making two-dimensional ordered arrays of nanocrystals. We replicated and improved upon previous results for making DNA lattices, increasing the size of the lattices to a length greater than

  7. Creep of plasma sprayed zirconia

    NASA Technical Reports Server (NTRS)

    Firestone, R. F.; Logan, W. R.; Adams, J. W.

    1982-01-01

    Specimens of plasma-sprayed zirconia thermal barrier coatings with three different porosities and different initial particle sizes were deformed in compression at initial loads of 1000, 2000, and 3500 psi and temperatures of 1100 C, 1250 C, and 1400 C. The coatings were stabilized with lime, magnesia, and two different concentrations of yttria. Creep began as soon as the load was applied and continued at a constantly decreasing rate until the load was removed. Temperature and stabilization had a pronounced effect on creep rate. The creep rate for 20% Y2O3-80% ZrO2 was 1/3 to 1/2 that of 8% Y2O3-92% ZrO2. Both magnesia and calcia stabilized ZrO2 crept at a rate 5 to 10 times that of the 20% Y2O3 material. A near proportionality between creep rate and applied stress was observed. The rate controlling process appeared to be thermally activated, with an activation energy of approximately 100 cal/gm mole K. Creep deformation was due to cracking and particle sliding.

  8. Fabrication and characterization of dense zirconia and zirconia-silica ceramic nanofibers.

    PubMed

    Xu, Xiaoming; Guo, Guangqing; Fan, Yuwei

    2010-09-01

    The objective of this study was to prepare dense zirconia-yttria (ZY), zirconia-silica (ZS) and zirconia-yttria-silica (ZYS) nanofibers as reinforcing elements for dental composites. Zirconium (IV) propoxide, yttrium nitrate hexahydrate, and tetraethyl orthosilicate (TEOS) were used as precursors for the preparation of zirconia, yttria, and silica sols. A small amount (1-1.5 wt%) of polyethylene oxide (PEO) was used as a carry polymer. The sols were preheated at 70 degrees C before electrospinning and their viscosity was measured with a viscometer at different heating time. The gel point was determined by viscosity-time (eta-t) curve. The ZY, ZS and ZYS gel nanofibers were prepared using a special reactive electrospinning device under the conditions near the gel point. The as-prepared gel nanofibers had diameters between 200 and 400 nm. Dense (nonporous) ceramic nanofibers of zirconia-yttria (96/4), zirconia-silica (80/20) and zirconia-yttria-silica (76.8/3.2/20) with diameter of 100-300 nm were obtained by subsequent calcinations at different temperatures. The gel and ceramic nanofibers obtained were characterized by scanning electron microscope (SEM), high-resolution field-emission scanning electron microscope (FE-SEM), thermogravimetric analyzer (TGA), differential scanning calorimeter (DSC), Fourier transform infrared spectrometer (FT-IR), and X-ray diffraction (XRD). SEM micrograph revealed that ceramic ZY nanofibers had grained structure, while ceramic ZS and ZYS nanofibers had smooth surfaces, both showing no visible porosity under FE-SEM. Complete removal of the polymer PEO was confirmed by TGA/DSC and FT-IR. The formation of tetragonal phase of zirconia and amorphous silica was proved by XRD. In conclusion, dense zirconia-based ceramic nanofibers can be fabricated using the new reactive sol-gel electrospinning technology with minimum organic polymer additives.

  9. Octahedral tilting, monoclinic phase and the phase diagram of PZT

    NASA Astrophysics Data System (ADS)

    Cordero, F.; Trequattrini, F.; Craciun, F.; Galassi, C.

    2011-10-01

    Anelastic and dielectric spectroscopy measurements on PbZr1-xTixO3 (PZT) close to the morphotropic (MPB) and antiferroelectric boundaries provide new insight into some controversial aspects of its phase diagram. No evidence is found of a border separating monoclinic (M) from rhombohedral (R) phases, in agreement with recent structural studies supporting a coexistence of the two phases over a broad composition range x < 0.5, with the fraction of M increasing toward the MPB. It is also discussed why the observed maximum of elastic compliance appears to be due to a rotational instability of the polarization linearly coupled to shear strain. Therefore it cannot be explained by extrinsic softening from finely twinned R phase alone, but indicates the presence also of M phase, not necessarily homogeneous. A new diffuse transition is found within the ferroelectric phase near x ˜ 0.1, at a temperature TIT higher than the well established boundary TT to the phase with tilted octahedra. It is proposed that around TIT the octahedra start rotating in a disordered manner and finally become ordered below TT. In this interpretation, the onset temperature for octahedral tilting monotonically increases up to the antiferroelectric transition of PbZrO3, and the depression of TT(x) below x = 0.18 would be a consequence of the partial relief of the mismatch between the average cation radii with the initial stage of tilting below TIT.

  10. Electronic spectra of semiconductor nanocrystals

    SciTech Connect

    Alivisatos, A.P.

    1993-12-31

    Semiconductor nanocrystals smaller than the bulk exciton show substantial quantum confinement effects. Recent experiments including Stark effect, resonance Raman, valence band photoemission, and near edge X-ray adsorption will be used to put together a picture of the nanocrystal electronic states.

  11. Nanocrystal/sol-gel nanocomposites

    DOEpatents

    Petruska, Melissa A.; Klimov, Victor L.

    2007-06-05

    The present invention is directed to solid composites including colloidal nanocrystals within a sol-gel host or matrix and to processes of forming such solid composites. The present invention is further directed to alcohol soluble colloidal nanocrystals useful in formation of sol-gel based solid composites.

  12. Photoemission studies of semiconductor nanocrystals

    SciTech Connect

    Hamad, K. S.; Roth, R.; Alivisatos, A. P.

    1997-04-01

    Semiconductor nanocrystals have been the focus of much attention in the last ten years due predominantly to their size dependent optical properties. Namely, the band gap of nanocrystals exhibits a shift to higher energy with decreasing size due to quantum confinement effects. Research in this field has employed primarily optical techniques to study nanocrystals, and in this respect this system has been investigated extensively. In addition, one is able to synthesize monodisperse, crystalline particles of CdS, CdSe, Si, InP, InAs, as well as CdS/HgS/CdS and CdSe/CdS composites. However, optical spectroscopies have proven ambiguous in determining the degree to which electronic excitations are interior or surface admixtures or giving a complete picture of the density of states. Photoemission is a useful technique for understanding the electronic structure of nanocrystals and the effects of quantum confinement, chemical environments of the nanocrystals, and surface coverages. Of particular interest to the authors is the surface composition and structure of these particles, for they have found that much of the behavior of nanocrystals is governed by their surface. Previously, the authors had performed x-ray photoelectron spectroscopy (XPS) on CdSe nanocrystals. XPS has proven to be a powerful tool in that it allows one to determine the composition of the nanocrystal surface.

  13. Method of synthesizing pyrite nanocrystals

    DOEpatents

    Wadia, Cyrus; Wu, Yue

    2013-04-23

    A method of synthesizing pyrite nanocrystals is disclosed which in one embodiment includes forming a solution of iron (III) diethyl dithiophosphate and tetra-alkyl-ammonium halide in water. The solution is heated under pressure. Pyrite nanocrystal particles are then recovered from the solution.

  14. Nanocrystal/sol-gel nanocomposites

    SciTech Connect

    Petruska, Melissa A; Klimov, Victor L

    2012-06-12

    The present invention is directed to solid composites including colloidal nanocrystals within a sol-gel host or matrix and to processes of forming such solid composites. The present invention is further directed to alcohol soluble colloidal nanocrystals useful in formation of sol-gel based solid composites

  15. Mechanical Properties of Nanocrystal Supercrystals

    SciTech Connect

    Tam, Enrico; Podsiadlo, Paul; Shevchenko, Elena; Ogletree, D. Frank; Delplancke-Ogletree, Marie-Paule; Ashby, Paul D.

    2009-12-30

    Colloidal nanocrystals attract significant interest due to their potential applications in electronic, magnetic, and optical devices. Nanocrystal supercrystals (NCSCs) are particularly appealing for their well ordered structure and homogeneity. The interactions between organic ligands that passivate the inorganic nanocrystal cores critically influence their self-organization into supercrystals, By investigating the mechanical properties of supercrystals, we can directly characterize the particle-particle interactions in a well-defined geometry, and gain insight into both the self-assembly process and the potential applications of nanocrystal supercrystals. Here we report nanoindentation studies of well ordered lead-sulfide (Pbs) nanocrystal supercrystals. Their modulus and hardness were found to be similar to soft polymers at 1.7 GPa and 70 MPa respectively and the fractures toughness was 39 KPa/m1/2, revealing the extremely brittle nature of these materials.

  16. Nanocrystal/sol-gel nanocomposites

    DOEpatents

    Klimov, Victor L.; Petruska, Melissa A.

    2010-05-25

    The present invention is directed to a process for preparing a solid composite having colloidal nanocrystals dispersed within a sol-gel matrix, the process including admixing colloidal nanocrystals with an amphiphilic polymer including hydrophilic groups selected from the group consisting of --COOH, --OH, --SO.sub.3H, --NH.sub.2, and --PO.sub.3H.sub.2 within a solvent to form an alcohol-soluble colloidal nanocrystal-polymer complex, admixing the alcohol-soluble colloidal nanocrystal-polymer complex and a sol-gel precursor material, and, forming the solid composite from the admixture. The present invention is also directed to the resultant solid composites and to the alcohol-soluble colloidal nanocrystal-polymer complexes.

  17. Grafting Sulfated Zirconia on Mesoporous Silica

    SciTech Connect

    Wang, Yong; Lee, Kwan Young; Choi, Saemin; Liu, Jun; Wang, Li Q.; Peden, Charles HF

    2007-06-01

    Sulfated zirconia has received considerable attention as a potential solid acid catalyst in recent years. In this paper, the preparation and properties of acid catalysts obtained by grafting ziconia with atomic precision on MCM-41 mesoporous silica were studied. TEM and potential titration characterizations revealed that ZrO2/MCM-41 with monolayer coverage can be obtained using this grafting technique. Sulfated ZrO2/MCM-41 exhibits improved thermal stability than that of bulk sulfated zirconia, as evidenced by temperature programmed characterizations and XRD analysis. Temperature programmed reaction of isopropanol was used to evaluate the acidity of sulfated ZrO2/MCM-41. It was found that the acid strength of sulfated ZrO2/MCM-41 with monolayer coverage is weaker than bulk sulfated zirconia but stronger than SiO2-Al2O3, a common strong acid catalyst.

  18. Processing of Alumina-Toughened Zirconia Composites

    NASA Technical Reports Server (NTRS)

    Bansal, Narottam P.; Choi, Sung R.

    2003-01-01

    Dense and crack-free 10-mol%-yttria-stabilized zirconia (10YSZ)-alumina composites, containing 0 to 30 mol% of alumina, have been fabricated by hot pressing. Release of pressure before onset of cooling was crucial in obtaining crack-free material. Hot pressing at 1600 C resulted in the formation of ZrC by reaction of zirconia with grafoil. However, no such reaction was observed at 1500 C. Cubic zirconia and -alumina were the only phases detected from x-ray diffraction indicating no chemical reaction between the composite constituents during hot pressing. Microstructure of the composites was analyzed by scanning electron microscopy and transmission electron microscopy. Density and elastic modulus of the composites followed the rule-of-mixtures. Addition of alumina to 10YSZ resulted in lighter, stronger, and stiffer composites by decreasing density and increasing strength and elastic modulus.

  19. Silicon nanocrystal inks, films, and methods

    DOEpatents

    Wheeler, Lance Michael; Kortshagen, Uwe Richard

    2015-09-01

    Silicon nanocrystal inks and films, and methods of making and using silicon nanocrystal inks and films, are disclosed herein. In certain embodiments the nanocrystal inks and films include halide-terminated (e.g., chloride-terminated) and/or halide and hydrogen-terminated nanocrystals of silicon or alloys thereof. Silicon nanocrystal inks and films can be used, for example, to prepare semiconductor devices.

  20. Local structures surrounding Zr in nanostructurally stabilized cubic zirconia: Structural origin of phase stability

    SciTech Connect

    Soo, Y. L.; Chen, P. J.; Huang, S. H.; Shiu, T. J.; Tsai, T. Y.; Chow, Y. H.; Lin, Y. C.; Weng, S. C.; Chang, S. L.; Wang, G.; Cheung, C. L.; Sabirianov, R. F.; Mei, W. N.; Namavar, F.; Haider, H.; Garvin, K. L.; Lee, J. F.; Lee, H. Y.; Chu, P. P.

    2008-12-01

    Local environment surrounding Zr atoms in the thin films of nanocrystalline zirconia (ZrO{sub 2}) has been investigated by using the extended x-ray absorption fine structure (EXAFS) technique. These films prepared by the ion beam assisted deposition exhibit long-range structural order of cubic phase and high hardness at room temperature without chemical stabilizers. The local structure around Zr probed by EXAFS indicates a cubic Zr sublattice with O atoms located on the nearest tetragonal sites with respect to the Zr central atoms, as well as highly disordered locations. Similar Zr local structure was also found in a ZrO{sub 2} nanocrystal sample prepared by a sol-gel method. Variations in local structures due to thermal annealing were observed and analyzed. Most importantly, our x-ray results provide direct experimental evidence for the existence of oxygen vacancies arising from local disorder and distortion of the oxygen sublattice in nanocrystalline ZrO{sub 2}. These oxygen vacancies are regarded as the essential stabilizing factor for the nanostructurally stabilized cubic zirconia.

  1. Chipping resistance of graded zirconia ceramics for dental crowns.

    PubMed

    Zhang, Y; Chai, H; Lee, J J-W; Lawn, B R

    2012-03-01

    A serious drawback of veneering porcelains is a pronounced susceptibility to chipping. Glass-infiltrated dense zirconia structures can now be produced with esthetic quality, making them an attractive alternative. In this study, we examined the hypothesis that such infiltrated structures are much more chip-resistant than conventional porcelains, and at least as chip-resistant as non-infiltrated zirconia. A sharp indenter was used to produce chips in flat and anatomically correct glass-infiltrated zirconia crown materials, and critical loads were measured as a function of distance from the specimen edge (flat) or side wall (crown). Control data were obtained on zirconia specimens without infiltration and on crowns veneered with porcelains. The results confirmed that the resistance to chipping in graded zirconia is more than 4 times higher than that of porcelain-veneered zirconia and is at least as high as that of non-veneered zirconia.

  2. Biomolecular Assembly of Gold Nanocrystals

    SciTech Connect

    Micheel, Christine Marya

    2005-05-20

    Over the past ten years, methods have been developed to construct discrete nanostructures using nanocrystals and biomolecules. While these frequently consist of gold nanocrystals and DNA, semiconductor nanocrystals as well as antibodies and enzymes have also been used. One example of discrete nanostructures is dimers of gold nanocrystals linked together with complementary DNA. This type of nanostructure is also known as a nanocrystal molecule. Discrete nanostructures of this kind have a number of potential applications, from highly parallel self-assembly of electronics components and rapid read-out of DNA computations to biological imaging and a variety of bioassays. My research focused in three main areas. The first area, the refinement of electrophoresis as a purification and characterization method, included application of agarose gel electrophoresis to the purification of discrete gold nanocrystal/DNA conjugates and nanocrystal molecules, as well as development of a more detailed understanding of the hydrodynamic behavior of these materials in gels. The second area, the development of methods for quantitative analysis of transmission electron microscope data, used computer programs written to find pair correlations as well as higher order correlations. With these programs, it is possible to reliably locate and measure nanocrystal molecules in TEM images. The final area of research explored the use of DNA ligase in the formation of nanocrystal molecules. Synthesis of dimers of gold particles linked with a single strand of DNA possible through the use of DNA ligase opens the possibility for amplification of nanostructures in a manner similar to polymerase chain reaction. These three areas are discussed in the context of the work in the Alivisatos group, as well as the field as a whole.

  3. Identification of monoclinic θ-phase dispersoids in a 6061 aluminium alloy

    NASA Astrophysics Data System (ADS)

    Buchanan, Karl; Ribis, Joël; Garnier, Jérôme; Colas, Kimberly

    2016-04-01

    Intermetallic dispersoids play an important role in controlling the 6xxx alloy series' grain distribution and increasing the alloy's toughness. The dispersoid distribution in a 6061 aluminium alloy (Al-Mg-Si) was analysed by transmission electron microscopy, selected area diffraction and energy-dispersive X-ray spectroscopy. The dispersoids had three unique crystal structures: simple cubic ?, body-centred cubic ? and monoclinic (C2/m). While the SC and BCC dispersoids have been well characterized in the literature, a detailed analysis of monoclinic dispersoids has not been presented. Therefore, the current work discusses the chemical composition, crystal structure and morphology of the monoclinic dispersoids.

  4. Improved Zirconia Oxygen-Separation Cell

    NASA Technical Reports Server (NTRS)

    Walsh, John V.; Zwissler, James G.

    1988-01-01

    Cell structure distributes feed gas more evenly for more efficent oxygen production. Multilayer cell structure containing passages, channels, tubes, and pores help distribute pressure evenly over zirconia electrolytic membrane. Resulting more uniform pressure distribution expected to improve efficiency of oxygen production.

  5. Cellulose nanocrystal submonolayers by spin coating.

    PubMed

    Kontturi, Eero; Johansson, Leena-Sisko; Kontturi, Katri S; Ahonen, Päivi; Thüne, Peter C; Laine, Janne

    2007-09-11

    Dilute concentrations of cellulose nanocrystal solutions were spin coated onto different substrates to investigate the effect of the substrate on the nanocrystal submonolayers. Three substrates were probed: silica, titania, and amorphous cellulose. According to atomic force microscopy (AFM) images, anionic cellulose nanocrystals formed small aggregates on the anionic silica substrate, whereas a uniform two-dimensional distribution of nanocrystals was achieved on the cationic titania substrate. The uniform distribution of cellulose nanocrystal submonolayers on titania is an important factor when dimensional analysis of the nanocrystals is desired. Furthermore, the amount of nanocrystals deposited on titania was multifold in comparison to the amounts on silica, as revealed by AFM image analysis and X-ray photoelectron spectroscopy. Amorphous cellulose, the third substrate, resulted in a somewhat homogeneous distribution of the nanocrystal submonolayers, but the amounts were as low as those on the silica substrate. These differences in the cellulose nanocrystal deposition were attributed to electrostatic effects: anionic cellulose nanocrystals are adsorbed on cationic titania in addition to the normal spin coating deposition. The anionic silica surface, on the other hand, causes aggregation of the weakly anionic cellulose nanocrystals which are forced on the repulsive substrate by spin coating. The electrostatically driven adsorption also influences the film thickness of continuous ultrathin films of cellulose nanocrystals. The thicker films of charged nanocrystals on a substrate of opposite charge means that the film thickness is not independent of the substrate when spin coating cellulose nanocrystals in the ultrathin regime (<100 nm).

  6. Direct silanization of zirconia for increased biointegration.

    PubMed

    Caravaca, Carlos; Shi, Liu; Balvay, Sandra; Rivory, Pascaline; Laurenceau, Emmanuelle; Chevolot, Yann; Hartmann, Daniel; Gremillard, Laurent; Chevalier, Jérôme

    2016-12-01

    High-performance bioinert ceramics such as zirconia have been used for biomedical devices since the early seventies. In order to promote osseointegration, the historical solution has been to increase the specific surface of the implant through roughness. Nevertheless these treatments on ceramics may create defects at the surface, exposing the material to higher chances of early failure. In zirconia, such treatments may also affect the stability of the surface. More recently, the interest of improving osseointegration of implants has moved the research focus towards the actual chemistry of the surface. Inspired by this, we have adapted the current knowledge and techniques of silica functionalization and applied it to successfully introduce 3-aminopropyldimethylethoxy silane (APDMES) directly on the surface of zirconia (3Y-TZP). We used plasma of oxygen to clean the surface and promote hydroxylation of the surface to increase silane density. The samples were extensively characterized by means of X-ray photoelectron spectroscopy (XPS) and contact angle, mechanically tested and its cytotoxicity was evaluated through cell adhesion and proliferation tests. Additionally, aging was studied to discard negative effects of the treatment on the stability of the tetragonal phase. No adverse effect was found on the mechanical response of treated samples. In addition, plasma-treated samples exhibited an unexpectedly higher resistance to aging. Finally, silane density was 35% lower than the one reported in literature for silica. However cells displayed a qualitatively higher spreading in opposition to the rounder appearance of cells on untreated zirconia. These results lay the foundations for the next generation of zirconia implants with biologically friendlier surfaces.

  7. Zirconia: cementation of prosthetic restorations. Literature review

    PubMed Central

    GARGARI, M.; GLORIA, F.; NAPOLI, E.; PUJIA, A.M.

    2011-01-01

    SUMMARY Aim of the work Aim of the work was to execute a review of the international literature about the cementation of zirconia restorations, analyzing the properties of the cements most commonly used in clinical activities. Materials and methods It was performed, through PubMed, a bibliographic search on the international literature of the last 10 years using the following limits: studies in English, in vitro studies, randomized clinical trial, reviews, meta-analysis, guide-lines. Were excluded from the search: descriptive studies, case reports, discussion articles, opinion’s leader. Results From studies results that common surface treatments (silanization, acid etching) are ineffective on zirconia because it has an inert surface without glassy component (on which this surface treatments act primarily), instead the sandblasting at 1atm with aluminium oxide (Al2O3) results significantly effective for the resulting roughening that increase the surface energy and the wettability of the material. Furthermore it has been shown that zinc phosphate-based cements, Bis-GMA-based and glass-ionomer cements can’t guarantee a stable long-term adhesion, instead resin cements containing phosphate monomer 10-methacryloyloxyidecyl-dihyidrogenphosphate (MDP) have shown higher adhesion and stability values than the other cements. In particular, it has seen that bond strength of zirconia copings on dentin, using MDP-based cement, is about 6,9MPa; this value is comparable to that obtained with gold copings cementation. Conclusions Analyzed studies have led to the following conclusions: sandblasting with aluminium oxide (Al2O3) is the best surface treatment to improve adhesion between resin cements and zirconia; resin cements containing phosphate ester monomers 10-methacryloyloxyidecyl-dihyidrogenphosphate (MDP) have shown in the studies an higher bond strength and stability after ageing treatment; the best procedure for cementing zirconia restorations results the combination of

  8. Development of a zirconia toughened hydroxyapatite

    NASA Astrophysics Data System (ADS)

    Mager, Carie Christine Wilkinson

    2000-10-01

    Because of its low fracture toughness (<1 MPa m 1/2) compared to bone (2--12 MPa m1/2), the use of HAp in dentistry and orthopedics is limited to low load bearing applications. In order to broaden its applications, HAp was reinforced through the addition of partially stabilized zirconia. HAp composites with varying amounts of zirconia were processed using a 2 level, 8 variable factorial design to determine the effect of various processing conditions on the stability of the zirconia and HAp phases and on the resulting toughening behavior of the composites. The processing conditions included in the design were; (a) milling times and fluid dispersion mediums; (b) sintering times and temperatures in ambient air and atmospheric pressure; and (c) hot isostatic pressing time and temperature in inert and "wet" environments. The effect of volume fraction and particle size of the zirconia in the range of 0--30 wt % and -0.9mum to -2.0mum respectively on the material's fracture toughness were also determined. The composites were also placed in a serum like solution for 6 months to study the effect of physiological environment on the various processing parameters and the resulting toughening behavior. The toughening behavior before and after in vitro exposure was monitored using micro Raman spectroscopy which enabled the size and shape of the transformation zone to, be quantified. The optimization of the design parameter's resulted in an increase in the fracture toughness by a factor of three and the six month in vitro study indicated that a zirconia toughened HAp implant could be processed so as to retain its hardness and toughness in vivo.

  9. Si nanocrystals and nanocrystal interfaces studied by positron annihilation

    NASA Astrophysics Data System (ADS)

    Kujala, J.; Slotte, J.; Tuomisto, F.; Hiller, D.; Zacharias, M.

    2016-10-01

    Si nanocrystals embedded in a SiO 2 matrix were studied with positron annihilation and photoluminescence spectroscopies. Analysis of the S- and W-parameters for the sample annealed at 800 °C reveals a positron trap at the interface between the amorphous nanodots and the surrounding matrix. Another trap state is observed in the 1150 °C heat treated samples where nanodots are in a crystalline form. Positrons are most likely trapped to defects related to dangling bonds at the surface of the nanocrystals. Passivation of the samples results on one hand in the decrease of the S-parameter implying a decrease in the open volume of the interface state and, on the other hand, in the strengthening of the positron annihilation signal from the interface. The intensity of the photoluminescence signal increases with the formation of the nanocrystals. Passivation of samples strengthens the photoluminescence signal, further indicating a successful deactivation of luminescence quenching at the nanocrystal surface. Strengthening of the positron annihilation signal and an increase in the photoluminescence intensity in passivated silicon nanocrystals suggests that the positron trap at the interface does not contribute to a significant extent to the exciton recombination in the nanocrystals.

  10. Synthesis and Doping of Silicon Nanocrystals for Versatile Nanocrystal Inks

    NASA Astrophysics Data System (ADS)

    Kramer, Nicolaas Johannes

    The impact of nanotechnology on our society is getting larger every year. Electronics are becoming smaller and more powerful, the "Internet of Things" is all around us, and data generation is increasing exponentially. None of this would have been possible without the developments in nanotechnology. Crystalline semiconductor nanoparticles (nanocrystals) are one of the latest developments in the field of nanotechnology. This thesis addresses three important challenges for the transition of silicon nanocrystals from the lab bench to the marketplace: A better understanding of the nanocrystal synthesis was obtained, the electronic properties of the nanocrystals were characterized and tuned, and novel silicon nanocrystal inks were formed and applied using simple coating technologies. Plasma synthesis of nanocrystals has numerous advantages over traditional solution-based synthesis methods. While the formation of nanoparticles in low pressure nonthermal plasmas is well known, the heating mechanism leading to their crystallization is poorly understood. A combination of comprehensive plasma characterization with a nanoparticle heating model presented here reveals the underlying plasma physics leading to crystallization. The model predicts that the nanoparticles reach temperatures as high as 900 K in the plasma as a result of heating reactions on the nanoparticle surface. These temperatures are well above the gas temperature and sufficient for complete nanoparticle crystallization. Moving the field of plasma nanoparticle synthesis to atmospheric pressures is important for lowering its cost and making the process attractive for industrial applications. The heating and charging model for silicon nanoparticles was adapted in Chapter 3 to study plasmas maintained over a wide range of pressures (10 -- 105 Pa). The model considers three collisionality regimes and determines the dominant contribution of each regime under various plasma conditions. Strong nanoparticle cooling at

  11. [Vibrational spectra of monoclinic diphosphates of formula AMP2O7].

    PubMed

    Serghini Idrissi, M; Rghioui, L; Nejjar, R; Benarafa, L; Saidi Idrissi, M; Lorriaux, A; Wallart, F

    2004-07-01

    The monoclinic pyrophosphates with AMP2O7 formula were synthesized. Their infrared and Raman spectra have been reported and analysed. The results of a force field calculation for CaCuP2O7 are presented.

  12. Assemblies of Cellulose Nanocrystals

    NASA Astrophysics Data System (ADS)

    Kumacheva, Eugenia

    The entropically driven coassembly of nanorods (cellulose nanocrystals, CNCs) and different types of nanoparticles (NPs), including dye-labeled latex NPs, carbon dots and plasmonic NPs was experimentally studied in aqueous suspensions and in solid films. In mixed CNC-NP suspensions, phase separation into an isotropic NP-rich and a chiral nematic CNC-rich phase took place; the latter contained a significant amount of NPs. Drying the mixed suspension resulted in CNC-NP films with planar disordered layers of NPs, which alternated with chiral nematic CNC-rich regions. In addition, NPs were embedded in the chiral nematic domains. The stratified morphology of the films, together with a random distribution of NPs in the anisotropic phase, led to the films having close-to-uniform fluorescence, birefringence, and circular dichroism properties.

  13. Preparation and Characterization of Zirconia-Coated Nanodiamonds as a Pt Catalyst Support for Methanol Electro-Oxidation

    PubMed Central

    Lu, Jing; Zang, Jianbing; Wang, Yanhui; Xu, Yongchao; Xu, Xipeng

    2016-01-01

    Zirconia-coated nanodiamond (ZrO2/ND) electrode material was successfully prepared by one-step isothermal hydrolyzing from ND-dispersed ZrOCl2·8H2O aqueous solution. High-resolution transmission electron microscopy reveals that a highly conformal and uniform ZrO2 shell was deposited on NDs by this simple method. The coating obtained at 90 °C without further calcination was mainly composed of monoclinic nanocrystalline ZrO2 rather than common amorphous Zr(OH)4 clusters. The ZrO2/NDs and pristine ND powder were decorated with platinum (Pt) nanoparticles by electrodeposition from 5 mM chloroplatinic acid solution. The electrochemical studies indicate that Pt/ZrO2/ND catalysts have higher electrocatalytic activity and better stability for methanol oxidation than Pt/ND catalysts in acid. PMID:28335361

  14. Compositional limits and analogs of monoclinic triple-chain silicates

    NASA Astrophysics Data System (ADS)

    Jenkins, David M.; Gilleaudeau, Geoffrey J.; Kawa, Cynthia; Dibiase, Jaclyn M.; Fokin, Maria

    2012-08-01

    Growing recognition of triple-chain silicates in nature has prompted experimental research into the conditions under which they can form and the extent of solid solution that is feasible for some key chemical substitutions. Experiments were done primarily in the range of 0.1-0.5 GPa and 200-850 °C for durations of 18-1,034 h. A wide range of bulk compositions were explored in this study that can be classified broadly into two groups: those that are Na free and involve various possible chemical substitutions into jimthompsonite (Mg10Si12O32(OH)4), and those that are Na bearing and involve chemical substitutions into the ideal end-member Na4Mg8Si12O32(OH)4. Numerous attempts to synthesize jimthompsonite or clinojimthompsonite were unsuccessful despite the type of starting material used (reagent oxides, magnesite + SiO2, talc + enstatite, or anthophyllite). Similarly, the chemical substitutions of F- for OH-, Mn2+, Ca2+, or Fe2+ for Mg2+, and 2Li+ for Mg2+ and a vacancy were unsuccessful at nucleating triple-chain silicates. Conversely, nearly pure yields of monoclinic triple-chain silicate could be made at temperatures of 440-630 °C and 0.2 GPa from the composition Na4Mg8Si12O32(OH)4, as found in previous studies, though its composition is most likely depleted in Na as evidenced by electron microprobe and FTIR analysis. Pure yields of triple-chain silicate were also obtained for the F-analog composition Na4Mg8Si12O32F4 at 550-750 °C and 0.2-0.5 GPa if a flux consisting of Na-halide salt and water in a 2:1 ratio by weight was used. In addition, limited chemical substitution could be documented for the substitutions of 2 Na+ for Na+ + H+ and of Mg2+ + vacancy for 2Na+. For the former, the Na content appears to be limited to 2.5 cations giving the ideal composition of Na2.5Mg8Si12O30.5(OH)5.5, while for the latter substitution the Na content may go as low as 1.1 cations giving the composition Na1.1Mg9.4Si12O31.9(OH)4.1 based on a fixed number of Si cations. Further

  15. Effects of cementation surface modifications on fracture resistance of zirconia

    PubMed Central

    Srikanth, Ramanathan; Kosmac, Tomaz; Bona, Alvaro Della; Yin, Ling; Zhang, Yu

    2015-01-01

    Objectives To examine the effects of glass infiltration (GI) and alumina coating (AC) on the indentation flexural load and four-point bending strength of monolithic zirconia. Methods Plate-shaped (12 mm × 12 mm × 1.0 mm or 1.5 mm or 2.0 mm) and bar-shaped (4 mm × 3 mm × 25 mm) monolithic zirconia specimens were fabricated. In addition to monolithic zirconia (group Z), zirconia monoliths were glass-infiltrated or alumina-coated on their tensile surfaces to form groups ZGI and ZAC, respectively. They were also glass-infiltrated on their upper surfaces, and glass-infiltrated or alumina-coated on their lower (tensile) surfaces to make groups ZGI2 and ZAC2, respectively. For comparison, porcelain-veneered zirconia (group PVZ) and monolithic lithium disilicate glass-ceramic (group LiDi) specimens were also fabricated. The plate-shaped specimens were cemented onto a restorative composite base for Hertzian indentation using a tungsten carbide spherical indenter with a radius of 3.2 mm. Critical loads for indentation flexural fracture at the zirconia cementation surface were measured. Strengths of bar-shaped specimens were evaluated in four-point bending. Results Glass infiltration on zirconia tensile surfaces increased indentation flexural loads by 32% in Hertzian contact and flexural strength by 24% in four-point bending. Alumina coating showed no significant effect on resistance to flexural damage of zirconia. Monolithic zirconia outperformed porcelain-veneered zirconia and monolithic lithium disilicate glass-ceramics in terms of both indentation flexural load and flexural strength. Significance While both alumina coating and glass infiltration can be used to effectively modify the cementation surface of zirconia, glass infiltration can further increase the flexural fracture resistance of zirconia. PMID:25687628

  16. Multilayered thermal insulation formed of zirconia bonded layers of zirconia fibers and metal oxide fibers and method for making same

    DOEpatents

    Wrenn, Jr., George E.; Holcombe, Jr., Cressie E.

    1988-01-01

    A multilayered thermal insulating composite is formed of a first layer of zirconia-bonded zirconia fibers for utilization near the hot phase or surface of a furnace or the like. A second layer of zirconia-bonded metal oxide fibers is attached to the zirconia fiber layer by a transition layer formed of intermingled zirconia fibers and metal oxide fibers. The thermal insulation is fabricated by vacuum molding with the layers being sequentially applied from aqueous solutions containing the fibers to a configured mandrel. A portion of the solution containing the fibers forming the first layer is intermixed with the solution containing the fibers of the second layer for forming the layer of mixed fibers. The two layers of fibers joined together by the transition layer are saturated with a solution of zirconium oxynitrate which provides a zirconia matrix for the composite when the fibers are sintered together at their nexi.

  17. Multilayered thermal insulation formed of zirconia bonded layers of zirconia fibers and metal oxide fibers and method for making same

    DOEpatents

    Wrenn, G.E. Jr.; Holcombe, C.E. Jr.

    1988-09-13

    A multilayered thermal insulating composite is formed of a first layer of zirconia-bonded zirconia fibers for utilization near the hot phase or surface of a furnace or the like. A second layer of zirconia-bonded metal oxide fibers is attached to the zirconia fiber layer by a transition layer formed of intermingled zirconia fibers and metal oxide fibers. The thermal insulation is fabricated by vacuum molding with the layers being sequentially applied from aqueous solutions containing the fibers to a configured mandrel. A portion of the solution containing the fibers forming the first layer is intermixed with the solution containing the fibers of the second layer for forming the layer of mixed fibers. The two layers of fibers joined together by the transition layer are saturated with a solution of zirconium oxynitrate which provides a zirconia matrix for the composite when the fibers are sintered together at their nexi.

  18. Zirconia abutments and restorations: from laboratory to clinical investigations.

    PubMed

    Ferrari, M; Vichi, A; Zarone, F

    2015-03-01

    In last years the use of zirconia in dentistry has become very popular. Unfortunately, the clinical indications for a dental use of zirconia are not completely clear yet, neither are their limitations. The objective of this review was to evaluate the basic science knowledge on zirconia and to discuss some aspects of the clinical behavior of zirconia-based restorations. In particular, one of the goals was highlighting the possible correlation between in vitro and in vivo studies. The definition of concepts like success, survival and failure was still debated and the correlation between in vitro results and predictability of clinical behavior was investigated.

  19. Overview of zirconia with respect to gas turbine applications

    NASA Technical Reports Server (NTRS)

    Cawley, J. D.

    1984-01-01

    Phase relationships and the mechanical properties of zirconia are examined as well as the thermal conductivity, deformation, diffusion, and chemical reactivity of this refractory material. Observations from the literature particular to plasma-sprayed material and implications for gas turbine engine applications are discussed. The literature review indicates that Mg-PSZ (partially stabilized zirconia) and Ca-PSZ are unsuitable for advanced gas turbine applications; a thorough characterization of the microstructure of plasma-sprayed zirconia is needed. Transformation-toughened zirconia may be suitable for use in monolithic components.

  20. Semiconductor nanocrystal-based phagokinetic tracking

    SciTech Connect

    Alivisatos, A Paul; Larabell, Carolyn A; Parak, Wolfgang J; Le Gros, Mark; Boudreau, Rosanne

    2014-11-18

    Methods for determining metabolic properties of living cells through the uptake of semiconductor nanocrystals by cells. Generally the methods require a layer of neutral or hydrophilic semiconductor nanocrystals and a layer of cells seeded onto a culture surface and changes in the layer of semiconductor nanocrystals are detected. The observed changes made to the layer of semiconductor nanocrystals can be correlated to such metabolic properties as metastatic potential, cell motility or migration.

  1. Mechanics of monoclinal systems in the Colorado Plateau during the Laramide orogeny

    NASA Astrophysics Data System (ADS)

    Yin, An

    1994-11-01

    Monoclines developed in the Colorado Plateau region during the Laramide orogeny are divided into western and eastern groups by a broad NNW trending antiform through the central part of the plateau. In the western group the major monoclines verge to the east, whereas in the eastern group the major monoclines verge to the west. Paleogeographic reconstruction based on paleocurrent indicators and sedimentary facies distribution suggests that the broad antiform was developed during the Laramide orogeny and was coeval with the formation of the monoclines in the plateau. This relationship implies that the monoclines were drag folds verging towards the center of the plateau as a response to the antiformal warping of the plateau. To simulate the warping of the plateau region and the stress distribution that produced the variable trends of the monoclines, an elastic thin plate model considering in-plane stress was developed. This model assumes that (1) sedimentation in the Laramide basins provided vertical loading along the edge of the plateau region, (2) frictional sliding was operating along the Laramide faults on the northern and eastern boundaries, and (3) the greatest regional compressive stress was oriented in the N 60 deg E direction and was applied uniformly along the western and southwestern sides of the plateau. Buoyancy due to instantaneous isostatic adjustment of crustal thickening or magmatic addition was also considered. The result of the model suggests that the frictional strength of the Uinta thrust system on the northern side of the plateau is at least 2 times greater than that along the Park Range and Sangre de Cristo thrust systems on the eastern side of the plateau in order to explain the observed monoclinal trends and the warping pattern within the plateau during the Laramide orogeny.

  2. (Perturbed angular correlations in zirconia ceramics)

    SciTech Connect

    Not Available

    1990-01-01

    This is the progress report for the first year of the currently-approved three year funding cycle. We have carried on a vigorous program of experimental and theoretical research on microscopic properties of zirconia and ceria using the Perturbed Angular Correlation (PAC) experimental technique. The experimental method was described in the original proposal and in a number of references as well as several of the technical reports that accompany this progress report.

  3. Making yttria-stabilized tetragonal zirconia translucent

    PubMed Central

    Zhang, Yu

    2014-01-01

    Objective The aim of this study was to provide a design guideline for developing tetragonal yttria-stabilized zirconia with improved translucency. Methods The translucency, the in-line transmission in particular, of 3 mol.% yttria-stabilized tetragonal zirconia (3Y-TZP) has been examined using the Rayleigh scattering model. The theory predicts that the in-line transmission of 3Y-TZP can be related to its thickness with grain size and birefringence the governing parameters. To achieve a threshold value of translucency, the critical grain size of 3Y-TZP was predicted for various thicknesses (0.3 – 2.0 mm). The threshold value was defined by a measured average in-line transmission value of a suite of dental porcelains with a common thickness of 1 mm. Our theoretical predictions were calibrated with one of the very few experimental data available in the literature. Results For a dense, high-purity zirconia, its in-line transmission increased with decreasing grain size and thickness. To achieve a translucency similar to that of dental porcelains, a nanocyrstalline 3Y-TZP structure was necessitated, due primarily to its large birefringence and high refractive index. Such a grain size dependence became more pronounced as the 3Y-TZP thickness increased. For example, at a thickness of 1.3 mm, the mean grain size of a translucent 3Y-TZP should be 82 nm. At 1.5 mm and 2 mm thicknesses, the mean grain size needed to be 77 nm and 70 nm, respectively. Significance A promising future for zirconia restorations, with combined translucency and mechanical properties, can be realized by reducing its grain size. PMID:25193781

  4. Niobia and tantala codoped orthorhombic zirconia ceramics

    SciTech Connect

    Hoeftberger, M.; Gritzner, G.

    1995-04-15

    During recent studies it was found that codoping of zirconia with niobia and tantala yielded very corrosion resistant, orthorhombic zirconia ceramics. The powders for those novel ceramics were made via the sol-gel technique by hydrolysis of the respective metal propoxides; a method which required dry-box techniques during the preparation of the alkoxides. In these studies the authors investigated the fabrication of precursor material from aqueous solutions. The preparation of aqueous solutions of salts of zirconium, niobium and tantalum is hampered by rapid hydrolysis. Premature hydrolysis of the chlorides and oxichlorides of niobium, tantalum and zirconium can be, however, prevented in aqueous solutions of oxalic acid. Thus the authors investigated the coprecipitation of hydroxides as precursors by reacting oxalic acid solutions of the respective cations with aqueous ammonia. In addition they studied the effects of calcination and of hydrothermal conversion of the hydroxides to oxides on the powder characteristics and on the mechanical properties of the niobia and tantala codoped zirconia ceramics.

  5. Large scale synthesis of nanostructured zirconia-based compounds from freeze-dried precursors

    SciTech Connect

    Gomez, A.; Villanueva, R.; Vie, D.; Murcia-Mascaros, S.; Martinez, E.; Beltran, A.; Sapina, F.; Vicent, M.; Sanchez, E.

    2013-01-15

    Nanocrystalline zirconia powders have been obtained at the multigram scale by thermal decomposition of precursors resulting from the freeze-drying of aqueous acetic solutions. This technique has equally made possible to synthesize a variety of nanostructured yttria or scandia doped zirconia compositions. SEM images, as well as the analysis of the XRD patterns, show the nanoparticulated character of those solids obtained at low temperature, with typical particle size in the 10-15 nm range when prepared at 673 K. The presence of the monoclinic, the tetragonal or both phases depends on the temperature of the thermal treatment, the doping concentration and the nature of the dopant. In addition, Rietveld refinement of the XRD profiles of selected samples allows detecting the coexistence of the tetragonal and the cubic phases for high doping concentration and high thermal treatment temperatures. Raman experiments suggest the presence of both phases also at relatively low treatment temperatures. - Graphical abstract: Zr{sub 1-x}A{sub x}O{sub 2-x/2} (A=Y, Sc; 0{<=}x{<=}0.12) solid solutions have been prepared as nanostructured powders by thermal decomposition of precursors obtained by freeze-drying, and this synthetic procedure has been scaled up to the 100 g scale. Highlights: Black-Right-Pointing-Pointer Zr{sub 1-x}A{sub x}O{sub 2-x/2} (A=Y, Sc; 0{<=}x{<=}0.12) solid solutions have been prepared as nanostructured powders. Black-Right-Pointing-Pointer The synthetic method involves the thermal decomposition of precursors obtained by freeze-drying. Black-Right-Pointing-Pointer The temperature of the thermal treatment controls particle sizes. Black-Right-Pointing-Pointer The preparation procedure has been scaled up to the 100 g scale. Black-Right-Pointing-Pointer This method is appropriate for the large-scale industrial preparation of multimetallic systems.

  6. Oxygen diffusion in niobia-doped zirconia as surrogate for oxide film on Zr-Nb alloy: AC impedance analysis

    NASA Astrophysics Data System (ADS)

    Yamana, Teppei; Arima, Tatsumi; Yoshihara, Takatoshi; Inagaki, Yaohiro; Idemitsu, Kazuya

    2013-11-01

    The oxygen conductivities and crystallographic properties of niobia-doped yttria-stabilized tetragonal zirconia with 0.0-2.6 wt% Nb2O5 were evaluated by the AC impedance analysis and the X-ray diffraction measurement, respectively. The tetragonality of zirconia increased with niobia content and approached ˜1.017 while the tetragonal-to-monoclinic phase transition occurred above ca. 1 wt% Nb2O5. On the other hand, oxygen conductivities of bulk and grain-boundary (GB) decreased with increasing niobia content. The bulk conductivity controlled the total ionic conductivity at high temperatures, and its activation energy had smaller dependence on temperature than that of GB. In addition to the effect of [VO] depletion by niobia addition, the behaviors of bulk and GB conductivities might be explained by the decrease of mobility of oxygen ion due to Coulomb repulsion between Nb5+ and VO and by no segregation of Nb ions in the space-charge layers, respectively.

  7. Linearly arranged polytypic CZTSSe nanocrystals

    PubMed Central

    Fan, Feng-Jia; Wu, Liang; Gong, Ming; Chen, Shi You; Liu, Guang Yao; Yao, Hong-Bin; Liang, Hai-Wei; Wang, Yi-Xiu; Yu, Shu-Hong

    2012-01-01

    Even colloidal polytypic nanostructures show promising future in band-gap tuning and alignment, researches on them have been much less reported than the standard nano-heterostructures because of the difficulties involved in synthesis. Up to now, controlled synthesis of colloidal polytypic nanocrsytals has been only realized in II-VI tetrapod and octopod nanocrystals with branched configurations. Herein, we report a colloidal approach for synthesizing non-branched but linearly arranged polytypic I2-II-IV-VI4 nanocrystals, with a focus on polytypic non-stoichiometric Cu2ZnSnSxSe4−x nanocrystals. Each synthesized polytypic non-stoichiometric Cu2ZnSnSxSe4−x nanocrystal is consisted of two zinc blende-derived ends and one wurtzite-derived center part. The formation mechanism has been studied and the phase composition can be tuned through adjusting the reaction temperature, which brings a new band-gap tuning approach to Cu2ZnSnSxSe4-x nanocrystals. PMID:23233871

  8. Controlling polymorphic structures and investigating electric properties of Ca-doped zirconia using solid state ceramic method

    SciTech Connect

    Emam, W.I.; Mabied, Ahmed F.; Hashem, H.M.; Selim, M.M.; El-Shabiny, A.M.; Ahmed Farag, I.S.

    2015-08-15

    Structural study of Zr{sub 1−x}Ca{sub x}O{sub 2−x} samples with x=0.01–0.15 were prepared using solid state ceramic method. X-ray diffraction analysis revealed a mixture of the high temperature phase and the monoclinic one for the samples with x≤0.05. On the other hand, the formation of a single high temperature cubic phase was observed within a concentration range of x=0.06–0.10. At concentrations higher than 0.10 the calcium zirconate phase was observed besides the dominant high temperature one. Rietveld refinement of the single phase data clearly revealed, that substitution of zirconium by calcium increases both the lattice parameters as well as the tetrahedral bond length. Ionic to electronic conductivity ratio enhanced considerably as Ca-doping level ascends. The dielectric constant shows strong temperature dependence at lower frequencies. The dielectric loss factor increases rapidly with the increase in temperature at lower frequencies, while decreases with the increase in frequency at higher temperatures. The ionic conduction is considered as the dominant process at higher temperatures. - Graphical abstract: Forming a high temperature cubic zirconia phase at 1200 °C using ceramic solid state method and aliovalent cation. - Highlights: • Formation the high temperature cubic polymorph of zirconia using Ca-doping. • Solid state ceramic method was used for preparing the cubic Ca-doped zirconia. • Substitution of zirconium by calcium increases the lattice parameters and the bond length. • Ionic to electronic conductivity ratio enhanced considerably as Ca-doping level increases.

  9. High-resolution and analytical TEM investigation of metastable-tetragonal phase stabilization in undoped nanocrystalline zirconia.

    PubMed

    Oleshko, Vladimir P; Howe, James M; Shukla, Satyajit; Seal, Sudipta

    2004-09-01

    Submicron and nano-sized nanocrystalline pure zirconia (ZrO2) powders having metastable tetragonal and tetragonal-plus-monoclinic crystal structures, respectively, were synthesized using the sol-gel technique. The as-precipitated and the calcinated ZrO2 powders were analyzed for their morphology, nanocrystallite size and structures, aggregation tendency, local electronic properties, and elemental compositions by conventional and high-resolution transmission electron microscopy and field-emission analytical electron microscopy, including energy-dispersive X-ray and electron energy-loss spectroscopies. The results from this study indicate that a combination of nanocrystallite size, strain-induced grain-growth confinement, and the simultaneous presence of the monoclinic phase can lead to stabilization of the metastable tetragonal-phase in undoped ZrO2. As a result, the tetragonal phase is stabilized within ZrO2 nanocrystallites up to 100 nm in size, which is 16 times larger than the previously reported critical size of 6 nm.

  10. Nanocrystal powered nanomotor

    DOEpatents

    Regan, Brian C.; Zettl, Alexander K.; Aloni, Shaul

    2011-01-04

    A nanoscale nanocrystal which may be used as a reciprocating motor is provided, comprising a substrate having an energy differential across it, e.g. an electrical connection to a voltage source at a proximal end; an atom reservoir on the substrate distal to the electrical connection; a nanoparticle ram on the substrate distal to the atom reservoir; a nanolever contacting the nanoparticle ram and having an electrical connection to a voltage source, whereby a voltage applied between the electrical connections on the substrate and the nanolever causes movement of atoms between the reservoir and the ram. Movement of the ram causes movement of the nanolever relative to the substrate. The substrate and nanolever preferably comprise multiwalled carbon nanotubes (MWNTs) and the atom reservoir and nanoparticle ram are preferably metal (e.g. indium) deposited as small particles on the MWNTs. The substrate may comprise a silicon chip that has been fabricated to provide the necessary electrodes and other electromechanical structures, and further supports an atomic track, which may comprise an MWNT.

  11. Nanocrystal assembly for tandem catalysis

    DOEpatents

    Yang, Peidong; Somorjai, Gabor; Yamada, Yusuke; Tsung, Chia-Kuang; Huang, Wenyu

    2014-10-14

    The present invention provides a nanocrystal tandem catalyst comprising at least two metal-metal oxide interfaces for the catalysis of sequential reactions. One embodiment utilizes a nanocrystal bilayer structure formed by assembling sub-10 nm platinum and cerium oxide nanocube monolayers on a silica substrate. The two distinct metal-metal oxide interfaces, CeO.sub.2--Pt and Pt--SiO.sub.2, can be used to catalyze two distinct sequential reactions. The CeO.sub.2--Pt interface catalyzed methanol decomposition to produce CO and H.sub.2, which were then subsequently used for ethylene hydroformylation catalyzed by the nearby Pt--SiO.sub.2 interface. Consequently, propanal was selectively produced on this nanocrystal bilayer tandem catalyst.

  12. Nanocrystals for luminescent solar concentrators.

    PubMed

    Bradshaw, Liam R; Knowles, Kathryn E; McDowall, Stephen; Gamelin, Daniel R

    2015-02-11

    Luminescent solar concentrators (LSCs) harvest sunlight over large areas and concentrate this energy onto photovoltaics or for other uses by transporting photons through macroscopic waveguides. Although attractive for lowering solar energy costs, LSCs remain severely limited by luminophore reabsorption losses. Here, we report a quantitative comparison of four types of nanocrystal (NC) phosphors recently proposed to minimize reabsorption in large-scale LSCs: two nanocrystal heterostructures and two doped nanocrystals. Experimental and numerical analyses both show that even the small core absorption of the leading NC heterostructures causes major reabsorption losses at relatively short transport lengths. Doped NCs outperform the heterostructures substantially in this critical property. A new LSC phosphor is introduced, nanocrystalline Cd(1-x)Cu(x)Se, that outperforms all other leading NCs by a significant margin in both small- and large-scale LSCs under full-spectrum conditions.

  13. Light transmittance by a multi-coloured zirconia material.

    PubMed

    Ueda, Kazuhiko; Güth, Jan-Frederik; Erdelt, Kurt; Stimmelmayr, Michael; Kappert, Heinrich; Beuer, Florian

    2015-01-01

    Full-contour zirconia restorations are gaining in popularity. Highly translucent zirconia materials and multi-coloured zirconia blocks might help to overcome the aesthetic drawbacks of traditional zirconia. This study evaluated the transmittance of visible light (400-700 nm) through the four different layers (Enamel Layer EL, Transition Layer 1 TL1, Transition Layer 2 TL2, Body Layer BL) of a multi-coloured zirconia block (KATANA™ Zirconia Multi-Layered Disc (ML)) using a spectrophotometer. Forty specimens (thickness of 1±0.05 mm) from each layer were examined and statistically evaluated at a confidence-level of 5%. Light transmittance was expressed as a percentage of the through-passing light. The following mean values (SD) were found: EL 32.8% (1.5), TL1 31.2% (1.3), TL2 25.4% (1.3) and BL 21.7% (1.1). Significant differences were found between all groups (ANOVA, Student-Newman-Keuls). This multi-coloured zirconia block showed four layers with different light transmittance capabilities. It might therefore be useful for enhancing the aesthetic appearance of full-contour zirconia restorations made from this material.

  14. Initial bacterial adhesion on resin, titanium and zirconia in vitro

    PubMed Central

    Lee, Byung-Chul; Jung, Gil-Yong; Kim, Dae-Joon

    2011-01-01

    PURPOSE The aim of this in vitro study was to investigate the adhesion of initial colonizer, Streptococcus sanguis, on resin, titanium and zirconia under the same surface polishing condition. MATERIALS AND METHODS Specimens were prepared from Z-250, cp-Ti and 3Y-TZP and polished with 1 µm diamond paste. After coating with saliva, each specimen was incubated with Streptococcus sanguis. Scanning electron microscope, crystal violet staining and measurement of fluorescence intensity resulting from resazurin reduction were performed for quantifying the bacterial adhesion. RESULTS Surface of resin composite was significantly rougher than that of titanium and zirconia, although all tested specimens are classified as smooth. The resin specimens showed lower value of contact angle compared with titanium and zirconia specimens, and had hydrophilic surfaces. The result of scanning electron microscopy demonstrated that bound bacteria were more abundant on resin in comparison with titanium and zirconia. When total biofilm mass determined by crystal violet, absorbance value of resin was significantly higher than that of titanium or zirconia. The result of relative fluorescence intensities also demonstrated that the highest fluorescence intensity was found on the surface of resin. Absorbance value and fluorescence intensity on titanium was not significantly different from those on zirconia. CONCLUSION Resin specimens showed the roughest surface and have a significantly higher susceptibility to adhere Streptococcus sanguis than titanium and zirconia when surfaces of each specimen were polished under same condition. There was no significant difference in bacteria adhesion between titanium and zirconia in vitro. PMID:21814616

  15. Measurement of elastic constants of monoclinic nickel-titanium and validation of first principles calculations

    SciTech Connect

    Stebner, A. P.; Brown, D. W.; Brinson, L. C.

    2013-05-27

    Polycrystalline, monoclinic nickel-titanium specimens were subjected to tensile and compressive deformations while neutron diffraction spectra were recorded in situ. Using these data, orientation-specific and macroscopic Young's moduli are determined from analysis of linear-elastic deformation exhibited by 13 unique orientations of monoclinic lattices and their relationships to each macroscopic stress and strain. Five of 13 elastic compliance constants are also identified: s{sub 11} = 1.15, s{sub 15} = -1.10, s{sub 22} = 1.34, s{sub 33} = 1.06, s{sub 35} = -1.54, all Multiplication-Sign 10{sup -2} GPa{sup -1}. Through these results, recent atomistic calculations of monoclinic nickel-titanium elastic constants are validated.

  16. Injected nanocrystals for targeted drug delivery

    PubMed Central

    Lu, Yi; Li, Ye; Wu, Wei

    2016-01-01

    Nanocrystals are pure drug crystals with sizes in the nanometer range. Due to the advantages of high drug loading, platform stability, and ease of scaling-up, nanocrystals have been widely used to deliver poorly water-soluble drugs. Nanocrystals in the blood stream can be recognized and sequestered as exogenous materials by mononuclear phagocytic system (MPS) cells, leading to passive accumulation in MPS-rich organs, such as liver, spleen and lung. Particle size, morphology and surface modification affect the biodistribution of nanocrystals. Ligand conjugation and stimuli-responsive polymers can also be used to target nanocrystals to specific pathogenic sites. In this review, the progress on injected nanocrystals for targeted drug delivery is discussed following a brief introduction to nanocrystal preparation methods, i.e., top-down and bottom-up technologies. PMID:27006893

  17. Semiconductor Nanocrystals for Biological Imaging

    SciTech Connect

    Fu, Aihua; Gu, Weiwei; Larabell, Carolyn; Alivisatos, A. Paul

    2005-06-28

    Conventional organic fluorophores suffer from poor photo stability, narrow absorption spectra and broad emission feature. Semiconductor nanocrystals, on the other hand, are highly photo-stable with broad absorption spectra and narrow size-tunable emission spectra. Recent advances in the synthesis of these materials have resulted in bright, sensitive, extremely photo-stable and biocompatible semiconductor fluorophores. Commercial availability facilitates their application in a variety of unprecedented biological experiments, including multiplexed cellular imaging, long-term in vitro and in vivo labeling, deep tissue structure mapping and single particle investigation of dynamic cellular processes. Semiconductor nanocrystals are one of the first examples of nanotechnology enabling a new class of biomedical applications.

  18. Anisotropy, phonon modes, and free charge carrier parameters in monoclinic β -gallium oxide single crystals

    NASA Astrophysics Data System (ADS)

    Schubert, M.; Korlacki, R.; Knight, S.; Hofmann, T.; Schöche, S.; Darakchieva, V.; Janzén, E.; Monemar, B.; Gogova, D.; Thieu, Q.-T.; Togashi, R.; Murakami, H.; Kumagai, Y.; Goto, K.; Kuramata, A.; Yamakoshi, S.; Higashiwaki, M.

    2016-03-01

    We derive a dielectric function tensor model approach to render the optical response of monoclinic and triclinic symmetry materials with multiple uncoupled infrared and far-infrared active modes. We apply our model approach to monoclinic β -Ga2O3 single-crystal samples. Surfaces cut under different angles from a bulk crystal, (010) and (2 ¯01 ), are investigated by generalized spectroscopic ellipsometry within infrared and far-infrared spectral regions. We determine the frequency dependence of 4 independent β -Ga2O3 Cartesian dielectric function tensor elements by matching large sets of experimental data using a point-by-point data inversion approach. From matching our monoclinic model to the obtained 4 dielectric function tensor components, we determine all infrared and far-infrared active transverse optic phonon modes with Au and Bu symmetry, and their eigenvectors within the monoclinic lattice. We find excellent agreement between our model results and results of density functional theory calculations. We derive and discuss the frequencies of longitudinal optical phonons in β -Ga2O3 . We derive and report density and anisotropic mobility parameters of the free charge carriers within the tin-doped crystals. We discuss the occurrence of longitudinal phonon plasmon coupled modes in β -Ga2O3 and provide their frequencies and eigenvectors. We also discuss and present monoclinic dielectric constants for static electric fields and frequencies above the reststrahlen range, and we provide a generalization of the Lyddane-Sachs-Teller relation for monoclinic lattices with infrared and far-infrared active modes. We find that the generalized Lyddane-Sachs-Teller relation is fulfilled excellently for β -Ga2O3 .

  19. Damage maps of veneered zirconia under simulated mastication.

    PubMed

    Kim, J-W; Kim, J-H; Janal, M N; Zhang, Y

    2008-12-01

    Zirconia-based restorations often fracture from chipping and/or delamination of the porcelain veneers. We hypothesized that veneer chipping/delamination is a result of the propagation of near-contact-induced partial cone cracks on the occlusal surface under mastication. Masticatory loading involves the opposing tooth sliding along the cuspal inner incline surface with an applied biting force. To test this hypothesis, we cemented flat porcelain-veneered zirconia plates onto dental composites and cyclically loaded them (contact-slide-liftoff) at an inclination angle as a simplified model of zirconia-based restorations under occlusion. In light of in situ observation of damage evolution in a transparent glass/zirconia/polycarbonate trilayer, post mortem damage evaluation of porcelain/zirconia/composite trilayers by a sectioning technique revealed that deep-penetrating occlusal surface partial cone fracture is the predominant fracture mode of porcelain veneers. Clinical relevance is discussed.

  20. Damage Maps of Veneered Zirconia under Simulated Mastication

    PubMed Central

    Kim, Jae-Won; Kim, Joo-Hyung; Janal, Malvin N.; Zhang, Yu

    2016-01-01

    Zirconia based restorations often fracture from chipping and/or delamination of the porcelain veneers. We hypothesize that veneer chipping/delamination is a result of the propagation of near-contact induced partial cone cracks on the occlusal surface under mastication. Masticatory loading involves the opposing tooth sliding along the cuspal inner incline surface with an applied biting force. To test this hypothesis, flat porcelain veneered zirconia plates were cemented to dental composites and cyclically loaded (contact–slide–liftoff) at an inclination angle as a simplified model of zirconia based restorations under occlusion. In the light of in-situ observation of damage evolution in a transparent glass/zirconia/polycarbonate trilayer, postmortem damage evaluation of porcelain/zirconia/composite trilayers using a sectioning technique revealed that deep penetrating occlusal surface partial cone fracture is the predominant fracture mode of porcelain veneers. Clinical relevance is discussed. PMID:19029080

  1. Selected-control hydrothermal synthesis and formation mechanism of monazite- and zircon-type LaVO(4) nanocrystals.

    PubMed

    Fan, Weiliu; Song, Xinyu; Bu, Yuxiang; Sun, Sixiu; Zhao, Xian

    2006-11-23

    Selective-controlled structure and shape of LaVO(4) nanocrystals were successfully synthesized by a simple hydrothermal method without the presence of catalysts or templates. It was found that tuning the pH of the growth solution was a crucial step for the control of the structure transformation, that is, from monoclinic (m-) to tetragonal (t-) phase, and morphology evolution of LaVO(4) nanocrystals. Further studies demonstrated that the morphology of the product had a strong dependence on the initial lanthanum sources. In the La(NO(3))(3) or LaCl(3) reaction system, pure t-LaVO(4) nanorods with uniform diameters about 10 nm could be obtained. But when using La(2)(SO(4))(3) as the lanthanum source, we can get t-LaVO(4) nanowiskers with broomlike morphology. The detailed systematic study had shown that a special dissolution-recrystallization transformation mechanism as well as an Ostwald ripening process was responsible for the phase control and anisotropic morphology evolution of the LaVO(4) nanocrystals. As a result, the controlled synthesis of m- and t-LaVO(4) not only has great theoretical significance in studying the polymorph control and selective synthesis of inorganic materials but also benefits the potential applications based on LaVO(4) nanocrystals owing to the unusual luminescent properties induced by structural transformation.

  2. Clinical assessment of enamel wear caused by monolithic zirconia crowns.

    PubMed

    Stober, T; Bermejo, J L; Schwindling, F S; Schmitter, M

    2016-08-01

    The purpose of this study was to measure enamel wear caused by antagonistic monolithic zirconia crowns and to compare this with enamel wear caused by contralateral natural antagonists. Twenty monolithic zirconia full molar crowns were placed in 20 patients. Patients with high activity of the masseter muscle at night (bruxism) were excluded. For analysis of wear, vinylpolysiloxane impressions were prepared after crown incorporation and at 6-, 12-, and 24-month follow-up. Wear of the occlusal contact areas of the crowns, of their natural antagonists, and of two contralateral natural antagonists (control teeth) was measured by use of plaster replicas and a 3D laser-scanning device. Differences of wear between the zirconia crown antagonists and the control teeth were investigated by means of two-sided paired Student's t-tests and linear regression analysis. After 2 years, mean vertical loss was 46 μm for enamel opposed to zirconia, 19-26 μm for contralateral control teeth and 14 μm for zirconia crowns. Maximum vertical loss was 151 μm for enamel opposed to zirconia, 75-115 μm for control teeth and 60 μm for zirconia crowns. Statistical analysis revealed significant differences between wear of enamel by zirconia-opposed teeth and by control teeth. Gender, which significantly affected wear, was identified as a possible confounder. Monolithic zirconia crowns generated more wear of opposed enamel than did natural teeth. Because of the greater wear caused by other dental ceramics, the use of monolithic zirconia crowns may be justified.

  3. Polarization states and dielectric responses of elastically clamped ferroelectric nanocrystals

    NASA Astrophysics Data System (ADS)

    Azovtsev, A. V.; Pertsev, N. A.

    2016-12-01

    Polarization states and physical properties of ferroelectrics depend on the mechanical boundary conditions due to electrostrictive coupling between electric polarization and lattice strains. Here, we describe theoretically both equilibrium thermodynamic states and electric permittivities of ferroelectric nanocrystals subjected to the elastic three-dimensional (3D) clamping by a surrounding dielectric material. The problem is solved by the minimization of a special thermodynamic potential that describes the case of an ellipsoidal ferroelectric inclusion embedded into a linear elastic matrix. Numerical calculations are performed for BaTiO3, PbTiO3, and Pb(Zr0.5Ti0.5)O3 nanoparticles surrounded by silica glass. It is shown that, in the case of BaTiO3 and PbTiO3, elastic 3D clamping may change the order of a ferroelectric phase transition from first to second. Furthermore, the mechanical inclusion-matrix interaction shifts the temperatures of structural transitions between different ferroelectric states and even eliminates some ferroelectric phases existing in stress-free BaTiO3 and Pb(Zr0.5Ti0.5)O3 crystals. Another important effect of elastic clamping is the lowering of the symmetry of ferroelectric states in ellipsoidal inclusions, where orthorhombic and monoclinic phases may form instead of the tetragonal and rhombohedral bulk counterparts. Finally, our thermodynamic calculations show that the dielectric responses of studied perovskite ferroelectrics are sensitive to matrix-induced clamping as well. For instance, dielectric peaks occurring at structural transitions between different ferroelectric phases in BaTiO3 appear to be much higher in spherical inclusions than in the freestanding crystal. Predicted clamping-induced enhancement of certain dielectric responses at room temperature indicates that composite materials comprising nanocrystals of perovskite ferroelectrics are promising for device applications requiring the use of high-permittivity dielectrics.

  4. Thermal conductivity of zirconia thermal barrier coatings

    NASA Technical Reports Server (NTRS)

    Dinwiddie, R. B.; Beecher, S. C.; Nagaraj, B. A.; Moore, C. S.

    1995-01-01

    Thermal barrier coatings (TBC's) applied to the hot gas components of turbine engines lead to enhanced fuel efficiency and component reliability. Understanding the mechanisms which control the thermal transport behavior of the TBC's is of primary importance. Physical vapor deposition (PVD) and plasma spraying (PS) are the two most commonly used coating techniques. These techniques produce coatings with unique microstructures which control their performance and stability. The PS coatings were applied with either standard powder or hollow sphere particles. The hollow sphere particles yielded a lower density and lower thermal conductivity coating. The thermal conductivity of both fully and partially stabilized zirconia, before and after thermal aging, will be compared. The thermal conductivity of the coatings permanently increases upon exposed to high temperatures. These increases are attributed to microstructural changes within the coatings. Sintering of the as-fabricated plasma sprayed lamellar structure is observed by scanning electron microscopy of coatings isothermally heat treated at temperatures greater than 1100 C. During this sintering process the planar porosity between lamella is converted to a series of small spherical pores. The change in pore morphology is the primary reason for the observed increase in thermal conductivity. This increase in thermal conductivity can be modeled using a relationship which depends on both the temperature and time of exposure. Although the PVD coatings are less susceptible to thermal aging effects, preliminary results suggest that they have a higher thermal conductivity than PS coatings, both before and after thermal aging. The increases in thermal conductivity due to thermal aging for partially stabilized plasma sprayed zirconia have been found to be less than for fully stabilized plasma sprayed zirconia coatings. The high temperature thermal diffusivity data indicate that if these coatings reach a temperature above 1100 C

  5. Thermal conductivity of zirconia thermal barrier coatings

    NASA Technical Reports Server (NTRS)

    Dinwiddie, R. B.; Beecher, S. C.; Nagaraj, B. A.; Moore, C. S.

    1995-01-01

    Thermal barrier coatings (TBC's) applied to the hot gas components of turbine engines lead to enhanced fuel efficiency and component reliability. Understanding the mechanisms which control the thermal transport behavior of the TBC's is of primary importance. Physical vapor description (PVD) and plasma spraying (PS) are the two most commonly used coating techniques. These techniques produce coatings with unique microstructures which control their performance and stability. The PS coatings were applied with either standard power or hollow sphere particles. The hollow sphere particles yielded a lower density and lower thermal conductivity coating. The thermal conductivity of both fully and partially stabilized zirconia, before and after thermal aging, will be compared. The thermal conductivity of the coatings permanently increase upon being exposed to high temperatures. These increases are attributed to microstructural changes within the coatings. Sintering of the as fabricated plasma sprayed lamellar structure is observed by scanning electron microscopy of coatings isothermally heat treated at temperatures greater than 1100 C. During this sintering process the planar porosity between lamella is converted to a series of small spherical pores. The change in pore morphology is the primary reason for the observed increase in thermal conductivity. This increase in thermal conductivity can be modeled using a relationship which depends on both the temperature and time of exposure. Although the PVD coatings are less susceptible to thermal aging effects, preliminary results suggest that they have a higher thermal conductivity than PS coatings, both before and after thermal aging. The increases in thermal conductivity due to thermal aging for partially stabilized plasma sprayed zirconia have been found to be less than for fully stabilized plasma sprayed zirconia coatings. The high temperature thermal diffusivity data indicates that if these coatings reach a temperature above

  6. Sem analysis zirconia-ceramic adhesion interface

    PubMed Central

    CARDELLI, P.; VERTUCCI, V.; MONTANI, M.; ARCURI, C.

    2015-01-01

    SUMMARY Objectives Modern dentistry increasingly tends to use materials aesthetically acceptable and biomimetic. Among these are zirconia and ceramics for several years, a combination that now has becoming synonym of aesthetic; however, what could be the real link between these two materials and especially its nature, remains a controversial topic debated in the literature. The aim of our study was to “underline” the type of bonding that could exist between these materials. Materials and methods To investigate the nature of this bond we used a SEM microscopy (Zeiss SUPRA 25). Different bilaminar specimens: “white” zirconia Zircodent® and ceramic “Noritake®”, after being tested with loading test in bending (three-point-bending) and FEM analysis, were analyzed by SEM. Fragments’ analysis in closeness of the fracture’s point has allowed us to be able to “see” if at large magnifications between these two materials, and without the use of linear, could exist a lasting bond and the possible type of failure that could incur. Results From our analysis of the specimens’ fragments analyzed after test Equipment, it is difficult to highlight a clear margin and no-adhesion zones between the two materials, although the analysis involving fragments adjacent to the fracture that has taken place at the time of Mechanical test Equipment. Conclusions According to our analysis and with all the clarification of the case, we can assume that you can obtain a long and lasting bond between the zirconia and ceramics. Agree to the data present in the literature, we can say that the type of bond varies according to the type of specimens and of course also the type of failure. In samples where the superstructure envelops the ceramic framework Zirconium we are in the presence of a cohesive failure, otherwise in a presence of adhesive failure. PMID:27555905

  7. Evidence for anisotropic dielectric properties of monoclinic hafnia using valence electron energy-loss spectroscopy in high-resolution transmission electron microscopy and ab initio time-dependent density-functional theory

    NASA Astrophysics Data System (ADS)

    Guedj, C.; Hung, L.; Zobelli, A.; Blaise, P.; Sottile, F.; Olevano, V.

    2014-12-01

    The effect of nanocrystal orientation on the energy loss spectra of monoclinic hafnia (m-HfO2) is measured by high resolution transmission electron microscopy (HRTEM) and valence energy loss spectroscopy (VEELS) on high quality samples. For the same momentum-transfer directions, the dielectric properties are also calculated ab initio by time-dependent density-functional theory (TDDFT). Experiments and simulations evidence anisotropy in the dielectric properties of m-HfO2, most notably with the direction-dependent oscillator strength of the main bulk plasmon. The anisotropic nature of m-HfO2 may contribute to the differences among VEELS spectra reported in literature. The good agreement between the complex dielectric permittivity extracted from VEELS with nanometer spatial resolution, TDDFT modeling, and past literature demonstrates that the present HRTEM-VEELS device-oriented methodology is a possible solution to the difficult nanocharacterization challenges given in the International Technology Roadmap for Semiconductors.

  8. Exciton polarizability in semiconductor nanocrystals.

    PubMed

    Wang, Feng; Shan, Jie; Islam, Mohammad A; Herman, Irving P; Bonn, Mischa; Heinz, Tony F

    2006-11-01

    The response of charge to externally applied electric fields is an important basic property of any material system, as well as one critical for many applications. Here, we examine the behaviour and dynamics of charges fully confined on the nanometre length scale. This is accomplished using CdSe nanocrystals of controlled radius (1-2.5 nm) as prototype quantum systems. Individual electron-hole pairs are created at room temperature within these structures by photoexcitation and are probed by terahertz (THz) electromagnetic pulses. The electronic response is found to be instantaneous even for THz frequencies, in contrast to the behaviour reported in related measurements for larger nanocrystals and nanocrystal assemblies. The measured polarizability of an electron-hole pair (exciton) amounts to approximately 10(4) A(3) and scales approximately as the fourth power of the nanocrystal radius. This size dependence and the instantaneous response reflect the presence of well-separated electronic energy levels induced in the system by strong quantum-confinement effects.

  9. "Nanocrystal bilayer for tandem catalysis"

    SciTech Connect

    Yamada, Yusuke; Tsung, Chia Kuang; Huang, Wenyu; Huo, Ziyang; E.Habas, Susan E; Soejima, Tetsuro; Aliaga, Cesar E; Samorjai, Gabor A; Yang, Peidong

    2011-01-24

    Supported catalysts are widely used in industry and can be optimized by tuning the composition and interface of the metal nanoparticles and oxide supports. Rational design of metal-metal oxide interfaces in nanostructured catalysts is critical to achieve better reaction activities and selectivities. We introduce here a new class of nanocrystal tandem catalysts that have multiple metal-metal oxide interfaces for the catalysis of sequential reactions. We utilized a nanocrystal bilayer structure formed by assembling platinum and cerium oxide nanocube monolayers of less than 10 nm on a silica substrate. The two distinct metal-metal oxide interfaces, CeO2-Pt and Pt-SiO2, can be used to catalyse two distinct sequential reactions. The CeO2-Pt interface catalysed methanol decomposition to produce CO and H2, which were subsequently used for ethylene hydroformylation catalysed by the nearby Pt-SiO2 interface. Consequently, propanal was produced selectively from methanol and ethylene on the nanocrystal bilayer tandem catalyst. This new concept of nanocrystal tandem catalysis represents a powerful approach towards designing high-performance, multifunctional nanostructured catalysts

  10. Microstructure and mechanical properties of bulk yttria-partially-stabilized zirconia

    NASA Technical Reports Server (NTRS)

    Valentine, P. G.; Maier, R. D.; Mitchell, T. E.

    1981-01-01

    A commercially available bulk 4.5 mole percent yttria-Y2O3)-partially-stabilized zirconia (PSZ) was studied by light microscopy, X-ray analysis, microhardness measurement, and fracture toughness testing. The growth of the precipitates and the phase transformations were studied as a function of aging in air at 1500 C. Aging cuves were constructed for both the as-received and the solution-annealed-and-quenched materials; the curves showed hardness peaks at 1397 and 1517 kg/sq mm, respectively. A total of twelve different types of tetragonal precipitates were found. The rectangular plate-shaped tetragonal precipitates were found to have a (110) habit plane. Grinding of the Y2O3 PSZ into powder did not cause a significant amount of metastable tetragonal precipitates to transform into the monoclinic phase, thus indicating that transformation toughening is not a significant mechanism for the material. The fracture toughness of the aged and of the unaged solution-annealed-and-quenched PSZ was found to be between 2 and 3 MN/cu m/2.

  11. Nanocrystals Research for Energy Efficient and Clean Energy Technologies:

    SciTech Connect

    Rosenthal, Sandra J

    2013-12-17

    Efforts centered on: nanocrystal photovoltaic fabrication, ultrafast dynamics and aberration-corrected STEM characterization of II-VI core, core/shell and alloyed nanocrystals, and fundamental investigation and applications of ultrasmall white light-emitting CdSe nanocrystal.

  12. On the relation between steep monoclinal flexure zones and steep hydraulic gradients.

    PubMed

    Yechieli, Y; Kafri, U; Wollman, S; Lyakhovsky, V; Weinberger, R

    2007-01-01

    Steep hydraulic gradients are found in association with steep monoclinal flexures. However, the physics of the reduction of the hydraulic conductivity, which is responsible for the steep gradients, has seldom been studied. We present results of hydrological and mechanical modeling aiming to study the effect of such steep hydraulic gradients demonstrated in the Judea Group Aquifer system, Israel. The hydrological configuration of steep dips and anisotropy between flows parallel and perpendicular to the bedding planes was simulated using the FEFLOW code. It exhibited a situation whereby part of the flow is oblique to the bedding planes and therefore some steepening of the hydraulic gradients occurred due to actual conductivity reduction. However, this reduction is not enough to account for the steeper gradients observed. The effect of a deep-seated reverse fault under the monocline on the permeability distribution within the structure was examined by numerical mechanical simulations. It exhibited a compressional stress distribution in the steep part of the monocline, which, due to shortening and closure of joints and voids, is presumably responsible for a significant pressure-induced permeability reduction. This process by itself in a layered structure, including interlayering of thin marl layers, could be responsible for the steep hydraulic gradients in the steep part of the monocline.

  13. Structural, microstructural and vibrational analyses of the monoclinic tungstate BiLuWO{sub 6}

    SciTech Connect

    Ait Ahsaine, H.; Taoufyq, A.; Patout, L.; Ezahri, M.; Benlhachemi, A.; Bakiz, B.; Villain, S.; Guinneton, F.; Gavarri, J.-R.

    2014-10-15

    The bismuth lutetium tungstate phase BiLuWO{sub 6} has been prepared using a solid state route with stoichiometric mixtures of oxide precursors. The obtained polycrystalline phase has been characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and Raman spectroscopy. In the first step, the crystal structure has been refined using Rietveld method: the crystal cell was resolved using monoclinic system (parameters a, b, c, β) with space group A2/m. SEM images showed the presence of large crystallites with a constant local nominal composition (BiLuW). TEM analyses showed that the actual local structure could be better represented by a superlattice (a, 2b, c, β) associated with space groups P2 or P2/m. The Raman spectroscopy showed the presence of vibrational bands similar to those observed in the compounds BiREWO{sub 6} with RE=Y, Gd, Nd. However, these vibrational bands were characterized by large full width at half maximum, probably resulting from the long range Bi/Lu disorder and local WO{sub 6} octahedron distortions in the structure. - Graphical abstract: The average structure of BiLuWO{sub 6} determined from X-ray diffraction data can be represented by A2/m space group. Experimental Electron Diffraction patterns along the [0vw] zone axes of the monoclinic structure and associated simulated patterns show the existence of a monoclinic superstructure with space group P2 or P2/m. - Highlights: • A new monoclinic BiLuWO{sub 6} phase has been elaborated from solid-state reaction. • The space group of the monoclinic disordered average structure should be A2/m. • Transmission electron microscopy leads to a superlattice with P2/m space group. • Raman spectroscopy suggests existence of local disorder.

  14. Biological reactivity of zirconia-hydroxyapatite composites.

    PubMed

    Silva, Viviane V; Lameiras, Fernando S; Lobato, Zélia I P

    2002-01-01

    Materials and devices intended for end-use applications as implants and medical devices must be evaluated to determine their biocompatibility potential in contact with physiological systems. The use of standard practices of biological testing provides a reasonable level of confidence concerning the response of a living organism to a given material or device, as well as guidance in selecting the proper procedures to be carried out for the screening of new or modified materials. This article presents results from cytotoxicity assays of cell culture, skin irritation, and acute toxicity by systemic and intracutaneous injections for powders, ceramic bodies, and extract liquids of hydroxyapatite (HA), calcia partially stabilized zirconia (ZO), and two types of zirconia-hydroxyapatite composites (Z4H6 and Z6H4) with potential for future use as orthopedic and dental implants. They indicate that these materials present potential for this type of application because they meet the requirements of the standard practices recommended for evaluating the biological reactivity of ATCC cell cultures (CCL1 NCTC clone 929 of mouse connective tissue and CCL 81 of monkey connective tissue) and animals (rabbit and mouse) with direct or indirect patient contact, or by the injection of specific extracts prepared from the material under test. In addition, studies involving short-term intramuscular and long-term implantation assays to estimate the reaction of living tissue to the composites studied, and investigations on long-term effects that these materials can cause on the cellular metabolism, are already in progress.

  15. Synthesis and characterizations of zirconia nanofiltration membranes

    SciTech Connect

    Vacassy, R.; Mouchet, C.; Guizard, C.

    1994-12-31

    In recent years inorganic membranes are being considered in microfiltration and ultrafiltration applications. A significant number of commercial processes utilizing inorganic membranes already exist. Nanofiltration has recently arisen as a new technique with a high application potential in the separation of organics and multivalent ions from water and effluents. Presently, polymer nanofiltration membranes are commercialized with a limited temperature and pH application range. New developments are expected with the aim of providing ceramic nanofilters suitable for harsh working conditions at high pH and high temperature, as well as with organic solvents. Here, the authors report a well adapted method based on the latest developments in sol-gel chemistry in order to prepare a microporous zirconia membrane. Zirconium propoxide used as a ceramic precursor is reacted with acetylacetone in an organic solvent. The use of acetylacetone ligands allows the control of particle growth along the process Loading a nanophase ceramic exhibiting connected micropores with pore diameter in 1 to 2 nm range. A tetragonal zirconia layer coated on a KERASEP{trademark} multichannel has been obtained at 400{degrees}C with pore diameter centered on 1 nm.

  16. Hafnia-rich mixed oxide ceramics of the system HfO2-ZrO2-TiO2 for heaters and heat exchangers in electrothermal thrusters: The effects of titania on selected electrical and mechanical properties of Hafnia-rich mixed oxides in the system Hafnia-Zirconia-Titania, volume 1

    NASA Technical Reports Server (NTRS)

    Staszak, Paul Russell; Wirtz, G. P.; Berg, M.; Brown, S. D.

    1988-01-01

    A study of the effects of titania on selected properties of hafnia-rich mixed oxides in the system hafnia-zirconia-titania (HZT) was made in the region 5 to 20 mol percent titania. The studied properties included electrical conductivity, thermal expansion, and fracture strength and toughness. The effects of titania on the properties were studied for the reduced state as well as the oxidized state of the sintered mixed oxides. X-ray analysis showed that the materials were not always single phase. The oxidized compositions went from being monoclinic solid solutions at low titania additions to having three phases (two monoclinic and a titanate phase) at high additions of titania. The reduced compositions showed an increasing cubic phase presence mixed with the monoclinic phase as titania was added. The electrical conductivity increased with temperature at approximately 0.1 mhos/cm at 1700 C for all compositions. The thermal expansion coefficient decreased with increasing titania as did the monoclinic to tetragonal transformation temperature. The fracture strength of the oxidized bars tended to decrease with the addition of titania owing to the presence of the second phase titania. The fracture strength of the reduced bars exhibited a minimum corresponding to a two-phase region of monoclinic and cubic phases. When the second phases were suppressed, the titania tended to increase the fracture strength slightly in both the oxidized and reduced states. The fracture toughness followed similar trends.

  17. Phase stability of thermal barrier oxides based on t'-zirconia with trivalent oxide additions

    NASA Astrophysics Data System (ADS)

    Rebollo Franco, Noemi Rosa

    Zirconia stabilized with 7+/-1 wt.% addition of yttria (7YSZ) is widely used for thermal barrier coatings (TBC's) on actively cooled gas turbine components, selected partly because of its superior durability under thermal cyclic conditions. As deposited, 7YSZ occurs as a metastable single-phase tetragonal solid solution (t') that is thermodynamically stable against the deleterious transformation to monoclinic upon cooling. However, at high temperatures t' is driven to decompose diffusionally into an equilibrium mixture of high-Y cubic and low-Y tetragonal; the latter becomes transformable to monoclinic compromising the mechanical integrity of the system. This dissertation explores the effects of trivalent stabilizers, including Y, Sc and selected rare-earth oxides (REO's), on the phase stability of the resulting solid solutions in zirconia. The REO additions are of interest because they can potentially enhance the insulation efficiency on the coating allowing higher operating temperatures. However, understanding of their effects on phase stability and potentially on cyclic durability at the projected use temperature in next generation engines (1200-1400°C) is insufficient to guide the design of coatings with the desirable combination of lower thermal conductivity and acceptable durability. Sc was also investigated because of previous reports on the higher phase stability of materials doped with Sc, and Y served as the baseline. The experimental approach is based on powders synthesized by reverse co-precipitation of precursor solutions, usually compacted and then subjected to a variety of heat treatments, following their evolution by means of X-ray diffractometry, dilatometry, transmission electron microscopy and Raman spectroscopy. The use of powders facilitated the synthesis of a wider range of compositions that would not have been possible by coating deposition approaches, and because the synthesis occurs at low temperature, it also enabled the starting

  18. Cellulose nanocrystals: synthesis, functional properties, and applications

    PubMed Central

    George, Johnsy; Sabapathi, SN

    2015-01-01

    Cellulose nanocrystals are unique nanomaterials derived from the most abundant and almost inexhaustible natural polymer, cellulose. These nanomaterials have received significant interest due to their mechanical, optical, chemical, and rheological properties. Cellulose nanocrystals primarily obtained from naturally occurring cellulose fibers are biodegradable and renewable in nature and hence they serve as a sustainable and environmentally friendly material for most applications. These nanocrystals are basically hydrophilic in nature; however, they can be surface functionalized to meet various challenging requirements, such as the development of high-performance nanocomposites, using hydrophobic polymer matrices. Considering the ever-increasing interdisciplinary research being carried out on cellulose nanocrystals, this review aims to collate the knowledge available about the sources, chemical structure, and physical and chemical isolation procedures, as well as describes the mechanical, optical, and rheological properties, of cellulose nanocrystals. Innovative applications in diverse fields such as biomedical engineering, material sciences, electronics, catalysis, etc, wherein these cellulose nanocrystals can be used, are highlighted. PMID:26604715

  19. Intermetallic Nanocrystals: Syntheses and Catalytic Applications.

    PubMed

    Yan, Yucong; Du, Jingshan S; Gilroy, Kyle D; Yang, Deren; Xia, Younan; Zhang, Hui

    2017-02-24

    At the forefront of nanochemistry, there exists a research endeavor centered around intermetallic nanocrystals, which are unique in terms of long-range atomic ordering, well-defined stoichiometry, and controlled crystal structure. In contrast to alloy nanocrystals with no elemental ordering, it is challenging to synthesize intermetallic nanocrystals with a tight control over their size and shape. Here, recent progress in the synthesis of intermetallic nanocrystals with controllable sizes and well-defined shapes is highlighted. A simple analysis and some insights key to the selection of experimental conditions for generating intermetallic nanocrystals are presented, followed by examples to highlight the viable use of intermetallic nanocrystals as electrocatalysts or catalysts for various reactions, with a focus on the enhanced performance relative to their alloy counterparts that lack elemental ordering. Within the conclusion, perspectives on future developments in the context of synthetic control, structure-property relationships, and applications are discussed.

  20. Phase transitions and doping in semiconductor nanocrystals

    NASA Astrophysics Data System (ADS)

    Sahu, Ayaskanta

    Colloidal semiconductor nanocrystals are a promising technological material because their size-dependent optical and electronic properties can be exploited for a diverse range of applications such as light-emitting diodes, bio-labels, transistors, and solar cells. For many of these applications, electrical current needs to be transported through the devices. However, while their solution processability makes these colloidal nanocrystals attractive candidates for device applications, the bulky surfactants that render these nanocrystals dispersible in common solvents block electrical current. Thus, in order to realize the full potential of colloidal semiconductor nanocrystals in the next-generation of solid-state devices, methods must be devised to make conductive films from these nanocrystals. One way to achieve this would be to add minute amounts of foreign impurity atoms (dopants) to increase their conductivity. Electronic doping in nanocrystals is still very much in its infancy with limited understanding of the underlying mechanisms that govern the doping process. This thesis introduces an innovative synthesis of doped nanocrystals and aims at expanding the fundamental understanding of charge transport in these doped nanocrystal films. The list of semiconductor nanocrystals that can be doped is large, and if one combines that with available dopants, an even larger set of materials with interesting properties and applications can be generated. In addition to doping, another promising route to increase conductivity in nanocrystal films is to use nanocrystals with high ionic conductivities. This thesis also examines this possibility by studying new phases of mixed ionic and electronic conductors at the nanoscale. Such a versatile approach may open new pathways for interesting fundamental research, and also lay the foundation for the creation of novel materials with important applications. In addition to their size-dependence, the intentional incorporation of

  1. An in vitro evaluation of the zirconia surface treatment by mesoporous zirconia coating on its bonding to resin cement.

    PubMed

    Zhang, Yanli; Sun, Ting; Liu, Ruoyu; Feng, Xiaoli; Chen, Aijie; Shao, Longquan

    2014-01-01

    The effect of zirconia surface treatment by mesoporous zirconia coating on the microtensile bond strength (MTBS) between zirconia and resin cement was investigated in this work. 160 zirconia specimens were prepared and divided into four groups according to surface treatments: (1) airborne-particle-abrasion treatment (APA); (2) glass infiltration and hydrofluoric acid treatment (GI+HF); (3) mesoporous zirconia coating (MZ); and (4) no treatment (C). The as-prepared zirconia specimens were bonded using Panavia F2.0 and RelyX Unicem. The MTBS values were tested using a universal testing machine, and data were analyzed using ANOVA and SNK methods (a=0.05). The MTBS values obtained after GI+HF and MZ treatments were significantly higher than those obtained after APA and C treatments (P<0.05), especially for samples cemented with Panavia F2.0. The results reveal that zirconia surface treatments using GI+HF and MZ yield higher bond strength than those using APA or C, regardless of the resin cements.

  2. Surface Structure of Aerobically Oxidized Diamond Nanocrystals

    DTIC Science & Technology

    2014-10-27

    distribution is unlimited. Surface Structure of Aerobically Oxidized Diamond Nanocrystals The views, opinions and/or findings contained in this report...2211 diamond nanocrystals, REPORT DOCUMENTATION PAGE 11. SPONSOR/MONITOR’S REPORT NUMBER(S) 10. SPONSOR/MONITOR’S ACRONYM(S) ARO 8. PERFORMING...Room 254, Mail Code 8725 New York, NY 10027 -7922 ABSTRACT Surface Structure of Aerobically Oxidized Diamond Nanocrystals Report Title We investigate

  3. Bulk and Interface Thermodynamics of Calcia-, and Yttria-doped Zirconia Ceramics: Nanograined Phase Stability

    NASA Astrophysics Data System (ADS)

    Drazin, John Walter

    Calcia-, and yttria- doped zirconia powders and samples are essential systems in academia and industry due to their observed bulk polymorphism. Pure zirconia manifests as Baddeleyite, a monoclinic structured mineral with 7-fold coordination. This bulk form of zirconia has little application due to its asymmetry. Therefore dopants are added to the grain in-order to induce phase transitions to either a tetragonal or cubic polymorph with the incorporation of oxygen vacancies due to the dopant charge mis-match with the zirconia matrix. The cubic polymorph has cubic symmetry such that these samples see applications in solid oxide fuel cells (SOFCs) due to the high oxygen vacancy concentrations and high ionic mobility at elevated temperatures. The tetragonal polymorph has slight asymmetry in the c-axis compared to the a-axis such that the tetragonal samples have increased fracture toughness due to an impact induced phase transformation to a cubic structure. These ceramic systems have been extensively studied in academia and used in various industries, but with the advent of nanotechnology one can wonder whether smaller grain samples will see improved characteristics similar to their bulk grain counterparts. However, there is a lack of data and knowledge of these systems in the nano grained region which provides us with an opportunity to advance the theory in these systems. The polymorphism seen in the bulk grains samples is also seen in the nano-grained samples, but at slightly distinct dopant concentrations. The current theory hypothesizes that a surface excess, gamma (J/m 2), can be added to the Gibbs Free energy equation to account for the additional free energy of the nano-grain atoms. However, these surface energies have been difficult to measure and therefore thermodynamic data on these nano-grained samples have been sparse. Therefore, in this work, I will use a well established water adsorption microcalorimetry apparatus to measure the water coverage isotherms

  4. On the interfacial fracture of porcelain/zirconia and graded zirconia dental structures.

    PubMed

    Chai, Herzl; Lee, James J-W; Mieleszko, Adam J; Chu, Stephen J; Zhang, Yu

    2014-08-01

    Porcelain fused to zirconia (PFZ) restorations are widely used in prosthetic dentistry. However, their susceptibility to fracture remains a practical problem. The failure of PFZ prostheses often involves crack initiation and growth in the porcelain, which may be followed by fracture along the porcelain/zirconia (P/Z) interface. In this work, we characterized the process of fracture in two PFZ systems, as well as a newly developed graded glass-zirconia structure with emphases placed on resistance to interfacial cracking. Thin porcelain layers were fused onto Y-TZP plates with or without the presence of a glass binder. The specimens were loaded in a four-point-bending fixture with the thin porcelain veneer in tension, simulating the lower portion of the connectors and marginal areas of a fixed dental prosthesis (FDP) during occlusal loading. The evolution of damage was observed by a video camera. The fracture was characterized by unstable growth of cracks perpendicular to the P/Z interface (channel cracks) in the porcelain layer, which was followed by stable cracking along the P/Z interface. The interfacial fracture energy GC was determined by a finite-element analysis taking into account stress-shielding effects due to the presence of adjacent channel cracks. The resulting GC was considerably less than commonly reported values for similar systems. Fracture in the graded Y-TZP samples occurred via a single channel crack at a much greater stress than for PFZ. No delamination between the residual glass layer and graded zirconia occurred in any of the tests. Combined with its enhanced resistance to edge chipping and good esthetic quality, graded Y-TZP emerges as a viable material concept for dental restorations.

  5. Germanium Nanocrystal Solar Cells

    NASA Astrophysics Data System (ADS)

    Holman, Zachary Charles

    Greenhouse gas concentrations in the atmosphere are approaching historically unprecedented levels from burning fossil fuels to meet the ever-increasing world energy demand. A rapid transition to clean energy sources is necessary to avoid the potentially catastrophic consequences of global warming. The sun provides more than enough energy to power the world, and solar cells that convert sunlight to electricity are commercially available. However, the high cost and low efficiency of current solar cells prevent their widespread implementation, and grid parity is not anticipated to be reached for at least 15 years without breakthrough technologies. Semiconductor nanocrystals (NCs) show promise for cheap multi-junction photovoltaic devices. To compete with photovoltaic materials that are currently commercially available, NCs need to be inexpensively cast into dense thin films with bulk-like electrical mobilities and absorption spectra that can be tuned by altering the NC size. The Group II-VI and IV-VI NC communities have had some success in achieving this goal by drying and then chemically treating colloidal particles, but the more abundant and less toxic Group IV NCs have proven more challenging. This thesis reports thin films of plasma-synthesized Ge NCs deposited using three different techniques, and preliminary solar cells based on these films. Germanium tetrachloride is dissociated in the presence of hydrogen in a nonthermal plasma to nucleate Ge NCs. Transmission electron microscopy and X-ray diffraction indicate that the particles are nearly monodisperse (standard deviations of 10-15% the mean particle diameter) and the mean diameter can be tuned from 4-15 nm by changing the residence time of the Ge NCs in the plasma. In the first deposition scheme, a Ge NC colloid is formed by reacting nanocrystalline powder with 1-dodecene and dispersing the functionalized NCs in a solvent. Films are then formed on substrates by drop-casting the colloid and allowing it to dry

  6. Ultrasonic cleaning of silica-coated zirconia influences bond strength between zirconia and resin luting material.

    PubMed

    Nishigawa, Goro; Maruo, Yukinori; Irie, Masao; Oka, Morihiko; Yoshihara, Kumiko; Minagi, Shogo; Nagaoka, Noriyuki; Yoshida, Yasuhiro; Suzuki, Kazuomi

    2008-11-01

    The purpose of this study was to evaluate how ultrasonic cleaning of silica-coated zirconia surfaces would influence the latter's bond strength to resin luting material. Forty zirconia specimens were divided into four groups: one air abrasion group and three silica-coated groups. Silica-coated specimens were cleaned with distilled water using an ultrasonic cleaner after tribochemical silica coating and then divided into three groups according to cleaning durations: 1 minute, 5 minutes, or without cleaning. Following which, resin luting material was polymerized against the specimens. After storage in water for 24 hours, the specimens were subjected to shear bond strength test. Shear bond strength of silica-coated group without cleaning was significantly higher than the other three groups, but there were no statistically significant differences among the three latter groups. SEM images suggested visible differences among the treatment methods. With EDXS analysis, it was revealed that ultrasonic cleaning decreased the silica content on the treated surfaces. Therefore, results showed that ultrasonic cleaning of tribochemically silica-coated zirconia surfaces decreased the adhesion efficacy to resin luting material.

  7. Quantitative tunneling spectroscopy of nanocrystals

    SciTech Connect

    First, Phillip N; Whetten, Robert L; Schaaff, T Gregory

    2007-05-25

    The proposed goals of this collaborative work were to systematically characterize the electronic structure and dynamics of 3-dimensional metal and semiconducting nanocrystals using scanning tunneling microscopy/spectroscopy (STM/STS) and ballistic electron emission spectroscopy (BEES). This report describes progress in the spectroscopic work and in the development of methods for creating and characterizing gold nanocrystals. During the grant period, substantial effort also was devoted to the development of epitaxial graphene (EG), a very promising materials system with outstanding potential for nanometer-scale ballistic and coherent devices ("graphene" refers to one atomic layer of graphitic, sp2 -bonded carbon atoms [or more loosely, few layers]). Funding from this DOE grant was critical for the initial development of epitaxial graphene for nanoelectronics

  8. Lead sulphide nanocrystal photodetector technologies

    NASA Astrophysics Data System (ADS)

    Saran, Rinku; Curry, Richard J.

    2016-02-01

    Light detection is the underlying principle of many optoelectronic systems. For decades, semiconductors including silicon carbide, silicon, indium gallium arsenide and germanium have dominated the photodetector industry. They can show excellent photosensitivity but are limited by one or more aspects, such as high production cost, high-temperature processing, flexible substrate incompatibility, limited spectral range or a requirement for cryogenic cooling for efficient operation. Recently lead sulphide (PbS) nanocrystals have emerged as one of the most promising new materials for photodetector fabrication. They offer several advantages including low-cost manufacturing, solution processability, size-tunable spectral sensitivity and flexible substrate compatibility, and they have achieved figures of merit outperforming conventional photodetectors. We review the underlying concepts, breakthroughs and remaining challenges in photodetector technologies based on PbS nanocrystals.

  9. Irradiation induced dislocations and vacancy generation in single crystal yttria stabilized zirconia

    NASA Astrophysics Data System (ADS)

    Johnsen, Jill Noel

    A determination of the most effective method of introducing defect clusters and forming nanocrystals in single crystal Yttria Stabilized Zirconia (YSZ) to increase its oxygen ion conductivity for use in solid oxide fuel cell has been investigated using several techniques. High-energy particle irradiation using 800 keV electrons and 20 MeV protons and Ar+ and Xe ++ ion implantation promote the introduction of defects. Thermal annealing and temperature cycling were performed both ex-situ and in-situ in a TEM to study the dynamic recovery behavior of the defects introduced by irradiation and the nucleation and growth of nanocrystals. This analysis found multiple outcomes to both light particle irradiation, with electrons and protons, and heavy charged particle irradiation, including Ar+ and Xe++. Electron irradiation produced very few vacancies, and therefore a very low dislocation density after high temperature annealing. The Xe++ and Ar+ irradiated samples show a high density of vacancy clusters. Evidence also shows nanocrystalline formation in Xe++ irradiated YSZ after a 20 minute anneal at 1040°C with grain sizes on the order of 10--50nm. Defect clusters formed in samples exposed to 20.4 MeV protons with a fluence of 1.00 x 1013 p/cm2 and thermally annealed at temperatures between 800°C and 1000°C. The samples became polycrystalline after a 75 minute anneal with a grain size of approximately 20nm and remained polycrystalline throughout the 120 minute anneal. Impedance spectroscopy measurements were conducted on proton irradiated samples with various annealing conditions. From the impedance results it is concluded that the minimum annealing conditions for a noticeable improvement in ionic conductivity are 1000°C for 2 hours and the 1200°C for 1 hour. These annealing conditions correspond to the conditions for nanocrystal formation as show by microstructural characterization. The proton irradiated YSZ ceramic samples annealed under these conditions were found

  10. Enhanced structural stability of nanoporous zirconia under irradiation of He

    SciTech Connect

    Yang, Tengfei; Huang, Xuejun; Wang, Chenxu; Zhang, Yanwen; Xue, Jianming; Yan, Sha; Wang, Yuguang

    2012-01-01

    This work reports a greatly enhanced tolerance for He irradiation-induced swelling in nanocrystalline zirconia film with interconnected nanoporous structure (hereinafter referred as to NC-C). Compared to bulk yttria-stabilized zirconia (YSZ) and another nanocrystalline zirconia film only with discrete nano voids (hereinafter referred as to NC-V), the NC-C film reveals good tolerance for irradiation of high-fluence He. No appreciable surface blistering can be found even at the highest fluence of 6 1017 cm2 in NCC film. From TEM analysis of as-irradiated samples, the enhanced tolerance for volume swelling in NCC film is attributed to the enhanced diffusion mechanism of deposited He via widely distributed nano channels. Furthermore, the growth of grain size is quite small for both nanocrystalline zirconia films after irradiation, which is ascribed to the decreasing of area of grain boundary due to loose structure and low energy of primary knock-on atoms for He ions.

  11. Dehydration and crystallization kinetics of zirconia-yttria gels

    SciTech Connect

    Ramanathan, S.; Muraleedharan, R.V.; Roy, S.K.; Nayar, P.K.K.

    1995-02-01

    Zirconia and zirconia-yttria gels containing 4 and 8 mol% yttria were obtained by coprecipitation and drying at 373 K. The dehydration and crystallization behavior of the dried gels was studied by DSC, TG, and XRD. The gels undergo elimination of water over a wide temperature range of 373--673 K. The peak temperature of the endotherm corresponding to dehydration and the kinetic constants for the process were not influenced by the yttria content of the gel. The enthalpy of dehydration observed was in good agreement with the heat of vaporization data. The dehydration was followed by a sharp exothermic crystallization process. The peak temperature of the exotherm and the activation energy of the process increased with an increase in yttria content, while the enthalpy of crystallization showed a decrease. The ``glow effect`` reduced with increasing yttria content. Pure zirconia crystallizes in the tetragonal form while the zirconia containing 4 and 8 mol% yttria appears to crystallize in the cubic form.

  12. The role of Nb in intensity increase of Er ion upconversion luminescence in zirconia

    SciTech Connect

    Smits, K. Sarakovskis, A.; Grigorjeva, L.; Millers, D.; Grabis, J.

    2014-06-07

    It is found that Nb co-doping increases the luminescence and upconversion luminescence intensity in rare earth doped zirconia. Er and Yb-doped nanocrystalline samples with or without Nb co-doping were prepared by sol-gel method and thermally annealed to check for the impact of phase transition on luminescence properties. Phase composition and grain sizes were examined by X-ray diffraction; the morphology was checked by scanning- and high-resolution transmission electron microscopes. Both steady-state and time-resolved luminescence were studied. Comparison of samples with different oxygen vacancy concentrations and different Nb concentrations confirmed the known assumption that oxygen vacancies are the main agents for tetragonal or cubic phase stabilization. The oxygen vacancies quench the upconversion luminescence; however, they also prevent agglomeration of rare-earth ions and/or displacement of rare-earth ions to grain surfaces. It is found that co-doping with Nb ions significantly (>20 times) increases upconversion luminescence intensity. Hence, ZrO{sub 2}:Er:Yb:Nb nanocrystals may show promise for upconversion applications.

  13. The Surface Chemistry of Metal Chalcogenide Nanocrystals

    NASA Astrophysics Data System (ADS)

    Anderson, Nicholas Charles

    The surface chemistry of metal chalcogenide nanocrystals is explored through several interrelated analytical investigations. After a brief discussion of the nanocrystal history and applications, molecular orbital theory is used to describe the electronic properties of semiconductors, and how these materials behave on the nanoscale. Quantum confinement plays a major role in dictating the optical properties of metal chalcogenide nanocrystals, however surface states also have an equally significant contribution to the electronic properties of nanocrystals due to the high surface area to volume ratio of nanoscale semiconductors. Controlling surface chemistry is essential to functionalizing these materials for biological imaging and photovoltaic device applications. To better understand the surface chemistry of semiconducting nanocrystals, three competing surface chemistry models are presented: 1.) The TOPO model, 2.) the Non-stoichiometric model, and 3.) the Neutral Fragment model. Both the non-stoichiometric and neutral fragment models accurately describe the behavior of metal chalcogenide nanocrystals. These models rely on the covalent bond classification system, which divides ligands into three classes: 1.) X-type, 1-electron donating ligands that balance charge with excess metal at the nanocrystal surface, 2.) L-type, 2-electron donors that bind metal sites, and 3.) Z-type, 2-electron acceptors that bind chalcogenide sites. Each of these ligand classes is explored in detail to better understand the surface chemistry of metal chalcogenide nanocrystals. First, chloride-terminated, tri-n-butylphosphine (Bu 3P) bound CdSe nanocrystals were prepared by cleaving carboxylate ligands from CdSe nanocrystals with chlorotrimethylsilane in Bu3P solution. 1H and 31P{1H} nuclear magnetic resonance spectra of the isolated nanocrystals allowed assignment of distinct signals from several free and bound species, including surface-bound Bu3P and [Bu3P-H]+[Cl]- ligands as well as a Bu

  14. Zirconia crowns - the new standard for single-visit dentistry?

    PubMed

    Wiedhahn, Klaus; Fritzsche, Günter; Wiedhahn, Claudine; Schenk, Olaf

    2016-01-01

    Zirconia crowns combine the advantages of metal restorations, such as minimally invasive tooth preparation and ease of cementation, with those of full ceramic crowns, such as low thermal conductivity and tooth color. With the introduction of a high-speed sintering procedure, it is possible to produce and cement zirconia crowns and small monolithic bridges in a Cerec Single Visit procedure. This new procedure is compared to established chairside methods.

  15. Biaxial flexural strength of bilayered zirconia using various veneering ceramics

    PubMed Central

    Chantranikul, Natravee

    2015-01-01

    PURPOSE The aim of this study was to evaluate the biaxial flexural strength (BFS) of one zirconia-based ceramic used with various veneering ceramics. MATERIALS AND METHODS Zirconia core material (Katana) and five veneering ceramics (Cerabien ZR; CZR, Lava Ceram; LV, Cercon Ceram Kiss; CC, IPS e.max Ceram; EM and VITA VM9; VT) were selected. Using the powder/liquid layering technique, bilayered disk specimens (diameter: 12.50 mm, thickness: 1.50 mm) were prepared to follow ISO standard 6872:2008 into five groups according to veneering ceramics as follows; Katana zirconia veneering with CZR (K/CZR), Katana zirconia veneering with LV (K/LV), Katana zirconia veneering with CC (K/CC), Katana zirconia veneering with EM (K/EM) and Katana zirconia veneering with VT (K/VT). After 20,000 thermocycling, load tests were conducted using a universal testing machine (Instron). The BFS were calculated and analyzed with one-way ANOVA and Tukey HSD (α=0.05). The Weibull analysis was performed for reliability of strength. The mode of fracture and fractured surface were observed by SEM. RESULTS It showed that K/CC had significantly the highest BFS, followed by K/LV. BFS of K/CZR, K/EM and K/VT were not significantly different from each other, but were significantly lower than the other two groups. Weibull distribution reported the same trend of reliability as the BFS results. CONCLUSION From the result of this study, the BFS of the bilayered zirconia/veneer composite did not only depend on the Young's modulus value of the materials. Further studies regarding interfacial strength and sintering factors are necessary to achieve the optimal strength. PMID:26576251

  16. Synthesis and catalytic activity of polysaccharide templated nanocrystalline sulfated zirconia

    SciTech Connect

    Sherly, K. B.; Rakesh, K.

    2014-01-28

    Nanoscaled materials are of great interest due to their unique enhanced optical, electrical and magnetic properties. Sulfate-promoted zirconia has been shown to exhibit super acidic behavior and high activity for acid catalyzed reactions. Nanocrystalline zirconia was prepared in the presence of polysaccharide template by interaction between ZrOCl{sub 2}⋅8H{sub 2}O and chitosan template. The interaction was carried out in aqueous phase, followed by the removal of templates by calcination at optimum temperature and sulfation. The structural and textural features were characterized by powder XRD, TG, SEM and TEM. XRD patterns showed the peaks of the diffractogram were in agreement with the theoretical data of zirconia with the catalytically active tetragonal phase and average crystalline size of the particles was found to be 9 nm, which was confirmed by TEM. TPD using ammonia as probe, FTIR and BET surface area analysis were used for analyzing surface features like acidity and porosity. The BET surface area analysis showed the sample had moderately high surface area. FTIR was used to find the type species attached to the surface of zirconia. UV-DRS found the band gap of the zirconia was found to be 2.8 eV. The benzylation of o-xylene was carried out batchwise in atmospheric pressure and 433K temperature using sulfated zirconia as catalyst.

  17. Chemical interaction mechanism of 10-MDP with zirconia.

    PubMed

    Nagaoka, Noriyuki; Yoshihara, Kumiko; Feitosa, Victor Pinheiro; Tamada, Yoshiyuki; Irie, Masao; Yoshida, Yasuhiro; Van Meerbeek, Bart; Hayakawa, Satoshi

    2017-03-30

    Currently, the functional monomer 10-methacryloyloxy-decyl-dihydrogen-phosphate (10-MDP) was documented to chemically bond to zirconia ceramics. However, little research has been conducted to unravel the underlying mechanisms. This study aimed to assess the chemical interaction and to demonstrate the mechanisms of coordination between 10-MDP and zirconium oxide using (1)H and (31)P magic angle spinning (MAS) nuclear magnetic resonance (NMR) and two dimensional (2D) (1)H → (31)P heteronuclear correlation (HETCOR) NMR. In addition, shear bond-strength (SBS) tests were conducted to determine the effect of 10-MDP concentration on the bonding effectiveness to zirconia. These SBS tests revealed a 10-MDP concentration-dependent SBS with a minimum of 1-ppb 10-MDP needed. (31)P-NMR revealed that one P-OH non-deprotonated of the PO3H2 group from 10-MDP chemically bonded strongly to zirconia. (1)H-(31)P HETCOR NMR indicated that the 10-MDP monomer can be adsorbed onto the zirconia particles by hydrogen bonding between the P=O and Zr-OH groups or via ionic interactions between partially positive Zr and deprotonated 10-MDP (P-O(-)). The combination of (1)H NMR and 2D (1)H-(31)P HETCOR NMR enabled to describe the different chemical states of the 10-MDP bonds with zirconia; they not only revealed ionic but also hydrogen bonding between 10-MDP and zirconia.

  18. Synthesis and catalytic activity of polysaccharide templated nanocrystalline sulfated zirconia

    NASA Astrophysics Data System (ADS)

    Sherly, K. B.; Rakesh, K.

    2014-01-01

    Nanoscaled materials are of great interest due to their unique enhanced optical, electrical and magnetic properties. Sulfate-promoted zirconia has been shown to exhibit super acidic behavior and high activity for acid catalyzed reactions. Nanocrystalline zirconia was prepared in the presence of polysaccharide template by interaction between ZrOCl2ṡ8H2O and chitosan template. The interaction was carried out in aqueous phase, followed by the removal of templates by calcination at optimum temperature and sulfation. The structural and textural features were characterized by powder XRD, TG, SEM and TEM. XRD patterns showed the peaks of the diffractogram were in agreement with the theoretical data of zirconia with the catalytically active tetragonal phase and average crystalline size of the particles was found to be 9 nm, which was confirmed by TEM. TPD using ammonia as probe, FTIR and BET surface area analysis were used for analyzing surface features like acidity and porosity. The BET surface area analysis showed the sample had moderately high surface area. FTIR was used to find the type species attached to the surface of zirconia. UV-DRS found the band gap of the zirconia was found to be 2.8 eV. The benzylation of o-xylene was carried out batchwise in atmospheric pressure and 433K temperature using sulfated zirconia as catalyst.

  19. Porous alumina and zirconia ceramics with tailored thermal conductivity

    NASA Astrophysics Data System (ADS)

    Gregorová, E.; Pabst, W.; Sofer, Z.; Jankovský, O.; Matějíček, J.

    2012-11-01

    The thermal conductivity of porous ceramics can be tailored by slip casting and uniaxial dry pressing, using either fugitive pore formers (saccharides) or partial sintering. Porous alumina and zirconia ceramics have been prepared using appropriate powder types (ungranulated for casting, granulated for pressing) and identical firing regimes (but different maximum temperatures in the case of partial sintering). Thermal diffusivities have been measured by the laser- and xenon-flash method and transformed into relative thermal conductivities, which enable a temperature-independent comparison between different materials. While the porosity can be controlled in a similar way for both materials when using pore formers, partial sintering exhibits characteristic differences between alumina and zirconia (for alumina porosities below 45 %, full density above 1600 °C, for zirconia porosities below 60 %, full density above 1300 °C). The different compaction behavior of alumina and zirconia (porosity after pressing 0.465 and 0.597, respectively) is reflected in the fact that for alumina the relative conductivity data of partially sintered materials are below the exponential prediction, while for zirconia they coincide with the latter. Notwithstanding these characteristic differences, for both alumina and zirconia it is possible to tailor the thermal conductivity from 100 % down to approx. 15 % of the solid phase value.

  20. Chemical interaction mechanism of 10-MDP with zirconia

    PubMed Central

    Nagaoka, Noriyuki; Yoshihara, Kumiko; Feitosa, Victor Pinheiro; Tamada, Yoshiyuki; Irie, Masao; Yoshida, Yasuhiro; Van Meerbeek, Bart; Hayakawa, Satoshi

    2017-01-01

    Currently, the functional monomer 10-methacryloyloxy-decyl-dihydrogen-phosphate (10-MDP) was documented to chemically bond to zirconia ceramics. However, little research has been conducted to unravel the underlying mechanisms. This study aimed to assess the chemical interaction and to demonstrate the mechanisms of coordination between 10-MDP and zirconium oxide using 1H and 31P magic angle spinning (MAS) nuclear magnetic resonance (NMR) and two dimensional (2D) 1H → 31P heteronuclear correlation (HETCOR) NMR. In addition, shear bond-strength (SBS) tests were conducted to determine the effect of 10-MDP concentration on the bonding effectiveness to zirconia. These SBS tests revealed a 10-MDP concentration-dependent SBS with a minimum of 1-ppb 10-MDP needed. 31P-NMR revealed that one P-OH non-deprotonated of the PO3H2 group from 10-MDP chemically bonded strongly to zirconia. 1H-31P HETCOR NMR indicated that the 10-MDP monomer can be adsorbed onto the zirconia particles by hydrogen bonding between the P=O and Zr-OH groups or via ionic interactions between partially positive Zr and deprotonated 10-MDP (P-O−). The combination of 1H NMR and 2D 1H-31P HETCOR NMR enabled to describe the different chemical states of the 10-MDP bonds with zirconia; they not only revealed ionic but also hydrogen bonding between 10-MDP and zirconia. PMID:28358121

  1. Evidence for photo-induced monoclinic metallic VO{sub 2} under high pressure

    SciTech Connect

    Hsieh, Wen-Pin Mao, Wendy L.; Trigo, Mariano; Reis, David A.; Andrea Artioli, Gianluca; Malavasi, Lorenzo

    2014-01-13

    We combine ultrafast pump-probe spectroscopy with a diamond-anvil cell to decouple the insulator-metal electronic transition from the lattice symmetry changing structural transition in the archetypal strongly correlated material vanadium dioxide. Coherent phonon spectroscopy enables tracking of the photo-excited phonon vibrational frequencies of the low temperature, monoclinic (M{sub 1})-insulating phase that transforms into the metallic, tetragonal rutile structured phase at high temperature or via non-thermal photo-excitations. We find that in contrast with ambient pressure experiments where strong photo-excitation promptly induces the electronic transition along with changes in the lattice symmetry, at high pressure, the coherent phonons of the monoclinic (M{sub 1}) phase are still clearly observed upon the photo-driven phase transition to a metallic state. These results demonstrate the possibility of synthesizing and studying transient phases under extreme conditions.

  2. Fabrication and photoelectrocatalytic properties of nanocrystalline monoclinic BiVO4 thin-film electrode.

    PubMed

    Zhou, Bin; Qu, Jiuhui; Zhao, Xu; Liu, Huijuan

    2011-01-01

    Monoclinic bismuth vanadate (BiVO4) thin film was fabricated on indium-tin oxide glass from an amorphous heteronuclear complex via dip-coating. After annealation at 400, 500, and 600 degrees C, the thin films were characterized by X-ray diffraction, field emission scanning electron microscopy, X-ray photoelectron spectroscopy, and UV-Vis spectrophotometry. The BiVO4 particles on the ITO glass surface had a monoclinic structure. The UV-Visible diffuse reflection spectra showed the BiVO4 thin film had photoabsorption properties, with a band gap around 2.5 eV. In addition, the thin film showed high visible photocatalytic activities towards 2,4-dichlorophenol and Bisphenol A degradation under visible light irradiation (lambda > 420 nm). Over 90% of the two organic pollutants were removed in 5 hr. A possible degradation mechanism of 2,4-dichlorophenol were also studied.

  3. Raman analysis of monoclinic Cu2SnS3 thin films

    NASA Astrophysics Data System (ADS)

    Berg, Dominik M.; Djemour, Rabie; Gütay, Levent; Siebentritt, Susanne; Dale, Phillip J.; Fontane, Xavier; Izquierdo-Roca, Victor; Pérez-Rodriguez, Alejandro

    2012-05-01

    Secondary phases like Cu2SnS3 are major obstacles for kesterite thin film solar cell applications. We prepare Cu2SnS3 using identical annealing conditions as used for the kesterite films. By x-ray diffraction, the crystal structure of Cu2SnS3 was identified as monoclinic. Polarization-dependent Raman investigations allowed the identification of the dominant peaks at 290 cm-1 and 352 cm-1 with the main A' symmetry vibrational modes from the monoclinic Cu2SnS3 phase. Furthermore, micro-resolved Raman investigations revealed local variations in the spectra that are attributed to a secondary phase (possibly Cu2Sn3S7). This exemplifies the abilities of micro-resolved Raman measurements in the detection of secondary phases.

  4. First-principles study of structural and elastic properties of monoclinic and orthorhombic BiMnO3.

    PubMed

    Mei, Zhi-Gang; Shang, Shun-Li; Wang, Yi; Liu, Zi-Kui

    2010-07-28

    The structural and elastic properties of BiMnO(3) with monoclinic (C 2/c) and orthorhombic (Pnma) ferromagnetic (FM) structures have been studied by first-principles calculations within LDA + U and GGA + U approaches. The equilibrium volumes and bulk moduli of BiMnO(3) phases are evaluated by equation of state (EOS) fittings, and the bulk properties predicted by LDA + U calculations are in better agreement with experiment. The orthorhombic phase is found to be more stable than the monoclinic phase at ambient pressure. A monoclinic to monoclinic phase transition is predicted to occur at a pressure of about 10 GPa, which is ascribed to magnetism versus volume instability of monoclinic BiMnO(3). The single-crystal elastic stiffness constants c(ij)s of the monoclinic and orthorhombic phases are investigated using the stress-strain method. The c(46) of the monoclinic phase is predicted to be negative. In addition, the polycrystalline elastic properties including bulk modulus, shear modulus, Young's modulus, bulk modulus-shear modulus ratio, Poisson's ratio, and elastic anisotropy ratio are determined based on the calculated elastic constants. The presently predicted phase transition and elastic properties open new directions for investigation of the phase transitions in BiMnO(3), and provide helpful guidance for the future elastic constant measurements.

  5. Changes in mobility of plastic crystal ethanol during its transformation into the monoclinic crystal state

    SciTech Connect

    Sanz, Alejandro Nogales, Aurora; Ezquerra, Tiberio A.; Puente-Orench, Inés; Jiménez-Ruiz, Mónica

    2014-02-07

    Transformation of deuterated ethanol from the plastic crystal phase into the monoclinic one is investigated by means of a singular setup combining simultaneously dielectric spectroscopy with neutron diffraction. We postulate that a dynamic transition from plastic crystal to supercooled liquid-like configuration through a deep reorganization of the hydrogen-bonding network must take place as a previous step of the crystallization process. Once these precursor regions are formed, subsequent crystalline nucleation and growth develop with time.

  6. Light transmittance of zirconia as a function of thickness and microhardness of resin cements under different thicknesses of zirconia

    PubMed Central

    Egilmez, Ferhan; Ergun, Gulfem; Kaya, Bekir M.

    2013-01-01

    Objective: The objective of this study was to compare microhardness of resin cements under different thicknesses of zirconia and the light transmittance of zirconia as a function of thickness. Study design: A total of 126 disc-shaped specimens (2 mm in height and 5 mm in diameter) were prepared from dual-cured resin cements (RelyX Unicem, Panavia F and Clearfil SA cement). Photoactivation was performed by using quartz tungsten halogen and light emitting diode light curing units under different thicknesses of zirconia. Then the specimens (n=7/per group) were stored in dry conditions in total dark at 37°C for 24 h. The Vicker’s hardness test was performed on the resin cement layer with a microhardness tester. Statistical significance was determined using multifactorial analysis of variance (ANOVA) (alpha=.05). Light transmittance of different thicknesses of zirconia (0.3, 0.5 and 0.8 mm) was measured using a hand-held radiometer (Demetron, Kerr). Data were analyzed using one-way ANOVA test (alpha=.05). Results: ANOVA revealed that resin cement and light curing unit had significant effects on microhardness (p < 0.001). Additionally, greater zirconia thickness resulted in lower transmittance. There was no correlation between the amount of light transmitted and microhardness of dual-cured resin cements (r = 0.073, p = 0.295). Conclusion: Although different zirconia thicknesses might result in insufficient light transmission, dual-cured resin cements under zirconia restorations could have adequate microhardness. Key words:Zirconia, microhardness, light transmittance, resin cement. PMID:23385497

  7. The creation of modulated monoclinic aperiodic composites in n-alkane/urea compounds

    SciTech Connect

    Mariette, Céline; Guérin, Laurent; Rabiller, Philippe; Chen, Yu-Sheng; Bosak, Alexei; Popov, Alexander; Hollingsworth, Mark D.; Toudic, Bertrand

    2014-09-12

    n-Dodecane/urea is a member of the prototype series of n-alkane/urea inclusion compounds. At room temperature, it presents a quasi-one dimensional liquid-like state for the confined guest molecules within the rigid, hexagonal framework of the urea host. At lower temperatures, we report the existence of two other phases. Below Tc=248 K there appears a phase with rank four superspace group P6122(00γ), the one typically observed at room temperature in n-alkane/urea compounds with longer guest molecules. A misfit parameter, defined by the ratio γ=ch/cg (chost/cguest), is found to be 0.632±0.005. Below Tc1=123 K, a monoclinic modulated phase is created with a constant shift along c of the guest molecules in adjacent channels. The maximal monoclinic space group for this structure is P1211(α0γ). We discuss analogies and differences with n-heptane/urea, which also presents a monoclinic, modulated low-temperature phase.

  8. The creation of modulated monoclinic aperiodic composites in n-alkane/urea compounds

    DOE PAGES

    Mariette, Céline; Guérin, Laurent; Rabiller, Philippe; ...

    2014-09-12

    n-Dodecane/urea is a member of the prototype series of n-alkane/urea inclusion compounds. At room temperature, it presents a quasi-one dimensional liquid-like state for the confined guest molecules within the rigid, hexagonal framework of the urea host. At lower temperatures, we report the existence of two other phases. Below Tc=248 K there appears a phase with rank four superspace group P6122(00γ), the one typically observed at room temperature in n-alkane/urea compounds with longer guest molecules. A misfit parameter, defined by the ratio γ=ch/cg (chost/cguest), is found to be 0.632±0.005. Below Tc1=123 K, a monoclinic modulated phase is created with a constantmore » shift along c of the guest molecules in adjacent channels. The maximal monoclinic space group for this structure is P1211(α0γ). We discuss analogies and differences with n-heptane/urea, which also presents a monoclinic, modulated low-temperature phase.« less

  9. Remarkable features in lattice-parameter ratios of crystals. II. Monoclinic and triclinic crystals.

    PubMed

    de Gelder, R; Janner, A

    2005-06-01

    The frequency distributions of monoclinic crystals as a function of the lattice-parameter ratios resemble the corresponding ones of orthorhombic crystals: an exponential component, with more or less pronounced sharp peaks, with in general the most important peak at the ratio value 1. In addition, the distribution as a function of the monoclinic angle beta has a sharp peak at 90 degrees and decreases sensibly at larger angles. Similar behavior is observed for the three triclinic angular parameters alpha, beta and gamma, with characteristic differences between the organic and metal-organic, bio-macromolecular and inorganic crystals, respectively. The general behavior observed for the hexagonal, tetragonal, orthorhombic, monoclinic and triclinic crystals {in the first part of this series [de Gelder & Janner (2005). Acta Cryst. B61, 287-295] and in the present case} is summarized and commented. The data involved represent 366 800 crystals, with lattice parameters taken from the Cambridge Structural Database, CSD (294 400 entries), the Protein Data Bank, PDB (18 800 entries), and the Inorganic Crystal Structure Database, ICSD (53 600 entries). A new general structural principle is suggested.

  10. Evaluation of physicochemical properties, and antimicrobial efficacy of monoclinic sulfur-nanocolloid

    NASA Astrophysics Data System (ADS)

    Roy Choudhury, Samrat; Mandal, Amrita; Chakravorty, Dipankar; Gopal, Madhuban; Goswami, Arunava

    2013-04-01

    Stable nanocolloids of monoclinic sulfur (β-SNPs) were prepared through `water-in-oil microemulsion technique' at room temperature after suitable modifications of the surface. The morphology (rod shaped; 50 nm in diameter) and allotropic nature (monoclinic) of the SNPs were investigated with Transmission Electron Microscopy and X-ray Diffraction technique. The surface modification, colloidal stability, and surface topology of β-SNPs were evaluated with Fourier Transform Infrared Spectroscopy, zeta potential analysis, and Atomic Force Microscopy. Thermal decomposition pattern of these nanosized particles was determined by Thermo Gravimetric Analysis (TGA). β-SNPs-colloids expressed excellent antimicrobial activities against a series of fungal and bacterial isolates with prominent deformities at their surface. In contrast, insignificant cytotoxicity was achieved against the human derived hepatoma (HepG2) cell line upon treatment with β-SNPs. A simultaneous study was performed to determine the stock concentration of β-SNP-colloids using a novel high phase liquid chromatographic method. Cumulative results of this study hence, elucidate the stabilization of nanosized monoclinic sulfur at room temperature and their potential antimicrobial efficacy over micron-sized sulfur.

  11. Metastable monoclinic ZnMoO4: hydrothermal synthesis, optical properties and photocatalytic performance.

    PubMed

    Lv, Li; Tong, Wenming; Zhang, Yanbing; Su, Yiguo; Wang, Xiaojing

    2011-11-01

    Metastable monoclinic ZnMoO4 was successfully synthesized via a hydrothermal route with variation of reaction temperatures and time at pH value of 5.7. Systematic sample characterizations were carried out, including X-ray powder diffraction, scanning electron microscopy, Fourier transformed infrared spectra, UV-visible diffuse reflectance spectra, and photoluminescence spectra. The results show that all as-prepared ZnMoO4 samples were demonstrated to crystallize in a pure-phase of monoclinic wolframite structure. All samples were formed in plate-like morphology. Six IR active vibrational bands were observed in the wave number range of 400-900 cm(-1). The band gap of as-prepared ZnMoO4 was estimated to be 2.86 eV by Tauc equation. Photoluminescence measurement indicates that as-prepared ZnMoO4 exhibits a broad blue-green emission under excitation wavelength of 280 nm at room temperature. Photocatalytic activity of as-prepared ZnMoO4 was examined by monitoring the degradation of methyl orange dye in an aqueous solution under UV radiation of 365 nm. The as-prepared ZnMoO4 obtained at 180 degrees C for 40 h showed the best photocatalytic activity with completing degradation of MO in irradiation time of 120 min. Consequently, monoclinic ZnMoO4 proved to be an efficient near visible light photocatalyst.

  12. Evaluation of structure and material properties of RF magnetron sputter-deposited yttria-stabilized zirconia thin films

    NASA Astrophysics Data System (ADS)

    Piascik, Jeffrey Robert

    Over the past several decades, research has focused on utilizing ceramic materials in new technological applications. Their uses have been primarily in applications that involve high temperatures or corrosive environments. Unfortunately, ceramic materials have been limited especially since they can be brittle, failing in a sudden and catastrophic manner. A strong emphasis on understanding mechanical properties of ceramics and ways to improving their strength and toughness, has led to many new technologies. The present work is part of a larger research initiative that is aimed at using RF magnetron sputter deposition of yttria-stabilized zirconia to improve the fracture toughness of brittle substrates (more specifically dental ceramics). Partially-stabilized zirconia (PSZ) has been studied extensively, due to its high temperature stability and stress-induced tetragonal to monoclinic (T⇒M) martensitic phase transformation. RF magnetron sputtering was chosen as the deposition method because of its versatility, especially the ability to deposit oxides at low temperatures. Initial investigations focused on the development of process-structure-properties of YSZ sputtered deposited thin films. The YSZ thin films were deposited over a range of temperatures (22--300°C), pressures (5--25 mTorr), and gas compositions (Ar:O2 ratio). Initial studies characterized a select set of properties in relation to deposition parameters including: refractive index, structure, and film stress. X-ray Diffraction (XRD) showed that the films are comprised of mainly monoclinic and tetragonal crystal phases. The film refractive index determined by prism coupling, depends strongly on deposition conditions and ranged from 1.959 to 2.223. Wafer bow measurements indicate that the sputtered YSZ films can have initial stress ranging from 86 MPa tensile to 192 MPa compressive, depending on the deposition parameters. Exposure to ambient conditions (25°C, 75% relative humidity) led to large increase

  13. Structure Map for Embedded Binary Alloy Nanocrystals

    SciTech Connect

    Yuan, C.W.; Shin, S.J.; Liao, C.Y.; Guzman, J.; Stone, P.R.; Watanabe, M.; Ager III, J.W.; Haller, E.E.; Chrzan, D.C.

    2008-09-20

    The equilibrium structure of embedded nanocrystals formed from strongly segregating binary-alloys is considered within a simple thermodynamic model. The model identifies two dimensionlessinterface energies that dictate the structure, and allows prediction of the stable structure for anychoice of these parameters. The resulting structure map includes three distinct nanocrystal mor-phologies: core/shell, lobe/lobe, and completely separated spheres.

  14. Hollow nanocrystals and method of making

    DOEpatents

    Alivisatos, A. Paul; Yin, Yadong; Erdonmez, Can Kerem

    2011-07-05

    Described herein are hollow nanocrystals having various shapes that can be produced by a simple chemical process. The hollow nanocrystals described herein may have a shell as thin as 0.5 nm and outside diameters that can be controlled by the process of making.

  15. Pinned emission from ultrasmall cadmium selenide nanocrystals.

    PubMed

    Dukes, Albert D; Schreuder, Michael A; Sammons, Jessica A; McBride, James R; Smith, Nathanael J; Rosenthal, Sandra J

    2008-09-28

    We report pinning of the emission spectrum in ultrasmall CdSe nanocrystals with a diameter of 1.7 nm and smaller. It was observed that the first emission feature ceased to blueshift once the band edge absorption reached 420 nm, though the band edge absorption continued to blueshift with decreasing nanocrystal diameter.

  16. Electronic displays using optically pumped luminescent semiconductor nanocrystals

    DOEpatents

    Weiss, Shimon; Schlam, Michael C; Alivisatos, A. Paul

    2014-03-25

    A multicolor electronic display is based on an array of luminescent semiconductor nanocrystals. Nanocrystals which emit tight of different colors are grouped into pixels. The nanocrystals are optically pumped to produce a multicolor display. Different sized nanocrystals are used to produce the different colors. A variety of pixel addressing systems can be used.

  17. Electronic displays using optically pumped luminescent semiconductor nanocrystals

    DOEpatents

    Weiss, Shimon; Schlamp, Michael C.; Alivisatos, A. Paul

    2010-04-13

    A multicolor electronic display is based on an array of luminescent semiconductor nanocrystals. Nanocrystals which emit light of different colors are grouped into pixels. The nanocrystals are optically pumped to produce a multicolor display. Different sized nanocrystals are used to produce the different colors. A variety of pixel addressing systems can be used.

  18. Electronic displays using optically pumped luminescent semiconductor nanocrystals

    DOEpatents

    Weiss, Shimon; Schlamp, Michael C; Alivisatos, A. Paul

    2014-02-11

    A multicolor electronic display is based on an array of luminescent semiconductor nanocrystals. Nanocrystals which emit light of different colors are grouped into pixels. The nanocrystals are optically pumped to produce a multicolor display. Different sized nanocrystals are used to produce the different colors. A variety of pixel addressing systems can be used.

  19. Electronic displays using optically pumped luminescent semiconductor nanocrystals

    DOEpatents

    Weiss, Shimon; Schlamp, Michael C.; Alivisatos, Paul A.

    2015-11-10

    A multicolor electronic display is based on an array of luminescent semiconductor nanocrystals. Nanocrystals which emit tight of different colors are grouped into pixels. The nanocrystals are optically pumped to produce a multicolor display. Different sized nanocrystals are used to produce the different colors. A variety of pixel addressing systems can be used.

  20. Electronic displays using optically pumped luminescent semiconductor nanocrystals

    DOEpatents

    Weiss, Shimon; Schlamp, Michael C.; Alivisatos, A. Paul

    2015-06-23

    A multicolor electronic display is based on an array of luminescent semiconductor nanocrystals. Nanocrystals which emit light of different colors are grouped into pixels. The nanocrystals are optically pumped to produce a multicolor display. Different sized nanocrystals are used to produce the different colors. A variety of pixel addressing systems can be used.

  1. Electronic displays using optically pumped luminescent semiconductor nanocrystals

    DOEpatents

    Weiss, Shimon; Schlamp, Michael C.; Alivisatos, A. Paul

    2011-09-27

    A multicolor electronic display is based on an array of luminescent semiconductor nanocrystals. Nanocrystals which emit light of different colors are grouped into pixels. The nanocrystals are optically pumped to produce a multicolor display. Different sized nanocrystals are used to produce the different colors. A variety of pixel addressing systems can be used.

  2. Electronic displays using optically pumped luminescent semiconductor nanocrystals

    DOEpatents

    Weiss, Shimon; Schlamp, Michael C.; Alivisatos, A. Paul

    2005-03-08

    A multicolor electronic display is based on an array of luminescent semiconductor nanocrystals. Nanocrystals which emit light of different colors are grouped into pixels. The nanocrystals are optically pumped to produce a multicolor display. Different sized nanocrystals are used to produce the different colors. A variety of pixel addressing systems can be used.

  3. pH control of the structure, composition, and catalytic activity of sulfated zirconia

    SciTech Connect

    Ivanov, Vladimir K.; Baranchikov, Alexander Ye.; Kopitsa, Gennady P.; Lermontov, Sergey A.; Yurkova, Lyudmila L.; Gubanova, Nadezhda N.; Ivanova, Olga S.; Lermontov, Anatoly S.; Rumyantseva, Marina N.; Vasilyeva, Larisa P.; Sharp, Melissa; Pranzas, P. Klaus; Tretyakov, Yuri D.

    2013-02-15

    We report a detailed study of structural and chemical transformations of amorphous hydrous zirconia into sulfated zirconia-based superacid catalysts. Precipitation pH is shown to be the key factor governing structure, composition and properties of amorphous sulfated zirconia gels and nanocrystalline sulfated zirconia. Increase in precipitation pH leads to substantial increase of surface fractal dimension (up to {approx}2.7) of amorphous sulfated zirconia gels, and consequently to increase in specific surface area (up to {approx}80 m{sup 2}/g) and simultaneously to decrease in sulfate content and total acidity of zirconia catalysts. Complete conversion of hexene-1 over as synthesized sulfated zirconia catalysts was observed even under ambient conditions. - Graphical abstract: Surface fractal dimension of amorphous sulfated zirconia and specific surface area and catalytic activity of crystalline sulfated zirconia as a function of precipitation pH. Highlights: Black-Right-Pointing-Pointer Structural transformation of amorphous hydrous zirconia into sulfated zirconia is studied. Black-Right-Pointing-Pointer Precipitation pH controls surface fractal dimension of amorphous zirconia gels. Black-Right-Pointing-Pointer Precipitation pH is the key factor governing properties of sulfated zirconia.

  4. Synthesis and characterization of embedded germanium nanocrystals

    NASA Astrophysics Data System (ADS)

    Xu, Qing

    Isotopically pure Ge nanocrystals have been synthesized by ion implantation followed by thermal annealing in amorphous silica and crystalline sapphire matrix. The structure, and the mechanical and thermal properties of the two systems are studied and compared. Ge cluster nucleation during implantation is observed in as-implanted silica samples. It results in the wide size distribution observed after thermal annealing. Theoretical calculations predict that if the nucleation during implantation can be suppressed, a much narrower size distribution is achievable. As-grown Ge nanocrystals are under large compressive stress, 1.2GPa for nanocrystals embedded in silica, and 4GPa for those embedded in sapphire. The stress can be gradually relieved by vapor etching, liberating the nanocrystals from the matrix as well as post-growth thermal treatments. One of the main sources of the stress observed in the sapphire system is the volume expansion of Ge clusters in the liquid/solid phase transformation which occurs during the cooling process from annealing temperature to room temperature, as the density of liquid Ge is larger by 4.6% than that of solid Ge. The large stress and damage in the sapphire matrix lead to a unique double-peak size distribution of the Ge nanocrystals. However, the in situ transmission electron microscopy (TEM) experiments indicate that the Ge nanocrystals embedded in silica are already in their solid phase at the annealing temperature. Therefore, the stress originates from other sources. Vapor etching with HF solutions enables a gradual exposure of embedded Ge nanocrystals in SiO2, while the liquid etching in HF solution leaves fully liberated Ge nanocrystals loosely packed on the Si substrate. Transfer of liberated Ge nanocrystals to other surfaces is achieved by solution dispersion and subsequent evaporation. The patterning of nanocrystals has been achieved by a combination of lithography, coimplantation and electron irradiation. The latter one will

  5. Copper Selenide Nanocrystals for Photothermal Therapy

    PubMed Central

    Hessel, Colin M.; Pattani, Varun; Rasch, Michael; Panthani, Matthew G.; Koo, Bonil; Tunnell, James W.; Korgel, Brian A.

    2011-01-01

    Ligand-stabilized copper selenide (Cu2−xSe) nanocrystals, approximately 16 nm in diameter, were synthesized by a colloidal hot injection method and coated with amphiphilic polymer. The nanocrystals readily disperse in water and exhibit strong near infrared (NIR) optical absorption with a high molar extinction coefficient of 7.7 × 107 cm−1 M−1 at 980 nm. When excited with 800 nm light, the Cu2−xSe nanocrystals produce significant photothermal heating with a photothermal transduction efficiency of 22%, comparable to nanorods and nanoshells of gold (Au). In vitro photothermal heating of Cu2−xSe nanocrystals in the presence of human colorectal cancer cell (HCT-116) led to cell destruction after 5 minutes of laser irradiation at 33 W/cm2, demonstrating the viabilitiy of Cu2−xSe nanocrystals for photothermal therapy applications. PMID:21553924

  6. Copper selenide nanocrystals for photothermal therapy.

    PubMed

    Hessel, Colin M; Pattani, Varun P; Rasch, Michael; Panthani, Matthew G; Koo, Bonil; Tunnell, James W; Korgel, Brian A

    2011-06-08

    Ligand-stabilized copper selenide (Cu(2-x)Se) nanocrystals, approximately 16 nm in diameter, were synthesized by a colloidal hot injection method and coated with amphiphilic polymer. The nanocrystals readily disperse in water and exhibit strong near-infrared (NIR) optical absorption with a high molar extinction coefficient of 7.7 × 10(7) cm(-1) M(-1) at 980 nm. When excited with 800 nm light, the Cu(2-x)Se nanocrystals produce significant photothermal heating with a photothermal transduction efficiency of 22%, comparable to nanorods and nanoshells of gold (Au). In vitro photothermal heating of Cu(2-x)Se nanocrystals in the presence of human colorectal cancer cell (HCT-116) led to cell destruction after 5 min of laser irradiation at 33 W/cm(2), demonstrating the viabilitiy of Cu(2-x)Se nanocrystals for photothermal therapy applications.

  7. Measuring the Valence of Nanocrystal Surfaces

    SciTech Connect

    Owen, Jonathan Scharle

    2016-11-30

    The goal of this project is to understand and control the interplay between nanocrystal stoichiometry, surface ligand binding and exchange, and the optoelectronic properties of semiconductor nanocrystals in solution and in thin solid films. We pursued three research directions with this goal in mind: 1) We characterized nanocrystal stoichiometry and its influence on the binding of L-type and X-type ligands, including the thermodynamics of binding and the kinetics of ligand exchange. 2) We developed a quantitative understanding of the relationship between surface ligand passivation and photoluminescence quantum yield. 3) We developed methods to replace the organic ligands on the nanocrystal with halide ligands and controllably deposit these nanocrystals into thin films, where electrical measurements were used to investigate the electrical transport and internanocrystal electronic coupling.

  8. Monoclinic pseudosymmetry in 2-phenoxybenzenesulfonamide, a triclinic structure having Z' = 4, and spontaneous resolution in monoclinic N-methyl-2-phenoxybenzenesulfonamide.

    PubMed

    Glidewell, Christopher; Low, John N; Skakle, Janet M S; Wardell, James L

    2004-05-01

    2-Phenoxybenzenesulfonamide, C(12)H(11)NO(3)S, (I), crystallizes in space group P-1 with Z' = 4, but the structure closely mimics the monoclinic space group P2(1)/b with Z' = 2. The molecules of (I) are linked by a combination of N-H...O and C-H...O hydrogen bonds into two independent chains of centrosymmetric edge-fused R(2)(2)(18) and R(6)(6)(34) rings. N-Methyl-2-phenoxybenzenesulfonamide, C(13)H(13)NO(3)S, (II), crystallizes in space group P2(1) with Z' = 1, and is an example of spontaneous resolution. The molecules are linked by N-H...O and C-H...O hydrogen bonds into chains of spiro-fused R(2)(2)(12) rings, and these chains are linked into sheets by a single C-H...pi(arene) hydrogen bond.

  9. Exploiting the colloidal nanocrystal library to construct electronic devices

    NASA Astrophysics Data System (ADS)

    Choi, Ji-Hyuk; Wang, Han; Oh, Soong Ju; Paik, Taejong; Sung, Pil; Sung, Jinwoo; Ye, Xingchen; Zhao, Tianshuo; Diroll, Benjamin T.; Murray, Christopher B.; Kagan, Cherie R.

    2016-04-01

    Synthetic methods produce libraries of colloidal nanocrystals with tunable physical properties by tailoring the nanocrystal size, shape, and composition. Here, we exploit colloidal nanocrystal diversity and design the materials, interfaces, and processes to construct all-nanocrystal electronic devices using solution-based processes. Metallic silver and semiconducting cadmium selenide nanocrystals are deposited to form high-conductivity and high-mobility thin-film electrodes and channel layers of field-effect transistors. Insulating aluminum oxide nanocrystals are assembled layer by layer with polyelectrolytes to form high-dielectric constant gate insulator layers for low-voltage device operation. Metallic indium nanocrystals are codispersed with silver nanocrystals to integrate an indium supply in the deposited electrodes that serves to passivate and dope the cadmium selenide nanocrystal channel layer. We fabricate all-nanocrystal field-effect transistors on flexible plastics with electron mobilities of 21.7 square centimeters per volt-second.

  10. Optoelectronic sensitization of carbon nanotubes by CdTe nanocrystals

    NASA Astrophysics Data System (ADS)

    Zebli, B.; Vieyra, H. A.; Carmeli, I.; Hartschuh, A.; Kotthaus, J. P.; Holleitner, A. W.

    2009-05-01

    We investigate the photoconductance of single-walled carbon nanotube-nanocrystal hybrids. The nanocrystals are bound to the nanotubes via molecular recognition. We find that the photoconductance of the hybrids can be adjusted by the absorption characteristics of the nanocrystals. In addition, the photoconductance of the hybrids surprisingly exhibits a slow time constant of about 1 ms after excitation of the nanocrystals. The data are consistent with a bolometrically induced current increase in the nanotubes caused by photon absorption in the nanocrystals.

  11. Bioactive and thermally compatible glass coating on zirconia dental implants.

    PubMed

    Kirsten, A; Hausmann, A; Weber, M; Fischer, J; Fischer, H

    2015-02-01

    The healing time of zirconia implants may be reduced by the use of bioactive glass coatings. Unfortunately, existing glasses are either bioactive like Bioglass 45S5 but thermally incompatible with the zirconia substrate, or they are thermally compatible but exhibit only a very low level of bioactivity. In this study, we hypothesized that a tailored substitution of alkaline earth metals and alkaline metals in 45S5 can lead to a glass composition that is both bioactive and thermally compatible with zirconia implants. A novel glass composition was analyzed using x-ray fluorescence spectroscopy, dilatometry, differential scanning calorimetry, and heating microscopy to investigate its chemical, physical, and thermal properties. Bioactivity was tested in vitro using simulated body fluid (SBF). Smooth and microstructured glass coatings were applied using a tailored spray technique with subsequent thermal treatment. Coating adhesion was tested on implants that were inserted in bovine ribs. The cytocompatibility of the coating was analyzed using L929 mouse fibroblasts. The coefficient of thermal expansion of the novel glass was shown to be slightly lower (11.58 · 10(-6) K(-1)) than that of the zirconia (11.67 · 10(-6) K(-1)). After storage in SBF, the glass showed reaction layers almost identical to the bioactive glass gold standard, 45S5. A process window between 800 °C and 910 °C was found to result in densely sintered and amorphous coatings. Microstructured glass coatings on zirconia implants survived a minimum insertion torque of 60 Ncm in the in vitro experiment on bovine ribs. Proliferation and cytotoxicity of the glass coatings was comparable with the controls. The novel glass composition showed a strong adhesion to the zirconia substrate and a significant bioactive behavior in the SBF in vitro experiments. Therefore, it holds great potential to significantly reduce the healing time of zirconia dental implants.

  12. Bioactive and Thermally Compatible Glass Coating on Zirconia Dental Implants

    PubMed Central

    Kirsten, A.; Hausmann, A.; Weber, M.; Fischer, J.

    2015-01-01

    The healing time of zirconia implants may be reduced by the use of bioactive glass coatings. Unfortunately, existing glasses are either bioactive like Bioglass 45S5 but thermally incompatible with the zirconia substrate, or they are thermally compatible but exhibit only a very low level of bioactivity. In this study, we hypothesized that a tailored substitution of alkaline earth metals and alkaline metals in 45S5 can lead to a glass composition that is both bioactive and thermally compatible with zirconia implants. A novel glass composition was analyzed using x-ray fluorescence spectroscopy, dilatometry, differential scanning calorimetry, and heating microscopy to investigate its chemical, physical, and thermal properties. Bioactivity was tested in vitro using simulated body fluid (SBF). Smooth and microstructured glass coatings were applied using a tailored spray technique with subsequent thermal treatment. Coating adhesion was tested on implants that were inserted in bovine ribs. The cytocompatibility of the coating was analyzed using L929 mouse fibroblasts. The coefficient of thermal expansion of the novel glass was shown to be slightly lower (11.58·10–6 K–1) than that of the zirconia (11.67·10–6 K–1). After storage in SBF, the glass showed reaction layers almost identical to the bioactive glass gold standard, 45S5. A process window between 800 °C and 910 °C was found to result in densely sintered and amorphous coatings. Microstructured glass coatings on zirconia implants survived a minimum insertion torque of 60 Ncm in the in vitro experiment on bovine ribs. Proliferation and cytotoxicity of the glass coatings was comparable with the controls. The novel glass composition showed a strong adhesion to the zirconia substrate and a significant bioactive behavior in the SBF in vitro experiments. Therefore, it holds great potential to significantly reduce the healing time of zirconia dental implants. PMID:25421839

  13. Orthodontic bracket bonding to glazed full-contour zirconia

    PubMed Central

    Kwak, Ji-Young; Jung, Hyo-Kyung; Choi, Il-Kyung

    2016-01-01

    Objectives This study evaluated the effects of different surface conditioning methods on the bond strength of orthodontic brackets to glazed full-zirconia surfaces. Materials and Methods Glazed zirconia (except for the control, Zirkonzahn Prettau) disc surfaces were pre-treated: PO (control), polishing; BR, bur roughening; PP, cleaning with a prophy cup and pumice; HF, hydrofluoric acid etching; AA, air abrasion with aluminum oxide; CJ, CoJet-Sand. The surfaces were examined using profilometry, scanning electron microscopy, and electron dispersive spectroscopy. A zirconia primer (Z-Prime Plus, Z) or a silane primer (Monobond-S, S) was then applied to the surfaces, yielding 7 groups (PO-Z, BR-Z, PP-S, HF-S, AA-S, AA-Z, and CJ-S). Metal bracket-bonded specimens were stored in water for 24 hr at 37℃, and thermocycled for 1,000 cycles. Their bond strengths were measured using the wire loop method (n = 10). Results Except for BR, the surface pre-treatments failed to expose the zirconia substructure. A significant difference in bond strengths was found between AA-Z (4.60 ± 1.08 MPa) and all other groups (13.38 ± 2.57 - 15.78 ± 2.39 MPa, p < 0.05). For AA-Z, most of the adhesive remained on the bracket. Conclusions For bracket bonding to glazed zirconia, a simple application of silane to the cleaned surface is recommended. A zirconia primer should be used only when the zirconia substructure is definitely exposed. PMID:27200278

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

    PubMed Central

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

    2015-01-01

    Monolithic macroporous zirconia (ZrO2) 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 m2 · g−1. The resultant dried gel is amorphous, whereas tetragonal ZrO2 and monoclinic ZrO2 are precipitated at 400 and 600 °C, respectively, without spoiling the macroporous morphology. After solvothermal treatment with an ethanol solution of ammonia, tetragonal ZrO2 monoliths with smooth skeletons and well-defined mesopores can be obtained, and the BET surface area is enhanced to 583.8 m2 · g−1. PMID:27877772

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

    PubMed

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

    2015-04-01

    Monolithic macroporous zirconia (ZrO2) 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 ZrO2 and monoclinic ZrO2 are precipitated at 400 and 600 °C, respectively, without spoiling the macroporous morphology. After solvothermal treatment with an ethanol solution of ammonia, tetragonal ZrO2 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).

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

    NASA Astrophysics Data System (ADS)

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

    2015-04-01

    Monolithic macroporous zirconia (ZrO2) 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 m2 · g-1. The resultant dried gel is amorphous, whereas tetragonal ZrO2 and monoclinic ZrO2 are precipitated at 400 and 600 °C, respectively, without spoiling the macroporous morphology. After solvothermal treatment with an ethanol solution of ammonia, tetragonal ZrO2 monoliths with smooth skeletons and well-defined mesopores can be obtained, and the BET surface area is enhanced to 583.8 m2 · g-1.

  17. Modeling of Zircon (ZrSiO{sub 4}) and Zirconia (ZrO{sub 2}) using ADF-GUI Software

    SciTech Connect

    Lwin, Maung Tin Moe; Amin, Yusoff Mohd; Kassim, Hasan Abu; Kamaluddin, Burhanuddin

    2010-07-07

    Natural zircon (ZrSiO{sub 4}) has very high concentration of Uranium and Thorium of up to 5000 ppm. Radioactive decay process of alpha particles from these impurities affects some changes like several atomic displacements in the crystalline structure of zircon. The amount of track density caused by alpha particles decay process of these radioactive materials in zircon can be decreased with annealing temperatures from 700 deg. C to 980 deg. C. Recently it has been extensively studied as the possible candidate material for immobilization of fission products and actinides. Besides, zirconia (ZrO{sub 2}), product from natural zircon, is widely used in industrial field because it has excellent chemical and mechanical properties at high temperature. Dielectric constant of monoclinic, cubic and tetragonal ZrO{sub 2} can be found in the range of 22, 35 and 50 by computer simulation works. In recent years, atomistic simulations and modeling have been studied, because a lot of computational techniques can offer atomic-level approaching with minimum errors in estimations. One favorite methods is Density Functional Theory (DFT). In this study, ADF-GUI software from DFT will be used to calculate the frequency and absorption Intensity of zircon and zirconia molecules. The data from calculations will be verified with experimental works such as Raman Spectroscopy, AFM and XRD.

  18. Coordinate-Invariant Lyddane-Sachs-Teller Relationship for Polar Vibrations in Materials with Monoclinic and Triclinic Crystal Systems.

    PubMed

    Schubert, Mathias

    2016-11-18

    A coordinate-invariant generalization of the Lyddane-Sachs-Teller relation is presented for polar vibrations in materials with monoclinic and triclinic crystal systems. The generalization is derived from an eigendielectric displacement vector summation approach, which is equivalent to the microscopic Born-Huang description of polar lattice vibrations in the harmonic approximation. An expression for a general oscillator strength is also described for materials with monoclinic and triclinic crystal systems. A generalized factorized form of the dielectric response characteristic for monoclinic and triclinic materials is proposed. The generalized Lyddane-Sachs-Teller relation is found valid for monoclinic β-Ga_{2}O_{3}, where accurate experimental data became available recently from a comprehensive generalized ellipsometry investigation [Phys. Rev. B 93, 125209 (2016)]. Data for triclinic crystal systems can be measured by generalized ellipsometry as well, and are anticipated to become available soon and results can be compared with the generalized relations presented here.

  19. 40 CFR 1065.284 - Zirconia (ZrO2) analyzer.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 34 2013-07-01 2013-07-01 false Zirconia (ZrO2) analyzer. 1065.284... Zirconia (ZrO2) analyzer. (a) Application. You may use a zirconia (ZrO2) analyzer to measure air-to-fuel...O2-based system must meet the linearity verification in § 1065.307. You may use a Zirconia...

  20. In vivo wear performance of highly cross-linked polyethylene vs. yttria stabilized zirconia and alumina stabilized zirconia at a mean seven-year follow-up

    PubMed Central

    2013-01-01

    Background Zirconia was introduced as an alternative to alumina for use in the femoral head. The yttria stabilized zirconia material was improved by adding alumina. We evaluated highly cross-linked polyethylene wear performance of zirconia in total hip arthroplasty. The hypothesis was that alumina stabilized zirconia could decrease highly cross-linked polyethylene wear. Methods Highly cross-linked polyethylene wear was measured with a computerized method (PolyWare) in 91 hips. The steady-state wear rates were measured based on the radiographs from the first year postoperatively to the final follow-up and were compared between hips with yttria stabilized zirconia and alumina stabilized zirconia. Results The steady-state wear rate of highly cross-linked polyethylene against zirconia was 0.02 mm/year at a mean follow-up of 7 years. No significant difference was observed between groups with yttria stabilized zirconia and alumina stabilized zirconia. Conclusions Addition of alumina to the zirconia material failed to show further reduction of highly cross-linked polyethylene wear and our hypothesis was not verified. PMID:23634809

  1. Shear bond strength of indirect composite material to monolithic zirconia

    PubMed Central

    2016-01-01

    PURPOSE This study aimed to evaluate the effect of surface treatments on bond strength of indirect composite material (Tescera Indirect Composite System) to monolithic zirconia (inCoris TZI). MATERIALS AND METHODS Partially stabilized monolithic zirconia blocks were cut into with 2.0 mm thickness. Sintered zirconia specimens were divided into different surface treatment groups: no treatment (control), sandblasting, glaze layer & hydrofluoric acid application, and sandblasting + glaze layer & hydrofluoric acid application. The indirect composite material was applied to the surface of the monolithic zirconia specimens. Shear bond strength value of each specimen was evaluated after thermocycling. The fractured surface of each specimen was examined with a stereomicroscope and a scanning electron microscope to assess the failure types. The data were analyzed using one-way analysis of variance (ANOVA) and Tukey LSD tests (α=.05). RESULTS Bond strength was significantly lower in untreated specimens than in sandblasted specimens (P<.05). No difference between the glaze layer and hydrofluoric acid application treated groups were observed. However, bond strength for these groups were significantly higher as compared with the other two groups (P<.05). CONCLUSION Combined use of glaze layer & hydrofluoric acid application and silanization are reliable for strong and durable bonding between indirect composite material and monolithic zirconia. PMID:27555895

  2. High-temperature zirconia insulation and method for making same

    DOEpatents

    Wrenn, G.E. Jr.; Holcombe, C.E. Jr.; Lewis, J. Jr.

    1988-05-10

    The present invention is directed to a highly pure, partially stabilized, fibrous zirconia composite for use as thermal insulation in environments where temperatures up to about 2,000 C are utilized. The composite of the present invention is fabricated into any suitable configuration such as a cone, cylinder, dome or the like by vacuum molding an aqueous slurry of partially stabilized zirconia fibers into a desired configuration on a suitably shaped mandrel. The molded fibers are infiltrated with zirconyl nitrate and the resulting structure is then dried to form a rigid structure which may be removed and placed in a furnace. The structure is then heated in air to a temperature of about 600 C for driving off the nitrate from the structure and for oxidizing the zirconyl ion to zirconia. Thereafter, the structure is heated to about 950 to 1,250 C to fuse the zirconia fibers at their nexi in a matrix of zirconia. The composite produced by the present invention is self-supporting and can be readily machined to desired final dimensions. Additional heating to about 1,800 to 2,000 C further improves structural rigidity.

  3. High-temperature zirconia insulation and method for making same

    DOEpatents

    Wrenn, Jr., George E.; Holcombe, Jr., Cressie E.; Lewis, Jr., John

    1988-01-01

    The present invention is directed to a highly pure, partially stabilized, fibrous zirconia composite for use as thermal insulation in environments where temperatures up to about 2000.degree. C. are utilized. The composite of the present invention is fabricated into any suitable configuration such as a cone, cylinder, dome or the like by vacuum molding an aqueous slurry of partially stabilized zirconia fibers into a desired configuration on a suitably shaped mandrel. The molded fibers are infiltrated with zirconyl nitrate and the resulting structure is then dried to form a rigid structure which may be removed and placed in a furnace. The structure is then heated in air to a temperature of about 600.degree. C. for driving off the nitrate from the structure and for oxidizing the zirconyl ion to zirconia. Thereafter, the structure is heated to about 950.degree. to 1,250.degree. C. to fuse the zirconia fibers at their nexi in a matrix of zirconia. The composite produced by the present invention is self-supporting and can be readily machined to desired final dimensions. Additional heating to about 1800.degree. to 2000.degree. C. further improves structural rigidity.

  4. High-temperature zirconia insulation and method for making same

    DOEpatents

    Wrenn, G.E. Jr.; Holcombe, C.E. Jr.; Lewis, J. Jr.

    The present invention is directed to a highly pure, partially stabilized, fibrous zirconia composite for use as thermal insulation in environments where temperatures up to about 2,000/sup 0/C are utilized. The composite of the present invention is fabricated into any suitable configuration such as a cone, cylinder dome or the like by vacuum molding an aqueous slurry of partially stabilized zirconia fibers into a desired configuration on a suitably shaped mandrel. The molded fibers are infiltrated with zirconyl nitrate and the resulting structure is then dried to form a rigid structure which may be removed and placed in a furnace. The structure is then heated in air to a temperature of about 600/sup 0/C for driving off the nitrate from the structure and for oxidizing the zirconyl ion to zirconia. Thereafter, the structure is heated to about 950/sup 0/ to 1,250/sup 0/C to fuse the zirconia fibers at their nexi in a matrix of zirconia. The composite produced by the present invention is self-supporting and can be readily machined to desired final dimensions. Additional heating to about 1800/sup 0/ to 2000/sup 0/C further improves structural rigidity.

  5. Corrosion behavior of zirconia in acidulated phosphate fluoride

    PubMed Central

    Thomas, Anie; Sridhar, Sathyanarayanan; Aghyarian, Shant; Watkins-curry, Pilanda; Chan, Julia Y.; Pozzi, Alessandro; Rodrigues, Danieli C.

    2016-01-01

    ABSTRACT Objective The corrosion behavior of zirconia in acidulated phosphate fluoride (APF) representing acidic environments and fluoride treatments was studied. Material and Methods Zirconia rods were immersed in 1.23% and 0.123% APF solutions and maintained at 37°C for determined periods of time. Surfaces of all specimens were imaged using digital microscopy and scanning electron microscopy (SEM). Sample mass and dimensions were measured for mass loss determination. Samples were characterized by powder X-ray diffraction (XRD) to detect changes in crystallinity. A biosensor based on electrochemical impedance spectroscopy (EIS) was used to detect ion dissolution of material into the immersion media. Results Digital microscopy revealed diminishing luster of the materials and SEM showed increased superficial corrosion of zirconia submerged in 1.23% APF. Although no structural change was found, the absorption of salts (sodium phosphate) onto the surface of the materials bathed in 0.123% APF was significant. EIS indicated a greater change of impedance for the immersion solutions with increasing bathing time. Conclusion Immersion of zirconia in APF solutions showed deterioration limited to the surface, not extending to the bulk of the material. Inferences on zirconia performance in acidic oral environment can be elucidated from the study. PMID:27008257

  6. Zirconia-silica based mesoporous desulfurization adsorbents

    NASA Astrophysics Data System (ADS)

    Palomino, Jessica M.; Tran, Dat T.; Kareh, Ana R.; Miller, Christopher A.; Gardner, Joshua M. V.; Dong, Hong; Oliver, Scott R. J.

    2015-03-01

    We report a series of mesoporous silicate sorbent materials templated by long-chain primary alkylamines that display record level of desulfurization of the jet fuel JP-8. Pure silica frameworks and those with a Si:Zr synthesis molar ratio ranging from 44:1 to 11:1 were investigated. The optimum sorbent was identified as dodecylamine-templated silica-zirconia synthesized from a gel with Si:Zr molar ratio of 15:1. With an optimized silver loading of 11 wt.%, a saturation adsorption capacity of 39.4 mgS g-1 and a silver efficiency of 1.21 molS mol Ag-1 were observed for JP-8. This sorbent displayed exceptional regenerability, maintaining 86% of its initial capacity in model fuel after solvent regeneration with diethyl ether. Low-cost, portable and reusable sorbents for the desulfurization of JP-8 jet fuel are needed to make solid oxide fuel cells (SOFCs) a reality for military power needs. SOFCs require ultra-low sulfur content fuel, which traditional desulfurization methods cannot achieve.

  7. Radiation damage in cubic-stabilized zirconia

    SciTech Connect

    Costantini, Jean-Marc; Beuneu, Francois; Weber, William J

    2013-01-01

    Cubic yttria-stabilized zirconia (YSZ) can be used for nuclear applications as an inert matrix for actinide immobilization or transmutation. Indeed, the large amount of native oxygen vacancies leads to a high radiation tolerance of this material owing to defect recombination occurring in the atomic displacements cascades induced by fast neutron irradiation or ion implantations, as showed by Molecular dynamics (MD) simulations. Amorphization cannot be obtained in YSZ either by nuclear-collision or electronic-excitation damage, just like in urania. A kind of polygonization structure with slightly disoriented crystalline domains is obtained in both cases. In the first steps of damage, specific isolated point defects (like F+-type color centers) and point-defect clusters are produced by nuclear collisions with charged particles or neutrons. Further increase of damage leads to dislocation-loop formation, then to collapse of the dislocation network into a polygonization structure. For swift heavy ion irradiations, a similar polygonization structure is obtained above a threshold stopping power value of about 20-30 keV nm-1.

  8. Mechanical behavior of mullite-zirconia composites

    NASA Astrophysics Data System (ADS)

    Sahnoune, F.; Saheb, N.

    2010-06-01

    In this work, mechanical properties of mullite-zirconia composites synthesised through reaction sintering of Algerian kaolin, α-Al2O3, and ZrO2 were characterized. Phases present and their transformations were characterized using x-ray diffraction. Hardness H and fracture toughness KIC were measured by Vickers indentation using a Zwick microhardness tester. The flexural strength was measured through three point bending test using an Instron Universal Testing Machine. It was found that the increase of ZrO2 content (from 0 to 32wt.%) decreased the microhardness of the composites from 14 to 10.8 GPa. However, the increase of ZrO2 content (from 0 to 24wt.%) increased the flexural strength of the composites from 142 to 390 MPa then decreased it with further increase of ZrO2 content. Also, the fracture toughness increased from 1.8 to 2.9 MPa.m1/2 with the increase of ZrO2 content from 0 to 32 wt.%; and the rate of the increase decreased at higher fractions of ZrO2 content. The average linear coefficient of thermal expansion (within the range 50 to 1450°C) for samples containing 0 and 16 wt.% ZrO2 sintered at 1600°C for 2 hours was 4.7 x10-6 K-1 and 5.2 x 10-6 K-1 respectively.

  9. Quantum theory of electroabsorption in semiconductor nanocrystals.

    PubMed

    Tepliakov, Nikita V; Leonov, Mikhail Yu; Baranov, Alexander V; Fedorov, Anatoly V; Rukhlenko, Ivan D

    2016-01-25

    We develop a simple quantum-mechanical theory of interband absorption by semiconductor nanocrystals exposed to a dc electric field. The theory is based on the model of noninteracting electrons and holes in an infinitely deep quantum well and describes all the major features of electroabsorption, including the Stark effect, the Franz-Keldysh effect, and the field-induced spectral broadening. It is applicable to nanocrystals of different shapes and dimensions (quantum dots, nanorods, and nanoplatelets), and will prove useful in modeling and design of electrooptical devices based on ensembles of semiconductor nanocrystals.

  10. Size quantization in Cu2Se nanocrystals

    NASA Astrophysics Data System (ADS)

    Govindraju, S.; Kalenga, M. P.; Airo, M.; Moloto, M. J.; Sikhwivhilu, L. M.; Moloto, N.

    2014-12-01

    Herein we report on the synthesis of size quantized copper selenide nanocrystals via the colloidal method. Different colours of the sample were obtained at different time intervals indicative of the sizes of the nanocrystals. The absorption band edges were blue-shifted from bulk indicative of quantum confinement. This was corroborated by the TEM results that showed very small particles ranging from 2 nm to 7 nm. This work therefore shows a phenomenon readily observed in cadmium chalcogenide nanocrystals but has never been reported for copper based chalcogenides.

  11. Controlling upconversion nanocrystals for emerging applications

    NASA Astrophysics Data System (ADS)

    Zhou, Bo; Shi, Bingyang; Jin, Dayong; Liu, Xiaogang

    2015-11-01

    Lanthanide-doped upconversion nanocrystals enable anti-Stokes emission with pump intensities several orders of magnitude lower than required by conventional nonlinear optical techniques. Their exceptional properties, namely large anti-Stokes shifts, sharp emission spectra and long excited-state lifetimes, have led to a diversity of applications. Here, we review upconversion nanocrystals from the perspective of fundamental concepts and examine the technical challenges in relation to emission colour tuning and luminescence enhancement. In particular, we highlight the advances in functionalization strategies that enable the broad utility of upconversion nanocrystals for multimodal imaging, cancer therapy, volumetric displays and photonics.

  12. Controlling upconversion nanocrystals for emerging applications.

    PubMed

    Zhou, Bo; Shi, Bingyang; Jin, Dayong; Liu, Xiaogang

    2015-11-01

    Lanthanide-doped upconversion nanocrystals enable anti-Stokes emission with pump intensities several orders of magnitude lower than required by conventional nonlinear optical techniques. Their exceptional properties, namely large anti-Stokes shifts, sharp emission spectra and long excited-state lifetimes, have led to a diversity of applications. Here, we review upconversion nanocrystals from the perspective of fundamental concepts and examine the technical challenges in relation to emission colour tuning and luminescence enhancement. In particular, we highlight the advances in functionalization strategies that enable the broad utility of upconversion nanocrystals for multimodal imaging, cancer therapy, volumetric displays and photonics.

  13. Multiexciton fluorescence from semiconductor nanocrystals

    NASA Astrophysics Data System (ADS)

    Fisher, Brent; Caruge, Jean-Michel; Chan, Yin-Thai; Halpert, Jonathan; Bawendi, Moungi G.

    2005-11-01

    We use transient photoluminescence to spectrally resolve the emission from 1, 2, and 3 electron-hole pairs states in CdSe colloidal nanocrystals with radii ranging between 2.3 and 5.2 nm. Temporally and spectrally resolved multiexciton emission from single NCs is also observed. The observation of multiexciton emission enables new experiments and potential applications at both the single NC level and using ensembles of NCs. First we discuss the use of single CdSe(CdZnS) core(shell) colloidal NCs (spheres and rods) to generate triggered photon pair emission at room temperature, with specific ordering of the pair's constituent photons. Second, we incorporate CdSe/ZnS core-shell nanocrystals into a TiO 2 host matrix and observe simultaneous two-state amplified spontaneous emission and lasing from both multiexcitonic transitions (1S 3/2-1S e and 1P 3/2-1P e) in a surface-emitting distributed feedback CdSe NC laser. From our data we deduce radiative lifetimes, quantum yields, stimulated emission gain, and power dependencies for the multiexciton transitions.

  14. Seismic transpressive basement faults and monocline development in a foreland basin (Eastern Guadalquivir, SE Spain)

    NASA Astrophysics Data System (ADS)

    Pedrera, A.; Ruiz-Constán, A.; Marín-Lechado, C.; Galindo-Zaldívar, J.; González, A.; Peláez, J. A.

    2013-12-01

    We examine the late Tortonian to present-day deformation of an active seismic sector of the eastern Iberian foreland basement of the Betic Cordillera, in southern Spain. Transpressive faults affecting Paleozoic basement offset up to Triassic rocks. Late Triassic clays and evaporites constitute a décollement level decoupling the basement rocks and a ~100 m thick cover of Jurassic carbonates. Monoclines trending NE-SW to ENE-WSW deform the Jurassic cover driven by the propagation of high-angle transpressive right-lateral basement faults. They favor the migration of clays and evaporites toward the propagated fault tip, i.e., the core of the anticline, resulting in fluid overpressure, fluid flow, and precipitation of fibrous gypsum parallel to a vertical σ3. The overall geometry of the studied monoclines, as well as the intense deformation within the clays and evaporites, reproduces three-layer discrete element models entailing a weak middle unit sandwiched between strong layers. Late Tortonian syn-folding sediments recorded the initial stages of the fault-propagation folding. Equivalent unexposed transpressive structures and associated monoclines reactivated under the present-day NW-SE convergence are recognized and analyzed in the Sabiote-Torreperogil region, using seismic reflection, gravity, and borehole data. A seismic series of more than 2100 low-magnitude earthquakes was recorded within a very limited area of the basement of this sector from October 2012 to May 2013. Seismic activity within a major NE-SW trending transpressive basement fault plane stimulated rupture along a subsidiary E-W (~N95°E) strike-slip relay fault. The biggest event (mbLg 3.9, MW 3.7) occurred at the junction between them in a transpressive relay sector.

  15. Structure of a monoclinic polymorph of human carbonic anhydrase II with a doubled a axis

    SciTech Connect

    Robbins, Arthur H.; Domsic, John F.; Agbandje-McKenna, Mavis; McKenna, Robert

    2010-05-01

    The crystal structure of human carbonic anhydrase II with a doubled a axis from that of the usually observed monoclinic cell has been determined and refined to 1.4 Å resolution. The two molecules comprising the asymmetric unit are related by a noncrystallographic translation of ½ along a, but one of the molecules has two alternate orientations related by a rotation of approximately 2°. The crystal structure of human carbonic anhydrase II with a doubled a axis from that of the usually observed monoclinic unit cell has been determined and refined to 1.4 Å resolution. The diffraction data with h = 2n + 1 were systematically weaker than those with h = 2n. Consequently, the scaling of the data, structure solution and refinement were challenging. The two molecules comprising the asymmetric unit are related by a noncrystallographic translation of ½ along a, but one of the molecules has two alternate positions related by a rotation of approximately 2°. This rotation axis is located near the edge of the central β-sheet, causing a maximum distance disparity of 1.7 Å between equivalent atoms on the diametrically opposite side of the molecule. The crystal-packing contacts are similar to two sequential combined unit cells along a of the previously determined monoclinic unit cell. Abnormally high final R{sub cryst} and R{sub free} values (20.2% and 23.7%, respectively) are not unusual for structures containing pseudo-translational symmetry and probably result from poor signal to noise in the weak h-odd data.

  16. A monoclinic form of dendocarbin A: a borderline case of one-dimensional isostructural polymorphism.

    PubMed

    Paz, Cristian; Burgos, Viviana; Suarez, Sebastián; Baggio, Ricardo

    2015-04-01

    The title compound, dendocarbin A [systematic name: (1R,5aS,9aS,9bR)-1-hydroxy-6,6,9a-trimethyldodecahydronaphtho[1,2-c]furan-3-one], C15H22O3, is a sesquiterpene lactone isolated from Drimys winteri var chilensis. The monoclinic phase described herein displays an identical molecular structure to the orthorhombic phase that we reported previously [Paz Robles et al. (2014). Acta Cryst. C70, 1007-1010], while varying significantly in chain pitch, and can thus be considered as a borderline case of one-dimensional isostructural polymorphism.

  17. Instantaneous band gap collapse in photoexcited monoclinic VO2 due to photocarrier doping.

    PubMed

    Wegkamp, Daniel; Herzog, Marc; Xian, Lede; Gatti, Matteo; Cudazzo, Pierluigi; McGahan, Christina L; Marvel, Robert E; Haglund, Richard F; Rubio, Angel; Wolf, Martin; Stähler, Julia

    2014-11-21

    Using femtosecond time-resolved photoelectron spectroscopy we demonstrate that photoexcitation transforms monoclinic VO2 quasi-instantaneously into a metal. Thereby, we exclude an 80 fs structural bottleneck for the photoinduced electronic phase transition of VO2. First-principles many-body perturbation theory calculations reveal a high sensitivity of the VO2 band gap to variations of the dynamically screened Coulomb interaction, supporting a fully electronically driven isostructural insulator-to-metal transition. We thus conclude that the ultrafast band structure renormalization is caused by photoexcitation of carriers from localized V 3d valence states, strongly changing the screening before significant hot-carrier relaxation or ionic motion has occurred.

  18. Dynamic annealing of defects in irradiated zirconia-based ceramics

    SciTech Connect

    Devanathan, Ram; Weber, William J.

    2008-03-06

    We have observed self-healing behavior in large scale molecular dynamics simulations of 30 keV Zr recoils in pure zirconia and 10 mole % yttria-stabilized zirconia. Our results reveal that dynamic annealing is highly effective during the first 5 ps of damage evolution, especially in the presence of oxygen structural vacancies introduced by aliovalent doping (Y3+ substitution for Zr4+). The presence of mobile oxygen vacancies results in near complete recovery of damage. Damage recovery on the cation sublattice is assisted by the anion sublattice recovery, which explains the remarkable radiation tolerance of stabilized zirconia. Ceramics engineered to heal themselves in this fashion hold great promise for use in high-radiation environments or for safely encapsulating high-level radioactive waste over geological time scales.

  19. Defect Interactions and Ionic Transport in Scandia Stabilized Zirconia

    SciTech Connect

    Devanathan, Ramaswami; Thevuthasan, Suntharampillai; Gale, Julian D.

    2009-06-24

    Atomistic simulation has been used to study ionic transport in scandia-stabilized zirconia, as well as scandia and yttria-co-doped zirconia, as a function of temperature and composition. The oxygen diffusion coefficient shows a peak at a composition of 6 mole % Sc2O3. Oxygen vacancies prefer to be second nearest neighbours to yttrium ions, but have little preference between first and second neighbour positions with respect to scandium ions. The Sc-O bond length is about 2.17 Å compared to 2.28 Å for the Y-O bond. Oxygen migration between cation tetrahedra is impeded less effectively by Sc-Sc edges than by Y-Y edges. A neutral cluster of two scandium ions with an oxygen vacancy in the common first neighbour position has a binding energy of -0.56 eV. The formation of such clusters may contribute to conductivity degradation of stabilized zirconia at elevated temperature.

  20. High-energy radiation damage in zirconia: Modeling results

    SciTech Connect

    Zarkadoula, E.; Devanathan, R.; Weber, W. J.; Seaton, M. A.; Todorov, I. T.; Nordlund, K.; Dove, M. T.; Trachenko, K.

    2014-02-28

    Zirconia is viewed as a material of exceptional resistance to amorphization by radiation damage, and consequently proposed as a candidate to immobilize nuclear waste and serve as an inert nuclear fuel matrix. Here, we perform molecular dynamics simulations of radiation damage in zirconia in the range of 0.1–0.5 MeV energies with account of electronic energy losses. We find that the lack of amorphizability co-exists with a large number of point defects and their clusters. These, importantly, are largely isolated from each other and therefore represent a dilute damage that does not result in the loss of long-range structural coherence and amorphization. We document the nature of these defects in detail, including their sizes, distribution, and morphology, and discuss practical implications of using zirconia in intense radiation environments.

  1. High-energy radiation damage in zirconia: modeling results

    SciTech Connect

    Zarkadoula, Evangelia; Devanathan, Ram; Weber, William J; Seaton, M; Todorov, I T; Nordlund, Kai; Dove, Martin T; Trachenko, Kostya

    2014-01-01

    Zirconia is viewed as a material of exceptional resistance to amorphization by radiation damage, and consequently proposed as a candidate to immobilize nuclear waste and serve as an inert nuclear fuel matrix. Here, we perform molecular dynamics simulations of radiation damage in zirconia in the range of 0.1-0.5 MeV energies with account of electronic energy losses. We nd that the lack of amorphizability co-exists with a large number of point defects and their clusters. These, importantly, are largely isolated from each other and therefore represent a dilute damage that does not result in the loss of long-range structural coherence and amorphization. We document the nature of these defects in detail, including their sizes, distribution and morphology, and discuss practical implications of using zirconia in intense radiation environments.

  2. High-energy radiation damage in zirconia: modeling results

    SciTech Connect

    Zarkadoula, Eva; Devanathan, Ram; Weber, William J.; Seaton, Michael; Todorov, Ilian; Nordlund, Kai; Dove, Martin T.; Trachenko, Kostya

    2014-02-28

    Zirconia has been viewed as a material of exceptional resistance to amorphization by radiation damage, and was consequently proposed as a candidate to immobilize nuclear waste and serve as a nuclear fuel matrix. Here, we perform molecular dynamics simulations of radiation damage in zirconia in the range of 0.1-0.5 MeV energies with the account of electronic energy losses. We find that the lack of amorphizability co-exists with a large number of point defects and their clusters. These, importantly, are largely disjoint from each other and therefore represent a dilute damage that does not result in the loss of long-range structural coherence and amorphization. We document the nature of these defects in detail, including their sizes, distribution and morphology, and discuss practical implications of using zirconia in intense radiation environments.

  3. High-energy radiation damage in zirconia: Modeling results

    NASA Astrophysics Data System (ADS)

    Zarkadoula, E.; Devanathan, R.; Weber, W. J.; Seaton, M. A.; Todorov, I. T.; Nordlund, K.; Dove, M. T.; Trachenko, K.

    2014-02-01

    Zirconia is viewed as a material of exceptional resistance to amorphization by radiation damage, and consequently proposed as a candidate to immobilize nuclear waste and serve as an inert nuclear fuel matrix. Here, we perform molecular dynamics simulations of radiation damage in zirconia in the range of 0.1-0.5 MeV energies with account of electronic energy losses. We find that the lack of amorphizability co-exists with a large number of point defects and their clusters. These, importantly, are largely isolated from each other and therefore represent a dilute damage that does not result in the loss of long-range structural coherence and amorphization. We document the nature of these defects in detail, including their sizes, distribution, and morphology, and discuss practical implications of using zirconia in intense radiation environments.

  4. Applicability of zirconia dental prostheses for metal allergy patients.

    PubMed

    Gökçen-Röhlig, Bilge; Saruhanoglu, Alp; Cifter, Ebru Demet; Evlioglu, Gulumser

    2010-01-01

    The aim of this study was to investigate the applicability of zirconium dioxide (zirconia) as a substitute for metal alloys in a group of metal allergy patients. Fourteen patients (eight women, six men) who had been restored with porcelain-fused-to-metal fixed partial dentures (FPDs) and had exhibited hypersensitivity lesions to dental alloys were enrolled in this study. Patients were previously patch-tested using standard testing substances authorized by the International Contact Dermatitis Research Group. Patients received FPDs with zirconia frameworks and occurrences of oral symptoms were evaluated. No hypersensitivity lesions in the mouth or on the skin were encountered during the follow-up period of 3 years. Zirconia FPDs may be an alternative to porcelain-fused-to-metal FPDs in patients with metal allergies.

  5. Resin cementation of zirconia ceramics with different bonding agents.

    PubMed

    Tanış, Merve Çakırbay; Akay, Canan; Karakış, Duygu

    2015-03-04

    The aim of this study was to evaluate the effects of sandblasting and different chemical bonding agents on shear bond strength of zirconia and conventional resin cement. In this study, 35 zirconia specimens were treated as follows: Group I: control; Group II: sandblasting; Group III: sandblasting + Monobond S; Group IV: sandblasting + Monobond Plus; Group V: sandblasting + Z-Prime Plus. The specimens in each group were bonded with conventional composite resin cement Variolink II. After cementation, specimens were stored in distilled water (at 37 °C) for 24 h and shear test was performed. The highest shear bond strength values were observed in Groups IV and V. The lowest shear bond strength values were observed in Group I. Using 10-methacryloyloxy-decyl dihydrogenphosphate monomer-containing priming agents, e.g. Monobond Plus and Z-PRIME Plus, combined with sandblasting can be an effective method for resin bonding of zirconia restorations.

  6. Thermodynamic properties of some metal oxide-zirconia systems

    NASA Technical Reports Server (NTRS)

    Jacobson, Nathan S.

    1989-01-01

    Metal oxide-zirconia systems are a potential class of materials for use as structural materials at temperatures above 1900 K. These materials must have no destructive phase changes and low vapor pressures. Both alkaline earth oxide (MgO, CaO, SrO, and BaO)-zirconia and some rare earth oxide (Y2O3, Sc2O3, La2O3, CeO2, Sm2O3, Gd2O3, Yb2O3, Dy2O3, Ho2O3, and Er2O3)-zirconia system are examined. For each system, the phase diagram is discussed and the vapor pressure for each vapor species is calculated via a free energy minimization procedure. The available thermodynamic literature on each system is also surveyed. Some of the systems look promising for high temperature structural materials.

  7. Resin cementation of zirconia ceramics with different bonding agents

    PubMed Central

    Tanış, Merve Çakırbay; Akay, Canan; Karakış, Duygu

    2015-01-01

    The aim of this study was to evaluate the effects of sandblasting and different chemical bonding agents on shear bond strength of zirconia and conventional resin cement. In this study, 35 zirconia specimens were treated as follows: Group I: control; Group II: sandblasting; Group III: sandblasting + Monobond S; Group IV: sandblasting + Monobond Plus; Group V: sandblasting + Z-Prime Plus. The specimens in each group were bonded with conventional composite resin cement Variolink II. After cementation, specimens were stored in distilled water (at 37 °C) for 24 h and shear test was performed. The highest shear bond strength values were observed in Groups IV and V. The lowest shear bond strength values were observed in Group I. Using 10-methacryloyloxy-decyl dihydrogenphosphate monomer-containing priming agents, e.g. Monobond Plus and Z-PRIME Plus, combined with sandblasting can be an effective method for resin bonding of zirconia restorations. PMID:26019653

  8. Study on the neotype zirconia's implant coated nanometer hydroxyapatite ceramics

    NASA Astrophysics Data System (ADS)

    Zhu, J. W.; Yang, D. W.

    2007-07-01

    In recent years, biologic ceramics is a popular material of implants and bioactive surface modification of dental implant became a research emphasis, which aims to improve bioactivity of implants materials and acquire firmer implants-bone interface. The zirconia ceramic has excellent mechanical properties and nanometer HA ceramics is a bioceramic well known for its bioactivity, therefore, nanometer HA ceramics coating on zirconia, allows combining the excellent mechanical properties of zirconia substrates with its bioactivity. This paper shows a new method for implant shape design and bioactive modification of dental implants surface. Zirconia's implant substrate was prepared by sintered method, central and lateral tunnels were drilled in the zirconia hollow porous cylindrical implants by laser processing. The HA powders and needle-like HA crystals were made by a wet precipitation and calcining method. Its surface was coated with nanometer HA ceramics which was used brush HA slurry and vacuum sintering. Mechanical testing results revealed that the attachment strength of nanometer HA ceramics coated zirconia samples is high. SEM and interface observation after inserted experiment indicated that calcium and phosphor content increased and symmetrically around coated implant-bone tissue interface. A significantly higher affinity index was demonstrated in vivo by histomorphometric evaluation in coated versus uncoated implants. SEM analysis demonstrated better bone adhesion to the material in coated implant at any situation. In addition, the hollow porous cylindrical implant coated with nanometer HA ceramics increase the interaction of bone and implant, the new bone induced into the surface of hollow porous cylindrical implant and through the most tunnels filled into central hole. The branch-like structure makes the implant and bone a body, which increased the contact area and decreased elastic ratio. Therefore, the macroscopical and microcosmic nested structure of

  9. Semiconductor-nanocrystal/conjugated polymer thin films

    DOEpatents

    Alivisatos, A. Paul; Dittmer, Janke J.; Huynh, Wendy U.; Milliron, Delia

    2014-06-17

    The invention described herein provides for thin films and methods of making comprising inorganic semiconductor-nanocrystals dispersed in semiconducting-polymers in high loading amounts. The invention also describes photovoltaic devices incorporating the thin films.

  10. Size-Dependent Raman Shifts for nanocrystals

    PubMed Central

    Gao, Yukun; Zhao, Xinmei; Yin, Penggang; Gao, Faming

    2016-01-01

    Raman spectroscopy is a very sensitive tool for probing semiconductor nanocrystals. The underlying mechanism behind the size-dependent Raman shifts is still quite controversial. Here we offer a new theoretical method for the quantum confinement effects on the Raman spectra of semiconductor nanocrystals. We propose that the shift of Raman spectra in nanocrystals can result from two overlapping effects: the quantum effect shift and surface effect shift. The quantum effect shift is extracted from an extended Kubo formula, the surface effect shift is determined via the first principles calculations. Fairly good prediction of Raman shifts can be obtained without the use of any adjustable parameter. Closer analysis shows that the size-dependent Raman shifts in Si nanocrystals mainly result from the quantum effect shifts. For nanodiamond, the proportion of surface effect shift in Raman shift is up to about 40%. Such model can also provide a good baseline for using Raman spectroscopy as a tool to measure size. PMID:27102066

  11. Solar induced growth of silver nanocrystals

    NASA Astrophysics Data System (ADS)

    Thøgersen, Annett; Muntingh, Georg

    2013-04-01

    The effect of solar irradiation on plasmonic silver nanocrystals has been investigated using transmission electron microscopy and size distribution analysis, in the context of solar cell applications for light harvesting. Starting from an initial collection of spherical nanocrystals on a carbon film whose sizes are log-normally distributed, solar irradiation causes the nanocrystals to grow, with one particle reaching a diameter of 638 nm after four hours of irradiation. In addition some of the larger particles lose their spherical shape. The average nanocrystal diameter was found to grow as predicted by the Ostwald ripening model, taking into account the range of area fractions of the samples. The size distribution stays approximately log-normal and does not reach one of the steady-state size distributions predicted by the Ostwald ripening model. This might be explained by the system being in a transient state.

  12. Semiconductor-nanocrystal/conjugated polymer thin films

    DOEpatents

    Alivisatos, A. Paul; Dittmer, Janke J.; Huynh, Wendy U.; Milliron, Delia

    2010-08-17

    The invention described herein provides for thin films and methods of making comprising inorganic semiconductor-nanocrystals dispersed in semiconducting-polymers in high loading amounts. The invention also describes photovoltaic devices incorporating the thin films.

  13. Nanocrystals: Shedding new light on silicon

    NASA Astrophysics Data System (ADS)

    Gösele, Ulrich

    2008-03-01

    Experiments in magnetic fields suggest that defects are responsible for light emission from silicon nanocrystals. However, when these defects are passivated with hydrogen, quantum effects become responsible for the emission.

  14. Self-assembly of lead chalcogenide nanocrystals.

    PubMed

    Quan, Zewei; Valentin-Bromberg, Loriana; Loc, Welley Siu; Fang, Jiye

    2011-05-02

    This review focuses on recent developments in the self-assembly of lead chalcogenide nanocrystals into two- and three-dimensional superstructures. Self-assembly is categorized by the shapes of building blocks, including nanospheres, nanocubes, nano-octahedra, and nanostars. In the section on nanospheres, rapid assemblies of lead chalcogenide-based multicomponent nanocrystals with additional components, such as semiconductors, noble metals, and magnetic nanocrystals, are further highlighted. In situ self-assembly of lead chalcogenide nanocrystals into one-dimensional nanostructures at elevated temperatures is also covered. Each section of this paper highlights examples extracted from recent publications. Finally, relatively novel properties and applications arising from lead chalcogenide superlattices as typical examples are also discussed.

  15. Tunable mid IR plasmon in GZO nanocrystals.

    PubMed

    Hamza, M K; Bluet, J-M; Masenelli-Varlot, K; Canut, B; Boisron, O; Melinon, P; Masenelli, B

    2015-07-28

    Degenerate metal oxide nanoparticles are promising systems to expand the significant achievements of plasmonics into the infrared (IR) range. Among the possible candidates, Ga-doped ZnO nanocrystals are particularly suited for mid IR, considering their wide range of possible doping levels and thus of plasmon tuning. In the present work, we report on the tunable mid IR plasmon induced in degenerate Ga-doped ZnO nanocrystals. The nanocrystals are produced by a plasma expansion and exhibit unprotected surfaces. Tuning the Ga concentration allows tuning the localized surface plasmon resonance. Moreover, the plasmon resonance is characterized by a large damping. By comparing the plasmon of nanocrystal assemblies to that of nanoparticles dispersed in an alumina matrix, we investigate the possible origins of such damping. We demonstrate that it partially results from the self-organization of the naked particles and also from intrinsic inhomogeneity of dopants.

  16. Composite material including nanocrystals and methods of making

    DOEpatents

    Bawendi, Moungi G.; Sundar, Vikram C.

    2008-02-05

    Temperature-sensing compositions can include an inorganic material, such as a semiconductor nanocrystal. The nanocrystal can be a dependable and accurate indicator of temperature. The intensity of emission of the nanocrystal varies with temperature and can be highly sensitive to surface temperature. The nanocrystals can be processed with a binder to form a matrix, which can be varied by altering the chemical nature of the surface of the nanocrystal. A nanocrystal with a compatibilizing outer layer can be incorporated into a coating formulation and retain its temperature sensitive emissive properties

  17. Composite material including nanocrystals and methods of making

    DOEpatents

    Bawendi, Moungi G.; Sundar, Vikram C.

    2010-04-06

    Temperature-sensing compositions can include an inorganic material, such as a semiconductor nanocrystal. The nanocrystal can be a dependable and accurate indicator of temperature. The intensity of emission of the nanocrystal varies with temperature and can be highly sensitive to surface temperature. The nanocrystals can be processed with a binder to form a matrix, which can be varied by altering the chemical nature of the surface of the nanocrystal. A nanocrystal with a compatibilizing outer layer can be incorporated into a coating formulation and retain its temperature sensitive emissive properties.

  18. Tailorable, Visible Light Emission From Silicon Nanocrystals

    SciTech Connect

    Samara, G.A.; Wilcoxon, J.P.

    1999-07-20

    J. P. Wilcoxon and G. A. Samara Crystalline, size-selected Si nanocrystals in the size range 1.8-10 nm grown in inverse micellar cages exhibit highly structured optical absorption and photoluminescence (PL) across the visible range of the spectrum. The most intense PL for the smallest nanocrystals produced This report was prepared as an account of work sponsored by an agency of the United States Government. Neither the United States Government nor any agency thereof, nor any of their employees, make any warranty, express or implied, or assumes any legal liability or responsibility for the accuracy, completeness, or usefulness of any information, apparatus, product, or process disclosed, or represents that its use would not infringe privately owned rights. Reference herein to any specific commercial product, process, or service by trade name, trademark, manufacturer, or otherwise does not necessarily constitute or imply its endorsement, recommendation, or favoring by the United States Government or any agency thereof. The views and opinions of authors expressed herein do not necessarily state or reflect those of the United States Government or any agency thereof. to induce a useful level of visible photoluminescence (PL) from silicon (Si). The approaches understood. Visible PL has been observed from Si nanocrystals, or quantum dots, produced by a variety of techniques including aerosols,2 colloids,3 and ion implantation.4 However, all of The optical absorption spectra of our nanocrystals are much richer in spectral features spectrum of bulk Si where the spectral features reflect the details of the band structure shown in nanocrystals estimated to have a Si core diameter of 1-2 nm. These measured quantum those in the spectrum of bulk Si in Fig. 1 are striking indicating that nanocrystals of this size 8-Room temperature PL results on an HPLC size-selected, purified 2 nm nanocrystals but blue shifted by -0.4 eV due to quantum confinement. Excitation at 245 nm yields

  19. Crystal structure of monoclinic calcium pyrophosphate dihydrate (m-CPPD) involved in inflammatory reactions and osteoarthritis.

    PubMed

    Gras, Pierre; Rey, Christian; André, Gilles; Charvillat, Cédric; Sarda, Stéphanie; Combes, Christèle

    2016-02-01

    Pure monoclinic calcium pyrophosphate dihydrate (m-CPPD) has been synthesized and characterized by synchrotron powder X-ray diffraction and neutron diffraction. Rietveld refinement of complementary diffraction data has, for the first time, allowed the crystal structure of m-CPPD to be solved. The monoclinic system P2(1)/n was confirmed and unit-cell parameters determined: a = 12.60842 (4), b = 9.24278 (4), c = 6.74885 (2) Å and β = 104.9916 (3)°. Neutron diffraction data especially have allowed the precise determination of the position of H atoms in the structure. The relationship between the m-CPPD crystal structure and that of the triclinic calcium pyrophosphate dihydrate (t-CPPD) phase as well as other pyrophosphate phases involving other divalent cations are discussed by considering the inflammatory potential of these phases and/or their involvement in different diseases. These original structural data represent a key step in the understanding of the mechanisms of crystal formation involved in different types of arthritis and to improve early detection of calcium pyrophosphate (CPP) phases in vivo.

  20. Monoclinic tridymite in clast-rich impact melt rock from the Chesapeake Bay impact structure

    USGS Publications Warehouse

    Jackson, J.C.; Horton, J.W.; Chou, I.-Ming; Belkin, H.E.

    2011-01-01

    X-ray diffraction and Raman spectroscopy confirm a rare terrestrial occurrence of monoclinic tridymite in clast-rich impact melt rock from the Eyreville B drill core in the Chesapeake Bay impact structure. The monoclinic tridymite occurs with quartz paramorphs after tridymite and K-feldspar in a microcrystalline groundmass of devitrified glass and Fe-rich smectite. Electron-microprobe analyses revealed that the tridymite and quartz paramorphs after tridymite contain different amounts of chemical impurities. Inspection by SEM showed that the tridymite crystal surfaces are smooth, whereas the quartz paramorphs contain irregular tabular voids. These voids may represent microporosity formed by volume decrease in the presence of fluid during transformation from tridymite to quartz, or skeletal growth in the original tridymite. Cristobalite locally rims spherulites within the same drill core interval. The occurrences of tridymite and cristobalite appear to be restricted to the thickest clast-rich impact melt body in the core at 1402.02-1407.49 m depth. Their formation and preservation in an alkali-rich, high-silica melt rock suggest initially high temperatures followed by rapid cooling.

  1. Lithostratigraphy and geochemistry of Upper Vendian‒Lower Cambrian deposits in the northeastern Baltic monocline

    NASA Astrophysics Data System (ADS)

    Podkovyrov, V. N.; Maslov, A. V.; Kuznetsov, A. B.; Ershova, V. B.

    2017-01-01

    The results of investigations of Upper Vendian‒Lower Cambrian deposits in the northeastern part of the Baltic monocline specify views on the evolution of depositional environments of sedimentary successions constituting the basal part of the sedimentary cover in inner areas of the northwestern East European Platform. It is shown that the Late Vendian and initial Cambrian were characterized by the consecutive influx of relatively mature terrigenous detrital material that originated from both the weathering crust of the Baltic Shield and new sources. Its deposition was interrupted by notable, although likely asynchronous, hiatuses, which are registered at the base of the Upper Vendian Vasileostrovskaya and Voronkovo formations and Lower Cambrian Lomonosov Formation. In the Late Vendian, sedimentary material was transported from the Baltic Shield, while beginning from the initial Early Cambrian the additional contribution to the formation of the sedimentary cover of the Baltic monocline was provided by coarse-grained sedimentary material from the Timan margin of the Baltica as follows from U‒Pb isotopic ages obtained for detrital zircons. At the same time, lithogeochemical parameters of fine-grained rocks experienced no substantial changes.

  2. Conformal Domain Miniaturization and Adaptive Monoclinic (Pseudo-orthorhombic) Ferroelectric States

    NASA Astrophysics Data System (ADS)

    Jin, Y. M.; Wang, Yu; Khachaturyan, A. G.; Li, J. F.; Viehland, D.

    2003-08-01

    Ferroelectric and ferroelastic phases with very low domain wall energies have been shown to form miniaturized microdomain structures. A theory of an adaptive ferroelectric phase has been developed to predict the microdomain-averaged crystal lattice parameters of this structurally inhomogeneous state. The theory is an extension of conventional martensite theory, applied to ferroelectric systems with very low domain wall energies. The cases of ferroelectric microdomains of tetragonal (FEt) symmetry are considered. It is shown that a nano-scale coherent mixture of microdomains can be interpreted as an adaptive ferroelectric phase, whose microdomain-averaged crystal lattice is monoclinic. The crystal lattice parameters of this monoclinic phase are self-adjusting parameters, which minimize the transformation stress. Self-adjustment is achieved by application of the invariant plane strain (IPS) to the parent cubic lattice, and the value of the self-adjusted parameters constitutes a mixture of the lattice constants of the parent and product phases. Experimental investigations of Pb(Mg1/3Nb2/3)O3-PbTiO3 (PMN-PT) and Pb(Zn1/3Nb2/3)O3-PbTiO3 (PZN-PT) single crystals confirm many of the predictions of this theory.

  3. Variable defect structures cause the magnetic low-temperature transition in natural monoclinic pyrrhotite

    NASA Astrophysics Data System (ADS)

    Koulialias, D.; Kind, J.; Charilaou, M.; Weidler, P. G.; Löffler, J. F.; Gehring, A. U.

    2016-02-01

    Non-stoichiometric monoclinic 4C pyrrhotite (Fe7S8) is a major magnetic remanence carrier in the Earth's crust and in extraterrestrial materials. Because of its low-temperature magnetic transition around 30 K also known as Besnus transition, which is considered to be an intrinsic property, this mineral phase is easily detectable in natural samples. Although the physical properties of pyrrhotite have intensively been studied, the mechanism behind the pronounced change in magnetization at the low-temperature transition is still debated. Here we report magnetization experiments on a pyrrhotite crystal (Fe6.6S8) that consists of a 4C and an incommensurate 5C* superstructure that are different in their defect structure. The occurrence of two superstructures is magnetically confirmed by symmetric inflection points in hysteresis measurements above the transition at about 30 K. The disappearance of the inflection points and the associated change of the hysteresis parameters indicate that the two superstructures become strongly coupled to form a unitary magnetic anisotropy system at the transition. From this it follows that the Besnus transition in monoclinic pyrrhotite is an extrinsic magnetic phenomenon with respect to the 4C superstructure and therefore the physics behind it is in fact different from that of the well-known Verwey transition.

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

    NASA Astrophysics Data System (ADS)

    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.

  5. Synthesis of new nanocrystal materials

    NASA Astrophysics Data System (ADS)

    Hassan, Yasser Hassan Abd El-Fattah

    Colloidal semiconductor nanocrystals (NCs) have sparked great excitement in the scientific community in last two decades. NCs are useful for both fundamental research and technical applications in various fields owing to their size and shape-dependent properties and their potentially inexpensive and excellent chemical processability. These NCs are versatile fluorescence probes with unique optical properties, including tunable luminescence, high extinction coefficient, broad absorption with narrow photoluminescence, and photobleaching resistance. In the past few years, a lot of attention has been given to nanotechnology based on using these materials as building blocks to design light harvesting assemblies. For instant, the pioneering applications of NCs are light-emitting diodes, lasers, and photovoltaic devices. Synthesis of the colloidal stable semiconductor NCs using the wet method of the pyrolysis of organometallic and chalcogenide precursors, known as hot-injection approach, is the chart-topping preparation method in term of high quality and monodisperse sized NCs. The advancement in the synthesis of these artificial materials is the core step toward their applications in a broad range of technologies. This dissertation focuses on exploring various innovative and novel synthetic methods of different types of colloidal nanocrystals, both inorganic semiconductors NCs, also known as quantum dots (QDs), and organic-inorganic metal halide-perovskite materials, known as perovskites. The work presented in this thesis focuses on pursuing fundamental understanding of the synthesis, material properties, photophysics, and spectroscopy of these nanostructured semiconductor materials. This thesis contains 6 chapters and conclusions. Chapters 1?3 focus on introducing theories and background of the materials being synthesized in the thesis. Chapter 4 demonstrates our synthesis of colloidal linker--free TiO2/CdSe NRs heterostructures with CdSe QDs grown in the presence of Ti

  6. Study of the Crack Propagation in Alumina Mullite Zirconia and Mullite Zirconia Composites Obtained by Reaction Sintering

    NASA Astrophysics Data System (ADS)

    Gheldane, Farid; Souya, Lotfi Ain; Bouras, Seddik

    2011-12-01

    We studied resistance to the propagation of cracks on composites mullite zirconia and mullite alumina zirconia using the flexure tests SENB. The second nuance presents an R-curve effect interesting compared to mullite zirconia where the effect hardly appears. For understanding the mechanisms toughening, we used the SEM observations which showed that resistance to the propagation is mainly connected to the cracks bridging. The crack lengths are often calculated on the basis of compliance evolution during the R-curve tests. We show that the cracks lengths calculated starting from compliance underestimate in an important way the crack true values. The not fissured ligaments, responsible of the bridging mechanisms, are indeed also the cause of the error induced on compliance.

  7. The effect of zirconia thickness on the biaxial flexural strength of zirconiaceramic bilayered discs.

    PubMed

    Sinmazisik, Gulden; Tarcin, Bilge; Demirbas, Bulent; Gulmez, Turgut; Bor, Emire; Ozer, Fusun

    2015-01-01

    The aim of this study was to assess the effect of zirconia core thickness on the biaxial flexural strength values of zirconia-porcelain bilayered discs. A total of 60 discs with 0.3, 0.4, and 0.5 mm thickness were obtained from a fully sintered zirconia block. A 1.5-mm thick layer of veneer porcelain was fired on the zirconia specimens and biaxial flexural strength tests were performed on the bilayered discs. In each group, the loading surface was the veneer porcelain in half of the specimens (core in tension) and the zirconia core surface in the other half (core in compression). The zirconia core thickness had no effect on the biaxial flexural strength of zirconiaporcelain bilayered discs when the core was in tension (p>0.05). Whereas, when the core was in compression, an increase in the zirconia core thickness resulted in an increase in the biaxial flexural strength (p<0.05).

  8. pH control of the structure, composition, and catalytic activity of sulfated zirconia

    NASA Astrophysics Data System (ADS)

    Ivanov, Vladimir K.; Baranchikov, Alexander Ye.; Kopitsa, Gennady P.; Lermontov, Sergey A.; Yurkova, Lyudmila L.; Gubanova, Nadezhda N.; Ivanova, Olga S.; Lermontov, Anatoly S.; Rumyantseva, Marina N.; Vasilyeva, Larisa P.; Sharp, Melissa; Pranzas, P. Klaus; Tretyakov, Yuri D.

    2013-02-01

    We report a detailed study of structural and chemical transformations of amorphous hydrous zirconia into sulfated zirconia-based superacid catalysts. Precipitation pH is shown to be the key factor governing structure, composition and properties of amorphous sulfated zirconia gels and nanocrystalline sulfated zirconia. Increase in precipitation pH leads to substantial increase of surface fractal dimension (up to ˜2.7) of amorphous sulfated zirconia gels, and consequently to increase in specific surface area (up to ˜80 m2/g) and simultaneously to decrease in sulfate content and total acidity of zirconia catalysts. Complete conversion of hexene-1 over as synthesized sulfated zirconia catalysts was observed even under ambient conditions.

  9. Use of spray-dried zirconia microspheres in the separation of immunoglobulins from cell culture supernatant.

    PubMed

    Subramanian, A; Carr, P W; McNeff, C V

    2000-08-18

    A method suitable for the isolation of monoclonal antibodies (MAbs) on novel zirconia microspheres (20-30 microm) is described. Zirconia microspheres were generated by spray drying colloidal zirconia. Spray-dried zirconia microspheres were further classified and characterized by X-ray diffraction, BET porosimetry and scanning electron microscopy. Spray-dried zirconia microspheres were modified with ethylenediamine-N,N'-tetra(methylenephosphonic) acid (EDTPA) to create a cation-exchange chromatographic support. The chromatographic behavior of a semi-preparative column packed with EDTPA-modified zirconia microspheres was evaluated and implications for scale-up are provided. EDTPA-modified zirconia microspheres were further used to purify MAbs from cell culture supernatant. Analysis by enzyme linked immunosorbent assay and gel electrophoresis demonstrate that MAbs can be recovered from a cell culture supernatant at high yield (92-98%) and high purity (>95%) in a single chromatographic step.

  10. Identification of peptide motif that binds to the surface of zirconia.

    PubMed

    Hashimoto, Kazuhiko; Yoshinari, Masao; Matsuzaka, Kenichi; Shiba, Kiyotaka; Inoue, Takashi

    2011-01-01

    A zirconia-binding peptide motif was identified using a peptide phage display system. Yttria stabilized zirconia beads and discs were used as the target. Quartz crystal microbalance was used to monitor the binding of phages to zirconia. Starting from a library of phages displaying random sequences of 12-mer peptides, we repeated cycles of biopanning against zirconia beads. After four cycles of biopanning, we isolated a phage clone Φ#17. DNA sequencing of the corresponding portion of Φ#17 unexpectedly revealed that it displayed a 58-mer peptide (amino acid sequence: WMPSDVDINDPQGGGSRPNLHQPKPAAEAASKKKSENRKVPFYSHSWY-SSMSEDKRGW). We found that Φ#17 had a 300-fold, significantly higher binding affinity for zirconia discs than phages displaying no peptide. In quartz crystal microbalance assay, a rapid increase in energy dissipation was observed from Φ#17 but not from the control phages, indicating that Φ#17 binds to the surface of zirconia via its displayed peptide. We successfully identified a peptide motif that binds zirconia.

  11. Surface quality of yttria-stabilized tetragonal zirconia polycrystal in CAD/CAM milling, sintering, polishing and sandblasting processes.

    PubMed

    Alao, Abdur-Rasheed; Stoll, Richard; Song, Xiao-Fei; Miyazaki, Takashi; Hotta, Yasuhiro; Shibata, Yo; Yin, Ling

    2017-01-01

    This paper studied the surface quality (damage, morphology, and phase transformation) of yttria-stabilized tetragonal zirconia polycrystal (Y-TZP) in CAD/CAM milling, and subsequent polishing, sintering and sandblasting processes applied in dental restorations. X-ray diffraction and scanning electron microscopy (SEM) were used to scan all processed surfaces to determine phase transformations and analyse surface damage morphology, respectively. The average surface roughness (Ra) and maximum roughness (Rz) for all processed surfaces were measured using desk-top SEM-assisted morphology analytical software. X-ray diffraction patterns prove the sintering-induced monoclinic-tetragonal phase transformation while the sandblasting-induced phase transformation was not detected. The CAD/CAM milling of pre-sintered Y-TZP produced very rough surfaces with extensive fractures and cracks. Simply polishing or sintering of milled pre-sintered surfaces did not significantly improve their surface roughness (ANOVA, p>0.05). Neither sintering-polishing of the milled surfaces could effectively improve the surface roughness (ANOVA, p>0.05). The best surface morphology was produced in the milling-polishing-sintering process, achieving Ra=0.21±0.03µm and Rz=1.73±0.04µm, which meets the threshold for bacterial retention. Sandblasting of intaglios with smaller abrasives was recommended as larger abrasive produced visible surface defects. This study provides technical insights into process selection for Y-TZP to achieve the improved restorative quality.

  12. Applying analytical ultracentrifugation to nanocrystal suspensions.

    PubMed

    Jamison, Jennifer A; Krueger, Karl M; Mayo, J T; Yavuz, Cafer T; Redden, Jacina J; Colvin, Vicki L

    2009-09-02

    While applied frequently in physical biochemistry to the study of protein complexes, the quantitative use of analytical ultracentrifugation (AUC) for nanocrystal analysis is relatively rare. Its application in nanoscience is potentially very powerful as it provides a measure of nanocrystal density, size and structure directly in the solution phase. Towards that end, this paper examines the best practices for applying data collection and analysis methods for AUC, geared towards the study of biomolecules, to the unique problems of nanoparticle analysis. Using uniform nanocrystals of cadmium selenide, we compared several schemes for analyzing raw sedimentation data. Comparable values of the mean sedimentation coefficients (s-value) were found using several popular analytical approaches; however, the distribution in sample s-values is best captured using the van Holde-Weischt algorithm. Measured s-values could be reproducibly collected if sample temperature and concentration were controlled; under these circumstances, the variability for average sedimentation values was typically 5%. The full shape of the distribution in s-values, however, is not easily subjected to quantitative interpretation. Moreover, the selection of the appropriate sedimentation speed is crucial for AUC of nanocrystals as the density of inorganic nanocrystals is much larger than that of solvents. Quantitative analysis of sedimentation properties will allow for better agreement between experimental and theoretical models of nanocrystal solution behavior, as well as providing deeper insight into the hydrodynamic size and solution properties of nanomaterials.

  13. The effect of resin cements and primer on retentive force of zirconia copings bonded to zirconia abutments with insufficient retention

    PubMed Central

    Kim, Seung-Mi; Yoon, Ji-Young; Lee, Myung-Hyun

    2013-01-01

    PURPOSE The purpose of this study was to investigate the effect of resin cements and primer on the retentive force of zirconia copings bonded to zirconia abutments with insufficient retention. MATERIALS AND METHODS Zirconia blocks (Lava, 3M ESPE, St. Paul, MN, USA) were obtained and forty sets of zirconia abutments and copings were fabricated using CAD/CAM technology. They were grouped into 4 categories as follows, depending on the types of resin cements used, and whether the primer is applied or not:Panavia F2.0 (P), Panavia F2.0 using Primer (PRIME Plus, Bisco Inc, Schaumburg, IL, USA) (PZ), Superbond C&B (S), and Superbond C&B using Primer (SZ). For each of the groups, the cementation was conducted. The specimens were kept in sterilized water (37℃) for 24 hours. Retentive forces were tested and measured, and a statistical analysis was carried out. The nature of failure was recorded. RESULTS The means and standard deviations of retentive force in Newton for each group were 265.15 ± 35.04 N (P), 318.21 ± 22.24 N (PZ), 445.13 ± 78.54 N (S) and 508.21 ± 79.48 N (SZ). Superbond C&B groups (S & SZ) showed significantly higher retentive force than Panavia F2.0 groups (P & PZ). In Panavia F2.0 groups, the use of primer was found to contribute to the increase of retentive force. On the other hand, in Superbond C&B groups, the use of primer did not influence the retention forces. Adhesive failure was observed in all groups. CONCLUSION This study suggests that cementation of the zirconia abutments and zirconia copings with Superbond C&B have a higher retentive force than Panavia F2.0. When using Panavia F2.0, the use of primer increases the retentive force. PMID:23755347

  14. Solution synthesis of germanium nanocrystals

    DOEpatents

    Gerung, Henry; Boyle, Timothy J.; Bunge, Scott D.

    2009-09-22

    A method for providing a route for the synthesis of a Ge(0) nanometer-sized material from. A Ge(II) precursor is dissolved in a ligand heated to a temperature, generally between approximately 100.degree. C. and 400.degree. C., sufficient to thermally reduce the Ge(II) to Ge(0), where the ligand is a compound that can bond to the surface of the germanium nanomaterials to subsequently prevent agglomeration of the nanomaterials. The ligand encapsulates the surface of the Ge(0) material to prevent agglomeration. The resulting solution is cooled for handling, with the cooling characteristics useful in controlling the size and size distribution of the Ge(0) materials. The characteristics of the Ge(II) precursor determine whether the Ge(0) materials that result will be nanocrystals or nanowires.

  15. Polyimide Cellulose Nanocrystal Composite Aerogels

    NASA Technical Reports Server (NTRS)

    Nguyen, Baochau N.; Meador, Mary Ann; Rowan, Stuart; Cudjoe, Elvis; Sandberg, Anna

    2014-01-01

    Polyimide (PI) aerogels are highly porous solids having low density, high porosity and low thermal conductivity with good mechanical properties. They are ideal for various applications including use in antenna and insulation such as inflatable decelerators used in entry, decent and landing operations. Recently, attention has been focused on stimuli responsive materials such as cellulose nano crystals (CNCs). CNCs are environmentally friendly, bio-renewable, commonly found in plants and the dermis of sea tunicates, and potentially low cost. This study is to examine the effects of CNC on the polyimide aerogels. The CNC used in this project are extracted from mantle of a sea creature called tunicates. A series of polyimide cellulose nanocrystal composite aerogels has been fabricated having 0-13 wt of CNC. Results will be discussed.

  16. A luminescent nanocrystal stress gauge

    SciTech Connect

    Choi, Charina; Koski, Kristie; Olson, Andrew; Alivisatos, Paul

    2010-10-25

    Microscale mechanical forces can determine important outcomes ranging from the site of material fracture to stem cell fate. However, local stresses in a vast majority of systems cannot be measured due to the limitations of current techniques. In this work, we present the design and implementation of the CdSe/CdS core/shell tetrapod nanocrystal, a local stress sensor with bright luminescence readout. We calibrate the tetrapod luminescence response to stress, and use the luminescence signal to report the spatial distribution of local stresses in single polyester fibers under uniaxial strain. The bright stress-dependent emission of the tetrapod, its nanoscale size, and its colloidal nature provide a unique tool that may be incorporated into a variety of micromechanical systems including materials and biological samples to quantify local stresses with high spatial resolution.

  17. 2009 Clusters, Nanocrystals & Nanostructures GRC

    SciTech Connect

    Lai-Sheng Wang

    2009-07-19

    For over thirty years, this Gordon Conference has been the premiere meeting for the field of cluster science, which studies the phenomena that arise when matter becomes small. During its history, participants have witnessed the discovery and development of many novel materials, including C60, carbon nanotubes, semiconductor and metal nanocrystals, and nanowires. In addition to addressing fundamental scientific questions related to these materials, the meeting has always included a discussion of their potential applications. Consequently, this conference has played a critical role in the birth and growth of nanoscience and engineering. The goal of the 2009 Gordon Conference is to continue the forward-looking tradition of this meeting and discuss the most recent advances in the field of clusters, nanocrystals, and nanostructures. As in past meetings, this will include new topics that broaden the field. In particular, a special emphasis will be placed on nanomaterials related to the efficient use, generation, or conversion of energy. For example, we anticipate presentations related to batteries, catalysts, photovoltaics, and thermoelectrics. In addition, we expect to address the controversy surrounding carrier multiplication with a session in which recent results addressing this phenomenon will be discussed and debated. The atmosphere of the conference, which emphasizes the presentation of unpublished results and lengthy discussion periods, ensures that attendees will enjoy a valuable and stimulating experience. Because only a limited number of participants are allowed to attend this conference, and oversubscription is anticipated, we encourage all interested researchers from academia, industry, and government institutions to apply as early as possible. An invitation is not required. We also encourage all attendees to submit their latest results for presentation at the poster sessions. We anticipate that several posters will be selected for 'hot topic' oral

  18. From fullerenes to nanocrystals and nanocrystal arrays: Novel preparation and characterization methods

    NASA Astrophysics Data System (ADS)

    Vezmar, Igor

    1998-09-01

    The success of cluster physics and chemistry and the macroscopic isolation of fullerenes motivated the research of nanometer-size from assemblies based on other elements. In this work an alternative fullerene generation method, utilizing the annealing of an all-carbon precursor formed in the reaction of halocarbons with alkali metals, has been demonstrated. Furthermore, a novel method of nanocrystal processing has been achieved via a compact, well-controlled, multi-stage inert gas flow system operating at near atmospheric pressure. The versatility and adaptability of the nanocrystal flow processor allows for the preparation of various nanostructured materials. Nanocrystal processing in the context of this work means the controlled growth of nanocrystals in a vapor phase environment, their annealing to obtain preferred morphologies, and subsequent full surface stabilization to facilitate collection and handling. The nanocrystal flow processor is coupled in-line to a time-of-flight mass spectrometer for real-time nanocrystal size and composition determination. Continuous sampling and mass analyzing of nanocrystals in the nanometer-diameter size range (up to one million Daltons) at part per billion concentrations has been achieved. Sampling of helium flows bearing benzene, fullerenes, as well as sodium, magnesium, silver, and cesium-iodide nanocrystals has been demonstrated. Using the nanocrystal processing approach, stable silver and gold nanocrystals of uniform size and shape distribution, passivated by self-assembled monolayers of long-chain thiol molecules were successfully prepared. The post-analysis of noble metal nanocrystals included optical spectroscopy, electron microscopy imaging and diffraction, x-ray diffraction and mass spectrometry. Stable and intense cluster beams from gold and silver nanocrystals were produced by laser desorption of molecular films. The mass onset of the desorbed entities corresponds directly to the dimensions of the nanocrystal core

  19. Synthesis of nanocrystals and nanocrystal self-assembly

    NASA Astrophysics Data System (ADS)

    Chen, Zhuoying

    Chapter 1. A general introduction is presented on nanomaterials and nanoscience. Nanoparticles are discussed with respect to their structure and properties. Ferroelectric materials and nanoparticles in particular are highlighted, especially in the case of the barium titanate, and their potential applications are discussed. Different nanocrystal synthetic techniques are discussed. Nanoparticle superlattices, the novel "meta-materials" built from self-assembly at the nanoscale, are introduced. The formation of nanoparticle superlattices and the importance and interest of synthesizing these nanostructures is discussed. Chapter 2. Advanced applications for high k dielectric and ferroelectric materials in the electronics industry continues to demand an understanding of the underlying physics in decreasing dimensions into the nanoscale. The first part of this chapter presents the synthesis, processing, and electrical characterization of nanostructured thin films (thickness ˜100 nm) of barium titanate BaTiO3 built from uniform nanoparticles (<20 nm in diameter) in diameter. Essential to our approach is an understanding of the nanoparticle as a building block, combined with an ability to integrate them into thin films that have uniform and characteristic electrical properties. We observe the BaTiO3 nanocrystals crystallize with evidence of tetragonality. Electric field dependent polarization measurements show spontaneous polarization and hysteresis, indicating ferroelectric behavior for the BaTiO 3 nanocrystalline films with grain sizes in the range of 10--30 nm. Dielectric measurements of the films show dielectic constants in the range of 85--90 over the 1 kHz--100 kHz, with low loss. We present nanocrystals as initial building blocks for the preparation of thin films which exhibit uniform nanostructured morphologies and grain sizes. In the second part of this chapter, a nonhydrolytic alcoholysis route to study the preparation of well-crystallized size-tunable BaTiO3

  20. Surface treatment of nanocrystal quantum dots after film deposition

    DOEpatents

    Sykora, Milan; Koposov, Alexey; Fuke, Nobuhiro

    2015-02-03

    Provided are methods of surface treatment of nanocrystal quantum dots after film deposition so as to exchange the native ligands of the quantum dots for exchange ligands that result in improvement in charge extraction from the nanocrystals.

  1. Low-temperature magnetic properties of monoclinic pyrrhotite with particular relevance to the Besnus transition

    NASA Astrophysics Data System (ADS)

    Volk, Michael W. R.; Gilder, Stuart A.; Feinberg, Joshua M.

    2016-12-01

    Monoclinic pyrrhotite (Fe7S8) owes its ferrimagnetism to an ordered array of Fe vacancies. Its magnetic properties change markedly around 30 K, in what is known as the Besnus transition. Plausible explanations for the Besnus transition are either due to changes in crystalline anisotropy from a transformation in crystal symmetry or from the establishment of a two-phase system with magnetic interaction between the two phases. To help resolve this discrepancy, we measured hysteresis loops every 5° and backfield curves every 10° in the basal plane of an oriented single crystal of monoclinic pyrrhotite at 300 K and every 2 K from 50 K through the Besnus transition until 20 K. Between 50 and 30 K, hysteresis loops possess double inflections between crystallographic a-axes and only a single inflection parallel to the a-axes. Magnetization energy calculations and relative differences of the loops show a sixfold symmetry in this temperature range. We propose that the inflections stem from magnetic axis switching, which is both field and temperature dependent, in a manner somewhat analogous to an isotropic point where magnetocrystalline constants change their sign. The Besnus transition is best characterized by changes in magnetic remanence and coercivity over a 6° temperature span (28-34 K) with a maximum rate of change at 30 K. A surprising yet puzzling finding is that the coercivity ratio becomes less than unity below the transition when fourfold symmetry arises. Because the changes in magnetic parameters are linked to the crystal structure, we conclude the Besnus transition owes its origin to a distortion of the crystallographic axes below 30 K rather than an apparition of a two-phase system. An isothermal magnetization of natural pyrrhotite cycled from room temperature to successively lower temperatures through the Besnus transition decreases 2-4 times less than equivalent grain sizes of magnetite, with less than a 10 per cent loss in remanence between 300 and 150 K

  2. Dissolution Behavior of Plutonium Containing Zirconia-Magnesia Ceramics

    SciTech Connect

    Kiel Holliday; Thomas Hartmann; Gary Cerefice; Ken Czerwinski

    2012-03-01

    This study explores the dissolution properties of zirconia-magnesia ceramics containing plutonium as the basis of an inert atrix nuclear fuel. The magnesium oxide phase remains pure MgO, while the zirconia incorporates a small amount of magnesium oxide along with all of the plutonium oxide and erbium oxide. The performance of the material under reactor and repository environments was examined. Reactor conditions are examined using a pressure vessel to expose the material to 300 degrees C water. To assess the performance of the material as a waste form it was submerged in 90 degrees C water for 1000 h. In both aqueous dissolution studies there was minimal release of less than 0.8 wt.% of plutonium from the material. To examine the potential for recycling, the dissolution behavior of the fuel matrix was examined in acidic solutions: pure nitric acid and a nitric acid-hydrofluoric acid-peroxide solution. Both acidic media exhibit potential for dissolving plutonium from the zirconia matrix. The experiments performed in this study are meant to lay a foundation for the chemical performance of zirconia-magnesia inert matrix fuel containing fissile material and burnable poison.

  3. Solid state dye lasers: rhodamines in silica-zirconia materials.

    PubMed

    Schultheiss, Silke; Yariv, Eli; Reisfeld, Renata; Breuer, Hans Dieter

    2002-05-01

    Silica-zirconia materials as well as silica-zirconia ormosils prepared by the sol-gel technique were doped with the laser dyes Rhodamine B and Rhodamine 6G and used as solid state dye lasers. The photostability and efficiency of the solid state laser samples were measured in a transverse pumping configuration by either a nitrogen laser or the second harmonic of a Nd-YAG laser. Under the excitation of a nitrogen laser the photostability of Rhodamine B in silica-zirconia materials was low and decreased with a growing amount of zirconia. The photophysical properties of the incorporated dyes were studied by time-resolved fluorescence spectroscopy. The fluorescence lifetimes of both dyes increased when the matrix was modified by organic compounds Furthermore, the threshold energy of Rhodamine 6G in two ormosils containing 3 and 50% methylsilica was measured. The results revealed that the threshold energy was lower for the matrix with a higher amount of ormosil while the slope efficiency was higher in the matrix containing 30% ormosil.

  4. Nanocrystal Bioassembly: Asymmetry, Proximity, and Enzymatic Manipulation

    SciTech Connect

    Claridge, Shelley A.

    2008-05-01

    Research at the interface between biomolecules and inorganic nanocrystals has resulted in a great number of new discoveries. In part this arises from the synergistic duality of the system: biomolecules may act as self-assembly agents for organizing inorganic nanocrystals into functional materials; alternatively, nanocrystals may act as microscopic or spectroscopic labels for elucidating the behavior of complex biomolecular systems. However, success in either of these functions relies heavily uponthe ability to control the conjugation and assembly processes.In the work presented here, we first design a branched DNA scaffold which allows hybridization of DNA-nanocrystal monoconjugates to form discrete assemblies. Importantly, the asymmetry of the branched scaffold allows the formation of asymmetric2assemblies of nanocrystals. In the context of a self-assembled device, this can be considered a step toward the ability to engineer functionally distinct inputs and outputs.Next we develop an anion-exchange high performance liquid chromatography purification method which allows large gold nanocrystals attached to single strands of very short DNA to be purified. When two such complementary conjugates are hybridized, the large nanocrystals are brought into close proximity, allowing their plasmon resonances to couple. Such plasmon-coupled constructs are of interest both as optical interconnects for nanoscale devices and as `plasmon ruler? biomolecular probes.We then present an enzymatic ligation strategy for creating multi-nanoparticle building blocks for self-assembly. In constructing a nanoscale device, such a strategy would allow pre-assembly and purification of components; these constructs can also act as multi-label probes of single-stranded DNA conformational dynamics. Finally we demonstrate a simple proof-of-concept of a nanoparticle analog of the polymerase chain reaction.

  5. Measurements of scattering anisotropy in dental tissue and zirconia ceramic

    NASA Astrophysics Data System (ADS)

    Fernández-Oliveras, Alicia; Pecho, Oscar E.; Rubiño, Manuel; Pérez, María M.

    2012-06-01

    Knowledge of the optical properties of biological structures is useful for clinical applications, especially when dealing with incoming biomaterials engineered to improve the benefits for the patient. One ceramic material currently used in restorative dentistry is yttrium cation-doped tetragonal zirconia polycrystal (3Y-TZP) because of its good mechanical properties. However, its optical properties have not been thoroughly studied. Many methods for the determination of optical parameters from biological media make the assumption that scattered light is isotropically distributed over all angles. Nevertheless, real biological materials may have an angular dependence on light scattering, which may affect the optical behaviour of the materials. Therefore, the recovery of the degree of anisotropy in the scattering angular distribution is important. The phase function that represents the scattering angular distribution is usually characterized by the anisotropy coefficient g, which equals the average cosine of the scattering angle. In this work, we measured angularscattering distributions for two zirconia ceramic samples, pre-sintered and sintered, with similar thicknesses (0.48 mm and 0.50 mm, respectively) and also for a human dentine sample (0.41 mm in thickness). The samples were irradiated with a He-Ne laser beam (λ = 632.8 nm) and the angular-scattering distributions were measured using a rotating goniometer. The g values yielded were: -0.7970 +/- 0.0016 for pre-sintered zirconia, -0.2074 +/- 0.0024 for sintered zirconia and 0.0620 +/- 0.0010 for dentine. The results show that zirconia sintering results in optical behaviour more similar to those of dentine tissue, in terms of scattering anisotropy.

  6. Electronic structure and optical properties of monoclinic clinobisvanite BiVO4.

    PubMed

    Zhao, Zongyan; Li, Zhaosheng; Zou, Zhigang

    2011-03-14

    Monoclinic clinobisvanite bismuth vanadate is an important material with wide applications. However, its electronic structure and optical properties are still not thoroughly understood. Density functional theory calculations were adopted in the present work, to comprehend the band structure, density of states, and projected wave function of BiVO(4). In particular, we put more emphasis upon the intrinsic relationship between its structure and properties. Based on the calculated results, its molecular-orbital bonding structure was proposed. And a significant phenomenon of optical anisotropy was observed in the visible-light region. Furthermore, it was found that its slightly distorted crystal structure enhances the lone-pair impact of Bi 6s states, leading to the special optical properties and excellent photocatalytic activities.

  7. A second monoclinic polymorph of (E)-phen­yl(pyridin-2-yl)methanone oxime

    PubMed Central

    Rodríguez-Mora, Monserrath I.; Reyes-Martínez, Reyna; Flores-Alamo, Marcos; García, Juventino J.; Morales-Morales, David

    2013-01-01

    The title compound, C12H10N2O, a second monoclinic poly­morph of (E)-phen­yl(pyridin-2-yl)methanone oxime crystallizes in the space group P21/n (Z = 4). The previously reported polymorph [Taga et al. (1990 ▶). Acta Cryst. C46, 2241–2243] occurs in the space group C2/c (Z = 8). In the crystal, pairs of bifurcated O—H⋯(N,O) hydrogen bonds link the mol­ecules into inversion dimers. The dimers are linked by C—H⋯π inter­actions, forming a linear arrangement. The dihedral angle between the pyridine and phenyl rings is 67.70 (8)°. PMID:23424575

  8. Calculation of thermodynamic, electronic, and optical properties of monoclinic Mg2NiH4

    SciTech Connect

    Myers, W.R.; Richardson, T.J.; Rubin, M.D.; Wang, L-W.

    2001-10-01

    Ab initio total-energy density functional theory is used to investigate the low temperature (LT) monoclinic form of Mg2NiH4. The calculated minimum energy geometry of LT Mg2NiH4 is close to that determined from neutron diffraction data, and the NiH4 complex is close to a regular tetrahedron. The enthalpies of the phase change to high temperature (HT) pseudo-cubic Mg2NiH4 and of hydrogen absorption by Mg2Ni are calculated and compared with experimental values. LT Mg2NiH4 is found to be a semiconductor with an indirect band gap of 1.4 eV. The optical dielectric function of LT Mg2NiH4 differs somewhat from that of the HT phase. A calculated thin film transmittance spectrum is consistent with an experimental spectrum.

  9. Surface roughness of zirconia for full-contour crowns after clinically simulated grinding and polishing.

    PubMed

    Hmaidouch, Rim; Müller, Wolf-Dieter; Lauer, Hans-Christoph; Weigl, Paul

    2014-12-01

    The aim of this study was to evaluate the effect of controlled intraoral grinding and polishing on the roughness of full-contour zirconia compared to classical veneered zirconia. Thirty bar-shaped zirconia specimens were fabricated and divided into two groups (n=15). Fifteen specimens (group 1) were glazed and 15 specimens (group 2) were veneered with feldspathic ceramic and then glazed. Prior to grinding, maximum roughness depth (Rmax) values were measured using a profilometer, 5 times per specimen. Simulated clinical grinding and polishing were performed on the specimens under water coolant for 15 s and 2 N pressure. For grinding, NTI diamonds burs with grain sizes of 20 µm, 10 µm, and 7.5 µm were used sequentially. The ground surfaces were polished using NTI kits with coarse, medium and fine polishers. After each step, Rmax values were determined. Differences between groups were examined using one-way analysis of variance (ANOVA). The roughness of group 1 was significantly lower than that of group 2. The roughness increased significantly after coarse grinding in both groups. The results after glazing were similar to those obtained after fine grinding for non-veneered zirconia. However, fine-ground veneered zirconia had significantly higher roughness than venerred, glazed zirconia. No significant difference was found between fine-polished and glazed zirconia, but after the fine polishing of veneered zirconia, the roughness was significantly higher than after glazing. It can be concluded that for full-contour zirconia, fewer defects and lower roughness values resulted after grinding and polishing compared to veneered zirconia. After polishing zirconia, lower roughness values were achieved compared to glazing; more interesting was that the grinding of glazed zirconia using the NTI three-step system could deliver smooth surfaces comparable to untreated glazed zirconia surfaces.

  10. Surface roughness of zirconia for full-contour crowns after clinically simulated grinding and polishing

    PubMed Central

    Hmaidouch, Rim; Müller, Wolf-Dieter; Lauer, Hans-Christoph; Weigl, Paul

    2014-01-01

    The aim of this study was to evaluate the effect of controlled intraoral grinding and polishing on the roughness of full-contour zirconia compared to classical veneered zirconia. Thirty bar-shaped zirconia specimens were fabricated and divided into two groups (n=15). Fifteen specimens (group 1) were glazed and 15 specimens (group 2) were veneered with feldspathic ceramic and then glazed. Prior to grinding, maximum roughness depth (Rmax) values were measured using a profilometer, 5 times per specimen. Simulated clinical grinding and polishing were performed on the specimens under water coolant for 15 s and 2 N pressure. For grinding, NTI diamonds burs with grain sizes of 20 µm, 10 µm, and 7.5 µm were used sequentially. The ground surfaces were polished using NTI kits with coarse, medium and fine polishers. After each step, Rmax values were determined. Differences between groups were examined using one-way analysis of variance (ANOVA). The roughness of group 1 was significantly lower than that of group 2. The roughness increased significantly after coarse grinding in both groups. The results after glazing were similar to those obtained after fine grinding for non-veneered zirconia. However, fine-ground veneered zirconia had significantly higher roughness than venerred, glazed zirconia. No significant difference was found between fine-polished and glazed zirconia, but after the fine polishing of veneered zirconia, the roughness was significantly higher than after glazing. It can be concluded that for full-contour zirconia, fewer defects and lower roughness values resulted after grinding and polishing compared to veneered zirconia. After polishing zirconia, lower roughness values were achieved compared to glazing; more interesting was that the grinding of glazed zirconia using the NTI three-step system could deliver smooth surfaces comparable to untreated glazed zirconia surfaces. PMID:25059249

  11. Structural evolution and electrochemistry of monoclinic NaNiO2 upon the first cycling process

    NASA Astrophysics Data System (ADS)

    Han, Man Huon; Gonzalo, Elena; Casas-Cabanas, Montse; Rojo, Teófilo

    2014-07-01

    Electrochemistry and structural evolution of monoclinic NaNiO2 as a cathode material for Na-ion battery is reported. The initial charge capacity reached 160 mA h g-1 and the following discharge capacity of 114.6 mA h g-1, within the voltage range of 4.0-1.5 V at C/10. The multiple phase transition leading to O‧3, P‧3, P″3, O″3, and O‴3 stacking types (NaNiO2, Na0.91NiO2, Na0.84NiO2, Na0.81NiO2 and Na0.79NiO2 transitions, respectively, according to a previous report) during the 1st charge/discharge process is analysed using ex situ and in situ XRD techniques, and the stoichiometry of each phase is herein revised. The charge/discharge profile shows a highly reversible nature of the cathode, except that fully sodiated phase could not be achieved at the subsequent discharge. Two new phases have been discovered: a monoclinic O3 structure (designated as O⁗3) at the beginning of the charge (and end of discharge) and a P3 structure (designated as P‴3) at 3.38 V that appeared only during the charge process. The composition of the new O⁗3-phase corresponds to Na0.83NiO2, which is the closest to the fully sodiated phase at room temperature achieved during the discharge process reported up to date, and the composition of the new P‴3-phase corresponds approximately to Na0.50NiO2.

  12. Paleomagnetic and structural evidence for oblique slip in a fault-related fold, Grayback monocline, Colorado

    USGS Publications Warehouse

    Tetreault, J.; Jones, C.H.; Erslev, E.; Larson, S.; Hudson, M.; Holdaway, S.

    2008-01-01

    Significant fold-axis-parallel slip is accommodated in the folded strata of the Grayback monocline, northeastern Front Range, Colorado, without visible large strike-slip displacement on the fold surface. In many cases, oblique-slip deformation is partitioned; fold-axis-normal slip is accommodated within folds, and fold-axis-parallel slip is resolved onto adjacent strike-slip faults. Unlike partitioning strike-parallel slip onto adjacent strike-slip faults, fold-axis-parallel slip has deformed the forelimb of the Grayback monocline. Mean compressive paleostress orientations in the forelimb are deflected 15??-37?? clockwise from the regional paleostress orientation of the northeastern Front Range. Paleomagnetic directions from the Permian Ingleside Formation in the forelimb are rotated 16??-42?? clockwise about a bedding-normal axis relative to the North American Permian reference direction. The paleostress and paleomagnetic rotations increase with the bedding dip angle and decrease along strike toward the fold tip. These measurements allow for 50-120 m of fold-axis-parallel slip within the forelimb, depending on the kinematics of strike-slip shear. This resolved horizontal slip is nearly equal in magnitude to the ???180 m vertical throw across the fold. For 200 m of oblique-slip displacement (120 m of strike slip and 180 m of reverse slip), the true shortening direction across the fold is N90??E, indistinguishable from the regionally inferred direction of N90??E and quite different from the S53??E fold-normal direction. Recognition of this deformational style means that significant amounts of strike slip can be accommodated within folds without axis-parallel surficial faulting. ?? 2008 Geological Society of America.

  13. Investigation of the femtosecond optical limiting properties of monoclinic copper niobate

    NASA Astrophysics Data System (ADS)

    Priyadarshani, N.; Venugopal Rao, S.; Sabari Girisun, T. C.

    2016-10-01

    Investigation of the third-order nonlinear optical properties and optical limiting behaviour of microstructured monoclinic phase copper niobate (CuNb2O6) was performed by the Z-scan technique using femtosecond laser pulses (800 nm, 150 fs, 80 MHz). CuNb2O6 was synthesized by solid-state reaction at a sintering temperature of 700 °C maintained at different times of 3, 6, 9 and 12 h. Formation of rods at higher reaction time of 12 h was observed and is attributed to the mass transport and coalescence processes. From the absorption tail of UV-Vis spectrum, the optical band gap was estimated to be 3.5 eV. In the fluorescence spectra, blue emission was observed near 430 nm and was assigned to the charge transfer from oxygen to central niobium of Nb-O6 octahedra. Open-aperture Z-scan data demonstrated the presence of nonlinear absorption in copper niobate and are ascribed to two-photon absorption process. Closed-aperture data indicated a sign reversal in nonlinear refraction as the sintering time increased. Third-order nonlinear optical coefficients were estimated, and the largest coefficient was observed for the rod-structured CuNb2O6. Copper niobate exhibited optical limiting behaviour, and the limiting threshold was found to be lowest for microrod structures (~0.21 µJ/cm2). Due to the top-notch third-order nonlinear optical coefficients and excellent limiting behaviour, monoclinic copper niobate microrods can be used as a potential material for utilization as an optical limiter for femtosecond pulses.

  14. Crystal structure of 8-hy-droxy-quinoline: a new monoclinic polymorph.

    PubMed

    Castañeda, Raúl; Antal, Sofia A; Draguta, Sergiu; Timofeeva, Tatiana V; Khrustalev, Victor N

    2014-09-01

    In an attempt to grow 8-hy-droxy-quinoline-acetamino-phen co-crystals from equimolar amounts of conformers in a chloro-form-ethanol solvent mixture at room temperature, the title compound, C9H7NO, was obtained. The mol-ecule is planar, with the hy-droxy H atom forming an intra-molecular O-H⋯N hydrogen bond. In the crystal, mol-ecules form centrosymmetric dimers via two O-H⋯N hydrogen bonds. Thus, the hy-droxy H atoms are involved in bifurcated O-H⋯N hydrogen bonds, leading to the formation of a central planar four-membered N2H2 ring. The dimers are bound by inter-molecular π-π stacking [the shortest C⋯C distance is 3.2997 (17) Å] and C-H⋯π inter-actions into a three-dimensional framework. The crystal grown represents a new monoclinic polymorph in the space group P21/n. The mol-ecular structure of the present monoclinic polymorph is very similar to that of the ortho-rhom-bic polymorph (space group Fdd2) studied previously [Roychowdhury et al. (1978 ▶). Acta Cryst. B34, 1047-1048; Banerjee & Saha (1986 ▶). Acta Cryst. C42, 1408-1411]. The structures of the two polymorphs are distinguished by the different geometries of the hydrogen-bonded dimers, which in the crystal of the ortho-rhom-bic polymorph possess twofold axis symmetry, with the central N2H2 ring adopting a butterfly conformation.

  15. Cadmium Stabilization Efficiency and Leachability by CdAl4O7 Monoclinic Structure.

    PubMed

    Su, Minhua; Liao, Changzhong; Chuang, Kui-Hao; Wey, Ming-Yen; Shih, Kaimin

    2015-12-15

    This study investigated the stabilization efficiencies of using an aluminum-rich precursor to incorporate simulated cadmium-bearing waste sludge and evaluated the leaching performance of the product phase. Cadmium oxide and γ-alumina mixtures with various Cd/Al molar ratios were fired at 800-1000 °C for 3 h. Cadmium could be crystallochemically incorporated by γ-alumina into CdAl4O7 monoclinic phase and the reaction was strongly controlled by the treatment temperature. The crystal structure details of CdAl4O7 were solved and refined with the Rietveld refinement method. According to the structural refinement results, the stabilization efficiencies were quantified and expressed as a transformation ratio (TR) with optimized processing parameters. The preferred treatment temperature was found to be 950 °C for mixtures with a Cd/Al molar ratio of 1/4, as its TR value indicated the cadmium incorporation was nearly completed after a 3 h treatment scheme. Constant-pH leaching tests (CPLT) were conducted by comparing the leachability of the CdO and CdAl4O7 phases in a pH 4.0 environment. A remarkable reduction in cadmium leachability could be achieved via monoclinic CdAl4O7 structure formation to effectively stabilize hazardous cadmium in the waste stream. The CPLT and X-ray photoelectron spectroscopy (XPS) results suggested incongruent dissolution behavior during the leaching of the CdAl4O7 phase.

  16. Size Effect of Embedded Nanocrystals in Floating Gate MOSFET Devices

    NASA Astrophysics Data System (ADS)

    Cheng, X. Z.; Jalil, M. B. A.; Samudra, G. S.

    2011-12-01

    We investigate the transport and retention properties of a floating-gate MOSFET memory device incorporating embedded nanocrystals. Of particular interest is the nanocrystal size effect on the retention lifetime of the device. The quantum confinement effects and changes to the electrostatic energy arising from the decrease of the nanocrystal size are analyzed both numerically and analytically.

  17. Metal halide solid-state surface treatment for nanocrystal materials

    DOEpatents

    Luther, Joseph M.; Crisp, Ryan; Beard, Matthew C.

    2016-04-26

    Methods of treating nanocrystal and/or quantum dot devices are described. The methods include contacting the nanocrystals and/or quantum dots with a solution including metal ions and halogen ions, such that the solution displaces native ligands present on the surface of the nanocrystals and/or quantum dots via ligand exchange.

  18. Comparison of peri-implant bone formation around injection-molded and machined surface zirconia implants in rabbit tibiae.

    PubMed

    Kim, Hong-Kyun; Woo, Kyung Mi; Shon, Won-Jun; Ahn, Jin-Soo; Cha, Seunghee; Park, Young-Seok

    2015-01-01

    The aim of this study was to compare osseointegration and surface characteristics of zirconia implants made by the powder injection molding (PIM) technique against those made by the conventional milling procedure in rabbit tibiae. Surface characteristics of 2 types of implants were evaluated. Sixteen rabbits received 2 types of external hex implants with similar geometry, either machined zirconia implants or PIM zirconia implants, in the tibiae. Removal torque tests and histomorphometric analyses were performed. The roughness of the PIM zirconia implants was higher than that of machined zirconia implants. The PIM zirconia implants exhibited significantly higher bone-implant contact and removal torque values than the machined zirconia implants (p<0.001). The osseointegration of the PIM zirconia implant is promising, and PIM, using the roughened mold etching technique, can produce substantially rougher surfaces on zirconia implants.

  19. Iron Oxide Nanocrystals for Magnetic Hyperthermia Applications

    PubMed Central

    Armijo, Leisha M.; Brandt, Yekaterina I.; Mathew, Dimple; Yadav, Surabhi; Maestas, Salomon; Rivera, Antonio C.; Cook, Nathaniel C.; Withers, Nathan J.; Smolyakov, Gennady A.; Adolphi, Natalie; Monson, Todd C.; Huber, Dale L.; Smyth, Hugh D. C.; Osiński, Marek

    2012-01-01

    Magnetic nanocrystals have been investigated extensively in the past several years for several potential applications, such as information technology, MRI contrast agents, and for drug conjugation and delivery. A specific property of interest in biomedicine is magnetic hyperthermia—an increase in temperature resulting from the thermal energy released by magnetic nanocrystals in an external alternating magnetic field. Iron oxide nanocrystals of various sizes and morphologies were synthesized and tested for specific losses (heating power) using frequencies of 111.1 kHz and 629.2 kHz, and corresponding magnetic field strengths of 9 and 25 mT. Polymorphous nanocrystals as well as spherical nanocrystals and nanowires in paramagnetic to ferromagnetic size range exhibited good heating power. A remarkable 30 °C temperature increase was observed in a nanowire sample at 111 kHz and magnetic field of 25 mT (19.6 kA/m), which is very close to the typical values of 100 kHz and 20 mT used in medical treatments.

  20. Field-effect electroluminescence in silicon nanocrystals.

    PubMed

    Walters, Robert J; Bourianoff, George I; Atwater, Harry A

    2005-02-01

    There is currently worldwide interest in developing silicon-based active optical components in order to leverage the infrastructure of silicon microelectronics technology for the fabrication of optoelectronic devices. Light emission in bulk silicon-based devices is constrained in wavelength to infrared emission, and in efficiency by the indirect bandgap of silicon. One promising strategy for overcoming these challenges is to make use of quantum-confined excitonic emission in silicon nanocrystals. A critical challenge for silicon nanocrystal devices based on nanocrystals embedded in silicon dioxide has been the development of a method for efficient electrical carrier injection. We report here a scheme for electrically pumping dense silicon nanocrystal arrays by a field-effect electroluminescence mechanism. In this excitation process, electrons and holes are both injected from the same semiconductor channel across a tunnelling barrier in a sequential programming process, in contrast to simultaneous carrier injection in conventional pn-junction light-emitting-diode structures. Light emission is strongly correlated with the injection of a second carrier into a nanocrystal that has been previously programmed with a charge of the opposite sign.

  1. Electrical conductivity of zirconia and yttrium-doped zirconia from Indonesian local zircon as prospective material for fuel cells

    NASA Astrophysics Data System (ADS)

    Apriany, Karima; Permadani, Ita; Syarif, Dani G.; Soepriyanto, Syoni; Rahmawati, Fitria

    2016-02-01

    In this research, zirconium dioxide, ZrO2, was synthesized from high-grade zircon sand that was founded from Bangka Island, Sumatra, Indonesia. The zircon sand is a side product of Tin mining plant industry. The synthesis was conducted by caustic fusion method with considering definite stoichiometric mole at every reaction step. Yttrium has been doped into the prepared zirconia by solid state reaction. The prepared materials were then being analyzed by X-ray diffraction equipped with Le Bail refinement to study its crystal structure and cell parameters. Electrical conductivity was studied through impedance measurement at a frequency range of 20 Hz- 5 MHz. Morphological analysis was conducted through Scanning Electron Microscopy (SEM) equipped with Energy Dispersive X-ray (EDX) for elemental analysis. The results show that the prepared yttrium stabilized zirconia, YSZ, was crystallized in the cubic structure with a space group of P42/NMC. The sintered zirconia and yttrium stabilized zirconia at 8 mol% of yttrium ions (8YSZ) show dense surface morphology with a grain size less than 10 pm. Elemental analysis on the sintered zirconia and 8YSZ show that sintering at 1500°C could eliminate the impurities, and the purity became 81.30%. Impedance analysis shows that ZrO2 provide grain and grain boundary conductivity meanwhile 8YSZ only provide grain mechanism. The yttrium doping enhanced the conductivity up to 1.5 orders. The ionic conductivity of the prepared 8YSZ is categorized as a good material with conductivity reach 7.01 x10-3 at 700 °C. The ionic conductivities are still lower than commercial 8YSZ at various temperature. It indicates that purity of raw material might significantly contribute to the electrical conductivity.

  2. Mechanical behaviors and phase transition of Ho{sub 2}O{sub 3} nanocrystals under high pressure

    SciTech Connect

    Yan, Xiaozhi; Ren, Xiangting; He, Duanwei E-mail: yangwg@hpstar.ac.cn; Chen, Bin; Yang, Wenge E-mail: yangwg@hpstar.ac.cn

    2014-07-21

    Mechanical properties and phase transition often show quite large crystal size dependent behavior, especially at nanoscale under high pressure. Here, we have investigated Ho{sub 2}O{sub 3} nanocrystals with in-situ x-ray diffraction and Raman spectroscopy under high pressure up to 33.5 GPa. When compared to the structural transition routine cubic -> monoclinic -> hexagonal phase in bulk Ho{sub 2}O{sub 3} under high pressure, the nano-sized Ho{sub 2}O{sub 3} shows a much higher onset transition pressure from cubic to monoclinic structure and followed by a pressure-induced-amorphization under compression. The detailed analysis on the Q (Q = 2π/d) dependent bulk moduli reveals the nanosized Ho{sub 2}O{sub 3} particles consist of a clear higher compressible shell and a less compressible core. Insight into these phenomena shed lights on micro-mechanism studies of the mechanical behavior and phase evolution for nanomaterials under high pressure, in general.

  3. Designer Nanocrystal Materials for Photovoltaics

    NASA Astrophysics Data System (ADS)

    Kagan, Cherie

    Advances in synthetic methods allow a wide range of semiconductor nanocrystals (NCs) to be tailored in size and shape and to be used as building blocks in the design of NC solids. However, the long, insulating ligands commonly employed in the synthesis of colloidal NCs inhibit strong interparticle coupling and charge transport once NCs are assembled into the solids state as NC arrays. We will describe the range of short, compact ligand chemistries we employ to exchange the long, insulating ligands used in synthesis and to increase interparticle coupling. These ligand exchange processes can have a dramatic influence on NC surface chemistry as well as NC organization in the solids, showing examples of short-range order. Synergistically, we use 1) thermal evaporation and diffusion and 2) wet-chemical methods to introduce extrinsic impurities and non-stoichiometry to passivate surface traps and dope NC solids. NC coupling and doping provide control over the density of states and the carrier type, concentration, mobility, and lifetime, which we characterize by a range of electronic and spectroscopic techniques. We will describe the importance of engineering device interfaces to design NC materials for solar photovoltaics.

  4. Prospects of nanoscience with nanocrystals

    SciTech Connect

    Kovalenko, Maksym V.; Manna, Liberato; Cabot, Andreu; Hens, Zeger; Talapin, Dmitri V.; Kagan, Cherie R.; Klimov, Victor I.; Rogach, Andrey L.; Reiss, Peter; Milliron, Delia J.; Guyot-Sionnnest, Philippe; Konstantatos, Gerasimos; Parak, Wolfgang J.; Hyeon, Taeghwan; Korgel, Brian A.; Murray, Christopher B.; Heiss, Wolfgang

    2015-01-22

    Colloidal nanocrystals (NCs, i.e., crystalline nanoparticles) have become an important class of materials with great potential for applications ranging from medicine to electronic and optoelectronic devices. Today's strong research focus on NCs has been prompted by the tremendous progress in their synthesis. Impressively narrow size distributions of just a few percent, rational shape-engineering, compositional modulation, electronic doping, and tailored surface chemistries are now feasible for a broad range of inorganic compounds. Furthermore, the performance of inorganic NC-based photovoltaic and lightemitting devices has become competitive to other state-of-the-art materials. Semiconductor NCs hold unique promise for near- and mid-infrared technologies, where very few semiconductor materials are available. On a purely fundamental side, new insights into NC growth, chemical transformations, and self-organization can be gained from rapidly progressing in situ characterization and direct imaging techniques. New phenomena are constantly being discovered in the photophysics of NCs and in the electronic properties of NC solids. In our Nano Focus, we review the state of the art in research on colloidal NCs focusing on the most recent works published in the last 2 years.

  5. Prospects of nanoscience with nanocrystals

    DOE PAGES

    Kovalenko, Maksym V.; Manna, Liberato; Cabot, Andreu; ...

    2015-01-22

    Colloidal nanocrystals (NCs, i.e., crystalline nanoparticles) have become an important class of materials with great potential for applications ranging from medicine to electronic and optoelectronic devices. Today's strong research focus on NCs has been prompted by the tremendous progress in their synthesis. Impressively narrow size distributions of just a few percent, rational shape-engineering, compositional modulation, electronic doping, and tailored surface chemistries are now feasible for a broad range of inorganic compounds. Furthermore, the performance of inorganic NC-based photovoltaic and lightemitting devices has become competitive to other state-of-the-art materials. Semiconductor NCs hold unique promise for near- and mid-infrared technologies, where verymore » few semiconductor materials are available. On a purely fundamental side, new insights into NC growth, chemical transformations, and self-organization can be gained from rapidly progressing in situ characterization and direct imaging techniques. New phenomena are constantly being discovered in the photophysics of NCs and in the electronic properties of NC solids. In our Nano Focus, we review the state of the art in research on colloidal NCs focusing on the most recent works published in the last 2 years.« less

  6. Prospects of nanoscience with nanocrystals.

    PubMed

    Kovalenko, Maksym V; Manna, Liberato; Cabot, Andreu; Hens, Zeger; Talapin, Dmitri V; Kagan, Cherie R; Klimov, Victor I; Rogach, Andrey L; Reiss, Peter; Milliron, Delia J; Guyot-Sionnnest, Philippe; Konstantatos, Gerasimos; Parak, Wolfgang J; Hyeon, Taeghwan; Korgel, Brian A; Murray, Christopher B; Heiss, Wolfgang

    2015-02-24

    Colloidal nanocrystals (NCs, i.e., crystalline nanoparticles) have become an important class of materials with great potential for applications ranging from medicine to electronic and optoelectronic devices. Today's strong research focus on NCs has been prompted by the tremendous progress in their synthesis. Impressively narrow size distributions of just a few percent, rational shape-engineering, compositional modulation, electronic doping, and tailored surface chemistries are now feasible for a broad range of inorganic compounds. The performance of inorganic NC-based photovoltaic and light-emitting devices has become competitive to other state-of-the-art materials. Semiconductor NCs hold unique promise for near- and mid-infrared technologies, where very few semiconductor materials are available. On a purely fundamental side, new insights into NC growth, chemical transformations, and self-organization can be gained from rapidly progressing in situ characterization and direct imaging techniques. New phenomena are constantly being discovered in the photophysics of NCs and in the electronic properties of NC solids. In this Nano Focus, we review the state of the art in research on colloidal NCs focusing on the most recent works published in the last 2 years.

  7. The structure and morphology of semiconductor nanocrystals

    SciTech Connect

    Kadavanich, Andreas V.

    1997-11-01

    Colloidal semiconductor nanocrystals were studied using High Resolution Transmission Electron Microscopy (HRTEM). Organically capped nanocrystals were found to have faceted shapes consistent with Wulff polyhedra after the effects of capping ligands on surface energies were taken into account. The basic shape thus derived for wurtzite (WZ) structure CdSe nanocrystals capped by tri-octyl phosphine oxide (TOPO) was a truncated hexagonal prism, elongated alone the <001> axis with (100) and (002) facets. This structure has C{sub 3v} point group symmetry. The main defect in this structure is a stacking fault (a single layer of zinc blende type stacking), which does not significantly affect the shape (does not alter the point group).

  8. Gold nanocrystals with DNA-directed morphologies

    NASA Astrophysics Data System (ADS)

    Ma, Xingyi; Huh, June; Park, Wounjhang; Lee, Luke P.; Kwon, Young Jik; Sim, Sang Jun

    2016-09-01

    Precise control over the structure of metal nanomaterials is important for developing advanced nanobiotechnology. Assembly methods of nanoparticles into structured blocks have been widely demonstrated recently. However, synthesis of nanocrystals with controlled, three-dimensional structures remains challenging. Here we show a directed crystallization of gold by a single DNA molecular regulator in a sequence-independent manner and its applications in three-dimensional topological controls of crystalline nanostructures. We anchor DNA onto gold nanoseed with various alignments to form gold nanocrystals with defined topologies. Some topologies are asymmetric including pushpin-, star- and biconcave disk-like structures, as well as more complex jellyfish- and flower-like structures. The approach of employing DNA enables the solution-based synthesis of nanocrystals with controlled, three-dimensional structures in a desired direction, and expands the current tools available for designing and synthesizing feature-rich nanomaterials for future translational biotechnology.

  9. Developing New Nanoprobes from Semiconductor Nanocrystals

    SciTech Connect

    Fu, Aihua

    2006-01-01

    In recent years, semiconductor nanocrystal quantum dots havegarnered the spotlight as an important new class of biological labelingtool. Withoptical properties superior to conventional organicfluorophores from many aspects, such as high photostability andmultiplexing capability, quantum dots have been applied in a variety ofadvanced imaging applications. This dissertation research goes along withlarge amount of research efforts in this field, while focusing on thedesign and development of new nanoprobes from semiconductor nanocrystalsthat are aimed for useful imaging or sensing applications not possiblewith quantum dots alone. Specifically speaking, two strategies have beenapplied. In one, we have taken advantage of the increasing capability ofmanipulating the shape of semiconductor nanocrystals by developingsemiconductor quantum rods as fluorescent biological labels. In theother, we have assembled quantum dots and gold nanocrystals into discretenanostructures using DNA. The background information and synthesis,surface manipulation, property characterization and applications of thesenew nanoprobes in a few biological experiments are detailed in thedissertation.

  10. Gold nanocrystals with DNA-directed morphologies

    PubMed Central

    Ma, Xingyi; Huh, June; Park, Wounjhang; Lee, Luke P.; Kwon, Young Jik; Sim, Sang Jun

    2016-01-01

    Precise control over the structure of metal nanomaterials is important for developing advanced nanobiotechnology. Assembly methods of nanoparticles into structured blocks have been widely demonstrated recently. However, synthesis of nanocrystals with controlled, three-dimensional structures remains challenging. Here we show a directed crystallization of gold by a single DNA molecular regulator in a sequence-independent manner and its applications in three-dimensional topological controls of crystalline nanostructures. We anchor DNA onto gold nanoseed with various alignments to form gold nanocrystals with defined topologies. Some topologies are asymmetric including pushpin-, star- and biconcave disk-like structures, as well as more complex jellyfish- and flower-like structures. The approach of employing DNA enables the solution-based synthesis of nanocrystals with controlled, three-dimensional structures in a desired direction, and expands the current tools available for designing and synthesizing feature-rich nanomaterials for future translational biotechnology. PMID:27633935

  11. Shaping metal nanocrystals through epitaxial seeded growth

    SciTech Connect

    Habas, Susan E.; Lee, Hyunjoo; Radmilovic, Velimir; Somorjai,Gabor A.; Yang, Peidong

    2008-02-17

    Morphological control of nanocrystals has becomeincreasingly important, as many of their physical and chemical propertiesare highly shape-dependent. Nanocrystal shape control for both single andmultiple material systems, however, remains fairly empirical andchallenging. New methods need to be explored for the rational syntheticdesign of heterostructures with controlled morphology. Overgrowth of adifferent material on well-faceted seeds, for example, allows for the useof the defined seed morphology to control nucleation and growth of thesecondary structure. Here, we have used highly faceted cubic Pt seeds todirect the epitaxial overgrowth of a secondary metal. We demonstrate thisconcept with lattice matched Pd to produce conformal shape-controlledcore-shell particles, and then extend it to lattice mismatched Au to giveanisotropic growth. Seeding with faceted nanocrystals may havesignificant potential towards the development of shape-controlledheterostructures with defined interfaces.

  12. Self-Organized Ultrathin Oxide Nanocrystals

    SciTech Connect

    Huo, Ziyang; Tsung, Chia-kuang; Huang, Wenyu; Fardy, Melissa; Yan, Ruoxue; Li, Yadong; Yang, Piedong; Zhang, Xiaofeng

    2009-01-08

    Sub-2-nm (down to one-unit cell) uniform oxide nanocrystals and highly ordered superstructures were obtained in one step using oleylamine and oleic acid as capping and structure directing agents. The cooperative nature of the nanocrystal growth and assembly resulted in mesoscopic one-dimensional ribbon-like superstructures made of these ultrathin nanocrystals. The process reported here is general and can be readily extended to the production of many other transition metal (TiO2, ZnO, Nb2O5) and rare earth oxide (Eu2O3, Sm2O3, Er2O3, Y2O3, Tb2O3, and Yb2O3) systems.

  13. Mechanical properties of yttria-stabilized zirconia ceramics

    NASA Astrophysics Data System (ADS)

    Shirooyeh A, Mahmood R.

    Superplasticity is a well-known characteristic of Y2O 3-stabilized tetragonal zirconia (3Y-TZP) ceramic composites at elevated temperatures. The present investigation was originated to evaluate the potential of producing zirconia ceramics suitable for achieving superplasticity. High purity 3 mol% Y2O3-stabilized tetragonal zirconia (3Y-TZP) ceramic composites containing 20 wt% alumina were successfully consolidated by application of Cold Isostatic Pressing (CIP) followed by a subsequent sintering process. Constant-stress tensile creep experiments at elevated temperatures were conducted in order to examine plastic deformation behavior of the material. In addition to mechanical testing data, the microstructure observations confirmed superplastic properties of the ceramic composite. It is also known that in order to attain High Strain Rate Superplasticity (HSRS) in zirconia ceramics, it is essential to retain a stable fine-grained microstructure at high temperatures. Experiments have confirmed that adding a second soft phase such as spinel can facilitate to reach high strain-rate superplasticity in zirconia ceramics by suppressing grain growth during sintering process and enhancing cation diffusion. In the present investigation, homogenous 3Y-TZP ceramic composite powders containing 30 vol% MgAl2O4 spinel were successfully prepared through both physical-based and chemical-based methods. An electric current-activated method known as Spark Plasma Sintering (SPS) was employed for powder consolidation process. This is a very rapid electric current-activated sintering technique having a heating rate of 300 K/min. The powder preparation and consolidation steps were carried out over a wide range of conditions to ensure a homogenous nanocomposite. The experiments showed that fully-dense zirconia ceramics with an average initial grain size of the order of ˜100 nm can be sintered at the relatively low processing temperature of 1373 K in 10 min. In order to study the

  14. Resin bonding of metal brackets to glazed zirconia with a porcelain primer

    PubMed Central

    Lee, Jung-Hwan; Lee, Milim; Kim, Kyoung-Nam

    2015-01-01

    Objective The aims of this study were to compare the shear bond strength between orthodontic metal brackets and glazed zirconia using different types of primer before applying resin cement and to determine which primer was more effective. Methods Zirconia blocks were milled and embedded in acrylic resin and randomly assigned to one of four groups: nonglazed zirconia with sandblasting and zirconia primer (NZ); glazed zirconia with sandblasting, etching, and zirconia primer (GZ); glazed zirconia with sandblasting, etching, and porcelain primer (GP); and glazed zirconia with sandblasting, etching, zirconia primer, and porcelain primer (GZP). A stainless steel metal bracket was bonded to each target surface with resin cement, and all specimens underwent thermal cycling. The shear bond strength of the specimens was measured by a universal testing machine. A scanning electron microscope, three-dimensional optical surface-profiler, and stereoscopic microscope were used to image the zirconia surfaces. The data were analyzed with one-way analyses of variance and the Fisher exact test. Results Group GZ showed significantly lower shear bond strength than did the other groups. No statistically significant differences were found among groups NZ, GP, and GZP. All specimens in group GZ showed adhesive failure between the zirconia and resin cement. In groups NZ and GP, bonding failed at the interface between the resin cement and bracket base or showed complex adhesive and cohesive failure. Conclusions Porcelain primer is the more appropriate choice for bonding a metal bracket to the surface of a full-contour glazed zirconia crown with resin cement. PMID:26629476

  15. Ferroelectric Self-Poling, Switching, and Monoclinic Domain Configuration in BiFeO 3 Thin Films

    DOE PAGES

    Beekman, C.; Siemons, W.; Chi, M.; ...

    2016-05-23

    Self-poling of ferroelectric films, i.e., a preferred, uniform direction of the ferroelectric polarization in as-grown samples is often observed yet poorly understood despite its importance for device applications. The multiferroic perovskite BiFeO3, which crystallizes in two distinct structural polymorphs depending on applied epitaxial strain, is well known to exhibit self-poling. This study investigates the effect of self-poling on the monoclinic domain configuration and the switching properties of the two polymorphs of BiFeO3 (R' and T') in thin films grown on LaAlO3 substrates with slightly different La0.3Sr0.7MnO3 buffer layers. Our study shows that the polarization state formed during the growth actsmore » as “imprint” on the polarization and that switching the polarization away from this self-poled direction can only be done at the expense of the sample's monoclinic domain configuration. We observed reduction of the monoclinic domain size and found that it was largely reversible; hence, the domain size is restored when the polarization is switched back to its original orientation. This is a direct consequence of the growth taking place in the polar phase (below Tc). Finally, switching the polarization away from the preferred configuration, in which defects and domain patterns synergistically minimize the system's energy, leads to a domain state with smaller (and more highly strained and distorted) monoclinic domains.« less

  16. Batteries: encapsulated monoclinic sulfur for stable cycling of li-s rechargeable batteries (adv. Mater. 45/2013).

    PubMed

    Moon, San; Jung, Young Hwa; Jung, Wook Ki; Jung, Dae Soo; Choi, Jang Wook; Kim, Do Kyung

    2013-12-03

    On page 6547 Do Kyung Kim, Jang Wook Choi and co-workers describe a highly aligned and carbon-encapsulated sulfur cathode synthesized with an AAO template that exhibits a high and long cycle life, and the best rate capability based on the complete encapsulation of sulfur (physical) and implementation of the monoclinic sulfur phase (chemical).

  17. Plasmonic Properties of Silicon Nanocrystals Doped with Boron and Phosphorus.

    PubMed

    Kramer, Nicolaas J; Schramke, Katelyn S; Kortshagen, Uwe R

    2015-08-12

    Degenerately doped silicon nanocrystals are appealing plasmonic materials due to silicon's low cost and low toxicity. While surface plasmonic resonances of boron-doped and phosphorus-doped silicon nanocrystals were recently observed, there currently is poor understanding of the effect of surface conditions on their plasmonic behavior. Here, we demonstrate that phosphorus-doped silicon nanocrystals exhibit a plasmon resonance immediately after their synthesis but may lose their plasmonic response with oxidation. In contrast, boron-doped nanocrystals initially do not exhibit plasmonic response but become plasmonically active through postsynthesis oxidation or annealing. We interpret these results in terms of substitutional doping being the dominant doping mechanism for phosphorus-doped silicon nanocrystals, with oxidation-induced defects trapping free electrons. The behavior of boron-doped silicon nanocrystals is more consistent with a strong contribution of surface doping. Importantly, boron-doped silicon nanocrystals exhibit air-stable plasmonic behavior over periods of more than a year.

  18. Composition-tunable alloyed semiconductor nanocrystals.

    PubMed

    Regulacio, Michelle D; Han, Ming-Yong

    2010-05-18

    The ability to engineer the band gap energy of semiconductor nanocrystals has led to the development of nanomaterials with many new exciting properties and applications. Band gap engineering has thus proven to be an effective tool in the design of new nanocrystal-based semiconductor devices. As reported in numerous publications over the last three decades, tuning the size of nanocrystalline semiconductors is one way of adjusting the band gap energy. On the other hand, research on band gap engineering via control of nanocrystal composition, which is achieved by adjusting the constituent stoichiometries of alloyed semiconductors, is still in its infancy. In this Account, we summarize recent research on colloidal alloyed semiconductor nanocrystals that exhibit novel composition-tunable properties. Alloying of two semiconductors at the nanometer scale produces materials that display properties distinct not only from the properties of their bulk counterparts but also from those of their parent semiconductors. As a result, alloyed nanocrystals possess additional properties that are composition-dependent aside from the properties that emerge due to quantum confinement effects. For example, although the size-dependent emission wavelength of the widely studied CdSe nanocrystals can be continuously tuned to cover almost the entire visible spectrum, the near-infrared (NIR) region is far outside its spectral range. By contrast, certain alloy compositions of nanocrystalline CdSe(x)Te(1-x), an alloy of CdSe and CdTe, can efficiently emit light in the NIR spectral window. These NIR-emitting nanocrystals are potentially useful in several biomedical applications. In addition, highly stable nanocrystals formed by alloying CdSe with ZnSe (i.e., Zn(x)Cd(1-x)Se) emit blue light with excellent efficiency, a property seldom achieved by the parent binary systems. As a result, these materials can be used in short-wavelength optoelectronic devices. In the future, we foresee new discoveries

  19. Silicon and germanium nanocrystals: properties and characterization

    PubMed Central

    Carvalho, Alexandra; Coutinho, José

    2014-01-01

    Summary Group-IV nanocrystals have emerged as a promising group of materials that extends the realm of application of bulk diamond, silicon, germanium and related materials beyond their traditional boundaries. Over the last two decades of research, their potential for application in areas such as optoelectronic applications and memory devices has been progressively unraveled. Nevertheless, new challenges with no parallel in the respective bulk material counterparts have arisen. In this review, we consider what has been achieved and what are the current limitations with regard to growth, characterization and modeling of silicon and germanium nanocrystals and related materials. PMID:25383290

  20. Cloning nanocrystal morphology with soft templates

    NASA Astrophysics Data System (ADS)

    Thapa, Dev Kumar; Pandey, Anshu

    2016-08-01

    In most template directed preparative methods, while the template decides the nanostructure morphology, the structure of the template itself is a non-general outcome of its peculiar chemistry. Here we demonstrate a template mediated synthesis that overcomes this deficiency. This synthesis involves overgrowth of silica template onto a sacrificial nanocrystal. Such templates are used to copy the morphologies of gold nanorods. After template overgrowth, gold is removed and silver is regrown in the template cavity to produce a single crystal silver nanorod. This technique allows for duplicating existing nanocrystals, while also providing a quantifiable breakdown of the structure - shape interdependence.

  1. Light Emission from Polymer-Semiconductor Nanocrystal (PFO-CdSe/ZnS) Structures

    NASA Astrophysics Data System (ADS)

    Nauka, K.; Gibson, G. A.; Sheng, X.; Yang, C. C.

    2007-04-01

    Electroluminescence was achieved from hybrid conjugated polymer (polyfluorene) — II-VI semiconductor nanocrystal structures. The energy of the carriers injected into the polymer was transferred into the nanocrystals causing light emission with a photon energy corresponding to the nanocrystals' bandgap. Undesirable polymer-nanocrystal phase segregation and presence of defective nanocrystals was responsible for the relatively low emission efficiency from the hybrid devices.

  2. Molecular Dynamics Simulations of Displacement Cascades in Single and Polycrystalline Zirconia

    SciTech Connect

    Du Jincheng

    2009-03-10

    Displacement cascades in zirconia have been studied using classical molecular dynamics simulations. Polycrystalline zirconia with nano-meter grains were created using Voronoi polyhedra construction and studied in comparison with single crystalline zirconia. The results show that displacement cascades with similar kinetic energy generated larger number of displaced atoms in polycrystalline than in the single crystal structure. The fraction of atoms with coordination number change was also higher in polycrystalline zirconia that was explained to be due to the diffusion of oxygen and relaxation at grain boundaries.

  3. Effect of Bismuth Oxide on the Microstructure and Electrical Conductivity of Yttria Stabilized Zirconia

    PubMed Central

    Liu, Liwei; Zhou, Zheng; Tian, He; Li, Jixue

    2016-01-01

    Bismuth oxide (Bi2O3)-doped yttria-stabilized zirconia (YSZ) were prepared via the solid state reaction method. X-ray diffraction and electron diffraction spectroscopy results indicate that doping with 2 mol% Bi2O3 and adding 10 mol% yttria result in a stable zirconia cubic phase. Adding Bi2O3 as a dopant increases the density of zirconia to above 96%, while reducing its normal sintering temperature by approximately 250 °C. Moreover, electrical impedance analyses show that adding Bi2O3 enhances the conductivity of zirconia, improving its capability as a solid electrolyte for intermediate or even lower temperatures. PMID:26985895

  4. In-vitro bioactivity of zirconia doped borosilicate glasses

    SciTech Connect

    Samudrala, Rajkumar; Azeem, P. Abdul E-mail: drazeem2002@yahoo.com

    2015-06-24

    Glass composition 31B{sub 2}O{sub 3}-20SiO{sub 2}-24.5Na{sub 2}O-(24.5-x) CaO-xZrO{sub 2} x=1,2,3,4,5 were prepared by melt-quenching Technique. The formation of hydroxyapatite layer on the surface of glasses after immersion in simulated body fluid (SBF) was explored through XRD, Fourier transform infrared (FTIR) and Scanning electron microscopy (SEM-EDX) analyses. In this report, we observed that hydroxyapatite formation for 5days of immersion time. Also observed that with increasing the immersion time up to 15days, higher amount of hydroxyapatite layer formation on the surface of glasses. The varying composition of zirconia in glass samples influences shown by XRD, FTIR studies. The present results indicate that, in-vitro bioactivity of glasses decreased with increasing zirconia incorporation.

  5. Ab-initio study of metal-zirconia interfaces

    NASA Astrophysics Data System (ADS)

    Kulkova, S.; Bakulin, A.; Hocker, S.; Schmauder, S.

    2012-08-01

    A comparative theoretical study of metal-zirconia interfaces with BCC and FCC metals was performed using pseudopotential approach with LDA and GGA approximation for exchange-correlation functional. It was shown that the high adhesion can be achieved at the O-terminated Me/ZrO2(001) interface with BCC metals that is related to large charge transfer from metal film to substrate and increase of an ionic contribution in the chemical bonding. The structural and electronic factors which are responsible for decrease of adhesion at differently oriented metal-zirconia interfaces are discussed. The influence of CaO, MgO and Y2O3 doping on the work of separation (Wsep) at Me(001)/c-ZrO2(001) is analyzed.

  6. Dissolving the Periodic Table in Zirconia: Data Mining for Insight

    NASA Astrophysics Data System (ADS)

    Meredig, Bryce; Wolverton, Chris

    2012-02-01

    A standard approach to understanding physical phenomena in materials is to manually search for clear trends or correlations in data (i.e., descriptors) governing those materials. Pettifor maps are a classic example of such empirically constructed models. But what if a data set is too large and/or chemically diverse to explain by straightforward human inspection? We present such a case by calculating from first principles the solubility thermodynamics of 70 dopant cations in cubic zirconia. This data set, spanning three charge states and most non-synthetic metals in the periodic table, defies simple ``manual'' explanation. Instead, we employ data mining algorithms and statistical methods to cluster the dopants into distinct classes, and then to build intuitive models for each class' thermodynamics in zirconia. Thus, we show that formal data mining techniques are a powerful means of elucidating meaningful property relationships in complex data sets.

  7. Preparation of mesoporous zirconia microspheres as inert matrix

    NASA Astrophysics Data System (ADS)

    Guo, Ting; Wang, Chen; Lv, Jinlong; Liang, Tongxiang

    2016-12-01

    Mesoporous zirconia microspheres, with a diameter of 900 μm, were prepared as an inert accelerator driven system (ADS) transmutation element matrix by the sol-gel method. The purpose of mesopores is to improve the adsorption capacity of inert matrix fuel (IMF) for minor actinides. The study indicated that the mesoporous zirconia performance was improved after the microspheres were hydrothermally treated at 150 °C, the specific surface area increased from 28.29 m2/g to 61.28 m2/g, and hydrothermal treatment avoided the cracking of the microspheres. Pre-decomposition of the organics during the hydrothermal process stabilized the mesoporous structure. The average pore diameter of mesoporous microsphere was 14.3 nm.

  8. Templated electrochemical deposition of zirconia thin films on "recordable CDs.".

    PubMed

    Yu, Hua-Zhong; Rowe, Aaron W; Waugh, Damien M

    2002-11-15

    In this paper, we describe a practical method of using gold films constructed from recordable compact disks (CD-Rs) as simple, inexpensive, and micropatterned conductive substrates for the fabrication of inorganic material microstructures. Extending from their application for the fabrication of self-assembled monolayers (SAMs) reported recently, bare and SAM-modified CD-R gold substrates have been used for template-directed electrodeposition of zirconia (ZrO2) thin films (i.e., the controlled formation of zirconia thin films on the different areas of the prefabricated, micrometer mountain-valley CD-R gold substrate surfaces). The present results demonstrate that the variation of the functional groups of the selected SAMs combined with electrodynamic control can be very successful to "customize" the formation and microstructure of functional inorganic thin films, which hold promise for modern technological applications.

  9. Synthesis of mesoporous zirconia using an amphoteric surfactant

    SciTech Connect

    Kim, A.Y.; Bruinsma, P.J.; Chen, Y.L.; Liu, J.

    1996-12-31

    An amphoteric surfactant, cocamidopropyl betaine, was used for the synthesis of mesoporous zirconia. The carboxylate functionality of the surfactant permitted strong bonding with soluble zirconium species, while the quaternary ammonium group ensured large headgroup area and high solubility under acidic conditions. An amphoteric co-template [betaine, or (carboxymethyl)trimethylammonium hydroxide] improved uniformity of the hexagonal mesophase. Transmission electron microscopy (TEM) of the as-synthesized zirconium sulfate mesophase indicated hexagonal mesostructure, and low-angle X-ray diffraction (XRD) showed a 41 {angstrom} primary d-spacing and two higher order reflections of a hexagonal lattice. High surface area zirconia was produced by controlled base treatment of the hexagonal mesophase with sodium hydroxide, followed by calcination. TEM and XRD indicated that the mesostructure was stable to 350 C.

  10. Tetragonal and cubic zirconia multilayered ceramic constructs created by EPD.

    PubMed

    Mochales, Carolina; Frank, Stefan; Zehbe, Rolf; Traykova, Tania; Fleckenstein, Christine; Maerten, Anke; Fleck, Claudia; Mueller, Wolf-Dieter

    2013-02-14

    The interest in electrophoretic deposition (EPD) for nanomaterials and ceramics production has widely increased due to the versatility of this technique to effectively combine different materials in unique shapes and structures. We successfully established an EPD layering process with submicrometer sized powders of Y-TZP with different mol percentages of yttrium oxide (3 and 8%) and produced multilayers of alternating tetragonal and cubic phases with a clearly defined interface. The rationale behind the design of these multilayer constructs was to optimize the properties of the final ceramic by combining the high mechanical toughness of the tetragonal phase of zirconia together with the high ionic conductivity of its cubic phase. In this work, a preliminary study of the mechanical properties of these constructs proved the good mechanical integrity of the multilayered constructs obtained as well as crack deflection in the interface between tetragonal and cubic zirconia layers.

  11. Antioxidant properties of cerium oxide nanocrystals as a function of nanocrystal diameter and surface coating.

    PubMed

    Lee, Seung Soo; Song, Wensi; Cho, Minjung; Puppala, Hema L; Nguyen, Phuc; Zhu, Huiguang; Segatori, Laura; Colvin, Vicki L

    2013-11-26

    This work examines the effect of nanocrystal diameter and surface coating on the reactivity of cerium oxide nanocrystals with H2O2 both in chemical solutions and in cells. Monodisperse nanocrystals were formed in organic solvents from the decomposition of cerium precursors, and subsequently phase transferred into water using amphiphiles as nanoparticle coatings. Quantitative analysis of the antioxidant capacity of CeO2-x using gas chromatography and a luminol test revealed that 2 mol of H2O2 reacted with every mole of cerium(III), suggesting that the reaction proceeds via a Fenton-type mechanism. Smaller diameter nanocrystals containing more cerium(III) were found to be more reactive toward H2O2. Additionally, the presence of a surface coating did not preclude the reaction between the nanocrystal surface cerium(III) and hydrogen peroxide. Taken together, the most reactive nanoparticles were the smallest (e.g., 3.8 nm diameter) with the thinnest surface coating (e.g., oleic acid). Moreover, a benchmark test of their antioxidant capacity revealed these materials were 9 times more reactive than commercial antioxidants such as Trolox. A unique feature of these antioxidant nanocrystals is that they can be applied multiple times: over weeks, cerium(IV) rich particles slowly return to their starting cerium(III) content. In nearly all cases, the particles remain colloidally stable (e.g., nonaggregated) and could be applied multiple times as antioxidants. These chemical properties were also observed in cell culture, where the materials were able to reduce oxidative stress in human dermal fibroblasts exposed to H2O2 with efficiency comparable to their solution phase reactivity. These data suggest that organic coatings on cerium oxide nanocrystals do not limit the antioxidant behavior of the nanocrystals, and that their redox cycling behavior can be preserved even when stabilized.

  12. Connecting the Particles in the Box - Controlled Fusion of Hexamer Nanocrystal Clusters within an AB6 Binary Nanocrystal Superlattice

    NASA Astrophysics Data System (ADS)

    Treml, Benjamin E.; Lukose, Binit; Clancy, Paulette; Smilgies, Detlef-M.; Hanrath, Tobias

    2014-10-01

    Binary nanocrystal superlattices present unique opportunities to create novel interconnected nanostructures by partial fusion of specific components of the superlattice. Here, we demonstrate the binary AB6 superlattice of PbSe and Fe2O3 nanocrystals as a model system to transform the central hexamer of PbSe nanocrystals into a single fused particle. We present detailed structural analysis of the superlattices by combining high-resolution X-ray scattering and electron microscopy. Molecular dynamics simulations show optimum separation of nanocrystals in agreement with the experiment and provide insights into the molecular configuration of surface ligands. We describe the concept of nanocrystal superlattices as a versatile `nanoreactor' to create and study novel materials based on precisely defined size, composition and structure of nanocrystals into a mesostructured cluster. We demonstrate `controlled fusion' of nanocrystals in the clusters in reactions initiated by thermal treatment and pulsed laser annealing.

  13. Connecting the Particles in the Box - Controlled Fusion of Hexamer Nanocrystal Clusters within an AB6 Binary Nanocrystal Superlattice

    PubMed Central

    Treml, Benjamin E.; Lukose, Binit; Clancy, Paulette; Smilgies, Detlef-M; Hanrath, Tobias

    2014-01-01

    Binary nanocrystal superlattices present unique opportunities to create novel interconnected nanostructures by partial fusion of specific components of the superlattice. Here, we demonstrate the binary AB6 superlattice of PbSe and Fe2O3 nanocrystals as a model system to transform the central hexamer of PbSe nanocrystals into a single fused particle. We present detailed structural analysis of the superlattices by combining high-resolution X-ray scattering and electron microscopy. Molecular dynamics simulations show optimum separation of nanocrystals in agreement with the experiment and provide insights into the molecular configuration of surface ligands. We describe the concept of nanocrystal superlattices as a versatile ‘nanoreactor' to create and study novel materials based on precisely defined size, composition and structure of nanocrystals into a mesostructured cluster. We demonstrate ‘controlled fusion' of nanocrystals in the clusters in reactions initiated by thermal treatment and pulsed laser annealing. PMID:25339169

  14. Oxygen production using solid-state zirconia electrolyte technology

    NASA Technical Reports Server (NTRS)

    Suitor, Jerry W.; Clark, Douglas J.

    1991-01-01

    High purity oxygen is required for a number of scientific, medical, and industrial applications. Traditionally, these needs have been met by cryogenic distillation or pressure swing adsorption systems designed to separate oxygen from air. Oxygen separation from air via solid-state zirconia electrolyte technology offers an alternative to these methods. The technology has several advantages over the traditional methods, including reliability, compactness, quiet operation, high purity output, and low power consumption.

  15. Directional solidification of the alumina-zirconia ceramic eutectic system

    SciTech Connect

    Boldt, Christopher

    1994-07-27

    It is possible to produce alumina-zirconia ceramic samples through existing solidification techniques. The resulting microstructures typically consist of rods of zirconia in an alumina matrix, although a lamellar structure has been noted in some cases. In nearly all cases, colony growth was present which may possibly result from grain size, repeated nucleation events, and lamellar oscillations. In the same vein, it appears that the amount of impurities within the system might be the underlying cause for the colony growth. Colony growth was diminished through impurity control as the higher purity samples exhibited colony free behavior. In addition to colony formations, faceted alumina dendrites or nonfaceted zirconia dendrites may result in the ceramic if the sample is solidified out of the coupled zone. In all cases, for larger-sized Bridgman samples, a lower limit in the eutectic spacing was noted. The solidification model which includes the kinetic effect has been developed, although the effect appears to be negligible under present experimental conditions. A spacing limit might also occur due to the result of heat flow problems. Heat flow out of the ceramic is difficult to control, often causing radial and not axial growth. This behavior is exaggerated in the presence of impurities. Thus, higher purity powders should always be used. Higher purity samples, in addition to yielding a more microstructurally uniform ceramic, also showed increased directionality. In the future, the kinetic model needs to be examined in more detail, and further research needs to be accomplished in the area of molten ceramics. Once better system constants are in place, the kinetic model will give a better indication of the behavior in the alumina-zirconia system.

  16. Advances in Zirconia Toughened Alumina Biomaterials for Total Joint Replacement

    PubMed Central

    Kurtz, Steven M.; Kocagöz, Sevi; Arnholt, Christina; Huet, Roland; Ueno, Masaru; Walter, William L.

    2014-01-01

    The objective of this article is to provide an up-to-date overview of zirconia-toughened alumina (ZTA) components used in total hip arthroplasties. The structure, mechanical properties, and available data regarding the clinical performance of ZTA are summarized. The advancements that have been made in understanding the in vivo performance of ZTA are investigated. This article concludes with a discussion of gaps in the literature related to ceramic biomaterials and avenues for future research. PMID:23746930

  17. Adsorption and decomposition of nitrous oxide on zirconia nanoparticles

    SciTech Connect

    Miller, T.M.; Grassian, V.H.

    1995-12-31

    Nitrous oxide, a by-product of several industrial processes, has some environmentally damaging effects. Since it has an atmospheric lifetime of over one hundred years, there is a great deal of interest in finding ways to limit the amount of nitrous oxide emitted into the atmosphere. Recently, zirconia and zirconia-based catalysts have been shown to be effective in catalyzing nitrous oxide decomposition. We have employed FT-IR spectroscopy to study the adsorption and decomposition of nitrous oxide on zirconia nanoparticles. The room temperature IR spectrum of adsorbed nitrous oxide is characterized by two intense absorption bands, the symmetric stretch and asymmetric stretch, that are shifted from the gas phase values. Experiments as a function of sample pretreatment temperature and site-blocker adsorption indicated that nitrous oxide adsorbs on Zr{sup 4+} sites and the mode of attachment is through the oxygen atom. Dissociation of nitrous oxide begins at temperatures above 350{degrees}C. The data suggest that Zr{sup 4+} may be the active site for nitrous oxide decomposition and the room temperature adsorbed species is perhaps a precursor to nitrous oxide decomposition.

  18. Nano-Engineered Cubic Zirconia for Orthopaedic Implant Applications

    NASA Astrophysics Data System (ADS)

    Namavar, F.; Rubinstein, A.; Sabirianov, R.; Thiele, G.; Sharp, J.; Pokharel, U.; Namavar, R.; Garvin, K.

    2012-02-01

    Osseointegration failure of the prosthesis prevents long-term stability, which contributes to pain, implant loosening, and infection that usually necessitates revision surgery. Cell attachment and spreading in vitro is generally mediated by adhesive proteins such as fibronectin and vitronectin. We designed and produced pure cubic zirconia (ZrO2) ceramic coatings by ion beam assisted deposition (IBAD) with nanostructures comparable to the size of proteins. Our ceramic coatings exhibit high hardness and a zero contact angle with serum. In contrast to Hydroxyapatite (HA), nano-engineered zirconia films possess excellent adhesion to all orthopaedic materials. Adhesion and proliferation experiments were performed with a bona fide mesenchymal stromal cells cell line (OMA-AD). Our experimental results indicated that nano-engineered cubic zirconia is superior in supporting growth, adhesion, and proliferation. We performed a comparative analysis of adsorption energies of the FN fragment using quantum mechanical calculations and Monte Carlo simulation on both types of surfaces: smooth and nanostructured. We have found that the initial FN fragment adsorbs significantly stronger on the nanostructured surface than on the smooth surface.

  19. Physicochemical properties, cytotoxicity, and antimicrobial activity of sulphated zirconia nanoparticles

    PubMed Central

    Mftah, Ae; Alhassan, Fatah H; Al-Qubaisi, Mothanna Sadiq; El Zowalaty, Mohamed Ezzat; Webster, Thomas J; Sh-eldin, Mohammed; Rasedee, Abdullah; Taufiq-Yap, Yun Hin; Rashid, Shah Samiur

    2015-01-01

    Nanoparticle sulphated zirconia with Brønsted acidic sites were prepared here by an impregnation reaction followed by calcination at 600°C for 3 hours. The characterization was completed using X-ray diffraction, thermal gravimetric analysis, Fourier transform infrared spectroscopy, Brunner-Emmett-Teller surface area measurements, scanning electron microscopy with energy dispersive X-ray spectroscopy, and transmission electron microscopy. Moreover, the anticancer and antimicrobial effects were investigated for the first time. This study showed for the first time that the exposure of cancer cells to sulphated zirconia nanoparticles (3.9–1,000 μg/mL for 24 hours) resulted in a dose-dependent inhibition of cell growth, as determined by (4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide assays. Similar promising results were observed for reducing bacteria functions. In this manner, this study demonstrated that sulphated zirconia nanoparticles with Brønsted acidic sites should be further studied for a wide range of anticancer and antibacterial applications. PMID:25632233

  20. Effect of cements on fracture resistance of monolithic zirconia crowns

    PubMed Central

    Nakamura, Keisuke; Mouhat, Mathieu; Nergård, John Magnus; Lægreid, Solveig Jenssen; Kanno, Taro; Milleding, Percy; Örtengren, Ulf

    2016-01-01

    Abstract Objectives The present study investigated the effect of cements on fracture resistance of monolithic zirconia crowns in relation to their compressive strength. Materials and methods Four different cements were tested: zinc phosphate cement (ZPC), glass-ionomer cement (GIC), self-adhesive resin-based cement (SRC) and resin-based cement (RC). RC was used in both dual cure mode (RC-D) and chemical cure mode (RC-C). First, the compressive strength of each cement was tested according to a standard (ISO 9917-1:2004). Second, load-to-failure test was performed to analyze the crown fracture resistance. CAD/CAM-produced monolithic zirconia crowns with a minimal thickness of 0.5 mm were prepared and cemented to dies with each cement. The crown–die samples were loaded until fracture. Results The compressive strength of SRC, RC-D and RC-C was significantly higher than those of ZPC and GIC (p < 0.05). However, there was no significant difference in the fracture load of the crown between the groups. Conclusion The values achieved in the load-to-failure test suggest that monolithic zirconia crowns with a minimal thickness of 0.5 mm may have good resistance against fracture regardless of types of cements. PMID:27335900

  1. Reliability and properties of ground Y-TZP-zirconia ceramics.

    PubMed

    Luthardt, R G; Holzhüter, M; Sandkuhl, O; Herold, V; Schnapp, J D; Kuhlisch, E; Walter, M

    2002-07-01

    Yttria-stabilized zirconia ceramics is a high-performance material with excellent biocompatibility and mechanical properties, which suggest its suitability for posterior fixed partial dentures. The hypothesis under examination is that the strength and reliability of Y-TZP zirconia ceramics are affected by the inner surface grinding of crowns, and vary with the grinding parameter. Flexural strength, surface roughness, and fracture toughness were determined on samples machined by face and peripheral grinding with varied feed velocities and cutting depths. Results have been compared with those on lapped samples. Analysis of variance and Weibull parameter were used for statistical analysis. It was found that inner surface grinding significantly reduces the strength and reliability of Y-TZP zirconia compared with the lapped control sample. Co-analysis of flexural strength, Weibull parameter, and fracture toughness showed counteracting effects of surface compressive stress and grinding-introduced surface flaws. In conclusion, grinding of Y-TZP needs to be optimized to achieve the CAD/CAM manufacture of all-ceramic restorations with improved strength and reliability.

  2. Novel Zirconia Surface Treatments for Enhanced Osseointegration: Laboratory Characterization

    PubMed Central

    Ewais, Ola H.; Al Abbassy, Fayza; Ghoneim, Mona M.; Aboushelib, Moustafa N.

    2014-01-01

    Purpose. The aim of this study was to evaluate three novel surface treatments intended to improve osseointegration of zirconia implants: selective infiltration etching treatment (SIE), fusion sputtering (FS), and low pressure particle abrasion (LPPA). The effects of surface treatments on roughness, topography, hardness, and porosity of implants were also assessed. Materials and Methods. 45 zirconia discs (19 mm in diameter × 3 mm in thickness) received 3 different surface treatments: selective infiltration etching, low pressure particle abrasion with 30 µm alumina, and fusion sputtering while nontreated surface served as control. Surface roughness was evaluated quantitatively using profilometery, porosity was evaluated using mercury prosimetry, and Vickers microhardness was used to assess surface hardness. Surface topography was analyzed using scanning and atomic force microscopy (α = 0.05). Results. There were significant differences between all groups regarding surface roughness (F = 1678, P < 0.001), porosity (F = 3278, P < 0.001), and hardness (F = 1106.158, P < 0.001). Scanning and atomic force microscopy revealed a nanoporous surface characteristic of SIE, and FS resulted in the creation of surface microbeads, while LPPA resulted in limited abrasion of the surface. Conclusion. Within the limitations of the study, changes in surface characteristics and topography of zirconia implants have been observed after different surface treatment approaches. Thus possibilities for enhanced osseointegration could be additionally offered. PMID:25349610

  3. A facile approach to the synthesis of non-porous and microporous sub-micron spherical zirconia and alumina-zirconia solid solution.

    PubMed

    Ghotbi, Mohammad Yeganeh; Nasiri, Vida; Rafiee, Mehdi

    2013-01-01

    Amorphous monodisperse sub-micron spherical zirconia and alumina/zirconia solid solution particles were prepared by hydrolysis of zirconium and aluminum salts in ethanol. The heat-treatment process of the amorphous materials in air atmosphere at 500°C for 2h leaded to the production of non-porous zirconia and alumina/zirconia solid solution in tetragonal phase. The alkaline etching process of the as-prepared alumina/zirconia solid solution resulted in the formation of mono-modal microporous material with specific surface area of 125.0 m(2) g(-1) in comparison with 2. 9m(2) g(-1) for the parent material. Thermal analysis of the solid solution revealed that the incorporation of aluminum ions in the zirconia structure has decreased the phase transformation temperature from amorphous to crystalline structure. Moreover, optical study confirmed the presence of oxygen vacancy defect by substitution of tetravalent cations, Zr(4+) by trivalent cations, Al(3+) in zirconia lattice.

  4. Phonon instability and pressure-induced isostructural semiconductor-semimetal transition of monoclinic V O2

    NASA Astrophysics Data System (ADS)

    He, Huabing; Gao, Heng; Wu, Wei; Cao, Shixun; Hong, Jiawang; Yu, Dehong; Deng, Guochu; Gao, Yanfeng; Zhang, Peihong; Luo, Hongjie; Ren, Wei

    2016-11-01

    Recent experiments have revealed an intriguing pressure-induced isostructural transition of the low temperature monoclinic V O2 and hinted to the existence of a new metallization mechanism in this system. The physics behind this isostructural phase transition and the metallization remains unresolved. In this work, we show that the isostructural transition is a result of pressure-induced instability of a phonon mode that relates to a CaC l2 -type of rotation of the oxygen octahedra, which alleviates, but does not completely remove, the dimerization and zigzagging arrangement of V atoms in the M1 phase. This phonon mode shows an increasing softening with pressure, ultimately leading to an isostructural phase transition characterized by the degree of the rotation of the oxygen octahedra. We also find that this phase transition is accompanied by an anisotropic compression, in excellent agreement with experiments. More interestingly, in addition to the experimentally identified M1' phase, we find a closely related M1 '' phase, which is nearly degenerate with the M1 ' phase. Unlike the M1 ' phase, which has a nearly pressure-independent electronic band gap, the gap of the M1 '' drops quickly at high pressures and vanishes at a theoretical pressure of about 40 GPa.

  5. Controlled synthesis and formation mechanism of monodispersive lanthanum vanadate nanowires with monoclinic structure

    SciTech Connect

    Tian, Li; Sun, Qiliang; Xu, Xijun; Li, Yaolin; Long, Yunfei; Zhu, Guangshan

    2013-04-15

    Monodisperse LaVO{sub 4} nanowires with relatively high aspect ratio larger than 50 have been prepared by a one-step solvothermal synthesis. This method provides a simple, inexpensive, controllable and reproducible process to produce LaVO{sub 4} nanowires with an average diameter of 15 nm and a high aspect ratio. The as-synthesized products have been characterized by powder X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and fast Fourier transform spectroscopy (FFT), indicative of a well-crystalline monoclinic structure and ascendant nanowire-morphology. The formation mechanism is suggested that oriented attachment plays a vital role in the growth of LaVO{sub 4} nanowires, which recommends a favorable route to fabricate similar morphological and structural nanometer materials. - Graphical abstract: The formation of LaVO{sub 4} nanowires is attributed to oriented attachment, a combination of nanocrystallites through their suitable surface planes, that is, with the same crystallographic orientations of [−120]. Highlights: ► Monodisperse LaVO{sub 4} nanowires with high aspect ratio have been prepared solvothermally without any templates. ► The morphology and structure of LaVO{sub 4} nanowires were characterized by XRD, SEM, TEM techniques. ► The formation mechanism of LaVO{sub 4} nanowires is suggested that oriented attachment plays a vital role.

  6. Synthesis of monoclinic IrTe2 under high pressure and its physical properties

    SciTech Connect

    Li, X.; Yan, J. -Q.; Singh, D. J.; Goodenough, J. B.; Zhou, J. -S.

    2015-10-12

    In a pressure-temperature (P-T) diagram for synthesizing IrTe2 compounds, the well-studied trigonal (H) phase with the CdI2-type structure is stable at low pressures. The superconducting cubic (C) phase can be synthesized under higher temperatures and pressures. A rhombohedral phase with the crystal structure similar to the C phase can be made at ambient pressure; but the phase contains a high concentration of Ir deficiency. Here, we report that a rarely studied monoclinic (M) phase can be stabilized in narrow ranges of pressure and temperature in this P-T diagram. Moreover, the peculiar crystal structure of the M-IrTe2 eliminates the tendency to form Ir-Ir dimers found in the H phase. The M phase has been fully characterized by structural determination and measurements of electrical resistivity, thermoelectric power, DC magnetization, and specific heat. These physical properties have been compared with those in the H and C phases of Ir1-xTe2. Finally, we present magnetic and transport properties and specific heat of the M-IrTe2 can be fully justified by calculations with the density-functional theory.

  7. Pressure induced tetragonal to monoclinic transition in RbN3 studied from first principles theory

    NASA Astrophysics Data System (ADS)

    Vaitheeswaran, G.; Babu, K. Ramesh

    2014-04-01

    Alkali metal azides are well known for their application as explosives and gas generators. They are used as precursors in synthesis of polymeric nitrogen, an ultimate green high energy density material. Among the alkali metal azides, rubidium azide RbN3 crystallizes in tetragonal structure with linear azide ions arranged in layers and binds through weak dispersive interactions. In this present work, we have studied the structural stability, electronic structure and optical properties of solid RbN3 by using van der Waals corrected density functional theory. We find that the ambient tetragonal structure undergoes a structural transition to monoclinic structure at 0.72 GPa, which is in good agreement with the experimental transition pressure of less than 1 GPa. The phonon frequencies at the gamma point are calculated and found that the lattice mode Eg softens under pressure which may supports the structural phase transition. The electronic band structure and optical properties are calculated by using Tran Blaha-modified Becke Johnson (TB-mBJ) functional and found that solid RbN3 is an insulator with a gap of 5.976 eV and the optical absorption starts with the UV light of wave length 207.5 nm.

  8. Monoclinic structured BiVO4 nanosheets: hydrothermal preparation, formation mechanism, and coloristic and photocatalytic properties.

    PubMed

    Zhang, Li; Chen, Dairong; Jiao, Xiuling

    2006-02-16

    Bismuth vanadate (BiVO(4)) nanosheets have been hydrothermally synthesized in the presence of sodium dodecyl benzene sulfonate (SDBS) as a morphology-directing template. The nanosheets were characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM) equipped with an X-ray energy dispersive spectrometer (EDS), X-ray photoelectron spectroscopy (XPS), IR spectroscopy, transmission electron microscopy (TEM), and high-resolution TEM (HR-TEM). The BiVO(4) nanosheets had a monoclinic structure, were ca. 10-40 nm thick, and showed a preferred (010) surface orientation. The formation mechanism and the effects of reaction temperature and time on the products were investigated. UV-visible diffuse reflection spectra indicated that the BiVO(4) nanosheets had outstanding spectral selectivity and improved color properties compared with the corresponding bulk materials. Furthermore, the nanosheets showed good visible photocatalytic activities as determined by degradation of N,N,N',N'-tetraethylated rhodamine (RB) under solar irradiation.

  9. Ab initio prediction of superdense tetragonal and monoclinic polymorphs of carbon

    SciTech Connect

    Li, Zhen -Zhen; Wang, Jian -Tao; Xu, Li -Fang; Chen, Changfeng

    2016-11-02

    The design and synthesis of three-dimensional denser carbons are one of the hot issues in condensed matter physics because of their fascinating properties. Here we identify by ab initio calculations several tetragonal and monoclinic polymorphs of carbon that adopt the t32, t32*, m32, and m32* structures in P4¯21c, P43212, P21/c, and C2 symmetry, respectively. These carbon polymorphs have large 32-atom unit cells in all-sp3 bonding networks comprising five- and six-membered rings that are dynamically stable, as verified by a phonon mode analysis. Electronic band structure calculations show that they are insulators with band gaps in the range of 5.19–5.41 eV, close to the calculated band gap of 5.34 eV for diamond. Remarkably, these carbon phases possess an extremely high atom number density exceeding that of diamond. Lastly, the present results establish different types of carbon phases and offer insights into their outstanding structural and electronic properties.

  10. Ab initio prediction of superdense tetragonal and monoclinic polymorphs of carbon

    DOE PAGES

    Li, Zhen -Zhen; Wang, Jian -Tao; Xu, Li -Fang; ...

    2016-11-02

    The design and synthesis of three-dimensional denser carbons are one of the hot issues in condensed matter physics because of their fascinating properties. Here we identify by ab initio calculations several tetragonal and monoclinic polymorphs of carbon that adopt the t32, t32*, m32, and m32* structures in P4¯21c, P43212, P21/c, and C2 symmetry, respectively. These carbon polymorphs have large 32-atom unit cells in all-sp3 bonding networks comprising five- and six-membered rings that are dynamically stable, as verified by a phonon mode analysis. Electronic band structure calculations show that they are insulators with band gaps in the range of 5.19–5.41 eV,more » close to the calculated band gap of 5.34 eV for diamond. Remarkably, these carbon phases possess an extremely high atom number density exceeding that of diamond. Lastly, the present results establish different types of carbon phases and offer insights into their outstanding structural and electronic properties.« less

  11. New monoclinic phase at the composition Cu2SnSe3 and its thermoelectric properties.

    PubMed

    Fan, Jing; Carrillo-Cabrera, Wilder; Akselrud, Lev; Antonyshyn, Iryna; Chen, Lidong; Grin, Yuri

    2013-10-07

    A new monoclinic phase (m2) of ternary diamond-like compound Cu2SnSe3 was synthesized by reaction of the elements at 850 K. The crystal structure of m2-Cu2SnSe3 was determined through electron diffraction tomography and refined by full-profile techniques using synchrotron X-ray powder diffraction data (space group Cc, a = 6.9714(2) Å, b = 12.0787(5) Å, c = 13.3935(5) Å, β = 99.865(5)°, Z = 8). Thermal analysis and annealing experiments suggest that m2-Cu2SnSe3 is a low-temperature phase, while the high-temperature phase has a cubic crystal structure. According to quantum chemical calculations, m2-Cu2SnSe3 is a narrow-gap semiconductor. A study of the chemical bonding, applying the electron localizability approach, reveals covalent polar Cu-Se and Sn-Se interactions in the crystal structure. Thermoelectric properties were measured on a specimen consolidated using spark plasma sintering (SPS), confirming the semiconducting character. The thermoelectric figure of merit ZT reaches a maximum value of 0.33 at 650 K.

  12. Discovery of Fe7O9: a new iron oxide with a complex monoclinic structure

    NASA Astrophysics Data System (ADS)

    Sinmyo, Ryosuke; Bykova, Elena; Ovsyannikov, Sergey V.; McCammon, Catherine; Kupenko, Ilya; Ismailova, Leyla; Dubrovinsky, Leonid

    2016-09-01

    Iron oxides are fundamentally important compounds for basic and applied sciences as well as in numerous industrial applications. In this work we report the synthesis and investigation of a new binary iron oxide with the hitherto unknown stoichiometry of Fe7O9. This new oxide was synthesized at high-pressure high-temperature (HP-HT) conditions, and its black single crystals were successfully recovered at ambient conditions. By means of single crystal X-ray diffraction we determined that Fe7O9 adopts a monoclinic C2/m lattice with the most distorted crystal structure among the binary iron oxides known to date. The synthesis of Fe7O9 opens a new portal to exotic iron-rich (M,Fe)7O9 oxides with unusual stoichiometry and distorted crystal structures. Moreover, the crystal structure and phase relations of such new iron oxide groups may provide new insight into the cycling of volatiles in the Earth’s interior.

  13. 13C NMR chemical shifts of the triclinic and monoclinic crystal forms of valinomycin.

    PubMed

    Kameda, Tsunenori; McGeorge, Gary; Orendt, Anita M; Grant, David M

    2004-07-01

    Two different crystalline polymorphs of valinomycin, the triclinic and monoclinic forms, have been studied by high resolution, solid state (13)C CP-MAS NMR spectroscopy. Although the two polymorphs of the crystal are remarkably similar, there are distinct differences in the isotropic chemical shifts between the two spectra. For the triclinic form, the carbon chemical shift tensor components for the alpha carbons adjacent to oxygen in the lactic acid and hydroxyisovaleric acid residues and the ester carbonyls of the valine residue were obtained using the FIREMAT experiment. From the measured components, it was found that the behavior of the isotropic chemical shift, delta(iso), for valine residue ester carbonyl carbons is predominately influenced by the intermediate component, delta(22). Additionally it was found that the smallest shift component, delta(33), for the L -lactic acid ( L -Lac) and D -alpha-hydroxyisovaleric acid ( D -Hyi) C(alpha)-O carbon was significantly displaced depending upon the nature of individual amino acid residues, and it is the delta(33) component that governs the behavior of delta(iso) in these alpha carbons.

  14. Monoclinic high-pressure polymorph of AlOOH predicted from first principles

    NASA Astrophysics Data System (ADS)

    Zhong, Xin; Hermann, Andreas; Wang, Yanchao; Ma, Yanming

    2016-12-01

    Aluminum oxide hydroxide, AlOOH, is a prototypical hydrous mineral in the geonomy. The study of the high-pressure phase evolution of AlOOH is of fundamental importance in helping to understand the role of hydrous minerals in the water storage and transport in Earth, as in other planets. Here, we have systematically investigated the high-pressure phase diagram of AlOOH up to 550 GPa using the efficient crystal structure analysis by particle swarm optimization (CALYPSO) algorithm in conjunction with first principles calculations. We predict a peculiar monoclinic phase (space group P 21/c , 16 atoms/cell, Z =4 ) as the most stable phase for AlOOH above 340 GPa. The occurrence of this new phase results in the breakup of symmetric linear O-H-O hydrogen bonds into asymmetric, bent O-H-O linkages and in sevenfold coordinated metal cations. The new P 21/c phase turns out to be a universal high-pressure phase in group 13 oxide hydroxides, and stable for both compressed GaOOH and InOOH. The formation of the new phase in all compounds is favored by volume reduction due to denser packing.

  15. Microsphere morphology tuning and photo-luminescence properties of monoclinic Y2WO6

    NASA Astrophysics Data System (ADS)

    Gao, Hong; Bai, Yulong; Zhang, Junying; Tang, Zilong

    2015-04-01

    Effects of the solution pH value and reaction time on the precursor morphology and photoluminescence properties are investigated for hydrothermally prepared monoclinic Y2WO6 phosphors. In the near-neutral environment, sodium dodecyl benzene sulfonate (SDBS) surfactant forms small microspheres micelles as template to synthesize microspherical precursor. H+ ions concentration affects the arrangement of negative ionic surfactant SDBS. As a result, jujube-liked and popcorn-like loose microspheres formed at low pH value. When the pH value is 5.2 and the hydrothermal reaction time reaches 24 h, respectively, the strongest luminescent intensity can be obtained. Under this condition, the precursor presented regular microsphere with diameter of 4.0 μm. After high-temperature heat treatment, the obtained phosphor particles still exhibit microsphere-like shape. Therefore, we provide an effective method to tune the morphology of Y2WO6 phosphors and study the relationship between morphology and luminescent performance.

  16. Discovery of Fe7O9: a new iron oxide with a complex monoclinic structure

    PubMed Central

    Sinmyo, Ryosuke; Bykova, Elena; Ovsyannikov, Sergey V.; McCammon, Catherine; Kupenko, Ilya; Ismailova, Leyla; Dubrovinsky, Leonid

    2016-01-01

    Iron oxides are fundamentally important compounds for basic and applied sciences as well as in numerous industrial applications. In this work we report the synthesis and investigation of a new binary iron oxide with the hitherto unknown stoichiometry of Fe7O9. This new oxide was synthesized at high-pressure high-temperature (HP-HT) conditions, and its black single crystals were successfully recovered at ambient conditions. By means of single crystal X-ray diffraction we determined that Fe7O9 adopts a monoclinic C2/m lattice with the most distorted crystal structure among the binary iron oxides known to date. The synthesis of Fe7O9 opens a new portal to exotic iron-rich (M,Fe)7O9 oxides with unusual stoichiometry and distorted crystal structures. Moreover, the crystal structure and phase relations of such new iron oxide groups may provide new insight into the cycling of volatiles in the Earth’s interior. PMID:27605075

  17. Synthesis of monoclinic IrTe2 under high pressure and its physical properties

    DOE PAGES

    Li, X.; Yan, J. -Q.; Singh, D. J.; ...

    2015-10-12

    In a pressure-temperature (P-T) diagram for synthesizing IrTe2 compounds, the well-studied trigonal (H) phase with the CdI2-type structure is stable at low pressures. The superconducting cubic (C) phase can be synthesized under higher temperatures and pressures. A rhombohedral phase with the crystal structure similar to the C phase can be made at ambient pressure; but the phase contains a high concentration of Ir deficiency. Here, we report that a rarely studied monoclinic (M) phase can be stabilized in narrow ranges of pressure and temperature in this P-T diagram. Moreover, the peculiar crystal structure of the M-IrTe2 eliminates the tendency tomore » form Ir-Ir dimers found in the H phase. The M phase has been fully characterized by structural determination and measurements of electrical resistivity, thermoelectric power, DC magnetization, and specific heat. These physical properties have been compared with those in the H and C phases of Ir1-xTe2. Finally, we present magnetic and transport properties and specific heat of the M-IrTe2 can be fully justified by calculations with the density-functional theory.« less

  18. Monoclinic polymorph of poly[aqua(μ4-hydrogen tartrato)sodium

    PubMed Central

    Al-Dajani, Mohammad T. M.; Abdallah, Hassan H.; Mohamed, Nornisah; Quah, Ching Kheng; Fun, Hoong-Kun

    2010-01-01

    A monoclinic polymorph of the title compound, [Na(C4H5O6)(H2O)]n, is reported and complements an ortho­rhom­bic form [Kubozono, Hirano, Nagasawa, Maeda & Kashino (1993 ▶). Bull. Chem. Soc. Jpn, 66, 2166–2173]. The asymmetric unit contains a hydrogen tartrate anion, an Na+ cation and a water mol­ecule. The Na+ ion is surrounded by seven O atoms derived from one independent and three symmetry-related hydrogen tartrate anions, and a water mol­ecule, forming a distorted penta­gonal–bipyramidal geometry. Independent units are linked via a pair of inter­molecular bifurcated O—H⋯O acceptor bonds, generating an R 2 1(6) ring motif to form polymeric two-dimensional arrays parallel to the (100) plane. In the crystal packing, the arrays are linked by adjacent ring motifs, together with additional inter­molecular O—H⋯O inter­actions, into a three-dimensional network. PMID:21579620

  19. Monoclinic polymorph of poly[aqua(μ(4)-hydrogen tartrato)sodium].

    PubMed

    Al-Dajani, Mohammad T M; Abdallah, Hassan H; Mohamed, Nornisah; Quah, Ching Kheng; Fun, Hoong-Kun

    2010-01-09

    A monoclinic polymorph of the title compound, [Na(C(4)H(5)O(6))(H(2)O)](n), is reported and complements an ortho-rhom-bic form [Kubozono, Hirano, Nagasawa, Maeda & Kashino (1993 ▶). Bull. Chem. Soc. Jpn, 66, 2166-2173]. The asymmetric unit contains a hydrogen tartrate anion, an Na(+) cation and a water mol-ecule. The Na(+) ion is surrounded by seven O atoms derived from one independent and three symmetry-related hydrogen tartrate anions, and a water mol-ecule, forming a distorted penta-gonal-bipyramidal geometry. Independent units are linked via a pair of inter-molecular bifurcated O-H⋯O acceptor bonds, generating an R(2) (1)(6) ring motif to form polymeric two-dimensional arrays parallel to the (100) plane. In the crystal packing, the arrays are linked by adjacent ring motifs, together with additional inter-molecular O-H⋯O inter-actions, into a three-dimensional network.

  20. Vibrational Spectroscopy and Phonon-Related Properties of the L-Aspartic Acid Anhydrous Monoclinic Crystal.

    PubMed

    Silva, A M; Costa, S N; Sales, F A M; Freire, V N; Bezerra, E M; Santos, R P; Fulco, U L; Albuquerque, E L; Caetano, E W S

    2015-12-10

    The infrared absorption and Raman scattering spectra of the monoclinic P21 l-aspartic acid anhydrous crystal were recorded and interpreted with the help of density functional theory (DFT) calculations. The effect of dispersive forces was taken into account, and the optimized unit cells allowed us to obtain the vibrational normal modes. The computed data exhibits good agreement with the measurements for low wavenumbers, allowing for a very good assignment of the infrared and Raman spectral features. The vibrational spectra of the two lowest energy conformers of the l-aspartic molecule were also evaluated using the hybrid B3LYP functional for the sake of comparison, showing that the molecular calculations give a limited description of the measured IR and Raman spectra of the l-aspartic acid crystal for wavenumbers below 1000 cm(-1). The results obtained reinforce the need to use solid-state calculations to describe the vibrational properties of molecular crystals instead of calculations for a single isolated molecule picture even for wavenumbers beyond the range usually associated with lattice modes (200 cm(-1) < ω < 1000 cm(-1)).

  1. Ab initio prediction of superdense tetragonal and monoclinic polymorphs of carbon

    NASA Astrophysics Data System (ADS)

    Li, Zhen-Zhen; Wang, Jian-Tao; Xu, Li-Fang; Chen, Changfeng

    2016-11-01

    The design and synthesis of three-dimensional denser carbons are one of the hot issues in condensed matter physics because of their fascinating properties. Here we identify by ab initio calculations several tetragonal and monoclinic polymorphs of carbon that adopt the t 32 , t 32* , m 32 , and m 32* structures in P 4 ¯21c , P 43212 , P 21/c , and C 2 symmetry, respectively. These carbon polymorphs have large 32-atom unit cells in all-s p3 bonding networks comprising five- and six-membered rings that are dynamically stable, as verified by a phonon mode analysis. Electronic band structure calculations show that they are insulators with band gaps in the range of 5.19-5.41 eV, close to the calculated band gap of 5.34 eV for diamond. Remarkably, these carbon phases possess an extremely high atom number density exceeding that of diamond. The present results establish different types of carbon phases and offer insights into their outstanding structural and electronic properties.

  2. A new crystal phase of ammonium nitrate: a monoclinic distortion of AN-IV

    NASA Astrophysics Data System (ADS)

    Oleynik, Ivan; Steele, Brad

    2015-06-01

    Ammonium nitrate (AN) is a major component of the energetic material ANFO. It is important to understand the high-pressure crystal phases and corresponding phase transitions of AN as its structural polymorphism might affect the energetic performance, including crystal density, detonation velocity and shock initiation of chemical reactions. A new crystal phase of AN is found using first principles evolutionary crystal structure search. It is a monoclinic distortion of phase IV of AN (AN-IV) in the P21/m space group (AN-P21/m). The calculated Raman spectrum of this new phase is consistent with the recently reported experimental Raman spectrum that contains two peaks at high pressures associated with the phase transition. The new phase is calculated to have lower free energy than AN-IV above 11.2 GPa, a pressure close to the experimentally reported phase transition pressure of 17 GPa. The calculated Raman spectra of both AN-P21/m and AN-IV as a function of pressure display good agreement with experiment up to 40 GPa.

  3. New phase of ammonium nitrate: A monoclinic distortion of AN-IV

    NASA Astrophysics Data System (ADS)

    Steele, Brad A.; Oleynik, Ivan I.

    2015-12-01

    A new phase of ammonium nitrate (AN) is found using first principles evolutionary crystal structure search. It is this polymorph that is associated with the phase transition to previously unidentified phase, which was detected in experiment at 17 GPa upon appearance of the two extra peaks in Raman spectrum. The new phase has a monoclinic unit cell in the P21/m space group symmetry (AN-P21/m) and is similar to the known phase IV of AN (AN-IV) except the ammonium molecules are oriented differently relative to the nitrate molecules. The calculated free energy of AN-P21/m is found to be lower than AN-IV at pressures above 10.83 GPa. The equation of state of both AN-P21/m and AN-IV phases (volume vs hydrostatic pressure at room temperature) has been obtained within the quasi-harmonic approximation. The calculated Raman spectrum of both AN-P21/m and AN-IV as a function of pressure is in a good agreement with experiment. The energetic competitiveness of AN-IV and AN-P21/m at ambient conditions suggests a possibility of the phase transition in a small pressure-temperature range near ambient pressure and temperature.

  4. Processing - microstructure relationships of chemically vapor deposited zirconia fiber coating for environmentally durable silicon carbide/silicon carbide composites

    NASA Astrophysics Data System (ADS)

    Lee, Jinil

    In SiC/SiC ceramic matrix composites, toughness is obtained by adding a fiber coating which provides a weak interface for crack deflection and debonding between the fiber and the matrix. However, the most commonly used fiber coatings, carbon and boron nitride, are unstable in oxidative environments. In the present study, the feasibility of using a chemically vapor deposited zirconia (CVD-ZrO 2) fiber coating as an oxidation-resistant interphase for SiC/SiC composites was investigated. The feasibility of the CVD-ZrO2 coating as a useful interphase for SiC/SiC composites was investigated with emphasis on developing critical processing-microstructure relationships. A study of morphological evolution in the CVD-ZrO2 coating suggested that a size-controlled displacive phase transformation from tetragonal ZrO2 (t-ZrO2) to monoclinic ZrO2 (m-ZrO2) was the key mechanism responsible for the weak interface behavior exhibited by the ZrO2 coating. The pre-delamination occurred as a result of (i) continuous formation of t-ZrO2 nuclei on the deposition surface; (ii) martensitic transformation of the tetragonal phase to a monoclinic phase upon reaching a critical grain size; and (iii) development of significant compressive hoop stresses due to the volume dilation associated with the transformation. We also discovered that low oxygen partial pressure in the CVD reactor was required for the nucleation of t-ZrO2 and was ultimately responsible for the delamination behavior. The effects of oxygen partial pressure on the nucleation behavior of the CVD-ZrO2 coating was systematically studied by intentionally adding the controlled amount of O2 into the CVD chamber. Characterization results suggested that the number density of t-ZrO2 nuclei apparently decreased with increasing the oxygen partial pressure from 0.004 to 1.6 Pa. Also, the coating layer became more columnar and contained larger m-ZrO2 grains. The observed relationships between the oxygen partial pressure and the morphological

  5. Chelating ligands for nanocrystals' surface functionalization.

    PubMed

    Querner, Claudia; Reiss, Peter; Bleuse, Joël; Pron, Adam

    2004-09-22

    A new family of ligands for the surface functionalization of CdSe nanocrystals is proposed, namely alkyl or aryl derivatives of carbodithioic acids (R-C(S)SH). The main advantages of these new ligands are as follows: they nearly quantitatively exchange the initial surface ligands (TOPO) in very mild conditions; they significantly improve the resistance of nanocrystals against photooxidation because of their ability of strong chelate-type binding to metal atoms; their relatively simple preparation via Grignard intermediates facilitates the development of new bifunctional ligands containing, in addition to the anchoring carbodithioate group, a second function, which enables the grafting of molecules or macromolecules of interest on the nanocrystal surface. To give an example of this approach, we report, for the first time, the grafting of an electroactive oligomer from the polyaniline family-aniline tetramer-on CdSe nanocrystals after their functionalization with 4-formyldithiobenzoic acid. The grafting proceeds via a condensation reaction between the aldehyde group of the ligand and the terminal primary amine group of the tetramer. The resulting organic/inorganic hybrid exhibits complete extinction of the fluorescence of its constituents, indicating efficient charge or energy transfer between the organic and the inorganic semiconductors.

  6. Thick-shell nanocrystal quantum dots

    DOEpatents

    Hollingsworth, Jennifer A.; Chen, Yongfen; Klimov, Victor I.; Htoon, Han; Vela, Javier

    2011-05-03

    Colloidal nanocrystal quantum dots comprising an inner core having an average diameter of at least 1.5 nm and an outer shell, where said outer shell comprises multiple monolayers, wherein at least 30% of the quantum dots have an on-time fraction of 0.80 or greater under continuous excitation conditions for a period of time of at least 10 minutes.

  7. Organization of 'nanocrystal molecules' using DNA

    NASA Astrophysics Data System (ADS)

    Alivisatos, A. Paul; Johnsson, Kai P.; Peng, Xiaogang; Wilson, Troy E.; Loweth, Colin J.; Bruchez, Marcel P.; Schultz, Peter G.

    1996-08-01

    PATTERNING matter on the nanometre scale is an important objective of current materials chemistry and physics. It is driven by both the need to further miniaturize electronic components and the fact that at the nanometre scale, materials properties are strongly size-dependent and thus can be tuned sensitively1. In nanoscale crystals, quantum size effects and the large number of surface atoms influence the, chemical, electronic, magnetic and optical behaviour2-4. 'Top-down' (for example, lithographic) methods for nanoscale manipulation reach only to the upper end of the nanometre regime5; but whereas 'bottom-up' wet chemical techniques allow for the preparation of mono-disperse, defect-free crystallites just 1-10 nm in size6-10, ways to control the structure of nanocrystal assemblies are scarce. Here we describe a strategy for the synthesis of'nanocrystal molecules', in which discrete numbers of gold nanocrystals are organized into spatially defined structures based on Watson-Crick base-pairing interactions. We attach single-stranded DNA oligonucleotides of defined length and sequence to individual nanocrystals, and these assemble into dimers and trimers on addition of a complementary single-stranded DNA template. We anticipate that this approach should allow the construction of more complex two-and three-dimensional assemblies.

  8. Heterostructures Prepared by Surface Modification of Nanocrystals

    ERIC Educational Resources Information Center

    Lee, Bo Hyun

    2009-01-01

    Inorganic nanocrystals (NCs) have drawn the attention from many researchers due to their promising potentials for next generation technologies, from photovoltaics to biological applications. Various types of NCs have become available by synthetic protocols developed in the last two decades. In addition, multicomponent hybrid NCs which can be…

  9. Developing new nanoprobes from semiconductor nanocrystals

    NASA Astrophysics Data System (ADS)

    Fu, Aihua

    In recent years, semiconductor nanocrystal quantum dots have garnered the spotlight as an important new class of biological labeling tool. With optical properties superior to conventional organic fluorophores from many aspects, such as high photostability and multiplexing capability, quantum dots have been applied in a variety of advanced imaging applications. This dissertation research goes along with large amount of research efforts in this field, while focusing on the design and development of new nanoprobes from semiconductor nanocrystals that are aimed for useful imaging or sensing applications not possible with quantum dots alone. Specifically speaking, two strategies have been applied. In one, we have taken advantage of the increasing capability of manipulating the shape of semiconductor nanocrystals by developing semiconductor quantum rods as fluorescent biological labels. In the other, we have assembled quantum dots and gold nanocrystals into discrete nanostructures using DNA. The background information and synthesis, surface manipulation, property characterization and applications of these new nanoprobes in a few biological experiments are detailed in the dissertation.

  10. Influence of surface modification techniques on shear bond strength between different zirconia cores and veneering ceramics

    PubMed Central

    Rismanchian, Mansour; Savabi, Omid; Ashtiani, Alireza Hashemi

    2011-01-01

    PURPOSE Veneering porcelain might be delaminated from underlying zirconia-based ceramics. The aim of this study was the evaluation of the effect of different surface treatments and type of zirconia (white or colored) on shear bond strength (SBS) of zirconia core and its veneering porcelain. MATERIALS AND METHODS Eighty zirconia disks (40 white and 40 colored; 10 mm in diameter and 4 mm thick) were treated with three different mechanical surface conditioning methods (Sandblasting with 110 µm Al2O3 particle, grinding, sandblasting and liner application). One group had received no treatment. These disks were veneered with 3 mm thick and 5 mm diameter Cercon Ceram Kiss porcelain and SBS test was conducted (cross-head speed = 1 mm/min). Two and one way ANOVA, Tukey's HSD Past hoc, and T-test were selected to analyzed the data (α=0.05). RESULTS In this study, the factor of different types of zirconia ceramics (P=.462) had no significant effect on SBS, but the factors of different surface modification techniques (P=.005) and interaction effect (P=.018) had a significant effect on SBS. Within colored zirconia group, there were no significant differences in mean SBS among the four surface treatment subgroups (P=0.183). Within white zirconia group, "Ground group" exhibited a significantly lower SBS value than "as milled" or control (P=0.001) and liner (P=.05) groups. CONCLUSION Type of zirconia did not have any effect on bond strength between zirconia core and veneer ceramic. Surface treatment had different effects on the SBS of the different zirconia types and grinding dramatically decreased the SBS of white zirconia-porcelain. PMID:22259706

  11. Effect of cation dopants in zirconia on interfacial properties in nickel/zirconia systems: an atomistic modeling study

    NASA Astrophysics Data System (ADS)

    Iskandarov, Albert M.; Ding, Yingna; Umeno, Yoshitaka

    2017-02-01

    Cation doping is often used to stabilize the cubic or tetragonal phase of zirconia for enhanced thermomechanical and electrochemical properties. In the present paper we report a combined density functional theory (DFT) and molecular dynamics study of the effect of Sc, Y, and Ce dopants on properties of Ni/\\text{Zr}{{\\text{O}}2} interfaces and nickel sintering. First, we develop an MD model that is based on DFT data for various nickel/zirconia interfaces. Then, we employ the model to simulate Ni nanoparticles coalescing on a zirconia surface. The results show the possibility of particle migration by means of fast sliding over the surface when the work of separation is small (<1.0\\text{J} {{\\text{m}}-2} ). The sliding observed for the O-terminated Ni(1 1 1)/\\text{Zr}{{\\text{O}}2} (1 1 1) interface is not affected by dopants in zirconia because the work of separation of the doped interface stays small. The most pronounced effect of the dopants is observed for the Zr-terminated Ni(1 1 1)/\\text{Zr}{{\\text{O}}2} (1 1 1) interface, which possesses a large work of separation (4.4\\text{J} {{\\text{m}}-2} ) and thus restricts the sliding mechanism of Ni nanoparticle migration. DFT calculations for the interface revealed that dopants with a smaller covalent radius result in a larger energy barriers for Ni diffusion. We analyze this effect and discuss how it can be used to suppress nickel sintering by using the dopant selection.

  12. Biomimetic synthesis of noble metal nanocrystals

    NASA Astrophysics Data System (ADS)

    Chiu, Chin-Yi

    At the nanometer scale, the physical and chemical properties of materials heavily depend on their sizes and shapes. This fact has triggered considerable efforts in developing controllable nanomaterial synthesis. The controlled growth of colloidal nanocrystal is a kinetic process, in which high-energy facets grow faster and then vanish, leading to a nanocrystal enclosed by low-energy facets. Identifying a surfactant that can selectively bind to a particular crystal facet and thus lower its surface energy, is critical and challenging in shape controlled synthesis of nanocrystals. Biomolecules exhibiting exquisite molecular recognition properties can be exploited to precisely engineer nanostructured materials. In the first part of my thesis, we employed the phage display technique to select a specific multifunctional peptide sequence which can bind on Pd surface and mediate Pd crystal nucleation and growth, achieving size controlled synthesis of Pd nanocrystals in aqueous solution. We further demonstrated a rational biomimetic approach to the predictable synthesis of nanocrystals enclosed by a particular facet in the case of Pt. Specifically, Pt {100} and Pt {111} facet-specific peptides were identified and used to synthesize Pt nanocubes and Pt nano-tetrahedrons, respectively. The mechanistic studies of Pt {111} facet-specific peptide had led us to study the facet-selective adsorption of aromatic molecules on noble metal surfaces. The discoveries had achieved the development of design strategies to select facet-selective molecules which can synthesize nanocrystals with expected shapes in both Pt and Pd system. At last, we exploited Pt facet-specific peptides and controlled the molecular interaction to produce one- and three- dimensional nanostructures composed of anisotropic nanoparticles in synthetic conditions without supramolecular pre-organization, demonstrating the full potential of biomolecules in mediating material formation process. My research on biomimetic

  13. Electronic and vibrational properties of yttria-stabilised zirconia from first-principles for 10-40 mol% Y2O3

    NASA Astrophysics Data System (ADS)

    Cousland, G. P.; Cui, X. Y.; Ringer, S.; Smith, A. E.; Stampfl, A. P. J.; Stampfl, C. M.

    2014-11-01

    Density-functional theory calculations are performed to investigate the electronic and vibrational density-of-states (DOS) for a series of recently predicted stable and metastable structures of yttria-stabilised zirconia (YSZ) with yttria (Y2O3) concentrations of 14, 17 and 20 mol%. Analogous quantities are also studied for the so-called δ-phase, which forms for 40 mol% yttria, as well as for model structures with ≈10.3 mol% yttria. These calculated results, together with those for the cubic, tetragonal and monoclinic phases of ZrO2, afford a comparison of structural, electronic and vibrational properties as a function of yttria concentration. With increasing yttria content, the electronic DOS exhibit a decrease in the valence band-width (of about 2.0 eV relative to the cubic phase) and a corresponding increase of the band-gap of 0.73 eV (from cubic to 40 mol% yttria containing ZrO2). Regarding the vibrational DOS (vDOS), the addition of yttria causes the peaks in the vDOS of ZrO2 to become less distinct, reflecting the more dense occupation of states due to the larger number of atoms in each primitive cell, and to the lower symmetry. The vDOS of the various YSZ structures appear qualitatively similar with contributions from O atoms spanning the whole frequency range and cation related contributions present for frequencies < 40 - 45 meV. With increasing yttria content, more Zr atoms become seven-fold coordinated as in monoclinic ZrO2, concominantly the vDOS increasingly resembles that of m-ZrO2, but with notable contributions from Y atoms, which has a main peak at about 17 meV, similar to that of Zr atoms.

  14. Infrared colloidal lead chalcogenide nanocrystals: synthesis, properties, and photovoltaic applications.

    PubMed

    Fu, Huiying; Tsang, Sai-Wing

    2012-04-07

    Simple solution phase, catalyst-free synthetic approaches that offer monodispersed, well passivated, and non-aggregated colloidal semiconductor nanocrystals have presented many research opportunities not only for fundamental science but also for technological applications. The ability to tune the electrical and optical properties of semiconductor nanocrystals by manipulating the size and shape of the crystals during the colloidal synthesis provides potential benefits to a variety of applications including photovoltaic devices, light-emitting diodes, field effect transistors, biological imaging/labeling, and more. Recent advances in the synthesis and characterization of colloidal lead chalcogenide nanocrystals and the achievements in colloidal PbS or PbSe nanocrystals solar cells have demonstrated the promising application of infrared-emitting colloidal lead chalcogenide nanocrystals in photovoltaic devices. Here, we review recent progress in the synthesis and optical properties of colloidal lead chalcogenide nanocrystals. We focus in particular upon the size- and shape-controlled synthesis of PbS, PbSe, and PbTe nanocrystals by using different precursors and various stabilizing surfactants for the growth of the colloidal nanocrystals. We also summarize recent advancements in the field of colloidal nanocrystals solar cells based on colloidal PbS and PbSe nanocrystals.

  15. Adopting the principles of collagen biomineralization for intrafibrillar infiltration of yttria-stabilized zirconia into three-dimensional collagen scaffolds

    PubMed Central

    Zhou, Bin; Niu, Li-na; Shi, Wei; Zhang, Wei; Arola, Dwayne D.; Breschi, Lorenzo; Mao, Jing; Pashley, David H.

    2014-01-01

    In this paper, we report a process for generating collagen-yttria-stabilized amorphous zirconia hybrid scaffolds by introducing acetylacetone-inhibited zirconia precursor nanodroplets into a poly(allylamine)-coated collagen matrix. This polyelectrolyte coating triggers intrafibrillar condensation of the precursors into amorphous zirconia, which is subsequently transformed into tetragonal yttria-stabilized zirconia after calcination. Our findings represent a new paradigm in the synthesis of non-naturally occurring collagen-based hybrid scaffolds under alcoholic mineralizing conditions. PMID:25477773

  16. Mechanical testing of thin-walled zirconia abutments

    PubMed Central

    CANULLO, Luigi; COELHO, Paulo G.; BONFANTE, Estevam A.

    2013-01-01

    Although the use of zirconia abutments for implant-supported restorations has gained momentum with the increasing demand for esthetics, little informed design rationale has been developed to characterize their fatigue behavior under different clinical scenarios. However, to prevent the zirconia from fracturing, the use of a titanium connection in bicomponent aesthetic abutments has been suggested. Objective: Mechanical testing of customized thin-walled titanium-zirconia abutments at the connection with the implant was performed in order to characterize the fatigue behavior and the failure modes for straight and angled abutments. Material and Methods: Twenty custom-made bi-component abutments were tested according to ISO 14801:2007 either at a straight or a 25º angle inclination (n=10 each group). Fatigue was conducted at 15 Hz for 5 million cycles in dry conditions at 20ºC±5ºC. Mean values and standard deviations were calculated for each group. All comparisons were performed by t-tests assuming unequal variances. The level of statistical significance was set at p≤0.05. Failed samples were inspected in a polarized-light and then in a scanning electron microscope. Results: Straight and angled abutments mean maximum load was 296.7 N and 1,145 N, the dynamic loading mean Fmax was 237.4 N and 240.7 N, respectively. No significant differences resulted between the straight and angled bi-component abutments in both static (p=0.253) and dynamic testing (p=0.135). A significant difference in the bending moment required for fracture was detected between the groups (p=0.01). Fractures in the angled group occurred mainly at the point of load application, whereas in the straight abutments, fractures were located coronally and close to the thinly designed areas at the cervical region. Conclusion: Angled or straight thin-walled zirconia abutments presented similar Fmax under fatigue testing despite the different bending moments required for fracture. The main implication is

  17. Aqueous foams stabilized by chitin nanocrystals.

    PubMed

    Tzoumaki, Maria V; Karefyllakis, Dimitris; Moschakis, Thomas; Biliaderis, Costas G; Scholten, Elke

    2015-08-21

    The aim of the present study was to explore the potential use of chitin nanocrystals, as colloidal rod-like particles, to stabilize aqueous foams. Chitin nanocrystals (ChN) were prepared by acid hydrolysis of crude chitin and foams were generated mainly by sonicating the respective dispersions. The foamability of the chitin nanocrystals was evaluated and the resulting foams were assessed for their stability, in terms of foam volume reduction and serum release patterns, during storage. Additionally, the samples were studied with light scattering and optical microscopy in order to explore the bubble size distribution and morphology of the foam. Nanocrystal concentration and charge density was varied to alter the packing of the crystals at the interface. At low concentrations of ChNs, foams were stable against coalescence and disproportionation for a period of three hours, whereas at higher concentrations, the foams were stable for several days. The enhanced stability of foams prepared with ChNs, compared to surfactant-stabilized foams, can be mainly attributed to the irreversible adsorption of the ChNs at the air-water interface, thereby providing Pickering stabilization. Both foam volume and stability of the foam were increased with an increase in ChNs concentration, and at pH values around the chitin's pKa (pH 7.0). Under these conditions, the ChNs show minimal electrostatic repulsion and therefore a higher packing of the nanocrystals is promoted. Moreover, decreased electrostatic repulsion enhances network formation between the ChNs in the aqueous films, thereby providing additional stability by gel formation. Overall, ChNs were proven to be effective in stabilizing foams, and may be useful in the design of Pickering-stabilized food grade foams.

  18. Durability of zirconia thermal-barrier ceramic coatings on air-cooled turbine blades in cyclic jet engine operation

    NASA Technical Reports Server (NTRS)

    Liebert, C. H.; Jacobs, R. E.; Stecura, S.; Morse, C. R.

    1976-01-01

    Thermal barrier ceramic coatings of stabilized zirconia over a bond coat of Ni Cr Al Y were tested for durability on air cooled turbine rotor blades in a research turbojet engine. Zirconia stabilized with either yttria, magnesia, or calcia was investigated. On the basis of durability and processing cost, the yttria stabilized zirconia was considered the best of the three coatings investigated.

  19. Development of alternative oxygen production source using a zirconia solid electrolyte membrane. Final report

    SciTech Connect

    Suitor, J.W.; Clark, D.J.; Losey, R.W.

    1990-08-01

    The objective of this multiyear effort was the development, fabrication and testing of a zirconia oxygen production module capable of delivering approximately 100 liters/minute (LPM) of oxygen. The work discussed in this report consists of development and improvement of the zirconia cell along with manufacture of cell components, preliminary design of the final plant, additional economic analysis and industrial participation. (VC)

  20. Development of alternative oxygen production source using a zirconia solid electrolyte membrane

    SciTech Connect

    Suitor, J.W.; Clark, D.J.; Losey, R.W.

    1990-08-01

    The objective of this multiyear effort was the development, fabrication and testing of a zirconia oxygen production module capable of delivering approximately 100 liters/minute (LPM) of oxygen. The work discussed in this report consists of development and improvement of the zirconia cell along with manufacture of cell components, preliminary design of the final plant, additional economic analysis and industrial participation. (VC)

  1. Simple Heat Treatment of Zirconia Ceramic Pre-Treated with Silane Primer to Improve Resin Bonding.

    PubMed

    Ha, Jung-Yun; Son, Jun Sik; Kim, Kyo-Han; Kwon, Tae-Yub

    2015-01-01

    Establishing a strong resin bond to dental zirconia ceramic remains difficult. Previous studies have shown that the conventional application of silane does not work well with zirconia. This paper reports that a silane pre-treatment of dental zirconia ceramic combined with subsequent heat treatment has potential as an adhesive cementation protocol for improving zirconia-resin bonding. Among the various concentrations (0.1 to 16 vol%) of experimental γ-methacryloxypropyltrimethoxysilane (γ-MPTS) primers assessed, the 1% solution was found to be the most effective in terms of the shear bond strength of the resin cement to dental zirconia ceramic. A high shear bond strength (approx. 30 MPa) was obtained when zirconia specimens were pre-treated with this primer and then heat-treated in a furnace for 60 min at 150 degrees C. Heat treatment appeared to remove the hydrophilic constituents from the silane film formed on the zirconia ceramic surface and accelerate the condensation reactions between the silanol groups of the hydrolyzed silane molecules at the zirconia/resin interface, finally making a more desirable surface for bonding with resin. This estimation was supported by Fourier transform infrared spectroscopy of the silanes prepared in this study.

  2. Effect of Zirconia Dental Implant Surfaces on Bone Integration: A Systematic Review and Meta-Analysis.

    PubMed

    Hafezeqoran, Ali; Koodaryan, Roodabeh

    2017-01-01

    Background. The information available about osseointegration and the bone to implant interaction of zirconia implants with various surface modifications is still far from sufficient. Objective. The purpose of this systematic review and meta-analysis was to evaluate and compare zirconia dental implants with different surface topographies, with a focus on bone to implant contact and removal torque. Methods. The systematic review of the extracted publications was performed to compare the bone to implant contact (BIC) with removal torque (RT) values of titanium dental implants and machined and surfaced modified zirconia implants. Results. A total of fifteen articles on BIC and RT values were included in the quantitative analysis. No significant difference in the BIC values was observed between titanium and machined zirconia implants (p = 0.373; 95% CI: -0.166 to 0.443). However, a significantly better BIC values were observed for acid etched zirconia implants compared with those of titanium implants (p = 0.032; 95% CI: 0.068 to 1.461). Unmodified zirconia implants showed favorable BIC values compared to modified-surface zirconia implants (p = 0.021; 95% CI: -0.973 to -0.080). Conclusion. Acid etched zirconia implants may serve as a possible substitute for successful osseointegration.

  3. Comparative fracture strength analysis of Lava and Digident CAD/CAM zirconia ceramic crowns

    PubMed Central

    Kwon, Taek-Ka; Pak, Hyun-Soon; Han, Jung-Suk; Lee, Jai-Bong; Kim, Sung-Hun

    2013-01-01

    PURPOSE All-ceramic crowns are subject to fracture during function. To minimize this common clinical complication, zirconium oxide has been used as the framework for all-ceramic crowns. The aim of this study was to compare the fracture strengths of two computer-aided design/computer-aided manufacturing (CAD/CAM) zirconia crown systems: Lava and Digident. MATERIALS AND METHODS Twenty Lava CAD/CAM zirconia crowns and twenty Digident CAD/CAM zirconia crowns were fabricated. A metal die was also duplicated from the original prepared tooth for fracture testing. A universal testing machine was used to determine the fracture strength of the crowns. RESULTS The mean fracture strengths were as follows: 54.9 ± 15.6 N for the Lava CAD/CAM zirconia crowns and 87.0 ± 16.0 N for the Digident CAD/CAM zirconia crowns. The difference between the mean fracture strengths of the Lava and Digident crowns was statistically significant (P<.001). Lava CAD/CAM zirconia crowns showed a complete fracture of both the veneering porcelain and the core whereas the Digident CAD/CAM zirconia crowns showed fracture only of the veneering porcelain. CONCLUSION The fracture strengths of CAD/CAM zirconia crowns differ depending on the compatibility of the core material and the veneering porcelain. PMID:23755332

  4. Sulfated zirconia as a proton conductor for fuel cells: Stability to hydrolysis and influence on catalysts

    NASA Astrophysics Data System (ADS)

    Tominaka, Satoshi; Momma, Toshiyuki; Scrosati, Bruno; Osaka, Tetsuya

    Sulfated zirconia is an inorganic solid superacid having sulfate groups covalently bonded to its surface. In this work, sulfated zirconia is synthesized by a solvent-free method to obtain it in the nanoparticle form. This nanostructured sulfated zirconia has been evaluated in terms of (i) chemical stability to hydrolysis and to hydrogen peroxide by thermogravimetric analysis, and (ii) influences on Pt catalyst activity by cyclic voltammetry using sulfated-zirconia dispersion as a supporting electrolyte solution. The results demonstrate that our sulfated zirconia is stable almost perfectly to hydrolysis but partly decomposed by a Fenton reagent containing hydrogen peroxide and Fe 2+. In addition, we show that oxygen reduction activity of Pt catalyst in a sulfated-zirconia dispersion is comparatively high (specific activity at 0.9 V vs. RHE, i 0.9: ca. 17 μA cm -2) compared to that in a 0.5 M sulfuric acid solution (i 0.9: ca. 15 μA cm -2). Finally, we demonstrate that sulfated zirconia does not influence hydrogen oxidation reaction. These results lead us to conclude that sulfated zirconia is a promising proton conductor for fuel cells.

  5. The Reinforcement Effect of Nano-Zirconia on the Transverse Strength of Repaired Acrylic Denture Base

    PubMed Central

    ArRejaie, Aws S.; Abdel-Halim, Mohamed Saber; Rahoma, Ahmed

    2016-01-01

    Objective. The aim of this study was to evaluate the effect of incorporation of glass fiber, zirconia, and nano-zirconia on the transverse strength of repaired denture base. Materials and Methods. Eighty specimens of heat polymerized acrylic resin were prepared and randomly divided into eight groups (n = 10): one intact group (control) and seven repaired groups. One group was repaired with autopolymerized resin while the other six groups were repaired using autopolymerized resin reinforced with 2 wt% or 5 wt% glass fiber, zirconia, or nano-zirconia particles. A three-point bending test was used to measure the transverse strength. The results were analyzed using SPSS and repeated measure ANOVA and post hoc least significance (LSD) test (P ≤ 0.05). Results. Among repaired groups it was found that autopolymerized resin reinforced with 2 or 5 wt% nano-zirconia showed the highest transverse strength (P ≤ 0.05). Repairs with autopolymerized acrylic resin reinforced with 5 wt% zirconia showed the lowest transverse strength value. There was no significant difference between the groups repaired with repair resin without reinforcement, 2 wt% zirconia, and glass fiber reinforced resin. Conclusion. Reinforcing of repair material with nano-zirconia may significantly improve the transverse strength of some fractured denture base polymers. PMID:27366150

  6. Development of alternative oxygen production source using a zirconia solid electrolyte membrane

    NASA Technical Reports Server (NTRS)

    Suitor, J. W.; Clark, D. J.; Losey, R. W.

    1990-01-01

    The objective of this multiyear effort was the development, fabrication and testing of a zirconia oxygen production module capable of delivering approximately 100 liters/minute (LPM) of oxygen. The work discussed in this report consists of development and improvement of the zirconia cell along with manufacture of cell components, preliminary design of the final plant, additional economic analysis and industrial participation.

  7. Effect of Zirconia Dental Implant Surfaces on Bone Integration: A Systematic Review and Meta-Analysis

    PubMed Central

    2017-01-01

    Background. The information available about osseointegration and the bone to implant interaction of zirconia implants with various surface modifications is still far from sufficient. Objective. The purpose of this systematic review and meta-analysis was to evaluate and compare zirconia dental implants with different surface topographies, with a focus on bone to implant contact and removal torque. Methods. The systematic review of the extracted publications was performed to compare the bone to implant contact (BIC) with removal torque (RT) values of titanium dental implants and machined and surfaced modified zirconia implants. Results. A total of fifteen articles on BIC and RT values were included in the quantitative analysis. No significant difference in the BIC values was observed between titanium and machined zirconia implants (p = 0.373; 95% CI: −0.166 to 0.443). However, a significantly better BIC values were observed for acid etched zirconia implants compared with those of titanium implants (p = 0.032; 95% CI: 0.068 to 1.461). Unmodified zirconia implants showed favorable BIC values compared to modified-surface zirconia implants (p = 0.021; 95% CI: −0.973 to −0.080). Conclusion. Acid etched zirconia implants may serve as a possible substitute for successful osseointegration. PMID:28299337

  8. Comparison of the translucency of shaded zirconia all-ceramic systems

    PubMed Central

    Ulusoy, Mutahhar

    2014-01-01

    PURPOSE The purpose of this study was to evaluate and compare the translucency of shaded zirconia all-ceramic systems. MATERIALS AND METHODS Translucency of 3 different zirconia all-ceramic systems colored by different techniques was compared with a lithium disilicate glass-ceramic (IPS e.max Press). Square-shaped specimens with 0.5 mm thickness were fabricated from In-Ceram YZ, ICE Zirkon and Katana systems in A1, A2 and A3.5 shades according to Vitapan Classical shade tab (n=11). Specimens were then veneered and glazed with corresponding veneer ceramic recommended by each zirconia system manufacturer and the total thickness was set to 1.5 mm. Translucency measurements were performed with VITA Easyshade Compact spectrophotometer after each stage and translucency parameter was calculated. Data were statistically analyzed with repeated measures ANOVA and Tukey multiple comparison test. RESULTS The control group was significantly more translucent than the zirconia systems (P<.05). ICE Zirkon cores showed the least translucency; neither In-Ceram YZ nor Katana systems were superior to each other in terms of translucency. Translucency of all specimens was decreased after veneering, and the translucency rankings were changed. CONCLUSION Coloring technique did not have a significant effect on translucency of zirconia cores. Although zirconia systems were less translucent than lithium disilicate glass ceramic, they had partial translucency and there were translucency differences among the zirconia systems. Chroma affected the translucency of precolored zirconia cores. PMID:25352964

  9. Air-particle abrasion on zirconia ceramic using different protocols: effects on biaxial flexural strength after cyclic loading, phase transformation and surface topography.

    PubMed

    Souza, Rodrigo O A; Valandro, Luiz F; Melo, Renata M; Machado, João P B; Bottino, Marco A; Ozcan, Mutlu

    2013-10-01

    This study evaluated the effect of different air-particle abrasion protocols on the biaxial flexural strength and structural stability of zirconia ceramics. Zirconia ceramic specimens (ISO 6872) (Lava, 3M ESPE) were obtained (N=336). The specimens (N=118, n=20 per group) were randomly assigned to one of the air-abrasion protocols: Gr1: Control (as-sintered); Gr2: 50 µm Al2O3 (2.5 bar); Gr3: 50 µm Al2O3 (3.5 bar); Gr4: 110 µm Al2O3(2.5 bar); Gr5: 110 µm Al2O3 (3.5 bar); Gr6: 30 µm SiO2 (2.5 bar) (CoJet); Gr7: 30 µm SiO2(3.5 bar); Gr8: 110 µm SiO2 (2.5 bar) (Rocatec Plus); and Gr9: 110 µm SiO2 (3.5 bar) (duration: 20 s, distance: 10 mm). While half of the specimens were tested immediately, the other half was subjected to cyclic loading in water (100,000 cycles; 50 N, 4 Hz, 37 °°C) prior to biaxial flexural strength test (ISO 6872). Phase transformation (t→m), relative amount of transformed monoclinic zirconia (FM), transformed zone depth (TZD) and surface roughness were measured. Particle type (p=0.2746), pressure (p=0.5084) and cyclic loading (p=0.1610) did not influence the flexural strength. Except for the air-abraded group with 110 µm Al2O3 at 3.5 bar, all air-abrasion protocols increased the biaxial flexural strength (MPa) (Controlnon-aged: 1,030 ± 153, Controlaged: 1,138 ± 138; Experimentalnon-aged: 1,307 ± 184-1,554 ± 124; Experimentalaged: 1,308 ± 118-1,451 ± 135) in both non-aged and aged conditions, respectively. Surface roughness (Ra) was the highest with 110 µm Al2O3(0.84 µm. FM values ranged from 0% to 27.21%, higher value for the Rocatec Plus (110 µm SiO2) and 110 µm Al2O3 groups at 3.5 bar pressure. TZD ranged between 0 and 1.43 µm, with the highest values for Rocatec Plus and 110 µm Al2O3 groups at 3.5 bar pressure.

  10. Microstructure-property relationships of chemically vapor deposited zirconia fiber coating for environmentally durable silicon carbide/silicon carbide composites

    NASA Astrophysics Data System (ADS)

    Li, Hao

    In SiC/SiC ceramic matrix composites, toughness is obtained by adding a fiber coating, which provides a weak interface for crack deflection and debonding between the fiber and the matrix. However, the most commonly used fiber coatings, carbon and boron nitride, are unstable in oxidative environments. In the present study, the feasibility of using a chemically vapor deposited zirconia (CVD-ZrO2) fiber coating as an oxidation-resistant interphase for SiC/SiC composites was investigated. A study of morphological evolution in the CVD-ZrO2 coating suggested that a size-controlled displacive phase transformation from tetragonal ZrO2 ( t-ZrO2) to monoclinic ZrO2 (m-ZrO 2) was the key mechanism responsible for the weak interface behavior exhibited by the ZrO2 coating. It appeared that a low oxygen partial pressure in the CVD reactor chamber was essential for the nucleation of t-ZrO2 and therefore was responsible for the delamination behavior. With this understanding of the weak interface mechanism, minicomposite specimens containing various ZrO2 fiber coating morphologies were fabricated and tested. A fractographic analysis showed that in-situ fiber strength and minicomposite failure loads were strongly dependent on the phase contents and microstructure of the ZrO2 coating. We determined that an optimum microstructure of the ZrO2 coating should contain a predelaminated interface surrounded by a dense outer layer. The outer layer was needed to protect the fiber from degradation during the subsequent SiC matrix infiltration procedure. A preliminary tensile stress-rupture study indicated that the ZrO2 coating exhibited promising performance in terms of providing the weak interface behavior and maintaining the thermal and oxidative stability at elevated temperatures.

  11. Structure and transformation of tactoids in cellulose nanocrystal suspensions

    PubMed Central

    Wang, Pei-Xi; Hamad, Wadood Y.; MacLachlan, Mark J.

    2016-01-01

    Cellulose nanocrystals obtained from natural sources are of great interest for many applications. In water, cellulose nanocrystals form a liquid crystalline phase whose hierarchical structure is retained in solid films after drying. Although tactoids, one of the most primitive components of liquid crystals, are thought to have a significant role in the evolution of this phase, they have evaded structural study of their internal organization. Here we report the capture of cellulose nanocrystal tactoids in a polymer matrix. This method allows us to visualize, for the first time, the arrangement of cellulose nanocrystals within individual tactoids by electron microscopy. Furthermore, we can follow the structural evolution of the liquid crystalline phase from tactoids to iridescent-layered films. Our insights into the early nucleation events of cellulose nanocrystals give important information about the growth of cholesteric liquid crystalline phases, especially for cellulose nanocrystals, and are crucial for preparing photonics-quality films. PMID:27143197

  12. Hybrid polymer-nanocrystal materials for photovoltaic applications.

    PubMed

    Zhou, Renjia; Xue, Jiangeng

    2012-07-16

    Hybrid polymer-nanocrystal photovoltaic (PV) cells have received much attention during the past decade as promising low-cost solar energy harvesting devices, and showed significant progress with power conversion efficiency reaching 5% recently. This review starts from the introduction of hybrid materials to their application in electronic devices, with particular focus on bulk-heterojunction hybrid polymer-nanocrystal PV devices. The synthesis, surface chemistry, and electronic properties of colloidal inorganic nanocrystals are described. The recent development of hybrid PV devices will be discussed from the perspective of tailoring both inorganic nanocrystals and conjugated polymers, controlling polymer-nanocrystal hybrid morphology, engineering polymer-nanocrystal interface, and optimizing device architecture. Finally, future directions for further advancing hybrid PV technology to potential commercialization are also discussed.

  13. Pyrite Nanocrystal Solar Cells: Promising, or Fool's Gold?

    PubMed

    Steinhagen, Chet; Harvey, Taylor B; Stolle, C Jackson; Harris, Justin; Korgel, Brian A

    2012-09-06

    Pyrite-phase iron sulfide (FeS2) nanocrystals were synthesized to form solvent-based dispersions, or "solar paint," to fabricate photovoltaic devices (PVs). Nanocrystals were sprayed onto substrates as absorber layers in devices with several different architectures, including Schottky barrier, heterojunction, and organic/inorganic hybrid architectures, to explore their viability as a PV material. None of the devices exhibited PV response. XRD and Raman spectroscopy confirmed the pyrite composition and phase purity of the nanocrystals. The electrical conductivity of the nanocrystal films was about 4 to 5 S/cm, more typical of metal nanocrystal films than semiconductor nanocrystal films, and the lack of PV response appears to derive from the highly conductive surface-related defects in pyrite that have been proposed.

  14. Study of nanocrystals in the dynamic slip zone

    NASA Astrophysics Data System (ADS)

    Sobolev, G. A.; Kireenkova, S. M.; Morozov, Yu. A.; Smul'skaya, A. I.; Vettegren, V. I.; Kulik, V. B.; Mamalimov, R. I.

    2012-09-01

    Mineral composition is studied and a search to detect nanocrystals is conducted in the surface layers of slickensides formed due to dynamic slip in arkose sandstone. The infrared and Raman spectroscopy show that the slickensided layer is composed of nanocrystals of montmorillonite and anatase measuring ≈15 nm and 3 nm, respectively. The crystalline lattice of the nanocrystals of montmorillonite is stretched by ≈2.5% while the lattice of the nanocrystals of anatase is compressed by ≈0.12%. Deeper than 3 mm below the slickenside surface, the sandstone contains nanocrystals of montmorillonite, beidellite and nontronite, quartz, plagioclase, and anatase. The nanocrystals of anatase have a linear size of ≈8 nm. Their crystalline lattice is compressed by ≈0.03%. It is supposed that montmorillonite in the slickensides was formed due to hydrolytic decomposition of silicates under friction of the fault planes sliding past each other.

  15. All-inorganic Germanium nanocrystal films by cationic ligand exchange

    DOE PAGES

    Wheeler, Lance M.; Nichols, Asa W.; Chernomordik, Boris D.; ...

    2016-01-21

    In this study, we introduce a new paradigm for group IV nanocrystal surface chemistry based on room temperature surface activation that enables ionic ligand exchange. Germanium nanocrystals synthesized in a gas-phase plasma reactor are functionalized with labile, cationic alkylammonium ligands rather than with traditional covalently bound groups. We employ Fourier transform infrared and 1H nuclear magnetic resonance spectroscopies to demonstrate the alkylammonium ligands are freely exchanged on the germanium nanocrystal surface with a variety of cationic ligands, including short inorganic ligands such as ammonium and alkali metal cations. This ionic ligand exchange chemistry is used to demonstrate enhanced transport inmore » germanium nanocrystal films following ligand exchange as well as the first photovoltaic device based on an all-inorganic germanium nanocrystal absorber layer cast from solution. This new ligand chemistry should accelerate progress in utilizing germanium and other group IV nanocrystals for optoelectronic applications.« less

  16. Hydrophobic starch nanocrystals preparations through crosslinking modification using citric acid.

    PubMed

    Zhou, Jiang; Tong, Jin; Su, Xingguang; Ren, Lili

    2016-10-01

    Biodegradable starch nanocrystals prepared by an acid treatment process were modified through crosslinking modification using citric acid as reactant by a dry reaction method. The occurrence of crosslinking modification was evaluated by Fourier transform infrared spectroscopy and swelling degree. X-ray diffraction, wettability tests and contact angle measurements were used to characterize the modified starch nanocrystals. It was found that the crosslinked starch nanocrystals displayed a higher affinity for low polar solvents such as dichloromethane. The surface of starch nanocrystals became more roughness after crosslinking modification with citric acid and the size decreased as revealed by scanning electron microscopy and dynamic light scattering results. XRD analysis showed that the crystalline structure of starch nanocrystals was basically not changed after the crosslinking modification with shorter heating time. The resulting hydrophobic starch nanocrystals are versatile precursors to the development of nanocomposites.

  17. All-Inorganic Germanium Nanocrystal Films by Cationic Ligand Exchange.

    PubMed

    Wheeler, Lance M; Nichols, Asa W; Chernomordik, Boris D; Anderson, Nicholas C; Beard, Matthew C; Neale, Nathan R

    2016-03-09

    We introduce a new paradigm for group IV nanocrystal surface chemistry based on room temperature surface activation that enables ionic ligand exchange. Germanium nanocrystals synthesized in a gas-phase plasma reactor are functionalized with labile, cationic alkylammonium ligands rather than with traditional covalently bound groups. We employ Fourier transform infrared and (1)H nuclear magnetic resonance spectroscopies to demonstrate the alkylammonium ligands are freely exchanged on the germanium nanocrystal surface with a variety of cationic ligands, including short inorganic ligands such as ammonium and alkali metal cations. This ionic ligand exchange chemistry is used to demonstrate enhanced transport in germanium nanocrystal films following ligand exchange as well as the first photovoltaic device based on an all-inorganic germanium nanocrystal absorber layer cast from solution. This new ligand chemistry should accelerate progress in utilizing germanium and other group IV nanocrystals for optoelectronic applications.

  18. All-inorganic Germanium nanocrystal films by cationic ligand exchange

    SciTech Connect

    Wheeler, Lance M.; Nichols, Asa W.; Chernomordik, Boris D.; Anderson, Nicholas C.; Beard, Matthew C.; Neale, Nathan R.

    2016-01-21

    In this study, we introduce a new paradigm for group IV nanocrystal surface chemistry based on room temperature surface activation that enables ionic ligand exchange. Germanium nanocrystals synthesized in a gas-phase plasma reactor are functionalized with labile, cationic alkylammonium ligands rather than with traditional covalently bound groups. We employ Fourier transform infrared and 1H nuclear magnetic resonance spectroscopies to demonstrate the alkylammonium ligands are freely exchanged on the germanium nanocrystal surface with a variety of cationic ligands, including short inorganic ligands such as ammonium and alkali metal cations. This ionic ligand exchange chemistry is used to demonstrate enhanced transport in germanium nanocrystal films following ligand exchange as well as the first photovoltaic device based on an all-inorganic germanium nanocrystal absorber layer cast from solution. This new ligand chemistry should accelerate progress in utilizing germanium and other group IV nanocrystals for optoelectronic applications.

  19. Influence of downsizing of zeolite crystals on the orthorhombic ↔ monoclinic phase transition in pure silica MFI-type

    NASA Astrophysics Data System (ADS)

    Kabalan, Ihab; Michelin, Laure; Rigolet, Séverinne; Marichal, Claire; Daou, T. Jean; Lebeau, Bénédicte; Paillaud, Jean-Louis

    2016-08-01

    The impact of crystal size on the transition orthorhombic ↔ monoclinic phase in MFI-type purely silica zeolites is investigated between 293 and 473 K using 29Si MAS NMR and powder X-ray diffraction. Three silicalite-1 zeolites are synthesized: a material constituted of micron-sized crystals, pseudospherical nanometer-sized crystals and hierarchical porous zeolites with a mesoporous network created by the use of a gemini-type diquaternary ammonium surfactant giving nanosheet zeolites. Our results show for the first time that the orthorhombic ↔ monoclinic phase transition already known for micron-sized particles also occurs in nanometer-sized zeolite crystals whereas our data suggest that the extreme downsizing of the zeolite crystal to one unit cell in thickness leads to an extinction of the phase transition.

  20. Cooperative effect of monoclinic distortion and sinusoidal modulation in the martensitic structure of Ni 2FeGa

    NASA Astrophysics Data System (ADS)

    Lu, J. B.; Yang, H. X.; Tian, H. F.; Zeng, L. J.; Ma, C.; Feng, L.; Wu, G. H.; Li, J. Q.; Jansen, J.

    2010-02-01

    The structural features of the "5M" martensitic phase in Ni 2FeGa alloys have been determined by electron diffraction using the multi-slice least-squares (MSLS) method. The results demonstrate that the "5M" phase contains an evident cooperative effect of monoclinic distortion and sinusoidal modulation along the [110] c direction. Theoretical simulations based on our refined data suggest that the "5M" martensitic phase observed in Ni-Fe-Ga and Ni-Mn-Ga has visible common behaviors in both stacking sequence and local structural distortion. Considering the cooperative effect of monoclinic distortion and sinusoidal modulation, we demonstrate that the "7M" martensitic phase could adopt two equivalent structural phases corresponding with the stacking sequences of (43-)2 and (52-)2, respectively.

  1. Synthesis and applications of heterostructured semiconductor nanocrystals

    NASA Astrophysics Data System (ADS)

    Khon, Elena

    Semiconductor nanocrystals (NCs) have been of great interest to researchers for several decades due to their unique optoelectronic properties. These nanoparticles are widely used for a variety of different applications. However, there are many unresolved issues that lower the efficiency and/or stability of devices which incorporate these NCs. Our research is dedicated to addressing these issues by identifying potential problems and resolving them, improving existing systems, generating new synthetic strategies, and/or building new devices. The general strategies for the synthesis of different nanocrystals were established in this work, one of which is the colloidal growth of gold domains onto CdS semiconductor nanocrystals. Control of shape and size was achieved simply by adjusting the temperature and the time of the reaction. Depending on the exact morphology of Au and CdS domains, fabricated nano-composites can undergo evaporation-induced self-assembly onto a substrate, which is very useful for building devices. CdS/Au heterostructures can assemble in two different ways: through end-to-end coupling of Au domains, resulting in the formation of one-dimensional chains; and via side-by-side packing of CdS nanorods, leading to the onset of two-dimensional superlattices. We investigated the nature of exciton-plasmon interactions in Au-tipped CdS nanorods using femtosecond transient absorption spectroscopy. The study demonstrated that the key optoelectronic properties of electrically coupled metal and semiconductor domains are significantly different from those observed in systems with weak inter-domain coupling. In particular, strongly-coupled nanocomposites promote mixing of electronic states at semiconductor-metal domain interfaces, which causes a significant suppression of both plasmon and exciton carrier excitations. Colloidal QDs are starting to replace organic molecules in many different applications, such as organic light emmiting diods (OLEDs), due to their

  2. Strong visible cooperative up-conversion emission in ZrO2:Yb3+ nanocrystals.

    PubMed

    De la Rosa, E; Salas, P; Díaz-Torres, L A; Martínez, A; Angeles, C

    2005-09-01

    Blue, green, and red emission was observed under infrared excitation in ZrO2:Yb3+ nanocrystals prepared by the sol-gel process. The structural characterization was performed by using XRD and HRTEM, suggesting that the crystalline phase of the nanoparticles is controlled by the active ion concentration being mainly tetragonal for 2 mol% of dopant and mainly monoclinic for 0.5 mol%. The blue emission was explained in terms of the cooperative deexcitation of an Yb-Yb pair, while the green and red bands were associated with the up-conversion of traces of Er ion. The number of photons involved in the luminescence process is analyzed in order to confirm that cooperative emission is produced by the interaction of an Yb pair and that the green and red emission are the results of energy transfer between Yb-Er ions. The high efficiency of all bands is explained in terms of the high surface area of the nanoparticles.

  3. Selective synthesis of monazite- and zircon-type LaVO(4) nanocrystals.

    PubMed

    Jia, Chun-Jiang; Sun, Ling-Dong; You, Li-Ping; Jiang, Xiao-Cheng; Luo, Feng; Pang, Yu-Cheng; Yan, Chun-Hua

    2005-03-03

    Pure monoclinic (m-) and tetragonal phased (t-) LaVO(4) nanocrystals could be obtained by a hydrothermal method in a controllable way with additives. It is found that chelating ligands, such as ethylenediaminetetraacetic acid [EDTA or H(4)L, where L(4-) = (CH(2)COO)(2)N(CH(2))(2)N(CH(2)COO)(2)(4-)], favor the formation of t-LaVO(4) and can induce the polymorph transformation from stable m-LaVO(4) to metastable t-LaVO(4). Further studies demonstrated the important roles of chelating ligands in this transformation process. Careful investigation over the phase transition from t- to m-LaVO(4) was also conducted with high-temperature X-ray diffraction (HTXRD) studies. The phase transition occurred at 850 degrees C, which is about 250 degrees C higher than for the bulk. The enhanced thermal stability of the nanosized metastable t-LaVO(4) may come from the small size effect. Our capability of obtaining and stabilizing t-LaVO(4) not only benefits the wider applications based on LaVO(4) due to the improved luminescent and catalytic performance but also provides a new idea in the studies of polymorph control and selective synthesis of inorganic materials.

  4. Use of zirconia ceramic in the DexAide right ventricular assist device journal bearing.

    PubMed

    Saeed, Diyar; Horvath, David J; Massiello, Alex L; Ootaki, Yoshio; Benefit, Stephen; Golding, Leonard A R; Fukamachi, Kiyotaka

    2010-02-01

    Our aim was to evaluate the potential use of zirconium oxide (zirconia) as a blood journal bearing material in the DexAide right ventricular assist device. The DexAide titanium stator was replaced by a zirconia stator in several blood pump builds, without changing the remaining pump hardware components. In vitro pump performance and efficiency were evaluated at a predetermined pump speed and flow. Motor power consumption decreased by 20%, and DexAide battery life was extended to over 12 h on two fully charged batteries. The zirconia stator was also successfully evaluated in a severe start/stop test pre- and postexposure of the zirconia to accelerated simulated biologic aging. This study's outcomes indicated the advantages of zirconia as an alternate journal bearing material for the DexAide device.

  5. Ferroelectric Self-Poling, Switching, and Monoclinic Domain Configuration in BiFeO 3 Thin Films

    SciTech Connect

    Beekman, C.; Siemons, W.; Chi, M.; Balke, N.; Howe, J. Y.; Ward, T. Z.; Maksymovych, P.; Budai, J. D.; Tischler, J. Z.; Xu, R.; Liu, W.; Christen, H. M.

    2016-05-23

    Self-poling of ferroelectric films, i.e., a preferred, uniform direction of the ferroelectric polarization in as-grown samples is often observed yet poorly understood despite its importance for device applications. The multiferroic perovskite BiFeO3, which crystallizes in two distinct structural polymorphs depending on applied epitaxial strain, is well known to exhibit self-poling. This study investigates the effect of self-poling on the monoclinic domain configuration and the switching properties of the two polymorphs of BiFeO3 (R' and T') in thin films grown on LaAlO3 substrates with slightly different La0.3Sr0.7MnO3 buffer layers. Our study shows that the polarization state formed during the growth acts as “imprint” on the polarization and that switching the polarization away from this self-poled direction can only be done at the expense of the sample's monoclinic domain configuration. We observed reduction of the monoclinic domain size and found that it was largely reversible; hence, the domain size is restored when the polarization is switched back to its original orientation. This is a direct consequence of the growth taking place in the polar phase (below Tc). Finally, switching the polarization away from the preferred configuration, in which defects and domain patterns synergistically minimize the system's energy, leads to a domain state with smaller (and more highly strained and distorted) monoclinic domains.

  6. Shaped nanocrystal particles and methods for working the same

    DOEpatents

    Alivisatos, A. Paul; Sher, Eric C.; Manna, Liberato

    2007-12-25

    Shaped nanocrystal particles and methods for making shaped nanocrystal particles are disclosed. One embodiment includes a method for forming a branched, nanocrystal particle. It includes (a) forming a core having a first crystal structure in a solution, (b) forming a first arm extending from the core having a second crystal structure in the solution, and (c) forming a second arm extending from the core having the second crystal structure in the solution.

  7. Shaped nanocrystal particles and methods for making the same

    DOEpatents

    Alivisatos, A Paul [Oakland, CA; Scher, Erik C [Menlo Park, CA; Manna, Liberato [Berkeley, CA

    2011-11-22

    Shaped nanocrystal particles and methods for making shaped nanocrystal particles are disclosed. One embodiment includes a method for forming a branched, nanocrystal particle. It includes (a) forming a core having a first crystal structure in a solution, (b) forming a first arm extending from the core having a second crystal structure in the solution, and (c) forming a second arm extending from the core having the second crystal structure in the solution.

  8. Organization of silicon nanocrystals by localized electrochemical etching

    NASA Astrophysics Data System (ADS)

    Ayari-Kanoun, Asma; Drouin, Dominique; Beauvais, Jacques; Lysenko, Vladimir; Nychyporuk, Tetyana; Souifi, Abdelkader

    2009-10-01

    An approach to form a monolayer of organized silicon nanocrystals on a monocrystalline Si wafer is reported. Ordered arrays of nanoholes in a silicon nitride layer were obtained by combining electron beam lithography and plasma etching. Then, a short electrochemical etching current pulse led to formation of a single Si nanocrystal per each nanohole. As a result, high quality silicon nanocrystal arrays were formed with well controlled and reproducible morphologies. In future, this approach can be used to fabricate single electron devices.

  9. Shaped nanocrystal particles and methods for making the same

    DOEpatents

    Alivisatos, A. Paul; Scher, Erik C; Manna, Liberato

    2013-12-17

    Shaped nanocrystal particles and methods for making shaped nanocrystal particles are disclosed. One embodiment includes a method for forming a branched, nanocrystal particle. It includes (a) forming a core having a first crystal structure in a solution, (b) forming a first arm extending from the core having a second crystal structure in the solution, and (c) forming a second arm extending from the core having the second crystal structure in the solution.

  10. Organization of silicon nanocrystals by localized electrochemical etching

    SciTech Connect

    Ayari-Kanoun, Asma; Drouin, Dominique; Beauvais, Jacques; Lysenko, Vladimir; Nychyporuk, Tetyana; Souifi, Abdelkader

    2009-10-12

    An approach to form a monolayer of organized silicon nanocrystals on a monocrystalline Si wafer is reported. Ordered arrays of nanoholes in a silicon nitride layer were obtained by combining electron beam lithography and plasma etching. Then, a short electrochemical etching current pulse led to formation of a single Si nanocrystal per each nanohole. As a result, high quality silicon nanocrystal arrays were formed with well controlled and reproducible morphologies. In future, this approach can be used to fabricate single electron devices.

  11. Clinical performance and failures of zirconia-based fixed partial dentures: a review literature

    PubMed Central

    Triwatana, Premwara; Nagaviroj, Noppavan

    2012-01-01

    PURPOSE Zirconia has been used in clinical dentistry for approximately a decade, and there have been several reports regarding the clinical performance and survival rates of zirconia-based restorations. The aim of this article was to review the literatures published from 2000 to 2010 regarding the clinical performance and the causes of failure of zirconia fixed partial dentures (FPDs). MATERIALS AND METHODS An electronic search of English peer-reviewed dental literatures was performed through PubMed to obtain all the clinical studies focused on the performance of the zirconia FPDs. The electronic search was supplemented by manual searching through the references of the selected articles for possible inclusion of some articles. Randomized controlled clinical trials, longitudinal prospective and retrospective cohort studies were the focuses of this review. Articles that did not focus on the restoration of teeth using zirconia-based restorations were excluded from this review. RESULTS There have been three studies for the study of zirconia single crowns. The clinical outcome was satisfactory (acceptable) according to the CDA evaluation. There have been 14 studies for the study of zirconia FPDs. The survival rates of zirconia anterior and posterior FPDs ranged between 73.9% - 100% after 2 - 5 years. The causes of failure were veneer fracture, ceramic core fracture, abutment tooth fracture, secondary caries, and restoration dislodgment. CONCLUSION The overall performance of zirconia FPDs was satisfactory according to either USPHS criteria or CDA evaluations. Fracture resistance of core and veneering ceramics, bonding between core and veneering materials, and marginal discrepancy of zirconia-based restorations were discussed as the causes of failure. Because of its repeated occurrence in many studies, future researches are essentially required to clarify this problem and to reduce the fracture incident. PMID:22737311

  12. Numerical model of a single nanocrystal devoted to the study of disordered nanocrystal floating gates of new flash memories

    NASA Astrophysics Data System (ADS)

    Leroy, Yann; Armeanu, Dumitru; Cordan, Anne-Sophie

    2011-05-01

    The improvement of our model concerning a single nanocrystal that belongs to a nanocrystal floating gate of a flash memory is presented. In order to extend the gate voltage range applicability of the model, the 3D continuum of states of either metallic or semiconducting electrodes is discretized into 2D subbands. Such an approach gives precise information about the mechanisms behind the charging or release processes of the nanocrystal. Then, the self-energy and screening effects of an electron within the nanocrystal are evaluated and introduced in the model. This enables a better determination of the operating point of the nanocrystal memory. The impact of those improvements on the charging or release time of the nanocrystal is discussed.

  13. Ultrasonication of Bismuth Telluride Nanocrystals Fabricated by Solvothermal Method

    NASA Technical Reports Server (NTRS)

    Chu, Sang-Hyon; Choi, Sang H.; Kim, Jae-Woo; King, Glen C.; Elliott, James R.

    2006-01-01

    The objective of this study is to evaluate the effect of ultrasonication on bismuth telluride nanocrystals prepared by solvothermal method. In this study, a low dimensional nanocrystal of bismuth telluride (Bi2Te3) was synthesized by a solvothermal process in an autoclave at 180 C and 200 psi. During the solvothermal reaction, organic surfactants effectively prevented unwanted aggregation of nanocrystals in a selected solvent while controlling the shape of the nanocrystal. The atomic ratio of bismuth and tellurium was determined by energy dispersive spectroscopy (EDS). The cavitational energy created by the ultrasonic probe was varied by the ultrasonication process time, while power amplitude remained constant. The nanocrystal size and its size distribution were measured by field emission scanning electron microscopy (FESEM) and a dynamic light scattering system. When the ultrasonication time increased, the average size of bismuth telluride nanocrystal gradually increased due to the direct collision of nanocrystals. The polydispersity of the nanocrystals showed a minimum when the ultrasonication was applied for 5 min. Keywords: bismuth telluride, nanocrystal, low-dimensional, ultrasonication, solvothermal

  14. Spectroscopy of intraband optical transitions in anisotropic semiconductor nanocrystals

    NASA Astrophysics Data System (ADS)

    Turkov, Vadim K.; Baimuratov, Anvar S.; Rukhlenko, Ivan D.; Baranov, Alexander V.; Fedorov, Anatoly V.

    2013-09-01

    We propose a new type of optical spectroscopy of anisotropic semiconductor nanocrystals, which is based on the welldeveloped stationary pump-probe technique, where the pump and probe fields are absorbed upon, respectively, interband and intraband transitions of the nanocrystals' electronic subsystem. We develop a general theory of intraband absorption based on the density matrix formalism. This theory can be applied to study degenerate eigenstates of electrons in semiconductor nanocrystals of different shapes and dimentions. We demonstrate that the angular dependence of intraband absorption by nonspherical nanocrystals enables investigating their shape and orientation, as well as the symmetry of quantum states excited by the probe field and selection rules of electronic transitions.

  15. Colloidal inorganic nanocrystals: Nucleation, growth and biological applications

    NASA Astrophysics Data System (ADS)

    Lynch, Jared James

    Colloidal inorganic nanocrystals are a class of material whose size ranges from a few nanometers to a hundred nanometers in dimension. These nanocrystals have size dependent properties that differ significantly from the bulk material counterparts. Due to their unique physical properties colloidal inorganic nanocrystals have several promising applications in a diverse range of areas, such as biomedical diagnosis, catalysis, plasmonics, high-density data storage and solar energy conversion. This dissertation presents the study of the formation of iron oxide nanocrystals under the influence of solvent and Ar gas bubbles, the phase transfer of metal oxide nanocrystals into water using inorganic ions, and the doping of semiconductor CdS/ZnS core/shell nanocrystals with copper and silver ions. First, the formation of iron oxide nanocrystals is investigated in the presence of boiling solvent or Ar bubbles. Using a non-injection based synthesis method, the thermal decomposition of iron oleate was studied under various reaction conditions, and the role of the bubbles on the nucleation and growth of iron oxide nanocrystals was determined. Kinetics studies were used to elucidate how latent heat transfer from the bubbles allows for "active monomers" to form preferentially from exothermic reactions taking place during nucleation. General insights into colloidal inorganic nanocrystal formation are discussed. Second, a non-injection based synthesis for CdS/ZnS core/shell nanocrystals is used to make high quality semiconductor particles which are intentionally doped with Cu or Ag ions. The Ag ions effect on the optical properties of the CdS/ZnS nanocrystals is investigated. The absorption and fluorescence of the samples is measured as a function of time and temperature. Proposed mechanisms for the observations are given and thoroughly discussed. Comparisons between previous results for Cu doped CdS/ZnS nanocrystals are also made to further understand how doping of semiconductor

  16. Bright White Light Emission from Ultrasmall Cadmium Selenide Nanocrystals

    SciTech Connect

    Rosson, Teresa; Claiborne, Sarah; McBride, James; Stratton, Benjamin S; Rosenthal, Sandra

    2012-01-01

    A simple treatment method using formic acid has been found to increase the fluorescence quantum yield of ultrasmall white light-emitting CdSe nanocrystals from 8% to 45%. Brighter white-light emission occurs with other carboxylic acids as well, and the magnitude of the quantum yield enhancement is shown to be dependent on the alkyl chain length. Additionally, the nanocrystal luminescence remains enhanced relative to the untreated nanocrystals over several days. This brightened emission opens the possibility for even further quantum yield improvement and potential for use of these white-light nanocrystals in solid-state lighting applications.

  17. Bright white light emission from ultrasmall cadmium selenide nanocrystals.

    PubMed

    Rosson, Teresa E; Claiborne, Sarah M; McBride, James R; Stratton, Benjamin S; Rosenthal, Sandra J

    2012-05-16

    A simple treatment method using formic acid has been found to increase the fluorescence quantum yield of ultrasmall white light-emitting CdSe nanocrystals from 8% to 45%. Brighter white-light emission occurs with other carboxylic acids as well, and the magnitude of the quantum yield enhancement is shown to be dependent on the alkyl chain length. Additionally, the nanocrystal luminescence remains enhanced relative to the untreated nanocrystals over several days. This brightened emission opens the possibility for even further quantum yield improvement and potential for use of these white-light nanocrystals in solid-state lighting applications.

  18. Lu-177-Labeled Zirconia Particles for Radiation Synovectomy.

    PubMed

    Polyak, Andras; Nagy, Lívia Naszályi; Drotár, Eszter; Dabasi, Gabriella; Jóba, Róbert P; Pöstényi, Zita; Mikolajczak, Renata; Bóta, Attila; Balogh, Lajos

    2015-12-01

    The present article describes the preparation of β-emitter lutetium-177-labeled zirconia colloid and its preliminary physicochemical and biological evaluation of suitability for local radionuclide therapy. The new (177)Lu-labeled therapeutic radiopharmaceutical candidate was based on the synthesis mode of a previously described zirconia nanoparticle system. The size and shape of the developed radiopharmaceutical compound were observed through a scanning electron microscope and dynamic light scattering methods. The radiocolloid had a 1.7 μm mean diameter and showed high in vitro radiochemical and colloid size stability at room temperature and during the blood sera stability test. After the in vitro characterizations, the product was investigated in the course of the treatment of a spontaneously diseased dog veterinary patient's hock joint completed with single-photon emission computed tomography (SPECT) imaging follow-up measurements and a dual-isotope SPECT imaging tests with conventional (99m)Tc-methanediphosphonic acid bone scintigraphy. In the treated dog, no clinical side-effects or signs of histopathological changes of the joints were recorded during the treatment. SPECT follow-up studies clearly and conspicuously showed the localization of the (177)Lu-labeled colloid in the hock joint as well as detectable but negligible leakages of the radiocolloid in the nearest lymph node. On the basis of biological follow-up tests, the orthopedic team assumed that the (177)Lu-labeled zirconia colloid-based local radionuclide therapy resulted in a significant and long-term improvement in clinical signs of the patient without any remarkable side-effects.

  19. Failure Probability of Three Designs of Zirconia Crowns.

    PubMed

    Ramos, Gabriela Freitas; Monteiro, Evelyn Barbosa; Bottino, Marco Antonio; Zhang, Yu; Marques de Melo, Renata

    2015-01-01

    This study used a two-parameter Weibull analysis for evaluation of the lifespan of fully or partially porcelain-/glaze-veneered zirconia crowns after fatigue test. A sample of 60 first molars were selected and prepared for full-coverage crowns with three different designs (n = 20): traditional (crowns with zirconia framework covered with feldspathic porcelain), modified (crowns partially covered with veneering porcelain), and monolithic (full-contour zirconia crowns). All specimens were treated with a glaze layer. Specimens were subjected to mechanical cycling (100 N, 3 Hz) with a piston with a hemispherical tip (Ø = 6 mm) until the specimens failed or up to 2 × 10⁶ cycles. Every 500,000 cycles, the fatigue tests were interrupted and stereomicroscopy (10×) was used to inspect the specimens for damage. The authors performed Weibull analysis of interval data to calculate the number of failures in each interval. The types and numbers of failures according to the groups were: cracking (13 traditional, 6 modified) and chipping (4 traditional) of the feldspathic porcelain, followed by delamination (1 traditional) at the veneer/core interface and debonding (2 monolithic) at the cementation interface. Weibull parameters (β, scale; η, shape), with a two-sided confidence interval of 95%, were: traditional-1.25 and 0.9 × 10⁶ cycles; modified-0.58 and 11.7 × 10⁶ cycles; and monolithic-1.05 and 16.5 × 10⁶ cycles. Traditional crowns showed greater susceptibility to fatigue, the modified group presented higher propensity to early failures, and the monolithic group showed no susceptibility to fatigue. The modified and monolithic groups presented the highest number of crowns with no failures after the fatigue test. The three crown designs presented significantly different behaviors under fatigue. The modified and monolithic groups presented less probability of failure after 2 × 10⁶ cycles.

  20. Failure probability of three designs of zirconia crowns

    PubMed Central

    Ramos, G. Freitas; Monteiro, E. Barbosa Carmona; Bottino, M.A.; Zhang, Y.; de Melo, R. Marques

    2015-01-01

    Objectives This study utilized a 2-parameter Weibull analysis for evaluation of lifetime of fully or partially porcelain-/glaze-veneered zirconia crowns after fatigue test. Methods Sixty first molars were selected and prepared for full-coverage crowns with three different designs(n = 20): Traditional –crowns with zirconia framework covered with feldspathic porcelain; Modified– crowns partially covered with veneering porcelain; and Monolithic–full-contour zirconia crowns. All specimens were treated with a glaze layer. Specimens were subjected to mechanical cycling (100N, 3Hz) with a piston with hemispherical tip (Ø=6 mm) until the specimens failed or up to 2×106 cycles. Every 500,000 cycles intervals, the fatigue tests were interrupted, and stereomicroscopy (10 X) was used to inspect the specimens for damage. We performed Weibull analysis of interval data to calculate the number of failures in each interval. Results The types and number of failures according to the groups were: cracking (Traditional-13, Modified-6) and chipping (Traditional-4) of the feldspathic porcelain, followed by delamination (Traditional-1) at the veneer/core interface and debonding (Monollithic-2) at the cementation interface. Weibull parameters (beta, scale; and eta, shape), with a two-sided confidence interval of 95%, were: Traditional – 1.25 and 0.9 × 106cycles; Modified– 0.58 and 11.7 × 106 cycles; and Monolithic – 1.05 and 16.5 × 106 cycles. Traditional crowns showed greater susceptibility to fatigue, the Modified group presented higher propensity to early failures, and the Monolithic group showed no susceptibility to fatigue. The Modified and Monolithic groups presented the highest number of crowns with no failures after the fatigue test. Conclusions The three crown designs presented significantly different behaviors under fatigue. The Modified and the Monolithic groups presented less probability to failure after 2×106cycles. PMID:26509988

  1. Photocatalytic Solar Fuel Generation on Semiconductor Nanocrystals

    NASA Astrophysics Data System (ADS)

    Feldmann, Jochen

    2015-03-01

    I will review our scientific work on photocatalytic solar fuel generation utilizing colloidal semiconductor nanocrystals decorated with catalytic metal clusters. In particular, nanocrystals made of CdS, TiO2 and organo-metal halide perovskites will be discussed. Key issues are the role of hole scavangers (M. Berr et al., Appl. Phys. Lett. 100, 223903 (2012)), the size and density of catalytic clusters (M. Berr et al.: Appl. Phys. Lett. 97, 093108 (2010) and Nano Letters 12, 5903 (2012) , and dependencies on external parameters such as pH (T. Simon et al., Nature Mat. 13, 1013 (2014)). Financially supported by the Bavarian Research Cluster ``Solar Technologies Go Hybrid: SolTech''.

  2. Atomic Diffusion within Individual Gold Nanocrystal

    PubMed Central

    Xiong, Gang; Clark, Jesse N.; Nicklin, Chris; Rawle, Jonathan; Robinson, Ian K.

    2014-01-01

    Due to their excess surface free energy and structural instabilities, nanoparticles exhibit interesting physical and chemical properties. There has been an ever-growing interest in investigating these properties, driven by the desire to further miniaturize electronic devices, develop new functional materials and catalysts. Here, the intriguing question of how diffusion evolves in a single nanoparticle is investigated by measuring the spatial and temporal variations of the diffracted coherent X-ray intensity during copper diffusion into a gold nanocrystal. Dislocation loops formed from the insertion of single layer of extra atoms between neighbouring gold host lattice planes are detected. Au-Cu alloy channels are found to penetrate the nanocrystal due to the differential diffusion rate along different directions. With the advent of higher brilliance sources and free-electron-lasers, Bragg Coherent X-ray Diffraction Imaging can play an important role in unveiling atomic behaviours in three dimensions for nanomaterials during various fundamental processes. PMID:25341377

  3. Stability of yttria-stabilized zirconia during pyroprocessing tests

    NASA Astrophysics Data System (ADS)

    Choi, Eun-Young; Lee, Jeong; Lee, Sung-Jai; Kim, Sung-Wook; Jeon, Sang-Chae; Cho, Soo Haeng; Oh, Seung Chul; Jeon, Min Ku; Lee, Sang Kwon; Kang, Hyun Woo; Hur, Jin-Mok

    2016-07-01

    In this study, the feasibility of yttria-stabilized zirconia (YSZ) was investigated for use as a ceramic material, which can be commonly used for both electrolytic reduction and electrorefining. First, the stability of YSZ in salts for electrolytic reduction and electrorefining was examined. Then, its stability was demonstrated by a series of pyroprocessing tests, such as electrolytic reduction, LiCl distillation, electrorefining, and LiClsbnd KCl distillation, using a single stainless steel wire mesh basket containing fuel and YSZ. A single basket was used by its transportation from one test to subsequent tests without the requirements for unloading.

  4. Superplasticity and joining of zirconia-based ceramics

    SciTech Connect

    Gutierrez-Mora, F.; Dominguez-Rodriguez, A.; Jimenez-Melendo, M.; Chaim, R.; Ravi, G.B.; Routbort, J.L.

    2000-07-01

    Steady-state creep and joining of alumina/zirconia composites containing alumina volume fractions of 20, 60 and 85% have been investigated between 1,250 and 1,350 C. Superplasticity of these compounds is controlled by grain-boundary sliding and the creep rate is a function of alumina volume fraction, not grain size. Using the principles of superplasticity, pieces of the composite have been joined by applying the stress required to achieve 5 to 10% strain to form a strong interface at temperatures as low as 1,200 C.

  5. Achieving optimal outcomes with all-zirconia crowns.

    PubMed

    Christensen, John Juel

    2014-01-01

    All-zirconia crowns are enjoying an unprecedented popularity. Dental laboratories are acquiring new equipment and adopting novel techniques, some of which require a learning curve. As a result, some crowns fabricated by computer-aided design/computer-aided manufacturing technology may come back to the dentist with unsatisfactory features. Dentists should carefully examine each crown under magnification prior to delivery to the patient. The dentist and dental laboratory should establish a close partnership with clear communication to yield the most favorable outcome for the patient.

  6. Thermal Conductivity of Alumina-Toughened Zirconia Composites

    NASA Technical Reports Server (NTRS)

    Bansal, Narottam P.; Zhu, Dong-Ming

    2003-01-01

    10-mol% yttria-stabilized zirconia (10YSZ)-alumina composites containing 0 to 30 mol% alumina were fabricated by hot pressing at 1500 C in vacuum. Thermal conductivity of the composites, determined at various temperatures using a steady-state laser heat flux technique, increased with increase in alumina content. Composites containing 0, 5, and 10-mol% alumina did not show any change in thermal conductivity with temperature. However, those containing 20 and 30-mol% alumina showed a decrease in thermal conductivity with increase in temperature. The measured values of thermal conductivity were in good agreement with those calculated from simple rule of mixtures.

  7. Crystalline mesoporous zirconia catalysts having stable tetragonal pore wall structure

    DOEpatents

    Sachtler, Wolfgang M. H.; Huang, Yin-Yan

    1998-01-01

    Methods for the preparation of new sulfated mesoporous zirconia materials/catalysts with crystalline pore walls of predominantly tetragonal crystal structure, characterized by nitrogen physisorption 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.

  8. Crystalline mesoporous zirconia catalysts having stable tetragonal pore wall structure

    DOEpatents

    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.

  9. Homogeneous precipitation synthesis and electrical properties of scandia stabilized zirconia

    NASA Astrophysics Data System (ADS)

    Xu, Gang; Zhang, Yawen; Liao, Chunsheng; Yan, Chunhua

    2001-12-01

    Homogeneous precipitation employing urea was utilized to prepare ultrafine and weakly-agglomerated 8 mol% scandia-stabilized zirconia (8ScSZ) powders. Their crystal structure, particle and electrical properties were investigated by scanning electron microscopy, high resolution transmission electron microscopy, X-ray diffraction, thermo-gravimetry and differential thermal analysis, BET surface area analysis, and impedance spectroscopy, respectively. 8ScSZ polycrystals in a pure cubic phase were obtained after sintering at a low temperature of 600 °C. Elevating sintering temperature can increase the oxide ion conductivity, especially the grain boundary conductivity.

  10. Maximizing esthetic results on zirconia-based restorations.

    PubMed

    Chang, Yi-Yuan

    2011-01-01

    With a flexural strength of approximately 900-1,100 MPa, zirconium oxide is one of the toughest all-ceramic materials available in dentistry.1 It can be used to fabricate both single-unit and long-span bridge frameworks. A moderate level of translucency makes it suitable for esthetically demanding clinical cases, such as restoring maxillary anterior teeth. A variety of well-designed porcelain veneering systems allow technicians to apply their artistic skills to create natural, lifelike restorations. A good balance of strength, precision, and translucency allows zirconia-based restorations to accommodate a variety of clinical situations.

  11. Process for making surfactant capped nanocrystals

    DOEpatents

    Alivisatos, A Paul; Rockenberger, Joerg

    2002-01-01

    Disclosed is a process for making surfactant capped nanocrystals of transition metal oxides. The process comprises reacting a metal cupferron complex of the formula M Cup, wherein M is a transition metal, and Cup is a cupferron, with a coordinating surfactant, the reaction being conducted at a temperature ranging from about 250 to about 300 C., for a period of time sufficient to complete the reaction.

  12. Colloidal Nanocrystals Fluoresced by Surface Coordination Complexes

    PubMed Central

    Wang, Guan; Ji, Jianwei; Zhang, Xinwen; Zhang, Yan; Wang, Qiangbin; You, Xiaozeng; Xu, Xiangxing

    2014-01-01

    Colloidal Nanocrystals (NCs) with fluorescence originating from surface complexes are successfully prepared. The components of these NCs range from insulator, semiconductor to metal, with either pure phase, doped or core/shell structures. The photoluminescence of these NCs can be reversibly tuned across the visible to infrared spectrum, and even allow multi-color emission. A light emitting device is fabricated and a new in vivo cell imaging method is performed to demonstrate the power of this technology for emerging applications. PMID:24970242

  13. Electronic transport in arrays of gold nanocrystals

    NASA Astrophysics Data System (ADS)

    Parthasarathy, Raghuveer

    We examine electronic transport through two-dimensional arrays of gold nanocrystals. Recently developed techniques of particle synthesis and array self-assembly provide ordered (and disordered) monolayers of six-nanometer diameter gold nanocrystals on substrates with in-plane electrodes. These well-characterized superlattices allow investigation of basic questions about electronic conduction in metal quantum dot assemblies, answers to which have previously remained elusive. We first address the relation between current and voltage. Central to transport is the Coulomb blockade, the energetic cost of adding a single electron to a nanocrystal. Theoretical studies suggest power-law scaling of current beyond a threshold voltage in Coulomb blockade dominated systems. In ordered arrays, our data follow a power-law form, but with a scaling exponent significantly higher than the theoretical prediction. In disordered arrays, power-law scaling is violated; we explain that disorder disturbs the branching of current-carrying paths responsible for power-law conduction. Second, we examine the effect of temperature on transport. We find a large low-temperature regime (up to about 100 K) in which thermal energy acts only to linearly suppress the threshold voltage, leaving the current scale unaffected. We provide a simple, analytic model of thermally assisted tunneling which quantitatively describes the data. Third, we develop a simple and novel technique to tune the interparticle electronic couplings of the arrays---deposition of small amounts of germanium on the monolayers. The germanium dopant lowers the voltage threshold, and also increases conductivity. It also increases the temperature dependence of transport, suggesting the introduction of trapped states between the gold nanocrystal cores.

  14. Colloidal nanocrystals fluoresced by surface coordination complexes.

    PubMed

    Wang, Guan; Ji, Jianwei; Zhang, Xinwen; Zhang, Yan; Wang, Qiangbin; You, Xiaozeng; Xu, Xiangxing

    2014-06-27

    Colloidal Nanocrystals (NCs) with fluorescence originating from surface complexes are successfully prepared. The components of these NCs range from insulator, semiconductor to metal, with either pure phase, doped or core/shell structures. The photoluminescence of these NCs can be reversibly tuned across the visible to infrared spectrum, and even allow multi-color emission. A light emitting device is fabricated and a new in vivo cell imaging method is performed to demonstrate the power of this technology for emerging applications.

  15. Supersonic Nanocrystal Deposition for Nanostructured Materials

    DTIC Science & Technology

    2001-11-01

    element. Previous work has characterized the nanoerystals produced by ablation of silver microparticles. In addition to silver and cadmium selenide , several...silver and cadmium selenide in argon the kinetic energy per atom is limited to 0.03 eV/atom while for helium it is up to 0.3 cV/atom. Therefore materials...2. Cadmium Selenide nanocrystals deposited at low kinetic energy in argon carrier gas. The main TEM micrograph shows the overall size distribution and

  16. Surface-Driven Magnetotransport in Perovskite Nanocrystals.

    PubMed

    Thi N'Goc, Ha Le; Mouafo, Louis Donald Notemgnou; Etrillard, Céline; Torres-Pardo, Almudena; Dayen, Jean-François; Rano, Simon; Rousse, Gwenaëlle; Laberty-Robert, Christel; Calbet, Jose Gonzales; Drillon, Marc; Sanchez, Clément; Doudin, Bernard; Portehault, David

    2017-03-01

    Unique insights into magnetotransport in 20 nm ligand-free La0.67 Sr0.33 MnO3 perovskite nanocrystals of nearly perfect crystalline quality reveal a chemically altered 0.8 nm thick surface layer that triggers exceptionally large magnetoresistance at low temperature, independently of the spin polarization of the ferromagnetic core. This discovery shows how the nanoscale impacts magnetotransport in a material widely spread as electrode in hybrid spintronic devices.

  17. Reconciling in vivo and in vitro kinetics of the polymorphic transformation in zirconia-toughened alumina for hip joints: III. Molecular scale mechanisms.

    PubMed

    Pezzotti, Giuseppe; Bal, B Sonny; Zanocco, Matteo; Marin, Elia; Sugano, Nobuhiko; McEntire, Bryan J; Zhu, Wenliang

    2017-02-01

    Understanding the intrinsic reason(s) for the enhanced tetragonal to monoclinic (t→m) polymorphic phase transformation observed on metal-stained surfaces of zirconia-toughened alumina (ZTA) requires detailed knowledge of off-stoichiometry reactions at the molecular scale. In this context, knowledge of the mechanism(s) for oxygen vacancy creation or annihilation at the material surface is a necessary prerequisite. The crucial aspect of the surface destabilization phenomenon, namely the availability of electrons and holes that allow for vacancy creation/annihilation, is elucidated in this paper. Metal-enhanced alterations of the oxygen sublattice in both Al2O3 and ZrO2 of the ZTA composite play a decisive role in accelerating the polymorphic transformation. According to spectroscopic evidences obtained through nanometer-scale analyses, enhanced annihilation of oxygen vacancies triggers polymorphic transformation in ZrO2 near the metal stain, while the overall Al2O3 lattice tends to dehydroxylate by forming oxygen vacancies. A mechanism for chemically driven "reactive metastability" is suggested, which results in accelerating the polymorphic transformation. The Al2O3 matrix is found to play a key-role in the ZrO2 transformation process, with unambiguous confirmation of oxygen and hydrogen transport at the material surface. It is postulated that this transport is mediated by migration of dissociated O and H elements at the surface of the stained transition metal as they become readily available by the thermally activated surrounding.

  18. Petrology of Karoo volcanic rocks in the southern Lebombo monocline, Mozambique

    NASA Astrophysics Data System (ADS)

    Melluso, Leone; Cucciniello, Ciro; Petrone, Chiara M.; Lustrino, Michele; Morra, Vincenzo; Tiepolo, Massimo; Vasconcelos, Lopo

    2008-11-01

    The Karoo volcanic sequence in the southern Lebombo monocline in Mozambique contains different silicic units in the form of pyroclastic rocks, and two different basalt types. The silicic units in the lower part of the Lebombo sequence are formed by a lower unit of dacites and rhyolites (67-80 wt.% SiO 2) with high Ba (990-2500 ppm), Zr (800-1100 ppm) and Y (130-240 ppm), which are part of the Jozini-Mbuluzi Formation, followed by a second unit, interlayered with the Movene basalts, of high-SiO 2 rhyolites (76-78 wt.%; the Sica Beds Formation), with low Sr (19-54 ppm), Zr (340-480 ppm) and Ba (330-850 ppm) plus rare quartz-trachytes (64-66 wt.% SiO 2), with high Nb and Rb contents (240-250 and 370-381 ppm, respectively), and relatively low Zr (450-460 ppm). The mafic rocks found at the top of the sequence are basalts and ferrobasalts belonging to the Movene Formation. The basalts have roughly flat mantle-normalized incompatible element patterns, with abundances of the most incompatible elements not higher than 25 times primitive mantle. The ferrobasalt has TiO 2 ˜ 4.7 wt.%, Fe 2O 3t = 16 wt.%, and high Y (100 ppm), Zr (420 ppm) and Ba (1000 ppm). The Movene basalts have initial (at 180 Ma) 87Sr/ 86Sr = 0.7052-0.7054 and 143Nd/ 144Nd = 0.51232, and the Movene ferrobasalt has even lower 87Sr/ 86Sr (0.70377) and higher 143Nd/ 144Nd (0.51259). The silicic rocks show a modest range of initial Sr-( 87Sr/ 86Sr = 0.70470-0.70648) and Nd-( 143Nd/ 144Nd = 0.51223-0.51243) isotope ratios. The less evolved dacites could have been formed after crystal fractionation of oxide-rich gabbroic cumulates from mafic parental magmas, whereas the most silica-rich rhyolites could have been formed after fractional crystallization of feldspars, pyroxenes, oxides, zircon and apatite from a parental dacite magma. The composition of the Movene basalts imply different feeding systems from those of the underlying Sabie River basalts.

  19. Extracting hot carriers from photoexcited semiconductor nanocrystals

    SciTech Connect

    Zhu, Xiaoyang

    2014-12-10

    This research program addresses a fundamental question related to the use of nanomaterials in solar energy -- namely, whether semiconductor nanocrystals (NCs) can help surpass the efficiency limits, the so-called “Shockley-Queisser” limit, in conventional solar cells. In these cells, absorption of photons with energies above the semiconductor bandgap generates “hot” charge carriers that quickly “cool” to the band edges before they can be utilized to do work; this sets the solar cell efficiency at a limit of ~31%. If instead, all of the energy of the hot carriers could be captured, solar-to-electric power conversion efficiencies could be increased, theoretically, to as high as 66%. A potential route to capture this energy is to utilize semiconductor nanocrystals. In these materials, the quasi-continuous conduction and valence bands of the bulk semiconductor become discretized due to confinement of the charge carriers. Consequently, the energy spacing between the electronic levels can be much larger than the highest phonon frequency of the lattice, creating a “phonon bottleneck” wherein hot-carrier relaxation is possible via slower multiphonon emission. For example, hot-electron lifetimes as long as ~1 ns have been observed in NCs grown by molecular beam epitaxy. In colloidal NCs, long lifetimes have been demonstrated through careful design of the nanocrystal interfaces. Due to their ability to slow electronic relaxation, semiconductor NCs can in principle enable extraction of hot carriers before they cool to the band edges, leading to more efficient solar cells.

  20. Fabrication and electronic transport studies of single nanocrystal systems

    SciTech Connect

    Klein, David Louis

    1997-05-01

    Semiconductor and metallic nanocrystals exhibit interesting electronic transport behavior as a result of electrostatic and quantum mechanical confinement effects. These effects can be studied to learn about the nature of electronic states in these systems. This thesis describes several techniques for the electronic study of nanocrystals. The primary focus is the development of novel methods to attach leads to prefabricated nanocrystals. This is because, while nanocrystals can be readily synthesized from a variety of materials with excellent size control, means to make electrical contact to these nanocrystals are limited. The first approach that will be described uses scanning probe microscopy to first image and then electrically probe surfaces. It is found that electronic investigations of nanocrystals by this technique are complicated by tip-sample interactions and environmental factors such as salvation and capillary forces. Next, an atomic force microscope technique for the catalytic patterning of the surface of a self assembled monolayer is described. In principle, this nano-fabrication technique can be used to create electronic devices which are based upon complex arrangements of nanocrystals. Finally, the fabrication and electrical characterization of a nanocrystal-based single electron transistor is presented. This device is fabricated using a hybrid scheme which combines electron beam lithography and wet chemistry to bind single nanocrystals in tunneling contact between closely spaced metallic leads. In these devices, both Au and CdSe nanocrystals show Coulomb blockade effects with characteristic energies of several tens of meV. Additional structure is seen the transport behavior of CdSe nanocrystals as a result of its electronic structure.