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Sample records for situ high-temperature x-ray

  1. X ray attenuation measurements for high-temperature materials characterization and in situ monitoring of damage accumulation

    NASA Astrophysics Data System (ADS)

    Baaklini, George Youssef

    1991-10-01

    The development and application is examined of x ray attenuation measurement systems that are capable of (1) characterizing density variations in high temperature materials, e.g., monolithic ceramics, ceramic and intermetallic matrix composites and (2) noninvasively monitoring damage accumulation and failure sequences in ceramic matrix composites under room temperature tensile testing. Results are presented in the development of (1) a point scan digital radiography system and (2) an in-situ x ray material testing system. The former is used to characterize silicon carbide and silicon nitride specimens and the latter is used to image the failure behavior of silicon carbide fiber reinforced reaction bonded silicon nitride matrix composites. Further, state of the art x ray computed tomography is studied to determine its capabilities and limitations in characterizing density variations of subscale engine components, e.g., a silicon carbide rotor, a silicon nitride blade, and a silicon carbide fiber reinforced beta titanium matrix rod, rotor, and ring. Microfocus radiography, conventional radiography, scanning acoustic microscopy, and metallography are used to substantiate the x ray computed tomography findings. Point scan digital radiography is a viable technique for characterization density variations in monolithic ceramic specimens. But it is very limited and time consuming in characterizing ceramic matrix composities. Precise x ray attenuation measurements, reflecting minute density variations, are achieved by photon counting and by using micro collimators at the source and the detector. X ray computed tomography is found to be a unique x ray attenuation measurement technique capable of providing cross sectional spatial density information in monolithic ceramics and metal matrix composites. X ray computed tomography is proven to accelerate generic composite component development. Radiographic evaluation before, during and after loading show the effect of preexisting

  2. MAX200x: In-situ X-ray Measurements at High Pressure and High Temperatures.

    NASA Astrophysics Data System (ADS)

    Lathe, C.; Mueller, H. J.; Wehber, M.; Lauterjung, J.; Schilling, F. R.

    2009-05-01

    Twenty years ago geoscientists from all over the world launched in-situ X-ray diffraction experiments under extreme pressure and temperature conditions at synchrotron beamlines. One of the first apparatus was installed at HASYLAB, MAX80, a single-stage multi-anvil system. MAX80 allows in-situ diffraction studies in conjunction with the simultaneous measurement of elastic properties up to 12 GPa and 1600 K. This very successful experiment, unique in Europe, is operated by Helmholtz Centre Potsdam and is used by more than twenty groups from different countries every year. Experiments for both, applied and basic research are conducted, ranging from life-sciences, chemistry, physics, over material sciences to geosciences. Today new materials and the use of high brilliant synchrotron sources allow constructing double-stage multi-anvil systems for X-ray diffraction to reach much higher pressures. The newly designed high-flux hard wiggler (HARWI-II) beamline is an ideal X-ray source for this kind of experiments. As only the uppermost few kilometres of the Earth (less than 0.1% of its radius) are accessible for direct observations (e.g. deep drilling), sophisticated techniques are required to observe and to understand the processes in the deep interior of our planet. In-situ studies are an excellent tool to investigate ongoing geodynamic processes within the laboratory. One of the fundamental regions to study geodynamic processes seems to be the so-called transition zone, the boundary between upper and lower Earth's mantle between 410 and 670 km depth. Mineral reactions, phase transitions, as wheel as fluid rock interaction in this area might have the potential to strongly influence and control the dynamic motions within our whole planet. Around 25 GPa and 2 000 K are required to simulate these processes in the laboratory. The new MAX200x will be an excellent tool for these ambitious experiments.

  3. An experimental system for high temperature X-ray diffraction studies with in situ mechanical loading

    PubMed Central

    Oswald, Benjamin B.; Schuren, Jay C.; Pagan, Darren C.; Miller, Matthew P.

    2013-01-01

    An experimental system with in situ thermomechanical loading has been developed to enable high energy synchrotron x-ray diffraction studies of crystalline materials. The system applies and maintains loads of up to 2250 N in uniaxial tension or compression at a frequency of up to 100 Hz. The furnace heats the specimen uniformly up to a maximum temperature of 1200 °C in a variety of atmospheres (oxidizing, inert, reducing) that, combined with in situ mechanical loading, can be used to mimic processing and operating conditions of engineering components. The loaded specimen is reoriented with respect to the incident beam of x-rays using two rotational axes to increase the number of crystal orientations interrogated. The system was used at the Cornell High Energy Synchrotron Source to conduct experiments on single crystal silicon and polycrystalline Low Solvus High Refractory nickel-based superalloy. The data from these experiments provide new insights into how stresses evolve at the crystal scale during thermomechanical loading and complement the development of high-fidelity material models. PMID:23556825

  4. In situ high-temperature X-ray diffraction characterization of yttrium-implanted extra low-carbon steel

    SciTech Connect

    Caudron, E.; Buscail, H.; Perrier, S.

    1999-11-01

    Yttrium-implanted and unimplanted extra low-carbon steel samples were analyzed at T = 700 C and under an oxygen partial pressure P{sub O2} = 0.041Pa for 24 h to show the yttrium implantation effect on extra low-carbon steel high-temperature corrosion resistance. Sample oxidation weight gains were studied by thermogravimetry, and structural analyses were performed using in situ high-temperature X-ray diffraction with the same experimental conditions. The aim of this paper is to show the initial nucleation stage of the main compounds induced by oxidation at high temperatures according to the initial sample treatment (yttrium-implanted or unimplanted). The results obtained by in situ high-temperature X-ray diffraction will be compared to those by thermogravimetry to show the existing correlation between weight gain curves and structural studies. Results allow one to understand the improved corrosion resistance of yttrium-implanted extra low-carbon steel at high temperatures.

  5. High pressure and high temperature in situ X-ray diffraction studies in the Paris-Edinburgh cell using a laboratory X-ray source†

    NASA Astrophysics Data System (ADS)

    Toulemonde, Pierre; Goujon, Céline; Laversenne, Laetitia; Bordet, Pierre; Bruyère, Rémy; Legendre, Murielle; Leynaud, Olivier; Prat, Alain; Mezouar, Mohamed

    2014-04-01

    We have developed a new laboratory experimental set-up to study in situ the pressure-temperature phase diagram of a given pure element or compound, its associated phase transitions, or the chemical reactions involved at high pressure and high temperature (HP-HT) between different solids and liquids. This new tool allows laboratory studies before conducting further detailed experiments using more brilliant synchrotron X-ray sources or before kinetic studies. This device uses the diffraction of X-rays produced by a quasi-monochromatic micro-beam source operating at the silver radiation (λ(Ag)Kα 1, 2≈0.56 Å). The experimental set-up is based on a VX Paris-Edinburgh cell equipped with tungsten carbide or sintered diamond anvils and uses standard B-epoxy 5 or 7 mm gaskets. The diffracted signal coming from the compressed (and heated) sample is collected on an image plate. The pressure and temperature calibrations were performed by diffraction, using conventional calibrants (BN, NaCl and MgO) for determination of the pressure, and by crossing isochores of BN, NaCl, Cu or Au for the determination of the temperature. The first examples of studies performed with this new laboratory set-up are presented in the article: determination of the melting point of germanium and magnesium under HP-HT, synthesis of MgB2 or C-diamond and partial study of the P, T phase diagram of MgH2.

  6. Chromium Reaction Mechanisms for Speciation using Synchrotron in-Situ High-Temperature X-ray Diffraction.

    PubMed

    Low, Fiona; Kimpton, Justin; Wilson, Siobhan A; Zhang, Lian

    2015-07-07

    We use in situ high-temperature X-ray diffraction (HT-XRD), ex-situ XRD and synchrotron X-ray absorption near edge structure spectroscopy (XANES) to derive fundamental insights into mechanisms of chromium oxidation during combustion of solid fuels. To mimic the real combustion environment, mixtures of pure eskolaite (Cr(3+)2O3), lime (CaO) and/or kaolinite [Al2Si2O5(OH)4] have been annealed at 600-1200 °C in air versus 1% O2 diluted by N2. Our results confirm for the first time that (1) the optimum temperature for Cr(6+) formation is 800 °C for the coexistence of lime and eskolaite; (2) upon addition of kaolinite into oxide mixture, the temperature required to produce chromatite shifts to 1000 °C with a remarkable reduction in the fraction of Cr(6+). Beyond 1000 °C, transient phases are formed that bear Cr in intermediate valence states, which convert to different species other than Cr(6+) in the cooling stage; (3) of significance to Cr mobility from the waste products generated by combustion, chromatite formed at >1000 °C has a glassy disposition that prevents its water-based leaching; and (4) Increasing temperature facilitates the migration of eskolaite particles into bulk lime and enhances the extent to which Cr(3+) is oxidized, thereby completing the oxidation of Cr(3+) to Cr(6+) within 10 min.

  7. In-situ X-ray structure measurements on aerodynamically levitated high temperature liquids

    SciTech Connect

    Weber, Richard; Benmore, Christopher; Mei Qiang; Wilding, Martin

    2009-01-29

    High energy, high flux X-ray sources enable new measurements of liquid and amorphous materials in extreme conditions. Aerodynamic levitation in combination with laser beam heating can be used to access high purity and non-equilibrium liquids at temperatures up to 3000 K. In this work, a small aerodynamic levitator was integrated with high energy beamline 11 ID-C at the Advanced Photon Source. Scattered X-rays were detected with a Mar345 image plate. The experiments investigated a series of binary in the CaO-Al{sub 2}O{sub 3}, MgO-SiO{sub 2}, SiO{sub 2}-Al{sub 2}O{sub 3} metal oxide compositions and pure SiO{sub 2}. The results show that the liquids exhibit large changes in structure when the predominant network former is diluted. Measurements on glasses with the same compositions as the liquids suggest that significant structural rearrangement consistent with a fragile-strong transition occurs in these reluctant glass forming liquids as they vitrify.

  8. Development of a new micro-furnace for "in situ" high-temperature single crystal X-ray diffraction measurements

    NASA Astrophysics Data System (ADS)

    Alvaro, Matteo; Angel, Ross J.; Marciano, Claudio; Zaffiro, Gabriele; Scandolo, Lorenzo; Mazzucchelli, Mattia L.; Milani, Sula; Rustioni, Greta; Domeneghetti, Chiara M.; Nestola, Fabrizio

    2015-04-01

    Several experimental methods to reliably determine elastic properties of minerals at non-ambient conditions have been developed. In particular, different techniques for generating high-pressure and high-temperature have been successfully adopted for single-crystal and powder X-ray diffraction measurements. High temperature devices for "in-situ" measurements should provide the most controlled isothermal environment as possible across the entire sample. It is intuitive that in general, thermal gradients across the sample increase as the temperature increases. Even if the small isothermal volume required for single-crystal X-ray diffraction experiments makes such phenomena almost negligible, the design of a furnace should also aim to reduce thermal gradients by including a large thermal mass that encloses the sample. However this solution often leads to complex design that results in a restricted access to reciprocal space or attenuation of the incident or diffracted intensity (with consequent reduction of the accuracy and/or precision in lattice parameter determination). Here we present a newly-developed H-shaped Pt-Pt/Rh resistance microfurnace for in-situ high-temperature single-crystal X-ray diffraction measurements. The compact design of the furnace together with the long collimator-sample-detector distance allows us to perform measurements up to 2θ = 70° with no further restrictions on any other angular movement. The microfurnace is equipped with a water cooling system that allows a constant thermal gradient to be maintained that in turn guarantees thermal stability with oscillations smaller than 5°C in the whole range of operating T of room-T to 1200°C. The furnace has been built for use with a conventional 4-circle Eulerian geometry equipped with point detector and automated with the SINGLE software (Angel and Finger 2011) that allows the effects of crystal offsets and diffractometer aberrations to be eliminated from the refined peak positions by the 8

  9. High-pressure, high-temperature deformation of dunite, eclogite, clinopyroxenite and garnetite using in situ X-ray diffraction

    NASA Astrophysics Data System (ADS)

    Farla, R.; Rosenthal, A.; Bollinger, C.; Petitgirard, S.; Guignard, J.; Miyajima, N.; Kawazoe, T.; Crichton, W. A.; Frost, D. J.

    2017-09-01

    The rheology of eclogite, garnetite and clinopyroxenite in the peridotitic upper mantle was experimentally investigated in a large volume press combined with in situ synchrotron X-ray diffraction techniques to study the impact on mantle convection resulting from the subduction of oceanic lithosphere. Experiments were carried out over a range of constant strain rates (2 ×10-6- 3 ×10-5 s-1), pressures (4.3 to 6.7 GPa) and temperatures (1050 to 1470 K). Results show substantial strength variations among eclogitic garnet and clinopyroxene and peridotitic olivine. At low temperatures (<1200 K), eclogite is over 1 GPa stronger than dunite. On the other hand, at high temperatures (>1400 K) eclogite is weaker than dunite by 0.2 GPa or more. Garnetite and clinopyroxenite exhibit higher strength than dunite at approximately 1200 K. However, at higher temperature (1370 K), clinopyroxenite is significantly weaker than garnetite (and dunite) by more than a factor of five. We explain these observations by transitions in deformation mechanisms among the mineral phases. In clinopyroxene, high temperature dislocation creep resulting in a strength reduction replaces low temperature twinning. Whereas garnet remains very rigid at all experimental conditions when nominally anhydrous ('dry'). Microstructural observations show phase segregation of clinopyroxene and garnet, development of a crystallographic and shape preferred orientation in the former but not in the latter, suggesting an overall weak seismic anisotropy. Detection of eclogite bodies in the peridotite-dominated mantle may only be possible via observation of high VP /VS1 ratios. A comparable or weaker rheology of eclogite to dunite suggests effective stirring and mixing of eclogite in the convecting mantle.

  10. Synchrotron X-ray micro-tomography at the Advanced Light Source: Developments in high-temperature in-situ mechanical testing

    NASA Astrophysics Data System (ADS)

    Barnard, Harold S.; MacDowell, A. A.; Parkinson, D. Y.; Mandal, P.; Czabaj, M.; Gao, Y.; Maillet, E.; Blank, B.; Larson, N. M.; Ritchie, R. O.; Gludovatz, B.; Acevedo, C.; Liu, D.

    2017-06-01

    At the Advanced Light Source (ALS), Beamline 8.3.2 performs hard X-ray micro-tomography under conditions of high temperature, pressure, mechanical loading, and other realistic conditions using environmental test cells. With scan times of 10s-100s of seconds, the microstructural evolution of materials can be directly observed over multiple time steps spanning prescribed changes in the sample environment. This capability enables in-situ quasi-static mechanical testing of materials. We present an overview of our in-situ mechanical testing capabilities and recent hardware developments that enable flexural testing at high temperature and in combination with acoustic emission analysis.

  11. Phase transition in Ba{sub 2}In{sub 2}O{sub 5} studied by in situ high temperature X-ray diffraction using synchrotron radiation

    SciTech Connect

    Rey, J. F. Q.; Ferreira, F. F.; Muccillo, E. N. S.

    2009-01-29

    The order-disorder phase transition in Ba{sub 2}In{sub 2}O{sub 5} high-temperature ionic conductor was systematically studied by in situ high-temperature X-ray diffraction using synchrotron radiation and electrical conductivity. Pure barium indate was prepared by solid state reactions at 1300 deg. C. The room-temperature structural characterization showed a high degree of phase homogeneity in the prepared material. The reduction of the order-disorder phase transition temperature was verified by electrical conductivity and high-temperature X-ray diffraction. The observed features were explained based on Fourier-transform infrared spectroscopy results that revealed the presence of hydroxyl species in the crystal lattice. The increase of the intensity of few diffraction peaks near the phase transition temperature suggests the formation of a superstructure before the orthorhombic-to-tetragonal phase transition.

  12. Aerodynamic levitator for in situ x-ray structure measurements on high temperature and molten nuclear fuel materials

    DOE PAGES

    Weber, J. K. R.; Tamalonis, A.; Benmore, C. J.; ...

    2016-07-01

    We integrated an aerodynamic levitator with carbon dioxide laser beam heating with a hermetically sealed controlled atmosphere chamber and sample handling mechanism. The system enabled containment of radioactive samples and control of the process atmosphere chemistry. Furthermore, the chamber was typically operated at a pressure of approximately 0.9 bars to ensure containment of the materials being processed. Samples 2.5-3 mm in diameter were levitated in flowing gas to achieve containerless conditions. Levitated samples were heated to temperatures of up to 3500 °C with a partially focused carbon dioxide laser beam. Sample temperature was measured using an optical pyrometer. The samplemore » environment was integrated with a high energy (100 keV) x-ray synchrotron beamline to enable in situ structure measurements to be made on levitated samples as they were heated, melted, and supercooled. Our system was controlled from outside the x-ray beamline hutch by using a LabVIEW program. Measurements have been made on hot solid and molten uranium dioxide and binary uranium dioxide-zirconium dioxide compositions.« less

  13. Aerodynamic levitator for in situ x-ray structure measurements on high temperature and molten nuclear fuel materials

    SciTech Connect

    Weber, J. K. R.; Alderman, O. L. G.; Tamalonis, A.; Sendelbach, S.; Benmore, C. J.; Hebden, A.; Williamson, M. A.

    2016-07-15

    An aerodynamic levitator with carbon dioxide laser beam heating was integrated with a hermetically sealed controlled atmosphere chamber and sample handling mechanism. The system enabled containment of radioactive samples and control of the process atmosphere chemistry. The chamber was typically operated at a pressure of approximately 0.9 bars to ensure containment of the materials being processed. Samples 2.5-3 mm in diameter were levitated in flowing gas to achieve containerless conditions. Levitated samples were heated to temperatures of up to 3500 °C with a partially focused carbon dioxide laser beam. Sample temperature was measured using an optical pyrometer. The sample environment was integrated with a high energy (100 keV) x-ray synchrotron beamline to enable in situ structure measurements to be made on levitated samples as they were heated, melted, and supercooled. The system was controlled from outside the x-ray beamline hutch by using a LabVIEW program. Measurements have been made on hot solid and molten uranium dioxide and binary uranium dioxide-zirconium dioxide compositions.

  14. Aerodynamic levitator for in situ x-ray structure measurements on high temperature and molten nuclear fuel materials

    SciTech Connect

    Weber, J. K. R.; Tamalonis, A.; Benmore, C. J.; Alderman, O. L. G.; Sendelbach, S.; Hebden, A.; Williamson, M. A.

    2016-07-01

    We integrated an aerodynamic levitator with carbon dioxide laser beam heating with a hermetically sealed controlled atmosphere chamber and sample handling mechanism. The system enabled containment of radioactive samples and control of the process atmosphere chemistry. Furthermore, the chamber was typically operated at a pressure of approximately 0.9 bars to ensure containment of the materials being processed. Samples 2.5-3 mm in diameter were levitated in flowing gas to achieve containerless conditions. Levitated samples were heated to temperatures of up to 3500 °C with a partially focused carbon dioxide laser beam. Sample temperature was measured using an optical pyrometer. The sample environment was integrated with a high energy (100 keV) x-ray synchrotron beamline to enable in situ structure measurements to be made on levitated samples as they were heated, melted, and supercooled. Our system was controlled from outside the x-ray beamline hutch by using a LabVIEW program. Measurements have been made on hot solid and molten uranium dioxide and binary uranium dioxide-zirconium dioxide compositions.

  15. Aerodynamic levitator for in situ x-ray structure measurements on high temperature and molten nuclear fuel materials

    NASA Astrophysics Data System (ADS)

    Weber, J. K. R.; Tamalonis, A.; Benmore, C. J.; Alderman, O. L. G.; Sendelbach, S.; Hebden, A.; Williamson, M. A.

    2016-07-01

    An aerodynamic levitator with carbon dioxide laser beam heating was integrated with a hermetically sealed controlled atmosphere chamber and sample handling mechanism. The system enabled containment of radioactive samples and control of the process atmosphere chemistry. The chamber was typically operated at a pressure of approximately 0.9 bars to ensure containment of the materials being processed. Samples 2.5-3 mm in diameter were levitated in flowing gas to achieve containerless conditions. Levitated samples were heated to temperatures of up to 3500 °C with a partially focused carbon dioxide laser beam. Sample temperature was measured using an optical pyrometer. The sample environment was integrated with a high energy (100 keV) x-ray synchrotron beamline to enable in situ structure measurements to be made on levitated samples as they were heated, melted, and supercooled. The system was controlled from outside the x-ray beamline hutch by using a LabVIEW program. Measurements have been made on hot solid and molten uranium dioxide and binary uranium dioxide-zirconium dioxide compositions.

  16. Aerodynamic levitator for in situ x-ray structure measurements on high temperature and molten nuclear fuel materials

    SciTech Connect

    Weber, J. K. R.; Tamalonis, A.; Benmore, C. J.; Alderman, O. L. G.; Sendelbach, S.; Hebden, A.; Williamson, M. A.

    2016-07-01

    We integrated an aerodynamic levitator with carbon dioxide laser beam heating with a hermetically sealed controlled atmosphere chamber and sample handling mechanism. The system enabled containment of radioactive samples and control of the process atmosphere chemistry. Furthermore, the chamber was typically operated at a pressure of approximately 0.9 bars to ensure containment of the materials being processed. Samples 2.5-3 mm in diameter were levitated in flowing gas to achieve containerless conditions. Levitated samples were heated to temperatures of up to 3500 °C with a partially focused carbon dioxide laser beam. Sample temperature was measured using an optical pyrometer. The sample environment was integrated with a high energy (100 keV) x-ray synchrotron beamline to enable in situ structure measurements to be made on levitated samples as they were heated, melted, and supercooled. Our system was controlled from outside the x-ray beamline hutch by using a LabVIEW program. Measurements have been made on hot solid and molten uranium dioxide and binary uranium dioxide-zirconium dioxide compositions.

  17. Aerodynamic levitator for in situ x-ray structure measurements on high temperature and molten nuclear fuel materials.

    PubMed

    Weber, J K R; Tamalonis, A; Benmore, C J; Alderman, O L G; Sendelbach, S; Hebden, A; Williamson, M A

    2016-07-01

    An aerodynamic levitator with carbon dioxide laser beam heating was integrated with a hermetically sealed controlled atmosphere chamber and sample handling mechanism. The system enabled containment of radioactive samples and control of the process atmosphere chemistry. The chamber was typically operated at a pressure of approximately 0.9 bars to ensure containment of the materials being processed. Samples 2.5-3 mm in diameter were levitated in flowing gas to achieve containerless conditions. Levitated samples were heated to temperatures of up to 3500 °C with a partially focused carbon dioxide laser beam. Sample temperature was measured using an optical pyrometer. The sample environment was integrated with a high energy (100 keV) x-ray synchrotron beamline to enable in situ structure measurements to be made on levitated samples as they were heated, melted, and supercooled. The system was controlled from outside the x-ray beamline hutch by using a LabVIEW program. Measurements have been made on hot solid and molten uranium dioxide and binary uranium dioxide-zirconium dioxide compositions.

  18. GAXRD and in situ X-ray diffraction characterizations of the yttrium implantation effect on pure iron oxidation at high temperature

    NASA Astrophysics Data System (ADS)

    Caudron, E.; Buscail, H.; Cueff, R.; Issartel, C.; Perrier, S.; Riffard, F.

    2002-07-01

    High temperature oxidation behaviours of yttrium implanted and unimplanted pure iron were analyzed at T=700^{circ}C and under oxygen partial pressure Po2=0.04 Pa for 24h by several X-ray diffraction techniques to understand the yttrium implantation effect on pure iron oxidation resistance at high temperature. Sample compositions and structures were investigated before and after yttrium implantation to determine the yttrium distributions and the main compounds induced by ion implantation. Yttrium implantation effects were characterized using analytical and structural techniques such as Rutherford Backscattering Spectrometry (RBS), Secondary Ion Mass Spectrometry (SIMS), Reflection High Energy Electron Diffraction (RHEED), X-ray Diffraction (XRD) and Glancing Angle X-ray Diffraction (GAXRD). Yttrium-implanted and unimplanted pure iron oxidation weight gains were studied by thermogravimetry and structural analyses were carried out by in-situ high temperature X-ray diffraction. The aim of this paper is to show the initial nucleation stage of the main compounds induced by pure iron oxidation at high temperature according to the surface treatment (yttrium implantation). The results obtained by Glancing angle X-ray diffraction and by in-situ high temperature X-ray diffraction allow to understand the better oxidation resistance observed in the case of yttrium implanted pure iron. Les comportements en oxydation à haute température (T=700^{circ}C - pression partielle d'oxygène Po2=0.04 Pa) du fer pur brut et implanté à l'yttrium ont été analysés pendant 24h par plusieurs techniques dc diffraction X afin de comprendre l'effet de l'yttrium sur la résistance à l'oxydation à haute température du fer pur. Les compositions et les analyses structurales ont été effectuées avant et après implantation pour déterminer les distributions en yttrium ainsi que les différents composés induits par l'implantion ionique. Les effets de l'implantation d'yttrium ont

  19. In situ high-temperature X-ray diffraction and spectroscopic study of fibroferrite, FeOH(SO4)·5H2O

    NASA Astrophysics Data System (ADS)

    Ventruti, Gennaro; Ventura, Giancarlo Della; Corriero, Nicola; Malferrari, Daniele; Gualtieri, Alessandro F.; Susta, Umberto; Lacalamita, Maria; Schingaro, Emanuela

    2016-09-01

    The thermal dehydration process of fibroferrite, FeOH(SO4)·5H2O, a secondary iron-bearing hydrous sulfate, was investigated by in situ high-temperature synchrotron X-ray powder diffraction (HT-XRPD), in situ high-temperature Fourier transform infrared spectroscopy (HT-FTIR) and thermal analysis (TGA-DTA) combined with evolved gas mass spectrometry. The data analysis allowed the determination of the stability fields and the reaction paths for this mineral as well as characterization of its high-temperature products. Five main endothermic peaks are observed in the DTA curve collected from room T up to 800 °C. Mass spectrometry of gases evolved during thermogravimetric analysis confirms that the first four mass loss steps are due to water emission, while the fifth is due to a dehydroxylation process; the final step is due to the decomposition of the remaining sulfate ion. The temperature behavior of the different phases occurring during the heating process was analyzed, and the induced structural changes are discussed. In particular, the crystal structure of a new phase, FeOH(SO4)·4H2O, appearing at about 80 °C due to release of one interstitial H2O molecule, was solved by ab initio real-space and reciprocal-space methods. This study contributes to further understanding of the dehydration mechanism and thermal stability of secondary sulfate minerals.

  20. In-Situ X-Ray Diffraction Observations of Low Temperature Ag-Nanoink Sintering and High Temperature Eutectic Reaction with Copper

    SciTech Connect

    Elmer, J. W.; Specht, Eliot D

    2012-01-01

    Nanoinks, which contain nm sized metallic particles suspended in an organic dispersant fluid, are finding numerous microelectronic applications. Nanoinks sinter at much lower temperatures than bulk metals due to their high surface area to volume ratio and small radius of curvature, which reduces their melting points significantly below their bulk values. The unusually low melting and sintering temperatures have unique potential for materials joining since their melting points increase dramatically after initial sintering. In this paper Ag nanoink is studied using in-situ synchrotron based x-ray diffraction to follow the kinetics of the initial sintering step by analysis of diffraction patterns, and to directly observe the high remelt temperature of sintered nanoinks. Ag nanoink is further explored as a possible eutectic bonding medium with copper by tracking phase transformations to high temperatures where melting occurs at the Ag-Cu eutectic temperature, demonstrating nanoinks as a viable eutectic bonding medium.

  1. Rapid, dynamic segregation of core forming melts: Results from in-situ High Pressure- High Temperature X-ray Tomography

    NASA Astrophysics Data System (ADS)

    Watson, H. C.; Yu, T.; Wang, Y.

    2011-12-01

    The timing and mechanisms of core formation in the Earth, as well as in Earth-forming planetesimals is a problem of significant importance in our understanding of the early evolution of terrestrial planets . W-Hf isotopic signatures in meteorites indicate that core formation in small pre-differentiated planetesimals was relatively rapid, and occurred over the span of a few million years. This time scale is difficult to achieve by percolative flow of the metallic phase through a silicate matrix in textural equilibrium. It has been suggested that during this active time in the early solar system, dynamic processes such as impacts may have caused significant deformation in the differentiating planetesimals, which could lead to much higher permeability of the core forming melts. Here, we have measured the change in permeability of core forming melts in a silicate matrix due to deformation. Mixtures of San Carlos olivine and FeS close to the equilibrium percolation threshold (~5 vol%FeS) were pre-synthesized to achieve an equilibrium microstructure, and then loaded into the rotational Drickamer apparatus at GSE-CARS, sector 13-BMD, at the Advanced Photon Source (Argonne National Laboratory). The samples were subsequently pressed to ~2GPa, and heated to 1100°C. Alternating cycles of rotation to collect X-ray tomography images, and twisting to deform the sample were conducted until the sample had been twisted by 1080°. Qualitative and quantitative analyses were performed on the resulting 3-dimensional x-ray tomographic images to evaluate the effect of shear deformation on permeability and migration velocity. Lattice-Boltzmann simulations were conducted, and show a marked increase in the permeability with increasing deformation, which would allow for much more rapid core formation in planetesimals.

  2. In-situ high temperature X-ray diffraction study on the phase transition process of polymetallic sulfide ore

    NASA Astrophysics Data System (ADS)

    Li, Guangshi; Cheng, Hongwei; Xiong, Xiaolu; Lu, Xionggang; Xu, Cong; Lu, Changyuan; Zou, Xingli; Xu, Qian

    2017-04-01

    The phase transformation of the polymetallic sulfide ore is quite complicated, especially the variety and diversity of the roasted intermediate. The mineralogy properties of the ore particles were characterized by XRF, ICP and SEM-EDS. The thermal stability of the complex ore was investigated using TG-DSC under different atmosphere (pure N2 and 1% O2-N2). The phase changes and intermediates were revealed by the in-situ XRD in pure N2 and 1% O2-N2 atmospheres with the temperature range from 25 to 800°C. These results indicated that the crystal transformation of the pyrrhotite from monoclinic to hexagonal at 320°C, and the pentlandite and chalcopyrite were decomposed into monosulfide solid solution in pure N2. While the pentlandite and chalcopyrite were completely oxidized into M*xFe3-xO4 (M*=Fe, Ni, Cu) and Fe2O3, which is also the final product of the ore sample oxidized under 1% O2-N2 atmosphere.

  3. In situ high temperature X-Ray diffraction study of the phase equilibria in the UO2-PuO2-Pu2O3 system

    NASA Astrophysics Data System (ADS)

    Belin, Renaud C.; Strach, Michal; Truphémus, Thibaut; Guéneau, Christine; Richaud, Jean-Christophe; Rogez, Jacques

    2015-10-01

    The region of the U-Pu-O phase diagram delimited by the compounds UO2-PuO2-Pu2O3 is known to exhibit a miscibility gap at low temperature. Consequently, MOX fuels with a composition entering this region could decompose into two fluorite phases and thus exhibit chemical heterogeneities. The experimental data on this domain found in the literature are scarce and usually provided using DTA that is not suitable for the investigation of such decomposition phenomena. In the present work, new experimental data, i.e. crystallographic phases, lattice parameters, phase fractions and temperature of phase separation, were measured in the composition range 0.14 < Pu/(U + Pu) < 0.62 and 1.85 < O/(U + Pu) < 2 from 298 to 1750 K using a novel in situ high temperature X-ray diffraction apparatus. A very good agreement is found between the temperature of phase separation determined from our results and using the thermodynamic model of the U-Pu-O system based on the CALPHAD method. Also, the combined use of thermodynamic calculations and XRD results refinement proved helpful in the determination of the O/M ratio of the samples during cooling. The methodology used in the current work might be useful to investigate other oxides systems exhibiting a miscibility gap.

  4. Coupling in-situ X-ray micro- and nano-tomography and discrete element method for investigating high temperature sintering of metal and ceramic powders

    NASA Astrophysics Data System (ADS)

    Yan, Zilin; Martin, Christophe L.; Bouvard, Didier; Jauffrès, David; Lhuissier, Pierre; Salvo, Luc; Olmos, Luis; Villanova, Julie; Guillon, Olivier

    2017-06-01

    The behaviour of various powder systems during high temperature sintering has been investigated by coupling X-ray microtomography and discrete element method (DEM). Both methods are particularly relevant to analyse particle interactions and porosity changes occurring during sintering. Two examples are presented. The first one deals with a copper powder including artificially created pores which sintering has been observed in situ at the European synchrotron and simulated by DEM. 3D images with a resolution of 1.5 μm have been taken at various times of the sintering cycle. The comparison of the real displacement of particle centers with the displacement derived from the mean field assumption demonstrates significant particle rearrangement in some regions of the sample. Although DEM simulation showed less rearrangement, it has been able to accurately predict the densification kinetics. The second example concerns multilayer ceramic capacitors (MLCCs) composed of hundreds of alternated metal electrode and ceramic dielectric layers. The observation of Ni-based MLCCs by synchrotron nanotomography at Argon National Laboratory with a spatial resolution between 10 and 50 nm allowed understanding the origin of heterogeneities formed in Ni layers during sintering. DEM simulations confirmed this analysis and provided clues for reducing these defects.

  5. The use of in situ powder X-ray diffraction in the investigation of dolomite as a potential reversible high-temperature CO2 sorbent.

    PubMed

    Readman, Jennifer E; Blom, Richard

    2005-03-21

    We report the use of gas sorption experiments and in situ powder X-ray diffraction to study the use of dolomite (MgCa(CO3)2) as a potential reversible high-temperature CO2 sorbent. When dolomite is treated in inert atmosphere at 900 degrees C it decomposes into separate CaO and MgO rich phases and dolomite is never reformed pon CO2 sorption. Gas sorption studies show that the calcined dolomite can go through several cycles of CO2 sorption/desorption in a reversible manner, however, the sorption capacity diminishes with each cycle. Only calcium seems to be involved in the CO2 sorption, while MgO acts as a carrier for the calcium phase. Some evidence of magnesium contamination of the calcium phase was found. BET and SEM measurements were carried out to find differences in the surface area/particle morphology that may explain similarities in the sorption capacities of dolomite and calcite (CaCO3).

  6. Isothermal nucleation and growth kinetics of Pd/Ag alloy phase via in-situ time-resolved high-temperature x-ray diffraction (HTXRD) analysis

    SciTech Connect

    Ayturk, Mahmut Engin; Payzant, E Andrew; Speakman, Scott A; Ma, Yi Hua

    2008-01-01

    Among several different approaches to form Pd/Ag alloys for hydrogen separation applications, ex-situ studies carried by conventional X-ray point scanning detectors might fail to reveal the key aspects of the phase transformation between Pd and Ag metals. In this respect, in-situ time-resolved high temperature X-ray diffraction (HTXRD) was employed to study the Pd/Ag alloy phase nucleation and growth kinetics. By the use of linear position sensitive detectors, advanced optics and profile fitting with the use of JADE-6.5 software, isothermal phase evolution of the Pd/Ag alloy at 500 C, 550 C and 600 C under hydrogen atmosphere were quantified to elucidate the mechanistic details of the Pd/Ag alloy phase nucleation and growth pattern. Analysis of the HTXRD data by the Avrami model indicated that the nucleation of the Pd/Ag alloy phase was instantaneous where the growth mechanism was through diffusion-controlled one-dimensional thickening of the Pd/Ag alloy layer. The value of the Avrami exponent, n, was found to increase with temperature with the values of 0.34, 0.39 and 0.67 at 500oC, 550oC and 600oC, respectively. In addition, parabolic rate law analysis suggested that the nucleation of the Pd/Ag alloy phase was through a heterogeneous nucleation mode, in which the nucleation sites were defined as the non-equilibrium defects. The cross-sectional SEI micrographs indicated that the Pd/Ag alloy phase growth was strongly dependent upon the deposition morphology of the as-synthesized Pd and Ag layers formed by the electroless plating. Based on the Avrami model and the parabolic rate law, the estimated activation energies for the phase transformation were 236.5 and 185.6 kJ/mol and in excellent agreement with the literature values (183-239.5 kJ/mol).

  7. Thermal stability of the Mobil Five type metallosilicate molecular sieves-An in situ high temperature X-ray diffraction study

    SciTech Connect

    Bhange, D.S.; Ramaswamy, Veda . E-mail: v.ramaswamy@ncl.res.in

    2007-05-03

    We have carried out in situ high temperature X-ray diffraction (HTXRD) studies of silicalite-1 (S-1) and metallosilicate molecular sieves containing iron, titanium and zirconium having Mobil Five (MFI) structure (iron silicalite-1 (FeS-1), titanium silicalite-1 (TS-1) and zirconium silicalite-1 (ZrS-1), respectively) in order to study the thermal stability of these materials. Isomorphous substitution of Si{sup 4+} by metal atoms is confirmed by the expansion of unit cell volume by X-ray diffraction (XRD) and the presence of Si-O-M stretching band at {approx}960 cm{sup -1} by Fourier transform infrared (FTIR) spectroscopy. Appearance of cristobalite phase is seen at 1023 and 1173 K in S-1 and FeS-1 samples. While the samples S-1 and FeS-1 decompose completely to cristobalite at 1173 and 1323 K, respectively, the other two samples are thermally stable upto 1623 K. This transformation is irreversible. Although all materials show a negative lattice thermal expansion, their lattice thermal expansion coefficients vary. The thermal expansion behavior in all samples is anisotropic with relative strength of contraction along 'a' axes is more than along 'b' and 'c' axes in S-1, TS-1, ZrS-1 and vice versa in FeS-1. Lattice thermal expansion coefficients ({alpha} {sub v}) in the temperature range 298-1023 K were -6.75 x 10{sup -6} K{sup -1} for S-1, -12.91 x 10{sup -6} K{sup -1} for FeS-1, -16.02 x 10{sup -6} K{sup -1} for TS-1 and -17.92 x 10{sup -6} K{sup -1} for ZrS-1. The highest lattice thermal expansion coefficients ({alpha} {sub v}) obtained were -11.53 x 10{sup -6} K{sup -1} for FeS-1 in temperature range 298-1173 K, -20.86 x 10{sup -6} K{sup -1} for TS-1 and -25.54 x 10{sup -6} K{sup -1} for ZrS-1, respectively, in the temperature range 298-1623 K. Tetravalent cation substitution for Si{sup 4+} in the lattice leads to a high thermal stability as compared to substitution by trivalent cations.

  8. A novel high-temperature furnace for combined in situ synchrotron X-ray diffraction and infrared thermal imaging to investigate the effects of thermal gradients upon the structure of ceramic materials

    PubMed Central

    Robinson, James B.; Brown, Leon D.; Jervis, Rhodri; Taiwo, Oluwadamilola O.; Millichamp, Jason; Mason, Thomas J.; Neville, Tobias P.; Eastwood, David S.; Reinhard, Christina; Lee, Peter D.; Brett, Daniel J. L.; Shearing, Paul R.

    2014-01-01

    A new technique combining in situ X-ray diffraction using synchrotron radiation and infrared thermal imaging is reported. The technique enables the application, generation and measurement of significant thermal gradients, and furthermore allows the direct spatial correlation of thermal and crystallographic measurements. The design and implementation of a novel furnace enabling the simultaneous thermal and X-ray measurements is described. The technique is expected to have wide applicability in material science and engineering; here it has been applied to the study of solid oxide fuel cells at high temperature. PMID:25178003

  9. A novel high-temperature furnace for combined in situ synchrotron X-ray diffraction and infrared thermal imaging to investigate the effects of thermal gradients upon the structure of ceramic materials.

    PubMed

    Robinson, James B; Brown, Leon D; Jervis, Rhodri; Taiwo, Oluwadamilola O; Millichamp, Jason; Mason, Thomas J; Neville, Tobias P; Eastwood, David S; Reinhard, Christina; Lee, Peter D; Brett, Daniel J L; Shearing, Paul R

    2014-09-01

    A new technique combining in situ X-ray diffraction using synchrotron radiation and infrared thermal imaging is reported. The technique enables the application, generation and measurement of significant thermal gradients, and furthermore allows the direct spatial correlation of thermal and crystallographic measurements. The design and implementation of a novel furnace enabling the simultaneous thermal and X-ray measurements is described. The technique is expected to have wide applicability in material science and engineering; here it has been applied to the study of solid oxide fuel cells at high temperature.

  10. X-ray emission from high temperature plasmas

    NASA Technical Reports Server (NTRS)

    Harries, W. L.

    1976-01-01

    The physical processes occurring in plasma focus devices were studied. These devices produce dense high temperature plasmas, which emit X rays of hundreds of KeV energy and one to ten billion neutrons per pulse. The processes in the devices seem related to solar flare phenomena, and would also be of interest for controlled thermonuclear fusion applications. The high intensity, short duration bursts of X rays and neutrons could also possibly be used for pumping nuclear lasers.

  11. Tensile testing of materials at high temperatures above 1700 °C with in situ synchrotron X-ray micro-tomography

    SciTech Connect

    Haboub, Abdel; Nasiatka, James R.; MacDowell, Alastair A.; Bale, Hrishikesh A.; Cox, Brian N.; Marshall, David B.; Ritchie, Robert O.

    2014-08-15

    A compact ultrahigh temperature tensile testing instrument has been designed and fabricated for in situ x-ray micro-tomography using synchrotron radiation at the Advanced Light Source, Lawrence Berkeley National Laboratory. It allows for real time x-ray micro-tomographic imaging of test materials under mechanical load at temperatures up to 2300 °C in controlled environments (vacuum or controlled gas flow). Sample heating is by six infrared halogen lamps with ellipsoidal reflectors arranged in a confocal configuration, which generates an approximately spherical zone of high heat flux approximately 5 mm in diameter. Samples are held between grips connected to a motorized stage that loads the samples in tension or compression with forces up to 2.2 kN. The heating chamber and loading system are water-cooled for thermal stability. The entire instrument is mounted on a rotation stage that allows stepwise recording of radiographs over an angular range of 180°. A thin circumferential (360°) aluminum window in the wall of the heating chamber allows the x-rays to pass through the chamber and the sample over the full angular range. The performance of the instrument has been demonstrated by characterizing the evolution of 3D damage mechanisms in ceramic composite materials under tensile loading at 1750 °C.

  12. Tensile testing of materials at high temperatures above 1700 °C with in situ synchrotron X-ray micro-tomography

    NASA Astrophysics Data System (ADS)

    Haboub, Abdel; Bale, Hrishikesh A.; Nasiatka, James R.; Cox, Brian N.; Marshall, David B.; Ritchie, Robert O.; MacDowell, Alastair A.

    2014-08-01

    A compact ultrahigh temperature tensile testing instrument has been designed and fabricated for in situ x-ray micro-tomography using synchrotron radiation at the Advanced Light Source, Lawrence Berkeley National Laboratory. It allows for real time x-ray micro-tomographic imaging of test materials under mechanical load at temperatures up to 2300 °C in controlled environments (vacuum or controlled gas flow). Sample heating is by six infrared halogen lamps with ellipsoidal reflectors arranged in a confocal configuration, which generates an approximately spherical zone of high heat flux approximately 5 mm in diameter. Samples are held between grips connected to a motorized stage that loads the samples in tension or compression with forces up to 2.2 kN. The heating chamber and loading system are water-cooled for thermal stability. The entire instrument is mounted on a rotation stage that allows stepwise recording of radiographs over an angular range of 180°. A thin circumferential (360°) aluminum window in the wall of the heating chamber allows the x-rays to pass through the chamber and the sample over the full angular range. The performance of the instrument has been demonstrated by characterizing the evolution of 3D damage mechanisms in ceramic composite materials under tensile loading at 1750 °C.

  13. Determination of the phase boundary of the omega to beta transition in Zr using in situ high-pressure and high-temperature X-ray diffraction

    SciTech Connect

    Ono, Shigeaki; Kikegawa, Takumi

    2015-05-15

    The high-pressure behavior of zirconium has been examined using the synchrotron X-ray diffraction technique to a pressure of 38 GPa and a temperature of 800 K employing a hydrothermal diamond anvil cell technique. The structural transition from the ω to the β phase was observed. This transition has a negative dP/dT gradient, which is in general agreement with those reported in previous studies. The transition boundary was determined to be, P (GPa)=41.2–0.025×T (K). The negative slope of the transition, dP/dT, determined in our study using the diamond anvil cell technique was less than half that estimated by the previous study using a large press apparatus. - Graphical abstract: Experimental results and phase boundary of the ω–β transition in Zr. - Highlights: • X-ray diffraction patterns of zirconium were measured by the synchrotron experiments. • High-pressure experiments were performed by an external-heated diamond anvil cell. • Phase diagram of zirconium was determined at high pressures and high temperatures. • Phase boundary between omega and beta transition has a negative dP/dT slope.

  14. Application of In Situ Neutron and X-Ray Measurements at High Temperatures in the Development of Co-Re-Based Alloys for Gas Turbines

    NASA Astrophysics Data System (ADS)

    Mukherji, Debashis; Rösler, Joachim; Wehrs, Juri; Strunz, Pavel; Beran, Přemysl; Gilles, Ralph; Hofmann, Michael; Hoelzel, Markus; Eckerlebe, Helmut; Szentmiklósi, Laszlo; Mácsik, Zsuzsanna

    2013-01-01

    Co-Re alloy development is prompted by the search for new materials for future gas turbines which can be used at temperatures considerably higher than the current day single crystal Ni-based superalloys. The Co-Re-based alloys have been designed to have very high melting range, and they are meant for application at +373 K (+100 °C) above Ni-superalloys. They are significantly different from the conventional Co-based alloys that are used in static components of today's gas turbines, and the Co-Re alloys have never been used for structural applications before. The Co-Re-Cr system has complex microstructure with many different phases present. Phase transformations and stabilities of fine strengthening precipitates at high temperatures remain mostly unexplored in the Co-Re alloys, and to develop basic understanding, model ternary and quaternary compositions were studied within the alloy development program. In situ neutron and synchrotron measurements at high temperatures were extensively used for this purpose, and some recent results from the in situ measurements are presented. In particular, the effect of boron doping in Co-Re alloys and the stabilities of the fine TaC precipitates at high temperatures were investigated. A fine dispersion of TaC precipitates strengthens some Co-Re alloys, and their stabilities at the application temperatures are critical. In the beginning, the alloy development strategy is very briefly discussed.

  15. Spectral and raw quasi in-situ energy dispersive X-ray data captured via a TEM analysis of an ODS austenitic stainless steel sample under 1 MeV Kr(2+) high temperature irradiation.

    PubMed

    Brooks, Adam J; Yao, Zhongwen

    2017-10-01

    The data presented in this article is related to the research experiment, titled: 'Quasi in-situ energy dispersive X-ray spectroscopy observation of matrix and solute interactions on Y-Ti-O oxide particles in an austenitic stainless steel under 1 MeV Kr(2+) high temperature irradiation' (Brooks et al., 2017) [1]. Quasi in-situ analysis during 1 MeV Kr(2+) 520 °C irradiation allowed the same microstructural area to be observed using a transmission electron microscope (TEM), on an oxide dispersion strengthened (ODS) austenitic stainless steel sample. The data presented contains two sets of energy dispersive X-ray spectroscopy (EDX) data collected before and after irradiation to 1.5 displacements-per-atom (~1.25×10(-3) dpa/s with 7.5×10(14) ions cm(-2)). The vendor software used to process and output the data is the Bruker Esprit v1.9 suite. The data includes the spectral (counts vs. keV energy) of the quasi in-situ scanned region (512×512 pixels at 56k magnification), along with the EDX scanning parameters. The.raw files from the Bruker Esprit v1.9 output are additionally included along with the.rpl data information files. Furthermore included are the two quasi in-situ HAADF images for visual comparison of the regions before and after irradiation. This in-situ experiment is deemed 'quasi' due to the thin foil irradiation taking place at an external TEM facility. We present this data for critical and/or extended analysis from the scientific community, with applications applying to: experimental data correlation, confirmation of results, and as computer based modeling inputs.

  16. High temperature x-ray micro-tomography

    NASA Astrophysics Data System (ADS)

    MacDowell, Alastair A.; Barnard, Harold; Parkinson, Dilworth Y.; Haboub, Abdel; Larson, Natalie; Zok, Frank; Panerai, Francesco; Mansour, Nagi N.; Bale, Hrishikesh; Gludovatz, Bernd; Acevedo, Claire; Liu, Dong; Ritchie, Robert O.

    2016-07-01

    There is increasing demand for 3D micro-scale time-resolved imaging of samples in realistic - and in many cases extreme environments. The data is used to understand material response, validate and refine computational models which, in turn, can be used to reduce development time for new materials and processes. Here we present the results of high temperature experiments carried out at the x-ray micro-tomography beamline 8.3.2 at the Advanced Light Source. The themes involve material failure and processing at temperatures up to 1750°C. The experimental configurations required to achieve the requisite conditions for imaging are described, with examples of ceramic matrix composites, spacecraft ablative heat shields and nuclear reactor core Gilsocarbon graphite.

  17. High temperature x-ray micro-tomography

    SciTech Connect

    MacDowell, Alastair A. Barnard, Harold; Parkinson, Dilworth Y.; Gludovatz, Bernd; Haboub, Abdel; Larson, Natalie; Zok, Frank; Panerai, Francesco; Mansour, Nagi N.; Bale, Hrishikesh; Acevedo, Claire; Liu, Dong; Ritchie, Robert O.

    2016-07-27

    There is increasing demand for 3D micro-scale time-resolved imaging of samples in realistic - and in many cases extreme environments. The data is used to understand material response, validate and refine computational models which, in turn, can be used to reduce development time for new materials and processes. Here we present the results of high temperature experiments carried out at the x-ray micro-tomography beamline 8.3.2 at the Advanced Light Source. The themes involve material failure and processing at temperatures up to 1750°C. The experimental configurations required to achieve the requisite conditions for imaging are described, with examples of ceramic matrix composites, spacecraft ablative heat shields and nuclear reactor core Gilsocarbon graphite.

  18. The influence of methanol on the chemical state of PtRu anodes in a high-temperature direct methanol fuel cell studied in situ by synchrotron-based near-ambient pressure x-ray photoelectron spectroscopy

    NASA Astrophysics Data System (ADS)

    Saveleva, Viktoriia A.; Daletou, Maria K.; Savinova, Elena R.

    2017-01-01

    Synchrotron radiation-based near-ambient pressure x-ray photoelectron spectroscopy (NAP-XPS) has recently become a powerful tool for the investigation of interfacial phenomena in electrochemical power sources such as batteries and fuel cells. Here we present an in situ NAP-XPS study of the anode of a high-temperature direct methanol fuel cell with a phosphoric acid-doped hydrocarbon membrane, which reveals an enhanced flooding of the Pt3Ru anode with phosphoric acid in the presence of methanol. An analysis of the electrode surface composition depending on the cell voltage and on the presence of methanol reveals the strong influence of the latter on the extent of Pt oxidation and on the transformation of Ru into Ru (IV) hydroxide.

  19. X-ray emission from high temperature plasmas

    NASA Technical Reports Server (NTRS)

    Harries, W. L.

    1974-01-01

    X-rays from a 25-hJ plasma focus apparatus were observed with pinhole cameras. The cameras consist of 0.4 mm diameter pinholes in 2 cm thick lead housing enclosing an X-ray intensifying screen at the image plane. Pictures recorded through thin aluminum foils or plastic sheets for X-ray energies sub gamma smaller than 15 keV show distributed X-ray emissions from the focussed plasma and from the anode surface. However, when thick absorbers are used, radial filamentary structure in the X-ray emission from the anode surface is revealed. Occasionally larger structures are observed in addition to the filaments. Possible mechanisms for the filamentary structure are discussed.

  20. X-ray emission from high temperature plasmas

    NASA Technical Reports Server (NTRS)

    Harries, W. L.

    1977-01-01

    The physical processes occurring in plasma focus devices were investigated with particular emphasis on X-ray emission. Topics discussed include: trajectories of high energy electrons; detection of ion trajectories; spatial distribution of neutron emission; space and time resolved emission of hard X-rays from a plasma focus; the staged plasma focus as a variation of the hypocloidal pinch; formation of current sheets in a staged plasma focus; and X-ray and neutron emission from a staged plasma focus. The possibility of operating dense plasma-focus type devices in multiple arrays beyond the scaling law for a single gun is discussed.

  1. X-ray emission from high temperature plasmas

    NASA Technical Reports Server (NTRS)

    Harries, W. L.

    1975-01-01

    The bremsstrahlung X-rays from a plasma focus device were investigated with emphasis on the emission versus position, time, energy, and angle of emission. It is shown that low energy X-rays come from the plasma focus region, but that the higher energy components come from the anode. The emission is anisotropic, the low energy polar diagram resembling a cardioid, while the high energy emission is a lobe into the anode. The plasma parameters were considered indicating that even in the dense focus, the plasma is collisionless near the axis. By considering the radiation patterns of relativistic electrons a qualitative picture is obtained, which explains the measured polar diagrams, assuming the electrons that produce the X-rays have velocity vectors lying roughly in a cone between the point of focus and the anode. The average electron energy is about 3keV at the focus and about 10 keV on the anode surface. Results are consistent with the converging beam model of neutron production.

  2. X-ray diffraction measurements in high magnetic fields and at high temperatures

    PubMed Central

    Mitsui, Yoshifuru; Koyama, Keiichi; Watanabe, Kazuo

    2009-01-01

    A system was developed measuring x-ray powder diffraction in high magnetic fields up to 5 T and at temperatures from 283 to 473 K. The stability of the temperature is within 1 K over 6 h. In order to examine the ability of the system, the high-field x-ray diffraction measurements were carried out for Si and a Ni-based ferromagnetic shape-memory alloy. The results show that the x-ray powder diffraction measurements in high magnetic fields and at high temperatures are useful for materials research. PMID:27877263

  3. High-temperature X-ray diffraction study of uranium-neptunium mixed oxides.

    PubMed

    Chollet, Mélanie; Belin, Renaud C; Richaud, Jean-Christophe; Reynaud, Muriel; Adenot, Frédéric

    2013-03-04

    Incorporating minor actinides (MAs = Am, Np, Cm) in UO2 fertile blankets is a viable option to recycle them. Despite this applied interest, phase equilibria between uranium and MAs still need to be thoroughly investigated, especially at elevated temperatures. In particular, few reports on the U-Np-O system are available. In the present work, we provide for the first time in situ high-temperature X-ray diffraction results obtained during the oxidation of (U1-yNpy)O2 uranium-neptunium mixed oxides up to 1373 K and discuss subsequent phase transformations. We show that (i) neptunium stabilizes the UO2-type fluorite structure at high temperature and that (ii) the U3O8-type orthorhombic structure is observed in a wide range of compositions. We clearly demonstrate the incorporation of neptunium in this phase, which was a controversial question in previous studies up to now. We believe it is the particular stability of the tetravalent state of neptunium that is responsible for the observed phase relationships.

  4. In-Situ X-ray Spectroscopic Studies of the Fundamental Chemistry of Pb and Pb-Bi Corrosion Processes at High Temperatures: Development and Assessment of Composite Corrosion Resistant Materials.

    SciTech Connect

    Carlo Segre

    2009-12-30

    Over the course of this project, we have a number of accomplishments. The following list is presented as a summary statement for the project. Specific details from previous Quarterly Reports are given. (1) We established that it is possible to use EXAFS to study the interface layer between a material and the liquid Pb overlayer. We have discovered that molybdenum grows a selflimiting oxide layer which does not spall even at the highest temperatures studied. There have been 2 publications resulting from these studies. (2) We have fabricated a high temperature environmental chamber capable of extending the Pb overlayer studies by varying the incident x-ray beam angle to perform depth profiling of the Pb layer. This chamber will continue to be available to nuclear materials program researchers who wish to use the MRCAT beam line. (3) We have developed a collaboration with researchers at the Paul Scherrer Institute to study corrosion layers on zircalloy. One publication has resulted from this collaboration and another is in progress. (4) We have developed a collaboration with Prof. G.R. Odette of UCSB in which we studied the local structure of Ti and Y in nanoclusters found in oxygen dispersion strengthened steels. There are two publications in progress form this collaboration and we have extended the project to anomalous small angle x-ray scattering as well as EXAFS. (5) We have promoted the use of EXAFS for the study of nuclear materials to the community over the past 4 years and we have begun to see an increase in demand for EXAFS from the community at the MRCAT beam line. (6) This grant was instrumental in nucleating interest in establishing a new Collaborative Access Team at the Advanced Photon Source, the Nuclear and Radiological Research CAT (NRR-CAT). The co-PI (Jeff Terry) is the lead investigator on this project and it has been approved by the APS Scientific Advisory Committee for further planning. The status of the NRR-CAT project is being discussed in a

  5. Integration of a broad beam ion source with a high-temperature x-ray diffraction vacuum chamber

    NASA Astrophysics Data System (ADS)

    Manova, D.; Bergmann, A.; Mändl, S.; Neumann, H.; Rauschenbach, B.

    2012-11-01

    Here, the integration of a low energy, linearly variable ion beam current density, mechanically in situ adjustable broad beam ion source with a high-temperature x-ray diffraction (XRD) vacuum chamber is reported. This allows in situ XRD investigation of phase formation and evolution processes induced by low energy ion implantation. Special care has been taken to an independent adjustment of the ion beam for geometrical directing towards the substrate, a 15 mm small ion source exit aperture to avoid a secondary sputter process of the chamber walls, linearly variable ion current density by using a pulse length modulation (PLM) for the accelerating voltages without changing the ion beam density profile, nearly homogeneous ion beam distribution over the x-ray footprint, together with easily replaceable Kapton® windows for x-rays entry and exit. By combining a position sensitive x-ray detector with this PLM-modulated ion beam, a fast and efficient time resolved investigation of low energy implantation processes is obtained in a compact experimental setup.

  6. Integration of a broad beam ion source with a high-temperature x-ray diffraction vacuum chamber.

    PubMed

    Manova, D; Bergmann, A; Mändl, S; Neumann, H; Rauschenbach, B

    2012-11-01

    Here, the integration of a low energy, linearly variable ion beam current density, mechanically in situ adjustable broad beam ion source with a high-temperature x-ray diffraction (XRD) vacuum chamber is reported. This allows in situ XRD investigation of phase formation and evolution processes induced by low energy ion implantation. Special care has been taken to an independent adjustment of the ion beam for geometrical directing towards the substrate, a 15 mm small ion source exit aperture to avoid a secondary sputter process of the chamber walls, linearly variable ion current density by using a pulse length modulation (PLM) for the accelerating voltages without changing the ion beam density profile, nearly homogeneous ion beam distribution over the x-ray footprint, together with easily replaceable Kapton(®) windows for x-rays entry and exit. By combining a position sensitive x-ray detector with this PLM-modulated ion beam, a fast and efficient time resolved investigation of low energy implantation processes is obtained in a compact experimental setup.

  7. Integration of a broad beam ion source with a high-temperature x-ray diffraction vacuum chamber

    SciTech Connect

    Manova, D.; Bergmann, A.; Maendl, S.; Neumann, H.; Rauschenbach, B.

    2012-11-15

    Here, the integration of a low energy, linearly variable ion beam current density, mechanically in situ adjustable broad beam ion source with a high-temperature x-ray diffraction (XRD) vacuum chamber is reported. This allows in situ XRD investigation of phase formation and evolution processes induced by low energy ion implantation. Special care has been taken to an independent adjustment of the ion beam for geometrical directing towards the substrate, a 15 mm small ion source exit aperture to avoid a secondary sputter process of the chamber walls, linearly variable ion current density by using a pulse length modulation (PLM) for the accelerating voltages without changing the ion beam density profile, nearly homogeneous ion beam distribution over the x-ray footprint, together with easily replaceable Kapton{sup Registered-Sign} windows for x-rays entry and exit. By combining a position sensitive x-ray detector with this PLM-modulated ion beam, a fast and efficient time resolved investigation of low energy implantation processes is obtained in a compact experimental setup.

  8. Applying X-ray Imaging Crystal Spectroscopy for Use as a High Temperature Plasma Diagnostic.

    PubMed

    Cao, Norman M; Mier Valdivia, Andrés M; Rice, John E

    2016-08-25

    X-ray spectra provide a wealth of information on high temperature plasmas; for example electron temperature and density can be inferred from line intensity ratios. By using a Johann spectrometer viewing the plasma, it is possible to construct profiles of plasma parameters such as density, temperature, and velocity with good spatial and time resolution. However, benchmarking atomic code modeling of X-ray spectra obtained from well-diagnosed laboratory plasmas is important to justify use of such spectra to determine plasma parameters when other independent diagnostics are not available. This manuscript presents the operation of the High Resolution X-ray Crystal Imaging Spectrometer with Spatial Resolution (HIREXSR), a high wavelength resolution spatially imaging X-ray spectrometer used to view hydrogen- and helium-like ions of medium atomic number elements in a tokamak plasma. In addition, this manuscript covers a laser blow-off system that can introduce such ions to the plasma with precise timing to allow for perturbative studies of transport in the plasma.

  9. In situ and glancing angle X-ray diffraction of the structure change during and after the high temperature oxidation at 1000 ^{circ}C in air of an yttrium-implanted 304 steel

    NASA Astrophysics Data System (ADS)

    Riffard, F.; Buscail, H.; Caudron, E.; Cueff, R.; Rabaste, F.; Issartel, C.

    2002-07-01

    A study has been made of the initial stages of oxidation of yttrium ion implanted 304 steel in an attempt to shed some light on the so-called `reactive element effect' observed on chromia forming alloys. In situ XRD was used in order to observe the initial local structural changes during the high temperature oxidation process, while glancing angle XRD was used to monitor the longer range structural transformations taking place near the surface after cooling of oxidised samples. The treatment by ion implantation promotes the intensive establishment of the chromic layer, which leads to the inhibition of the formation of iron rich oxides, by preventing the diffusion of iron through the more compact and more uniform layer initially formed than it would be in the absence of yttrium. However, the identification of yttried phases could not be established. L'effet bénéfique d'un traitement par implantation ionique d'yttrium sur un acier 304 a été mis en évidence par le suivi d'analyses in situ développées par diffraction des rayons X au cours de son oxydation isotherme à 1000^{circ}C sous air. Malgré l'altération superficielle du substrat, le traitement par implantation ionique favorise l'établissement accéléré de la couche de chromine et inhibe la formation au cours du processus d'oxydation des oxydes contenant du fer, réputés peu protecteurs, car faiblement adhérents. Des analyses conduites après refroidissement des échantillons oxydés par diffraction des rayons X sous incidence rasante révèlent la localisation de la structure spinelle au manganèse à l'interface le plus externe. L'identification de phases yttriées n'a cependant pu être établie.

  10. In situ X-ray-based imaging of nano materials

    DOE PAGES

    Weker, Johanna Nelson; Huang, Xiaojing; Toney, Michael F.

    2016-02-13

    We study functional nanomaterials that are heterogeneous and understanding their behavior during synthesis and operation requires high resolution diagnostic imaging tools that can be used in situ. Over the past decade, huge progress has been made in the development of X-ray based imaging, including full field and scanning microscopy and their analogs in coherent diffractive imaging. Currently, spatial resolution of about 10 nm and time resolution of sub-seconds are achievable. For catalysis, X-ray imaging allows tracking of particle chemistry under reaction conditions. In energy storage, in situ X-ray imaging of electrode particles is providing important insight into degradation processes. Recently,more » both spatial and temporal resolutions are improving to a few nm and milliseconds and these developments will open up unprecedented opportunities.« less

  11. In-situ mechanical testing during X-ray diffraction

    SciTech Connect

    Van Swygenhoven, Helena Van Petegem, Steven

    2013-04-15

    Deforming metals during recording X-ray diffraction patterns is a useful tool to get a deeper understanding of the coupling between microstructure and mechanical behaviour. With the advances in flux, detector speed and focussing techniques at synchrotron facilities, in-situ mechanical testing is now possible during powder diffraction and Laue diffraction. The basic principle is explained together with illustrative examples.

  12. Monitoring synchrotron X-ray-induced radiolysis effects on metal (Fe, W) ions in high-temperature aqueous fluids.

    PubMed

    Mayanovic, Robert A; Anderson, Alan J; Dharmagunawardhane, Hingure A N; Pascarelli, Sakura; Aquilanti, Giuliana

    2012-09-01

    Radiolysis-induced effects on aqueous tungsten ions are observed to form a precipitate within seconds upon exposure to a synchrotron X-ray micro-beam in a WO(3) + H(2)O system at 873 K and 200 MPa. In situ Fe K-edge energy-dispersive X-ray absorption spectroscopy (ED-XAS) measurements were made on Fe(II)Cl(2) aqueous solutions to 773 K in order to study the kinetics of high-temperature reactions of Fe(2+) and Fe(3+) ions with transient radiolysis species. The radiolytic reactions in a fluid sample within a hydrothermal diamond anvil cell result in oxidation of the Fe(2+) ion at 573 K and reduction of Fe(3+) at temperatures between 673 and 773 K and of the Fe(2+) ion at 773 K. The edge-energy drift evident in the ED-XAS data directly reflects the kinetics of reactions resulting in oxidation and/or reduction of the Fe(2+) and Fe(3+) ions in the aqueous solutions at high temperatures. The oxidation and reduction trends are found to be highly consistent, making reliable determinations of reaction kinetics possible.

  13. High temperature monitoring of silicon carbide ceramics by confocal energy dispersive X-ray fluorescence spectrometry

    NASA Astrophysics Data System (ADS)

    Li, Fangzuo; Liu, Zhiguo; Sun, Tianxi

    2016-04-01

    In the present work, we presented an alternative method for monitoring of the oxidation situation of silicon carbide (SiC) ceramics at various high temperatures in air by measuring the Compton-to-Rayleigh intensity ratios (ICo/IRa) and effective atomic numbers (Zeff) of SiC ceramics with the confocal energy dispersive X-ray fluorescence (EDXRF) spectrometer. A calibration curve of the relationship between ICo/IRa and Zeff was established by using a set of 8 SiC calibration samples. The sensitivity of this approach is so high that it can be easily distinguished samples of Zeff differing from each other by only 0.01. The linear relationship between the variation of Zeff and the variations of contents of C, Si and O of SiC ceramics were found, and the corresponding calculation model of the relationship between the ΔZ and the ΔCC, ΔCSi, and ΔCO were established. The variation of contents of components of the tested SiC ceramics after oxidation at high temperature was quantitatively calculated based on the model. It was shown that the results of contents of carbon, silicon and oxygen obtained by this method were in good agreement with the results obtained by XPS, giving values of relative deviation less than 1%. It was concluded that the practicality of this proposed method for monitoring of the oxidation situation of SiC ceramics at high temperatures was acceptable.

  14. In situ synchrotron based x-ray techniques as monitoring tools for atomic layer deposition

    SciTech Connect

    Devloo-Casier, Kilian Detavernier, Christophe; Dendooven, Jolien

    2014-01-15

    Atomic layer deposition (ALD) is a thin film deposition technique that has been studied with a variety of in situ techniques. By exploiting the high photon flux and energy tunability of synchrotron based x-rays, a variety of new in situ techniques become available. X-ray reflectivity, grazing incidence small angle x-ray scattering, x-ray diffraction, x-ray fluorescence, x-ray absorption spectroscopy, and x-ray photoelectron spectroscopy are reviewed as possible in situ techniques during ALD. All these techniques are especially sensitive to changes on the (sub-)nanometer scale, allowing a unique insight into different aspects of the ALD growth mechanisms.

  15. In situ soft X-ray absorption spectroscopy of flames

    NASA Astrophysics Data System (ADS)

    Frank, Jonathan H.; Shavorskiy, Andrey; Bluhm, Hendrik; Coriton, Bruno; Huang, Erxiong; Osborn, David L.

    2014-10-01

    The feasibility of in situ soft X-ray absorption spectroscopy for imaging carbonaceous species in hydrocarbon flames is demonstrated using synchrotron radiation. Soft X-rays are absorbed by core level electrons in all carbon atoms regardless of their molecular structure. Core electron spectroscopy affords distinct advantages over valence spectroscopy, which forms the basis of traditional laser diagnostic techniques for combustion. In core level spectroscopy, the transition linewidths are predominantly determined by the instrument response function and the decay time of the core-hole, which is on the order of a femtosecond. As a result, soft X-ray absorption measurements can be performed in flames with negligible Doppler and collisional broadening. Core level spectroscopy has the further advantage of measuring all carbonaceous species regardless of molecular structure in the far-edge region, whereas near-edge features are molecule specific. Interferences from non-carbon flame species are unstructured and can be subtracted. In the present study, absorption measurements in the carbon K-edge region are demonstrated in low-pressure ( P total = 20-30 Torr) methane jet flames. Two-dimensional imaging of the major carbonaceous species, CH4, CO2, and CO, is accomplished by tuning the synchrotron radiation to the respective carbon K-edge, near-edge X-ray absorption fine structure (NEXAFS) transitions and scanning the burner.

  16. In Situ X-Ray Analysis of Protein Crystals in Low-Birefringent And X-Ray Transmissive Plastic Microchannels

    SciTech Connect

    Ng, J.D.; Clark, P.J.; Stevens, R.C.; Kuhn, P.

    2009-05-22

    Plastic microchannel crystallization template designs made from inexpensive cyclic olefin copolymers have been shown to be low-birefringent, X-ray transmissive and compatible with microfluidic fabrication in restricted geometry. The model proteins thaumatin, lysozyme and bacteriorhodopsin demonstrated the feasibility of conducting counter-diffusion equilibration within the new plastic configuration. Crystals of each of these proteins were directly evaluated in situ using synchrotron radiation and their diffraction quality was evaluated without invasive manipulation or cryofreezing. Protein crystals able to produce complete X-ray data sets were used to calculate electron-density maps for structure determination. Fluidic crystallization in the plastic platform was also coupled with a commercialized automated imager and an in situ X-ray scanner that allowed optical and X-ray inspection of crystallization hits. The results demonstrate the feasibility of rapid nanovolume counter-diffusion crystallization experiments without the need for additional instrumentation.

  17. A gas-tight Cu K alpha x-ray transparent reaction chamber for high-temperature x-ray diffraction analyses of halide gas/solid reactions.

    PubMed

    Shian, Samuel; Sandhage, Kenneth H

    2009-11-01

    An externally heated, x-ray transparent reaction chamber has been developed to enable the dynamic high temperature x-ray diffraction (HTXRD) analysis of a gas/solid [TiF(4)(g)/SiO(2)(s)] reaction involving a halide gas reactant formed at elevated temperatures (up to 350 degrees C) from a condensed source (TiF(4) powder) sealed within the chamber. The reaction chamber possessed x-ray transparent windows comprised of a thin (13 microm) internal layer of Al foil and a thicker (125 microm) external Kapton film. After sealing the SiO(2) specimens (diatom frustules or Stober spheres) above TiF(4) powder within the reaction chamber, the chamber was heated to a temperature in the range of 160-350 degrees C to allow for internal generation of TiF(4)(g). The TiF(4)(g) underwent a metathetic reaction with the SiO(2) specimen to yield a TiOF(2)(s) product. HTXRD analysis, using Cu K alpha x rays passed through the Kapton/Al windows of the chamber, was used to track the extent of SiO(2) consumption and/or TiOF(2) formation with time. The Al foil inner layer of the windows protected the Kapton film from chemical attack by TiF(4)(g), whereas the thicker, more transparent Kapton film provided the mechanical strength needed to contain this gas. By selecting an appropriate combination of x-ray transparent materials to endow such composite windows with the required thermal, chemical, and mechanical performance, this inexpensive reaction chamber design may be applied to the HTXRD analyses of a variety of gas/solid reactions.

  18. In situ synchrotron x-ray photon beam characterization

    SciTech Connect

    Kyele, Nicholas R.; Silfhout, Roelof G. van; Manolopoulos, Spyros; Nikitenko, S.

    2007-03-15

    We have investigated two in situ methods of measuring x-ray beam parameters such as integrated intensity, position, and intensity distribution. These virtually transparent methods both rely on the collection of scattered radiation from a thin amorphous foil. The scattered radiation is collected by an active pixel sensor placed below the foil, well out of the direction of the beam path. These methods measure a cross-sectional image of the beam as opposed to a profile or beam centroid position provided by existing in situ detection methods. We present the results of measurements taken at a third generation synchrotron radiation source and provide analytical methods of deriving beam profile, position, and absolute intensity.

  19. X-ray imaging for studying behavior of liquids at high pressures and high temperatures using Paris-Edinburgh press.

    PubMed

    Kono, Yoshio; Kenney-Benson, Curtis; Shibazaki, Yuki; Park, Changyong; Wang, Yanbin; Shen, Guoyin

    2015-07-01

    Several X-ray techniques for studying structure, elastic properties, viscosity, and immiscibility of liquids at high pressures have been integrated using a Paris-Edinburgh press at the 16-BM-B beamline of the Advanced Photon Source. Here, we report the development of X-ray imaging techniques suitable for studying behavior of liquids at high pressures and high temperatures. White X-ray radiography allows for imaging phase separation and immiscibility of melts at high pressures, identified not only by density contrast but also by phase contrast imaging in particular for low density contrast liquids such as silicate and carbonate melts. In addition, ultrafast X-ray imaging, at frame rates up to ∼10(5) frames/second (fps) in air and up to ∼10(4) fps in Paris-Edinburgh press, enables us to investigate dynamics of liquids at high pressures. Very low viscosities of melts similar to that of water can be reliably measured. These high-pressure X-ray imaging techniques provide useful tools for understanding behavior of liquids or melts at high pressures and high temperatures.

  20. X-ray imaging for studying behavior of liquids at high pressures and high temperatures using Paris-Edinburgh press

    SciTech Connect

    Kono, Yoshio; Kenney-Benson, Curtis; Park, Changyong; Shen, Guoyin; Shibazaki, Yuki; Wang, Yanbin

    2015-07-15

    Several X-ray techniques for studying structure, elastic properties, viscosity, and immiscibility of liquids at high pressures have been integrated using a Paris-Edinburgh press at the 16-BM-B beamline of the Advanced Photon Source. Here, we report the development of X-ray imaging techniques suitable for studying behavior of liquids at high pressures and high temperatures. White X-ray radiography allows for imaging phase separation and immiscibility of melts at high pressures, identified not only by density contrast but also by phase contrast imaging in particular for low density contrast liquids such as silicate and carbonate melts. In addition, ultrafast X-ray imaging, at frame rates up to ∼10{sup 5} frames/second (fps) in air and up to ∼10{sup 4} fps in Paris-Edinburgh press, enables us to investigate dynamics of liquids at high pressures. Very low viscosities of melts similar to that of water can be reliably measured. These high-pressure X-ray imaging techniques provide useful tools for understanding behavior of liquids or melts at high pressures and high temperatures.

  1. X-ray induced chemical reaction revealed by in-situ X-ray diffraction and scanning X-ray microscopy in 15 nm resolution (Conference Presentation)

    NASA Astrophysics Data System (ADS)

    Ge, Mingyuan; Liu, Wenjun; Bock, David; De Andrade, Vincent; Yan, Hanfei; Huang, Xiaojing; Marschilok, Amy; Takeuchi, Esther; Xin, Huolin; Chu, Yong S.

    2016-09-01

    The detection sensitivity of synchrotron-based X-ray techniques has been largely improved due to the ever increasing source brightness, which have significantly advanced ex-situ and in-situ research for energy materials, such as lithium-ion batteries. However, the strong beam-matter interaction arisen from the high beam flux can significantly modify the material structure. The parasitic beam-induced effect inevitably interferes with the intrinsic material property, which brings difficulties in interpreting experimental results, and therefore requires comprehensive evaluation. Here we present a quantitative in-situ study of the beam-effect on one electrode material Ag2VO2PO4 using four different X-ray probes with different radiation dose rate. The material system we reported exhibits interesting and reversible radiation-induced thermal and chemical reactions, which was further evaluated under electron microscopy to illustrate the underlying mechanism. The work we presented here will provide a guideline in using synchrotron X-rays to distinguish the materials' intrinsic behavior from extrinsic structure changed induced by X-rays, especially in the case of in-situ and operando study where the materials are under external field of either temperature or electric field.

  2. In situ Monitoring of Synchrotron X-Ray-Induced Radiolysis Effects on Chromium Species Using X-Ray Absorption Spectroscopy

    NASA Astrophysics Data System (ADS)

    Men, S.; Anderson, A. J.; Mayanovic, R. A.

    2017-05-01

    Synchrotron X-ray radiolysis-induced redox in a chromium aqueous solution was monitored using in situ X-ray absorption spectroscopy. The radiolysis in the fluid sample within a specifically designed hydrothermal diamond anvil cell caused the oxidation of Cr(III) to Cr(VI) upon heating from room temperature to 400°C, and reduction of Cr(VI) to Cr(III) at 500°C. The two fitted components of the pre-edge features of the Cr K-edge spectra were used to identify the presence of Cr(VI) in the solution.

  3. A diamond anvil cell with resistive heating for high pressure and high temperature x-ray diffraction and absorption studies.

    PubMed

    Pasternak, Sebastien; Aquilanti, Giuliana; Pascarelli, Sakura; Poloni, Roberta; Canny, Bernard; Coulet, Marie-Vanessa; Zhang, Lin

    2008-08-01

    In this paper we describe a prototype of a diamond anvil cell (DAC) for high pressure/high temperature studies. This DAC combines the use of a resistive oven of 250 W power in a very small volume, associated with special conical seats for Boehler-type diamond anvils in order to have a large angular acceptance. To protect the diamond anvils from burning and to avoid the oven oxidation, the heated DAC is enclosed in a vacuum chamber. The assemblage was used to study the melting curve of germanium at high pressure (up to 20 GPa) and high temperature (up to 1200 K) using x-ray diffraction and x-ray absorption spectroscopy.

  4. A diamond anvil cell for x-ray fluorescence measurements of trace elements in fluids at high pressure and high temperature.

    PubMed

    Petitgirard, Sylvain; Daniel, Isabelle; Dabin, Yves; Cardon, Hervé; Tucoulou, Rémi; Susini, Jean

    2009-03-01

    We present a new diamond anvil cell (DAC), hereafter called the fluoX DAC, dedicated for x-ray fluorescence (XRF) analysis of trace elements in fluids under high pressure and high temperature to 10 GPa and 1273 K at least. This new setup has allowed measurement of Rb, Sr, Y, Zr, with concentrations of 50 ppm to 5.6 GPa and 1273 K. The characteristics of the fluoX DAC consist in an optimized shielding and collection geometry in order to reduce the background level in XRF spectrum. Consequently, minimum detection limits of 0.3 ppm were calculated for the abovementioned elements in this new setup. This new DAC setup coupled to the hard x-rays focusing beamline ID22 (ESRF, France) offers the possibility to analyze in situ at high pressure and high temperature, ppm level concentrations of heavy elements, rare earth elements, and first transition metals, which are of prime importance in geochemical processes. The fluoX DAC is also suitable to x-ray diffraction over the same high pressure-temperature range.

  5. Low Energy X-Ray and Electron Physics and Technology for High-Temperature Plasma Diagnostics

    DTIC Science & Technology

    1987-10-01

    cransmission band for Che rejeccion of such background radiacions around Che 500-1000 eV region by combining as a primary monochromator a 300 ßg...X-Radiations of the Solar Corona," Technical Report No. 7, 1-413, AFOSR 66-2446 (September 1966). 30. "X-Ray Absorption in the 2 to

  6. Electro-deposition of Cu studied with in situ electrochemical scanning transmission x-ray microscopy

    NASA Astrophysics Data System (ADS)

    Hitchcock, A. P.; Qin, Z.; Rosendahl, S. M.; Lee, V.; Reynolds, M.; Hosseinkhannazer, H.

    2016-01-01

    Soft X-ray scanning transmission X-ray microscopy (STXM) was used to investigate Cu deposition onto, and stripping from a Au surface. Cu 2p spectromicroscopy was used to analyze initial and final states (ex situ processing) and follow the processes in situ. The in situ experiments were carried out using a static electrochemical cell with an electrolyte layer thickness of ˜1 μm. A new apparatus for in situ electrochemical STXM is described.

  7. Note: High-pressure in situ x-ray laminography using diamond anvil cell

    NASA Astrophysics Data System (ADS)

    Nomura, Ryuichi; Uesugi, Kentaro

    2016-04-01

    A high-pressure in situ X-ray laminography technique was developed using a newly designed, laterally open diamond anvil cell. A low X-ray beam of 8 keV energy was used, aiming at future application to dual energy X-ray chemical imaging techniques. The effects of the inclination angle and the imaging angle range were evaluated at ambient pressure using the apparatus. Sectional images of ruby ball samples were successfully reconstructed at high pressures, up to approximately 50 GPa. The high-pressure in situ X-ray laminography technique is expected to provide new insights into the deep Earth sciences.

  8. Note: High-pressure in situ x-ray laminography using diamond anvil cell

    SciTech Connect

    Nomura, Ryuichi; Uesugi, Kentaro

    2016-04-15

    A high-pressure in situ X-ray laminography technique was developed using a newly designed, laterally open diamond anvil cell. A low X-ray beam of 8 keV energy was used, aiming at future application to dual energy X-ray chemical imaging techniques. The effects of the inclination angle and the imaging angle range were evaluated at ambient pressure using the apparatus. Sectional images of ruby ball samples were successfully reconstructed at high pressures, up to approximately 50 GPa. The high-pressure in situ X-ray laminography technique is expected to provide new insights into the deep Earth sciences.

  9. X-ray spectroscopy of high temperature plasma in solar flares

    NASA Astrophysics Data System (ADS)

    Culhane, J. L.

    X-ray spectroscopic observations with high wavelength resolution provide information on plasma density, temperature, and emission, together with bulk and turbulent velocity data for the hot plasma. Observations carried out during the 1980 solar maximum with spectrometers on the SMM, P78-1, and Hinotori spacecraft are examined with emphasis on the advances made possible by these missions. During the next solar maximum, flare studies with particular emphasis on the impulsive phase will be undertaken by the Japanese Solar-A mission. Those instruments is designed to study the hot plasma are described, and their proposed role in clarifying the nature of the impulsive phase is discussed.

  10. Quantitative Homogeneity and In-Contact Particles of High Temperature Reactors (htr) Compacts Determination via X-Ray Tomography

    NASA Astrophysics Data System (ADS)

    Lecomte, G.; Tisseur, D.; Létang, J. M.; Banchet, J.; Vitali, M. P.

    2008-02-01

    In AREVA Nuclear Power's High Temperature Reactor (HTR) design called ANTARES, fuel consists of compacts composed of few thousands millimetric quasi-spherical particles dispersed in a graphite matrix. Compact homogeneity, defined as the homogeneous particles spatial distribution in the matrix, as well as the possibility of obtaining particles in contact, need to be assessed since they condition the thermo-mechanical behavior of the nuclear fuel under irradiation. In this paper, image and data processing algorithms are developed to do so, based on X-Ray tomographic images.

  11. X-ray Compton scattering experiments for fluid alkali metals at high temperatures and pressures

    SciTech Connect

    Matsuda, K. Fukumaru, T.; Kimura, K.; Yao, M.; Tamura, K.; Katoh, M.; Kajihara, Y.; Inui, M.; Itou, M.; Sakurai, Y.

    2015-08-17

    We have developed a high-pressure vessel and a cell for x-ray Compton scattering measurements of fluid alkali metals. Measurements have been successfully carried out for alkali metal rubidium at elevated temperatures and pressures using synchrotron radiation at SPring-8. The width of Compton profiles (CPs) of fluid rubidium becomes narrow with decreasing fluid density, which indicates that the CPs sensitively detect the effect of reduction in the valence electron density. At the request of all authors of the paper, and with the agreement of the Proceedings Editor, an updated version of this article was published on 10 September 2015. The original article supplied to AIP Publishing was not the final version and contained PDF conversion errors in Formulas (1) and (2). The errors have been corrected in the updated and re-published article.

  12. X-ray Compton scattering experiments for fluid alkali metals at high temperatures and pressures

    NASA Astrophysics Data System (ADS)

    Matsuda, K.; Fukumaru, T.; Kimura, K.; Tamura, K.; Katoh, M.; Kajihara, Y.; Inui, M.; Yao, M.; Itou, M.; Sakurai, Y.

    2015-08-01

    We have developed a high-pressure vessel and a cell for x-ray Compton scattering measurements of fluid alkali metals. Measurements have been successfully carried out for alkali metal rubidium at elevated temperatures and pressures using synchrotron radiation at SPring-8. The width of Compton profiles (CPs) of fluid rubidium becomes narrow with decreasing fluid density, which indicates that the CPs sensitively detect the effect of reduction in the valence electron density. At the request of all authors of the paper, and with the agreement of the Proceedings Editor, an updated version of this article was published on 10 September 2015. The original article supplied to AIP Publishing was not the final version and contained PDF conversion errors in Formulas (1) and (2). The errors have been corrected in the updated and re-published article.

  13. High temperature X-ray diffraction, Raman spectroscopy and dielectric studies on yttrium orthochromites

    SciTech Connect

    Mall, Ashish Kumar; Garg, Ashish; Gupta, Rajeev

    2016-05-06

    The structural, thermal and dielectric properties of YCrO{sub 3} ceramic prepared by solid state reaction method have been investigated by a combination of XRD, Raman spectroscopy and permittivity measurement. The X-ray diffraction spectra shows single phase orthorhombically distorted perovskite structure with Pnma symmetry over a wide range of temperature 300K to 1100K. Impedance spectroscopy study on the sample showed that the dielectric constant, tangent loss and ac conductivity with frequency increases on increasing the temperature. Dielectric measurement shows a relaxor like transition at about 460K. Non-Debye type relaxation is observed with activation energy of 0.25 eV extracted from ac conductivity at 11 kHz frequency. We believe that the oxygen ion vacancies play an important role in conduction processes in addition to polaron hopping at higher temperatures. Raman scattering measurements were performed over a wide temperature range from 300K to 600 K. The line width of the modes due to CrO{sub 6} bending and in-plane O{sub 2} stretching broadens with increasing temperature.

  14. Lead iodide X-ray and gamma-ray spectrometers for room and high temperature operation

    SciTech Connect

    Hermon, H.; James, R.B.; Cross, E.

    1997-02-01

    In this study, we report on the results of the investigation of lead iodide material properties. The effectiveness of zone refining purification methods on the material purity is determined by ICP-MS and ICP-OES and correlated to the electrical and physical material properties. We show that this zone refining method is very efficient in removing impurities from lead iodide and we also determine the segregation coefficient for some of these impurities. Triple axis x- ray diffraction (TAD) analysis has been used to determine the crystalline perfection of the lead iodide after applying various cutting, etching, and fabrication methods. The soft lead iodide crystal was found to be damaged when cleaved by a razor blade, but by using a diamond wheel saw, followed by etching, the crystallinity of the material was improved, as observed by TAD. Low temperature photoluminescence also indicates an improvement in the material properties of the purified lead iodide. Electrical properties of lead iodide such as carrier mobility, were calculated based on carrier- phonon scattering. The results for the electrical properties were in good agreement with the experimental data.

  15. Resonant inelastic x-ray scattering as a band structure probe of high-temperature superconductors

    NASA Astrophysics Data System (ADS)

    Kanasz-Nagy, Marton; Shi, Yifei; Klich, Israel; Demler, Eugene

    I will analyze recent resonant inelastic x-ray scattering (RIXS) experimental data on YBa2Cu3O6 + x [Minola et al., Phys. Rev. Lett. 114, 217003 (2015)] within quasi-particle theory. This measurement has been performed with the incoming photon energy detuned at several values from the resonance maximum, and, surprisingly, the data shows much weaker dependence on detuning than expected from recent measurements on a different cuprate superconductor, Bi2Sr2CuO6 + x [Guarise et al., Nat. Commun. 5, 5760 (2014)]. I will demonstrate, that this discrepancy, originally attributed to collective magnetic excitations, can be understood in terms of the differences between the band structures of these materials. We found good agreement between theory and experiment over a large range of dopings [M. Kanasz-Nagy et al., arXiv:1508.06639]. Moreover, I will demonstrate that the RIXS signal depends sensitively on excitations at energies well above the Fermi surface, that are inaccessible to traditionally used band structure probes, such as angle-resolved photoemission spectroscopy. This makes RIXS a powerful probe of band structure, not suffering from surface preparation problems and small sample sizes, making it potentially applicable to a wide range of materials. The work of M. K.-N. was supported by the Harvard-MIT CUA, NSF Grant No. DMR-1308435, AFOSR Quantum Simulation MURI, the ARO-MURI on Atomtronics, and ARO MURI Quism program.

  16. Upgrades of imaging x-ray crystal spectrometers for high-resolution and high-temperature plasma diagnostics on EAST

    SciTech Connect

    Lyu, B. Wang, F. D.; Fu, J.; Li, Y. Y.; Pan, X. Y.; Chen, J.; Wan, B. N.; Bitter, M.; Hill, K. W.; Delgado-Aparicio, L. F.; Pablant, N.; Lee, S. G.; Shi, Y. J.; Ye, M. Y.

    2014-11-15

    Upgrade of the imaging X-ray crystal spectrometers continues in order to fulfill the high-performance diagnostics requirements on EAST. For the tangential spectrometer, a new large pixelated two-dimensional detector was deployed on tokamaks for time-resolved X-ray imaging. This vacuum-compatible detector has an area of 83.8 × 325.3 mm{sup 2}, a framing rate over 150 Hz, and water-cooling capability for long-pulse discharges. To effectively extend the temperature limit, a double-crystal assembly was designed to replace the previous single crystals for He-like argon line measurement. The tangential spectrometer employed two crystal slices attached to a common substrate and part of He- and H-like Ar spectra could be recorded on the same detector when crystals were chosen to have similar Bragg angles. This setup cannot only extend the measurable Te up to 10 keV in the core region, but also extend the spatial coverage since He-like argon ions will be present in the outer plasma region. Similarly, crystal slices for He-like iron and argon spectra were adopted on the poloidal spectrometer. Wavelength calibration for absolute rotation velocity measurement will be studied using cadmium characteristic L-shell X-ray lines excited by plasma radiation. A Cd foil is placed before the crystal and can be inserted and retracted for in situ wavelength calibration. The Geant4 code was used to estimate X-ray fluorescence yield and optimize the thickness of the foil.

  17. High-temperature X-ray diffraction and Raman spectroscopy of diopside and pseudowollastonite

    NASA Astrophysics Data System (ADS)

    Richet, Pascal; Mysen, Bjorn O.; Ingrin, Jannick

    Diopside (CaMgSi2O6) and pseudowollastonite (CaSiO3) have been studied by X-ray powder diffraction and Raman spectroscopy up to their respective melting points. In agreement with previous unit-cell parameters determinations below 1100 K, thermal expansion of diopside along the a and c axis is much smaller than along the b axis. For pseudowollastonite, the axis expansivity increases slightly in the order b>a>c. For both minerals, the change in unit-cell angles is very small and there are no anomalous variations of the other unit-cell parameters near the melting point. With increasing temperatures, the main changes observed in the Raman spectra are strong increases of the linewidths for those bands which mainly represent Si-O-Si bending (near 600 cm-1) or involve Ca-O or Mg-O stretching, in the range 270-500 cm-1 for diopside, and 240-450 cm-1 for pseudowollastonite. At temperatures near the onset of calorimetric premelting effects, this extensive band widening results in a broad Raman feature that can no longer be deconvoluted into its individual components. No significant changes affect the Si-O streching modes. For both diopside and pseudowollastonite, premelting appears to be associated with enhanced dynamics of the alkaline-earth elements. This conclusion contrasts markedly with that drawn for sodium metasilicate in which weaker bonding of sodium allows the silicate framework to distort and deform in such a way as to prefigure the silicate entities present in the melt.

  18. High temperature crystal chemistry and thermal expansion of synthetic powellite (CaMoO4): A high temperature X-ray diffraction (HT-XRD) study

    NASA Astrophysics Data System (ADS)

    Achary, S. N.; Patwe, S. J.; Mathews, M. D.; Tyagi, A. K.

    2006-04-01

    In this communication, the high temperature crystal chemistry of scheelite type (space group: I41/a) CaMoO4 (powellite) is reported. The details of the high temperature crystal structures were obtained by high temperature X-ray diffractometer (HT-XRD) data in the temperature range of 25 1000 °C. The lattice thermal expansions of this compound show the an-isotropic behavior, with the coefficient of thermal expansion along c-axis (αc) is almost double of that along the a-axis (αa). The average values of thermal expansion coefficient for CaMoO4 are: αa=13.5×10-6 and αc=22.8×10-6 °C. The typical thermal expansion behavior is basically controlled by the temperature-induced expansion of the Ca O bonds, i.e. by the thermal expansion of the CaO8 polyhedra. The MoO4 polyhedra acts as typical rigid unit, with virtually no expansion. The preliminary data analysis for CaWO4 indicates almost similar values of thermal expansion coefficients, viz. αa=12.7×10-6 and αc=21.4×10-6/°C (for CaWO4) in the same temperature range. The further details are explained in this manuscript.

  19. Time-resolved in situ powder X-ray diffraction reveals the mechanisms of molten salt synthesis.

    PubMed

    Moorhouse, Saul J; Wu, Yue; Buckley, Hannah C; O'Hare, Dermot

    2016-11-24

    We report the first use of high-energy monochromatic in situ X-ray powder diffraction to gain unprecedented insights into the chemical processes occurring during high temperature, lab-scale metal oxide syntheses. During the flux synthesis of the n = 4 Aurivillius phase, Bi5Ti3Fe0.5Cr0.5O15 at 950 °C in molten Na2SO4 we observe the progression of numerous metastable phases. Using sequential multiphase Rietveld refinement of the time-dependent in situ XRD data, we are able to obtain mechanistic understanding of this reaction under a range of conditions.

  20. High-resolution spectroscopic diagnostics of very high-temperature plasmas in the hard x-ray regime

    SciTech Connect

    Widmann, Klaus

    1999-12-06

    Motivated by the need for establishing a reliable database useful for the application of x-ray spectroscopic tools for the diagnostic of very high temperature plasmas, high-resolution crystal spectrometer measurements have been performed investigating the characteristic K-shell radiation of highly charged krypton and xenon. The measurements, which have been performed at the Electron-Beam-Ion-Trap (EBIT) facility of the Lawrence Livermore National Laboratory, include the investigation of the n = 2 → 1 transitions in heliumlike krypton (Kr34+) and innershell excited lithiumlike krypton (Kr{sup 33+}) utilizing a conventional reflection-type crystal spectrometer of von Hamos geometry. The electron-excitation-energy selective measurements map the contribution of the dielectronic recombination lines providing the means of accurate interpretation of the line profiles of the characteristic Kα x-ray emission of plasmas. The high-resolution measurements of the n = 2 → 1 transitions in heliumlike xenon (Xe52+) and hydrogenlike xenon (Xe53+) were based on a new transmission-type crystal spectrometer of DuMond geometry. The resolving power of the developed spectrometer was sufficient for charge state specific observation allowing the determination of the electron-impact excitation cross section for the hydrogen- and heliumlike Kα transitions. The disagreement with theoretically predicted values is a measure of the magnitude of the Breit interaction for the highly charged high-Z ions.

  1. X-ray grating interferometer for in situ and at-wavelength wavefront metrology.

    PubMed

    Kayser, Yves; David, Christian; Flechsig, Uwe; Krempasky, Juraj; Schlott, Volker; Abela, Rafael

    2017-01-01

    A wavefront metrology setup based on the X-ray grating interferometry technique for spatially resolved, quantitative, in situ and at-wavelength measurements of the wavefront at synchrotron radiation and hard X-ray free-electron laser beamlines is reported. Indeed, the ever-increasing demands on the optical components to preserve the wavefront shape and the coherence of the delivered X-ray beam call for more and more sensitive diagnostic instruments. Thanks to its angular sensitivity, X-ray grating interferometry has been established in recent years as an adequate wavefront-sensing technique for quantitatively assessing the quality of the X-ray wavefront under working conditions and hence for the in situ investigation of X-ray optical elements. In order to characterize the optical elements at any given beamline by measuring the aberrations introduced in the wavefront, a transportable X-ray grating interferometry setup was realised at the Swiss Light Source (SLS). The instrument, which is expected to be a valuable tool for investigating the quality of the X-ray beam delivered at an endstation, will be described hereafter in terms of the hardware setup and the related data analysis procedure. Several exemplary experiments performed at the X05DA Optics beamline of the SLS will be presented.

  2. Quantifying phosphoric acid in high-temperature polymer electrolyte fuel cell components by X-ray tomographic microscopy.

    PubMed

    Eberhardt, S H; Marone, F; Stampanoni, M; Büchi, F N; Schmidt, T J

    2014-11-01

    Synchrotron-based X-ray tomographic microscopy is investigated for imaging the local distribution and concentration of phosphoric acid in high-temperature polymer electrolyte fuel cells. Phosphoric acid fills the pores of the macro- and microporous fuel cell components. Its concentration in the fuel cell varies over a wide range (40-100 wt% H3PO4). This renders the quantification and concentration determination challenging. The problem is solved by using propagation-based phase contrast imaging and a referencing method. Fuel cell components with known acid concentrations were used to correlate greyscale values and acid concentrations. Thus calibration curves were established for the gas diffusion layer, catalyst layer and membrane in a non-operating fuel cell. The non-destructive imaging methodology was verified by comparing image-based values for acid content and concentration in the gas diffusion layer with those from chemical analysis.

  3. The nondestructive evaluation of high temperature conditioned concrete in conjunction with acoustic emission and x-ray computed tomography

    NASA Astrophysics Data System (ADS)

    Su, Yu-Min; Hou, Tsung-Chin; Lin, Li-Chiang; Chen, Gwan-Ying; Pan, Huang-Hsing

    2016-04-01

    Portland Cement Concrete plays a vital part of protecting structural rebars or steels when high-temperature fire incidents occur, that induces loss of evaporate water, dehydration of CH, and deconstruction of C-S-H. The objective of the study was to assess fire-damaged concrete in conjunction with nondestructive evaluation methods of acoustic emission, visual inspections, and X-ray computed tomography. The experimental program was to mix an Ordinary Portland Cement concrete firstly. Concrete cylinders with twenty-day moisture cure were treated in a furnace with 400 and 600°C for one hour. After temperature is cooled down, the concrete cylinders were brought to air or moisture re-curing for ten days. Due to the incident of the furnace, acoustic emission associated with splitting tensile strength test was not able to continue. Future efforts are planned to resume this unfinished task. However, two proposed tasks were executed and completed, namely visual inspections and voids analysis on segments obtained from X-ray CT facility. Results of visual inspections on cross-sectional and cylindrical length of specimens showed that both aggregates and cement pastes turned to pink or red at 600°C. More surface cracks were generated at 600°C than that at 400°C. On the other hand, voids analysis indicated that not many cracks were generated and voids were remedied at 400°C. However, a clear tendency was found that remedy by moisture curing may heal up to 2% voids of the concrete cylinder that was previously subject to 600°C of high temperature conditioning.

  4. In-situ X-ray diffraction study of carbonate formation and decomposition in perovskite-type BCFZ

    NASA Astrophysics Data System (ADS)

    Efimov, Konstantin; Czuprat, Oliver; Feldhoff, Armin

    2011-05-01

    The effect of CO 2 on the two phase perovskite with average composition of BaCo 0.4Fe 0.4Zr 0.2O 3- δ is investigated by in-situ X-ray diffraction (XRD) as well as transmission electron microscopy (TEM). Partial decomposition of the BCFZ into high-temperature rhombohedral BaCO 3 polymorph was observed during annealing in an atmosphere, which contained 50 vol% CO 2/50 vol% N 2 at 1173 K. This carbonate structure is not quenchable and cannot be detected by ex-situ methods. Additionally, the reversible phase transition of BaCO 3 from orthorhombic to rhombohedral to cubic at different temperatures accompanied by formation of CoO was shown by in-situ XRD and TEM. Furthermore, complete regeneration of perovskite phase was obtained after high-temperature treatment under CO 2-free conditions.

  5. Determination of the solubility of tin indium oxide using in situ and ex x-ray diffraction

    SciTech Connect

    Gonzalez, G. B.; Mason, T. O.; Okasinski, J. S.; Buslaps, T.; Honkimaki, V.

    2012-02-01

    A novel approach to determine the thermodynamic solubility of tin in indium oxide via the exsolution from tin overdoped nano-ITO powders is presented. High-energy, in situ and ex situ synchrotron X-ray diffraction was utilized to study the solubility limit at temperatures ranging from 900 C to 1375 C. The tin exsolution from overdoped nanopowders and the formation of In{sub 4}Sn{sub 3}O{sub 12} were observed in situ during the first 4-48 h of high-temperature treatment. Samples annealed between 900 C and 1175 C were also studied ex situ with heat treatments for up to 2060 h. Structural results obtained from Rietveld analysis include compositional phase analysis, atomic positions, and lattice parameters. The tin solubility in In{sub 2}O{sub 3} was determined using the phase analysis compositions from X-ray diffraction and the elemental compositions obtained from X-ray fluorescence. Experimental complications that can lead to incorrect tin solubility values in the literature are discussed.

  6. In-situ X-ray diffraction system using sources and detectors at fixed angular positions

    DOEpatents

    Gibson, David M.; Gibson, Walter M.; Huang, Huapeng

    2007-06-26

    An x-ray diffraction technique for measuring a known characteristic of a sample of a material in an in-situ state. The technique includes using an x-ray source for emitting substantially divergent x-ray radiation--with a collimating optic disposed with respect to the fixed source for producing a substantially parallel beam of x-ray radiation by receiving and redirecting the divergent paths of the divergent x-ray radiation. A first x-ray detector collects radiation diffracted from the sample; wherein the source and detector are fixed, during operation thereof, in position relative to each other and in at least one dimension relative to the sample according to a-priori knowledge about the known characteristic of the sample. A second x-ray detector may be fixed relative to the first x-ray detector according to the a-priori knowledge about the known characteristic of the sample, especially in a phase monitoring embodiment of the present invention.

  7. A portable X-ray diffraction apparatus for in situ analyses of masters' paintings

    NASA Astrophysics Data System (ADS)

    Eveno, Myriam; Duran, Adrian; Castaing, Jacques

    2010-09-01

    It is rare that the analyses of materials in paintings can be carried out by taking micro-samples. Valuable works of art are best studied in situ by non-invasive techniques. For that purpose, a portable X-ray diffraction and fluorescence apparatus has been designed and constructed at the C2RMF. This apparatus has been used for paintings of Rembrandt, Leonardo da Vinci, Van Gogh, Mantegna, etc. Results are given to illustrate the performance of X-ray diffraction, especially when X-ray fluorescence does not bring sufficient information to conclude.

  8. In situ X-ray powder diffraction, synthesis, and magnetic properties of InVO{sub 3}

    SciTech Connect

    Lundgren, Rylan J.; Cranswick, Lachlan M.D.; Bieringer, Mario . E-mail: Mario_Bieringer@umanitoba.ca

    2006-12-15

    We report the first synthesis and high-temperature in situ X-ray diffraction study of InVO{sub 3}. Polycrystalline InVO{sub 3} has been prepared via reduction of InVO{sub 4} using a carbon monoxide/carbon dioxide buffer gas. InVO{sub 3} crystallizes in the bixbyite structure in space group Ia-3 (206) with a=9.80636(31) A with In{sup 3+}/V{sup 3+} disorder on the (8b) and (24d) cation sites. In situ powder X-ray diffraction experiments and thermal gravimetric analysis in a CO/CO{sub 2} buffer gas revealed the existence of the metastable phase InVO{sub 3}. Bulk samples with 98.5(2)% purity were prepared using low-temperature reduction methods. The preparative methods limited the crystallinity of this new phase to approximately 225(50) A. Magnetic susceptibility and neutron diffraction experiments suggest a spin-glass ground state for InVO{sub 3}. - Graphical abstract: In situ powder X-ray diffractograms for the reduction of InVO{sub 4} in CO/CO{sub 2}. The three temperature regions show the conversion of InVO{sub 4} to InVO{sub 3} and final decomposition into In{sub 2}O{sub 3} and V{sub 2}O{sub 3}.

  9. Design of a continuous-flow reactor for in situ x-ray absorption spectroscopy of solids in supercritical fluids.

    PubMed

    Dreher, M; De Boni, E; Nachtegaal, M; Wambach, J; Vogel, F

    2012-05-01

    This paper presents the design and performance of a novel high-temperature and high-pressure continuous-flow reactor, which allows for x-ray absorption spectroscopy or diffraction in supercritical water and other fluids under high pressure and temperature. The in situ cell consists of a tube of sintered, polycrystalline aluminum nitride, which is tolerant to corrosive chemical media, and was designed to be stable at temperatures up to 500 °C and pressures up to 30 MPa. The performance of the reactor is demonstrated by the measurement of extended x-ray absorption fine structure spectra of a carbon-supported ruthenium catalyst during the continuous hydrothermal gasification of ethanol in supercritical water at 400 °C and 24 MPa.

  10. In situ anodization of aluminum surfaces studied by x-ray reflectivity and electrochemical impedance spectroscopy

    SciTech Connect

    Bertram, F. Evertsson, J.; Messing, M. E.; Mikkelsen, A.; Lundgren, E.; Zhang, F.; Pan, J.; Carlà, F.; Nilsson, J.-O.

    2014-07-21

    We present results from the anodization of an aluminum single crystal [Al(111)] and an aluminum alloy [Al 6060] studied by in situ x-ray reflectivity, in situ electrochemical impedance spectroscopy and ex situ scanning electron microscopy. For both samples, a linear increase of oxide film thickness with increasing anodization voltage was found. However, the slope is much higher in the single crystal case, and the break-up of the oxide film grown on the alloy occurs at a lower anodization potential than on the single crystal. The reasons for these observations are discussed as are the measured differences observed for x-ray reflectivity and electrochemical impedance spectroscopy.

  11. In-situ non-ambient X-ray diffraction studies of indium tungstate

    SciTech Connect

    Baiz, Tamam I.; Heinrich, Christophe P.; Banek, Nathan A.; Vivekens, Boris L.; Lind, Cora

    2012-03-15

    In situ variable temperature and high pressure X-ray diffraction studies were carried out on indium tungstate (In{sub 2}W{sub 3}O{sub 12}). This material displays positive volume expansion in both its low temperature monoclinic and high temperature orthorhombic phases, with negative thermal expansion along the a axis and positive thermal expansion along the b and c axes. Upon hydrostatic compression in a diamond anvil cell, one crystalline to crystalline phase transition is observed in the range 1.9 to 2.7 GPa, and progressive irreversible amorphization occurs at pressures above 4.3 GPa. The crystalline high pressure phase appears to be isostructural to previously observed high pressure phases in other A{sub 2}M{sub 3}O{sub 12} compounds. - Graphical abstract: Variable pressure X-ray diffraction patterns of In{sub 2}W{sub 3}O{sub 12} collected in a diamond anvil cell. A phase transition is clearly observed between 2.2 and 2.7 GPa, followed by irreversible amorphization. Highlights: Black-Right-Pointing-Pointer The structure of In{sub 2}W{sub 3}O{sub 12} was studied as a function of temperature and pressure. Black-Right-Pointing-Pointer Uniaxial negative thermal expansion was observed above 250 Degree-Sign C. Black-Right-Pointing-Pointer A pressure-induced phase transition occurred between 2.2 and 2.7 GPa. Black-Right-Pointing-Pointer Pressure-induced irreversible amorphization was observed above 4.3 GPa.

  12. In-situ observations of catalytic surface reactions with soft x-rays under working conditions.

    PubMed

    Toyoshima, Ryo; Kondoh, Hiroshi

    2015-03-04

    Catalytic chemical reactions proceeding on solid surfaces are an important topic in fundamental science and industrial technologies such as energy conversion, pollution control and chemical synthesis. Complete understanding of the heterogeneous catalysis and improving its efficiency to an ultimate level are the eventual goals for many surface scientists. Soft x-ray is one of the prime probes to observe electronic and structural information of the target materials. Most studies in surface science using soft x-rays have been performed under ultra-high vacuum conditions due to the technical limitation, though the practical catalytic reactions proceed under ambient pressure conditions. However, recent developments of soft x-ray based techniques operating under ambient pressure conditions have opened a door to the in-situ observation of materials under realistic environments. The near-ambient-pressure x-ray photoelectron spectroscopy (NAP-XPS) using synchrotron radiation enables us to observe the chemical states of surfaces of condensed matters under the presence of gas(es) at elevated pressures, which has been hardly conducted with the conventional XPS technique. Furthermore, not only the NAP-XPS but also ambient-pressure compatible soft x-ray core-level spectroscopies, such as near-edge absorption fine structure (NEXAFS) and x-ray emission spectroscopy (XES), have been significantly contributing to the in-situ observations. In this review, first we introduce recent developments of in-situ observations using soft x-ray techniques and current status. Then we present recent new findings on catalytically active surfaces using soft x-ray techniques, particularly focusing on the NAP-XPS technique. Finally we give a perspective on the future direction of this emerging technique.

  13. Thermoluminescence, ESR and x-ray diffraction studies of CaSO4 : Dy phosphor subjected to post preparation high temperature thermal treatment

    NASA Astrophysics Data System (ADS)

    Bakshi, A. K.; Patwe, S. J.; Bhide, M. K.; Sanyal, B.; Natarajan, V.; Tyagi, A. K.; Kher, R. K.

    2008-01-01

    Thermoluminescence (TL), electron spin resonance (ESR) and x ray diffraction studies of CaSO4 : Dy phosphor subjected to post preparation high temperature treatment were carried out. Analysis of the TL glow curve indicated that the dosimetric glow peak at 240 °C reduces, whereas the low temperature satellite peak increases with the increase in the annealing temperature in the range 650-1000 °C. The influence of the annealing atmosphere on the TL glow curve structure was also observed. Reduction of the photoluminescence intensity of the annealed phosphor indicated that the environment of Dy3+ ions might have undergone some change due to high temperature treatment. Reduction in the ESR signal intensity corresponding to O_{3}^{-} and SO_{3}^{-} radicals was observed initially with the increase in the annealing temperaure; subsequently their intensity increased with temperature. Signals due to the SO_{4}^{-} radical vanished, when the phosphor was annealed beyond 800 °C. A signal corresponding to SH2- radicals was also observed in the ESR spectra for samples subjected to annealing in the temperature regime 800-1000 °C. XRD of the in situ annealed phosphor showed a change in the unit cell parameters. An endothermic peak at 860 °C in the DTA spectrum was observed.

  14. Hard X-ray-induced damage on carbon-binder matrix for in situ synchrotron transmission X-ray microscopy tomography of Li-ion batteries.

    PubMed

    Lim, Cheolwoong; Kang, Huixiao; De Andrade, Vincent; De Carlo, Francesco; Zhu, Likun

    2017-05-01

    The electrode of Li-ion batteries is required to be chemically and mechanically stable in the electrolyte environment for in situ monitoring by transmission X-ray microscopy (TXM). Evidence has shown that continuous irradiation has an impact on the microstructure and the electrochemical performance of the electrode. To identify the root cause of the radiation damage, a wire-shaped electrode is soaked in an electrolyte in a quartz capillary and monitored using TXM under hard X-ray illumination. The results show that expansion of the carbon-binder matrix by the accumulated X-ray dose is the key factor of radiation damage. For in situ TXM tomography, intermittent X-ray exposure during image capturing can be used to avoid the morphology change caused by radiation damage on the carbon-binder matrix.

  15. In situ laser heating and radial synchrotron x-ray diffraction in a diamond anvil cell

    SciTech Connect

    Kunz, Martin; Caldwell, Wendel A.; Miyagi, Lowell; Wenk, Hans-Rudolf

    2007-06-15

    We report a first combination of diamond anvil cell radial x-ray diffraction with in situ laser heating. The laser-heating setup of ALS beamline 12.2.2 was modified to allow one-sided heating of a sample in a diamond anvil cell with an 80 W yttrium lithium fluoride laser while probing the sample with radial x-ray diffraction. The diamond anvil cell is placed with its compressional axis vertical, and perpendicular to the beam. The laser beam is focused onto the sample from the top while the sample is probed with hard x-rays through an x-ray transparent boron-epoxy gasket. The temperature response of preferred orientation of (Fe,Mg)O is probed as a test experiment. Recrystallization was observed above 1500 K, accompanied by a decrease in stress.

  16. In situ laser heating and radial synchrotron x-ray diffraction in a diamond anvil cell.

    PubMed

    Kunz, Martin; Caldwell, Wendel A; Miyagi, Lowell; Wenk, Hans-Rudolf

    2007-06-01

    We report a first combination of diamond anvil cell radial x-ray diffraction with in situ laser heating. The laser-heating setup of ALS beamline 12.2.2 was modified to allow one-sided heating of a sample in a diamond anvil cell with an 80 W yttrium lithium fluoride laser while probing the sample with radial x-ray diffraction. The diamond anvil cell is placed with its compressional axis vertical, and perpendicular to the beam. The laser beam is focused onto the sample from the top while the sample is probed with hard x-rays through an x-ray transparent boron-epoxy gasket. The temperature response of preferred orientation of (Fe,Mg)O is probed as a test experiment. Recrystallization was observed above 1500 K, accompanied by a decrease in stress.

  17. Electrochemical cell for in-situ x-ray characterization

    SciTech Connect

    Doughty, D.H.; Ingersoll, D.; Rodriguez, M.A.

    1998-08-04

    An electrochemical cell suitable for in-situ XRD analysis is presented. Qualitative information such as phase formation and phase stability can be easily monitored using the in-situ cell design. Quantitative information such as lattice parameters and kinetic behavior is also straightforward. Analysis of the LiMn&sub2;O&sub4; spinel using this cell design shows that the lattice undergoes two major structural shrinkages at approx. 4.0 V and approx. 4.07 V during charging. These shrinkages correlate well with the two electrochemical waves observed and indicate the likelihood of two separate redox processes which charging and discharging.

  18. Probing electrode/electrolyte interfaces in situ by X-ray spectroscopies: old methods, new tricks.

    PubMed

    Wu, Cheng Hao; Weatherup, Robert S; Salmeron, Miquel B

    2015-11-11

    Electrode/electrolyte interfaces play a vital role in various electrochemical systems, but in situ characterization of such buried interfaces remains a major challenge. Several efforts to develop techniques or to modify existing techniques to study such interfaces are showing great promise to overcome this challenge. Successful examples include electrochemical scanning tunneling microscopy (EC-STM), surface-sensitive vibrational spectroscopies, environmental transmission electron microscopy (E-TEM), and surface X-ray scattering. Other techniques such as X-ray core-level spectroscopies are element-specific and chemical-state-specific, and are being widely applied in materials science research. Herein we showcase four types of newly developed strategies to probe electrode/electrolyte interfaces in situ with X-ray core-level spectroscopies. These include the standing wave approach, the meniscus approach, and two liquid cell approaches based on X-ray photoelectron spectroscopy and soft X-ray absorption spectroscopy. These examples demonstrate that with proper modifications, many ultra-high-vacuum based techniques can be adapted to study buried electrode/electrolyte interfaces and provide interface-sensitive, element- and chemical-state-specific information, such as solute distribution, hydrogen-bonding network, and molecular reorientation. At present, each method has its own specific limitations, but all of them enable in situ and operando characterization of electrode/electrolyte interfaces that can provide important insights into a variety of electrochemical systems.

  19. Application of the high-temperature x-ray diffraction method to the diffusion study in the MgO-AI2O3 system

    NASA Astrophysics Data System (ADS)

    Zhang, P.; Karwan-Baczewska, J.; Du, S.; Seetharaman, S.

    1996-10-01

    A mathematical model has been developed to study the kinetics of formation of spinel (MgAl2O4) using the high-temperature X-ray diffraction method. Experiments have been carried out for the MgO-Al2O3 system on an X-ray diffractometer in the temperature range of 1373 to 1673 K. Equimolar mixtures of MgO and A12O3 powders have been employed as the starting samples. The interdiffusivity values calculated from the high-temperature X-ray diffraction data using the present model are in good agreement with those obtained by diffusion couple experiments. The activation energy for the interdiffusion process has been found to be 354.2 kJ/mol in the temperature range 1473 to 1873 K.

  20. In situ X-ray Scattering and Dynamical Modeling of Pd Catalyst Nanoparticles Formed in Flames

    SciTech Connect

    Wang, Juan; Seifert, Sönke; Winans, Randall E.; Tolmachoff, Erik; Xin, Yuxuan; Chen, Dongping; Wang, Hai; Anderson, Scott L.

    2015-08-20

    It has previously been demonstrated that organopalladium precursors can break down under combustion conditions, forming nanoparticles that catalyze ignition. Here, we use in situ small-angle X-ray scattering (SAXS) to probe the formation and growth of palladium nanoparticles in an ethylene fl ame doped with 28 ppm (mol) of Pd(acetate) 2 . The particles appear to nucleate in the fl ame front and are observed by SAXS to grow in size and mass in the high-temperature region of the fl ame ( ~ 2200 K) with median diameters that evolve from 1.5 to 3.0 nm. Transmission electron microscopy of particles collected on a grid located outside the fl ame shows that the particles are metallic palladium with sizes comparable to those determined by SAXS. Molecular dynamics simulation of particles of selected sizes indicates that at the fl ame temperature the particles are molten and the average mass density of the particle material is notably smaller than that of bulk, liquid Pd at the melting point. Both experimental and computational results point to homogeneous nucleation and particle - particle coalescence as mechanisms for particle formation and growth. Aerosol dynamics simulation reproduces the time evolution of the particle size distribution and suggests that a substantial fraction of the particles must be electrically charged during their growth process.

  1. In situ X-ray diffraction based investigation of crystallization in solution deposited PZT thin films

    NASA Astrophysics Data System (ADS)

    Nittala, Krishna

    Solution deposited PZT based thin films have potential applications in embedded decoupling capacitors and pulse discharge capacitors. During solution deposition, precursor solution is deposited onto a substrate to obtain an amorphous film. The film is then crystallized by heating it at a high temperature (˜600 - 700°C). Conditions during the crystallization anneal such as precursor stoichiometry in solution, heating rate and adhesion layer in the substrate are known to influence phase and texture evolution in these films. However, a mechanistic understanding of the changes taking place in these thin films during crystallization is lacking. A better understanding of the crystallization processes in these thin films could enable tailoring the properties of thin films to suit specific applications. To explore the crystallization process in solution deposited PZT thin films, high temperature in situ laboratory and synchrotron X-ray diffraction based techniques were developed. Taking advantage of the high X-ray flux available at synchrotron facilities such as beamline 6-ID-B, Advanced Photon Source, Argonne National Laboratory, crystalline phases formed in the thin films during crystallization at the high heating rates (0.5 -- 60°C/s) typically used during film processing could be measured. Using a 2-D detector for these measurements allowed the simultaneous measurement of both phase and texture information during crystallization. Analytical treatment of the unconventional diffraction geometry used during the synchrotron based measurements was performed to develop methodologies for quantitative estimation of texture components. The nominal lead content in the starting solutions and the heating rate used during crystallization was observed to influence the sequence of phases formed during crystallization of the films. In films crystallized at fast heating rates, titanium segregation, probably due to diffusion of titanium from the adhesion layer, was observed. To

  2. In situ X-ray-based imaging of nano materials

    SciTech Connect

    Weker, Johanna Nelson; Huang, Xiaojing; Toney, Michael F.

    2016-02-13

    We study functional nanomaterials that are heterogeneous and understanding their behavior during synthesis and operation requires high resolution diagnostic imaging tools that can be used in situ. Over the past decade, huge progress has been made in the development of X-ray based imaging, including full field and scanning microscopy and their analogs in coherent diffractive imaging. Currently, spatial resolution of about 10 nm and time resolution of sub-seconds are achievable. For catalysis, X-ray imaging allows tracking of particle chemistry under reaction conditions. In energy storage, in situ X-ray imaging of electrode particles is providing important insight into degradation processes. Recently, both spatial and temporal resolutions are improving to a few nm and milliseconds and these developments will open up unprecedented opportunities.

  3. Simple load frame for in situ computed tomography and x-ray tomographic microscopy

    SciTech Connect

    Breunig, T.M. ); Stock, S.R.; Brown, R.C. )

    1993-05-01

    In many instances, the response of a sample to external stimuli must be observed repeatedly during the course of an experiment. The sequence in which features are formed is often critical to proper identification of the mechanisms operating, for example, in fatigue and fracture. Merely observing what is visible at the surface of the sample can be misleading or can provide inadequate information about what governs fatigue crack growth or about what controls the fracture process. X-ray imaging allows one to observe the interior of samples and is an attractive technique to use with in situ stressing of test specimens. Here, a simple compact, inexpensive load frame is described for in situ x-ray computed tomography and for very high resolution computed tomography, termed x-ray tomographic microscopy. The load frame is evaluated, and its use is illustrated by observations of crack closure as a function of load in a notched tensile sample of Al-Li-2090.

  4. Evolution of magma textures during deformation: Insights from in situ X-ray tomography experiments

    NASA Astrophysics Data System (ADS)

    Degruyter, W.; Cordonnier, B.; Manga, M.; Haboub, A.; Andrews, B. J.; Dennen, R. L.; MacDowell, A.; Parkinson, D. Y.

    2012-12-01

    Pyroclasts provide snapshots of the state of the magma at fragmentation or emplacement. Their textures record the deformation and degassing magma underwent prior to quenching. Understanding the link between the final texture and the processes that created them requires experimental reproduction of volcanic conditions under constrained parameters. Technological advances at the X-ray tomography beamline at the Advanced Light Source, Lawrence Berkeley National Laboratory have now made it possible to visualize magma in 3D as it is being deformed at high temperature, which allows us to visualize and quantify the processes that form pyroclasts. We use a fast readout camera that allows tomography on a few minutes timescale in combination with a high temperature uni-axial apparatus transparent to tomography. We heated obsidian samples from Big Glass Mountain, California and andesitic glass from Pahoa, California at various temperatures up to 1400 K. After an initial foaming stage, the samples were subjected to pure shear flow at strain-rates varying between 10-6 s-1 and 10-2 s-1. Magma rheology measurements in the past have typically been restricted to bulk measurements and visualization before and after the experiment. This limits the ability to interpret the measured relationship between stress and strain-rate and the evolution of texture. The in situ scanning allows us to track the deformation or relaxation of individual bubbles, development of strain localization, crack initiation and makes it possible to directly correlate these processes to the bulk measurements of stress and strain. These new measurements will improve the interpretation of the textures found within the products produced by volcanic eruptions.

  5. Developments in synchrotron x-ray micro-tomography for in-situ materials analysis at the Advanced Light Source

    NASA Astrophysics Data System (ADS)

    Barnard, Harold S.; MacDowell, A. A.; Parkinson, D. Y.; Venkatakrishnan, S. V.; Panerai, F.; Mansour, N. N.

    2016-10-01

    The Advanced Light Source (ALS) is a third-generation synchrotron X-ray source that operates as a user facility with more than 40 beamlines hosting over 2000 users per year. Synchrotron sources like the ALS provide high quality X-ray beams, with flux that is several orders of magnitude higher than lab-based sources. This is particularly advantageous for dynamic applications because it allows for high-speed, high-resolution imaging and microscale tomography. The hard X-ray beamline 8.3.2 at the Advanced Light Source enables imaging of samples at high temperatures and pressures, with mechanical loading and other realistic conditions using environmental test cells. These test cells enable experimental observation of samples undergoing dynamic microstructural changes in-situ. We present recent instrumentation developments that allow for continuous tomography with scan rates approaching 1 Hz per 3D image. In addition, our use of iterative reconstruction techniques allows for improved image quality despite fewer images and low exposure times used during fast tomography compared to traditional Fourier reconstruction methods.

  6. A Rotational and Axial Motion System Load Frame Insert for In Situ High Energy X-Ray Studies (Postprint)

    DTIC Science & Technology

    2015-09-08

    AFRL-RX-WP-JA-2016-0273 A ROTATIONAL AND AXIAL MOTION SYSTEM LOAD FRAME INSERT FOR IN SITU HIGH ENERGY X - RAY STUDIES (POSTPRINT...SUBTITLE A ROTATIONAL AND AXIAL MOTION SYSTEM LOAD FRAME INSERT FOR IN SITU HIGH ENERGY X - RAY STUDIES (POSTPRINT) 5a. CONTRACT NUMBER FA8650-14...final publication is available at http://dx.doi.org/10.1063/1.4927855 14. ABSTRACT (Maximum 200 words) High energy x - ray characterization methods hold

  7. Functional materials analysis using in situ and in operando X-ray and neutron scattering

    PubMed Central

    Peterson, Vanessa K.; Papadakis, Christine M.

    2015-01-01

    In situ and in operando studies are commonplace and necessary in functional materials research. This review highlights recent developments in the analysis of functional materials using state-of-the-art in situ and in operando X-ray and neutron scattering and analysis. Examples are given covering a number of important materials areas, alongside a description of the types of information that can be obtained and the experimental setups used to acquire them. PMID:25866665

  8. Functional materials analysis using in situ and in operando X-ray and neutron scattering.

    PubMed

    Peterson, Vanessa K; Papadakis, Christine M

    2015-03-01

    In situ and in operando studies are commonplace and necessary in functional materials research. This review highlights recent developments in the analysis of functional materials using state-of-the-art in situ and in operando X-ray and neutron scattering and analysis. Examples are given covering a number of important materials areas, alongside a description of the types of information that can be obtained and the experimental setups used to acquire them.

  9. Modular deposition chamber for in situ X-ray experiments during RF and DC magnetron sputtering.

    PubMed

    Krause, Bärbel; Darma, Susan; Kaufholz, Marthe; Gräfe, Hans Hellmuth; Ulrich, Sven; Mantilla, Miguel; Weigel, Ralf; Rembold, Steffen; Baumbach, Tilo

    2012-03-01

    A new sputtering system for in situ X-ray experiments during DC and RF magnetron sputtering is described. The outstanding features of the system are the modular design of the vacuum chamber, the adjustable deposition angle, the option for plasma diagnostics, and the UHV sample transfer in order to access complementary surface analysis methods. First in situ diffraction and reflectivity measurements during RF and DC deposition of vanadium carbide demonstrate the performance of the set-up.

  10. In situ fine tuning of bendable soft x-ray mirrors using a lateral shearing interferometer

    NASA Astrophysics Data System (ADS)

    Merthe, Daniel J.; Goldberg, Kenneth A.; Yashchuk, Valeriy V.; McKinney, Wayne R.; Celestre, Richard; Mochi, Iacopo; MacDougall, James; Morrison, Gregory Y.; Rekawa, Senajith B.; Anderson, Erik; Smith, Brian V.; Domning, Edward E.; Padmore, Howard

    2013-05-01

    Broadly applicable, in situ at-wavelength metrology methods for x-ray optics are currently under development at the Advanced Light Source. We demonstrate the use of quantitative wavefront feedback from a lateral shearing interferometer for the suppression of aberrations. With the high sensitivity provided by the interferometer we were able to optimally tune the bending couples of a single elliptical mirror (NA=2.7 mrad) in order to focus a beam of soft x-rays (1.24 keV) to a nearly diffraction-limited beam waist size of 156(±10) nm.

  11. In situ laser heating and radial synchrotron X-ray diffraction ina diamond anvil cell

    SciTech Connect

    Kunz, Martin; Caldwell, Wendel A.; Miyagi, Lowell; Wenk,Hans-Rudolf

    2007-06-29

    We report a first combination of diamond anvil cell radialx-ray diffraction with in situ laser heating. The laser-heating setup ofALS beamline 12.2.2 was modified to allow one-sided heating of a samplein a diamond anvil cell with an 80 W yttrium lithium fluoride laser whileprobing the sample with radial x-ray diffraction. The diamond anvil cellis placed with its compressional axis vertical, and perpendicular to thebeam. The laser beam is focused onto the sample from the top while thesample is probed with hard x-rays through an x-ray transparentboron-epoxy gasket. The temperature response of preferred orientation of(Fe,Mg)O is probed as a test experiment. Recrystallization was observedabove 1500 K, accompanied by a decrease in stress.

  12. In situ X-ray probing reveals fingerprints of surface platinum oxide.

    PubMed

    Friebel, Daniel; Miller, Daniel J; O'Grady, Christopher P; Anniyev, Toyli; Bargar, John; Bergmann, Uwe; Ogasawara, Hirohito; Wikfeldt, Kjartan Thor; Pettersson, Lars G M; Nilsson, Anders

    2011-01-07

    In situ X-ray absorption spectroscopy (XAS) at the Pt L(3) edge is a useful probe for Pt-O interactions at polymer electrolyte membrane fuel cell (PEMFC) cathodes. We show that XAS using the high energy resolution fluorescence detection (HERFD) mode, applied to a well-defined monolayer Pt/Rh(111) sample where the bulk penetrating hard X-rays probe only surface Pt atoms, provides a unique sensitivity to structure and chemical bonding at the Pt-electrolyte interface. Ab initio multiple-scattering calculations using the FEFF code and complementary extended X-ray absorption fine structure (EXAFS) results indicate that the commonly observed large increase of the white-line at high electrochemical potentials on PEMFC cathodes originates from platinum oxide formation, whereas previously proposed chemisorbed oxygen-containing species merely give rise to subtle spectral changes.

  13. In Situ X-Ray Probing Reveals Fingerprints of Surface Platinum Oxide

    SciTech Connect

    Friebel, Daniel

    2011-08-24

    In situ x-ray absorption spectroscopy (XAS) at the Pt L{sub 3} edge is a useful probe for Pt-O interactions at polymer electrolyte membrane fuel cell (PEMFC) cathodes. We show that XAS using the high energy resolution fluorescence detection (HERFD) mode, applied to a well-defined monolayer Pt/Rh(111) sample where the bulk penetrating hard x-rays probe only surface Pt atoms, provides a unique sensitivity to structure and chemical bonding at the Pt-electrolyte interface. Ab initio multiple-scattering calculations using the FEFF8 code and complementary extended x-ray absorption fine structure (EXAFS) results indicate that the commonly observed large increase of the white-line at high electrochemical potentials on PEMFC cathodes originates from platinum oxide formation, whereas previously proposed chemisorbed oxygen-containing species merely give rise to subtle spectral changes.

  14. Custom AFM for X-ray beamlines: in situ biological investigations under physiological conditions

    PubMed Central

    Gumí-Audenis, B.; Carlà, F.; Vitorino, M. V.; Panzarella, A.; Porcar, L.; Boilot, M.; Guerber, S.; Bernard, P.; Rodrigues, M. S.; Sanz, F.; Giannotti, M. I.; Costa, L.

    2015-01-01

    A fast atomic force microscope (AFM) has been developed that can be installed as a sample holder for grazing-incidence X-ray experiments at solid/gas or solid/liquid interfaces. It allows a wide range of possible investigations, including soft and biological samples under physiological conditions (hydrated specimens). The structural information obtained using the X-rays is combined with the data gathered with the AFM (morphology and mechanical properties), providing a unique characterization of the specimen and its dynamics in situ during an experiment. In this work, lipid monolayers and bilayers in air or liquid environment have been investigated by means of AFM, both with imaging and force spectroscopy, and X-ray reflectivity. In addition, this combination allows the radiation damage induced by the beam on the sample to be studied, as has been observed on DOPC and DPPC supported lipid bilayers under physiological conditions. PMID:26524300

  15. Hydrothermal formation of tobermorite studied by in situ X-ray diffraction under autoclave condition.

    PubMed

    Kikuma, Jun; Tsunashima, Masamichi; Ishikawa, Tetsuji; Matsuno, Shin-ya; Ogawa, Akihiro; Matsui, Kunio; Sato, Masugu

    2009-09-01

    Hydrothermal formation of tobermorite from a pre-cured cake has been investigated by transmission X-ray diffraction (XRD) using high-energy X-rays from a synchrotron radiation source in combination with a newly designed autoclave cell. The autoclave cell has a large and thin beryllium window for wide-angle X-ray diffraction; nevertheless, it withstands a steam pressure of more than 1.2 MPa, which enables in situ XRD measurements in a temperature range of 373 to 463 K under a saturated steam pressure. Formation and/or decomposition of several components has been successfully observed during 7.5 h of reaction time. From the intensity changes of the intermediate materials, namely non-crystalline C-S-H and hydroxylellestadite, two pathways for tobermorite formation have been confirmed. Thus, the newly developed autoclave cell can be used for the analyses of reaction mechanisms under specific atmospheres and temperatures.

  16. IN SITU STUDIES OF CORROSION USING X-RAY ABSORPTION NEAR SPECTROSCOPY (XANES)

    SciTech Connect

    ISAACS, H.S.; SCHMUKI, P.; VIRTANEN, S.

    2001-03-25

    Applications of x-ray absorption near-edge spectroscopy (XANES) and the design of cells for in situ corrosion studies are reviewed. Passive films studies require very thin metal or alloy layers be used having a thickness of the order of the films formed because of penetration of the x-ray beam into the metal substrate. The depth of penetration in water also limits the thickness of solutions that can be used because of water reduces the x-ray intensity. Solution thickness must also be limited in studies of conversion layer formation studies because the masking of the Cr in solution. Illustrative examples are taken from the anodic behavior of Al-Cr alloys, the growth of passive films on Fe and stainless steels, and the formation of chromate conversion layers on Al.

  17. High pressure High Temperature X-ray studies in the laser heated diamond anvil cell - Problems and solutions -

    NASA Astrophysics Data System (ADS)

    Mezouar, M.; Garbarino, G.; Svitlik, V.; Dewaele, A.

    2016-12-01

    The laser-heated diamond anvil cell (DAC) is the only static technique that can create extreme temperatures at extreme pressures (P>200 GPa). Temperatures in excess of 5000K can be achieved for samples under pressure in diamond cells by heating with high-power infrared lasers. Because of their low absorption by the diamond anvils, hard X-rays are ideal for probing micro-samples subjected to such extreme conditions. The array of X-ray techniques that was initially restricted to structural measurements using X-Ray diffraction is now extended to include several others such as inelastic X-ray Scattering, Mossbauer spectroscopy and EXAFS. As a direct consequence, many scientific breakthroughs have been achieved across fields ranging from Earth and planetary sciences to fundamental physics, chemistry and materials science. However, despite these important technical and scientific achievements, this kind of experiments still remains very challenging. The difficulties originate from multiple factors including undesired chemical reactions, inaccurate high P-T metrology, and uncertainty in the relative alignment of X-ray and laser beams. In melting studies using X-rays, additional problems can occur such as the use of an unambiguous melting criterion. In this presentation, these problems will be discussed and possible solutions proposed.

  18. High temperature X-ray diffraction study of the oxidation products and kinetics of uranium-plutonium mixed oxides.

    PubMed

    Strach, Michal; Belin, Renaud C; Richaud, Jean-Christophe; Rogez, Jacques

    2014-12-15

    The oxidation products and kinetics of two sets of mixed uranium-plutonium dioxides containing 14%, 24%, 35%, 46%, 54%, and 62% plutonium treated in air were studied by means of in situ X-ray diffraction (XRD) from 300 to 1773 K every 100 K. The first set consisted of samples annealed 2 weeks before performing the experiments. The second one consisted of powdered samples that sustained self-irradiation damage. Results were compared with chosen literature data and kinetic models established for UO2. The obtained diffraction patterns were used to determine the temperature of the hexagonal M3O8 (M for metal) phase formation, which was found to increase with Pu content. The maximum observed amount of the hexagonal phase in wt % was found to decrease with Pu addition. We conclude that plutonium stabilizes the cubic phases during oxidation, but the hexagonal phase was observed even for the compositions with 62 mol % Pu. The results indicate that self-irradiation defects have a slight impact on the kinetics of oxidation and the lattice parameter even after the phase transformation. It was concluded that the lattice constant of the high oxygen phase was unaffected by the changes in the overall O/M when it was in equilibrium with small quantities of M3O8. We propose that the observed changes in the high oxygen cubic phase lattice parameter are a result of either cation migration or an increase in the miscibility of oxygen in this phase. The solubility of Pu in the hexagonal phase was estimated to be below 14 mol % even at elevated temperatures.

  19. Note: Sample chamber for in situ x-ray absorption spectroscopy studies of battery materials

    SciTech Connect

    Pelliccione, CJ; Timofeeva, EV; Katsoudas, JP; Segre, CU

    2014-12-01

    In situ x-ray absorption spectroscopy (XAS) provides element-specific characterization of both crystalline and amorphous phases and enables direct correlations between electrochemical performance and structural characteristics of cathode and anode materials. In situ XAS measurements are very demanding to the design of the experimental setup. We have developed a sample chamber that provides electrical connectivity and inert atmosphere for operating electrochemical cells and also accounts for x-ray interactions with the chamber and cell materials. The design of the sample chamber for in situ measurements is presented along with example XAS spectra from anode materials in operating pouch cells at the Zn and Sn K-edges measured in fluorescence and transmission modes, respectively. (C) 2014 AIP Publishing LLC.

  20. Facility for combined in situ magnetron sputtering and soft x-ray magnetic circular dichroism

    SciTech Connect

    Telling, N. D.; Laan, G. van der; Georgieva, M. T.; Farley, N. R. S.

    2006-07-15

    An ultrahigh vacuum chamber that enables the in situ growth of thin films and multilayers by magnetron sputtering techniques is described. Following film preparation, x-ray absorption spectroscopy (XAS) and x-ray magnetic circular dichroism (XMCD) measurements are performed by utilizing an in vacuum electromagnet. XMCD measurements on sputtered thin films of Fe and Co yield spin and orbital moments that are consistent with those obtained previously on films measured in transmission geometry and grown in situ by evaporation methods. Thin films of FeN prepared by reactive sputtering are also examined and reveal an apparent enhancement in the orbital moment for low N content samples. The advantages of producing samples for in situ XAS and XMCD studies by magnetron sputtering are discussed.

  1. Reactor for nano-focused x-ray diffraction and imaging under catalytic in situ conditions

    NASA Astrophysics Data System (ADS)

    Richard, M.-I.; Fernández, S.; Hofmann, J. P.; Gao, L.; Chahine, G. A.; Leake, S. J.; Djazouli, H.; De Bortoli, Y.; Petit, L.; Boesecke, P.; Labat, S.; Hensen, E. J. M.; Thomas, O.; Schülli, T.

    2017-09-01

    A reactor cell for in situ studies of individual catalyst nanoparticles or surfaces by nano-focused (coherent) x-ray diffraction has been developed. Catalytic reactions can be studied in flow mode in a pressure range of 10-2-103 mbar and temperatures up to 900 °C. This instrument bridges the pressure and materials gap at the same time within one experimental setup. It allows us to probe in situ the structure (e.g., shape, size, strain, faceting, composition, and defects) of individual nanoparticles using a nano-focused x-ray beam. Here, the setup was used to observe strain and facet evolution of individual model Pt catalysts during in situ experiments. It can be used for heating other (non-catalytically active) nanoparticles (e.g., nanowires) in inert or reactive gas atmospheres or vacuum as well.

  2. In situ surface/interface x-ray diffractometer for oxide molecular beam epitaxy

    SciTech Connect

    Lee, J. H.; Tung, I. C.; Chang, S. -H.; Bhattacharya, A.; Fong, D. D.; Freeland, J. W.; Hong, Hawoong

    2016-01-01

    In situ studies of oxide molecular beam epitaxy by synchrotron x-ray scattering has been made possible by upgrading an existing UHV/molecular beam epitaxy (MBE) six-circle diffractometer system. For oxide MBE growth, pure ozone delivery to the chamber has been made available, and several new deposition sources have been made available on a new 12 in. CF (ConFlat, a registered trademark of Varian, Inc.) flange. X-ray diffraction has been used as a major probe for film growth and structures for the system. In the original design, electron diffraction was intended for the secondary diagnostics available without the necessity of the x-ray and located at separate positions. Deposition of films was made possible at the two diagnostic positions. And, the aiming of the evaporation sources is fixed to the point between two locations. Ozone can be supplied through two separate nozzles for each location. Also two separate thickness monitors are installed. Additional features of the equipment are also presented together with the data taken during typical oxide film growth to illustrate the depth of information available via in situ x-ray techniques.

  3. In situ surface/interface x-ray diffractometer for oxide molecular beam epitaxy

    SciTech Connect

    Lee, J. H.; Freeland, J. W.; Hong, Hawoong; Tung, I. C.; Chang, S.-H.; Bhattacharya, A.; Fong, D. D.

    2016-01-15

    In situ studies of oxide molecular beam epitaxy by synchrotron x-ray scattering has been made possible by upgrading an existing UHV/molecular beam epitaxy (MBE) six-circle diffractometer system. For oxide MBE growth, pure ozone delivery to the chamber has been made available, and several new deposition sources have been made available on a new 12 in. CF (ConFlat, a registered trademark of Varian, Inc.) flange. X-ray diffraction has been used as a major probe for film growth and structures for the system. In the original design, electron diffraction was intended for the secondary diagnostics available without the necessity of the x-ray and located at separate positions. Deposition of films was made possible at the two diagnostic positions. And, the aiming of the evaporation sources is fixed to the point between two locations. Ozone can be supplied through two separate nozzles for each location. Also two separate thickness monitors are installed. Additional features of the equipment are also presented together with the data taken during typical oxide film growth to illustrate the depth of information available via in situ x-ray techniques.

  4. In situ surface/interface x-ray diffractometer for oxide molecular beam epitaxy.

    PubMed

    Lee, J H; Tung, I C; Chang, S-H; Bhattacharya, A; Fong, D D; Freeland, J W; Hong, Hawoong

    2016-01-01

    In situ studies of oxide molecular beam epitaxy by synchrotron x-ray scattering has been made possible by upgrading an existing UHV/molecular beam epitaxy (MBE) six-circle diffractometer system. For oxide MBE growth, pure ozone delivery to the chamber has been made available, and several new deposition sources have been made available on a new 12 in. CF (ConFlat, a registered trademark of Varian, Inc.) flange. X-ray diffraction has been used as a major probe for film growth and structures for the system. In the original design, electron diffraction was intended for the secondary diagnostics available without the necessity of the x-ray and located at separate positions. Deposition of films was made possible at the two diagnostic positions. And, the aiming of the evaporation sources is fixed to the point between two locations. Ozone can be supplied through two separate nozzles for each location. Also two separate thickness monitors are installed. Additional features of the equipment are also presented together with the data taken during typical oxide film growth to illustrate the depth of information available via in situ x-ray techniques.

  5. Cyclic olefin homopolymer-based microfluidics for protein crystallization and in situ X-ray diffraction.

    PubMed

    Emamzadah, Soheila; Petty, Tom J; De Almeida, Victor; Nishimura, Taisuke; Joly, Jacques; Ferrer, Jean Luc; Halazonetis, Thanos D

    2009-09-01

    Microfluidics is a promising technology for the rapid identification of protein crystallization conditions. However, most of the existing systems utilize silicone elastomers as the chip material which, despite its many benefits, is highly permeable to water vapour. This limits the time available for protein crystallization to less than a week. Here, the use of a cyclic olefin homopolymer-based microfluidics system for protein crystallization and in situ X-ray diffraction is described. Liquid handling in this system is performed in 2 mm thin transparent cards which contain 500 chambers, each with a volume of 320 nl. Microbatch, vapour-diffusion and free-interface diffusion protocols for protein crystallization were implemented and crystals were obtained of a number of proteins, including chicken lysozyme, bovine trypsin, a human p53 protein containing both the DNA-binding and oligomerization domains bound to DNA and a functionally important domain of Arabidopsis Morpheus' molecule 1 (MOM1). The latter two polypeptides have not been crystallized previously. For X-ray diffraction analysis, either the cards were opened to allow mounting of the crystals on loops or the crystals were exposed to X-rays in situ. For lysozyme, an entire X-ray diffraction data set at 1.5 A resolution was collected without removing the crystal from the card. Thus, cyclic olefin homopolymer-based microfluidics systems have the potential to further automate protein crystallization and structural genomics efforts.

  6. Cyclic olefin homopolymer-based microfluidics for protein crystallization and in situ X-ray diffraction

    SciTech Connect

    Emamzadah, Soheila; Petty, Tom J.; De Almeida, Victor; Nishimura, Taisuke; Joly, Jacques; Ferrer, Jean-Luc; Halazonetis, Thanos D.

    2009-09-01

    A cyclic olefin homopolymer-based microfluidics system has been established for protein crystallization and in situ X-ray diffraction. Microfluidics is a promising technology for the rapid identification of protein crystallization conditions. However, most of the existing systems utilize silicone elastomers as the chip material which, despite its many benefits, is highly permeable to water vapour. This limits the time available for protein crystallization to less than a week. Here, the use of a cyclic olefin homopolymer-based microfluidics system for protein crystallization and in situ X-ray diffraction is described. Liquid handling in this system is performed in 2 mm thin transparent cards which contain 500 chambers, each with a volume of 320 nl. Microbatch, vapour-diffusion and free-interface diffusion protocols for protein crystallization were implemented and crystals were obtained of a number of proteins, including chicken lysozyme, bovine trypsin, a human p53 protein containing both the DNA-binding and oligomerization domains bound to DNA and a functionally important domain of Arabidopsis Morpheus’ molecule 1 (MOM1). The latter two polypeptides have not been crystallized previously. For X-ray diffraction analysis, either the cards were opened to allow mounting of the crystals on loops or the crystals were exposed to X-rays in situ. For lysozyme, an entire X-ray diffraction data set at 1.5 Å resolution was collected without removing the crystal from the card. Thus, cyclic olefin homopolymer-based microfluidics systems have the potential to further automate protein crystallization and structural genomics efforts.

  7. Speciation of Gold Nanoparticles by Ex Situ Extended X-ray Absorption Fine Structure and X-ray Absorption Near Edge Structure.

    PubMed

    Giorgetti, Marco; Aquilanti, Giuliana; Ballarin, Barbara; Berrettoni, Mario; Cassani, Maria Cristina; Fazzini, Silvia; Nanni, Daniele; Tonelli, Domenica

    2016-07-05

    A combined X-ray absorption near edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) methodology is here presented on a series of partially and fully reduced Au(III) samples. This allows monitoring the relative fraction of Au(III) and Au(0) in the studied samples, displaying a consistent and independent outcome. The strategy followed is based, for the first time, on two structural models that can be fitted simultaneously, and it evaluates the correlation among strongly correlated parameters such as coordination number and the Debye-Waller factor. The results of the present EXAFS and XANES approach can be extended to studies based on X-ray absorption spectroscopy experiments for the in situ monitoring of the formation of gold nanoclusters.

  8. Electrochemical flowcell for in-situ investigations by soft x-ray absorption and emission spectroscopy.

    PubMed

    Schwanke, C; Golnak, R; Xiao, J; Lange, K M

    2014-10-01

    A new liquid flow-cell designed for electronic structure investigations at the liquid-solid interface by soft X-ray absorption and emission spectroscopy is presented. A thin membrane serves simultaneously as a substrate for the working electrode and solid state samples as well as for separating the liquid from the surrounding vacuum conditions. In combination with counter and reference electrodes this approach allows in-situ studies of electrochemical deposition processes and catalytic reactions at the liquid-solid interface in combination with potentiostatic measurements. As model system in-situ monitoring of the deposition process of Co metal from a 10 mM CoCl2 aqueous solution by X-ray absorption and emission spectroscopy is presented.

  9. Electrochemical flowcell for in-situ investigations by soft x-ray absorption and emission spectroscopy

    SciTech Connect

    Schwanke, C.; Lange, K. M.; Golnak, R.; Xiao, J.

    2014-10-15

    A new liquid flow-cell designed for electronic structure investigations at the liquid-solid interface by soft X-ray absorption and emission spectroscopy is presented. A thin membrane serves simultaneously as a substrate for the working electrode and solid state samples as well as for separating the liquid from the surrounding vacuum conditions. In combination with counter and reference electrodes this approach allows in-situ studies of electrochemical deposition processes and catalytic reactions at the liquid-solid interface in combination with potentiostatic measurements. As model system in-situ monitoring of the deposition process of Co metal from a 10 mM CoCl{sub 2} aqueous solution by X-ray absorption and emission spectroscopy is presented.

  10. Two-dimensional in situ metrology of X-ray mirrors using the speckle scanning technique

    PubMed Central

    Wang, Hongchang; Kashyap, Yogesh; Laundy, David; Sawhney, Kawal

    2015-01-01

    In situ metrology overcomes many of the limitations of existing metrology techniques and is capable of exceeding the performance of present-day optics. A novel technique for precisely characterizing an X-ray bimorph mirror and deducing its two-dimensional (2D) slope error map is presented. This technique has also been used to perform fast optimization of a bimorph mirror using the derived 2D piezo response functions. The measured focused beam size was significantly reduced after the optimization, and the slope error map was then verified by using geometrical optics to simulate the focused beam profile. This proposed technique is expected to be valuable for in situ metrology of X-ray mirrors at synchrotron radiation facilities and in astronomical telescopes. PMID:26134795

  11. Two-dimensional in situ metrology of X-ray mirrors using the speckle scanning technique.

    PubMed

    Wang, Hongchang; Kashyap, Yogesh; Laundy, David; Sawhney, Kawal

    2015-07-01

    In situ metrology overcomes many of the limitations of existing metrology techniques and is capable of exceeding the performance of present-day optics. A novel technique for precisely characterizing an X-ray bimorph mirror and deducing its two-dimensional (2D) slope error map is presented. This technique has also been used to perform fast optimization of a bimorph mirror using the derived 2D piezo response functions. The measured focused beam size was significantly reduced after the optimization, and the slope error map was then verified by using geometrical optics to simulate the focused beam profile. This proposed technique is expected to be valuable for in situ metrology of X-ray mirrors at synchrotron radiation facilities and in astronomical telescopes.

  12. Development of in situ, at-wavelength metrology for soft x-ray nano-focusing

    SciTech Connect

    Yuan, Sheng Sam; Yashchuk, Valeriy V.; Goldberg, Kenneth A.; Celestre, Richard; McKinney, Wayne R.; Morrison, Gregory Y.; Warwick, Tony; Padmore, Howard A.

    2010-09-19

    At the Advanced Light Source (ALS), we are developing broadly applicable, high-accuracy, in situ, at-wavelength wavefront slope measurement techniques for Kirkpatrick-Baez (KB) mirror nano-focusing. We describe here details of the metrology beamline endstation, the at-wavelength tests, and an original alignment method that have already allowed us to precisely set a bendable KB mirror to achieve a FWHM focused spot size of ~;;120 nm, at 1-nm soft x-ray wavelength.

  13. Ablation of NIF Targets and Diagnostic Components by High Power Lasers and X-Rays from High Temperature Plasmas

    SciTech Connect

    Eder, D.C; Anderson, A.T.; Braun, D.G; Tobin, M.T.

    2000-04-19

    The National Ignition Facility (NIF) will consist of 192 laser beams that have a total energy of up to 1.8 MJ in the 3rd harmonic ({lambda} = 0.35 {micro}m) with the amount of 2nd harmonic and fundamental light depending on the pulse shape. Material near best focus of the 3rd harmonic light will be vaporized/ablated very rapidly, with a significant fraction of the laser energy converted into plasma x rays. Additional plasma x rays can come from imploding/igniting capsule inside Inertial Confinement Fusion (ICF) hohlraums. Material from outer portions of the target, diagnostic components, first-wall material, and optical components, are ablated by the plasma x rays. Material out to a radius of order 3 cm from target center is also exposed to a significant flux of 2nd harmonic and fundamental laser light. Ablation can accelerate the remaining material to high velocities if it has been fragmented or melted. In addition, the high velocity debris wind of the initially vaporized material pushes on the fragments/droplets and increases their velocity. The high velocity shrapnel fragments/droplets can damage the fused silica shields protecting the final optics in NIF. We discuss modeling efforts to calculate vaporization/ablation, x-ray generation, shrapnel production, and ways to mitigate damage to the shields.

  14. In Situ Soft X-ray Spectroscopy Characterization of Interfacial Phenomena in Energy Materials and Devices

    NASA Astrophysics Data System (ADS)

    Guo, Jinghua; Liu, Yi-Sheng; Kapilashrami, Mukes; Glans, Per-Anders; Bora, Debajeet; Braun, Artur; Velasco Vélez, Juan Jesús; Salmeron, Miquel; ALS/LBNL Team; EMPA, MSD/LBNL Collaboration

    2015-03-01

    Advanced energy technology arises from the understanding in basic science, thus rest in large on in-situ/operando characterization tools for observing the physical and chemical interfacial processes, which has been largely limited in a framework of thermodynamic and kinetic concepts or atomic and nanoscale. In many important energy systems such as energy conversion, energy storage and catalysis, advanced materials and functionality in devices are based on the complexity of material architecture, chemistry and interactions among constituents within. To understand and thus ultimately control the energy conversion and energy storage applications calls for in-situ/operando characterization tools. Soft X-ray spectroscopy offers a number of very unique features. We will present our development of the in-situ/operando soft X-ray spectroscopic tools of catalytic and electrochemical reactions in recent years, and reveal how to overcome the challenge that soft X-rays cannot easily peek into the high-pressure catalytic cells or liquid electrochemical cells. In this presentation a number of examples are given, including the nanocatalysts and the recent experiment performed for studying the hole generation in a specifically designed photoelectrochemical cell under operando conditions. The ALS is supported by the the U.S. Department of Energy.

  15. Portable apparatus for in situ x-ray diffraction and fluorescence analyses of artworks.

    PubMed

    Eveno, Myriam; Moignard, Brice; Castaing, Jacques

    2011-10-01

    A portable X-ray fluorescence/X-ray diffraction (XRF/XRD) system for artwork studies has been designed constructed and tested. It is based on Debye Scherrer XRD in reflection that takes advantage of many recent improvements in the handling of X-rays (polycapillary optics; advanced two-dimensional detection). The apparatus is based on a copper anode air cooled X-ray source, and the XRD analysis is performed on a 5-20 μm thick layer from the object surface. Energy dispersive XRF elemental analysis can be performed at the same point as XRD, giving elemental compositions that support the interpretation of XRD diagrams. XRF and XRD analyses were tested to explore the quality and the limits of the analytical technique. The XRD diagrams are comparable in quality with diagrams obtained with conventional laboratory equipment. The mineral identification of materials in artwork is routinely performed with the portable XRF-XRD system. Examples are given for ceramic glazes containing crystals and for paintings where the determination of pigments is still a challenge for nondestructive analysis. For instance, lead compounds that provide a variety of color pigments can be easily identified as well as a pigment such as lapis lazuli that is difficult to identify by XRF alone. More than 70 works of art have been studied in situ in museums, monuments, etc. In addition to ceramics and paintings, these works include bronzes, manuscripts, etc., which permit improvement in the comprehension of ancient artistic techniques.

  16. An in situ electrochemical soft X-ray spectromicroscopy investigation of Fe galvanically coupled to Au.

    PubMed

    Gianoncelli, A; Kaulich, B; Kiskinova, M; Prasciolu, M; Urzo, B D; Bozzini, B

    2011-06-01

    In this paper we report a pioneering electrochemical study of the galvanic coupling of Au and Fe in neutral aqueous solutions containing sulphate and fluoride ions, carried out by synchrotron-based in situ soft X-ray imaging and X-ray absorption microspectroscopy. The investigation was performed at the TwinMic X-ray Microscopy station at Elettra synchrotron facility combining X-ray imaging with μ-XAS with sub-micron lateral resolution. Using a purposely developed model thin-layer wet cell the morphology and chemical evolution of Fe electrodes in contact with aqueous solutions containing Na2SO4 and NaF have been investigated. The obtained results shed light on fundamental aspects regarding stability of Fe-based metallic bipolar plates in different electrochemical environments, an important issue for durability of polymer-electrolyte fuel cells. Imaging morphological features typical of the relevant electrochemical processes with chemical contrast, yields details on the spatial distribution and speciation of Fe resulting from corrosion of the Fe electrodes in the working fuel cells.

  17. An in situ real-time x-ray diffraction study of phase segregation in Au-Pt nanoparticles.

    PubMed

    Malis, O; Radu, M; Mott, D; Wanjala, B; Luo, J; Zhong, C-J

    2009-06-17

    In situ real-time x-ray diffraction was used to study phase segregation and coarsening of Au-Pt nanoparticles supported on silica powder, and porous alumina membranes. Contrary to the expectations from the bulk phase diagram, silica supported Au-Pt nanoparticles have an alloyed structure that is preserved even after extensive annealing at temperatures as high at 700 degrees C. In stark contrast, alumina supported Au-Pt nanoparticles exhibit a rich phase behaviour that is sensitive to alloy composition and the details of the synthesis process. In particular, low-density as-prepared Au(41)Pt(59) nanoparticles exhibit the signature of incipient phase segregation that develops into full phase separation during annealing at high temperature.

  18. Note: Experiments in hard x-ray chemistry: In situ production of molecular hydrogen and x-ray induced combustion

    SciTech Connect

    Pravica, Michael; Bai Ligang; Liu Yu; Galley, Martin; Robinson, John; Park, Changyong; Hatchett, David

    2012-03-15

    We have successfully loaded H{sub 2} into a diamond anvil cell at high pressure using the synchrotron x-ray induced decomposition of NH{sub 3}BH{sub 3}. In a second set of studies, radiation-assisted release of O{sub 2} from KCLO{sub 3}, H{sub 2} release from NH{sub 3}BH{sub 3}, and reaction of these gases in a mixture of the reactants to form liquid water using x-rays at ambient conditions was observed. Similar observations were made using a KCLO{sub 3} and NaBH{sub 4} mixture. Depending on reaction conditions, an explosive or far slower reaction producing water was observed.

  19. In situ Raman and X-ray spectroscopies to monitor microbial activities under high hydrostatic pressure.

    PubMed

    Oger, Phil M; Daniel, Isabelle; Picard, Aude

    2010-02-01

    Until recently, monitoring of cells and cellular activities at high hydrostatic pressure (HHP) was mainly limited to ex situ observations. Samples were analyzed prior to and following the depressurization step to evaluate the effect of the pressure treatment. Such ex situ measurements have several drawbacks: (i) it does not allow for kinetic measurements and (ii) the depressurization step often leads to artifactual measurements. Here, we describe recent advances in diamond anvil cell (DAC) technology to adapt it to the monitoring of microbial processes in situ. The modified DAC is asymmetrical, with a single anvil and a diamond window to improve imaging quality and signal collection. Using this novel DAC combined to Raman and X-ray spectroscopy, we monitored the metabolism of glucose by baker's yeast and the reduction of selenite by Agrobacterium tumefaciens in situ under HHP. In situ spectroscopy is also a promising tool to study piezophilic microorganisms.

  20. A portable molecular beam epitaxy system for in situ x-ray investigations at synchrotron beamlines.

    PubMed

    Slobodskyy, T; Schroth, P; Grigoriev, D; Minkevich, A A; Hu, D Z; Schaadt, D M; Baumbach, T

    2012-10-01

    A portable synchrotron molecular beam epitaxy (MBE) system is designed and applied for in situ investigations. The growth chamber is equipped with all the standard MBE components such as effusion cells with shutters, main shutter, cooling shroud, manipulator, reflection high energy electron diffraction setup, and pressure gauges. The characteristic feature of the system is the beryllium windows which are used for in situ x-ray measurements. An UHV sample transfer case allows in vacuo transfer of samples prepared elsewhere. We describe the system design and demonstrate its performance by investigating the annealing process of buried InGaAs self-organized quantum dots.

  1. A portable molecular beam epitaxy system for in situ x-ray investigations at synchrotron beamlines

    SciTech Connect

    Slobodskyy, T.; Schroth, P.; Grigoriev, D.; Minkevich, A. A.; Baumbach, T.; Hu, D. Z.; Schaadt, D. M.

    2012-10-15

    A portable synchrotron molecular beam epitaxy (MBE) system is designed and applied for in situ investigations. The growth chamber is equipped with all the standard MBE components such as effusion cells with shutters, main shutter, cooling shroud, manipulator, reflection high energy electron diffraction setup, and pressure gauges. The characteristic feature of the system is the beryllium windows which are used for in situ x-ray measurements. An UHV sample transfer case allows in vacuo transfer of samples prepared elsewhere. We describe the system design and demonstrate its performance by investigating the annealing process of buried InGaAs self-organized quantum dots.

  2. High-temperature differential emission measure and altitude variations in the temperature and density of solar flare coronal X-ray sources

    NASA Astrophysics Data System (ADS)

    Jeffrey, Natasha L. S.; Kontar, Eduard P.; Dennis, Brian R.

    2015-12-01

    The detailed knowledge of plasma heating and acceleration region properties presents a major observational challenge in solar flare physics. Using the Ramaty High Energy Solar Spectroscopic Imager (RHESSI), the high temperature differential emission measure, DEM(T), and the energy-dependent spatial structure of solar flare coronal sources were studied quantitatively. The altitude of the coronal X-ray source was observed to increase with energy by ~+0.2 arcsec/keV between 10 and 25 keV. Although an isothermal model can fit the thermal X-ray spectrum observed by RHESSI, such a model cannot account for the changes in altitude, and multi-thermal coronal sources are required where the temperature increases with altitude. For the first time, we show how RHESSI imaging information can be used to constrain the DEM(T) of a flaring plasma. We developed a thermal bremsstrahlung X-ray emission model with inhomogeneous temperature and density distributions to simultaneously reproduce i) DEM(T); ii) altitude as a function of energy; and iii) vertical extent of the flaring coronal source versus energy. We find that the temperature-altitude gradient in the region is ~+0.08 keV/arcsec (~1.3 MK/Mm). Similar altitude-energy trends in other flares suggest that the majority of coronal X-ray sources are multi-thermal and have strong vertical temperature and density gradients with a broad DEM(T).

  3. Development of a speckle-based portable device for in situ metrology of synchrotron X-ray mirrors

    PubMed Central

    Kashyap, Yogesh; Wang, Hongchang; Sawhney, Kawal

    2016-01-01

    A portable device for in situ metrology of synchrotron X-ray mirrors based on the near-field speckle scanning technique has been developed. Ultra-high angular sensitivity is achieved by scanning a piece of abrasive paper or filter membrane in the X-ray beam. In addition to the compact setup and ease of implementation, a user-friendly graphical user interface has been developed to ensure that optimizing active X-ray mirrors is simple and fast. The functionality and feasibility of this device have been demonstrated by characterizing and optimizing X-ray mirrors. PMID:27577767

  4. Development of a speckle-based portable device for in situ metrology of synchrotron X-ray mirrors.

    PubMed

    Kashyap, Yogesh; Wang, Hongchang; Sawhney, Kawal

    2016-09-01

    A portable device for in situ metrology of synchrotron X-ray mirrors based on the near-field speckle scanning technique has been developed. Ultra-high angular sensitivity is achieved by scanning a piece of abrasive paper or filter membrane in the X-ray beam. In addition to the compact setup and ease of implementation, a user-friendly graphical user interface has been developed to ensure that optimizing active X-ray mirrors is simple and fast. The functionality and feasibility of this device have been demonstrated by characterizing and optimizing X-ray mirrors.

  5. High-resolution hard x-ray spectroscopy of high-temperature plasmas using an array of quantum microcalorimeters.

    PubMed

    Thorn, Daniel B; Gu, Ming F; Brown, Greg V; Beiersdorfer, Peter; Porter, F Scott; Kilbourne, Caroline A; Kelley, Richard L

    2008-10-01

    Quantum microcalorimeters show promise in being able to fully resolve x-ray spectra from heavy highly charged ions, such as would be found in hot plasmas with temperatures in excess of 50 keV. Quantum microcalorimeter arrays are able to achieve this as they have a high-resolving power and good effective quantum efficiency for hard x-ray photons up to 60 keV. To demonstrate this, we present a measurement using an array of thin HgTe quantum microcalorimeters to measure the K-shell spectrum of hydrogenlike through carbonlike praseodymium (Z=57). With this device we are able to attain a resolving power, E/DeltaE, of 1000 at a photon energy of 37 keV.

  6. X-ray Spectropolarimetry of high temperature and high density plasma supported by LLNL Electron Beam Ion Trap Experiments

    SciTech Connect

    Shlyaptseva, A S; Kantsyrev, V L; Ouart, N D; Fedin, D A; Neill, P; Harris, C; Hamasha, S M; Hansen, S B; Safronova, U I; Beiersdorfer, P; Petrashen, A G

    2004-03-15

    Plasma polarization spectroscopy work done by our group since the 3rd US-Japan PPS Workshop is overviewed. Theoretically, the polarization dependence on various electron distribution functions for He-like, Ne-like, and Ni-like x-ray transitions for a wide range of Z has been investigated. In particular, this study was focused on the polarization dependence for monoenergetic and steep electron distribution functions. The diagnostically important spectral lines and features of K-, L-, and M-shell ions were identified which can be used in x-ray spectropolarimetry of plasma. Importance of polarization-sensitive LLNL Electron Beam Ion Trap data is emphasized. The results of the UNR polarization-sensitive Ti and Mo x-pinch experiments are discussed.

  7. In Situ Mineralogical Analysis of Planetary Materials Using X-Ray Diffraction and X-Ray Fluorescence

    NASA Technical Reports Server (NTRS)

    Sarrazin, P.; Blake, D.; Vaniman, D.; Chang, Sherwood (Technical Monitor)

    1996-01-01

    Remote observations of Mars have led scientists to believe that its early climate was similar to that of the early Earth, having had abundant liquid water and a dense atmosphere. One of the most fascinating questions of recent times is whether simple bacterial life developed on Mars (as it did on the Earth) during this early element period. Analyses of SNC meteorites have broadened considerably our knowledge of the chemistry of certain types of Martian rocks, underscoring the tantalizing possibility of early hydrothermal systems and even of ancient bacterial life. Detailed analyses of SNC meteorites in Terrestrial laboratories utilize the most sophisticated organic, isotopic and microscopic techniques in existence. Indeed; it is unlikely that the key biogenic indicators used in McKay et al (ibid) could be identified by a remote instrument on the surface of Mars. As a result, it is probable that any robotic search for evidence of an ancient Martian biosphere will have as its focus the identification of key minerals in likely host rocks rather than the direct detection of organic or isotopic biomarkers. Even on a sample return mission, mineralogical screening will be utilized to choose the most likely candidate rocks. X-ray diffraction (XRD) is the only technique that can provide a direct determination of the crystal structures of the phases present within a sample. When many different crystalline phases are present, quantitative analysis is better constrained if used in conjunction with a determination of elemental composition, obtainable by X-ray fluorescence (XRF) using the same X-ray source as for XRD. For planetary surface analysis, a remote instrument combining XRD and XRF could be used for mineralogical characterization of both soils and rocks. We are designing a remote XRD/XRF instrument with this objective in mind. The instrument concept pays specific attention to constraints in sample preparation, weight, volume, power, etc. Based on the geometry of a

  8. Synchrotron x-ray microdiffraction reveals intrinsic structural features of amyloid deposits in situ.

    PubMed

    Briki, Fatma; Vérine, Jérôme; Doucet, Jean; Bénas, Philippe; Fayard, Barbara; Delpech, Marc; Grateau, Gilles; Riès-Kautt, Madeleine

    2011-07-20

    Amyloidoses are increasingly recognized as a major public health concern in Western countries. All amyloidoses share common morphological, structural, and tinctorial properties. These consist of staining by specific dyes, a fibrillar aspect in electron microscopy and a typical cross-β folding in x-ray diffraction patterns. Most studies that aim at deciphering the amyloid structure rely on fibers generated in vitro or extracted from tissues using protocols that may modify their intrinsic structure. Therefore, the fine details of the in situ architecture of the deposits remain unknown. Here, we present to our knowledge the first data obtained on ex vivo human renal tissue sections using x-ray microdiffraction. The typical cross-β features from fixed paraffin-embedded samples are similar to those formed in vitro or extracted from tissues. Moreover, the fiber orientation maps obtained across glomerular sections reveal an intrinsic texture that is correlated with the glomerulus morphology. These results are of the highest importance to understanding the formation of amyloid deposits and are thus expected to trigger new incentives for tissue investigation. Moreover, the access to intrinsic structural parameters such as fiber size and orientation using synchrotron x-ray microdiffraction, could provide valuable information concerning in situ mechanisms and deposit formation with potential benefits for diagnostic and therapeutic purposes. Copyright © 2011 Biophysical Society. Published by Elsevier Inc. All rights reserved.

  9. In situ surface/interface x-ray diffractometer for oxide molecular beam epitaxy

    DOE PAGES

    Lee, J. H.; Tung, I. C.; Chang, S. -H.; ...

    2016-01-05

    In situ studies of oxide molecular beam epitaxy by synchrotron x-ray scattering has been made possible by upgrading an existing UHV/molecular beam epitaxy (MBE) six-circle diffractometer system. For oxide MBE growth, pure ozone delivery to the chamber has been made available, and several new deposition sources have been made available on a new 12 in. CF (ConFlat, a registered trademark of Varian, Inc.) flange. X-ray diffraction has been used as a major probe for film growth and structures for the system. In the original design, electron diffraction was intended for the secondary diagnostics available without the necessity of the x-raymore » and located at separate positions. Deposition of films was made possible at the two diagnostic positions. And, the aiming of the evaporation sources is fixed to the point between two locations. Ozone can be supplied through two separate nozzles for each location. Also two separate thickness monitors are installed. Finally, additional features of the equipment are also presented together with the data taken during typical oxide film growth to illustrate the depth of information available via in situ x-ray techniques.« less

  10. High-temperature in situ crystallographic observation of reversible gas sorption in impermeable organic cages.

    PubMed

    Baek, Seung Bin; Moon, Dohyun; Graf, Robert; Cho, Woo Jong; Park, Sung Woo; Yoon, Tae-Ung; Cho, Seung Joo; Hwang, In-Chul; Bae, Youn-Sang; Spiess, Hans W; Lee, Hee Cheon; Kim, Kwang S

    2015-11-17

    Crystallographic observation of adsorbed gas molecules is a highly difficult task due to their rapid motion. Here, we report the in situ single-crystal and synchrotron powder X-ray observations of reversible CO2 sorption processes in an apparently nonporous organic crystal under varying pressures at high temperatures. The host material is formed by hydrogen bond network between 1,3,5-tris-(4-carboxyphenyl)benzene (H3BTB) and N,N-dimethylformamide (DMF) and by π-π stacking between the H3BTB moieties. The material can be viewed as a well-ordered array of cages, which are tight packed with each other so that the cages are inaccessible from outside. Thus, the host is practically nonporous. Despite the absence of permanent pathways connecting the empty cages, they are permeable to CO2 at high temperatures due to thermally activated molecular gating, and the weakly confined CO2 molecules in the cages allow direct detection by in situ single-crystal X-ray diffraction at 323 K. Variable-temperature in situ synchrotron powder X-ray diffraction studies also show that the CO2 sorption is reversible and driven by temperature increase. Solid-state magic angle spinning NMR defines the interactions of CO2 with the organic framework and dynamic motion of CO2 in cages. The reversible sorption is attributed to the dynamic motion of the DMF molecules combined with the axial motions/angular fluctuations of CO2 (a series of transient opening/closing of compartments enabling CO2 molecule passage), as revealed from NMR and simulations. This temperature-driven transient molecular gating can store gaseous molecules in ordered arrays toward unique collective properties and release them for ready use.

  11. High-temperature in situ crystallographic observation of reversible gas sorption in impermeable organic cages

    PubMed Central

    Baek, Seung Bin; Moon, Dohyun; Graf, Robert; Cho, Woo Jong; Park, Sung Woo; Yoon, Tae-Ung; Cho, Seung Joo; Hwang, In-Chul; Bae, Youn-Sang; Spiess, Hans W.; Lee, Hee Cheon; Kim, Kwang S.

    2015-01-01

    Crystallographic observation of adsorbed gas molecules is a highly difficult task due to their rapid motion. Here, we report the in situ single-crystal and synchrotron powder X-ray observations of reversible CO2 sorption processes in an apparently nonporous organic crystal under varying pressures at high temperatures. The host material is formed by hydrogen bond network between 1,3,5-tris-(4-carboxyphenyl)benzene (H3BTB) and N,N-dimethylformamide (DMF) and by π–π stacking between the H3BTB moieties. The material can be viewed as a well-ordered array of cages, which are tight packed with each other so that the cages are inaccessible from outside. Thus, the host is practically nonporous. Despite the absence of permanent pathways connecting the empty cages, they are permeable to CO2 at high temperatures due to thermally activated molecular gating, and the weakly confined CO2 molecules in the cages allow direct detection by in situ single-crystal X-ray diffraction at 323 K. Variable-temperature in situ synchrotron powder X-ray diffraction studies also show that the CO2 sorption is reversible and driven by temperature increase. Solid-state magic angle spinning NMR defines the interactions of CO2 with the organic framework and dynamic motion of CO2 in cages. The reversible sorption is attributed to the dynamic motion of the DMF molecules combined with the axial motions/angular fluctuations of CO2 (a series of transient opening/closing of compartments enabling CO2 molecule passage), as revealed from NMR and simulations. This temperature-driven transient molecular gating can store gaseous molecules in ordered arrays toward unique collective properties and release them for ready use. PMID:26578758

  12. In situ X-ray diffraction study on the growth kinetics of NiO nanoparticles.

    PubMed

    Meneses, C T; Almeida, J M A; Sasaki, J M

    2010-05-01

    The growth kinetics of NiO nanoparticles have been studied by in situ X-ray diffraction using two detection systems (conventional and imaging plate). NiO nanoparticles were formed by thermal decomposition after heating of an amorphous compound formed by the coprecipitation method. It was found that the detection method using an imaging plate is more efficient than the conventional detection mode for observing changes in the crystallite growth of nanocrystalline materials. Studies have been carried out to investigate the effects of the heating rates on the particles growth. The results suggest that the growth process of the particles is accelerated when the samples are treated at low heating rates. The evolution of particles size and the diffusion coefficient obtained from X-ray powder diffraction patterns are discussed in terms of the thermal conditions for the two types of detection.

  13. Diffraction imaging for in situ characterization of double-crystal X-ray monochromators

    SciTech Connect

    Stoupin, Stanislav; Liu, Zunping; Heald, Steve M.; Brewe, Dale; Meron, Mati

    2015-10-30

    In this paper, imaging of the Bragg-reflected X-ray beam is proposed and validated as an in situ method for characterization of the performance of double-crystal monochromators under the heat load of intense synchrotron radiation. A sequence of images is collected at different angular positions on the reflectivity curve of the second crystal and analyzed. The method provides rapid evaluation of the wavefront of the exit beam, which relates to local misorientation of the crystal planes along the beam footprint on the thermally distorted first crystal. The measured misorientation can be directly compared with the results of finite element analysis. Finally, the imaging method offers an additional insight into the local intrinsic crystal quality over the footprint of the incident X-ray beam.

  14. In situ x-ray diffraction measurements of the capillary fountain jet produced via ultrasonic atomization

    NASA Astrophysics Data System (ADS)

    Yano, Yohko F.; Douguchi, Junya; Kumagai, Atsushi; Iijima, Takao; Tomida, Yukinobu; Miyamoto, Toshiaki; Matsuura, Kazuo

    2006-11-01

    In situ x-ray diffraction measurements were carried out for investigating the liquid structure in the ultrasonic fountain jet to consider the mechanism of the "ultrasonic ethanol separation" reported by Sato et al. [J. Chem. Phys. 114, 2382 (2001)]. For pure liquids (water and ethanol), it was found that the high frequency ultrasound does not affect the liquid structure microscopically. For the 20mol% ethanol-water mixture, the estimated ethanol mole fraction in the ultrasonic fountain jet by using the position of the main maximum in the x-ray diffraction profile coincided with that in the reservoir. This result suggests that the ethanol separation is not caused by any distorted liquid structure under the ultrasound irradiation and occurs when or after the generation of the liquid droplet mist.

  15. In situ x-ray diffraction measurements of the capillary fountain jet produced via ultrasonic atomization.

    PubMed

    Yano, Yohko F; Douguchi, Junya; Kumagai, Atsushi; Iijima, Takao; Tomida, Yukinobu; Miyamoto, Toshiaki; Matsuura, Kazuo

    2006-11-07

    In situ x-ray diffraction measurements were carried out for investigating the liquid structure in the ultrasonic fountain jet to consider the mechanism of the "ultrasonic ethanol separation" reported by Sato et al. [J. Chem. Phys. 114, 2382 (2001)]. For pure liquids (water and ethanol), it was found that the high frequency ultrasound does not affect the liquid structure microscopically. For the 20 mol % ethanol-water mixture, the estimated ethanol mole fraction in the ultrasonic fountain jet by using the position of the main maximum in the x-ray diffraction profile coincided with that in the reservoir. This result suggests that the ethanol separation is not caused by any distorted liquid structure under the ultrasound irradiation and occurs when or after the generation of the liquid droplet mist.

  16. Solution spectroelectrochemical cell for in situ X-ray absorption fine structure

    SciTech Connect

    Antonio, M.R.; Soderholm, L.; Song, I.

    1995-06-12

    A purpose-built spectroelectrochemical cell for in situ fluorescence XAFS (X-ray Absorption Fine Structure) measurements of bulk solution species during constant-potential electrolysis is described. The cell performance was demonstrated by the collection of europium L{sub 3}-edge XANES (X-ray Absorption Near Edge Structure) throughout the course of electrolysis of an aqueous solution of EuCl{sub 3}{center_dot}6H{sub 2}O in 1 M H{sub 2}SO{sub 4}. The europium L{sub 3}-edge resonances reported here for the Eu{sup III} and Eu{sup II} ions demonstrate that their 2p{sub 3/2} {yields} 5d electronic transition probabilities are not the same.

  17. In situ/Operando studies of electrocatalysts using hard X-ray spectroscopy

    DOE PAGES

    Lassalle-Kaiser, Benedikt; Gul, Sheraz; Kern, Jan; ...

    2017-05-02

    This review focuses on the use of X-ray absorption and emission spectroscopy techniques using hard X-rays to study electrocatalysts under in situ/operando conditions. The importance and the versatility of methods in the study of electrodes in contact with the electrolytes are described, when they are being cycled through the catalytic potentials during the progress of the oxygen-evolution, oxygen reduction and hydrogen evolution reactions. The catalytic oxygen evolution reaction is illustrated with examples using three oxides, Co, Ni and Mn, and two sulfides, Mo and Co. These are used as examples for the hydrogen evolution reaction. A bimetallic, bifunctional oxygen evolvingmore » and oxygen reducing Ni/Mn oxide is also presented. The various advantages and constraints in the use of these techniques and the future outlook are discussed.« less

  18. In situ X-ray diffraction studies of (de)lithiation mechanism in silicon nanowire anodes.

    PubMed

    Misra, Sumohan; Liu, Nian; Nelson, Johanna; Hong, Seung Sae; Cui, Yi; Toney, Michael F

    2012-06-26

    Silicon is a promising anode material for Li-ion batteries due to its high theoretical specific capacity. From previous work, silicon nanowires (SiNWs) are known to undergo amorphorization during lithiation, and no crystalline Li-Si product has been observed. In this work, we use an X-ray transparent battery cell to perform in situ synchrotron X-ray diffraction on SiNWs in real time during electrochemical cycling. At deep lithiation voltages the known metastable Li(15)Si(4) phase forms, and we show that avoiding the formation of this phase, by modifying the SiNW growth temperature, improves the cycling performance of SiNW anodes. Our results provide insight on the (de)lithiation mechanism and a correlation between phase evolution and electrochemical performance for SiNW anodes.

  19. In situ compressive damage of cement paste characterized by lab source X-ray computer tomography

    SciTech Connect

    Wan, Keshu; Xue, Xiaobo

    2013-08-15

    This paper aims at illustrating the potential of lab source X-ray CT for studying the damage behavior of cement based materials through in situ load experiments. This approach permits quantifying the microstructure prior and during loading. The load damage is separated from the specimen deformation using an image interpolation method. A quantitative relationship between external load and internal specimen damage is analyzed using the statistical information of gray scale values of the CT data. Local damage degrees are defined on 3D subset, and the 3D spatial distribution of damage information is clarified in this research. - Highlights: • On line damage is characterized by lab source X-ray CT. • Loading damage is separated with the specimen deformation. • Local damage is analyzed using gray scale values of the CT data. • 3D spatial distribution of the local damage information is clarified.

  20. Diffraction imaging for in situ characterization of double-crystal X-ray monochromators

    DOE PAGES

    Stoupin, Stanislav; Liu, Zunping; Heald, Steve M.; ...

    2015-10-30

    In this paper, imaging of the Bragg-reflected X-ray beam is proposed and validated as an in situ method for characterization of the performance of double-crystal monochromators under the heat load of intense synchrotron radiation. A sequence of images is collected at different angular positions on the reflectivity curve of the second crystal and analyzed. The method provides rapid evaluation of the wavefront of the exit beam, which relates to local misorientation of the crystal planes along the beam footprint on the thermally distorted first crystal. The measured misorientation can be directly compared with the results of finite element analysis. Finally,more » the imaging method offers an additional insight into the local intrinsic crystal quality over the footprint of the incident X-ray beam.« less

  1. Instrument for x-ray absorption spectroscopy with in situ electrical control characterizations

    SciTech Connect

    Huang, Chun-Chao; Chang, Shu-Jui; Yang, Chao-Yao; Tseng, Yuan-Chieh; Chou, Hsiung

    2013-12-15

    We report a synchrotron-based setup capable of performing x-ray absorption spectroscopy and x-ray magnetic circular dichroism with simultaneous electrical control characterizations. The setup can enable research concerning electrical transport, element- and orbital-selective magnetization with an in situ fashion. It is a unique approach to the real-time change of spin-polarized electronic state of a material/device exhibiting magneto-electric responses. The performance of the setup was tested by probing the spin-polarized states of cobalt and oxygen of Zn{sub 1-x}Co{sub x}O dilute magnetic semiconductor under applied voltages, both at low (∼20 K) and room temperatures, and signal variations upon the change of applied voltage were clearly detected.

  2. Analysis of heat-affected zone phase transformations using in situ spatially resolved x-ray diffraction with synchrotron radiation

    SciTech Connect

    Elmer, J.W.; Wong, J.; Froeba, M.; Waide, P.A.; Larson, E.M.

    1996-03-01

    Spatially resolved X-ray diffraction (SRXRD) consists of producing a submillimeter size X-ray beam from an intense synchrotron radiation source to perform real-time diffraction measurements on solid materials. This technique was used int his study to investigate the crystal phases surrounding a liquid weld pool in commercial purity titanium and to determine the location of the phase boundary separating the high-temperature body-centered-cubic (bcc) {beta} phase from the low-temperature hexagonal-close-packed (hcp) {alpha} phase. The experiments were carried out at the Stanford Synchrotron Radiation Laboratory (SSRL) using a 0.25 x 0.50 mm X-ray probe that could be positioned with 10-{micro}m precision on the surface of a quasistationary gas tungsten arc weld (GTAW). The SRXRD results showed characteristic hcp, bcc, and liquid diffraction patterns at various points along the sample, starting from the base metal through the heat-affected zone (HAZ) and into the weld pool, respectively. Analyses of the SRXRD data show the coexistence of bcc and hcp phases in the partially transformed (outer) region of the HAZ and single-phase bcc in the fully transformed (inner) region of the HAZ. Postweld metallographic examinations of the HAZ, combined with a conduction-based thermal model of the weld, were correlated with the SRXRD results. Finally, analysis of the diffraction intensities of the hcp and bcc phases was performed on the SRXRD data to provide additional information about the microstructural conditions that may exist in the HAZ at temperature during welding. This work represents the first direct in situ mapping of phase boundaries in fusion welds.

  3. In situ characterization of Grade 92 steel during tensile deformation using concurrent high energy X-ray diffraction and small angle X-ray scattering

    NASA Astrophysics Data System (ADS)

    Wang, Leyun; Li, Meimei; Almer, Jonathan

    2013-09-01

    The tensile deformation in Grade 92 steel was studied in situ using simultaneous high energy X-ray diffraction (HE-XRD), radiography, and small angle X-ray scattering (SAXS) at room temperature (RT), 400, and 650 °C. Temperature-dependent elastic properties, i.e. Young's modulus and Poisson's ratio, were measured for α-Fe matrix, M23C6 and Nb(C,N) phases in various crystallographic orientation. Significant differences in the evolution of lattice strain, peak broadening/sharpening, and void development in the α-Fe matrix, M23C6 and Nb(C,N) precipitates revealed markedly different deformation and damage mechanisms at low and high temperature in the alloy. The strengthening effect of each type of precipitates measured by lattice strain agrees with the dislocation pile-up model at room temperature, while a different dislocation behavior was observed at 650 °C. Void volume fraction as a function of strain measured by SAXS can be described by a classic void nucleation and growth model at room temperature but not at 650 °C, implying a different damage process at high temperature. The ultimate tensile strength is ordered as RT > 400 °C > 650 °C; strain to failure is ordered as 650 °C > RT > 400 °C. For the 650 °C test, there was a long softening stage between the UTS and specimen necking. M23C6 and Nb(C,N) precipitates were identified in the Fe matrix. At RT and 400 °C, apparent load transfer from the matrix to the precipitates took place after the matrix's early yielding. Measured von Mises stresses in the precipitates can be quantitatively explained using the established models of precipitate strengthening. Increase of dislocation density with deformation caused peak broadening in both matrix and precipitates. At 650 °C, load transfer was much less, and peak broadening was also largely subdued at 650 °C. Anisotropy of lattice strains was observed both in the matrix and precipitates. The elastic modulus of Fe (2 0 0) is lower than Fe (2 1 1) and Fe (2 2 0

  4. Beamline electrostatic levitator for in situ high energy x-ray diffraction studies of levitated solids and liquids

    SciTech Connect

    Gangopadhyay, A.K.; Lee, G.W.; Kelto, K.F.; Rogers, J.R.; Goldman, A.I.; Robinson, D.S.; Rathz, T.J.; Hyers, R.W.

    2010-07-19

    Determinations of the phase formation sequence, crystal structures and the thermo-physical properties of materials at high temperatures are hampered by contamination from the sample container and environment. Containerless processing techniques, such as electrostatic (ESL), electromagnetic, aerodynamic, and acoustic levitation, are most suitable for these studies. An adaptation of ESL for in situ structural studies of a wide range of materials using high energy (30-130 keV) x rays at a synchrotron source is described here. This beamline ESL (BESL) allows the in situ determination of the atomic structures of equilibrium solid and liquid phases, undercooled liquids and time-resolved studies of solid-solid and liquid-solid phase transformations. The use of area detectors enables the rapid acquisition of complete diffraction patterns over a wide range (0.5-14 {angstrom}{sup -1}) of reciprocal space. The wide temperature range (300-2500 K), containerless processing environment under high vacuum (10{sup -7}-10{sup -8} Torr), and fast data acquisition capability, make BESL particularly well suited for phase stability studies of high temperature solids and liquids. An additional, but important, feature of BESL is the capability for simultaneous measurements of a host of thermo-physical properties including the specific heat, enthalpy of transformation, solidus and liquidus temperatures, density, viscosity, and surface tension, all on the same sample during the structural measurements.

  5. In Situ Solid-State Reactions Monitored by X-ray Absorption Spectroscopy: Temperature-Induced Proton Transfer Leads to Chemical Shifts.

    PubMed

    Stevens, Joanna S; Walczak, Monika; Jaye, Cherno; Fischer, Daniel A

    2016-10-24

    The dramatic colour and phase alteration with the solid-state, temperature-dependent reaction between squaric acid and 4,4'-bipyridine has been probed in situ with X-ray absorption spectroscopy. The electronic and chemical sensitivity to the local atomic environment through chemical shifts in the near-edge X-ray absorption fine structure (NEXAFS) revealed proton transfer from the acid to the bipyridine base through the change in nitrogen protonation state in the high-temperature form. Direct detection of proton transfer coupled with structural analysis elucidates the nature of the solid-state process, with intermolecular proton transfer occurring along an acid-base chain followed by a domino effect to the subsequent acid-base chains, leading to the rapid migration along the length of the crystal. NEXAFS thereby conveys the ability to monitor the nature of solid-state chemical reactions in situ, without the need for a priori information or long-range order.

  6. Fiducial marker application method for position alignment of in situ multimodal x-ray experiments and reconstructions

    SciTech Connect

    Shade, Paul A.; Menasche, David B; Bernier, Joel V.; Kenesei, Peter; Park, Jun-Sang; Suter, Robert; Schuren, Jay C.; Turner, Todd J.

    2016-04-01

    An evolving suite of X-ray characterization methods are presently available to the materials community, providing a great opportunity to gain new insight into material behavior and provide critical validation data for materials models. Two critical and related issues are sample repositioning during an in situ experiment and registration of multiple data sets after the experiment. To address these issues, a method is described which utilizes a focused ion-beam scanning electron microscope equipped with a micromanipulator to apply gold fiducial markers to samples for X-ray measurements. The method is demonstrated with a synchrotron X-ray experiment involving in situ loading of a titanium alloy tensile specimen.

  7. X-Ray Diffraction and Fluorescence Measurements for In-situ Planetary Instruments

    NASA Astrophysics Data System (ADS)

    Hansford, G.; Hill, K. S.; Vernon, D.; Ambrosi, R. M.; Bridges, J.; Hutchinson, I.

    2010-12-01

    The X-Ray Diffraction (XRD) instruments are core components of the forthcoming NASA Mars Science Laboratory (MSL) and ESA/NASA EXOMARS missions and will provide the first demonstrations of an XRF/XRD instrument’s capabilities in-situ on an extraterrestrial planetary surface. The University of Leicester team is part of the Italy-UK collaboration that is responsible for building the ExoMars X-Ray Diffraction instrument, Mars XRD. The ExoMars X-ray diffraction instrument incorporates an 55-Fe radioisotope source and three fixed-position CCDs to simultaneously acquire an X-Ray fluorescence spectrum and a diffraction pattern providing a measurement of both elemental and mineralogical composition [1]. The CCDs cover an angular range from 6 to 65-deg enabling the analysis of silicates, from clays, or other phyllosilicates characterised by varying d-spacings, to oxides, and carbonates or evaporites. The identification of hydrous minerals may help identify past Martian hydrothermal systems capable of preserving traces of life. Here we present some initial findings from XRF and XRD tests carried out at the University of Leicester using an 55-Fe source and X-ray sensitive CCD [1]. The XRD/XRD test system consists of a single CCD on a motorised arm, an 55-Fe X-ray source, source collimator and a sample table which approximately replicate the reflection geometry of the XRD instrument. It was used to test geological reference standard materials and Martian analogues. Incidence angle and CCD angles on both the diffraction and fluorescence results were evaluated. A key area of interest is the effect of sample roughness on the XRD/XRF results. We present results from testing pressed powder pellet samples of varying surface roughness, and a comparison with model results [2]. So far we have found that increased roughness causes a reduced intensity at lower take-off angles. Several methods for measuring surface roughness of the samples have been used including an Alicona Infinite

  8. [Application of in situ micro energy dispersive X-ray fluorescence analysis in mineralogy].

    PubMed

    Yang, Hai; Ge, Liang-Quan; Gu, Yi; Zhang, Qing-Xian; Xiong, Sheng-Qing

    2013-11-01

    Thirteen rock samples were collected for studying the variation of element content in the mineral during the alteration process from Xinjiang, China. The IED-6000 in situ micro energy dispersive X-ray fluorescence developed by CDUT was applied to get chemical and physical data from minerals. The non-destructive spectrometer is based on a low-power Mo-anode X-ray tube and a Si-PIN peltier cooled X-ray detector. The unique design of the tube's probe allows very close coupling of polycapillary and makes the use of micro-area measurement feasible and efficient. The spectrometer can be integrated into any microscope for analysis. The long axis diameter of beam spot is about 110 microm. According to micro-EDXRF measurement, the tetrahedrite was corrected to pyrite, improving the efficiency and accuracy of the mineral identification. The feldspar of mineralized rock sample is rich in Cu and Zn which can be used as prospecting indicator elements. Element content of Cr, Mn and Co shows negative correlation with the degree of mineralization.

  9. Fiber-optic based in situ atomic spectroscopy for manufacturing of x-ray optics

    NASA Astrophysics Data System (ADS)

    Atanasoff, George; Metting, Christopher J.; von Bredow, Hasso

    2016-09-01

    The manufacturing of multilayer Laue (MLL) components for X-ray optics by physical vapor deposition (PVD) requires high precision and accuracy that presents a significant process control challenge. Currently, no process control system provides the accuracy, long-term stability and broad capability for adoption in the manufacturing of X-ray optics. In situ atomic absorption spectroscopy is a promising process control solution, capable of monitoring the deposition rate and chemical composition of extremely thin metal silicide films during deposition and overcoming many limitations of the traditional methods. A novel in situ PVD process control system for the manufacturing of high-precision thin films, based on combined atomic absorption/emission spectrometry in the vicinity of the deposited substrate, is described. By monitoring the atomic concentration in the plasma region independently from the film growth on the deposited substrate, the method allows deposition control of extremely thin films, compound thin films and complex multilayer structures. It provides deposition rate and film composition measurements that can be further utilized for dynamic feedback process control. The system comprises a reconfigurable hardware module located outside the deposition chamber with hollow cathode light sources and a fiber-optic-based frame installed inside the deposition chamber. Recent experimental results from in situ monitoring of Al and Si thin films deposited by DC and RF magnetron sputtering at a variety of plasma conditions and monitoring configurations are presented. The results validate the operation of the system in the deposition of compound thin films and provide a path forward for use in manufacturing of X-Ray optics.

  10. In situ X-ray pair distribution function analysis of geopolymer gel nanostructure formation kinetics.

    PubMed

    White, Claire E; Provis, John L; Bloomer, Breaunnah; Henson, Neil J; Page, Katharine

    2013-06-14

    With the ever-increasing environmentally-driven demand for technologically advanced structural materials, geopolymer cement is fast becoming a viable alternative to traditional cements due to its proven engineering characteristics and the reduction in CO2 emitted during manufacturing (as much as 80% less CO2 emitted in manufacture, compared to ordinary Portland cement). Nevertheless, much remains unknown regarding the kinetics of reaction responsible for nanostructural evolution during the geopolymerisation process. Here, in situ X-ray total scattering measurements and pair distribution function (PDF) analysis are used to quantify the extent of reaction as a function of time for alkali-activated metakaolin/slag geopolymer binders, including the impact of various activators (alkali hydroxide/silicate) on the kinetics of the geopolymerisation reaction. Quantifying the reaction process in situ from X-ray PDF data collected during the initial ten hours can provide an estimate of the total reaction extent, but when combined with data obtained at longer times (128 days here) enables more accurate determination of the overall rate of reaction. To further assess the initial stages of the geopolymerisation reaction process, a pseudo-single step first order rate equation is fitted to the extent of reaction data, which reveals important mechanistic information regarding the role of free silica in the activators in the evolution of the binder systems. Hence, it is shown that in situ X-ray PDF analysis is an ideal experimental local structure tool to probe the reaction kinetics of complex reacting systems involving transitions between disordered/amorphous phases, of which geopolymerisation is an important example.

  11. In Situ Soft X-ray Spectromicroscopy of Early Tricalcium Silicate Hydration.

    PubMed

    Bae, Sungchul; Kanematsu, Manabu; Hernández-Cruz, Daniel; Moon, Juhyuk; Kilcoyne, David; Monteiro, Paulo J M

    2016-12-01

    The understanding and control of early hydration of tricalcium silicate (C₃S) is of great importance to cement science and concrete technology. However, traditional characterization methods are incapable of providing morphological and spectroscopic information about in situ hydration at the nanoscale. Using soft X-ray spectromicroscopy, we report the changes in morphology and molecular structure of C₃S at an early stage of hydration. In situ C₃S hydration in a wet cell, beginning with induction (~1 h) and acceleration (~4 h) periods of up to ~8 h, was studied and compared with ex situ measurements in the deceleration period after 15 h of curing. Analysis of the near-edge X-ray absorption fine structure showed that the Ca binding energy and energy splitting of C₃S changed rapidly in the early age of hydration and exhibited values similar to calcium silicate hydrate (C-S-H). The formation of C-S-H nanoseeds in the C₃S solution and the development of a fibrillar C-S-H morphology on the C₃S surface were visualized. Following this, silicate polymerization accompanied by C-S-H precipitation produced chemical shifts in the peaks of the main Si K edge and in multiple scattering. However, the silicate polymerization process did not significantly affect the Ca binding energy of C-S-H.

  12. Corrosion of an alloy studied in situ with synchrotron x-ray diffraction

    NASA Astrophysics Data System (ADS)

    Renner, Frank; Lee, Tien-Lin; Kolb, Dieter M.; Stierle, Andreas; Dosch, Helmut; Zegenhagen, Jorg

    2004-03-01

    Corrosion processes are mostly electrochemical in nature. For the basic understanding of corrosion and similar technical processes, in-situ structural methods capable of atomic resolution, such as scanning probe microscopy or hard X-ray techniques are necessary. We used in-situ X-ray diffraction and in addition ex-situ AFM, to study Cu_3Au(111) single crystal surfaces in 0.1M H_2SO4 electrolyte as a function of electrode potential in the sub-critical regime. This binary metal alloys serves as model systems for more complicated technically utilized metal alloys. During the initial electrochemical corrosion, Cu atoms are dissolved and a passivating layer is formed. The experiments show the formation of an epitaxial and highly strained ultra-thin Cu_xAu_1-x(111) phase on the surface at a potential where Cu dissolution starts. At higher potentials, thicker epitaxial Au islands are growing on the surface. AFM images reveal a surface, densely packed with Au islands of a homogeneous size-distribution. On a prolonged timescale, a percolating, porous morphology of the surface evolves by ripening, even at an electrode potential well below the critical potential.

  13. X-ray microscopy for in situ characterization of 3D nanostructural evolution in the laboratory

    NASA Astrophysics Data System (ADS)

    Hornberger, Benjamin; Bale, Hrishikesh; Merkle, Arno; Feser, Michael; Harris, William; Etchin, Sergey; Leibowitz, Marty; Qiu, Wei; Tkachuk, Andrei; Gu, Allen; Bradley, Robert S.; Lu, Xuekun; Withers, Philip J.; Clarke, Amy; Henderson, Kevin; Cordes, Nikolaus; Patterson, Brian M.

    2015-09-01

    X-ray microscopy (XRM) has emerged as a powerful technique that reveals 3D images and quantitative information of interior structures. XRM executed both in the laboratory and at the synchrotron have demonstrated critical analysis and materials characterization on meso-, micro-, and nanoscales, with spatial resolution down to 50 nm in laboratory systems. The non-destructive nature of X-rays has made the technique widely appealing, with potential for "4D" characterization, delivering 3D micro- and nanostructural information on the same sample as a function of sequential processing or experimental conditions. Understanding volumetric and nanostructural changes, such as solid deformation, pore evolution, and crack propagation are fundamental to understanding how materials form, deform, and perform. We will present recent instrumentation developments in laboratory based XRM including a novel in situ nanomechanical testing stage. These developments bridge the gap between existing in situ stages for micro scale XRM, and SEM/TEM techniques that offer nanometer resolution but are limited to analysis of surfaces or extremely thin samples whose behavior is strongly influenced by surface effects. Several applications will be presented including 3D-characterization and in situ mechanical testing of polymers, metal alloys, composites and biomaterials. They span multiple length scales from the micro- to the nanoscale and different mechanical testing modes such as compression, indentation and tension.

  14. In Situ Soft X-ray Spectromicroscopy of Early Tricalcium Silicate Hydration

    PubMed Central

    Bae, Sungchul; Kanematsu, Manabu; Hernández-Cruz, Daniel; Moon, Juhyuk; Kilcoyne, David; Monteiro, Paulo J. M.

    2016-01-01

    The understanding and control of early hydration of tricalcium silicate (C3S) is of great importance to cement science and concrete technology. However, traditional characterization methods are incapable of providing morphological and spectroscopic information about in situ hydration at the nanoscale. Using soft X-ray spectromicroscopy, we report the changes in morphology and molecular structure of C3S at an early stage of hydration. In situ C3S hydration in a wet cell, beginning with induction (~1 h) and acceleration (~4 h) periods of up to ~8 h, was studied and compared with ex situ measurements in the deceleration period after 15 h of curing. Analysis of the near-edge X-ray absorption fine structure showed that the Ca binding energy and energy splitting of C3S changed rapidly in the early age of hydration and exhibited values similar to calcium silicate hydrate (C–S–H). The formation of C–S–H nanoseeds in the C3S solution and the development of a fibrillar C–S–H morphology on the C3S surface were visualized. Following this, silicate polymerization accompanied by C–S–H precipitation produced chemical shifts in the peaks of the main Si K edge and in multiple scattering. However, the silicate polymerization process did not significantly affect the Ca binding energy of C–S–H. PMID:28774096

  15. Simulations of in situ x-ray diffraction from uniaxially compressed highly textured polycrystalline targets

    SciTech Connect

    McGonegle, David Wark, Justin S.; Higginbotham, Andrew; Milathianaki, Despina; Remington, Bruce A.

    2015-08-14

    A growing number of shock compression experiments, especially those involving laser compression, are taking advantage of in situ x-ray diffraction as a tool to interrogate structure and microstructure evolution. Although these experiments are becoming increasingly sophisticated, there has been little work on exploiting the textured nature of polycrystalline targets to gain information on sample response. Here, we describe how to generate simulated x-ray diffraction patterns from materials with an arbitrary texture function subject to a general deformation gradient. We will present simulations of Debye-Scherrer x-ray diffraction from highly textured polycrystalline targets that have been subjected to uniaxial compression, as may occur under planar shock conditions. In particular, we study samples with a fibre texture, and find that the azimuthal dependence of the diffraction patterns contains information that, in principle, affords discrimination between a number of similar shock-deformation mechanisms. For certain cases, we compare our method with results obtained by taking the Fourier transform of the atomic positions calculated by classical molecular dynamics simulations. Illustrative results are presented for the shock-induced α–ϵ phase transition in iron, the α–ω transition in titanium and deformation due to twinning in tantalum that is initially preferentially textured along [001] and [011]. The simulations are relevant to experiments that can now be performed using 4th generation light sources, where single-shot x-ray diffraction patterns from crystals compressed via laser-ablation can be obtained on timescales shorter than a phonon period.

  16. MEASURING THE PLASTIC RESPONSE IN POLYCRSYTALLINE MATERIALS USING IN-SITU X-RAY DIFFRACTION

    SciTech Connect

    Hawreliak, J; Butterfield, M; El-Dasher, B; McNaney, J; Lorenzana, H

    2008-10-01

    The insight provided by ultra-fast lattice level measurements during high strain rate high pressure experiments is key to understanding kinetic material properties like plasticity. In-situ x-ray diffraction provides a diagnostic technique which can be used to study the governing physical phenomena of plasticity at the relevant time and spatial scale. Here we discuss the recent development of a geometry capable of investigating plasticity in polycrystalline foils. We also present some preliminary data of investigations into shock compressed rolled copper foils.

  17. Confocal X-ray fluorescence spectrometer for in-situ analyses of paintings

    NASA Astrophysics Data System (ADS)

    Trojek, Tomáš; Prokeš, Radek; Šefců, Radka; Bilavčíková, Hana; Čechák, Tomáš

    2017-08-01

    This paper describes the properties of the newly constructed device for confocal X-ray fluorescence analysis that was tested with a sample plate consisting of 19 combinations of two single pigment layers. The preparation of this experimental wooden board with layered systems was based on knowledge of the panel painting techniques of Bohemian collections from the National Gallery in Prague dating back to the 14th and 15th centuries. The design of the confocal setup allows its transport and the in-situ measurement of paintings in depositories or even in exhibition areas. The advantages of our confocal setup with movable collimating optics are also described.

  18. In-situ x-ray absorption study of copper films in ground watersolutions

    SciTech Connect

    Kvashnina, K.O.; Butorin, S.M.; Modin, A.; Soroka, I.; Marcellini, M.; Nordgren, J.; Guo, J.-H.; Werme, L.

    2007-10-29

    This study illustrates how the damage from copper corrosion can be reduced by modifying the chemistry of the copper surface environment. The surface modification of oxidized copper films induced by chemical reaction with Cl{sup -} and HCO{sub 3}{sup -} in aqueous solutions was monitored by in situ X-ray absorption spectroscopy. The results show that corrosion of copper can be significantly reduced by adding even a small amount of sodium bicarbonate. The studied copper films corroded quickly in chloride solutions, whereas the same solution containing 1.1 mM HCO{sub 3}{sup -} prevented or slowed down the corrosion processes.

  19. In-Situ Silver Acetylide Silver Nitrate Explosive Deposition Measurements Using X-Ray Fluorescence.

    SciTech Connect

    Covert, Timothy Todd

    2014-09-01

    The Light Initiated High Explosive facility utilized a spray deposited coating of silver acetylide - silver nitrate explosive to impart a mechanical shock into targets of interest. A diagnostic was required to measure the explosive deposition in - situ. An X - ray fluorescence spectrometer was deployed at the facility. A measurement methodology was developed to measure the explosive quantity with sufficient accuracy. Through the use of a tin reference material under the silver based explosive, a field calibration relationship has been developed with a standard deviation of 3.2 % . The effect of the inserted tin material into the experiment configuration has been explored.

  20. In-situ probing of lattice response in shock compressed materials using x-ray diffraction

    SciTech Connect

    Hawreliak, J; Butterfield, M; Davies, H; El-Dasher, B; Higginbotham, A; Kalantar, D; Kimminau, G; McNaney, J; Milathianaki, D; Murphy, W; Nagler, B; Lorenzana, H; Park, N; Remington, B; Thorton, L; Whitcher, T; Wark, J; Lorenzana, H

    2007-07-17

    Lattice level measurements of material response under extreme conditions are required to build a phenomenological understanding of the shock response of solids. We have successfully used laser produced plasma x-ray sources coincident with laser driven shock waves to make in-situ measurements of the lattice response during shock compression for both single crystal and polycrystalline materials. Using a detailed analysis of shocked single crystal iron which has undergone the {alpha} - {var_epsilon} phase transition we can constrain the transition mechanism to be consistent with a compression and shuffle of alternate lattice planes.

  1. IN-SITU PROBING OF LATTICE RESPONSE IN SHOCK COMPRESSED MATERIALS USING X-RAY DIFFRACTION

    SciTech Connect

    Hawreliak, James; Butterfield, Martin; El-Dasher, Bassem; Kalantar, Daniel; McNaney, James; Remington, Bruce; Lorenzana, Hector; Davies, Huw; Park, Nigel; Thorton, Lee; Higginbotham, Andrew; Kimminau, Giles; Murphy, William; Nagler, Bob; Whitcher, Thomas; Wark, Justin; Milathianaki, Despina

    2007-12-12

    Lattice level measurements of material response under extreme conditions are required to build a phenomenological understanding of the shock response of solids. We have successfully used laser produced plasma x-ray sources coincident with laser driven shock waves to make in-situ measurements of the lattice response during shock compression for both single crystal and polycrystalline materials. Using a detailed analysis of shocked single crystal iron which has undergone the {alpha}-{epsilon} phase transition we can constrain the transition mechanism to be consistent with a compression and shuffle of alternate lattice planes.

  2. Structural study on Ni nanowires in an anodic alumina membrane by using in situ heating extended x-ray absorption fine structure and x-ray diffraction techniques.

    PubMed

    Cai, Quan; Zhang, Junxi; Chen, Xing; Chen, Zhongjun; Wang, Wei; Mo, Guang; Wu, Zhonghua; Zhang, Lide; Pan, Wei

    2008-03-19

    Polycrystalline Ni nanowires have been prepared by electrochemical deposition in an anodic alumina membrane template with a nanopore size of about 60 nm. In situ heating extended x-ray absorption fine structure and x-ray diffraction techniques are used to probe the atomic structures. The nanowires are identified as being mixtures of nanocrystallites and amorphous phase. The nanocrystallites have the same thermal expansion coefficient, of 1.7 × 10(-5) K(-1), as Ni bulk; however, the amorphous phase has a much larger thermal expansion coefficient of 3.5 × 10(-5) K(-1). Details of the Ni nanowire structures are discussed in this paper.

  3. Study of calcium-containing orthophosphates of NaZr{sub 2}(PO{sub 4}){sub 3} structural type by high-temperature X-ray diffraction

    SciTech Connect

    Orlova, A. I.; Kanunov, A. E.; Samoilov, S. G.; Kazakova, A. Yu.; Kazantsev, G. N.

    2013-03-15

    Orthophosphates Ca{sub 0.5}Ti{sub 2}(PO{sub 4}){sub 3}, Ca{sub 0.5}Zr{sub 2}(PO{sub 4}){sub 3}, Ca{sub 0.75}Zr{sub 2}(SiO{sub 4}){sub 0.5}(PO{sub 4}){sub 2.5}, and CaMg{sub 0.5}Zr{sub 1.5}(PO{sub 4}){sub 3} (structural type NaZr{sub 2}(PO{sub 4}){sub 3}), having different occupancies of interframework positions by calcium, have been prepared by the sol-gel method with the subsequent thermal treatment of dried gels and investigated by IR spectroscopy and X-ray diffraction. The analytical indexing of X-ray diffraction patterns is performed within the sp. gr. R3{sup -}. High-temperature X-ray diffraction was used to investigate the behavior of the orthophosphates upon heating: thermal expansion in the temperature range of 20-610 Degree-Sign C (up to 500 Degree-Sign C for Ca{sub 0.5}Zr{sub 2}(PO{sub 4}){sub 3}). The coefficients of thermal expansion are calculated from the shift of diffraction peaks. The unit-cell parameters of crystals at different temperatures are determined. The dependences of thermal expansion and its anisotropy on the occupancy of cation M positions by calcium are revealed.

  4. Investigation of high-temperature bright plasma X-ray sources produced in 5-MA X-pinch experiments.

    PubMed

    Sinars, D B; McBride, R D; Pikuz, S A; Shelkovenko, T A; Wenger, D F; Cuneo, M E; Yu, E P; Chittenden, J P; Harding, E C; Hansen, S B; Peyton, B P; Ampleford, D J; Jennings, C A

    2012-10-12

    Using solid, machined X-pinch targets driven by currents rising from 0 to 5-6 MA in 60 ns, we observed bright spots of 5-9-keV continuum radiation from 5±2-μm diameter regions. The >6-keV radiation is emitted in about 0.4 ns, and the bright spots are roughly 75 times brighter than the bright spots measured at 1 MA. A total x-ray power of 10 TW peak and yields of 165±20 kJ were emitted from a 3-mm height. The 3-5-keV continuum radiation had a 50-90-GW peak power and 0.15-0.35-kJ yield. The continuum is plausibly from a 1275±75-eV blackbody or alternatively from a 3500±500-eV bremsstrahlung source.

  5. A flexible gas flow reaction cell for in situ x-ray absorption spectroscopy studies

    SciTech Connect

    Kroner, Anna B. Gilbert, Martin; Duller, Graham; Cahill, Leo; Leicester, Peter; Woolliscroft, Richard; Shotton, Elizabeth J.; Mohammed, Khaled M. H.

    2016-07-27

    A capillary-based sample environment with hot air blower and integrated gas system was developed at Diamond to conduct X-ray absorption spectroscopy (XAS) studies of materials under time-resolved, in situ conditions. The use of a hot air blower, operating in the temperature range of 298-1173 K, allows introduction of other techniques e.g. X-ray diffraction (XRD), Raman spectroscopy for combined techniques studies. The flexibility to use either quartz or Kapton capillaries allows users to perform XAS measurement at energies as low as 5600 eV. To demonstrate performance, time-resolved, in situ XAS results of Rh catalysts during the process of activation (Rh K-edge, Ce L{sub 3}-edge and Cr K-edge) and the study of mixed oxide membrane (La{sub 0.6}Sr{sub 0.4}Co{sub 0.2}Fe{sub 0.8}O{sub 3−δ}) under various partial oxygen pressure conditions are described.

  6. In meso in situ serial X-ray crystallography of soluble and membrane proteins

    SciTech Connect

    Huang, Chia-Ying; Olieric, Vincent; Ma, Pikyee; Panepucci, Ezequiel; Diederichs, Kay; Wang, Meitian; Caffrey, Martin

    2015-05-14

    A method for performing high-throughput in situ serial X-ray crystallography with soluble and membrane proteins in the lipid cubic phase is described. It works with microgram quantities of protein and lipid (and ligand when present) and is compatible with the most demanding sulfur SAD phasing. The lipid cubic phase (LCP) continues to grow in popularity as a medium in which to generate crystals of membrane (and soluble) proteins for high-resolution X-ray crystallographic structure determination. To date, the PDB includes 227 records attributed to the LCP or in meso method. Among the listings are some of the highest profile membrane proteins, including the β{sub 2}-adrenoreceptor–G{sub s} protein complex that figured in the award of the 2012 Nobel Prize in Chemistry to Lefkowitz and Kobilka. The most successful in meso protocol to date uses glass sandwich crystallization plates. Despite their many advantages, glass plates are challenging to harvest crystals from. However, performing in situ X-ray diffraction measurements with these plates is not practical. Here, an alternative approach is described that provides many of the advantages of glass plates and is compatible with high-throughput in situ measurements. The novel in meso in situ serial crystallography (IMISX) method introduced here has been demonstrated with AlgE and PepT (alginate and peptide transporters, respectively) as model integral membrane proteins and with lysozyme as a test soluble protein. Structures were solved by molecular replacement and by experimental phasing using bromine SAD and native sulfur SAD methods to resolutions ranging from 1.8 to 2.8 Å using single-digit microgram quantities of protein. That sulfur SAD phasing worked is testament to the exceptional quality of the IMISX diffraction data. The IMISX method is compatible with readily available, inexpensive materials and equipment, is simple to implement and is compatible with high-throughput in situ serial data collection at

  7. Experimental novaculite deformation: interpretation of in-situ X-ray diffraction data using EPSC models

    NASA Astrophysics Data System (ADS)

    Thomas, S.; Willenweber, A.; Cline, C. J.; Sas, M.; Pape, D.; Erickson, B.; Bright, T.; Burnley, P. C.

    2012-12-01

    The deformation behavior of fine-grained polycrystalline quartz (novaculite) was studied experimentally using in-situ X-ray diffraction and theoretically by elastic plastic self consistent modeling (EPSC). Previous experimental work has shown that different subpopulations of crystals experience different stress levels during high pressure deformation and reflection stresses may lead to poor approximations of macroscopic sample stresses, since in-situ diffraction data originates from grain scale phenomena rather than macroscopic sample properties [1]. In this context EPSC models have been utilized to interpret diffraction data, i.e., to independently derive the macroscopic sample load and to directly compare results with diffraction data. In our study a series of novaculite samples with 645 ± 50 wt ppm H2O was deformed in different regimes of disclocation-creep, at 2.5 GPa and up to ~1000 °C, in the D-DIA apparatus at the NSLS X17B2 beamline. In-situ synchrotron X-ray diffraction was used to monitor the sample stress state during controlled deformation and to observe the strain behavior of the individual lattice reflections of novaculite. Lattice strains were calculated from measured lattice spacings. The macroscopic sample strain was determined by sample radiographs. The strains provide information about how individual grains or grain populations react to stress depending on their orientation within the aggregate. We observe a reproducible elastic slope across the series of experiments and a temperature dependence of individual lattice strains and yield strength. In addition, EPSC models were calculated to theoretically determine macroscopic sample stresses and to match measured rheological sample properties with simulations. Depending on deformation conditions measured elastic lattice strains could be matched by activating basal and/or prism and/or pyramidal slip systems of the crystal structure. Here, we present EPSC models, compare macroscopic stresses

  8. In situ azimuthal rotation device for linear dichroism measurements in scanning transmission x-ray microscopy

    NASA Astrophysics Data System (ADS)

    Hernández-Cruz, D.; Hitchcock, A. P.; Tyliszczak, T.; Rousseau, M.-E.; Pézolet, M.

    2007-03-01

    A novel miniature rotation device used in conjunction with a scanning transmission x-ray microscope is described. It provides convenient in situ sample rotation to enable measurements of linear dichroism at high spatial resolution. The design, fabrication, and mechanical characterization are presented. This device has been used to generate quantitative maps of the spatial distribution of the orientation of proteins in several different spider and silkworm silks. Specifically, quantitative maps of the dichroic signal at the C 1s→π*amide transition in longitudinal sections of the silk fibers give information about the spatial orientation, degree of alignment, and spatial distribution of protein peptide bonds. A new approach for analyzing the dichroic signal to extract orientation distributions, in addition to magnitudes of aligned components, is presented and illustrated with results from Nephila clavipes dragline spider silk measured using the in situ rotation device.

  9. In-situ reactive of x-ray optics by glow discharge

    SciTech Connect

    Johnson, E.D.; Garrett, R.F.

    1987-01-01

    We have developed a method of in-situ reactive glow discharge cleaning of x-ray optical surfaces which is capable of complete removal of carbon contamination. Our work is the first to successfully clean an entire optical system in-situ and characterize its performance at short wavelengths (as low as 10 /angstrom/). The apparatus required is quite simple and can easily be fitted to most existing UHV (ultra high vacuum) mirror boxes of monochromators. The advantages of this technique over previously available methods include dramatic improvements in instrument performance and reductions in down time since the whole process typically takes a few days. This paper will briefly describe our results and detail the experimental considerations for application of the technique on different monochromator geometries. Possible improvements and extensions of the technique are also discussed.

  10. Advanced in situ metrology for x-ray beam shaping with super precision.

    PubMed

    Wang, Hongchang; Sutter, John; Sawhney, Kawal

    2015-01-26

    We report a novel method for in situ metrology of an X-ray bimorph mirror by using the speckle scanning technique. Both the focusing beam and the "tophat" defocussed beam have been generated by optimizing the bimorph mirror in a single iteration. Importantly, we have demonstrated that the angular sensitivity for measuring the slope error of an optical surface can reach accuracy in the range of two nanoradians. When compared with conventional ex-situ metrology techniques, the method enables a substantial increase of around two orders of magnitude in the angular sensitivity and opens the way to a previously inaccessible region of slope error measurement. Such a super precision metrology technique will be beneficial for both the manufacture of polished mirrors and the optimization of beam shaping.

  11. Mass Spectrometry Guided In Situ Proteolysis to Obtain Crystals for X-ray Structure Determination

    SciTech Connect

    Gheyi, Tarun; Rodgers, Logan; Romero, Richard; Sauder, J. Michael; Burley, Stephen K.

    2012-04-30

    A strategy for increasing the efficiency of protein crystallization/structure determination with mass spectrometry has been developed. This approach combines insights from limited proteolysis/mass spectrometry and crystallization via in situ proteolysis. The procedure seeks to identify protease-resistant polypeptide chain segments from purified proteins on the time-scale of crystal formation, and subsequently crystallizing the target protein in the presence of the optimal protease at the right relative concentration. We report our experience with 10 proteins of unknown structure, two of which yielded high-resolution X-ray structures. The advantage of this approach comes from its ability to select only those structure determination candidates that are likely to benefit from application of in situ proteolysis, using conditions most likely to result in formation of a stable proteolytic digestion product suitable for crystallization.

  12. Identification of key deformation mechanisms of polyethylene materials via in-situ x-ray scattering

    NASA Astrophysics Data System (ADS)

    Hermel-Davidock, Theresa; Degroot, Willem; Demirors, Mehmet; Landes, Brian; Patel, Rajen; Peltier, Tracy

    2006-03-01

    Changes in the microstructure of ethylene based copolymers can be used to modify and enhance their mechanical performance. In this study, the effects of comonomer content, molecular weight, and molecular weight distribution on the mechanical performance of select polyethylene polymers were examined. Two key performance parameters for commercial polymer materials, especially in the area of blown film applications, are tear resistance and puncture resistance. However, polyethylene films exhibiting very different Dart and Elmendorf tear values cannot be differentiated by standard tensile test methods even though they exhibit very similar morphology. Alternative methods to link morphology and mechanical response need to be found. Wide-angle and small-angle x-ray scattering was collected during in-situ tensile testing to understand how compositional and structural differences affect the mechanical response of semicrystalline polyethylene polymers. Microstructural changes observed during the in-situ deformation process are correlated to Elmendorf tear and Dart impact performance for both intrinsic and blown film samples.

  13. Identification of key deformation mechanisms of polyethylene materials via in-situ x-ray scattering

    NASA Astrophysics Data System (ADS)

    Hermel-Davidock, Theresa; Landes, Brian; Demirors, Mehmet

    2008-03-01

    Changes in the microstructure of ethylene based copolymers can be used to modify and enhance their mechanical performance. In this study, the effects of comonomer content, molecular weight, and molecular weight distribution on the mechanical performance of select polyethylene polymers were examined. Two key performance parameters for commercial polymer materials, especially in the area of blown film applications, are tear resistance and puncture resistance. However, polyethylene films which exhibit very similar morphology often exhibit very different Dart and Elmendorf tear values which cannot be differentiated by standard tensile test methods. Alternative methods to link morphology and mechanical response need to be found. Wide-angle and small-angle x-ray scattering was collected during in-situ tensile testing to understand how compositional and structural differences affect the mechanical response of semicrystalline polyethylene polymers. Microstructural changes observed during the in-situ deformation process are correlated to Elmendorf tear performance for both intrinsic and blown film samples.

  14. Orthoclase surface structure dissolution measured in situ by x-ray reflectivity and atomic force microscopy.

    SciTech Connect

    Sturchio, N. C.; Fenter, P.; Cheng, L.; Teng, H.

    2000-11-28

    Orthoclase (001) surface topography and interface structure were measured during dissolution by using in situ atomic force microscopy (AFM) and synchrotrons X-ray reflectivity at pH 1.1-12.9 and T = 25-84 C. Terrace roughening at low pH and step motion at high pH were the main phenomena observed, and dissolution rates were measured precisely. Contrasting dissolution mechanisms are inferred for low- and high-pH conditions. These observations clarify differences in alkali feldspar dissolution mechanisms as a function of pH, demonstrate a new in situ method for measuring face-specific dissolution rates on single crystals, and improve the fundamental basis for understanding alkali feldspar weathering processes.

  15. Non-destructive in situ study of "Mad Meg" by Pieter Bruegel the Elder using mobile X-ray fluorescence, X-ray diffraction and Raman spectrometers

    NASA Astrophysics Data System (ADS)

    Van de Voorde, Lien; Van Pevenage, Jolien; De Langhe, Kaat; De Wolf, Robin; Vekemans, Bart; Vincze, Laszlo; Vandenabeele, Peter; Martens, Maximiliaan P. J.

    2014-07-01

    "Mad Meg", a figure of Flemish folklore, is the subject of a famous oil-on-panel painting by the Flemish renaissance artist Pieter Bruegel the Elder, exhibited in the Museum Mayer van den Bergh (Antwerp, Belgium). This article reports on the in situ chemical characterization of this masterpiece by using currently available state-of-the-art portable analytical instruments. The applied non-destructive analytical approach involved the use of a) handheld X-ray fluorescence instrumentation for retrieving elemental information and b) portable X-ray fluorescence/X-ray diffraction instrumentation and laser-based Raman spectrometers for obtaining structural/molecular information. Next to material characterization of the used pigments and of the different preparation layers of the painting, also the verification of two important historical iconographic hypotheses is performed concerning the economic way of painting by Brueghel, and whether or not he used blue smalt pigment for painting the boat that appears towards the top of the painting. The pigments identified are smalt pigment (65% SiO2 + 15% K2O + 10% CoO + 5% Al2O3) for the blue color present in all blue areas of the painting, probably copper resinate for the green colors, vermillion (HgS) as red pigment and lead white is used to form different colors. The comparison of blue pigments used on different areas of the painting gives no differences in the elemental fingerprint which confirms the existing hypothesis concerning the economic painting method by Bruegel.

  16. In meso in situ serial X-ray crystallography of soluble and membrane proteins

    PubMed Central

    Huang, Chia-Ying; Olieric, Vincent; Ma, Pikyee; Panepucci, Ezequiel; Diederichs, Kay; Wang, Meitian; Caffrey, Martin

    2015-01-01

    The lipid cubic phase (LCP) continues to grow in popularity as a medium in which to generate crystals of membrane (and soluble) proteins for high-resolution X-ray crystallographic structure determination. To date, the PDB includes 227 records attributed to the LCP or in meso method. Among the listings are some of the highest profile membrane proteins, including the β2-adrenoreceptor–Gs protein complex that figured in the award of the 2012 Nobel Prize in Chemistry to Lefkowitz and Kobilka. The most successful in meso protocol to date uses glass sandwich crystallization plates. Despite their many advantages, glass plates are challenging to harvest crystals from. However, performing in situ X-ray diffraction measurements with these plates is not practical. Here, an alternative approach is described that provides many of the advantages of glass plates and is compatible with high-throughput in situ measurements. The novel in meso in situ serial crystallography (IMISX) method introduced here has been demonstrated with AlgE and PepT (alginate and peptide transporters, respectively) as model integral membrane proteins and with lysozyme as a test soluble protein. Structures were solved by molecular replacement and by experimental phasing using bromine SAD and native sulfur SAD methods to resolutions ranging from 1.8 to 2.8 Å using single-digit microgram quantities of protein. That sulfur SAD phasing worked is testament to the exceptional quality of the IMISX diffraction data. The IMISX method is compatible with readily available, inexpensive materials and equipment, is simple to implement and is compatible with high-throughput in situ serial data collection at macromolecular crystallography synchrotron beamlines worldwide. Because of its simplicity and effectiveness, the IMISX approach is likely to supplant existing in meso crystallization protocols. It should prove particularly attractive in the area of ligand screening for drug discovery and development. PMID

  17. Development of an in situ temperature stage for synchrotron X-ray spectromicroscopy

    NASA Astrophysics Data System (ADS)

    Chakraborty, R.; Serdy, J.; West, B.; Stuckelberger, M.; Lai, B.; Maser, J.; Bertoni, M. I.; Culpepper, M. L.; Buonassisi, T.

    2015-11-01

    In situ characterization of micro- and nanoscale defects in polycrystalline thin-film materials is required to elucidate the physics governing defect formation and evolution during photovoltaic device fabrication and operation. X-ray fluorescence spectromicroscopy is particularly well-suited to study defects in compound semiconductors, as it has a large information depth appropriate to study thick and complex materials, is sensitive to trace amounts of atomic species, and provides quantitative elemental information, non-destructively. Current in situ methods using this technique typically require extensive sample preparation. In this work, we design and build an in situ temperature stage to study defect kinetics in thin-film solar cells under actual processing conditions, requiring minimal sample preparation. Careful selection of construction materials also enables controlled non-oxidizing atmospheres inside the sample chamber such as H2Se and H2S. Temperature ramp rates of up to 300 °C/min are achieved, with a maximum sample temperature of 600 °C. As a case study, we use the stage for synchrotron X-ray fluorescence spectromicroscopy of CuInxGa1-xSe2 (CIGS) thin-films and demonstrate predictable sample thermal drift for temperatures 25-400 °C, allowing features on the order of the resolution of the measurement technique (125 nm) to be tracked while heating. The stage enables previously unattainable in situ studies of nanoscale defect kinetics under industrially relevant processing conditions, allowing a deeper understanding of the relationship between material processing parameters, materials properties, and device performance.

  18. Development of an in situ temperature stage for synchrotron X-ray spectromicroscopy

    SciTech Connect

    Chakraborty, R. E-mail: buonassisi@mit.edu; Serdy, J.; Culpepper, M. L.; Buonassisi, T. E-mail: buonassisi@mit.edu; West, B.; Stuckelberger, M.; Bertoni, M. I.; Lai, B.; Maser, J.

    2015-11-15

    In situ characterization of micro- and nanoscale defects in polycrystalline thin-film materials is required to elucidate the physics governing defect formation and evolution during photovoltaic device fabrication and operation. X-ray fluorescence spectromicroscopy is particularly well-suited to study defects in compound semiconductors, as it has a large information depth appropriate to study thick and complex materials, is sensitive to trace amounts of atomic species, and provides quantitative elemental information, non-destructively. Current in situ methods using this technique typically require extensive sample preparation. In this work, we design and build an in situ temperature stage to study defect kinetics in thin-film solar cells under actual processing conditions, requiring minimal sample preparation. Careful selection of construction materials also enables controlled non-oxidizing atmospheres inside the sample chamber such as H{sub 2}Se and H{sub 2}S. Temperature ramp rates of up to 300 °C/min are achieved, with a maximum sample temperature of 600 °C. As a case study, we use the stage for synchrotron X-ray fluorescence spectromicroscopy of CuIn{sub x}Ga{sub 1−x}Se{sub 2} (CIGS) thin-films and demonstrate predictable sample thermal drift for temperatures 25–400 °C, allowing features on the order of the resolution of the measurement technique (125 nm) to be tracked while heating. The stage enables previously unattainable in situ studies of nanoscale defect kinetics under industrially relevant processing conditions, allowing a deeper understanding of the relationship between material processing parameters, materials properties, and device performance.

  19. Development of an in situ temperature stage for synchrotron X-ray spectromicroscopy.

    PubMed

    Chakraborty, R; Serdy, J; West, B; Stuckelberger, M; Lai, B; Maser, J; Bertoni, M I; Culpepper, M L; Buonassisi, T

    2015-11-01

    In situ characterization of micro- and nanoscale defects in polycrystalline thin-film materials is required to elucidate the physics governing defect formation and evolution during photovoltaic device fabrication and operation. X-ray fluorescence spectromicroscopy is particularly well-suited to study defects in compound semiconductors, as it has a large information depth appropriate to study thick and complex materials, is sensitive to trace amounts of atomic species, and provides quantitative elemental information, non-destructively. Current in situ methods using this technique typically require extensive sample preparation. In this work, we design and build an in situ temperature stage to study defect kinetics in thin-film solar cells under actual processing conditions, requiring minimal sample preparation. Careful selection of construction materials also enables controlled non-oxidizing atmospheres inside the sample chamber such as H2Se and H2S. Temperature ramp rates of up to 300 °C/min are achieved, with a maximum sample temperature of 600 °C. As a case study, we use the stage for synchrotron X-ray fluorescence spectromicroscopy of CuIn(x)Ga(1-x)Se2 (CIGS) thin-films and demonstrate predictable sample thermal drift for temperatures 25-400 °C, allowing features on the order of the resolution of the measurement technique (125 nm) to be tracked while heating. The stage enables previously unattainable in situ studies of nanoscale defect kinetics under industrially relevant processing conditions, allowing a deeper understanding of the relationship between material processing parameters, materials properties, and device performance.

  20. In meso in situ serial X-ray crystallography of soluble and membrane proteins.

    PubMed

    Huang, Chia Ying; Olieric, Vincent; Ma, Pikyee; Panepucci, Ezequiel; Diederichs, Kay; Wang, Meitian; Caffrey, Martin

    2015-06-01

    The lipid cubic phase (LCP) continues to grow in popularity as a medium in which to generate crystals of membrane (and soluble) proteins for high-resolution X-ray crystallographic structure determination. To date, the PDB includes 227 records attributed to the LCP or in meso method. Among the listings are some of the highest profile membrane proteins, including the β2-adrenoreceptor-Gs protein complex that figured in the award of the 2012 Nobel Prize in Chemistry to Lefkowitz and Kobilka. The most successful in meso protocol to date uses glass sandwich crystallization plates. Despite their many advantages, glass plates are challenging to harvest crystals from. However, performing in situ X-ray diffraction measurements with these plates is not practical. Here, an alternative approach is described that provides many of the advantages of glass plates and is compatible with high-throughput in situ measurements. The novel in meso in situ serial crystallography (IMISX) method introduced here has been demonstrated with AlgE and PepT (alginate and peptide transporters, respectively) as model integral membrane proteins and with lysozyme as a test soluble protein. Structures were solved by molecular replacement and by experimental phasing using bromine SAD and native sulfur SAD methods to resolutions ranging from 1.8 to 2.8 Å using single-digit microgram quantities of protein. That sulfur SAD phasing worked is testament to the exceptional quality of the IMISX diffraction data. The IMISX method is compatible with readily available, inexpensive materials and equipment, is simple to implement and is compatible with high-throughput in situ serial data collection at macromolecular crystallography synchrotron beamlines worldwide. Because of its simplicity and effectiveness, the IMISX approach is likely to supplant existing in meso crystallization protocols. It should prove particularly attractive in the area of ligand screening for drug discovery and development.

  1. First use of portable system coupling X-ray diffraction and X-ray fluorescence for in-situ analysis of prehistoric rock art.

    PubMed

    Beck, L; Rousselière, H; Castaing, J; Duran, A; Lebon, M; Moignard, B; Plassard, F

    2014-11-01

    Study of prehistoric art is playing a major role in the knowledge of human evolution. Many scientific methods are involved in this investigation including chemical analysis of pigments present on artefacts or applied to cave walls. In the past decades, the characterization of coloured materials was carried on by taking small samples. This procedure had two main disadvantages: slight but existing damage of the paintings and limitation of the number of samples. Thanks to the advanced development of portable systems, in-situ analysis of pigment in cave can be now undertaken without fear for this fragile Cultural Heritage. For the first time, a portable system combining XRD and XRF was used in an underground and archaeological environment for prehistoric rock art studies. In-situ non-destructive analysis of black prehistoric drawings and determination of their composition and crystalline structure were successfully carried out. Original results on pigments used 13,000 years ago in the cave of Rouffignac (France) were obtained showing the use of two main manganese oxides: pyrolusite and romanechite. The capabilities of the portable XRD-XRF system have been demonstrated for the characterization of pigments as well as for the analysis of rock in a cave environment. This first in-situ experiment combining X-ray diffraction and X-ray fluorescence open up new horizons and can fundamentally change our approach of rock art studies.

  2. X-Ray Diffraction and Fluorescence Measurements for In Situ Planetary Instruments

    NASA Astrophysics Data System (ADS)

    Hansford, G.; Hill, K. S.; Talboys, D.; Vernon, D.; Ambrosi, R.; Bridges, J.; Hutchinson, I.; Marinangeli, L.

    2011-12-01

    The ESA/NASA ExoMars mission, due for launch in 2018, has a combined X-ray fluorescence/diffraction instrument, Mars-XRD, as part of the onboard analytical laboratory. The results of some XRF (X-ray fluorescence) and XRD (X-ray diffraction) tests using a laboratory chamber with representative performance are reported. A range of standard geological reference materials and analogues were used in these tests. The XRD instruments are core components of the forthcoming NASA Mars Science Laboratory (MSL) and ESA/NASA ExoMars missions and will provide the first demonstrations of the capabilities of combined XRD/XRF instrumentation in situ on an extraterrestrial planetary surface. The University of Leicester team is part of the Italy-UK collaboration that is responsible for building the ExoMars X-ray diffraction instrument, Mars-XRD [1,2]. Mars-XRD incorporates an Fe-55 radioisotope source and three fixed-position charge-coupled devices (CCDs) to simultaneously acquire an X-ray fluorescence spectrum and a diffraction pattern providing a measurement of both elemental and mineralogical composition. The CCDs cover an angular range of 2θ = 6° to 73° enabling the analysis of a wide range of geologically important minerals including phyllosilicates, feldspars, oxides, carbonates and evaporites. The identification of hydrous minerals may help identify past Martian hydrothermal systems capable of preserving traces of life. Here we present some initial findings from XRF and XRD tests carried out at the University of Leicester using an Fe-55 source and X-ray sensitive CCD. The XRF/XRD test system consists of a single CCD on a motorised arm, an Fe-55 X-ray source, a collimator and a sample table which approximately replicate the reflection geometry of the Mars-XRD instrument. It was used to test geological reference standard materials and Martian analogues. This work was funded by the Science and Technology Facilities Council, UK. References [1] Marinangeli, L., Hutchinson, I

  3. In-situ X-ray diffraction combined with scanning AC nanocalorimetry applied to a Fe0.84Ni0.16 thin-film sample

    PubMed Central

    Gregoire, John M.; Xiao, Kechao; McCluskey, Patrick J.; Dale, Darren; Cuddalorepatta, Gayatri; Vlassak, Joost J.

    2013-01-01

    We combine the characterization techniques of scanning AC nanocalorimetry and x-ray diffraction to study phase transformations in complex materials system. Micromachined nanocalorimeters have excellent performance for high-temperature and high-scanning-rate calorimetry measurements. Time-resolved X-ray diffraction measurements during in-situ operation of these devices using synchrotron radiation provide unprecedented characterization of thermal and structural material properties. We apply this technique to a Fe0.84Ni0.16 thin-film sample that exhibits a martensitic transformation with over 350 K hysteresis, using an average heating rate of 85 K/s and cooling rate of 275 K/s. The apparatus includes an array of nanocalorimeters in an architecture designed for combinatorial studies. PMID:23825802

  4. An In-situ X-ray Scattering Study During Uniaxial Stretching of Ionic Liquid/Ultra-high Molecular Weight Polyethylene Blends

    SciTech Connect

    X Li; Y Mao; H Ma; F Zuo; B Hsiao; B Chu

    2011-12-31

    An ionic liquid (IL) 1-docosanyl-3-methylimidazolium bromide was incorporated into ultra-high molecular weight polyethylene (UHMWPE) and formed IL/UHMWPE blends by solution mixing. The structure evolution of these blends during uniaxial stretching was followed by in-situ synchrotron wide-angle X-ray diffraction (WAXD) and small-angle X-ray scattering (SAXS) techniques. During deformation at room temperature, deformation-induced phase transformation from orthorhombic to monoclinic phase was observed in both IL/UHMWPE blends and neat UHMWPE. The elongation-to-break ratios of IL/UHMWPE blends were found to increase by 2-3 times compared with that of pure UHMWPE, while the tensile strength remained about the same. In contrast, during deformation at high temperature (120 C), no phase transformation was observed. However, the blend samples showed much better toughness, higher crystal orientation and higher tilting extent of lamellar structure at high strains.

  5. An In-Situ X-ray Scattering Study during Uniaxial Stretching of Ionic liquid/Ultra-High Molecular Weight Polyethylene Blend

    NASA Astrophysics Data System (ADS)

    Li, Xiaowei; Mao, Yimin; Ma, Hongyang; Hsiao, Benjamin S.

    2011-03-01

    The 1-docosanyl-3-methylimidazolium bromide ionic liquid (IL) was incorporated into ultra-high molecular weight polyethylene (UHMWPE) to form IL/UHWMPE blend by solution mixing. The structure evolution of this blend system during uniaxial stretching was followed by in-situ synchrotron wide-angle X-ray diffraction (WAXD) and small-angle X-ray scattering (SAXS) techniques. During deformation at room temperature, the elongation-to-break ratio of the IL/UHMWPE blend increased by 2 - 3 times compared with pure UHMWPE sample, where the blend did not lose the tensile strength. Deformation-induced phase transformation from orthorhombic to monoclinic phase was observed in both blend and neat UHMWPE. During deformation at high temperature (120& circ; C), no phase transformation was observed in both samples. However, the blend showed better toughness, higher crystal orientation, and tilted lamellar structure at high strains.

  6. Compact x-ray microradiograph for in situ imaging of solidification processes: Bringing in situ x-ray micro-imaging from the synchrotron to the laboratory

    SciTech Connect

    Rakete, C.; Baumbach, C.; Goldschmidt, A.; Samberg, D.; Schroer, C. G.; Breede, F.; Stenzel, C.; Zimmermann, G.; Pickmann, C.; Houltz, Y.; Lockowandt, C.; Svenonius, O.; Wiklund, P.; Mathiesen, R. H.

    2011-10-15

    A laboratory based high resolution x-ray radiograph was developed for the investigation of solidification dynamics in alloys. It is based on a low-power microfocus x-ray tube and is potentially appropriate for x-ray diagnostics in space. The x-ray microscope offers a high spatial resolution down to approximately 5 {mu}m. Dynamic processes can be resolved with a frequency of up to 6 Hz. In reference experiments, the setup was optimized to yield a high contrast for AlCu-alloys. With samples of about 150 {mu}m thickness, high quality image sequences of the solidification process were obtained with high resolution in time and space.

  7. Development of in-line furnace for in-situ nanoscale resolution x-ray microscopy

    NASA Astrophysics Data System (ADS)

    Eng, Christopher; Chen-Wiegart, Yu-Chen K.; Wang, Jun

    2013-09-01

    Full field transmission x-ray microscopy (TXM) is a newly developed x-ray imaging technique to provide quantitative and non-destructive 3D characterization of the complex microstructure of materials at nanometer resolution. A key missing component is an in situ apparatus enabling the imaging of the complex structural evolution of the materials and to correlate the structural change with a material's functionality under real operating conditions. This work describes the design of an environmental cell which satisfies the requirements for in situ TXM studies. The limited space within the TXM presents a spatial constraint which prohibits the use of conventional heaters, as well as requiring consideration in designing for safe and controlled operation of the system and alignment of the cell with the beam. A gravity drip-fed water cooling jacket was installed in place around the heating module to maintain critical components of the microscope at safe operating temperatures. A motion control system consisting of pulse width modulated DC motor driven XYZ translation stages was developed to facilitate fine alignment of the cell. Temperature of the sample can be controlled remotely and accurately through a controller to temperatures as high as 1200 K. Heating zone measurement was carried out and shows a 500 x 500 x 500 μm3 homogeneous zone volume for sample area, which is a critical parameter to ensure accurate observation of structural evolution at nanometer scale with a sample in size of tens of microns. Application on Ni particles for in situ oxidation experiment and dehydrogenation of aluminum hydride is also discussed.

  8. Near-isothermal furnace for in situ and real time X-ray radiography solidification experiments.

    PubMed

    Becker, M; Dreißigacker, C; Klein, S; Kargl, F

    2015-06-01

    In this paper, we present a newly developed near-isothermal X-ray transparent furnace for in situ imaging of solidification processes in thin metallic samples. We show that the furnace is ideally suited to study equiaxed microstructure evolution and grain interaction. To observe the growth dynamics of equiaxed dendritic structures, a minimal temperature gradient across the sample is required. A uniform thermal profile inside a circular sample is achieved by positioning the sample in the center of a cylindrical furnace body surrounded by a circular heater arrangement. Performance tests with the hypo-eutectic Al-15wt.%Cu and the near-eutectic Al-33wt.%Cu alloys validate the near-isothermal character of the sample environment. Controlled cooling rates of less than 0.5 K min(-1) up to 10 K min(-1) can be achieved in a temperature range of 720 K-1220 K. Integrated in our rotatable laboratory X-ray facility, X-RISE, the furnace provides a large field of view of 10.5 mm in diameter and a high spatial resolution of ∼4 μm. With the here presented furnace, equiaxed dendrite growth models can be rigorously tested against experiments on metal alloys by, e.g., enabling dendrite growth velocities to be determined as a function of undercooling or solutal fields in front of the growing dendrite to be measured.

  9. Near-isothermal furnace for in situ and real time X-ray radiography solidification experiments

    SciTech Connect

    Becker, M. Dreißigacker, C.; Klein, S.; Kargl, F.

    2015-06-15

    In this paper, we present a newly developed near-isothermal X-ray transparent furnace for in situ imaging of solidification processes in thin metallic samples. We show that the furnace is ideally suited to study equiaxed microstructure evolution and grain interaction. To observe the growth dynamics of equiaxed dendritic structures, a minimal temperature gradient across the sample is required. A uniform thermal profile inside a circular sample is achieved by positioning the sample in the center of a cylindrical furnace body surrounded by a circular heater arrangement. Performance tests with the hypo-eutectic Al-15wt.%Cu and the near-eutectic Al-33wt.%Cu alloys validate the near-isothermal character of the sample environment. Controlled cooling rates of less than 0.5 K min{sup −1} up to 10 K min{sup −1} can be achieved in a temperature range of 720 K–1220 K. Integrated in our rotatable laboratory X-ray facility, X-RISE, the furnace provides a large field of view of 10.5 mm in diameter and a high spatial resolution of ∼4 μm. With the here presented furnace, equiaxed dendrite growth models can be rigorously tested against experiments on metal alloys by, e.g., enabling dendrite growth velocities to be determined as a function of undercooling or solutal fields in front of the growing dendrite to be measured.

  10. Novel in-situ x-ray diffraction measurement of ferrroelectric superlattice properties during growth

    NASA Astrophysics Data System (ADS)

    Bein, Benjamin; Hsing, Hsiang-Chun; Callori, Sara J.; Sinsheimer, John; Dawber, Matthew

    2015-03-01

    Ferroelectric domains, surface termination, average lattice parameter and bilayer thickness were monitored by in-situ x-ray diffraction during the growth of BaTiO3/SrTiO<3 (BTO/STO) superlattices by off-axis RF magnetron sputtering. A new x-ray diffraction technique was employed which makes effective use of the custom growth chamber, pilatus detector and synchrotron radiation available at beamline X21, NSLS, BNL. The technique allows for scan times substantially faster than the growth of a single layer of material, allowing continuous monitoring of multiple structural parameters as the film grows. The effect of electric boundary conditions was investigated by growing the same superlattice alternatively on STO substrates and 20nm SrRuO3 (SRO) thin films grown on STO substrates. Besides the fundamental knowledge gained from these studies, being able to monitor the structural parameters of a growing ferroelectric superlattice at this level of detail provides numerous insights which can guide the growth of higher quality ferroelectric superlattices in general. Supported by NSF: DMR-1055413.

  11. Bismuth tri- and tetraarylcarboxylates: crystal structures, in situ X-ray diffraction, intermediates and luminescence.

    PubMed

    Feyand, Mark; Köppen, Milan; Friedrichs, Gernot; Stock, Norbert

    2013-09-09

    A systematic investigation of the systems Bi(3+)/carboxylic acid/HNO3 for the tri- and tetracarboxylic acids pyromellitic acid (H4Pyr), trimellitic acid (H3Tri) and trimesic acid (H3BTC) acid led to the discovery of five new bismuth carboxylates. Structural characterisation allowed the influence of the linker geometry and the Bi(3+):linker molar ratio in the starting solution on the crystal structure to be determined. The crystallisation of three selected compounds was investigated by in situ energy-dispersive X-ray diffraction. Three new crystalline intermediates were observed within minutes, and two of them could be isolated by quenching of the reaction mixture. Their crystal structures were determined from laboratory and synchrotron X-ray powder diffraction data and allowed a possible reaction pathway to be established. In depth characterisation of the luminescence properties of the three bismuth pyromellate compounds was carried out. Fluorescence and phosphorescence could be assigned to (mainly) ligand- and metal-based transitions. The polymorphs of Bi(HPyr) exhibit different luminescence properties, although their structures are very similar. Surprisingly, doping of the three host structures with Eu(3+) and Tb(3+) ions was only successful for one of the polymorphs.

  12. An apparatus for in situ x-ray scattering measurements during polymer injection molding

    NASA Astrophysics Data System (ADS)

    Rendon, Stanley; Fang, Jun; Burghardt, Wesley R.; Bubeck, Robert A.

    2009-04-01

    We report a novel instrument for synchrotron-based in situ x-ray scattering measurements during injection molding processing. It allows direct, real-time monitoring of molecular-scale structural evolution in polymer materials undergoing a complex processing operation. The instrument is based on a laboratory-scale injection molding machine, and employs customized mold tools designed to allow x-ray access during mold filling and subsequent solidification, while providing sufficient robustness to withstand high injection pressures. The use of high energy, high flux synchrotron radiation, and a fast detector allows sufficiently rapid data acquisition to resolve time-dependent orientation dynamics in this transient process. Simultaneous monitoring of temperature and pressure signals allows transient scattering data to be referenced to various stages of the injection molding cycle. Representative data on a commercial liquid crystalline polymer, Vectra® B950, are presented to demonstrate the features of this apparatus; however, it may find application in a wide range of polymeric materials such as nanocomposites, semicrystalline polymers and fiber-reinforced thermoplastics.

  13. An apparatus for in situ x-ray scattering measurements during polymer injection molding.

    PubMed

    Rendon, Stanley; Fang, Jun; Burghardt, Wesley R; Bubeck, Robert A

    2009-04-01

    We report a novel instrument for synchrotron-based in situ x-ray scattering measurements during injection molding processing. It allows direct, real-time monitoring of molecular-scale structural evolution in polymer materials undergoing a complex processing operation. The instrument is based on a laboratory-scale injection molding machine, and employs customized mold tools designed to allow x-ray access during mold filling and subsequent solidification, while providing sufficient robustness to withstand high injection pressures. The use of high energy, high flux synchrotron radiation, and a fast detector allows sufficiently rapid data acquisition to resolve time-dependent orientation dynamics in this transient process. Simultaneous monitoring of temperature and pressure signals allows transient scattering data to be referenced to various stages of the injection molding cycle. Representative data on a commercial liquid crystalline polymer, Vectra(R) B950, are presented to demonstrate the features of this apparatus; however, it may find application in a wide range of polymeric materials such as nanocomposites, semicrystalline polymers and fiber-reinforced thermoplastics.

  14. In situ high-temperature visible microspectroscopy for volcanic materials.

    PubMed

    Yamanoi, Yuta; Nakashima, Satoru

    2005-11-01

    In situ high-temperature visible microspectroscopy has been developed in order to study color change kinetics of volcanic materials. Olivine thin sections put on a synthetic alumina plate are heated on a heating stage at 600-800 degrees C under a visible microspectroscope. Changes in visible absorption spectra are monitored every 60 s for 5 hours. The obtained high-temperature visible spectra showed a gradual increase with time in absorbance in the shorter wavelength region (400-600 nm). The 430 nm absorbance (ligand field transition of Fe3+ increased more with time at higher temperatures. Assuming diffusional transport in plane sheets, apparent diffusion coefficients were determined at temperatures of 600-800 degrees C. The activation energy for this diffusion in olivine is 208 +/- 17 kJ/mol. This activation energy value is similar to those for the metal vacancy diffusion in olivine. This newly developed in situ high-temperature visible microspectroscopy can provide kinetic measurements of visible spectral change of materials at high temperatures such as volcanic materials.

  15. Final Report on Developing Microstructure-Property Correlation in Reactor Materials using in situ High-Energy X-rays

    SciTech Connect

    Li, Meimei; Almer, Jonathan D.; Yang, Yong; Tan, Lizhen

    2016-01-01

    This report provides a summary of research activities on understanding microstructure – property correlation in reactor materials using in situ high-energy X-rays. The report is a Level 2 deliverable in FY16 (M2CA-13-IL-AN_-0403-0111), under the Work Package CA-13-IL-AN_- 0403-01, “Microstructure-Property Correlation in Reactor Materials using in situ High Energy Xrays”, as part of the DOE-NE NEET Program. The objective of this project is to demonstrate the application of in situ high energy X-ray measurements of nuclear reactor materials under thermal-mechanical loading, to understand their microstructure-property relationships. The gained knowledge is expected to enable accurate predictions of mechanical performance of these materials subjected to extreme environments, and to further facilitate development of advanced reactor materials. The report provides detailed description of the in situ X-ray Radiated Materials (iRadMat) apparatus designed to interface with a servo-hydraulic load frame at beamline 1-ID at the Advanced Photon Source. This new capability allows in situ studies of radioactive specimens subject to thermal-mechanical loading using a suite of high-energy X-ray scattering and imaging techniques. We conducted several case studies using the iRadMat to obtain a better understanding of deformation and fracture mechanisms of irradiated materials. In situ X-ray measurements on neutron-irradiated pure metal and model alloy and several representative reactor materials, e.g. pure Fe, Fe-9Cr model alloy, 316 SS, HT-UPS, and duplex cast austenitic stainless steels (CASS) CF-8 were performed under tensile loading at temperatures of 20-400°C in vacuum. A combination of wide-angle X-ray scattering (WAXS), small-angle X-ray scattering (SAXS), and imaging techniques were utilized to interrogate microstructure at different length scales in real time while the specimen was subject to thermal-mechanical loading. In addition, in situ X-ray studies were

  16. Atomic Structure of Pt3Ni Nanoframe Electrocatalysts by in Situ X-ray Absorption Spectroscopy.

    PubMed

    Becknell, Nigel; Kang, Yijin; Chen, Chen; Resasco, Joaquin; Kornienko, Nikolay; Guo, Jinghua; Markovic, Nenad M; Somorjai, Gabor A; Stamenkovic, Vojislav R; Yang, Peidong

    2015-12-23

    Understanding the atomic structure of a catalyst is crucial to exposing the source of its performance characteristics. It is highly unlikely that a catalyst remains the same under reaction conditions when compared to as-synthesized. Hence, the ideal experiment to study the catalyst structure should be performed in situ. Here, we use X-ray absorption spectroscopy (XAS) as an in situ technique to study Pt3Ni nanoframe particles which have been proven to be an excellent electrocatalyst for the oxygen reduction reaction (ORR). The surface characteristics of the nanoframes were probed through electrochemical hydrogen underpotential deposition and carbon monoxide electrooxidation, which showed that nanoframe surfaces with different structure exhibit varying levels of binding strength to adsorbate molecules. It is well-known that Pt-skin formation on Pt-Ni catalysts will enhance ORR activity by weakening the binding energy between the surface and adsorbates. Ex situ and in situ XAS results reveal that nanoframes which bind adsorbates more strongly have a rougher Pt surface caused by insufficient segregation of Pt to the surface and consequent Ni dissolution. In contrast, nanoframes which exhibit extremely high ORR activity simultaneously demonstrate more significant segregation of Pt over Ni-rich subsurface layers, allowing better formation of the critical Pt-skin. This work demonstrates that the high ORR activity of the Pt3Ni hollow nanoframes depends on successful formation of the Pt-skin surface structure.

  17. Time-resolved and in-situ X-ray scattering methods beyond photoactivation: Utilizing high-flux X-ray sources for the study of ubiquitous non-photoactive proteins.

    PubMed

    Jain, Rohit; Techert, Simone

    2016-01-01

    X-ray scattering technique, comprising of small-angle/wide-angle X-ray scattering (SAXS/WAXS) techniques is increasingly used to characterize the structure and interactions of biological macromolecules and their complexes in solution. It is a method of choice to characterize the flexible, partially folded and unfolded protein systems. X-ray scattering is the last resort for proteins that cannot be investigated by crystallography or NMR and acts as a complementary technique with different biophysical techniques to answer challenging scientific questions. The marriage of the X-ray scattering technique with the fourth dimension "time" yields structural dynamics and kinetics information for protein motions in hierarchical timescales from picoseconds to days. The arrival of the high-flux X-ray beam at third generation synchrotron sources, exceptional X-ray optics, state-of-the-art detectors, upgradation of X-ray scattering beamlines with microfluidics devices and advanced X-ray scattering data analysis procedures are the important reasons behind the shining years of X-ray scattering technique. The best days of the X-ray scattering technique are on the horizon with the advent of the nanofocus X-ray scattering beamlines and fourth generation X-ray lightsources, i.e., free electron lasers (XFELs). Complementary to the photon-triggered time-resolved X-ray scattering techniques, we will present an overview of the time-resolved and in-situ X-ray scattering techniques for structural dynamics of ubiquitous non-photoactive proteins.

  18. Fluorescence X-ray absorption spectroscopy using a Ge pixel array detector: application to high-temperature superconducting thin-film single crystals.

    PubMed

    Oyanagi, H; Tsukada, A; Naito, M; Saini, N L; Lampert, M O; Gutknecht, D; Dressler, P; Ogawa, S; Kasai, K; Mohamed, S; Fukano, A

    2006-07-01

    A Ge pixel array detector with 100 segments was applied to fluorescence X-ray absorption spectroscopy, probing the local structure of high-temperature superconducting thin-film single crystals (100 nm in thickness). Independent monitoring of pixel signals allows real-time inspection of artifacts owing to substrate diffractions. By optimizing the grazing-incidence angle theta and adjusting the azimuthal angle phi, smooth extended X-ray absorption fine structure (EXAFS) oscillations were obtained for strained (La,Sr)2CuO4 thin-film single crystals grown by molecular beam epitaxy. The results of EXAFS data analysis show that the local structure (CuO6 octahedron) in (La,Sr)2CuO4 thin films grown on LaSrAlO4 and SrTiO3 substrates is uniaxially distorted changing the tetragonality by approximately 5 x 10(-3) in accordance with the crystallographic lattice mismatch. It is demonstrated that the local structure of thin-film single crystals can be probed with high accuracy at low temperature without interference from substrates.

  19. Hydride reorientation in Zircaloy-4 examined by in situ synchrotron X-ray diffraction

    NASA Astrophysics Data System (ADS)

    Weekes, H. E.; Jones, N. G.; Lindley, T. C.; Dye, D.

    2016-09-01

    The phenomenon of stress-reorientation has been investigated using in situ X-ray diffraction during the thermomechanical cycling of hydrided Zircaloy-4 tensile specimens. Results have shown that loading along a sample's transverse direction (TD) leads to a greater degree of hydride reorientation when compared to rolling direction (RD)-aligned samples. The elastic lattice micro-strains associated with radially oriented hydrides have been revealed to be greater than those oriented circumferentially, a consequence of strain accommodation. Evidence of hydride redistribution after cycling, to α-Zr grains oriented in a more favourable orientation when under an applied stress, has also been observed and its behaviour has been found to be highly dependent on the loading axis. Finally, thermomechanical loading across multiple cycles has been shown to reduce the difference in terminal solid solubility of hydrogen during dissolution (TSSD,H) and precipitation (TSSP,H).

  20. In situ synchrotron X-ray diffraction study of hydrides in Zircaloy-4 during thermomechanical cycling

    NASA Astrophysics Data System (ADS)

    Cinbiz, Mahmut N.; Koss, Donald A.; Motta, Arthur T.; Park, Jun-Sang; Almer, Jonathan D.

    2017-04-01

    The d-spacing evolution of both in-plane and out-of-plane hydrides has been studied using in situ synchrotron radiation X-ray diffraction during thermo-mechanical cycling of cold-worked stress-relieved Zircaloy-4. The structure of the hydride precipitates is such that the δ{111} d-spacing of the planes aligned with the hydride platelet face is greater than the d-spacing of the 111 planes aligned with the platelet edges. Upon heating from room temperature, the δ{111} planes aligned with hydride plate edges exhibit bi-linear thermally-induced expansion. In contrast, the d-spacing of the (111) plane aligned with the hydride plate face initially contracts upon heating. These experimental results can be understood in terms of a reversal of stress state associated with precipitating or dissolving hydride platelets within the α-zirconium matrix.

  1. Compact low power infrared tube furnace for in situ X-ray powder diffraction.

    PubMed

    Doran, A; Schlicker, L; Beavers, C M; Bhat, S; Bekheet, M F; Gurlo, A

    2017-01-01

    We describe the development and implementation of a compact, low power, infrared heated tube furnace for in situ powder X-ray diffraction experiments. Our silicon carbide (SiC) based furnace design exhibits outstanding thermal performance in terms of accuracy control and temperature ramping rates while simultaneously being easy to use, robust to abuse and, due to its small size and low power, producing minimal impact on surrounding equipment. Temperatures in air in excess of 1100 °C can be controlled at an accuracy of better than 1%, with temperature ramping rates up to 100 °C/s. The complete "add-in" device, minus power supply, fits in a cylindrical volume approximately 15 cm long and 6 cm in diameter and resides as close as 1 cm from other sensitive components of our experimental synchrotron endstation without adverse effects.

  2. Kinetics of Methane Hydrate Decomposition Studied via in Situ Low Temperature X-ray Powder Diffraction

    SciTech Connect

    Everett, Susan M; Rawn, Claudia J; Keffer, David J.; Mull, Derek L; Payzant, E Andrew; Phelps, Tommy Joe

    2013-01-01

    Gas hydrates are known to have a slowed decomposition rate at ambient pressure and temperatures below the melting point of ice termed self-preservation or anomalous preservation. As hydrate exothermically decomposes, gas is released and water of the clathrate cages transforms into ice. Two regions of slowed decomposition for methane hydrate, 180 200 K and 230 260 K, were observed, and the kinetics were studied by in situ low temperature x-ray powder diffraction. The kinetic constants for ice formation from methane hydrate were determined by the Avrami model within each region and activation energies, Ea, were determined by the Arrhenius plot. Ea determined from the data for 180 200 K was 42 kJ/mol and for 230 260 K was 22 kJ/mol. The higher Ea in the colder temperature range was attributed to a difference in the microstructure of ice between the two regions.

  3. Compact low power infrared tube furnace for in situ X-ray powder diffraction

    NASA Astrophysics Data System (ADS)

    Doran, A.; Schlicker, L.; Beavers, C. M.; Bhat, S.; Bekheet, M. F.; Gurlo, A.

    2017-01-01

    We describe the development and implementation of a compact, low power, infrared heated tube furnace for in situ powder X-ray diffraction experiments. Our silicon carbide (SiC) based furnace design exhibits outstanding thermal performance in terms of accuracy control and temperature ramping rates while simultaneously being easy to use, robust to abuse and, due to its small size and low power, producing minimal impact on surrounding equipment. Temperatures in air in excess of 1100 °C can be controlled at an accuracy of better than 1%, with temperature ramping rates up to 100 °C/s. The complete "add-in" device, minus power supply, fits in a cylindrical volume approximately 15 cm long and 6 cm in diameter and resides as close as 1 cm from other sensitive components of our experimental synchrotron endstation without adverse effects.

  4. Development of a combined portable x-ray fluorescence and Raman spectrometer for in situ analysis

    NASA Astrophysics Data System (ADS)

    Guerra, M.; Longelin, S.; Pessanha, S.; Manso, M.; Carvalho, M. L.

    2014-06-01

    In this work, we have built a portable X-ray fluorescence (XRF) spectrometer in a planar configuration coupled to a Raman head and a digital optical microscope, for in situ analysis. Several geometries for the XRF apparatus and digital microscope are possible in order to overcome spatial constraints and provide better measurement conditions. With this combined spectrometer, we are now able to perform XRF and Raman measurements in the same point without the need for sample collection, which can be crucial when dealing with cultural heritage objects, as well as forensic analysis. We show the capabilities of the spectrometer by measuring several standard reference materials, as well as other samples usually encountered in cultural heritage, geological, as well as biomedical studies.

  5. Titanium boride equation of state determined by in-situ X-ray diffraction.

    PubMed

    Ono, Shigeaki; Kikegawa, Takumi

    2016-12-01

    The equation of state (EOS) of titanium boride, TiB2, was investigated by in situ X-ray diffraction in a diamond anvil cell and multianvil high-pressure apparatus. The pressure-volume-temperature (P-V-T) data were collected at up to 111 GPa and room temperature for the diamond-anvil cell experiments and at up to 15 GPa and 1300 K for the multianvil experiments. No phase transition was observed through the entire range of experimental conditions. The pressure-volume data at room temperature were fitted using a Vinet EOS to obtain the isothermal bulk modulus, BT0 = 256.7 GPa, and its pressure derivative, B' T0 = 3.83. When fitting a thermal EOS using the P-V-T data for the multianvil experiments, we find that [Formula: see text] = 0.095 (GPa/K) and α 0 = 2.49 × 10(-5) K(-1).

  6. In-situ x-ray characterization of wurtzite formation in GaAs nanowires

    NASA Astrophysics Data System (ADS)

    Krogstrup, Peter; Hannibal Madsen, Morten; Hu, Wen; Kozu, Miwa; Nakata, Yuka; Nygârd, Jesper; Takahasi, Masamitu; Feidenhans'l, Robert

    2012-02-01

    In-situ monitoring of the crystal structure formation during Ga-assisted GaAs nanowire growth on Si(111) substrates has been performed in a combined molecular beam epitaxy growth and x-ray characterization experiment. Under Ga rich conditions, we show that an increase in the V/III ratio increases the formation rate of the wurtzite structure. Moreover, the response time for changes in the structural phase formation to changes in the beam fluxes is observed to be much longer than predicted time scales of adatom kinetics and liquid diffusion. This suggests that the morphology of the growth interface plays the key role for the relative growth structure formation rates.

  7. Development of a combined portable x-ray fluorescence and Raman spectrometer for in situ analysis.

    PubMed

    Guerra, M; Longelin, S; Pessanha, S; Manso, M; Carvalho, M L

    2014-06-01

    In this work, we have built a portable X-ray fluorescence (XRF) spectrometer in a planar configuration coupled to a Raman head and a digital optical microscope, for in situ analysis. Several geometries for the XRF apparatus and digital microscope are possible in order to overcome spatial constraints and provide better measurement conditions. With this combined spectrometer, we are now able to perform XRF and Raman measurements in the same point without the need for sample collection, which can be crucial when dealing with cultural heritage objects, as well as forensic analysis. We show the capabilities of the spectrometer by measuring several standard reference materials, as well as other samples usually encountered in cultural heritage, geological, as well as biomedical studies.

  8. In situ synchrotron x-ray studies of ferroelectric thin films.

    SciTech Connect

    Fong, D. D.; Eastman, J. A.; Stephenson, G. B.; Fuoss, P. H.; Streiffer, S. K.; Thompson, C.; Auciello, O.; Materials Science Division; Northern Illinois Univ.

    2005-03-01

    In situ synchrotron X-ray scattering was used to observe both the growth of PbTiO{sub 3} films by metal-organic chemical vapor deposition and the behavior of the ferroelectric phase transition as a function of film thickness. The dependences of growth mode and deposition rate on gas flows and substrate temperature were determined by homoepitaxial growth studies on thick films (>50 nm). These studies facilitated the growth of thin coherently strained PbTiO{sub 3} films on SrTiO{sub 3} (001) substrates, with thicknesses ranging from 2 to 42 nm. Experiments on the ferroelectric phase transition as a function of film thickness were carried out in these films under controlled mechanical and electrical boundary conditions.

  9. In situ synchrotron X-ray diffraction study of hydrides in Zircaloy-4 during thermomechanical cycling

    DOE PAGES

    Cinbiz, Mahmut N.; Koss, Donald A.; Motta, Arthur T.; ...

    2017-02-20

    The d-spacing evolution of both in-plane and out-of-plane hydrides has been studied using in situ synchrotron radiation X-ray diffraction during thermo-mechanical cycling of cold-worked stress-relieved Zircaloy-4. The structure of the hydride precipitates is such that the δ{111} d-spacing of the planes aligned with the hydride platelet face is greater than the d-spacing of the 111 planes aligned with the platelet edges. Upon heating from room temperature, the δ{111} planes aligned with hydride plate edges exhibit bi-linear thermally-induced expansion. In contrast, the d-spacing of the (111) plane aligned with the hydride plate face initially contracts upon heating. Furthermore, these experimental resultsmore » can be understood in terms of a reversal of stress state associated with precipitating or dissolving hydride platelets within the α-zirconium matrix.« less

  10. In Situ Study of Silicon Electrode Lithiation with X-ray Reflectivity

    DOE PAGES

    Cao, Chuntian; Steinrück, Hans-Georg; Shyam, Badri; ...

    2016-10-26

    Surface sensitive X-ray reflectivity (XRR) measurements were performed to investigate the electrochemical lithiation of a native oxide terminated single crystalline silicon (100) electrode in real time during the first galvanostatic discharge cycle. This allows us to gain nanoscale, mechanistic insight into the lithiation of Si and the formation of the solid electrolyte interphase (SEI). We describe an electrochemistry cell specifically designed for in situ XRR studies and have determined the evolution of the electron density profile of the lithiated Si layer (LixSi) and the SEI layer with subnanometer resolution. We propose a three-stage lithiation mechanism with a reaction limited, layer-by-layermore » lithiation of the Si at the LixSi/Si interface.« less

  11. In Situ Study of Silicon Electrode Lithiation with X-ray Reflectivity

    SciTech Connect

    Cao, Chuntian; Steinrück, Hans-Georg; Shyam, Badri; Stone, Kevin H.; Toney, Michael F.

    2016-10-26

    Surface sensitive X-ray reflectivity (XRR) measurements were performed to investigate the electrochemical lithiation of a native oxide terminated single crystalline silicon (100) electrode in real time during the first galvanostatic discharge cycle. This allows us to gain nanoscale, mechanistic insight into the lithiation of Si and the formation of the solid electrolyte interphase (SEI). We describe an electrochemistry cell specifically designed for in situ XRR studies and have determined the evolution of the electron density profile of the lithiated Si layer (LixSi) and the SEI layer with subnanometer resolution. We propose a three-stage lithiation mechanism with a reaction limited, layer-by-layer lithiation of the Si at the LixSi/Si interface.

  12. Uranium oxidation kinetics monitored by in-situ X-ray diffraction

    NASA Astrophysics Data System (ADS)

    Zalkind, S.; Rafailov, G.; Halevy, I.; Livneh, T.; Rubin, A.; Maimon, H.; Schweke, D.

    2017-03-01

    The oxidation kinetics of U-0.1 wt%Cr at oxygen pressures of 150 Torr and the temperature range of 90-150 °C was studied by means of in-situ X-ray diffraction (XRD). A "breakaway" in the oxidation kinetics is found at ∼0.25 μm, turning from a parabolic to a linear rate law. At the initial stage of oxidation the growth plane of UO2(111) is the prominent one. As the oxide thickens, the growth rate of UO2(220) plane increases and both planes grow concurrently. The activation energies obtained for the oxide growth are Qparabolic = 17.5 kcal/mol and Qlinear = 19 kcal/mol. Enhanced oxidation around uranium carbide (UC) inclusions is clearly observed by scanning electron microscopy (SEM).

  13. Orthorhombic boron oxide under pressure: In situ study by X-ray diffraction and Raman scattering

    NASA Astrophysics Data System (ADS)

    Cherednichenko, Kirill A.; Le Godec, Yann; Kalinko, Aleksandr; Mezouar, Mohamed; Solozhenko, Vladimir L.

    2016-11-01

    High-pressure phase of boron oxide, orthorhombic β-B2O3, has been studied in situ by synchrotron X-ray diffraction to 22 GPa and Raman scattering to 46 GPa at room temperature. The bulk modulus of β-B2O3 has been found to be 169(3) GPa that is in good agreement with our ab initio calculations. Raman and IR spectra of β-B2O3 have been measured at ambient pressure; all experimentally observed bands have been attributed to the theoretically calculated ones, and the mode assignment has been performed. Based on the data on Raman shift as a function of pressure, combined with equation-of-state data, the Grüneisen parameters of all experimentally observed Raman bands have been calculated. β-B2O3 enriched by 10B isotope has been synthesized, and the effect of boron isotopic substitution on Raman spectra has been studied.

  14. In situ surface X-ray scattering of stepped surface of platinum: Pt(311).

    PubMed

    Nakahara, Akira; Nakamura, Masashi; Sumitani, Kazushi; Sakata, Osami; Hoshi, Nagahiro

    2007-10-23

    Surface structure of a stepped surface of Pt, Pt(311) (=2(100)-(111)), has been determined under potential control in 0.1 M HClO4 with the use of in situ surface X-ray scattering (SXS). The crystal truncation rods (CTRs) are reproduced well with the (1x2) missing-row model. Relaxation of surface layers, which is observed on the low-index planes of Pt, is not found on Pt(311) in the "adsorbed hydrogen region". CTRs at 0.10 (RHE) have the same feature as those at 0.50 V, showing that the surface layers of Pt(311) have no potential dependence. Scanning tunneling microscopy (STM) also supports the (1x2) structure of Pt(311) in 0.1 M HClO4.

  15. Quadrupole lamp furnace for high temperature (up to 2050 K) synchrotron powder x-ray diffraction studies in air in reflection geometry

    SciTech Connect

    Sarin, P.; Yoon, W.; Jurkschat, K.; Zschack, P.; Kriven, W. M.

    2006-09-15

    A four-lamp thermal image furnace has been developed to conduct high temperature x-ray diffraction in reflection geometry on oxide ceramic powder samples in air at temperatures {<=}2050 K using synchrotron radiation. A refractory crucible made of Pt20%Rh alloy was used as a specimen holder. A material with well characterized lattice expansion properties was used as an internal crystallographic thermometer to determine the specimen temperature and displacement. The performance of the apparatus was verified by measurement of the thermal expansion properties of CeO{sub 2}, MgO, and Pt which were found to be within {+-}3% of the acceptable values. The advantages, limitations, and important considerations of the instrument developed are discussed.

  16. High-Temperature Phase Transitions in CsH2PO4 Under Ambient and High-Pressure Conditions: A Synchrotron X-ray Diffraction Study

    SciTech Connect

    Botez,C.; Hermosillo, J.; Zhang, J.; Qian, J.; Zhao, Y.; Majzlan, J.; Chianelli, R.; Pantea, C.

    2007-01-01

    To clarify the microscopic origin of the temperature-induced three-order-of-magnitude jump in the proton conductivity of CsH2PO4 (superprotonic behavior), we have investigated its crystal structure modifications within the 25-300 C temperature range under both ambient- and high-pressure conditions using synchrotron x-ray diffraction. Our high-pressure data show no indication of the thermal decomposition/polymerization at the crystal surface recently proposed as the origin of the enhanced proton conductivity. Instead, we found direct evidence that the superprotonic behavior of the title material is associated with a polymorphic structural transition to a high-temperature cubic phase. Our results are in excellent agreement with previous high-pressure ac impedance measurements.

  17. Quadrupole lamp furnace for high temperature (up to 2050 K) synchrotron powder x-ray diffraction studies in air in reflection geometry.

    SciTech Connect

    Sarin, P.; Yoon, W.; Jurkschat, K.; Zschack, P.; Kriven, W. M.; Univ. of Illinois; Frederick-Seitz Materials Research Lab.

    2006-09-01

    A four-lamp thermal image furnace has been developed to conduct high temperature x-ray diffraction in reflection geometry on oxide ceramic powder samples in air at temperatures {le} 2050 K using synchrotron radiation. A refractory crucible made of Pt20%Rh alloy was used as a specimen holder. A material with well characterized lattice expansion properties was used as an internal crystallographic thermometer to determine the specimen temperature and displacement. The performance of the apparatus was verified by measurement of the thermal expansion properties of CeO{sub 2}, MgO, and Pt which were found to be within {+-} 3% of the acceptable values. The advantages, limitations, and important considerations of the instrument developed are discussed.

  18. Single-pulse x-ray diffraction using polycapillary optics for in situ dynamic diffraction

    SciTech Connect

    Maddox, B. R. Akin, M. C. Teruya, A.; Hunt, D.; Hahn, D.; Cradick, J.; Morgan, D. V.

    2016-08-15

    Diagnostic use of single-pulse x-ray diffraction (XRD) at pulsed power facilities can be challenging due to factors such as the high flux and brightness requirements for diffraction and the geometric constraints of experimental platforms. By necessity, the x-ray source is usually positioned very close, within a few inches of the sample. On dynamic compression platforms, this puts the x-ray source in the debris field. We coupled x-ray polycapillary optics to a single-shot needle-and-washer x-ray diode source using a laser-based alignment scheme to obtain high-quality x-ray diffraction using a single 16 ns x-ray pulse with the source >1 m from the sample. The system was tested on a Mo sample in reflection geometry using 17 keV x-rays from a Mo anode. We also identified an anode conditioning effect that increased the x-ray intensity by 180%. Quantitative measurements of the x-ray focal spot produced by the polycapillary yielded a total x-ray flux on the sample of 3.3 ± 0.5 × 10{sup 7} molybdenum Kα photons.

  19. Single-pulse x-ray diffraction using polycapillary optics for in situ dynamic diffraction.

    PubMed

    Maddox, B R; Akin, M C; Teruya, A; Hunt, D; Hahn, D; Cradick, J; Morgan, D V

    2016-08-01

    Diagnostic use of single-pulse x-ray diffraction (XRD) at pulsed power facilities can be challenging due to factors such as the high flux and brightness requirements for diffraction and the geometric constraints of experimental platforms. By necessity, the x-ray source is usually positioned very close, within a few inches of the sample. On dynamic compression platforms, this puts the x-ray source in the debris field. We coupled x-ray polycapillary optics to a single-shot needle-and-washer x-ray diode source using a laser-based alignment scheme to obtain high-quality x-ray diffraction using a single 16 ns x-ray pulse with the source >1 m from the sample. The system was tested on a Mo sample in reflection geometry using 17 keV x-rays from a Mo anode. We also identified an anode conditioning effect that increased the x-ray intensity by 180%. Quantitative measurements of the x-ray focal spot produced by the polycapillary yielded a total x-ray flux on the sample of 3.3 ± 0.5 × 10(7) molybdenum Kα photons.

  20. In situ flow cell for combined X-ray absorption spectroscopy, X-ray diffraction, and mass spectrometry at high photon energies under solar thermochemical looping conditions

    NASA Astrophysics Data System (ADS)

    Rothensteiner, Matthäus; Jenni, Joel; Emerich, Hermann; Bonk, Alexander; Vogt, Ulrich F.; van Bokhoven, Jeroen A.

    2017-08-01

    An in situ/operando flow cell for transmission mode X-ray absorption spectroscopy (XAS), X-ray diffraction (XRD), and combined XAS/XRD measurements in a single experiment under the extreme conditions of two-step solar thermochemical looping for the dissociation of water and/or carbon dioxide was developed. The apparatus exposes materials to relevant conditions of both the auto-reduction and the oxidation sub-steps of the thermochemical cycle at ambient temperature up to 1773 K and enables determination of the composition of the effluent gases by online quadrupole mass spectrometry. The cell is based on a tube-in-tube design and is heated by means of a focusing infrared furnace. It was tested successfully for carbon dioxide splitting. In combined XAS/XRD experiments with an unfocused beam, XAS measurements were performed at the Ce K edge (40.4 keV) and XRD measurements at 64.8 keV and 55.9 keV. Furthermore, XRD measurements with a focused beam at 41.5 keV were carried out. Equimolar ceria-hafnia was auto-reduced in a flow of argon and chemically reduced in a flow of hydrogen/helium. Under reducing conditions, all cerium(iv) was converted to cerium(iii) and a cation-ordered pyrochlore-type structure was formed, which was not stable upon oxidation in a flow of carbon dioxide.

  1. In-situ X-ray diffraction study of phase transformations in the Am-O system

    SciTech Connect

    Lebreton, Florent; Belin, Renaud C.

    2012-12-15

    In the frame of minor actinides recycling, americium can be transmuted by adding it in UO{sub 2} or (U, Pu)O{sub 2} fuels. Americium oxides exhibiting a higher oxygen potential than U or Pu oxides, its addition alters the fuel properties. To comprehend its influence, a thorough knowledge of the Am-O phase equilibria diagram and of thermal expansion behavior is of main interest. Due to americium scarcity and high radiotoxicity, few experimental reports on this topic are available. Here we present in-situ high-temperature XRD results on the reduction from AmO{sub 2} to Am{sub 2}O{sub 3}. We show that fluorite (Fm-3m) AmO{sub 2} is reduced to cubic (Ia-3) C Prime -type Am{sub 2}O{sub 3+{delta}}, and then into hexagonal (P6{sub 3}/mmc) A-type Am{sub 2}O{sub 3}, which remains stable up to 1840 K. We also demonstrate the transitional existence of the monoclinic (C2/m) B-type Am{sub 2}O{sub 3}. At last, we describe, for the first time, the thermal expansion behavior of the hexagonal Am{sub 2}O{sub 3} between room temperature and 1840 K. - Graphical abstract: Americium dioxide was in situ studied by high-temperature X-ray diffraction. First, fluorite AmO{sub 2} is reduced to cubic C Prime -type Am{sub 2}O{sub 3+{delta}} and then transforms into hexagonal A-type Am{sub 2}O{sub 3}, which remains stable up to 1840 K. Then, we demonstrate the transitional existence of monoclinic B-type Am{sub 2}O{sub 3}. At last, we describe, for the first time, the thermal expansion of A-type Am{sub 2}O{sub 3} between room temperature and 1840 K. This work may contribute to a better understanding of Am oxide behavior. Highlights: Black-Right-Pointing-Pointer We realize an in-situ high-temperature X-ray diffraction study on an AmO{sub 2} sample. Black-Right-Pointing-Pointer Fluorite AmO{sub 2} transforms to cubic Am{sub 2}O{sub 3+{delta}} and then to hexagonal Am{sub 2}O{sub 3}. Black-Right-Pointing-Pointer Little-known monoclinic Am{sub 2}O{sub 3} is observed during the cubic

  2. In Situ X-ray Synchrotron Tomographic Imaging During the Compression of Hyperelastic Polymeric Materials

    SciTech Connect

    Patterson, Brian M.; Cordes, Nikolaus L.; Henderson, Kevin; Williams, Jason J.; Stannard, Tyler; Singh, Sudhanshu S.; Ovejero, Angel Rodriguez; Xiao, Xianghui; Robinson, Mathew; Chawla, Nikhilesh

    2016-01-01

    Cellular structures are present in many modern and natural materials and their proper utilization is crucial within many industries. Characterizing their structural and mechanical properties is complicated, in that they often have a stochastic cellular structure, and in addition, they often have hyperelastic (i.e., non-linear) mechanical properties. Understanding the 3D structure and the dynamic response of polymer foams to mechanical stress is key to predicting lifetime performance, damage pathways, and stress recovery. Therefore, to gain a more complete picture, experiments which are designed to understand their mechanical properties must simultaneously acquire performance metrics during loading. In situ synchrotron X-ray computed tomography (CT) can image these cellular materials in 3D during uniaxial compression at a 10-2 s-1 strain rate. By utilizing the high X-ray photon flux and high speed camera provided by beamline 2-BM at the Advanced Photon Source (APS), it is possible to collect a full 3D tomogram (900 radiographs as the sample is rotated 180°) within 1 s. Rotating the sample stage in a washing machine motion allows for a 1 s tomogram to be collected every fifth second. In this study, a series of 20 tomograms were collected as the sample was continuously stressed to a nominal 60% compression. Several types of silicone foams with various structures were used to explore this technique. Stress-strain curves, collected simultaneously with the 3D tomograms, can be used to directly correlate the morphology with the mechanical performance and visualize in real-time, the buckling of ligaments. In addition, this method allows for the accurate measurement of the Poisson’s ratio as a function of compression. Coupling this moderate strain rate 3D data with finite element analysis provides a direct comparison between the true mechanical response and the modeled performance and adds a level of robustness that is not possible with other techniques

  3. In Situ Ambient Pressure X-ray Photoelectron Spectroscopy Studies of Lithium-Oxygen Redox Reactions

    PubMed Central

    Lu, Yi-Chun; Crumlin, Ethan J.; Veith, Gabriel M.; Harding, Jonathon R.; Mutoro, Eva; Baggetto, Loïc; Dudney, Nancy J.; Liu, Zhi; Shao-Horn, Yang

    2012-01-01

    The lack of fundamental understanding of the oxygen reduction and oxygen evolution in nonaqueous electrolytes significantly hinders the development of rechargeable lithium-air batteries. Here we employ a solid-state Li4+xTi5O12/LiPON/LixV2O5 cell and examine in situ the chemistry of Li-O2 reaction products on LixV2O5 as a function of applied voltage under ultra high vacuum (UHV) and at 500 mtorr of oxygen pressure using ambient pressure X-ray photoelectron spectroscopy (APXPS). Under UHV, lithium intercalated into LixV2O5 while molecular oxygen was reduced to form lithium peroxide on LixV2O5 in the presence of oxygen upon discharge. Interestingly, the oxidation of Li2O2 began at much lower overpotentials (~240 mV) than the charge overpotentials of conventional Li-O2 cells with aprotic electrolytes (~1000 mV). Our study provides the first evidence of reversible lithium peroxide formation and decomposition in situ on an oxide surface using a solid-state cell, and new insights into the reaction mechanism of Li-O2 chemistry. PMID:23056907

  4. In Situ Synchrotron X-ray Study of Ultrasound Cavitation and Its Effect on Solidification Microstructures

    SciTech Connect

    Mi, Jiawei; Tan, Dongyue; Lee, Tung Lik

    2014-12-11

    Considerable progress has been made in studying the mechanism and effectiveness of using ultrasound waves to manipulate the solidification microstructures of metallic alloys. However, uncertainties remain in both the underlying physics of how microstructures evolve under ultrasonic waves, and the best technological approach to control the final microstructures and properties. We used the ultrafast synchrotron X-ray phase contrast imaging facility housed at the Advanced Photon Source, Argonne National Laboratory, US to study in situ the highly transient and dynamic interactions between the liquid metal and ultrasonic waves/bubbles. The dynamics of ultrasonic bubbles in liquid metal and their interactions with the solidifying phases in a transparent alloy were captured in situ. The experiments were complemented by the simulations of the acoustic pressure field, the pulsing of the bubbles, and the associated forces acting onto the solidifying dendrites. The study provides more quantitative understanding on how ultrasonic waves/bubbles influence the growth of dendritic grains and promote the grain multiplication effect for grain refinement.

  5. In Situ Ambient Pressure X-ray Photoelectron Spectroscopy Studies of Lithium-Oxygen Redox Reactions

    NASA Astrophysics Data System (ADS)

    Lu, Yi-Chun; Crumlin, Ethan J.; Veith, Gabriel M.; Harding, Jonathon R.; Mutoro, Eva; Baggetto, Loïc; Dudney, Nancy J.; Liu, Zhi; Shao-Horn, Yang

    2012-10-01

    The lack of fundamental understanding of the oxygen reduction and oxygen evolution in nonaqueous electrolytes significantly hinders the development of rechargeable lithium-air batteries. Here we employ a solid-state Li4+xTi5O12/LiPON/LixV2O5 cell and examine in situ the chemistry of Li-O2 reaction products on LixV2O5 as a function of applied voltage under ultra high vacuum (UHV) and at 500 mtorr of oxygen pressure using ambient pressure X-ray photoelectron spectroscopy (APXPS). Under UHV, lithium intercalated into LixV2O5 while molecular oxygen was reduced to form lithium peroxide on LixV2O5 in the presence of oxygen upon discharge. Interestingly, the oxidation of Li2O2 began at much lower overpotentials (~240 mV) than the charge overpotentials of conventional Li-O2 cells with aprotic electrolytes (~1000 mV). Our study provides the first evidence of reversible lithium peroxide formation and decomposition in situ on an oxide surface using a solid-state cell, and new insights into the reaction mechanism of Li-O2 chemistry.

  6. Rapid thermal processing chamber for in-situ x-ray diffraction

    SciTech Connect

    Ahmad, Md. Imteyaz; Van Campen, Douglas G.; Yu, Jiafan; Pool, Vanessa L.; Van Hest, Maikel F. A. M.; Toney, Michael F.; Fields, Jeremy D.; Parilla, Philip A.; Ginley, David S.

    2015-01-15

    Rapid thermal processing (RTP) is widely used for processing a variety of materials, including electronics and photovoltaics. Presently, optimization of RTP is done primarily based on ex-situ studies. As a consequence, the precise reaction pathways and phase progression during the RTP remain unclear. More awareness of the reaction pathways would better enable process optimization and foster increased adoption of RTP, which offers numerous advantages for synthesis of a broad range of materials systems. To achieve this, we have designed and developed a RTP instrument that enables real-time collection of X-ray diffraction data with intervals as short as 100 ms, while heating with ramp rates up to 100 °Cs{sup −1}, and with a maximum operating temperature of 1200 °C. The system is portable and can be installed on a synchrotron beamline. The unique capabilities of this instrument are demonstrated with in-situ characterization of a Bi{sub 2}O{sub 3}-SiO{sub 2} glass frit obtained during heating with ramp rates 5 °C s{sup −1} and 100 °C s{sup −1}, revealing numerous phase changes.

  7. In Situ Synchrotron X-ray Study of Ultrasound Cavitation and Its Effect on Solidification Microstructures

    NASA Astrophysics Data System (ADS)

    Mi, Jiawei; Tan, Dongyue; Lee, Tung Lik

    2015-08-01

    Considerable progress has been made in studying the mechanism and effectiveness of using ultrasound waves to manipulate the solidification microstructures of metallic alloys. However, uncertainties remain in both the underlying physics of how microstructures evolve under ultrasonic waves, and the best technological approach to control the final microstructures and properties. We used the ultrafast synchrotron X-ray phase contrast imaging facility housed at the Advanced Photon Source, Argonne National Laboratory, US to study in situ the highly transient and dynamic interactions between the liquid metal and ultrasonic waves/bubbles. The dynamics of ultrasonic bubbles in liquid metal and their interactions with the solidifying phases in a transparent alloy were captured in situ. The experiments were complemented by the simulations of the acoustic pressure field, the pulsing of the bubbles, and the associated forces acting onto the solidifying dendrites. The study provides more quantitative understanding on how ultrasonic waves/bubbles influence the growth of dendritic grains and promote the grain multiplication effect for grain refinement.

  8. Synchrotron X-Ray Microprobe In-Situ Analysis of Extraterrestrial Particles Collected in Aerogel on the MIR Space Station

    NASA Technical Reports Server (NTRS)

    Flynn, G. J.; Sutton, S. R.; Horz, F.

    2000-01-01

    Using in-situ x-ray fluorescence, we determined the Cr/Fe, Mn/Fe and Ni/Fe of a particle captured in aerogel on MIR are approximately chondritic, indicating an extraterrestrial origin. Impurity of the aerogel precluded determining the Cu and Zn.

  9. Distinct charge dynamics in battery electrodes revealed by in situ and operando soft X-ray spectroscopy

    PubMed Central

    Liu, Xiaosong; Wang, Dongdong; Liu, Gao; Srinivasan, Venkat; Liu, Zhi; Hussain, Zahid; Yang, Wanli

    2013-01-01

    Developing high-performance batteries relies on material breakthroughs. During the past few years, various in situ characterization tools have been developed and have become indispensible in studying and the eventual optimization of battery materials. However, soft X-ray spectroscopy, one of the most sensitive probes of electronic states, has been mainly limited to ex situ experiments for battery research. Here we achieve in situ and operando soft X-ray absorption spectroscopy of lithium-ion battery cathodes. Taking advantage of the elemental, chemical and surface sensitivities of soft X-rays, we discover distinct lithium-ion and electron dynamics in Li(Co1/3Ni1/3Mn1/3)O2 and LiFePO4 cathodes in polymer electrolytes. The contrast between the two systems and the relaxation effect in LiFePO4 is attributed to a phase transformation mechanism, and the mesoscale morphology and charge conductivity of the electrodes. These discoveries demonstrate feasibility and power of in situ soft X-ray spectroscopy for studying integrated and dynamic effects in batteries. PMID:24100759

  10. Distinct charge dynamics in battery electrodes revealed by in situ and operando soft X-ray spectroscopy.

    PubMed

    Liu, Xiaosong; Wang, Dongdong; Liu, Gao; Srinivasan, Venkat; Liu, Zhi; Hussain, Zahid; Yang, Wanli

    2013-01-01

    Developing high-performance batteries relies on material breakthroughs. During the past few years, various in situ characterization tools have been developed and have become indispensible in studying and the eventual optimization of battery materials. However, soft X-ray spectroscopy, one of the most sensitive probes of electronic states, has been mainly limited to ex situ experiments for battery research. Here we achieve in situ and operando soft X-ray absorption spectroscopy of lithium-ion battery cathodes. Taking advantage of the elemental, chemical and surface sensitivities of soft X-rays, we discover distinct lithium-ion and electron dynamics in Li(Co(¹/₃)Ni(¹/₃)Mn(¹/₃))O₂ and LiFePO₄ cathodes in polymer electrolytes. The contrast between the two systems and the relaxation effect in LiFePO₄ is attributed to a phase transformation mechanism, and the mesoscale morphology and charge conductivity of the electrodes. These discoveries demonstrate feasibility and power of in situ soft X-ray spectroscopy for studying integrated and dynamic effects in batteries.

  11. In-situ X-ray Nanocharacterization of Defect Kinetics in Chalcogenide Solar Cell Materials

    SciTech Connect

    Bertoni, Mariana; Lai, Barry; Masser, Jorg; Buonassisi, Tonio

    2016-09-21

    ) correlate positively, and In negatively with charge collection efficiency for cells with low Ga content, both at grain boundaries and in grain cores. For cells with high Ga content, the charge collection efficiency depends to much lesser extent on the elemental distribution. The objective is three folded: (1) develop an x-ray in-situ microscopy capability to simulate growth and processing conditions, (2) apply it to elucidate performance-governing defect kinetics in chalcogenide solar cell materials, and (3) to study approaches to engineer materials from the nanoscale up. The development of these capabilities will enable experimental characterization to take place under actual processing and operating conditions and it will have impact well beyond the proposed research, enabling future studies on a large variety of materials system where electronic properties depend on underlying structural or chemical inhomogeneities.

  12. Density measurements and structural properties of liquid and amorphous metals under high pressure studied by in situ X-ray scattering (Invited)

    NASA Astrophysics Data System (ADS)

    Morard, G.; Garbarino, G.; Andrault, D.; Antonangeli, D.; Guignot, N.; Siebert, J.; Roberge, M.; Boulard, E.; Lincot, A.; Denoeud, A.; Petitgirard, S.

    2013-12-01

    Density determination for crystalline materials under high pressure and high temperature is straightforward using X-ray diffraction. For liquid and amorphous materials, it is more complicated due to the absence of long-range order. Different high pressure techniques have been developed: in-situ X-ray absorption 1-4 or ex-situ sink/float method 5-8. However, these techniques suffer several limitations, such as the limited pressure range or the long exposure time required. We have implemented an in situ X-ray diffraction analysis method suitable for the determination of Pressure-Volume-Temperature equations of state (P-V-T EoS) in the critical case of liquid and amorphous materials over an extended thermodynamic range (T>2000 K and P> 40 GPa). This method is versatile, it can be applied to data obtained using various angle-dispersive X-ray diffraction high-pressure apparatus and, contrary to in situ X-ray absorption techniques, is independent from the sample geometry. Further advantage is the fast data acquisition (between 10 to 300 seconds integration time). Information on macroscopic bulk properties (density) and local atomic arrangement (pair distribution function g(r)) can be gathered in parallel. To illustrate the method, we present studies on liquid Fe-S alloys in Paris Edinburgh press and in laser-heated diamond anvil cell, and measurements on Ce glass in diamond anvil cell at room temperature. References 1 G. Shen, N. Sata, M. Newville et al., App. Phys. Lett. 81 (8), 1411 (2002). 2 C. Sanloup, F. Guyot, P. Gillet et al., Geophys. Res. Lett. 27 (6), 811 (2000). 3 Y. Katayama, K. Tsuji, O. Shimomura et al., J. Synch. Rad. 5, 1023 (1998). 4 T. Sato and N. Funamori, Phys. Rev. Lett. 101, 255502 (2008). 5 R. Knoche and R. W. Luth, Chem. Geol. 128, 229 (1996). 6 P.S. Balog, R.A. Secco, D.C. Rubie et al., J. Geophys. Res. 108 (B2), 2124 (2003). 7 C. B. Agee and D. Walker, J. Geophys. Res. 93 (B4), 3437 (1988). 8 E. Ohtani, A. Suzuki, and T. Kato, Proc. Jpn. Acad

  13. Data of low-dose phase-based X-ray imaging for in situ soft tissue engineering assessments

    PubMed Central

    Izadifar, Zohreh; Honaramooz, Ali; Wiebe, Sheldon; Belev, George; Chen, Xiongbiao; Chapman, Dean

    2016-01-01

    This article presents the data of using three phase-based X-ray imaging techniques to characterize biomaterial scaffold and soft tissues in situ, as reported in our study “Low-dose phase-based X-ray imaging techniques for in situ soft tissue engineering assessments” [1]. The examined parameters include the radiation dose, scan time, and image quality, which are all critical to longitudinal in situ live animal assessments. The data presented were obtained from three dimensional imaging of scaffolds in situ cartilage by means of synchrotron-based computed tomography-diffraction enhanced imaging (CT-DEI), analyzer based imaging (CT-ABI), and in-line phase contrast imaging (CT-PCI) at standard and low dose imaging modalities. PMID:26909381

  14. X-Ray Diffraction in Situ Study of Phase Formation and Amorphous-To Transformation in FeCuNbSiB Alloys

    NASA Astrophysics Data System (ADS)

    Tuong, Le Thi Cat; Phuc, Phan Vinh; Nghi, Nguyen Hoang

    2001-04-01

    This paper presents some reeenl results of a X-ray in situ study of phase formation process and amorphous-to-nanocrystalline transformation in FeCuNbSiB alloy. Measurements were carried out on the diffractometer Siemens-D5000 with high temperature attachment. Our experiments were performed in both isothermal and nonisothermal regimes in argon atmosphere with time periods from a minute to 3 hours and different temperatures ranging from room temperature to 900°C. The X-ray diffraction data were used to determine the amount of crystalline fraction rs temperature and vs time. Both the first amorphous halo and the (110) diffraction peak of the bcc Fe-based solid solution were fitted, after background substruction. by means of the pseudo-voigt function. The grain sizes for even annealing temperature were determined by the X-ray profile analysis and using Bruker Win-Crysize program package. The kinetics of the nanocrystallization process was investigated and the activation energy was estimated. All the obtained results were compared with those of conventional studies.

  15. Design and Operation of an In Situ High Pressure Reaction Cell for X-Ray Absorption Spectroscopy

    NASA Astrophysics Data System (ADS)

    Bare, Simon R.; Yang, N.; Kelly, S. D.; Mickelson, G. E.; Modica, F. S.

    2007-02-01

    The design and initial operation of an in situ catalysis reaction cell for x-ray absorption spectroscopy measurements at high pressure is described. The design is based on an x-ray transparent tube fabricated from beryllium. This forms a true plug flow reactor for catalysis studies. The reactor is coupled to a portable microprocessor-controlled versatile feed system, and incorporates on-line analysis of reaction products. XAFS data recorded during the reduction of a NiRe/carbon catalyst at 4 bar are used to illustrate the performance of the reactor.

  16. In situ characterization of catalysts and membranes in a microchannel under high-temperature water gas shift reaction conditions

    NASA Astrophysics Data System (ADS)

    Cavusoglu, G.; Dallmann, F.; Lichtenberg, H.; Goldbach, A.; Dittmeyer, R.; Grunwaldt, J.-D.

    2016-05-01

    Microreactor technology with high heat transfer in combination with stable catalysts is a very attractive approach for reactions involving major heat effects such as methane steam reforming and to some extent, also the high temperature water gas shift (WGS) reaction. For this study Rh/ceria catalysts and an ultrathin hydrogen selective membrane were characterized in situ in a microreactor specially designed for x-ray absorption spectroscopic measurements under WGS conditions. The results of these experiments can serve as a basis for further development of the catalysts and membranes.

  17. In Situ X-ray Diffraction Studies of Cathode Materials in Lithium Batteries

    SciTech Connect

    Yang, X. Q.; Sun, X.; McBreen, J.; Mukerjee, S.; Gao, Yuan; Yakovleva, M. V.; Xing, X. K.; Daroux, M. L.

    1998-11-01

    There is an increasing interest in lithiated transition metal oxides because of their use as cathodes in lithium batteries. LiCoO{sub 2}, LiNiO{sub 2} and LiMn{sub 2}O{sub 4} are the three most widely used and studied materials, At present, although it is relative expensive and toxic, LiCoO{sub 2} is the material of choice in commercial lithium ion batteries because of its ease of manufacture, better thermal stability and cycle life. However, the potential use of lithium ion batteries with larger capacity for power tools and electric vehicles in the future will demand new cathode materials with higher energy density, lower cost and better thermal stability. LiNiO{sub 2} is isostructural with LiCoO{sub 2}. It offers lower cost and high energy density than LiCoO{sub 2}. However, it has much poorer thermal stability than LiCoO{sub 2}, in the charged (delithiated) state. Co, Al, and other elements have been used to partially replace Ni in LiNiO{sub 2} system in order to increase the thermal stability. LiMn{sub 2}O{sub 4} has the highest thermal stability and lowest cost and toxicity. However, the low energy density and poor cycle life at elevated temperature are the major obstacles for this material. In order to develop safer, cheaper, and better performance cathode materials, the in-depth understanding of the relationships between the thermal stability and structure, performance and structure are very important. The performance here includes energy density and cycle life of the cathode materials. X-ray diffraction (XRD) is one of the most powerful tools to study these relationships. The pioneer ex situ XRD work on cathode materials for lithium batteries was done by Ohzuku. His XRD studies on LiMn{sub 2}O{sub 4}, LiCoO{sub 2}, LiNiO{sub 2}, LiNi{sub 0.5}Co{sub 0.5}O{sub 2}, and LiAl{sub x}Ni{sub 1-x}O{sub 2} cathodes at different states of charge have provided important guidelines for the development of these new materials. However, the kinetic nature of the battery

  18. New developments in laser-heated diamond anvil cell with in situ synchrotron x-ray diffraction at High Pressure Collaborative Access Team

    SciTech Connect

    Meng, Yue; Hrubiak, Rostislav; Rod, Eric; Shen, Guoyin; Boehler, Reinhard

    2015-07-15

    An overview of the in situ laser heating system at the High Pressure Collaborative Access Team, with emphasis on newly developed capabilities, is presented. Since its establishment at the beamline 16-ID-B a decade ago, laser-heated diamond anvil cell coupled with in situ synchrotron x-ray diffraction has been widely used for studying the structural properties of materials under simultaneous high pressure and high temperature conditions. Recent developments in both continuous-wave and modulated heating techniques have been focusing on resolving technical issues of the most challenging research areas. The new capabilities have demonstrated clear benefits and provide new opportunities in research areas including high-pressure melting, pressure-temperature-volume equations of state, chemical reaction, and time resolved studies.

  19. New developments in laser-heated diamond anvil cell with in situ synchrotron x-ray diffraction at High Pressure Collaborative Access Team.

    PubMed

    Meng, Yue; Hrubiak, Rostislav; Rod, Eric; Boehler, Reinhard; Shen, Guoyin

    2015-07-01

    An overview of the in situ laser heating system at the High Pressure Collaborative Access Team, with emphasis on newly developed capabilities, is presented. Since its establishment at the beamline 16-ID-B a decade ago, laser-heated diamond anvil cell coupled with in situ synchrotron x-ray diffraction has been widely used for studying the structural properties of materials under simultaneous high pressure and high temperature conditions. Recent developments in both continuous-wave and modulated heating techniques have been focusing on resolving technical issues of the most challenging research areas. The new capabilities have demonstrated clear benefits and provide new opportunities in research areas including high-pressure melting, pressure-temperature-volume equations of state, chemical reaction, and time resolved studies.

  20. New developments in laser-heated diamond anvil cell with in situ synchrotron x-ray diffraction at High Pressure Collaborative Access Team

    DOE PAGES

    Meng, Yue; Hrubiak, Rostislav; Rod, Eric; ...

    2015-07-17

    An overview of the in situ laser heating system at the High Pressure Collaborative Access Team, with emphasis on newly developed capabilities, is presented. Since its establishment at the beamline 16-ID-B a decade ago, laser-heated diamond anvil cell coupled with in situ synchrotron x-ray diffraction has been widely used for studying the structural properties of materials under simultaneous high pressure and high temperature conditions. Recent developments in both continuous-wave and modulated heating techniques have been focusing on resolving technical issues of the most challenging research areas. Furthermore, the new capabilities have demonstrated clear benefits and provide new opportunities in researchmore » areas including high-pressure melting, pressure-temperature-volume equations of state, chemical reaction, and time resolved studies.« less

  1. New developments in laser-heated diamond anvil cell with in situ synchrotron x-ray diffraction at High Pressure Collaborative Access Team

    SciTech Connect

    Meng, Yue; Hrubiak, Rostislav; Rod, Eric; Boehler, Reinhard; Shen, Guoyin

    2015-07-17

    An overview of the in situ laser heating system at the High Pressure Collaborative Access Team, with emphasis on newly developed capabilities, is presented. Since its establishment at the beamline 16-ID-B a decade ago, laser-heated diamond anvil cell coupled with in situ synchrotron x-ray diffraction has been widely used for studying the structural properties of materials under simultaneous high pressure and high temperature conditions. Recent developments in both continuous-wave and modulated heating techniques have been focusing on resolving technical issues of the most challenging research areas. Furthermore, the new capabilities have demonstrated clear benefits and provide new opportunities in research areas including high-pressure melting, pressure-temperature-volume equations of state, chemical reaction, and time resolved studies.

  2. Recent progress on synchrotron-based in-situ soft X-ray spectroscopy for energy materials.

    PubMed

    Liu, Xiaosong; Yang, Wanli; Liu, Zhi

    2014-12-10

    Soft X-ray spectroscopy (SXS) techniques such as photoelectron spectroscopy, soft X-ray absorption spectroscopy and X-ray emission spectroscopy are efficient and direct tools to probe electronic structures of materials. Traditionally, these surface sensitive soft X-ray techniques that detect electrons or photons require high vacuum to operate. Many recent in situ instrument developments of these techniques have overcome this vacuum barrier. One can now study many materials and model devices under near ambient, semi-realistic, and operando conditions. Further developments of integrating the realistic sample environments with efficient and high resolution detection methods, particularly at the high brightness synchrotron light sources, are making SXS an important tool for the energy research community. In this progress report, we briefly describe the basic concept of several SXS techniques and discuss recent development of SXS instruments. We then present several recent studies, mostly in situ SXS experiments, on energy materials and devices. Using these studies, we would like to highlight that the integration of SXS and in situ environments can provide in-depth insight of material's functionality and help researchers in new energy material developments. The remaining challenges and critical research directions are discussed at the end. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. In situ alkali-silica reaction observed by x-ray microscopy

    SciTech Connect

    Kurtis, K.E.; Monteiro, P.J.M.; Brown, J.T.; Meyer-Ilse, W.

    1997-04-01

    In concrete, alkali metal ions and hydroxyl ions contributed by the cement and reactive silicates present in aggregate can participate in a destructive alkali-silica reaction (ASR). This reaction of the alkalis with the silicates produces a gel that tends to imbibe water found in the concrete pores, leading to swelling of the gel and eventual cracking of the affected concrete member. Over 104 cases of alkali-aggregate reaction in dams and spillways have been reported around the world. At present, no method exists to arrest the expansive chemical reaction which generates significant distress in the affected structures. Most existing techniques available for the examination of concrete microstructure, including ASR products, demand that samples be dried and exposed to high pressure during the observation period. These sample preparation requirements present a major disadvantage for the study of alkali-silica reaction. Given the nature of the reaction and the affect of water on its products, it is likely that the removal of water will affect the morphology, creating artifacts in the sample. The purpose of this research is to observe and characterize the alkali-silica reaction, including each of the specific reactions identified previously, in situ without introducing sample artifacts. For observation of unconditioned samples, x-ray microscopy offers an opportunity for such an examination of the alkali-silica reaction. Currently, this investigation is focusing on the effect of calcium ions on the alkali-silica reaction.

  4. Kinetics of methane hydrate decomposition studied via in situ low temperature X-ray powder diffraction.

    PubMed

    Everett, S Michelle; Rawn, Claudia J; Keffer, David J; Mull, Derek L; Payzant, E Andrew; Phelps, Tommy J

    2013-05-02

    Gas hydrate is known to have a slowed decomposition rate at ambient pressure and temperatures below the melting point of ice. As hydrate exothermically decomposes, gas is released and water of the clathrate cages transforms into ice. Based on results from the decomposition of three nominally similar methane hydrate samples, the kinetics of two regions, 180-200 and 230-260 K, within the overall decomposition range 140-260 K, were studied by in situ low temperature X-ray powder diffraction. The kinetic rate constants, k(a), and the reaction mechanisms, n, for ice formation from methane hydrate were determined by the Avrami model within each region, and activation energies, E(a), were determined by the Arrhenius plot. E(a) determined from the data for 180-200 K was 42 kJ/mol and for 230-260 K was 22 kJ/mol. The higher E(a) in the colder temperature range was attributed to a difference in the microstructure of ice between the two regions.

  5. Hydrazine reduction of transition metal oxides - In situ characterization using X-ray photoelectron spectroscopy

    NASA Technical Reports Server (NTRS)

    Littrell, D. M.; Tatarchuk, B. J.

    1986-01-01

    The transition metal oxides (TMOs) V2O5, FeO3, Co3O4, NiO, CuO, and ZnO were exposed to hydrazine at various pressures. The metallic surfaces were surveyed by in situ X-ray photoelectron spectroscopy to determine the irrelative rate of reduction by hydrazine. The most easily reducible oxide, CuO, could be reduced to the metallic state at room temperature and 10 to the -6th torr. The reaction is first order with respect to CuO, with an activation energy of about 35 kJ/mol. Two types of adsorption were seen to occur at 295 K: (1) a reversible component in which the measured N:Cu ratio increased to 0.60 at hydrazine pressures up to 0.5 torr, and (2) an irreversible component, with a N:Cu ratio of 0.28, which could not be removed by extended vacuum pumping. The results of this study are useful for the identification of TMO's that can be used as solid neatallizers of hydrazine spills, and for the preparation of metal surfaces for electroplating and evaporative thin-film coating.

  6. Geopolymerisation Kinetics. 1. In situ Energy-Dispersive X-ray Diffractometry

    SciTech Connect

    Provis,J.; van Deventer, J.

    2007-01-01

    In situ energy-dispersive X-ray diffractometry, using a polychromatic synchrotron beam and a 'laboratory-sized' sample, is used to provide a direct measurement of the kinetics of geopolymerisation. The effects of sample SiO{sub 2}/Al{sub 2}O{sub 3} ratio, Na/(Na+K) ratio and reaction temperature are investigated. The results obtained support recent propositions that the initial gel phase formed during geopolymerisation is later transformed to a second, probably more-ordered gel phase, and provide detailed information regarding the rate of formation of the first gel phase during the first 3 h of reaction. Increasing the SiO{sub 2}/Al{sub 2}O{sub 3} ratio generally decreases the initial rate of reaction, with the highest SiO{sub 2}/Al{sub 2}O{sub 3} ratio samples showing what appears to be a pause in the reaction corresponding roughly to the solidification of the geopolymeric binder. Mixed (Na,K)-aluminosilicate geopolymers with moderate SiO{sub 2}/Al{sub 2}O{sub 3} ratios behave similarly to pure Na- or K-aluminosilicate compositions of higher SiO{sub 2}/Al{sub 2}O{sub 3} ratio. Fitting a simplified first-order rate expression to the overall reaction process at different temperatures allows the calculation of an effective overall activation energy, which may be useful in comparing geopolymerisation of slurries with different compositions.

  7. Rapid terrestrial core formation from in situ X-ray computed microtomography

    NASA Astrophysics Data System (ADS)

    Chen, B.; Zhang, D.; Leng, W.; Jackson, J. M.; Wang, Y.; Yu, T.; Liu, J.; Li, J.

    2011-12-01

    The timescale of the terrestrial core formation constrained from the hafnium-tungsten chronometer is within 30 million years after the Solar System formation (e.g. Kleine et al., 2002; Yin et al., 2002). Possible mechanisms for core formation include diapiric instability of iron-rich liquids and percolation of the liquids through the solid silicate matrix. Core-mantle segregation by diapiric instabilities is thought to be a more rapid and efficient core formation process compared with percolation (Stevenson, 1981; Rubie et al., 2007; Golabek et al., 2008). Our experimental results from in situ X-ray computed microtomography show that at 1-1.5 GPa the iron-sulfur and iron-carbon liquids sank through the underlying olivine layer at a speed consistent with the measured core formation timescale. Our three-dimensional tomography data taken at various heating stages revealed that the iron-rich liquid diapirs in olivine induced percolative flow channeling processes, which affects the rheology of olivine and thus facilitates the sinking of iron-rich diapirs. Numerical simulations of diapir sinking based on the tomography observations suggest that the percolative flow channeling process accompanying the iron diapirs could significantly reduce the time for core formation segregation by a factor of 2 or more, depending on the viscosity reduction ratio caused by the percolative flow. Our study sheds new light on core formation processes in the Earth and terrestrial-like planetary bodies, contributing to our understanding of the origin and dynamics of planetary cores.

  8. Strains in Thermally Growing Alumina Films Measured in-situ usingSynchrotron X-rays

    SciTech Connect

    Hou, P.Y.; Paulikas, A.P.; Veal, B.W.

    2006-01-02

    Strains in thermally grown oxides have been measured in-situ, as the oxides develop and evolve. Extensive data have been acquired from oxides grown in air at elevated temperatures on different model alloys that form Al{sub 2}O{sub 3}. Using synchrotron x-rays at the Advanced Photon Source (Beamline 12BM, Argonne National Laboratory), Debye-Scherrer diffraction patterns from the oxidizing specimen were recorded every 5 minutes during oxidation and subsequent cooling. The diffraction patterns were analyzed to determine strains in the oxides, as well as phase changes and the degree of texture. To study a specimen's response to stress perturbation, the oxidizing temperature was quickly cooled from 1100 to 950 C to impose a compressive thermal stress in the scale. This paper describes this new experimental approach and gives examples from oxidized {beta}-NiAl, Fe-20Cr-10Al, Fe-28Al-5Cr and H{sub 2}-annealed Fe-28Al-5Cr (all at. %) alloys to illustrate some current understanding of the development and relaxation of growth stresses in Al{sub 2}O{sub 3}.

  9. Scanning of Adsorption Hysteresis In Situ with Small Angle X-Ray Scattering

    PubMed Central

    Mitropoulos, Athanasios Ch.; Favvas, Evangelos P.; Stefanopoulos, Konstantinos L.; Vansant, Etienne F.

    2016-01-01

    Everett’s theorem-6 of the domain theory was examined by conducting adsorption in situ with small angle x-ray scattering (SAXS) supplemented by the contrast matching technique. The study focuses on the spectrum differences of a point to which the system arrives from different scanning paths. It is noted that according to this theorem at a common point the system has similar macroscopic properties. Furthermore it was examined the memory string of the system. We concluded that opposite to theorem-6: a) at a common point the system can reach in a finite (not an infinite) number of ways, b) a correction for the thickness of the adsorbed film prior to capillary condensation is necessary, and c) the scattering curves although at high-Q values coincide, at low-Q values are different indicating different microscopic states. That is, at a common point the system holds different metastable states sustained by hysteresis effects. These metastable states are the ones which highlight the way of a system back to a return point memory (RPM). Entering the hysteresis loop from different RPMs different histories are implanted to the paths toward the common point. Although in general the memory points refer to relaxation phenomena, they also constitute a characteristic feature of capillary condensation. Analogies of the no-passing rule and the adiabaticity assumption in the frame of adsorption hysteresis are discussed. PMID:27741263

  10. Boron phosphide under pressure: In situ study by Raman scattering and X-ray diffraction

    SciTech Connect

    Solozhenko, Vladimir L.; Kurakevych, Oleksandr O.; Le Godec, Yann; Kurnosov, Aleksandr V.; Oganov, Artem R.

    2014-07-21

    Cubic boron phosphide, BP, has been studied in situ by X-ray diffraction and Raman scattering up to 55 GPa at 300 K in a diamond anvil cell. The bulk modulus of B{sub 0} = 174(2) GPa has been established, which is in excellent agreement with our ab initio calculations. The data on Raman shift as a function of pressure, combined with equation-of-state (EOS) data, allowed us to estimate the Grüneisen parameters of the TO and LO modes of zinc-blende structure, γ{sub G}{sup TO }= 1.26 and γ{sub G}{sup LO }= 1.13, just like in the case of other A{sup III}B{sup V} diamond-like phases, for which γ{sub G}{sup TO }> γ{sub G}{sup LO }≅ 1. We also established that the pressure dependence of the effective electro-optical constant α is responsible for a strong change in relative intensities of the TO and LO modes from I{sub TO}/I{sub LO} ∼ 0.25 at 0.1 MPa to I{sub TO}/I{sub LO} ∼ 2.5 at 45 GPa, for which we also find excellent agreement between experiment and theory.

  11. In situ X-ray observation and simulation of ratcheting-fatigue interactions in solder joints

    NASA Astrophysics Data System (ADS)

    Shi, Liting; Mei, Yunhui; Chen, Gang; Chen, Xu

    2017-01-01

    Reflow voids created by solder oxidation reduce the reliability of lap joints. In situ visualization of reflow voids in Sn-3Ag-0.5Cu (SAC305) lap-shear solder joints under cyclic stressing was realized by X-ray computed tomography (CT), while the ratcheting deformation of the solder joints was monitored by a non-contact displacement detecting system (NDDS). The results revealed that the shape evolution of reflow voids in solder joints, as characterized by the sphericity of the voids, can be divided into three stages: i.e., the initial stage with a sharp drop, a stable stage, and a rapidly declining stage. A new evolution law for describing the progress of sphericity was proposed, and was further introduced into a viscoplastic constitutive model based on the OW-AF nonlinear kinematic hardening rule. The damage-coupled OW-AF model yielded an accurate estimation of the whole-life ratcheting behavior of Sn-3Ag-0.5Cu (SAC305) lap-shear solder joints. [Figure not available: see fulltext.

  12. A rotational and axial motion system load frame insert for in situ high energy x-ray studies

    SciTech Connect

    Shade, Paul A. Schuren, Jay C.; Turner, Todd J.; Blank, Basil; Kenesei, Peter; Goetze, Kurt; Lienert, Ulrich; Almer, Jonathan; Suter, Robert M.; Bernier, Joel V.; Li, Shiu Fai; Lind, Jonathan

    2015-09-15

    High energy x-ray characterization methods hold great potential for gaining insight into the behavior of materials and providing comparison datasets for the validation and development of mesoscale modeling tools. A suite of techniques have been developed by the x-ray community for characterizing the 3D structure and micromechanical state of polycrystalline materials; however, combining these techniques with in situ mechanical testing under well characterized and controlled boundary conditions has been challenging due to experimental design requirements, which demand new high-precision hardware as well as access to high-energy x-ray beamlines. We describe the design and performance of a load frame insert with a rotational and axial motion system that has been developed to meet these requirements. An example dataset from a deforming titanium alloy demonstrates the new capability.

  13. Reactive sputter magnetron reactor for preparation of thin films and simultaneous in situ structural study by X-ray diffraction.

    PubMed

    Bürgi, J; Neuenschwander, R; Kellermann, G; García Molleja, J; Craievich, A F; Feugeas, J

    2013-01-01

    The purpose of the designed reactor is (i) to obtain polycrystalline and∕or amorphous thin films by controlled deposition induced by a reactive sputtering magnetron and (ii) to perform a parallel in situ structural study of the deposited thin films by X-ray diffraction, in real time, during the whole growth process. The designed reactor allows for the control and precise variation of the relevant processing parameters, namely, magnetron target-to-sample distance, dc magnetron voltage, and nature of the gas mixture, gas pressure and temperature of the substrate. On the other hand, the chamber can be used in different X-ray diffraction scanning modes, namely, θ-2θ scanning, fixed α-2θ scanning, and also low angle techniques such as grazing incidence small angle X-ray scattering and X-ray reflectivity. The chamber was mounted on a standard four-circle diffractometer located in a synchrotron beam line and first used for a preliminary X-ray diffraction analysis of AlN thin films during their growth on the surface of a (100) silicon wafer.

  14. Evaluation of dual energy x-ray absorptiometry for in situ measurement of bone mineral density of equine metacarpi.

    PubMed

    McClure, S R; Glickman, L T; Glickman, N W; Weaver, C M

    2001-05-01

    To determine the accuracy and precision of dual energy x-ray absorptiometry (DEXA) for measuring bone mineral density in horses in situ. Sample Population-12 randomly selected forelimbs from 12 horses. Metacarpi were scanned in 2 planes and DEXA measurements obtained for 6 regions of interest (ROI). Each ROI was isolated and bone density measured by Archimedes' principle. Linear regression analysis was used to determine the correlation between the 2 measurements at each ROI. An additional metacarpus was measured 10 times to determine the coefficient of variation for both techniques. Dual energy x-ray absorptiometry and bone density were significantly associated at multiple ROI. The addition of age, weight, and soft tissue or bone thickness improved these associations. Repeated measurements had a low coefficient of variation. Dual energy x-ray absorptiometry can be used to accurately and precisely measure the bone density in the equine metacarpus. Dual energy x-ray absorptiometry appears suitable for serial in vivo measurement of bone density of the equine metacarpus. Dual energy x-ray absorptiometry may be used for studies to evaluate the effects of diet or drugs on bone density or density changes from bone remodeling that develop prior to stress fractures.

  15. X-ray lasers

    SciTech Connect

    Elton, R.C.

    1990-01-01

    This paper provides a source that surveys the fundamentals of x-ray lasers and summarizes recent advances. The author emphasizes x-ray lasers created using high temperature plasmas as the medium. Specific topics discussed included electron-collisional excitation pumping, plasma laser pumping, and gamma-ray lasers. Numerous literature references provided.

  16. Soft x-ray spectrometer for in situ monitoring of thin-film growth

    NASA Astrophysics Data System (ADS)

    Skytt, Per; Englund, Carl J.; Wassdahl, Nial; Mancini, Derrick C.; Nordgren, Joseph

    1994-11-01

    We have designed and constructed a compact spectrometer dedicated to in-situ characterization of thin films during deposition, using soft x-ray emission spectroscopy. It consists of a Rowland-circle mounted spherical grating and entrance slit, or slit array to enhance throughput. A 2D position-sensitive detector (microchannel plate stack and resistive anode) is mounted tangent to the image of the slit(s) on the Rowland circle. The instrument covers an energy range of 240 - 700 eV using a 300 1/mm grating in the first order. Thus, the spectrometer simultaneously records K emission for low-Z elements C through F, while L emission for 3D metals can be recorded in first or higher orders. The resolution is approximately 300, allowing chemical analysis. Both detector and grating are housed in a vacuum chamber that is turbomolecularly pumped to a pressure below 10(superscript -6) Torr. The instrument can be attached to any process chamber using a standard UHV flange. The slit extends into the process chamber separated from the housing by a valve. This valve can be closed, or in one of two open positions where thin foils serve as vacuum windows to protect the detector and grating, and as filters to reduce background counts from UV light. The spectrometer has successfully monitored a variety of processes in situ, including growth of optical TiN films by reactive magnetron sputter deposition, synchrotron radiation induced CVD of metallic films, and hot-filament CVD growth of diamond.

  17. In situ spectroscopic investigation of hyperthermophilic metal-respiring archaea at high-temperature

    NASA Astrophysics Data System (ADS)

    Ménez, B.; Bureau, H.; Gouget, B.; Avoscan, L.; Simionovici, A.; Somogyi, A.

    2003-04-01

    The main issue of this study is developing methodologies that can improve abilities to characterize life in extreme habitats. In particular, it aims at evaluating the possibility of monitoring microorganisms mediated reactions involving metals by using non destructive X-ray microprobe combined with high pressure and temperature micro-reactors. The first step was dedicated to the study of metal-respiring organisms that achieve growth with oxyanions of arsenate and selenate as their electron acceptors for the oxidation of organic substrates or H2, forming elemental selenium or arsenite, respectively, as the reduction products. We focused on a strictly anaerobic hyperthermophilic archaea, Pyrobaculum arsenaticum, recently isolated and well adapted to high levels of arsenate and selenate (Huber et al., 2000, System. Appl. Microbiol., 23, 305). We report here the first in situ X-ray Absorption Near Edge Structure (XANES) spectroscopic characterization of the oxidation state of selenium following microbial respiration at high temperature. A Basset-modified Hydrothermal Diamond Anvil Cell (HDAC) acts as anaerobic micro-reactor to reproduce extreme temperature and pressure conditions for life and allows, together with the direct visual observation of the organisms, the microbeam characterization of the changes of metal concentration and speciation induced by microbial activity. The measurements were performed at the ESRF on undulator beamline ID22. P. arsenaticum together with its culture medium, doped with selenate (50 μM), were loaded under N_2 atmosphere in the HDAC. High-resolution X-ray fluorescence and selenium K-edge XANES spectra were collected alternatively and continuously at high temperature (up to 95^oC), allowing for the time-resolved monitoring of the chemical evolution of the culture medium. Data processing is still in progress. In the long-term, our aim is, on one hand, to shed light on the tolerance in terms of temperature, pressure and metal

  18. Temperature effect of elastic anisotropy and internal strain development in advanced nanostructured alloys: An in-situ synchrotron X-ray investigation

    DOE PAGES

    Gan, Yingye; Mo, Kun; Yun, Di; ...

    2017-03-19

    Nanostructured ferritic alloys (NFAs) are promising structural materials for advanced nuclear systems due to their exceptional radiation tolerance and high-temperature mechanical properties. Their remarkable properties result from the ultrafine ultrahigh density Y-Ti-O nanoclusters dispersed within the ferritic matrix. In this work, we performed in-situ synchrotron X-ray diffraction tests to study the tensile deformation process of the three types of NFAs: 9YWTV, 14YWT-sm13, and 14YWT-sm170 at both room temperature and elevated temperatures. A technique was developed, combining Kroner's model and X-ray measurement, to determine the intrinsic monocrystal elastic-stiffness constants, and polycrystal Young's modulus and Poisson's ratio of the NFAs. Temperature dependencemore » of elastic anisotropy was observed in the NFAs. Lastly, an analysis of intergranular strain and strengthening factors determined that 14YWT-sm13 had a higher resistance to temperature softening compared to 9YWTV, attributed to the more effective nanoparticle strengthening during high-temperature mechanical loading.« less

  19. High temperature x-ray diffraction studies on antiferroelectric and ferroelectric phase transitions in (Pb1-xBax)ZrO3 (x=0.05,0.10)

    NASA Astrophysics Data System (ADS)

    Pokharel, Bhadra P.; Pandey, Dhananjai

    2001-09-01

    We have carried out high temperature x-ray diffraction studies on (Pb1-xBax)ZrO3(PBZ) to correlate the large thermal hysteresis (˜100 °C for x=0.05) and irreversibility (for x=0.10) of the antiferroelectric (AFE)-ferroelectric (FE) phase transition observed in dielectric measurements with structural changes. It is shown that for both the compositions, the sequence of phase transitions during heating is orthorhombic antiferroelectric (AO) to rhombohedral ferroelectric (FR) and then to cubic paraelectric (PC). The wide phase coexistence region (˜80 °C for x=0.05 and ˜160 °C for x=0.10) and the arrest of the FR to AO transition for x=0.10 during cooling strongly indicate first order character of the AO-FR transition. It is shown that the transformation strains associated with the AO to FR transition increases with Ba2+ concentration from a value of 0.6% for x=0 to 0.9% for 0.10. Similarities of the AO-FR transition in PBZ with nonthermoelastic martensitic transformations are pointed out. The FR to PC transition is also shown to be first order but with a small thermal hysteresis (˜10 °C) and a small discontinuous change in the cell volume (˜0.5%).

  20. Soft x-ray emission of galliumlike rare-earth atoms produced by high-temperature low-density tokamak and high-density laser plasmas

    SciTech Connect

    Fournier, K.B.; Goldstein, W.H.; Osterheld, A. ); Finkenthal, M.; Lippmann, S.; Huang, L.K.; Moos, H.W. ); Spector, N. )

    1994-09-01

    Spectra of rare-earth atoms praseodymium, [ital Z]=59, to ytterbium, [ital Z]=70, emitted from the high-temperature (1 keV) low-density (10[sup 13] cm[sup [minus]3]) TEXT tokamak (at the Fusion Research Center, University of Texas, Austin) and high-density (10[sup 20] cm[sup [minus]3]) laser plasmas have been recorded in the soft-x-ray range of 50--200 A with an image intensifier detector and on photographic plates. The brightest [ital n]=4 to [ital n]=4 transitions of galliumlike ions have been identified and their emission patterns have been studied by comparison with [ital ab] [ital initio] atomic structure calculations and collisional radiative models under the respective plasma conditions. We have investigated the use of the ratios of the intensities of 4-4 transitions as indicators of plasma densities. This is possible owing to the doublet structure of the galliumlike ground state, which leads to a strong density dependence for ratios of transitions between low-lying levels. We have also used semiempirical ionization balance calculations to characterize the charge state distribution of the tokamak plasmas, in preparation for an investigation of the use of ratios of galliumlike to zinclike and copperlike emission features as indicators of whether the impurities are in coronal equilibrium or undergoing ionization.

  1. Thermal Stability of NaxCrO2 for Rechargeable Sodium Batteries; Studies by High-Temperature Synchrotron X-ray Diffraction.

    PubMed

    Yabuuchi, Naoaki; Ikeuchi, Issei; Kubota, Kei; Komaba, Shinichi

    2016-11-30

    Thermal stability and phase transition processes of NaCrO2 and Na0.5CrO2 are carefully examined by high-temperature synchrotron X-ray diffraction method. O3-type NaCrO2 shows anisotropic thermal expansion on heating, which is a common character as layered materials, without phase transition in the temperature range of 27-527 °C. In contrast, for the desodiated phase, in-plane distorted P3-type layered oxide (P'3 Na0.5CrO2), phase transition occurs in the following order. Monoclinic distortion associated with Na/vacancy ordering is gradually lost on heating, and its symmetry increases and changes to a rhombohedral lattice at 207 °C. On further heating, phase segregation to two P3 layered metastable phases, which have different interlayer distances (17.0 and 13.5 Å, presumably sodium-rich and sodium-free P3 phases, respectively) are observed on heating to 287-477 °C, but oxygen loss is not observed. Oxygen loss is observed at temperatures only above 500 °C, resulting in the formation of corundum-type Cr2O3 and O3 NaCrO2 as thermodynamically stable phases. From these results, possibility of NaxCrO2 as a positive electrode material for safe rechargeable sodium batteries is also discussed.

  2. X-ray photochemical alteration of planetary samples during in situ micro-XRF analysis

    NASA Astrophysics Data System (ADS)

    Flannery, D. T.; Tuite, M. L., Jr.; Hodyss, R. P.; Allwood, A.; Bhartia, R.; Abbey, W. J.; Williford, K. H.

    2015-12-01

    PIXL (Planetary Instrument for X-ray Lithochemistry; selected for the Mars 2020 mission contact science payload) uses a polycapillary to focus X-rays to a ~100 μm spot on sample surfaces, providing higher spatial resolution, higher X-ray flux, and higher fluorescence counts compared to previously flown planetary XRF instruments. Photochemical changes in organic materials occurring during investigations employing x-rays have been reported, particularly for biological samples examined in synchrotrons (e.g. George et al., J. Synchrotron Radiation, 19:875-876). However, little is known about the effect energies and fluxes typical to micro-XRF instruments may have on the organic molecules that are commonly preserved in rocks and sediments. In particular, it is essential to understand the effect of micro-XRF on organics preserved near surfaces that are later subjected to contact science that focuses on organic geochemistry (e.g. UV Raman/fluorescence instruments). We report results of an investigation in which samples containing organic molecules were exposed to X-ray energies and fluxes typical to micro-XRF. Samples containing alkanes and polycyclic aromatic hydrocarbons were characterized by GC-MS and UV Raman/fluorescence before being subjected to various X-ray energies and fluxes typical of PIXL. Following x-ray irradiation, samples were again characterized by GC-MS and UV Raman/fluorescence in order to characterize photochemical effects.

  3. In situ x-ray microscopic observation of the electromigration in passivated Cu interconnects

    NASA Astrophysics Data System (ADS)

    Schneider, G.; Hambach, D.; Niemann, B.; Kaulich, B.; Susini, J.; Hoffmann, N.; Hasse, W.

    2001-03-01

    X-ray imaging of electromigration in a passivated Cu interconnect was performed with 100-nm spatial resolution. A time sequence of 200 images, recorded with the European Synchrotron Radiation Facility x-ray microscope in 2.2 h at 4 keV photon energy, visualizes the mass flow of Cu at current densities up to 2×107 A/cm2. Due to the high penetration power through matter and the element specific image contrast, x-ray microscopy is a unique tool for time-resolved, quantitative mass transport measurements in interconnects. Model calculations predict that failures in operating microprocessors are detectable with 30 nm resolution by nanotomography.

  4. Design and Operation of a High Pressure Reaction Cell for in situ X-ray Absorption Spectroscopy

    SciTech Connect

    Bare,S.; Yang, N.; Kelly, S.; Mickelson, G.; Modica, F.

    2007-01-01

    X-ray absorption spectroscopy measurements of catalytic reactions have been instrumental in advancing the understanding of catalytic processes. These measurements require an in situ catalysis reaction cell with unique properties. Here we describe the design and initial operation of an in situ/operando catalysis reaction cell for transmission X-ray absorption spectroscopy measurements. The cell is designed: to be an ideal catalytic reactor with no mass transfer effects; to give the same conversion and selectivity under similar space velocities as standard laboratory micro-reactors; to be operational temperatures up to 600 {sup o}C and pressures up to 14 bar; to be X-ray transparent allowing XAS measurement to be collected in transmission for all elements with Z {>=} 23 (vanadium K-edge at 5.5 keV); to measure the actual catalyst bed temperature; to not use o-ring seals, or water cooling; to be robust, compact, easy to assemble, and use, and relatively low cost to produce. The heart of the cell is fabricated from an X-ray transparent beryllium tube that forms a plug flow reactor. XAFS data recorded during the reduction of a Re/{gamma}-A{sub 2}O{sub 3} catalyst as a function of hydrogen pressure from 0.05 to 8 bar, and from a Pt-Sn/{gamma}-A{sub 2}O{sub 3} catalyst during n-heptane reforming are given as initial examples of the versatility of the reactor.

  5. In situ surface/interface x-ray diffractometer for oxide molecular beam epitaxy

    SciTech Connect

    Lee, J. H.; Tung, I. C.; Chang, S. -H.; Bhattacharya, A.; Fong, D. D.; Freeland, J. W.; Hong, Hawoong

    2016-01-05

    In situ studies of oxide molecular beam epitaxy by synchrotron x-ray scattering has been made possible by upgrading an existing UHV/molecular beam epitaxy (MBE) six-circle diffractometer system. For oxide MBE growth, pure ozone delivery to the chamber has been made available, and several new deposition sources have been made available on a new 12 in. CF (ConFlat, a registered trademark of Varian, Inc.) flange. X-ray diffraction has been used as a major probe for film growth and structures for the system. In the original design, electron diffraction was intended for the secondary diagnostics available without the necessity of the x-ray and located at separate positions. Deposition of films was made possible at the two diagnostic positions. And, the aiming of the evaporation sources is fixed to the point between two locations. Ozone can be supplied through two separate nozzles for each location. Also two separate thickness monitors are installed. Finally, additional features of the equipment are also presented together with the data taken during typical oxide film growth to illustrate the depth of information available via in situ x-ray techniques.

  6. In situ synchrotron x-ray spectroscopy of ruthenium nanoparticles modified with selenium for an oxygen reduction reaction.

    SciTech Connect

    Inukai, J.; Cao, D.; Wieckowski, A.; Chang, K.-C.; Menzel, A.; Komanicky, V.; You, H.; Univ. Illinois; Univ. Yamanashi

    2007-11-15

    We used in situ Se K-edge X-ray spectroscopy to characterize Ru nanoparticles chemically modified with submonolayers of selenium (Se/Ru) [Cao et al. J. Electrochem. Soc. 2006, 153, A869]. X-ray powder diffraction verified that the Se/Ru catalyst had metallic Ru cores. The in situ X-ray absorption near edge structure taken at the open circuit potential showed that there were both elemental and oxidized selenium on the as-prepared Se/Ru samples. All selenium oxide was reduced to the elemental form of selenium by applying negative potentials. By applying positive potentials, selenium was subsequently reoxidized. The analysis of the extended X-ray absorption fine structure shows the appearance of selenium hydration (Se-OH{sub 2}) in a deaerated solution, which was not observed during the oxygen reduction reaction. We present evidence that Se-free Ru atoms play an important role in the ORR activity of the Se/Ru catalyst studied in this paper.

  7. In-situ synchrotron x-ray spectroscopy of ruthenium nanoparticles modified with selenium for oxygen reduction reaction.

    SciTech Connect

    Inukai, J.; Cao, D.; Wieckowski, A.; Chang, K.-C.; Menzel, A.; Komanicky, V.; You, H.; Materials Science Division; Univ. of Illinois; Univ. of Yamanashi

    2007-11-15

    We used in situ Se K-edge X-ray spectroscopy to characterize Ru nanoparticles chemically modified with submonolayers of selenium (Se/Ru) [Cao et al. J. Electrochem. Soc. 2006, 153, A869]. X-ray powder diffraction verified that the Se/Ru catalyst had metallic Ru cores. The in situ X-ray absorption near edge structure taken at the open circuit potential showed that there were both elemental and oxidized selenium on the as-prepared Se/Ru samples. All selenium oxide was reduced to the elemental form of selenium by applying negative potentials. By applying positive potentials, selenium was subsequently reoxidized. The analysis of the extended X-ray absorption fine structure shows the appearance of selenium hydration (Se-OH{sub 2}) in a deaerated solution, which was not observed during the oxygen reduction reaction. We present evidence that Se-free Ru atoms play an important role in the ORR activity of the Se/Ru catalyst studied in this paper.

  8. In situ X-ray tomographic microscopy observations of vesiculation of bubble-free and bubble-bearing magmas

    NASA Astrophysics Data System (ADS)

    Pistone, Mattia; Caricchi, Luca; Fife, Julie L.; Mader, Kevin; Ulmer, Peter

    2015-12-01

    Magma degassing is thought to play a major role in magma fractionation, transport, storage, and volcanic eruption dynamics. However, the conditions that determine when and how magma degassing operates prior to and during an eruption remain poorly constrained. We performed experiments to explore if the initial presence of gas bubbles in magma influences the capability of gas to escape from the magma. Vesiculation of natural H2O-poor (<<1 wt.%) silicic obsidian glasses was investigated by in situ, high-temperature (above the glass transition) experiments using synchrotron-based X-ray tomographic microscopy with high spatial (3 μm/pixel) and temporal resolution (1 second per 3D dataset). As a validation, a second set of experiments was performed on identical starting materials using a Karl-Fisher titration setup to quantify the amount of extracted gas that escapes via volatile diffusion and/or bubble coalescence during vesiculation. In both sets of experiments, vesiculation was triggered by heating the samples at room pressure. Our results suggest that the presence of pre-existing gas bubbles during a nucleation event significantly decreases the tendency of bubbles to coalesce and inhibits magma outgassing. In contrast, in initially bubble-free samples, the nucleation and growth of bubbles is accompanied by significant coalescence and outgassing. We infer that volatile-undersaturated (i.e. bubble-free) magmas in the reservoirs are more likely to erupt effusively, while the presence of excess gas already at depth (i.e. bubble-bearing systems) increases the likelihood of explosive eruptions.

  9. In Situ Ptychography of Heterogeneous Catalysts using Hard X-Rays: High Resolution Imaging at Ambient Pressure and Elevated Temperature.

    PubMed

    Baier, Sina; Damsgaard, Christian D; Scholz, Maria; Benzi, Federico; Rochet, Amélie; Hoppe, Robert; Scherer, Torsten; Shi, Junjie; Wittstock, Arne; Weinhausen, Britta; Wagner, Jakob B; Schroer, Christian G; Grunwaldt, Jan-Dierk

    2016-02-01

    A new closed cell is presented for in situ X-ray ptychography which allows studies under gas flow and at elevated temperature. In order to gain complementary information by transmission and scanning electron microscopy, the cell makes use of a Protochips E-chipTM which contains a small, thin electron transparent window and allows heating. Two gold-based systems, 50 nm gold particles and nanoporous gold as a relevant catalyst sample, were used for studying the feasibility of the cell. Measurements showing a resolution around 40 nm have been achieved under a flow of synthetic air and during heating up to temperatures of 933 K. An elevated temperature exhibited little influence on image quality and resolution. With this study, the potential of in situ hard X-ray ptychography for investigating annealing processes of real catalyst samples is demonstrated. Furthermore, the possibility to use the same sample holder for ex situ electron microscopy before and after the in situ study underlines the unique possibilities available with this combination of electron microscopy and X-ray microscopy on the same sample.

  10. In-plate protein crystallization, in situ ligand soaking and X-ray diffraction.

    PubMed

    le Maire, Albane; Gelin, Muriel; Pochet, Sylvie; Hoh, François; Pirocchi, Michel; Guichou, Jean François; Ferrer, Jean Luc; Labesse, Gilles

    2011-09-01

    X-ray crystallography is now a recognized technique for ligand screening, especially for fragment-based drug design. However, protein crystal handling is still tedious and limits further automation. An alternative method for the solution of crystal structures of proteins in complex with small ligands is proposed. Crystallization drops are directly exposed to an X-ray beam after cocrystallization or soaking with the desired ligands. The use of dedicated plates in connection with an optimal parametrization of the G-rob robot allows efficient data collection. Three proteins currently under study in our laboratory for ligand screening by X-ray crystallography were used as validation test cases. The protein crystals belonged to different space groups, including a challenging monoclinic case. The resulting diffraction data can lead to clear ligand recognition, including indication of alternating conformations. These results demonstrate a possible method for automation of ligand screening by X-ray crystallography.

  11. Geological Carbon Sequestration: new insights from in-situ Synchrotron X-ray Microtomography

    NASA Astrophysics Data System (ADS)

    Voltolini, M.; Kwon, T.; Ajo Franklin, J. B.

    2012-12-01

    In a world with rapidly increasing atmospheric CO2 concentrations, a variety of scalable technologies are being considered to mitigate emissions from the combustion of fossil fuels; among these approaches, geological carbon storage (GCS) is being actively tested at a variety of subsurface sites. Despite these activities, a mechanistic understanding of multiphase flow in scCO2/brine systems at the pore scale is still being developed. The distribution of scCO2 in the pore space controls a variety of processes at the continuum scale including CO2 dissolution rate (by way of brine/CO2 contact area), capillary trapping, and residual brine fraction. Virtually no dynamic measurements of the pore-scale distribution of scCO2 in real geological samples have been made in three dimensions leaving models describing multi-phase fluid dynamics, reactive transport, and geophysical properties reliant on analog systems (often using fewer spatial dimensions, different fluids, or lower pressures) or theoretical models describing phase configurations. We present dynamic pore-scale imagery of scCO2 invasion dynamics in a 3D geological sample, in this case a quartz-rich sandstone core extracted from the Domengine Fm, a regionally extensive unit which is currently a target for future GCS operations in the Sacramento Basin. This dataset, acquired using synchrotron X-ray micro tomography (SXR-μCT) and high speed radiography, was made possible by development of a controlled P/T flow-through triaxial cell compatible with X-ray imaging in the 8-40 keV range. These experiments successfully resolved scCO2 and brine phases at a spatial resolution of 4.47 μm while the sample was kept at in situ conditions (45°C, 9 MPa pore pressure, 14 MPa hydrostatic confining stress) during drainage and imbibition cycles. Image volumes of the dry, brine saturated, and partially scCO2 saturated sample were captured and were used to correlate aspects of rock microstructure to development of the invasion front

  12. In situ X-ray Microscopy Studies of Electromigration in Copper Interconnects

    NASA Astrophysics Data System (ADS)

    Schneider, G.; Meyer, M.-A.; Zschech, E.; Denbeaux, G.; Neuhäusler, U.; Guttmann, P.

    2003-09-01

    Real-time X-ray microscopy is applied for degradation studies to understand electromigration-induced transport processes in on-chip copper interconnects. The material transport in inlaid Cu line/via structures is observed with about 40 nm lateral resolution. The image sequences show void formation, migration and nucleation processes. Correlation of the real-time X-ray images with post-mortem SEM micrographs is used to discuss degradation mechanisms in inlaid copper interconnects. Due to the high penetration power of X-rays through matter and its high spatial resolution, X-ray microscopy (XRM) overcomes several limitations of conventional microscopic techniques. It utilizes the natural absorption contrast between the structures of interest, i.e. for on-chip copper interconnects embedded in dielectrics. Due to their different X-ray absorption characteristics at 0.52 keV, even different silicon compounds like Si, SiO2, and Si3N4 can be distinguished in X-ray images of thinned layers as demonstrated. For failure analysis of thicker layers, phase contrast microscopy in the multi-keV photon energy range is proposed.

  13. Shock Melting of Iron Silicide as Determined by In Situ X-ray Diffraction.

    NASA Astrophysics Data System (ADS)

    Newman, M.; Kraus, R. G.; Wicks, J. K.; Smith, R.; Duffy, T. S.

    2016-12-01

    The equation of state of core alloys at pressures and temperatures near the solid-liquid coexistence curve is important for understanding the dynamics at the inner core boundary of the Earth and super-Earths. Here, we present a series of laser driven shock experiments on textured polycrystalline Fe-15Si. These experiments were conducted at the Omega and Omega EP laser facilities. Particle velocities in the Fe-15Si samples were measured using a line VISAR and were used to infer the thermodynamic state of the shocked samples. In situ x-ray diffraction measurements were used to probe the melting transition and investigate the potential decomposition of Fe-15Si in to hcp and B2 structures. This work examines the kinetic effects of decomposition due to the short time scale of dynamic compression experiments. In addition, the thermodynamic data collected in these experiments adds to a limited body of information regarding the equation of state of Fe-15Si, which is a candidate for the composition in Earth's outer core. Our experimental results show a highly textured solid phase upon shock compression to pressures ranging from 170 to 300 GPa. Below 320 GPa, we observe diffraction peaks consistent with decomposition of the D03 starting material in to an hcp and a cubic (potentially B2) structure. Upon shock compression above 320 GPa, the intense and textured solid diffraction peaks give way to diffuse scattering and loss of texture, consistent with melting along the Hugoniot. When comparing these results to that of pure iron, we can ascertain that addition of 15 wt% silicon increases the equilibrium melting temperature significantly, or that the addition of silicon significantly increases the metastability of the solid phase, relative to the liquid. This work was performed under the auspices of the U.S. Department of Energy by Lawrence Livermore National Laboratory under Contract DE-AC52-07NA27344.

  14. A modular reactor design for in situ synchrotron x-ray investigation of atomic layer deposition processes

    SciTech Connect

    Klug, Jeffrey A. Emery, Jonathan D.; Martinson, Alex B. F.; Proslier, Thomas; Weimer, Matthew S.; Yanguas-Gil, Angel; Elam, Jeffrey W.; Seifert, Sönke; Schlepütz, Christian M.; Hock, Adam S.

    2015-11-15

    Synchrotron characterization techniques provide some of the most powerful tools for the study of film structure and chemistry. The brilliance and tunability of the Advanced Photon Source allow access to scattering and spectroscopic techniques unavailable with in-house laboratory setups and provide the opportunity to probe various atomic layer deposition (ALD) processes in situ starting at the very first deposition cycle. Here, we present the design and implementation of a portable ALD instrument which possesses a modular reactor scheme that enables simple experimental switchover between various beamlines and characterization techniques. As first examples, we present in situ results for (1) X-ray surface scattering and reflectivity measurements of epitaxial ZnO ALD on sapphire, (2) grazing-incidence small angle scattering of MnO nucleation on silicon, and (3) grazing-incidence X-ray absorption spectroscopy of nucleation-regime Er{sub 2}O{sub 3} ALD on amorphous ALD alumina and single crystalline sapphire.

  15. In situ X-ray diffraction monitoring of a mechanochemical reaction reveals a unique topology metal-organic framework

    NASA Astrophysics Data System (ADS)

    Katsenis, Athanassios D.; Puškarić, Andreas; Štrukil, Vjekoslav; Mottillo, Cristina; Julien, Patrick A.; Užarević, Krunoslav; Pham, Minh-Hao; Do, Trong-On; Kimber, Simon A. J.; Lazić, Predrag; Magdysyuk, Oxana; Dinnebier, Robert E.; Halasz, Ivan; Friščić, Tomislav

    2015-03-01

    Chemical and physical transformations by milling are attracting enormous interest for their ability to access new materials and clean reactivity, and are central to a number of core industries, from mineral processing to pharmaceutical manufacturing. While continuous mechanical stress during milling is thought to create an environment supporting nonconventional reactivity and exotic intermediates, such speculations have remained without proof. Here we use in situ, real-time powder X-ray diffraction monitoring to discover and capture a metastable, novel-topology intermediate of a mechanochemical transformation. Monitoring the mechanochemical synthesis of an archetypal metal-organic framework ZIF-8 by in situ powder X-ray diffraction reveals unexpected amorphization, and on further milling recrystallization into a non-porous material via a metastable intermediate based on a previously unreported topology, herein named katsenite (kat). The discovery of this phase and topology provides direct evidence that milling transformations can involve short-lived, structurally unusual phases not yet accessed by conventional chemistry.

  16. A modular reactor design for in situ synchrotron X-ray investigation of atomic layer deposition processes

    SciTech Connect

    Klug, Jeffrey A.; Weimer, Matthew S.; Emery, Jonathan D.; Yanguas-Gil, Angel; Seifert, Sonke; Schleputz, Christian M.; Martinson, Alex B. F.; Elam, Jeffrey W.; Hock, Adam S.; Proslier, Thomas

    2015-11-01

    Synchrotron characterization techniques provide some of the most powerful tools for the study of film structure and chemistry. The brilliance and tunability of the Advanced Photon Source allow access to scattering and spectroscopic techniques unavailable with in-house laboratory setups and provide the opportunity to probe various atomic layer deposition (ALD) processes in situ starting at the very first deposition cycle. Here, we present the design and implementation of a portable ALD instrument which possesses a modular reactor scheme that enables simple experimental switchover between various beamlines and characterization techniques. As first examples, we present \\textit{in situ} results for 1.) X-ray surface scattering and reflectivity measurements of epitaxial ZnO ALD on sapphire, 2.) grazing-incidence small angle scattering of MnO nucleation on silicon, and 3.) grazing-incidence X-ray absorption spectroscopy of nucleation-regime Er2O3 ALD on amorphous ALD alumina and single crystalline sapphire.

  17. Quantifying the Nucleation and Growth Kinetics of Microwave Nanochemistry Enabled by in Situ High-Energy X-ray Scattering.

    PubMed

    Liu, Qi; Gao, Min-Rui; Liu, Yuzi; Okasinski, John S; Ren, Yang; Sun, Yugang

    2016-01-13

    The fast reaction kinetics presented in the microwave synthesis of colloidal silver nanoparticles was quantitatively studied, for the first time, by integrating a microwave reactor with in situ X-ray diffraction at a high-energy synchrotron beamline. Comprehensive data analysis reveals two different types of reaction kinetics corresponding to the nucleation and growth of the Ag nanoparticles. The formation of seeds (nucleation) follows typical first-order reaction kinetics with activation energy of 20.34 kJ/mol, while the growth of seeds (growth) follows typical self-catalytic reaction kinetics. Varying the synthesis conditions indicates that the microwave colloidal chemistry is independent of concentration of surfactant. These discoveries reveal that the microwave synthesis of Ag nanoparticles proceeds with reaction kinetics significantly different from the synthesis present in conventional oil bath heating. The in situ X-ray diffraction technique reported in this work is promising to enable further understanding of crystalline nanomaterials formed through microwave synthesis.

  18. In-situ GISAXS monitoring of ultrashort period W/B4C multilayer x-ray mirror growth

    NASA Astrophysics Data System (ADS)

    Hodas, Martin; Siffalovic, Peter; Halahovets, Yuriy; Pelletta, Marco; Vegso, Karol; Jergel, Matej; Majkova, Eva

    2015-08-01

    Ultrashort period multilayer X-ray mirrors with the layer thickness down to 1 nm or less represent a technological challenge. Here, the layer thickness becomes comparable to the interface roughness and discontinuous layers producing strong diffuse scattering may appear. The grazing-incidence small-angle X-ray scattering (GISAXS) is a unique nondestructive technique to probe the mirror quality in terms of the statistical interface roughness and its correlation properties. We present the first in-situ laboratory GISAXS experiments of monitoring the multilayer mirror growth in order to better understand and optimize the deposition process. A microfocus X-ray source IμS with focusing Montel optics (Incoatec) and 2D X-ray detector Pilatus 200K (Dectris) were mounted on a custom-designed dual-ion beam sputtering apparatus (Bestec). Two W/B4C mirrors with 15 periods of 1.8 nm and 2.1 nm were prepared as determined from the post-deposition specular X-ray reflectivity measurements. The in-situ GISAXS tracking was done by a fast repeated collection of the GISAXS frames with the integration time of 8 s at the incidence angle of 0.25 degree. Two distinct features along qz at qy = 0, namely Yoneda and Bragg-like (BL) multilayer peaks evolved in the GISAXS pattern. Oscillatory behavior of the latter in terms of intensity and FWHM was observed after the initial stage. Lateral cuts of the diffuse scattering concentration stripes surrounding BL peaks in particular GISAXS frames provided temporal evolution of the correlation and fractal interface parameters. Their potential for tailoring the multilayer properties is discussed.

  19. In situ flash x-ray high-speed computed tomography for the quantitative analysis of highly dynamic processes

    NASA Astrophysics Data System (ADS)

    Moser, Stefan; Nau, Siegfried; Salk, Manfred; Thoma, Klaus

    2014-02-01

    The in situ investigation of dynamic events, ranging from car crash to ballistics, often is key to the understanding of dynamic material behavior. In many cases the important processes and interactions happen on the scale of milli- to microseconds at speeds of 1000 m s-1 or more. Often, 3D information is necessary to fully capture and analyze all relevant effects. High-speed 3D-visualization techniques are thus required for the in situ analysis. 3D-capable optical high-speed methods often are impaired by luminous effects and dust, while flash x-ray based methods usually deliver only 2D data. In this paper, a novel 3D-capable flash x-ray based method, in situ flash x-ray high-speed computed tomography is presented. The method is capable of producing 3D reconstructions of high-speed processes based on an undersampled dataset consisting of only a few (typically 3 to 6) x-ray projections. The major challenges are identified, discussed and the chosen solution outlined. The application is illustrated with an exemplary application of a 1000 m s-1 high-speed impact event on the scale of microseconds. A quantitative analysis of the in situ measurement of the material fragments with a 3D reconstruction with 1 mm voxel size is presented and the results are discussed. The results show that the HSCT method allows gaining valuable visual and quantitative mechanical information for the understanding and interpretation of high-speed events.

  20. In Situ Grazing Incidence X-Ray Diffraction Study of Electrochemically Deposited Pb Monolayer on Ag(111),

    DTIC Science & Technology

    1987-05-12

    potential for the deposition of Pb2 on a Pb electrode and hence is termed underpotential deposition (UPD). 19 No additional lead is deposited until...K. 0 In Situ Grazing Incidence X-ray Diffraction Study Interim Technical Report of Electrochemically Deposited Pb rMbno layers on...nunoalayer adsorbed at a metal-liquid interface. Diffraction peaks were * ~. observed from a monoalayer of lead electrochemicially deposited onto a

  1. Monitoring potassium metal electrodeposition from an ionic liquid using in situ electrochemical-X-ray photoelectron spectroscopy

    NASA Astrophysics Data System (ADS)

    Wibowo, Rahmat; Aldous, Leigh; Jacobs, Robert M. J.; Manan, Ninie S. A.; Compton, Richard G.

    2011-06-01

    The real time electrodeposition of potassium has been monitored for the first time in an ionic liquid using in situ electrodeposition-X-ray photoelectron spectroscopy (XPS). The ionic liquid used was N-butyl- N-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide ([C 4mpyrr][ NTf 2]), and electrodeposition occurred at a nickel mesh electrode. Potassium electrochemistry was monitored at the ionic liquid-vacuum-electrode interface using a novel cell design.

  2. A flow cell for in situ synchrotron x-ray diffraction studies of scale formation under Bayer processing conditions

    NASA Astrophysics Data System (ADS)

    Webster, Nathan A. S.; Madsen, Ian C.; Loan, Melissa J.; Scarlett, Nicola V. Y.; Wallwork, Kia S.

    2009-08-01

    The design, construction, and commissioning of a stainless steel flow cell for in situ synchrotron x-ray diffraction studies of scale formation under Bayer processing conditions is described. The use of the cell is demonstrated by a study of Al(OH)3 scale formation on a mild steel substrate from synthetic Bayer liquor at 70 °C. The cell design allows for interchangeable parts and substrates and would be suitable for the study of scale formation in other industrial processes.

  3. Grain rotation and lattice deformation during photoinduced chemical reactions revealed by in situ X-ray nanodiffraction.

    PubMed

    Huang, Zhifeng; Bartels, Matthias; Xu, Rui; Osterhoff, Markus; Kalbfleisch, Sebastian; Sprung, Michael; Suzuki, Akihiro; Takahashi, Yukio; Blanton, Thomas N; Salditt, Tim; Miao, Jianwei

    2015-07-01

    In situ X-ray diffraction (XRD) and transmission electron microscopy (TEM) have been used to investigate many physical science phenomena, ranging from phase transitions, chemical reactions and crystal growth to grain boundary dynamics. A major limitation of in situ XRD and TEM is a compromise that has to be made between spatial and temporal resolution. Here, we report the development of in situ X-ray nanodiffraction to measure high-resolution diffraction patterns from single grains with up to 5 ms temporal resolution. We observed, for the first time, grain rotation and lattice deformation in chemical reactions induced by X-ray photons: Br(-) + hv → Br + e(-) and e(-) + Ag(+) → Ag(0). The grain rotation and lattice deformation associated with the chemical reactions were quantified to be as fast as 3.25 rad s(-1) and as large as 0.5 Å, respectively. The ability to measure high-resolution diffraction patterns from individual grains with a temporal resolution of several milliseconds is expected to find broad applications in materials science, physics, chemistry and nanoscience.

  4. In-situ X-ray CT results of damage evolution in L6 ordinary chondrite meteorites

    SciTech Connect

    Cuadra, Jefferson A.; Hazeli, Kavan; Ramesh, K. T.; Martz, Harry

    2016-06-17

    These are slides about in-situ X-ray CT results of damage evolution in L6 ordinary chondrite meteorites. The following topics are covered: mechanical and thermal damage characterization, list of Grosvenor Mountain (GRO) meteorite samples, in-situ x-ray compression test setup, GRO-chipped reference at 0 N - existing cracks, GRO-chipped loaded at 1580 N, in-situ x-ray thermal fatigue test setup, GRO-B14 room temperature reference, GRO-B14 Cycle 47 at 200°C, GRO-B14 Cycle 47 at room temperature, conclusions from qualitative analysis, future work and next steps. Conclusions are the following: Both GRO-Chipped and GRO-B14 had existing voids and cracks within the volume. These sites with existing damage were selected for CT images from mechanically and thermally loaded scans since they are prone to damage initiation. The GRO-Chipped sample was loaded to 1580 N which resulted in a 14% compressive engineering strain, calculated using LVDT. Based on the CT cross sectional images, the GRO-B14 sample at 200°C has a thermal expansion of approximately 96 μm in height (i.e. ~1.6% engineering strain).

  5. Performance and characteristics of a high pressure, high temperature capillary cell with facile construction for operando x-ray absorption spectroscopy

    SciTech Connect

    Bansode, Atul; Urakawa, Atsushi; Guilera, Gemma; Simonelli, Laura; Avila, Marta; Cuartero, Vera

    2014-08-15

    We demonstrate the use of commercially available fused silica capillary and fittings to construct a cell for operando X-ray absorption spectroscopy (XAS) for the study of heterogeneously catalyzed reactions under high pressure (up to 200 bars) and high temperature (up to 280 °C) conditions. As the first demonstration, the cell was used for CO{sub 2} hydrogenation reaction to examine the state of copper in a conventional Cu/ZnO/Al{sub 2}O{sub 3} methanol synthesis catalyst. The active copper component of the catalyst was shown to remain in the metallic state under supercritical reaction conditions, at 200 bars and up to 260 °C. With the coiled heating system around the capillary, one can easily change the length of the capillary and control the amount of catalyst under investigation. With precise control of reactant(s) flow, the cell can mimic and serve as a conventional fixed-bed micro-reactor system to obtain reliable catalytic data. This high comparability of the reaction performance of the cell and laboratory reactors is crucial to gain insights into the nature of actual active sites under technologically relevant reaction conditions. The large length of the capillary can cause its bending upon heating when it is only fixed at both ends because of the thermal expansion. The degree of the bending can vary depending on the heating mode, and solutions to this problem are also presented. Furthermore, the cell is suitable for Raman studies, nowadays available at several beamlines for combined measurements. A concise study of CO{sub 2} phase behavior by Raman spectroscopy is presented to demonstrate a potential of the cell for combined XAS-Raman studies.

  6. Experimental Study of High-Temperature Fracture Propagation in Anthracite and Destruction of Mudstone from Coalfield Using High-Resolution Microfocus X-ray Computed Tomography

    NASA Astrophysics Data System (ADS)

    Xiao, Yang; Lu, Jun-Hui; Wang, Cai-Ping; Deng, Jun

    2016-09-01

    The coalfield fire is determined by fractures of coal and rock that provide tunnel for gases and heat exchange. To study fracture propagation at high temperatures, high-resolution X-ray computed tomography (CT) was used to scan anthracite and mudstone samples collected from the Qinshui coalfield, Shanxi Province, northern China. The samples were scanned at 100 °C intervals as they were subjected to temperatures of up to 500 °C. Three-dimensional images were reconstructed by the CT software to analyze changes in the fractures and pores in the samples. The experimental results show that fracturing of anthracite began at 200 °C. The generation rate of fractures in the coal samples increases slowly below 300 °C, but above 300 °C there is a sharp increase in fracture development. This indicates that the thermal fracturing temperature threshold for anthracite is 300 °C. During the experiment, it was found that preexisting fractures, voids, and regenerative fractures formed around the hard portions of anthracite particles or along the weak boundaries between particles. Some regenerative fractures developed along the fabric of the relatively crystalline particles within the particle and terminate at the edge of the particle or where the fracture encounters a harder portion of coal. Some fractures even expanded enough to be transformed into voids as temperatures rose. In the mudstone, the porosity changed suddenly at 300 °C. This indicated that there was a void generated at 200 °C, but the void expanded when the temperature was increased. However, changes in the void were not obvious from 200 to 300 °C.

  7. Performance and characteristics of a high pressure, high temperature capillary cell with facile construction for operando x-ray absorption spectroscopy.

    PubMed

    Bansode, Atul; Guilera, Gemma; Cuartero, Vera; Simonelli, Laura; Avila, Marta; Urakawa, Atsushi

    2014-08-01

    We demonstrate the use of commercially available fused silica capillary and fittings to construct a cell for operando X-ray absorption spectroscopy (XAS) for the study of heterogeneously catalyzed reactions under high pressure (up to 200 bars) and high temperature (up to 280 °C) conditions. As the first demonstration, the cell was used for CO2 hydrogenation reaction to examine the state of copper in a conventional Cu/ZnO/Al2O3 methanol synthesis catalyst. The active copper component of the catalyst was shown to remain in the metallic state under supercritical reaction conditions, at 200 bars and up to 260 °C. With the coiled heating system around the capillary, one can easily change the length of the capillary and control the amount of catalyst under investigation. With precise control of reactant(s) flow, the cell can mimic and serve as a conventional fixed-bed micro-reactor system to obtain reliable catalytic data. This high comparability of the reaction performance of the cell and laboratory reactors is crucial to gain insights into the nature of actual active sites under technologically relevant reaction conditions. The large length of the capillary can cause its bending upon heating when it is only fixed at both ends because of the thermal expansion. The degree of the bending can vary depending on the heating mode, and solutions to this problem are also presented. Furthermore, the cell is suitable for Raman studies, nowadays available at several beamlines for combined measurements. A concise study of CO2 phase behavior by Raman spectroscopy is presented to demonstrate a potential of the cell for combined XAS-Raman studies.

  8. Synchrotron x-ray spectroscopy of EuHN O3 aqueous solutions at high temperatures and pressures and Nb-bearing silicate melt phases coexisting with hydrothermal fluids using a modified hydrothermal diamond anvil cell and rail assembly

    USGS Publications Warehouse

    Mayanovic, Robert A.; Anderson, Alan J.; Bassett, William A.; Chou, I.-Ming

    2007-01-01

    A modified hydrothermal diamond anvil cell (HDAC) rail assembly has been constructed for making synchrotron x-ray absorption spectroscopy, x-ray fluorescence, and x-ray mapping measurements on fluids or solid phases in contact with hydrothermal fluids up to ???900??C and 700 MPa. The diamond anvils of the HDAC are modified by laser milling grooves or holes, for the reduction of attenuation of incident and fluorescent x rays and sample cavities. The modified HDAC rail assembly has flexibility in design for measurement of light elements at low concentrations or heavy elements at trace levels in the sample and the capability to probe minute individual phases of a multiphase fluid-based system using focused x-ray microbeam. The supporting rail allows for uniform translation of the HDAC, rotation and tilt stages, and a focusing mirror, which is used to illuminate the sample for visual observation using a microscope, relative to the direction of the incident x-ray beam. A structure study of Eu(III) aqua ion behavior in high-temperature aqueous solutions and a study of Nb partitioning and coordination in a silicate melt in contact with a hydrothermal fluid are described as applications utilizing the modified HDAC rail assembly. ?? 2007 American Institute of Physics.

  9. Synchrotron x-ray spectroscopy of Eu/HNO{sub 3} aqueous solutions at high temperatures and pressures and Nb-bearing silicate melt phases coexisting with hydrothermal fluids using a modified hydrothermal diamond anvil cell and rail assembly

    SciTech Connect

    Mayanovic, Robert A.; Anderson, Alan J.; Bassett, William A.; Chou, I-Ming

    2007-05-15

    A modified hydrothermal diamond anvil cell (HDAC) rail assembly has been constructed for making synchrotron x-ray absorption spectroscopy, x-ray fluorescence, and x-ray mapping measurements on fluids or solid phases in contact with hydrothermal fluids up to {approx}900 deg. C and 700 MPa. The diamond anvils of the HDAC are modified by laser milling grooves or holes, for the reduction of attenuation of incident and fluorescent x rays and sample cavities. The modified HDAC rail assembly has flexibility in design for measurement of light elements at low concentrations or heavy elements at trace levels in the sample and the capability to probe minute individual phases of a multiphase fluid-based system using focused x-ray microbeam. The supporting rail allows for uniform translation of the HDAC, rotation and tilt stages, and a focusing mirror, which is used to illuminate the sample for visual observation using a microscope, relative to the direction of the incident x-ray beam. A structure study of Eu(III) aqua ion behavior in high-temperature aqueous solutions and a study of Nb partitioning and coordination in a silicate melt in contact with a hydrothermal fluid are described as applications utilizing the modified HDAC rail assembly.

  10. X-ray irradiation of soda-lime glasses studied in situ with surface plasmon resonance spectroscopy

    SciTech Connect

    Serrano, A.; Galvez, F.; Rodriguez de la Fuente, O.; Garcia, M. A.

    2013-03-21

    We present here a study of hard X-ray irradiation of soda-lime glasses performed in situ and in real time. For this purpose, we have used a Au thin film grown on glass and studied the excitation of its surface plasmon resonance (SPR) while irradiating the sample with X-rays, using a recently developed experimental setup at a synchrotron beamline [Serrano et al., Rev. Sci. Instrum. 83, 083101 (2012)]. The extreme sensitivity of the SPR to the features of the glass substrate allows probing the modifications caused by the X-rays. Irradiation induces color centers in the soda-lime glass, modifying its refractive index. Comparison of the experimental results with simulated data shows that both, the real and the imaginary parts of the refractive index of soda-lime glasses, change upon irradiation in time intervals of a few minutes. After X-ray irradiation, the effects are partially reversible. The defects responsible for these modifications are identified as non-bridging oxygen hole centers, which fade by recombination with electrons after irradiation. The kinetics of the defect formation and fading process are also studied in real time.

  11. In-Situ X-Ray Microscopy of Phase and Composition Distributions in Metal Alloys During Solidification

    NASA Technical Reports Server (NTRS)

    Kaukler, William F.; Curreri, Peter A.

    1999-01-01

    This research applies a state of the art X-ray Transmission Microscope, to image the solidification of metallic or semiconductor alloys in real-time. By employing a hard x-ray source with sub-micron dimensions, resolutions of up to 3 gm can be obtained with magnifications of over 800 X. Specimen growth conditions were optimized and the best imaging technologies applied to maintain x-ray image resolution, contrast and sensitivity. In addition, a special furnace design is required to permit controlled growth conditions and still offer maximum resolution and image contrast. We have successfully imaged in real-time: interfacial morphologies, phase growth, coalescence, incorporation of phases into the growing interface, and the solute boundary layer in the liquid at the solid-liquid inter-face. We have also measured true local growth rates and can evaluate segregation structures in the solid; a form of in-situ metallography. Composition gradients within the specimen cause vafiations in absorption of the flux such that the final image represents a spatial integral of composition (or thickness). During this study, the growth of secondary phase fibers and lameilae from eutectic and monotectic alloys have been imaged during solidification, in real-time, for the first time in bulk metal alloys. Keywords: x-ray, microscope, solidification, microfocus, real-time, microstructure

  12. Development of high-performance X-ray transparent crystallization plates for in situ protein crystal screening and analysis

    SciTech Connect

    Soliman, Ahmed S. M.; Warkentin, Matthew; Apker, Benjamin; Thorne, Robert E.

    2011-07-01

    An optically, UV and X-ray transparent crystallization plate suitable for in situ analysis has been developed. The plate uses contact line pinning rather than wells to confine the liquids. X-ray transparent crystallization plates based upon a novel drop-pinning technology provide a flexible, simple and inexpensive approach to protein crystallization and screening. The plates consist of open cells sealed top and bottom by thin optically, UV and X-ray transparent films. The plates do not need wells or depressions to contain liquids. Instead, protein drops and reservoir solution are held in place by rings with micrometre dimensions that are patterned onto the bottom film. These rings strongly pin the liquid contact lines, thereby improving drop shape and position uniformity, and thus crystallization reproducibility, and simplifying automated image analysis of drop contents. The same rings effectively pin solutions containing salts, proteins, cryoprotectants, oils, alcohols and detergents. Strong pinning by rings allows the plates to be rotated without liquid mixing to 90° for X-ray data collection or to be inverted for hanging-drop crystallization. The plates have the standard SBS format and are compatible with standard liquid-handling robots.

  13. In-Situ X-Ray Microscopy of Phase and Composition Distributions in Metal Alloys During Solidification

    NASA Technical Reports Server (NTRS)

    Kaukler, William F.; Curreri, Peter A.

    1999-01-01

    This research applies a state of the art X-ray Transmission Microscope, to image the solidification of metallic or semiconductor alloys in real-time. By employing a hard x-ray source with sub-micron dimensions, resolutions of up to 3 gm can be obtained with magnifications of over 800 X. Specimen growth conditions were optimized and the best imaging technologies applied to maintain x-ray image resolution, contrast and sensitivity. In addition, a special furnace design is required to permit controlled growth conditions and still offer maximum resolution and image contrast. We have successfully imaged in real-time: interfacial morphologies, phase growth, coalescence, incorporation of phases into the growing interface, and the solute boundary layer in the liquid at the solid-liquid inter-face. We have also measured true local growth rates and can evaluate segregation structures in the solid; a form of in-situ metallography. Composition gradients within the specimen cause vafiations in absorption of the flux such that the final image represents a spatial integral of composition (or thickness). During this study, the growth of secondary phase fibers and lameilae from eutectic and monotectic alloys have been imaged during solidification, in real-time, for the first time in bulk metal alloys. Keywords: x-ray, microscope, solidification, microfocus, real-time, microstructure

  14. In Situ X-ray Microtomography of Stress Corrosion Cracking and Corrosion Fatigue in Aluminum Alloys

    NASA Astrophysics Data System (ADS)

    Singh, Sudhanshu S.; Stannard, Tyler J.; Xiao, Xianghui; Chawla, Nikhilesh

    2017-08-01

    Structural materials are subjected to combinations of stress and corrosive environments that work synergistically to cause premature failure. Therefore, studies on the combined effect of stress and corrosive environments on material behavior are required. Existing studies have been performed in two dimensions that are inadequate for full comprehension of the three-dimensional (3D) processes related to stress corrosion cracking (SCC) and corrosion-fatigue (CF) behavior. Recently, x-ray synchrotron tomography has evolved as an excellent technique to obtain the microstructure in 3D. Moreover, being nondestructive in nature, x-ray synchrotron tomography is well suited to study the evolution of microstructure with time (4D, or fourth dimension in time). This article presents our recent 4D studies on SCC and CF of Al 7075 alloys using x-ray synchrotron tomography.

  15. Note: Setup for chemical atmospheric control during in situ grazing incidence X-ray scattering of printed thin films

    NASA Astrophysics Data System (ADS)

    Pröller, Stephan; Moseguí González, Daniel; Zhu, Chenhuii; Schaible, Eric; Wang, Cheng; Müller-Buschbaum, Peter; Hexemer, Alexander; Herzig, Eva M.

    2017-06-01

    In order to tailor the assembling of polymers and organic molecules, a deeper understanding of the kinetics involved in thin film production is necessary. While post-production characterization only provides insight on the final film structure, more sophisticated experimental setups are needed to probe the structure formation processes in situ during deposition. The drying kinetics of a deposited organic thin film strongly influences the assembling process on the nanometer scale. This work presents an experimental setup that enables fine control of the atmosphere composition surrounding the sample during slot die coating, while simultaneously probing the film formation kinetics using in situ grazing incidence X-ray scattering and spectroscopy.

  16. Note: Setup for chemical atmospheric control during in situ grazing incidence X-ray scattering of printed thin films.

    PubMed

    Pröller, Stephan; Moseguí González, Daniel; Zhu, Chenhuii; Schaible, Eric; Wang, Cheng; Müller-Buschbaum, Peter; Hexemer, Alexander; Herzig, Eva M

    2017-06-01

    In order to tailor the assembling of polymers and organic molecules, a deeper understanding of the kinetics involved in thin film production is necessary. While post-production characterization only provides insight on the final film structure, more sophisticated experimental setups are needed to probe the structure formation processes in situ during deposition. The drying kinetics of a deposited organic thin film strongly influences the assembling process on the nanometer scale. This work presents an experimental setup that enables fine control of the atmosphere composition surrounding the sample during slot die coating, while simultaneously probing the film formation kinetics using in situ grazing incidence X-ray scattering and spectroscopy.

  17. The Oxford-Diamond In Situ Cell for studying chemical reactions using time-resolved X-ray diffraction.

    PubMed

    Moorhouse, Saul J; Vranješ, Nenad; Jupe, Andrew; Drakopoulos, Michael; O'Hare, Dermot

    2012-08-01

    A versatile, infrared-heated, chemical reaction cell has been assembled and commissioned for the in situ study of a range of chemical syntheses using time-resolved energy-dispersive X-ray diffraction (EDXRD) on Beamline I12 at the Diamond Light Source. Specialized reactor configurations have been constructed to enable in situ EDXRD investigation of samples under non-ambient conditions. Chemical reactions can be studied using a range of sample vessels such as alumina crucibles, steel hydrothermal autoclaves, and glassy carbon tubes, at temperatures up to 1200 °C.

  18. The Oxford-Diamond In Situ Cell for studying chemical reactions using time-resolved X-ray diffraction

    NASA Astrophysics Data System (ADS)

    Moorhouse, Saul J.; Vranješ, Nenad; Jupe, Andrew; Drakopoulos, Michael; O'Hare, Dermot

    2012-08-01

    A versatile, infrared-heated, chemical reaction cell has been assembled and commissioned for the in situ study of a range of chemical syntheses using time-resolved energy-dispersive X-ray diffraction (EDXRD) on Beamline I12 at the Diamond Light Source. Specialized reactor configurations have been constructed to enable in situ EDXRD investigation of samples under non-ambient conditions. Chemical reactions can be studied using a range of sample vessels such as alumina crucibles, steel hydrothermal autoclaves, and glassy carbon tubes, at temperatures up to 1200 °C.

  19. In-situ X-ray nano-CT System for Polymer Electrolyte Fuel Cells under Operating Conditions

    NASA Astrophysics Data System (ADS)

    Sekizawa, O.; Uruga, T.; Ishiguro, N.; Matsui, H.; Higashi, K.; Sakata, T.; Iwasawa, Y.; Tada, M.

    2017-06-01

    We developed two types of in-situ three-dimensional imaging systems on the basis of full-field transmission X-ray computed tomography (XCT) methods for polymer electrolyte fuel cells (PEFCs) under operating conditions at beamline BL36XU at SPring-8. One was for a wide field of view (more than 500 μm) to obtain the whole membrane electrode assembly (MEA) images, and the other was for nano spatial resolution (less than 100 nm) using a Fresnel zone plate as objective optics. We succeeded in in-situ three-dimensional visualization of an MEA in PEFC using both XCT measurement systems and show preliminary results.

  20. Note: A novel method for in situ loading of gases via x-ray induced chemistry

    SciTech Connect

    Pravica, Michael; Bai, Ligang; Park, Changyong; Liu, Yu; Galley, Martin; Robinson, John; Bhattacharya, Neelanjan

    2011-12-14

    We have developed and demonstrated a novel method to load oxygen in a sealed diamond anvil cell via the x-ray induced decomposition of potassium chlorate. By irradiating a pressurized sample of an oxidizer (KClO{sub 3}) with either monochromatic or white beam x-rays from the Advanced Photon Source at ambient temperature and variable pressure, we succeeded in creating a localized region of molecular oxygen surrounded by unreacted sample which was confirmed via Raman spectroscopy. We anticipate that this technique will be useful in loading even more challenging, difficult-to-load gases such as hydrogen and also to load multiple gases.

  1. Note: A novel method for in situ loading of gases via x-ray induced chemistry

    NASA Astrophysics Data System (ADS)

    Pravica, Michael; Bai, Ligang; Park, Changyong; Liu, Yu; Galley, Martin; Robinson, John; Bhattacharya, Neelanjan

    2011-10-01

    We have developed and demonstrated a novel method to load oxygen in a sealed diamond anvil cell via the x-ray induced decomposition of potassium chlorate. By irradiating a pressurized sample of an oxidizer (KClO3) with either monochromatic or white beam x-rays from the Advanced Photon Source at ambient temperature and variable pressure, we succeeded in creating a localized region of molecular oxygen surrounded by unreacted sample which was confirmed via Raman spectroscopy. We anticipate that this technique will be useful in loading even more challenging, difficult-to-load gases such as hydrogen and also to load multiple gases.

  2. Measurements of liquid and glass structures using in-situ high energy x-ray and neutron scattering

    SciTech Connect

    Weber, Richard; Benmore, C. J.; Skinner, Lawrie; Neuefeind, Joerg C; Tumber, Sonia; Jennings, G; Santodonato, Louis J; Jin, D; Du, Jincheng; Parise, John B

    2013-01-01

    Investigation of high temperature molten materials and their evolution to the amorphous state is often hampered by unwanted reactions with container surfaces. This work used aerodynamic levitation in combination with laser beam heating to study high melting point materials that can form supercooled liquids or glasses. Details of the instruments that are being used at the Advanced Photon Source and the Spallation Neutron Source to study molten oxides with high energy x-ray scattering and neutron diffraction with isotope substitution are presented. Examples of measurements are used to illustrate the use of the instruments. Plans for further development and application of the capabilities are presented.

  3. High-temperature X-ray diffraction and thermal expansion of nanocrystalline and coarse-crystalline acanthite α-Ag2S and argentite β-Ag2S.

    PubMed

    Sadovnikov, S I; Gusev, A I; Chukin, A V; Rempel, A A

    2016-02-14

    An in situ study of thermal expansion of polymorphic phases of coarse-crystalline and nanocrystalline silver sulfide - monoclinic acanthite α-Ag2S and cubic argentite β-Ag2S - has been carried out for the first time using the high-temperature X-ray diffraction method. The temperature dependencies of the unit cell parameters of acanthite and argentite in the interval of 300-623 K have been determined, and the thermal expansion coefficients of acanthite and argentite have been found. It is shown that the observed difference in the thermal expansion coefficients for nano- and coarse-crystalline acanthite is due to the small particle size of nanocrystalline silver sulfide leading to the growth of anharmonicity of atomic vibrations. It is established by differential thermal analysis that a reversible polymorphic acanthite-argentite phase transformation takes place at ∼449-450 K and the phase transformation enthalpy is equal to ∼3.7-3.9 kJ mol(-1).

  4. Using in situ X-ray reflectivity to study protein adsorption on hydrophilic and hydrophobic surfaces: benefits and limitations.

    PubMed

    Richter, Andrew G; Kuzmenko, Ivan

    2013-04-30

    We have employed in situ X-ray reflectivity (IXRR) to study the adsorption of a variety of proteins (lysozyme, cytochrome c, myoglobin, hemoglobin, serum albumin, and immunoglobulin G) on model hydrophilic (silicon oxide) and hydrophobic surfaces (octadecyltrichlorosilane self-assembled monolayers), evaluating this recently developed technique for its applicability in the area of biomolecular studies. We report herein the highest resolution depiction of adsorbed protein films, greatly improving on the precision of previous neutron reflectivity (NR) results and previous IXRR studies. We were able to perform complete scans in 5 min or less with the maximum momentum transfer of at least 0.52 Å(-1), allowing for some time-resolved information about the evolution of the protein film structure. The three smallest proteins (lysozyme, cytochrome c, and myoglobin) were seen to deposit as fully hydrated, nondenatured molecules onto hydrophilic surfaces, with indications of particular preferential orientations. Time evolution was observed for both lysozyme and myoglobin films. The larger proteins were not observed to deposit on the hydrophilic substrates, perhaps because of contrast limitations. On hydrophobic surfaces, all proteins were seen to denature extensively in a qualitatively similar way but with a rough trend that the larger proteins resulted in lower coverage. We have generated high-resolution electron density profiles of these denatured films, including capturing the growth of a lysozyme film. Because the solution interface of these denatured films is diffuse, IXRR cannot unambiguously determine the film extent and coverage, a drawback compared to NR. X-ray radiation damage was systematically evaluated, including the controlled exposure of protein films to high-intensity X-rays and exposure of the hydrophobic surface to X-rays before adsorption. Our analysis showed that standard measuring procedures used for XRR studies may lead to altered protein films

  5. Diffusion and nucleation in multilayer growth of PTCDI-C8 studied with in situ X-ray growth oscillations and real-time small angle X-ray scattering

    NASA Astrophysics Data System (ADS)

    Zykov, Anton; Bommel, Sebastian; Wolf, Christopher; Pithan, Linus; Weber, Christopher; Beyer, Paul; Santoro, Gonzalo; Rabe, Jürgen P.; Kowarik, Stefan

    2017-02-01

    We study nucleation and multilayer growth of the perylene derivative PTCDI-C8 and find a persistent layer-by-layer growth, transformation of island shapes, and an enhancement of molecular diffusivity in upper monolayers (MLs). These findings result from the evaluation of the ML-dependent island densities, obtained by in situ real-time grazing incidence small angle X-ray scattering measurements and simultaneous X-ray growth oscillations. Complementary ex situ atomic force microscopy snapshots of different growth stages agree quantitatively with both X-ray techniques. The rate and temperature-dependent island density is analyzed using different mean-field nucleation models. Both a diffusion limited aggregation and an attachment limited aggregation model yield in the first two MLs the same critical nucleus size i, similar surface diffusion attempt frequencies in the 1019-1020 s-1 range, and a decrease of the diffusion barrier Ed in the 2nd ML by 140 meV.

  6. Novel cell design for combined in situ acoustic emission and x-ray diffraction study during electrochemical cycling of batteries

    SciTech Connect

    Rhodes, Kevin; Meisner, Roberta; Daniel, Claus; Kirkham, Melanie; Parish, Chad M.; Dudney, Nancy

    2011-07-15

    An in situ acoustic emission (AE) and x-ray diffraction cell for use in the study of battery electrode materials has been designed and tested. This cell uses commercially available coin cell hardware retrofitted with a metalized polyethylene terephthalate (PET) disk, which acts as both an x-ray window and a current collector. In this manner, the use of beryllium and its associated cost and hazards is avoided. An AE sensor may be affixed to the cell face opposite the PET window in order to monitor degradation effects, such as particle fracture, during cell cycling. Silicon particles, which were previously studied by the AE technique, were tested in this cell as a model material. The performance of these cells compared well with unmodified coin cells, while providing information about structural changes in the active material as the cell is repeatedly charged and discharged.

  7. Novel cell design for combined in situ acoustic emission and x-ray diffraction study during electrochemical cycling of batteries

    NASA Astrophysics Data System (ADS)

    Rhodes, Kevin; Kirkham, Melanie; Meisner, Roberta; Parish, Chad M.; Dudney, Nancy; Daniel, Claus

    2011-07-01

    An in situ acoustic emission (AE) and x-ray diffraction cell for use in the study of battery electrode materials has been designed and tested. This cell uses commercially available coin cell hardware retrofitted with a metalized polyethylene terephthalate (PET) disk, which acts as both an x-ray window and a current collector. In this manner, the use of beryllium and its associated cost and hazards is avoided. An AE sensor may be affixed to the cell face opposite the PET window in order to monitor degradation effects, such as particle fracture, during cell cycling. Silicon particles, which were previously studied by the AE technique, were tested in this cell as a model material. The performance of these cells compared well with unmodified coin cells, while providing information about structural changes in the active material as the cell is repeatedly charged and discharged.

  8. An ultra-high vacuum electrochemical flow cell for in situ/operando soft X-ray spectroscopy study

    SciTech Connect

    Bora, Debajeet K. E-mail: jguo@lbl.gov; Glans, Per-Anders; Pepper, John; Liu, Yi-Sheng; Guo, J.-H. E-mail: jguo@lbl.gov; Du, Chun; Wang, Dunwei

    2014-04-15

    An in situ flow electrochemical cell has been designed and fabricated to allow better seal under UHV chamber thus to achieve a good signal to noise ratio in fluorescence yield detection of X-ray absorption spectra for spectroelectrochemical study. The cell also stabilizes the thin silicon nitride membrane window in an effective manner so that the liquid cell remains intact during X-ray absorption experiments. With the improved design of the liquid cell, electrochemical experiments such as cyclic voltammetry have been performed for 10 cycles with a good stability of sample window. Also an operando electrochemical experiment during photoelectrochemistry has been performed on n-type hematite electrode deposited on silicon nitride window. The experiment allows us to observe the formation of two extra electronic transitions before pre edge of O K-edge spectra.

  9. In situ X-ray powder diffraction studies of the synthesis of graphene oxide and formation of reduced graphene oxide

    NASA Astrophysics Data System (ADS)

    Storm, Mie Møller; Johnsen, Rune E.; Norby, Poul

    2016-08-01

    Graphene oxide (GO) and reduced graphene oxide (rGO) are important materials in a wide range of fields. The modified Hummers methods, for synthesizing GO, and subsequent thermal reduction to rGO, are often employed for production of rGO. However, the mechanism behinds these syntheses methods are still unclear. We present an in situ X-ray diffraction study of the synthesis of GO and thermal reduction of GO. The X-ray diffraction revealed that the Hummers method includes an intercalation state and finally formation of additional crystalline material. The formation of GO is observed during both the intercalation and the crystallization stage. During thermal reduction of GO three stages were observed: GO, a disordered stage, and the rGO stage. The appearance of these stages depends on the heating ramp. The aim of this study is to provide deeper insight into the chemical and physical processes during the syntheses.

  10. In Situ Heater Design for Nanoscale Synchrotron-Based Full-Field Transmission X-Ray Microscopy

    SciTech Connect

    Kiss, Andrew M.; Harris, William M.; Nakajo, Arata; Wang, Steve; Vila-Comamala, Joan; Deriy, Alex; Chiu, Wilson K. S.

    2015-03-05

    Abstract

    The oxidation of nickel powder under a controlled gas and temperature environment was studied using synchrotron-based full-field transmission X-ray microscopy. The use of this technique allowed for the reaction to be imagedin situat 55 nm resolution. The setup was designed to fit in the limited working distance of the microscope and to provide the gas and temperature environments analogous to solid oxide fuel cell operating conditions. Chemical conversion from nickel to nickel oxide was confirmed using X-ray absorption near-edge structure. Using an unreacted core model, the reaction rate as a function of temperature and activation energy were calculated. This method can be applied to study many other chemical reactions requiring similar environmental conditions.

  11. In-situ x-ray scattering investigation of strain in thin-film morphological evolution of homoepitaxial Ag(001)

    NASA Astrophysics Data System (ADS)

    Hayden, S. T.; Kim, C.; Conrad, E. H.; Gramlich, M. W.; Miceli, P. F.

    2010-03-01

    Because it escapes detection in most experimental probes of surfaces, the role of strain during film growth has not been widely investigated. However, large strain fields arise from vacancy nano-clusters [C. Kim et al., APL 91, 093131 (2007)] that can be incorporated during film growth at lower temperatures. It has also been suggested that extreme surface morphologies, resulting from a deposition flux at grazing angles, might lead to significant strain [Y. Shim et. al., PRL 101, 11601 (2008)]. Because of its simultaneous sensitivity to both the surface and the subsurface, x-ray scattering is a particularly valuable technique for exploring the role of strain in epitaxial crystal growth. This talk will discuss our recent in-situ x-ray diffuse scattering and reflectivity measurements, performed at the Advanced Photon Source, which investigate the low temperature homoepitaxial growth of Ag(001).

  12. In situ study of the Porticello Bronzes by portable X-ray fluorescence and laser-induced breakdown spectroscopy

    NASA Astrophysics Data System (ADS)

    Ferretti, M.; Cristoforetti, G.; Legnaioli, S.; Palleschi, V.; Salvetti, A.; Tognoni, E.; Console, E.; Palaia, P.

    2007-12-01

    This paper reports the results of a measurement campaign performed at the National Museum of Magna Grecia in Reggio Calabria (Italy). Portable X-Ray Fluorescence (XRF) and Laser-Induced Breakdown Spectroscopy (LIBS) instrumentation allowed in situ analysis of several bronze pieces belonging to the group of the so-called Porticello Bronzes. The find occurred at sea, off the village of Porticello (Reggio Calabria) in 1969 and consists of a number of fragments, including a bearded head, pertaining to at least two statues. The use of X-Ray Fluorescence and Laser-Induced Breakdown Spectroscopy techniques allowed for a classification of the fragments according to their elemental composition. The fragments appear to belong to at least two different statues; although, in general, the compositional classification agrees well with the stylistic analysis of the fragments, significant improvements with respect to previous achievements emerge from the joint results of the two techniques used.

  13. An X-Ray Microprobe for In-Situ Stone and Wood Characterization

    NASA Astrophysics Data System (ADS)

    Lovoi, P.; Asmus, J. F.

    NonDestructive Testing (NDT) has become an essential ingredient in the conservation of artworks and in the preservation of historic buildings. In many instances it is necessary to characterize the underlying strata of an artistic or historic object in order to plan technical conservation measures, to understand its history, to authenticate it, or to search for hidden features. X-ray and gamma-ray radiography as well as infrared imaging have been ubiquitous in conservation practice for generations. Recent decades have also seen the introduction of ultrasonic imaging, thermovision, x-ray fluorescence, neutron activation analyses, holographic interferometry, isotopic and trace element analyses, the electron microprobe, the laser microprobe, microwave impulse radar, eddy current imaging, and fiber-optic imaging. Unfortunately, for mainstream conservation and preservation some of these technologies are too costly or difficult to be implemented in any general way. In other instances penetration is too superficial or signals from the depth of interest are masked by interferences. Nevertheless, sufficiently important problems have arisen to warrant the utilization of each of the above NDT technologies as well as still others. A new diagnostic device has been introduced into the conservation field. Stone characterization analyses are reported using miniature x-ray devices that can be inserted into cracks and holes in specimens of interest. The family of x-ray tubes employed in these studies range in diameter from 1 to 6 mm. Operating voltages up to 50 kV are available. Electrical power and cooling are delivered through a flexible cable that has a bend diameter of less than 3 cm. Thus, it was possible to insert the x-ray tube into small holes and cracks in marble stones. In this manner radiographs of the outer strata of stones (and embedded metal pins) have been produced without having to transmit through the entire thickness of large blocks. It should also be possible to

  14. In situ X-ray photoelectron and Auger electron spectroscopic characterization of reaction mechanisms during Li-ion cycling.

    PubMed

    Tang, Ching-Yen; Haasch, Richard T; Dillon, Shen J

    2016-11-03

    The complex nature of Li-ion battery reactions along with their sensitivity to environmental exposure necessitates in situ characterization, particularly for surface sensitive methods. In this work, we demonstrate in situ X-ray photoelectron spectroscopy and in situ Auger electron spectroscopy applied to characterize the evolution of bonding and chemistry during cycling of nanoparticle electrodes. We apply the method to study the conversion reaction associated with Li insertion and extraction from CuO nanoparticle electrodes. This approach circumvents the need for ion sputtering and mechanical erosion, previously required to remove solid electrolyte interphase during ex situ measurements. This allows the elucidation of the changes in Cu oxidation state, during initial Li insertion, without the introduction of artifacts that have caused prior disagreement in the published literature.

  15. A Next-Generation Hard X-Ray Nanoprobe Beamline for In Situ Studies of Energy Materials and Devices

    NASA Astrophysics Data System (ADS)

    Maser, Jörg; Lai, Barry; Buonassisi, Tonio; Cai, Zhonghou; Chen, Si; Finney, Lydia; Gleber, Sophie-Charlotte; Jacobsen, Chris; Preissner, Curt; Roehrig, Chris; Rose, Volker; Shu, Deming; Vine, David; Vogt, Stefan

    2014-01-01

    The Advanced Photon Source is developing a suite of new X-ray beamlines to study materials and devices across many length scales and under real conditions. One of the flagship beamlines of the APS upgrade is the In Situ Nanoprobe (ISN) beamline, which will provide in situ and operando characterization of advanced energy materials and devices under varying temperatures, gas ambients, and applied fields, at previously unavailable spatial resolution and throughput. Examples of materials systems include inorganic and organic photovoltaic systems, advanced battery systems, fuel cell components, nanoelectronic devices, advanced building materials and other scientifically and technologically relevant systems. To characterize these systems at very high spatial resolution and trace sensitivity, the ISN will use both nanofocusing mirrors and diffractive optics to achieve spots sizes as small as 20 nm. Nanofocusing mirrors in Kirkpatrick-Baez geometry will provide several orders of magnitude increase in photon flux at a spatial resolution of 50 nm. Diffractive optics such as zone plates and/or multilayer Laue lenses will provide a highest spatial resolution of 20 nm. Coherent diffraction methods will be used to study even small specimen features with sub-10 nm relevant length scale. A high-throughput data acquisition system will be employed to significantly increase operations efficiency and usability of the instrument. The ISN will provide full spectroscopy capabilities to study the chemical state of most materials in the periodic table, and enable X-ray fluorescence tomography. In situ electrical characterization will enable operando studies of energy and electronic devices such as photovoltaic systems and batteries. We describe the optical concept for the ISN beamline, the technical design, and the approach for enabling a broad variety of in situ studies. We furthermore discuss the application of hard X-ray microscopy to study defects in multi-crystalline solar cells, one

  16. A Next-Generation Hard X-Ray Nanoprobe Beamline for In Situ Studies of Energy Materials and Devices

    SciTech Connect

    Maser, Jong; Lai, Barry; Buonassisi, Toni; Cai, Zhonghou; Chen, Si; Finney, Lydia; Gleber, Sophie-Charlotte; Jacobsen, Chris; Preissner, Curt; Chris Roehrig; Rose, Volker; Shu, Deming; Vine, David; Vogt, Stefan

    2013-08-20

    The Advanced Photon Source is developing a suite of new X-ray beamlines to study materials and devices across many length scales and under real conditions. One of the flagship beamlines of the APS upgrade is the In Situ Nanoprobe (ISN) beamline, which will provide in situ and operando characterization of advanced energy materials and devices under varying temperatures, gas ambients, and applied fields, at previously unavailable spatial resolution and throughput. Examples of materials systems include inorganic and organic photovoltaic systems, advanced battery systems, fuel cell components, nanoelectronic devices, advanced building materials and other scientifically and technologically relevant systems. To characterize these systems at very high spatial resolution and trace sensitivity, the ISN will use both nanofocusing mirrors and diffractive optics to achieve spots sizes as small as 20 nm. Nanofocusing mirrors in Kirkpatrick–Baez geometry will provide several orders of magnitude increase in photon flux at a spatial resolution of 50 nm. Diffractive optics such as zone plates and/or multilayer Laue lenses will provide a highest spatial resolution of 20 nm. Coherent diffraction methods will be used to study even small specimen features with sub-10 nm relevant length scale. A high-throughput data acquisition system will be employed to significantly increase operations efficiency and usability of the instrument. The ISN will provide full spectroscopy capabilities to study the chemical state of most materials in the periodic table, and enable X-ray fluorescence tomography. In situ electrical characterization will enable operando studies of energy and electronic devices such as photovoltaic systems and batteries. We also describe the optical concept for the ISN beamline, the technical design, and the approach for enabling a broad variety of in situ studies. Furthermore, we discuss the application of hard X-ray microscopy to study defects in multi-crystalline solar

  17. X-ray structure analysis of a metalloprotein with enhanced active-site resolution using in situ x-ray absorption near edge structure spectroscopy.

    PubMed

    Arcovito, Alessandro; Benfatto, Maurizio; Cianci, Michele; Hasnain, S Samar; Nienhaus, Karin; Nienhaus, G Ulrich; Savino, Carmelinda; Strange, Richard W; Vallone, Beatrice; Della Longa, Stefano

    2007-04-10

    X-ray absorption spectroscopy is exquisitely sensitive to the coordination geometry of an absorbing atom and therefore allows bond distances and angles of the surrounding atomic cluster to be measured with atomic resolution. By contrast, the accuracy and resolution of metalloprotein active sites obtainable from x-ray crystallography are often insufficient to analyze the electronic properties of the metals that are essential for their biological functions. Here, we demonstrate that the combination of both methods on the same metalloprotein single crystal yields a structural model of the protein with exceptional active-site resolution. To this end, we have collected an x-ray diffraction data set to 1.4-A resolution and Fe K-edge polarized x-ray absorption near edge structure (XANES) spectra on the same cyanomet sperm whale myoglobin crystal. The XANES spectra were quantitatively analyzed by using a method based on the multiple scattering approach, which yielded Fe-heme structural parameters with +/-(0.02-0.07)-A accuracy on the atomic distances and +/-7 degrees on the Fe-CN angle. These XANES-derived parameters were subsequently used as restraints in the crystal structure refinement. By combining XANES and x-ray diffraction, we have obtained an cyanomet sperm whale myoglobin structural model with a higher precision of the bond lengths and angles at the active site than would have been possible with crystallographic analysis alone.

  18. Estimation of bearing contact angle in-situ by X-ray kinematography

    NASA Technical Reports Server (NTRS)

    Fowler, P. H.; Manders, F.

    1982-01-01

    The mounted, preloaded contact angle of the structural bearings in the assembled design mechanical assembly was measured. A modification of the Turns method is presented, based upon the clarity and definition of moving parts achieved with X-ray technique and cinematic display. Contact angle is estimated by counting the number of bearings passing a given point as a function of number of turns of the shaft. Ball and pitch diameter variations are discussed. Ball train and shaft angle uncertainties are also discussed.

  19. The molecular pathway to ZIF-7 microrods revealed by in situ time-resolved small- and wide-angle X-ray scattering, quick-scanning extended X-ray absorption spectroscopy, and DFT calculations.

    PubMed

    Goesten, Maarten; Stavitski, Eli; Pidko, Evgeny A; Gücüyener, Canan; Boshuizen, Bart; Ehrlich, Steven N; Hensen, Emiel J M; Kapteijn, Freek; Gascon, Jorge

    2013-06-10

    We present an in situ small- and wide-angle X-ray scattering (SAXS/WAXS) and quick-scanning extended X-ray absorption fine-structure (QEXAFS) spectroscopy study on the crystallization of the metal-organic framework ZIF-7. In combination with DFT calculations, the self-assembly and growth of ZIF-7 microrods together with the chemical function of the crystal growth modulator (diethylamine) are revealed at all relevant length scales, from the atomic to the full crystal size.

  20. In situ microfluidic dialysis for biological small-angle X-ray scattering

    PubMed Central

    Skou, Magda; Skou, Søren; Jensen, Thomas G.; Vestergaard, Bente; Gillilan, Richard E.

    2014-01-01

    Owing to the demand for low sample consumption and automated sample changing capabilities at synchrotron small-angle X-ray (solution) scattering (SAXS) beamlines, X-ray microfluidics is receiving continuously increasing attention. Here, a remote-controlled microfluidic device is presented for simultaneous SAXS and ultraviolet absorption measurements during protein dialysis, integrated directly on a SAXS beamline. Microfluidic dialysis can be used for monitoring structural changes in response to buffer exchange or, as demonstrated, protein concentration. By collecting X-ray data during the concentration procedure, the risk of inducing protein aggregation due to excessive concentration and storage is eliminated, resulting in reduced sample consumption and improved data quality. The proof of concept demonstrates the effect of halted or continuous flow in the microfluidic device. No sample aggregation was induced by the concentration process at the levels achieved in these experiments. Simulations of fluid dynamics and transport properties within the device strongly suggest that aggregates, and possibly even higher-order oligomers, are preferentially retained by the device, resulting in incidental sample purification. Hence, this versatile microfluidic device enables investigation of experimentally induced structural changes under dynamically controllable sample conditions. PMID:25242913

  1. Observing the in situ chiral modification of Ni nanoparticles using scanning transmission X-ray microspectroscopy

    NASA Astrophysics Data System (ADS)

    Watson, David J.; Acharya, Sushma; Nicklin, Richard E. J.; Held, Georg

    2014-11-01

    Enantioselective heterogeneous hydrogenation of Cdbnd O bonds is of great potential importance in the synthesis of chirally pure products for the pharmaceutical and fine chemical industries. One of the most widely studied examples of such a reaction is the hydrogenation of β-ketoesters and β-diketoesters over Ni-based catalysts in the presence of a chiral modifier. Here we use scanning transmission X-ray microscopy combined with near-edge X-ray absorption fine structure spectroscopy (STXM/NEXAFS) to investigate the adsorption of the chiral modifier, namely (R,R)-tartaric acid, onto individual nickel nanoparticles. The C K-edge spectra strongly suggest that tartaric acid deposited onto the nanoparticle surfaces from aqueous solutions undergoes a keto-enol tautomerisation. Furthermore, we are able to interrogate the Ni L2,3-edge resonances of individual metal nanoparticles which, combined with X-ray diffraction (XRD) patterns showed them to consist of a pure nickel phase rather than the more thermodynamically stable bulk nickel oxide. Importantly, there appears to be no "particle size effect" on the adsorption mode of the tartaric acid in the particle size range ~ 90-~ 300 nm.

  2. Phospholipid mesophases at solid interfaces: in-situ X-ray diffraction and spin-label studies.

    PubMed

    Rappolt, Michael; Amenitsch, Heinz; Strancar, Janez; Teixeira, Cilaine V; Kriechbaum, Manfred; Pabst, Georg; Majerowicz, Monika; Laggner, Peter

    2004-11-29

    In this work, we report on recent investigations, both on the global and on the local molecular architecture of supported phospholipid model membranes. A brief theoretical introduction explains how global structural information on supramolecular lipid ensembles can be retrieved from surface X-ray diffraction measurements as well as how spin-label electron paramagnetic resonance spectroscopy (EPR) provides complementary information on the local environment of probe molecules. The combination of especially designed X-ray cells with the technique of small- and wide-angle X-ray surface scattering makes it possible to explore various fields of lipid research and its applications. Examples for different physico-chemical conditions are presented: (i) in situ chemistry under excess of water conditions demonstrating how solid-supported lipid films sense salinity, (ii) the 3D electron density reconstruction of a vesicle-fusion intermediate under controlled humidity, and (iii) complementary temperature and pressure effects on oriented phospholipid samples. Further, special attention has been given to the influence of different film preparation techniques with respect to quality and the defect structure manifestation. To resolve the proportions and local properties of defects in a hydrated lipid-deposited surface, spin-label EPR was applied. The results from 9.6 GHz EPR as well as from 1.2 GHz EPR suggest the alignment to be in the range between 30% and 80%. In addition, slow time-dependent EPR measurements point to nano-structural rearrangements due to water flow and reduction of alignment quality.

  3. Short-period cyclic loading system for in situ X-ray observation of anelastic properties at high pressure

    NASA Astrophysics Data System (ADS)

    Yoshino, Takashi; Yamazaki, Daisuke; Tange, Yoshinori; Higo, Yuji

    2016-10-01

    To determine the anelastic properties of materials of the Earth's interior, a short-period cyclic loading system was installed for in situ X-ray radiographic observation under high pressure to the multi-anvil deformation DIA press at the bending magnet beam line BL04B1 at SPring-8. The hydraulic system equipped with a piston controlled by a solenoid was designed so as to enable producing smooth sinusoidal stress in a wide range of oscillation period from 0.2 to 100 s and generating variable amplitudes. Time resolved X-ray radiography imaging of the sample and reference material provides their strain as a function of time during cyclic loading. A synchrotron X-ray radiation source allows us to resolve their strain variation with time even at the short period (<1 s). The minimum resolved strain is as small as 10-4, and the shortest oscillation period to detect small strain is 0.5 s. Preliminary experimental results exhibited that the new system can resolve attenuation factor Q-1 at upper mantle conditions. These results are in quantitative agreement with previously reported data obtained at lower pressures.

  4. In situ X-ray powder diffraction studies of the synthesis of graphene oxide and formation of reduced graphene oxide

    SciTech Connect

    Storm, Mie Møller Johnsen, Rune E.; Norby, Poul

    2016-08-15

    Graphene oxide (GO) and reduced graphene oxide (rGO) are important materials in a wide range of fields. The modified Hummers methods, for synthesizing GO, and subsequent thermal reduction to rGO, are often employed for production of rGO. However, the mechanism behinds these syntheses methods are still unclear. We present an in situ X-ray diffraction study of the synthesis of GO and thermal reduction of GO. The X-ray diffraction revealed that the Hummers method includes an intercalation state and finally formation of additional crystalline material. The formation of GO is observed during both the intercalation and the crystallization stage. During thermal reduction of GO three stages were observed: GO, a disordered stage, and the rGO stage. The appearance of these stages depends on the heating ramp. The aim of this study is to provide deeper insight into the chemical and physical processes during the syntheses. - Graphical abstract: In situ X-ray diffraction results for of the modified Hummers synthesis and the thermal reduction of graphene oxide, revealing three stages for both syntheses as well as new GO diffraction peaks and unidentified crystalline material for the Hummers synthesis and a disordered stage for the thermal reduction of graphene oxide. Display Omitted - Highlights: • Hummers synthesis consists of three stages: dissolution, intercalation and crystal. • GO is produced early on during the synthesis and display new diffraction peaks. • An unidentified triclinic phase is observed for the Hummers synthesis. • Thermal reduction of GO display three stages: GO, a disordered stage and rGO. • In situ XRD indicate reformation of rGO even for fast heated thermal reduction.

  5. In-situ x-ray monitoring of damage accumulation in SiC/RBSN tensile specimens

    NASA Technical Reports Server (NTRS)

    Baaklini, George Y.; Bhatt, Ramakrishna T.

    1991-01-01

    The room-temperature tensile testing of silicon carbide fiber reinforced reaction-bonded silicon nitride (SiC/RBSN) composite specimens was monitored by using in-situ x ray film radiography. Radiographic evaluation before, during, and after loading provided data on the effect of preexisting volume flaws (high density impurities, and local density variations) on the fracture behavior of composites. Results from (0)1, (0)3, (0)5, and (0)8 composite specimens, showed that x ray film radiography can monitor damage accumulations during tensile loading. Matrix cracking, fiber-matrix debonding, and fiber pullout were imaged throughout the tensile loading history of the specimens. Further, in-situ film radiography was found to be a helpful and practical technique for estimating interfacial shear strength between the SiC fiber and the RBSN matrix by the matrix crack spacing method. It is concluded that pretest, in-situ, and post-test radiography can provide for a greater understanding of ceramic matrix composite mechanical behavior, a verification of related experimental procedures, and a validation and development of related analytical models.

  6. In-situ Synchrotron X-ray Microdiffraction Study of Lattice Rotation in Polycrystalline Materials during Uniaxial Deformations

    SciTech Connect

    Joo, H.D.; Bark, C.W.; Koo, Y.M.; Kim, K.H.; Tamura, N.

    2004-05-12

    Recent experiments have shown that formation of dislocation cell structures and rotation of structural elements at the macroscopic level are fundamental to the development of plastic deformation. However, attention should also be focused on micro-volumes because local stress and strain can significantly differ from their averaged values at the macroscale. In-situ orientation measurements in copper polycrystals during uniaxial deformation were performed using synchrotron x-ray microdiffraction at the Advanced Light Source. We observed heterogeneities in deformation-induced microstructure within individual grains. Different slip systems in particular can be simultaneously activated among neighboring volume elements of individual grains.

  7. In-situ X-Ray Analysis of the Electrolyte-Solid Interface

    DTIC Science & Technology

    1994-05-31

    of the underpotential deposition (UPD) family. That is, the Cu is more strongly bound to the Pt than it is to itself. This makes it possible to...34 " Underpotential - Deposited Cu Monolayer on Pt", T.M. Hayes, W. Li, G. Liang, C.M. Lo, T.E. Furtak, E.A. Creek, P. Samanta, and L. Wang, in X-ray...Journal of the American Vacuum Society, (to be submitted 1994) 5.2 Presentations 0 " Underpotential Deposited Cu Monolayer on Pt", T. M. Hayes, L

  8. Phase transitions in freeze-dried systems - quantification using in situ synchrotron X-ray diffractometry

    SciTech Connect

    Varshney, Dushyant B.; Sundaramurthi, Prakash; Kumar, Satyendra; Shalaev, Evgenyi Y.; Kang, Shin-Woong; Gatlin, Larry A.; Suryanarayanan, Raj

    2009-09-02

    The purpose is: (1) To develop a synchrotron X-ray diffraction (SXRD) method to monitor phase transitions during the entire freeze-drying cycle. Aqueous sodium phosphate buffered glycine solutions with initial glycine to buffer molar ratios of 1:3 (17:50 mM), 1:1 (50 mM) and 3:1 were utilized as model systems. (2) To investigate the effect of initial solute concentration on the crystallization of glycine and phosphate buffer salt during lyophilization. Phosphate buffered glycine solutions were placed in a custom-designed sample cell for freeze-drying. The sample cell, covered with a stainless steel dome with a beryllium window, was placed on a stage capable of controlled cooling and vacuum drying. The samples were cooled to -50 C and annealed at -20 C. They underwent primary drying at -25 C under vacuum until ice sublimation was complete and secondary drying from 0 to 25 C. At different stages of the freeze-drying cycle, the samples were periodically exposed to synchrotron X-ray radiation. An image plate detector was used to obtain time-resolved two-dimensional SXRD patterns. The ice, {beta}-glycine and DHPD phases were identified based on their unique X-ray peaks. When the solutions were cooled and annealed, ice formation was followed by crystallization of disodium hydrogen phosphate dodecahydrate (DHPD). In the primary drying stage, a significant increase in DHPD crystallization followed by incomplete dehydration to amorphous disodium hydrogen phosphate was evident. Complete dehydration of DHPD occurred during secondary drying. Glycine crystallization was inhibited throughout freeze-drying when the initial buffer concentration (1:3 glycine to buffer) was higher than that of glycine. A high-intensity X-ray diffraction method was developed to monitor the phase transitions during the entire freeze-drying cycle. The high sensitivity of SXRD allowed us to monitor all the crystalline phases simultaneously. While DHPD crystallizes in frozen solution, it dehydrates

  9. Low-dose phase-based X-ray imaging techniques for in situ soft tissue engineering assessments.

    PubMed

    Izadifar, Zohreh; Honaramooz, Ali; Wiebe, Sheldon; Belev, George; Chen, Xiongbiao; Chapman, Dean

    2016-03-01

    In tissue engineering, non-invasive imaging of biomaterial scaffolds and tissues in living systems is essential to longitudinal animal studies for assessments without interrupting the repair process. Conventional X-ray imaging is inadequate for use in soft tissue engineering due to the limited absorption difference between the soft tissue and biomaterial scaffolds. X-ray phase-based imaging techniques that derive contrast from refraction or phase effects rather than absorption can provide the necessary contrast to see low-density biomaterial scaffolds and tissues in large living systems. This paper explores and compares three synchrotron phase-based X-ray imaging techniques-computed tomography (CT)-diffraction enhanced imaging (DEI), -analyzer based imaging (ABI), and -phase contrast imaging (PCI)-for visualization and characterization of low-density biomaterial scaffolds and tissues in situ for non-invasive soft tissue engineering assessments. Intact pig joints implanted with polycaprolactone scaffolds were used as the model to assess and compare the imaging techniques in terms of different qualitative and quantitative criteria. For long-term in vivo live animal imaging, different strategies for reducing the imaging radiation dose and scan time-reduced number of CT projections, region of interest, and low resolution imaging-were examined with the presented phase-based imaging techniques. The results demonstrated promising capabilities of the phase-based techniques for visualization of biomaterial scaffolds and soft tissues in situ. The low-dose imaging strategies were illustrated effective for reducing the radiation dose to levels appropriate for live animal imaging. The comparison among the imaging techniques suggested that CT-DEI has the highest efficiency in retaining image contrast at considerably low radiation doses.

  10. In-Situ Observations of Phase Transformations During Welding of 1045 Steel using Spatially Resolved and Time Resolved X-Ray Diffraction

    SciTech Connect

    Elmer, J; Palmer, T; DebRoy, T

    2005-10-28

    Synchrotron-based methods have been developed at Lawrence Livermore National Laboratory (LLNL) for the direct observation of microstructure evolution during welding. These techniques, known as spatially resolved (SRXRD) and time resolved (TRXRD) x-ray diffraction, allow in-situ experiments to be performed during welding and provide direct observations of high temperature phases that form under the intense thermal cycles that occur. This paper presents observations of microstructural evolution that occur during the welding of a medium carbon AISI 1045 steel, using SRXRD to map the phases that are present during welding, and TRXRD to dynamically observe transformations during rapid heating and cooling. SRXRD was further used to determine the influence of welding heat input on the size of the high temperature austenite region, and the time required to completely homogenize this region during welding. These data can be used to determine the kinetics of phase transformations under the steep thermal gradients of welds, as well as benchmark and verify phase transformation models.

  11. Silver in geological fluids from in situ X-ray absorption spectroscopy and first-principles molecular dynamics

    NASA Astrophysics Data System (ADS)

    Pokrovski, Gleb S.; Roux, Jacques; Ferlat, Guillaume; Jonchiere, Romain; Seitsonen, Ari P.; Vuilleumier, Rodolphe; Hazemann, Jean-Louis

    2013-04-01

    The molecular structure and stability of species formed by silver in aqueous saline solutions typical of hydrothermal settings were quantified using in situ X-ray absorption spectroscopy (XAS) measurements, quantum-chemical modeling of near-edge absorption spectra (XANES) and extended fine structure spectra (EXAFS), and first-principles molecular dynamics (FPMD). Results show that in nitrate-bearing acidic solutions to at least 200 °C, silver speciation is dominated by the hydrated Ag+ cation surrounded by 4-6 water molecules in its nearest coordination shell with mean Ag-O distances of 2.32 ± 0.02 Å. In NaCl-bearing acidic aqueous solutions of total Cl concentration from 0.7 to 5.9 mol/kg H2O (m) at temperatures from 200 to 450 °C and pressures to 750 bar, the dominant species are the di-chloride complex AgCl2- with Ag-Cl distances of 2.40 ± 0.02 Å and Cl-Ag-Cl angle of 160 ± 10°, and the tri-chloride complex AgCl32- of a triangular structure and mean Ag-Cl distances of 2.60 ± 0.05 Å. With increasing temperature, the contribution of the tri-chloride species decreases from ˜50% of total dissolved Ag in the most concentrated solution (5.9m Cl) at 200 °C to less than 10-20% at supercritical temperatures for all investigated solutions, so that AgCl2- becomes by far the dominant Ag-bearing species at conditions typical of hydrothermal-magmatic fluids. Both di- and tri-chloride species exhibit outer-sphere interactions with the solvent as shown by the detection, using FPMD modeling, of H2O, Cl-, and Na+ at distances of 3-4 Å from the silver atom. The species fractions derived from XAS and FPMD analyses, and total AgCl(s) solubilities, measured in situ in this work from the absorption edge height of XAS spectra, are in accord with thermodynamic predictions using the stability constants of AgCl2- and AgCl32- from Akinfiev and Zotov (2001) and Zotov et al. (1995), respectively, which are based on extensive previous AgCl(s) solubility measurements. These data

  12. In situ EXAFS, X-ray diffraction and photoluminescence for high-pressure studies.

    PubMed

    Sapelkin, A V; Bayliss, S C; Russell, D; Clark, S M; Dent, A J

    2000-07-01

    A new facility for simultaneous extended X-ray absorption of fine structure (EXAFS), X-ray diffraction and photoluminescence measurements under high pressures has been developed for use on station 9.3 at the Daresbury Laboratory Synchrotron Radiation Source. This high-pressure facility can be used at any suitable beamline at a synchrotron source. Full remote operation of the rig allows simultaneous collection of optical and structural data while varying the pressure. The set-up is very flexible and can be tailored for a particular experiment, such as time- or temperature-dependent measurements. A new approach to the collection of high-pressure EXAFS data is also presented. The approach significantly shortens the experimental times and allows a dramatic increase in the quality of EXAFS data collected. It also opens up the possibility for EXAFS data collection at any pressure which can be generated using a diamond cell. The high quality of data collected is demonstrated with a GaN case study. Particular attention will be paid to the use of energy-dispersive EXAFS and quick-scanning EXAFS techniques under pressure.

  13. In-situ high-pressure x-ray diffraction study of zinc ferrite nanoparticles

    SciTech Connect

    Ferrari, S.; Kumar, R. S.; Grinblat, F.; Aphesteguy, J. C.; Saccone, F. D.; Errandonea, D.

    2016-04-23

    We have studied the high-pressure structural behavior of zinc ferrite (ZnFe2O4) nanoparticles by powder X-ray diffraction measurements up to 47 GPa. We found that the cubic spinel structure of ZnFe2O4 remains up to 33 GPa and a phase transition is induced beyond this pressure. The high-pressure phase is indexed to an orthorhombic CaMn2O4-type structure. Upon decompression the low- and high-pressure phases coexist. The compressibility of both structures was also investigated. We have observed that the lattice parameters of the high-pressure phase behave anisotropically upon compression. Further, we predict possible phase transition around 55 GPa. For comparison, we also studied the compression behavior of magnetite (Fe3O4) nanoparticles by X-ray diffraction up to 23 GPa. Spinel-type ZnFe2O4 and Fe3O4 nanoparticles have a bulk modulus of 172 (20) GPa and 152 (9) GPa, respectively. Lastly, this indicates that in both cases the nanoparticles do not undergo a Hall-Petch strengthening.

  14. In-situ high-pressure x-ray diffraction study of zinc ferrite nanoparticles

    DOE PAGES

    Ferrari, S.; Kumar, R. S.; Grinblat, F.; ...

    2016-04-23

    We have studied the high-pressure structural behavior of zinc ferrite (ZnFe2O4) nanoparticles by powder X-ray diffraction measurements up to 47 GPa. We found that the cubic spinel structure of ZnFe2O4 remains up to 33 GPa and a phase transition is induced beyond this pressure. The high-pressure phase is indexed to an orthorhombic CaMn2O4-type structure. Upon decompression the low- and high-pressure phases coexist. The compressibility of both structures was also investigated. We have observed that the lattice parameters of the high-pressure phase behave anisotropically upon compression. Further, we predict possible phase transition around 55 GPa. For comparison, we also studied themore » compression behavior of magnetite (Fe3O4) nanoparticles by X-ray diffraction up to 23 GPa. Spinel-type ZnFe2O4 and Fe3O4 nanoparticles have a bulk modulus of 172 (20) GPa and 152 (9) GPa, respectively. Lastly, this indicates that in both cases the nanoparticles do not undergo a Hall-Petch strengthening.« less

  15. In-situ X-ray Synchrotron Microtomography: Real Time Pore Structure Evolution during Olivine Carbonation

    NASA Astrophysics Data System (ADS)

    Zhu, W.; Fusseis, F.; Lisabeth, H. P.; Xiao, X.

    2013-12-01

    Mineral carbonation has been proposed as a promising method for long-term, secure sequestration of carbon dioxide. In porous rocks, fluid-rock interactions can significantly alter the pore space and thus exert important controls over the rate and extent of carbonation. We constructed an x-ray transparent pressure cell [Fusseis et al., 2013] to investigate the real time pore structure evolution during mineral carbonation in porous olivine aggregates. In each experiment, a sintered olivine sample was subjected to a confining pressure of 13 MPa and a pore pressure of 10 MPa, with a sodium bicarbonate solution (NaHCO3 at 1.5 M) as pore fluid. At these pressure conditions, the cell was heated to 473 K. Constant pressure and temperature conditions were maintained during the length of the experiments, lasting 72-120 hours. Using a polychromatic beam in the 2-BM upstream hutch at the Advanced Photon Source, 3-dimensional (3-D) microtomography data were collected in 20 seconds with 30-minute interval. A novel phase retrieval reconstruction algorithm [Paganin et al., 2002] was used to reconstruct microtomographic datasets with a voxel size of ~1.1 micron. The microtomography images at different stages of the carbonation process reveal progressive growth of new crystals in the pore space. Integration of a x-ray transparent pressure vessel with flow through capacity and 3-D microtomography provides a novel research direction of studying the coupled chemo-hydro-thermal-mechanical processes in rocks.

  16. Characterization by X-ray tomography of granulated alumina powder during in situ die compaction

    SciTech Connect

    Cottrino, Sandrine; Jorand, Yves Maire, Eric; Adrien, Jérôme

    2013-07-15

    Compaction process, the aim of which being to obtain green bodies with low porosity and small size, is often used before sintering treatment. Prior to die filling, the ceramic powder is generally granulated to improve flowability. However during compaction, density heterogeneity and critical size defects may appear due to intergranule and granule-die wall frictions. In this work, the influence of granule formulation on the compact morphology has been studied. To do so, a compaction setup was installed inside an X-ray tomography equipment so that the evolution of the compact morphology could be analysed during the whole compaction process. We have demonstrated that high humidity rate and the addition of binder in the granule formulation increase density heterogeneity and generate larger defects. - Highlights: • An original compaction set up was installed inside an X-Ray tomography equipment. • The compaction process of granulated ceramic powder is imaged. • The compact green microstructure is quantified and related to the compaction stages. • The most detrimental defects of dry-pressed parts are caused by hollow granules. • Formulations without binder allow a reduction of the number of large defects.

  17. In Situ identification of mineral resources with an X-ray-optical "Hand-Lens" instrument

    NASA Technical Reports Server (NTRS)

    Marshall, J.; Koppel, L.; Bratton, C.; Metzger, E.; Hecht, M.

    1997-01-01

    The recognition of material resources on a planetary surface requires exploration strategies not dissimilar to those employed by early field geologists who searched for ore deposits primarily from surface clues. In order to determine the location of mineral ores or other materials, it will be necessary to characterize host terranes at regional or subregional scales. This requires geographically broad surveys in which statistically significant numbers of samples are rapidly scanned from a roving platform. To enable broad-scale, yet power-conservative planetary-surface exploration, we are developing an instrument that combines x-ray diffractometry (XRD), x-ray fluorescence spectrometry (XRF), and optical capabilities; the instrument can be deployed at the end of a rover's robotic arm, without the need for sample capture or preparation. The instrument provides XRD data for identification of mineral species and lithological types; diffractometry of minerals is conducted by ascertaining the characteristic lattice parameters or "d-spacings" of mineral compounds. D-spacings of 1.4 to 25 angstroms can be determined to include the large molecular structures of hydrated minerals such as clays. The XRF data will identify elements ranging from carbon (Atomic Number = 6) to elements as heavy as barium (Atomic Number = 56).

  18. In Situ identification of mineral resources with an X-ray-optical "Hand-Lens" instrument

    NASA Technical Reports Server (NTRS)

    Marshall, J.; Koppel, L.; Bratton, C.; Metzger, E.; Hecht, M.

    1997-01-01

    The recognition of material resources on a planetary surface requires exploration strategies not dissimilar to those employed by early field geologists who searched for ore deposits primarily from surface clues. In order to determine the location of mineral ores or other materials, it will be necessary to characterize host terranes at regional or subregional scales. This requires geographically broad surveys in which statistically significant numbers of samples are rapidly scanned from a roving platform. To enable broad-scale, yet power-conservative planetary-surface exploration, we are developing an instrument that combines x-ray diffractometry (XRD), x-ray fluorescence spectrometry (XRF), and optical capabilities; the instrument can be deployed at the end of a rover's robotic arm, without the need for sample capture or preparation. The instrument provides XRD data for identification of mineral species and lithological types; diffractometry of minerals is conducted by ascertaining the characteristic lattice parameters or "d-spacings" of mineral compounds. D-spacings of 1.4 to 25 angstroms can be determined to include the large molecular structures of hydrated minerals such as clays. The XRF data will identify elements ranging from carbon (Atomic Number = 6) to elements as heavy as barium (Atomic Number = 56).

  19. In-situ high-pressure x-ray diffraction study of zinc ferrite nanoparticles

    SciTech Connect

    Ferrari, S.; Kumar, R. S.; Grinblat, F.; Aphesteguy, J. C.; Saccone, F. D.; Errandonea, D.

    2016-04-23

    We have studied the high-pressure structural behavior of zinc ferrite (ZnFe2O4) nanoparticles by powder X-ray diffraction measurements up to 47 GPa. We found that the cubic spinel structure of ZnFe2O4 remains up to 33 GPa and a phase transition is induced beyond this pressure. The high-pressure phase is indexed to an orthorhombic CaMn2O4-type structure. Upon decompression the low- and high-pressure phases coexist. The compressibility of both structures was also investigated. We have observed that the lattice parameters of the high-pressure phase behave anisotropically upon compression. Further, we predict possible phase transition around 55 GPa. For comparison, we also studied the compression behavior of magnetite (Fe3O4) nanoparticles by X-ray diffraction up to 23 GPa. Spinel-type ZnFe2O4 and Fe3O4 nanoparticles have a bulk modulus of 172 (20) GPa and 152 (9) GPa, respectively. Lastly, this indicates that in both cases the nanoparticles do not undergo a Hall-Petch strengthening.

  20. In-situ X-ray diffraction snapshotting: Determination of the kinetics of a photodimerization within a single crystal

    PubMed Central

    Hu, Fei-Long; Wang, Shu-Long; Lang, Jian-Ping; Abrahams, Brendan F.

    2014-01-01

    In a single-crystal-to-single-crystal (SCSC) transformation, a preformed three-dimensional coordination polymer,[Ni3(oba)2(bpe)2(SO4)(H2O)4]·H2O (H2oba = 4,4′-oxydibenzoic acid; bpe = (E)-1,2-di(pyridin-4-yl)ethane) (1), was shown to undergo a [2+2] cycloaddition reaction upon exposure to UV irradiation. The kinetics of this reaction were followed by taking “snapshots” of the solid state transformation using in situ single crystal X-ray crystallography; a first order process was indicated. The reaction rate was influenced by many factors such as the separation of the sample from the UV light source, the heat produced by the UV irradiation, the light flux of the UV lamp used, the size of the single-crystal and the powder samples. The investigation of the kinetics was complemented by 1H NMR studies. The results clearly demonstrate that in situ single-crystal X-ray diffraction is able to provide useful insights into the gradual formation of the photoproducts and the reaction processes. The work also offers a clear indication that it is possible to use the technique to study the kinetics of other photocycloaddition reactions and SCSC processes in general. PMID:25351677

  1. A new transmission x-ray microscope for in-situ nano-tomography at the APS (Conference Presentation)

    NASA Astrophysics Data System (ADS)

    De Andrade, Vincent; Deriy, Alex; Wojcik, Michael; Gürsoy, Doga; Shu, Deming; Mooney, Tim; Peterson, Kevin M.; Glowacki, Arthur; Yue, Ke; Yang, Xiaogang; Vescovi, Rafael; De Carlo, Francesco

    2016-10-01

    A new Transmission X-ray Microscope (TXM), optimized for in-situ nano-tomography experiments, has been designed and built at the Advanced Photon Source (APS). The instrument has been in operation for the last two years and is supporting users over large fields of Science, from energy storage and material science to natural sciences. The flexibility of our X-ray microscope design permits evolutionary geometries and can accommodate relatively heavy, up to 5 kg, and bulky in-situ cells while ensuring high spatial resolution, which is expected to improve steadily thanks to the support of the RD program led by the APS-Upgrade project on Fresnel zone plates (FZP). The robust sample stack, designed with minimum degrees of freedom shows a stability better than 4 nm rms at the sample location. The TXM operates with optics fabricated in-house. A spatial resolution of 30 nm per voxel has been demonstrated when the microscope operates with a 60 nm outermost zone width FZP with a measured efficiency of 18% at 8 keV. 20 nm FZP are also currently available and should be in routine use within the next few months once a new matching condenser is produced. In parallel, efficiency is being improved with opto-mechanical engineering (FZP stacking system) and software developments (more efficient reconstruction algorithms combined with different data acquisition schemes), enabling 3D dynamic studies when sample evolution occurs within a couple of tens of seconds.

  2. In-situ transmission x-ray microscopy study of photon-induced oxidation of silver nanowires

    NASA Astrophysics Data System (ADS)

    Yu, Le; Sun, Yugang; Wang, Yuxin; Cai, Zhonghou; Han, Ping; Cheng, X. M.

    Oxidation of metal nanoparticles usually follows a Kirkendall process to transform solid nanoparticles to hollow metal oxide nanoshells. However the morphological trajectory of nanoparticles and the mass diffusion kinetics involved in the nanoscale Kirkendall process are complex. In this presentation we report the use of in-situ transmission x-ray microscopy (TXM) to directly image individual silver nanowires under oxidation atmosphere, which are created from radiolysis of air under illumination of the focused synchrotron x-ray beam. The in-situ results clearly show the morphological transformation from solid silver nanowires to hollow nanotubes in the course of oxidation reaction of silver. Quantitative analysis of the time-resolved TXM images provides unprecedented details on reaction kinetics and mass diffusion kinetics associated with the oxidation process. Work at Bryn Mawr College is supported by NSF Grant #1207085. Use of the Advanced Photon Source and the Center for Nanoscale Materials at Argonne National Laboratory was supported by the U. S. Department of Energy, Office of Science, Office of Basic Energy Sciences, under Contract No. DE-AC02-06CH11357.

  3. In situ observation of dynamic electrodeposition processes by soft x-ray fluorescence microspectroscopy and keyhole coherent diffractive imaging

    NASA Astrophysics Data System (ADS)

    Bozzini, Benedetto; Kourousias, George; Gianoncelli, Alessandra

    2017-03-01

    This paper describes two novel in situ microspectroscopic approaches to the dynamic study of electrodeposition processes: x-ray fluorescence (XRF) mapping with submicrometric space resolution and keyhole coherent diffractive imaging (kCDI) with nanometric lateral resolution. As a case study, we consider the pulse-plating of nanocomposites with polypyrrole matrix and Mn x Co y O z dispersoids, a prospective cathode material for zinc-air batteries. This study is centred on the detailed measurement of the elemental distributions developing in two representative subsequent growth steps, based on the combination of in situ identical-location XRF microspectroscopy—accompanied by soft-x ray absorption microscopy—and kCDI. XRF discloses space and time distributions of the two electrodeposited metals and kCDI on the one hand allows nanometric resolution and on the other hand provides complementary absorption as well as phase contrast modes. The joint information derived from these two microspectroscopies allows measurement of otherwise inaccessible observables that are a prerequisite for electrodeposition modelling and control accounting for dynamic localization processes.

  4. Size dependent behavior of Fe3O4 crystals during electrochemical (de)lithiation: an in situ X-ray diffraction, ex situ X-ray absorption spectroscopy, transmission electron microscopy and theoretical investigation.

    PubMed

    Bock, David C; Pelliccione, Christopher J; Zhang, Wei; Timoshenko, Janis; Knehr, K W; West, Alan C; Wang, Feng; Li, Yan; Frenkel, Anatoly I; Takeuchi, Esther S; Takeuchi, Kenneth J; Marschilok, Amy C

    2017-08-09

    The iron oxide magnetite, Fe3O4, is a promising conversion type lithium ion battery anode material due to its high natural abundance, low cost and high theoretical capacity. While the close packing of ions in the inverse spinel structure of Fe3O4 enables high energy density, it also limits the kinetics of lithium ion diffusion in the material. Nanosizing of Fe3O4 to reduce the diffusion path length is an effective strategy for overcoming this issue and results in improved rate capability. However, the impact of nanosizing on the multiple structural transformations that occur during the electrochemical (de)lithiation reaction in Fe3O4 is poorly understood. In this study, the influence of crystallite size on the lithiation-conversion mechanisms in Fe3O4 is investigated using complementary X-ray techniques along with transmission electron microscopy (TEM) and continuum level simulations on electrodes of two different Fe3O4 crystallite sizes. In situ X-ray diffraction (XRD) measurements were utilized to track the changes to the crystalline phases during (de)lithiation. X-ray absorption spectroscopy (XAS) measurements at multiple points during the (de)lithiation processes provided local electronic and atomic structural information. Tracking the crystalline and nanocrystalline phases during the first (de)lithiation provides experimental evidence that (1) the lithiation mechanism is non-uniform and dependent on crystallite size, where increased Li(+) diffusion length in larger crystals results in conversion to Fe(0) metal while insertion of Li(+) into spinel-Fe3O4 is still occurring, and (2) the disorder and size of the Fe metal domains formed when either material is fully lithiated impacts the homogeneity of the FeO phase formed during the subsequent delithiation.

  5. Note: Setup for chemical atmospheric control during in situ grazing incidence X-ray scattering of printed thin films

    DOE PAGES

    Pröller, Stephan; Moseguí González, Daniel; Zhu, Chenhuii; ...

    2017-06-01

    In order to tailor the assembling of polymers and organic molecules, a deeper understanding of the kinetics involved in thin film production is necessary. While post-production characterization only provides insight on the final film structure, more sophisticated experimental setups are needed to probe the structure formation processes in situ during deposition. The drying kinetics of a deposited organic thin film strongly influences the assembling process on the nanometer scale. Lastly, this work presents an experimental setup that enables fine control of the atmosphere composition surrounding the sample during slot die coating, while simultaneously probing the film formation kinetics using inmore » situ grazing incidence X-ray scattering and spectroscopy.« less

  6. High-Energy Synchrotron X-Ray Diffraction for In Situ Diffuse Scattering Studies of Bulk Single Crystals

    NASA Astrophysics Data System (ADS)

    Daniels, John E.; Jo, Wook; Donner, Wolfgang

    2012-01-01

    High-energy synchrotron x-ray scattering offers a powerful technique for investigation of single-crystal material structures. Large, mm-sized crystals can be used, allowing complex in situ sample environments to be employed. Here, we demonstrate how this technique can be applied for the collection of single-crystal diffuse scattering volumes from the electro-active material 96%Bi0.5Na0.5TiO3-4%BaTiO3 while electric fields are applied in situ. The data obtained allow correlation of the atomic and nanoscale structures with the observed macroscopic electro-active properties of interest. This article presents a recent study relating the nanoscale stacking fault structure in BNT-BT to the relaxor-ferroelectric nature of the material [Daniels et al. in Appl. Phys. Lett. 98, 252904 (2011)], and extends this study with further experimental description and analysis.

  7. Repeated crack healing in MAX-phase ceramics revealed by 4D in situ synchrotron X-ray tomographic microscopy

    PubMed Central

    Sloof, Willem G.; Pei, Ruizhi; McDonald, Samuel A.; Fife, Julie L.; Shen, Lu; Boatemaa, Linda; Farle, Ann-Sophie; Yan, Kun; Zhang, Xun; van der Zwaag, Sybrand; Lee, Peter D.; Withers, Philip J.

    2016-01-01

    MAX phase materials are emerging as attractive engineering materials in applications where the material is exposed to severe thermal and mechanical conditions in an oxidative environment. The Ti2AlC MAX phase possesses attractive thermomechanical properties even beyond a temperature of 1000 K. An attractive feature of this material is its capacity for the autonomous healing of cracks when operating at high temperatures. Coupling a specialized thermomechanical setup to a synchrotron X-ray tomographic microscopy endstation at the TOMCAT beamline, we captured the temporal evolution of local crack opening and healing during multiple cracking and autonomous repair cycles at a temperature of 1500 K. For the first time, the rate and position dependence of crack repair in pristine Ti2AlC material and in previously healed cracks has been quantified. Our results demonstrate that healed cracks can have sufficient mechanical integrity to make subsequent cracks form elsewhere upon reloading after healing. PMID:26972608

  8. Repeated crack healing in MAX-phase ceramics revealed by 4D in situ synchrotron X-ray tomographic microscopy.

    PubMed

    Sloof, Willem G; Pei, Ruizhi; McDonald, Samuel A; Fife, Julie L; Shen, Lu; Boatemaa, Linda; Farle, Ann-Sophie; Yan, Kun; Zhang, Xun; van der Zwaag, Sybrand; Lee, Peter D; Withers, Philip J

    2016-03-14

    MAX phase materials are emerging as attractive engineering materials in applications where the material is exposed to severe thermal and mechanical conditions in an oxidative environment. The Ti2AlC MAX phase possesses attractive thermomechanical properties even beyond a temperature of 1000 K. An attractive feature of this material is its capacity for the autonomous healing of cracks when operating at high temperatures. Coupling a specialized thermomechanical setup to a synchrotron X-ray tomographic microscopy endstation at the TOMCAT beamline, we captured the temporal evolution of local crack opening and healing during multiple cracking and autonomous repair cycles at a temperature of 1500 K. For the first time, the rate and position dependence of crack repair in pristine Ti2AlC material and in previously healed cracks has been quantified. Our results demonstrate that healed cracks can have sufficient mechanical integrity to make subsequent cracks form elsewhere upon reloading after healing.

  9. Microscopic theory of resonant soft-x-ray scattering in materials with charge order: the example of charge stripes in high-temperature cuprate superconductors.

    PubMed

    Benjamin, David; Abanin, Dmitry; Abbamonte, Peter; Demler, Eugene

    2013-03-29

    We present a microscopic theory of resonant soft-x-ray scattering that accounts for the delocalized character of valence electrons. Unlike past approaches based on local form factors, our functional determinant method treats realistic band structures. This method builds upon earlier theoretical work in mesoscopic physics and accounts for excitonic effects as well as the orthogonality catastrophe arising from interaction between the core hole and the valence band electrons. We show that the two-peak structure observed near the O K edge of stripe-ordered La1.875Ba0.125CuO4 is due to dynamical nesting within the canonical cuprate band structure. Our results provide evidence for reasonably well-defined, high-energy quasiparticles in cuprates and establish resonant soft-x-ray scattering as a bulk-sensitive probe of the electron quasiparticles.

  10. In Situ Identification of Mineral Resources with an X-Ray-Optical "Hands-Lens" Instrument

    NASA Astrophysics Data System (ADS)

    Marshall, J.; Koppel, L.; Bratton, C.; Metzger, E.; Hecht, M.

    1999-09-01

    The recognition of material resources on a planetary surface requires exploration strategies not dissimilar to those employed by early field geologists who searched for ore deposits primarily from surface clues. In order to determine the location of mineral ores or other materials, it will be necessary to characterize host terranes at regional or subregional scales. This requires geographically broad surveys in which statistically significant numbers of samples are rapidly scanned from a roving platform. To enable broad-scale, yet power-conservative planetary-surface exploration, we are developing an instrument that combines x-ray diffractometry (XRD), x-ray fluorescence spectrometry (XRF), and optical capabilities; the instrument can be deployed at the end of a rover's robotic arm, without the need for sample capture or preparation. The instrument provides XRD data for identification of mineral species and lithological types; diffractometry of minerals is conducted by ascertaining the characteristic lattice parameters or "d-spacings" of mineral compounds. D-spacings of 1.4 to 25 angstroms can be determined to include the large molecular structures of hydrated minerals such as clays. The XRF data will identify elements ranging from carbon (Atomic Number = 6) to elements as heavy as barium (Atomic Number = 56). While a sample is being x-rayed, the instrument simultaneously acquires an optical image of the sample surface at magnifications from lx to at least 50x (200x being feasible, depending on the sample surface). We believe that imaging the sample is extremely important as corroborative sample-identification data (the need for this capability having been illustrated by the experience of the Pathfinder rover). Very few geologists would rely on instrument data for sample identification without having seen the sample. Visual inspection provides critical recognition data such as texture, crystallinity, granularity, porosity, vesicularity, color, lustre, opacity, and

  11. In Situ Identification of Mineral Resources with an X-Ray-Optical "Hands-Lens" Instrument

    NASA Technical Reports Server (NTRS)

    Marshall, J.; Koppel, L.; Bratton, C.; Metzger, E.; Hecht, M.

    1999-01-01

    The recognition of material resources on a planetary surface requires exploration strategies not dissimilar to those employed by early field geologists who searched for ore deposits primarily from surface clues. In order to determine the location of mineral ores or other materials, it will be necessary to characterize host terranes at regional or subregional scales. This requires geographically broad surveys in which statistically significant numbers of samples are rapidly scanned from a roving platform. To enable broad-scale, yet power-conservative planetary-surface exploration, we are developing an instrument that combines x-ray diffractometry (XRD), x-ray fluorescence spectrometry (XRF), and optical capabilities; the instrument can be deployed at the end of a rover's robotic arm, without the need for sample capture or preparation. The instrument provides XRD data for identification of mineral species and lithological types; diffractometry of minerals is conducted by ascertaining the characteristic lattice parameters or "d-spacings" of mineral compounds. D-spacings of 1.4 to 25 angstroms can be determined to include the large molecular structures of hydrated minerals such as clays. The XRF data will identify elements ranging from carbon (Atomic Number = 6) to elements as heavy as barium (Atomic Number = 56). While a sample is being x-rayed, the instrument simultaneously acquires an optical image of the sample surface at magnifications from lx to at least 50x (200x being feasible, depending on the sample surface). We believe that imaging the sample is extremely important as corroborative sample-identification data (the need for this capability having been illustrated by the experience of the Pathfinder rover). Very few geologists would rely on instrument data for sample identification without having seen the sample. Visual inspection provides critical recognition data such as texture, crystallinity, granularity, porosity, vesicularity, color, lustre, opacity, and

  12. System for in situ studies of atmospheric corrosion of metal films using soft x-ray spectroscopy and quartz crystal microbalance.

    PubMed

    Forsberg, J; Duda, L-C; Olsson, A; Schmitt, T; Andersson, J; Nordgren, J; Hedberg, J; Leygraf, C; Aastrup, T; Wallinder, D; Guo, J-H

    2007-08-01

    We present a versatile chamber ("atmospheric corrosion cell") for soft x-ray absorption/emission spectroscopy of metal surfaces in a corrosive atmosphere allowing novel in situ electronic structure studies. Synchrotron x rays passing through a thin window separating the corrosion cell interior from a beamline vacuum chamber probe a metal film deposited on a quartz crystal microbalance (QCM) or on the inside of the window. We present some initial results on chloride induced corrosion of iron surfaces in humidified synthetic air. By simultaneous recording of QCM signal and soft x-ray emission from the corroding sample, correlation between mass changes and variations in spectral features is facilitated.

  13. In Situ Structural Studies of the Underpotential Deposition of Copper onto an Iodine Covered Platinum Surface Using X-Ray Standing Waves

    DTIC Science & Technology

    1991-01-01

    ABSTRAc C We present initial results of an in situ structural investigation of the underpotential deposition of copper on an iodine covered platinum...compare the result of surface coverage isotherms derived from both electrochemical and x-ray measurements. 1. INTRODUCIION The underpotential deposition ...the underpotential deposition of copper on an iodine covered platinum/carbon layered synthetic microstructure. 2 THEORETICAL BACKGROUND X-ray standing

  14. A Team Approach to the Development of Gamma Ray and x Ray Remote Sensing and in Situ Spectroscopy for Planetary Exploration Missions

    NASA Technical Reports Server (NTRS)

    Trombka, J. I.; Floyd, S.; Ruitberg, A.; Evans, L.; Starr, R.; Metzger, A.; Reedy, R.; Drake, D.; Moss, C.; Edwards, B.

    1993-01-01

    An important part of the investigation of planetary origin and evolution is the determination of the surface composition of planets, comets, and asteroids. Measurements of discrete line X-ray and gamma ray emissions from condensed bodies in space can be used to obtain both qualitative and quantitative elemental composition information. The Planetary Instrumentation Definition and Development Program (PIDDP) X-Ray/Gamma Ray Team has been established to develop remote sensing and in situ technologies for future planetary exploration missions.

  15. In-situ High Temperature Phase Transformations in Ceramics

    DTIC Science & Technology

    2009-07-28

    in high temperature combustion environments leads to accelerated oxidation of Si-based ceramics and composites, such as silicon carbide ( SiC ) fiber...have been achieved in silicon carbide reinforced with continuous, graphite-coated, silicon carbide fibers. The graphite acts as a debonding layer...reinforced SiC ceramic matrix composites (SiCf/ SiC CMCs) and monolithic silicon nitride (Si3N4), and severely limits their application in gas

  16. In situ x-ray scattering studies of the Au(111)/electrolyte interface

    SciTech Connect

    Wang, Jia; Ocko, B.M.; Davenport, A.J.; Isaacs, H.S.

    1991-12-31

    The adsorption of anions at the Au(111) electrode and the subsequent effect on the gold surface structure have been investigated using x-ray specular reflectivity and grazing incident angle diffraction techniques. The top layer of gold atoms undergoes a reversible phase transition between the (1{times}1) bulk termination and a (23{times}{radical}{bar 3}) reconstructed phase on changing the potential. The shifts of the phase transition potential in NaCland NaBr solutions from the one in NaF can be understood by the anion adsorption induced charge effect. The reconstruction formation rate increases in chloride and bromide solutions due to an increase in the surface mobility with anion adsorption. Adsorbed chloride and bromide monolayers can be monitored during a potential scan by the specular reflectivity.

  17. In situ x-ray scattering studies of the Au(111)/electrolyte interface

    SciTech Connect

    Wang, Jia; Ocko, B.M.; Davenport, A.J.; Isaacs, H.S.

    1991-01-01

    The adsorption of anions at the Au(111) electrode and the subsequent effect on the gold surface structure have been investigated using x-ray specular reflectivity and grazing incident angle diffraction techniques. The top layer of gold atoms undergoes a reversible phase transition between the (1{times}1) bulk termination and a (23{times}{radical}{bar 3}) reconstructed phase on changing the potential. The shifts of the phase transition potential in NaCland NaBr solutions from the one in NaF can be understood by the anion adsorption induced charge effect. The reconstruction formation rate increases in chloride and bromide solutions due to an increase in the surface mobility with anion adsorption. Adsorbed chloride and bromide monolayers can be monitored during a potential scan by the specular reflectivity.

  18. In situ X-ray nanotomography of metal surfaces during electropolishing

    SciTech Connect

    Nave, Maryana I.; Allen, Jason P.; Karen Chen-Wiegart, Yu-chen; Wang, Jun; Kalidindi, Surya R.; Kornev, Konstantin G.

    2015-10-15

    A low voltage electropolishing of metal wires is attractive for nanotechnology because it provides centimeter long and micrometer thick probes with the tip radius of tens of nanometers. Using X-ray nanotomography we studied morphological transformations of the surface of tungsten wires in a specially designed electrochemical cell where the wire is vertically submersed into the KOH electrolyte. We show that stability and uniformity of the probe span is supported by a porous shell growing at the surface of tungsten oxide and shielding the wire surface from flowing electrolyte. We discovered that the kinetics of shell growth at the triple line, where meniscus meets the wire, is very different from that of the bulk of electrolyte. Many metals follow similar electrochemical transformations hence the discovered morphological transformations of metal surfaces are expected to play significant role in many natural and technological applications.

  19. In situ X-ray nanotomography of metal surfaces during electropolishing

    DOE PAGES

    Nave, Maryana I.; Allen, Jason P.; Karen Chen-Wiegart, Yu-chen; ...

    2015-10-15

    A low voltage electropolishing of metal wires is attractive for nanotechnology because it provides centimeter long and micrometer thick probes with the tip radius of tens of nanometers. Using X-ray nanotomography we studied morphological transformations of the surface of tungsten wires in a specially designed electrochemical cell where the wire is vertically submersed into the KOH electrolyte. We show that stability and uniformity of the probe span is supported by a porous shell growing at the surface of tungsten oxide and shielding the wire surface from flowing electrolyte. We discovered that the kinetics of shell growth at the triple line,more » where meniscus meets the wire, is very different from that of the bulk of electrolyte. Many metals follow similar electrochemical transformations hence the discovered morphological transformations of metal surfaces are expected to play significant role in many natural and technological applications.« less

  20. In situ X-ray nanotomography of metal surfaces during electropolishing

    PubMed Central

    Nave, Maryana I.; Allen, Jason P.; Karen Chen-Wiegart, Yu-chen; Wang, Jun; Kalidindi, Surya R.; Kornev, Konstantin G.

    2015-01-01

    A low voltage electropolishing of metal wires is attractive for nanotechnology because it provides centimeter long and micrometer thick probes with the tip radius of tens of nanometers. Using X-ray nanotomography we studied morphological transformations of the surface of tungsten wires in a specially designed electrochemical cell where the wire is vertically submersed into the KOH electrolyte. It is shown that stability and uniformity of the probe span is supported by a porous shell growing at the surface of tungsten oxide and shielding the wire surface from flowing electrolyte. It is discovered that the kinetics of shell growth at the triple line, where meniscus meets the wire, is very different from that of the bulk of electrolyte. Many metals follow similar electrochemical transformations hence the discovered morphological transformations of metal surfaces are expected to play significant role in many natural and technological applications. PMID:26469184

  1. In situ X-ray nanotomography of metal surfaces during electropolishing

    NASA Astrophysics Data System (ADS)

    Nave, Maryana I.; Allen, Jason P.; Karen Chen-Wiegart, Yu-Chen; Wang, Jun; Kalidindi, Surya R.; Kornev, Konstantin G.

    2015-10-01

    A low voltage electropolishing of metal wires is attractive for nanotechnology because it provides centimeter long and micrometer thick probes with the tip radius of tens of nanometers. Using X-ray nanotomography we studied morphological transformations of the surface of tungsten wires in a specially designed electrochemical cell where the wire is vertically submersed into the KOH electrolyte. It is shown that stability and uniformity of the probe span is supported by a porous shell growing at the surface of tungsten oxide and shielding the wire surface from flowing electrolyte. It is discovered that the kinetics of shell growth at the triple line, where meniscus meets the wire, is very different from that of the bulk of electrolyte. Many metals follow similar electrochemical transformations hence the discovered morphological transformations of metal surfaces are expected to play significant role in many natural and technological applications.

  2. Advanced environmental control as a key component in the development of ultrahigh accuracy ex situ metrology for x-ray optics

    NASA Astrophysics Data System (ADS)

    Yashchuk, Valeriy V.; Artemiev, Nikolay A.; Lacey, Ian; McKinney, Wayne R.; Padmore, Howard A.

    2015-10-01

    The advent of fully coherent free-electron laser and diffraction-limited synchrotron radiation storage ring sources of x-rays is catalyzing the development of new ultrahigh accuracy metrology methods. To fully exploit these sources, metrology needs to be capable of determining the figure of an optical element with subnanometer height accuracy. The major limiting factors of the current absolute accuracy of ex situ metrology are drift errors due to temporal instabilities of the lab's environmental conditions and systematic errors inherent to the metrology instruments. Here, we discuss in detail work at the Advanced Light Source X-Ray Optics Laboratory on building of advanced environmental control that is a key component in the development of ultrahigh accuracy ex situ metrology for x-ray optics. By a few examples, we show how the improvement of the environmental conditions in the lab allows us to significantly gain efficiency in performing ex situ metrology with high-quality x-ray mirrors. The developed concepts and approaches, included in the design of the new X-Ray Optics Laboratory, are described in detail. These data are essential for construction and successful operation of a modern metrology facility for x-ray optics, as well as high-precision measurements in many fields of experimental physics.

  3. MapX An In Situ, Full-frame X-Ray Spectroscopic Imager for Planetary Science and Astrobiology

    NASA Technical Reports Server (NTRS)

    Blake, David; Sarrazin, Philippe; Thompson, Kathleen; Bristow, Thomas

    2017-01-01

    Microbial life exploits micron-scale disequilibria at boundaries where valence, chemical potential, pH, Eh, etc. vary on a length scale commensurate with the organisms - 10's to 100's of microns. The detection of accumulations of the biogenic elements C,N,O,P,S at appropriate concentrations on or in a mineral/ice substrate would constitute permissive evidence of extant life, but context is also required. Does the putative biosignature exist under habitable conditions? Under what conditions of P, T, and chemical potential was the host mineralogy formed? MapX is an in situ robotic spacecraft instrument that images the biogenic elements C, N, O, P, S, as well as the cations of the rock-forming minerals (Na, Mg, Al, Si, K, Ca, Ti, Cr, Mn, Fe) and important anions such as Cl, Fl. MapX provides element maps with less than or equal to100 microns resolution over a 2.5 cm X 2.5 cm area, as well as quantitative XRF spectra from ground- or instrument-selected Regions of Interest (ROI). XRF spectra are converted to mineralogies using ground- or instrument-based algorithms. Either X-ray tube or radioisotope sources such as 244Cm (Alpha-particle and gamma- ray fluorescence) can be used. Fluoresced sample Xrays are imaged onto an X-ray sensitive CCD through an X-ray MicroPore Optic (MPO). The MapX design as well as baseline performance requirements for a MapX instrument intended for life detection / identification of habitable environments will be presented.

  4. Reaction cell for in situ soft x-ray absorption spectroscopy and resonant inelastic x-ray scattering measurements of heterogeneous catalysis up to 1 atm and 250 °C.

    PubMed

    Kristiansen, P T; Rocha, T C R; Knop-Gericke, A; Guo, J H; Duda, L C

    2013-11-01

    We present a novel in situ reaction cell for heterogeneous catalysis monitored in situ by x-ray absorption spectroscopy (XAS) and resonant inelastic x-ray scattering (RIXS). The reaction can be carried out at a total pressure up to 1 atm, a regime that has not been accessible to comparable in situ techniques and thus closes the pressure gap to many industrial standard conditions. Two alternate catalyst geometries were tested: (A) a thin film evaporated directly onto an x-ray transparent membrane with a flowing reaction gas mixture behind it or (B) a powder placed behind both the membrane and a gap of flowing reaction gas mixture. To illustrate the working principle and feasibility of our reaction cell setup we have chosen ethylene epoxidation over a silver catalyst as a test case. The evolution of incorporated oxygen species was monitored by total electron/fluorescence yield O K-XAS as well as O K-RIXS, which is a powerful method to separate contributions from inequivalent sites. We find that our method can reliably detect transient species that exist during catalytic reaction conditions that are hardly accessible using other spectroscopic methods.

  5. Reaction cell for in situ soft x-ray absorption spectroscopy and resonant inelastic x-ray scattering measurements of heterogeneous catalysis up to 1 atm and 250 °C

    SciTech Connect

    Kristiansen, P. T.; Rocha, T. C. R.; Knop-Gericke, A.; Guo, J. H.; Duda, L. C.

    2013-11-15

    We present a novel in situ reaction cell for heterogeneous catalysis monitored in situ by x-ray absorption spectroscopy (XAS) and resonant inelastic x-ray scattering (RIXS). The reaction can be carried out at a total pressure up to 1 atm, a regime that has not been accessible to comparable in situ techniques and thus closes the pressure gap to many industrial standard conditions. Two alternate catalyst geometries were tested: (A) a thin film evaporated directly onto an x-ray transparent membrane with a flowing reaction gas mixture behind it or (B) a powder placed behind both the membrane and a gap of flowing reaction gas mixture. To illustrate the working principle and feasibility of our reaction cell setup we have chosen ethylene epoxidation over a silver catalyst as a test case. The evolution of incorporated oxygen species was monitored by total electron/fluorescence yield O K-XAS as well as O K-RIXS, which is a powerful method to separate contributions from inequivalent sites. We find that our method can reliably detect transient species that exist during catalytic reaction conditions that are hardly accessible using other spectroscopic methods.

  6. High-temperature behaviour of astrophyllite, K2NaFe7 2+Ti2(Si4O12)2O2(OH)4F: a combined X-ray diffraction and Mössbauer spectroscopic study

    NASA Astrophysics Data System (ADS)

    Zhitova, Elena S.; Krivovichev, Sergey V.; Hawthorne, Frank C.; Krzhizhanovskaya, Maria G.; Zolotarev, Andrey A.; Abdu, Yassir A.; Yakovenchuk, Viktor N.; Pakhomovsky, Yakov A.; Goncharov, Alexey G.

    2017-09-01

    High-temperature X-ray powder-diffraction study of astrophyllite, K2NaFe7 2+Ti2(Si4O12)2O2(OH)4F, and investigation of the samples annealed at 600 and 700 °C, reveal the occurrence of a phase transformation due to the thermal iron oxidation coupled with (1) deprotonation according to the scheme Fe2+ + OH- → Fe3+ + O2- + ½H2 ↑, and (2) defluorination according to the scheme Fe2+ + F- → Fe3+ + O2-. The phase transformation occurs at 500 °C, it is irreversible and without symmetry changes. The mineral decomposes at 775 °C. Both astrophyllite and its high-temperature dehydroxylated (HT) modification are triclinic, P-1. The unit-cell parameters are a = 5.3752(1), b = 11.8956(3), c = 11.6554(3) Å, α = 113.157(3), β = 94.531(2), γ = 103.112(2)º, V = 655.47(3) Å3 for unheated astrophyllite, and a = 5.3287(4), b = 11.790(1), c = 11.4332(9) Å, α = 112.530(8), β = 94.539(6), γ = 103.683(7)º, V = 633.01(9) Å3 for the HT (annealed) modification of astrophyllite. The oxidation of iron is confirmed: (1) by the presence of an exothermic effect at 584 °C in the DTA/TG curves in an Ar-O atmosphere and its absence in an Ar-Ar atmosphere and (2) by ex situ Mössbauer spectroscopy that showed the oxidation of Fe2+ to Fe3+ in the samples heated to 700 °C. Deprotonation was detected by the evolution of IR spectra in the region 3600-3000 cm-1 for astrophyllite and its HT modification. Defluorination was detected by the presence of F in the electron microprobe analysis of unheated astrophyllite and the absence of F in the analysis of unpolished heated astrophyllite. The significant difference between astrophyllite and its HT modification is in the reduction of the M-O interatomic distances after heating to 500 °C and the distortion indices of the MO6 and Dφ6 octahedra. Thermal behaviour of astrophyllite in the 25-475 °C temperature range can be described as a volume thermal expansion with maximal coefficient of thermal expansion in the direction perpendicular to

  7. In situ rheological measurements at extreme pressure and temperature using synchrotron X-ray diffraction and radiography.

    PubMed

    Raterron, Paul; Merkel, Sébastien

    2009-11-01

    Dramatic technical progress seen over the past decade now allows the plastic properties of materials to be investigated under extreme pressure and temperature conditions. Coupling of high-pressure apparatuses with synchrotron radiation significantly improves the quantification of differential stress and specimen textures from X-ray diffraction data, as well as specimen strains and strain rates by radiography. This contribution briefly reviews the recent developments in the field and describes state-of-the-art extreme-pressure deformation devices and analytical techniques available today. The focus here is on apparatuses promoting deformation at pressures largely in excess of 3 GPa, namely the diamond anvil cell, the deformation-DIA apparatus and the rotational Drickamer apparatus, as well as on the methods used to carry out controlled deformation experiments while quantifying X-ray data in terms of materials rheological parameters. It is shown that these new techniques open the new field of in situ investigation of materials rheology at extreme conditions, which already finds multiple fundamental applications in the understanding of the dynamics of Earth-like planet interior.

  8. In situ X-ray studies of adlayer-induced crystal nucleation at the liquid-liquid interface

    SciTech Connect

    Elsen, Annika; Festersen, Sven; Runge, Benjamin; Koops, Christian T.; Ocko, Benjamin M.; Deutsch, Moshe; Seeck, Oliver H.; Murphy, Bridget M.; Magnussen, Olaf M.

    2013-05-29

    Crystal nucleation and growth at a liquid–liquid interface is studied on the atomic scale by in situ Å-resolution X-ray scattering methods for the case of liquid Hg and an electrochemical dilute electrolyte containing Pb2+, F-, and Br- ions. In the regime negative of the Pb amalgamation potential Φrp = -0.70 V, no change is observed from the surface-layered structure of pure Hg. Upon potential-induced release of Pb2+ from the Hg bulk at Graphic, the formation of an intriguing interface structure is observed, comprising a well-defined 7.6-Å–thick adlayer, decorated with structurally related 3D crystallites. Both are identified by their diffraction peaks as PbFBr, preferentially aligned with their Graphic axis along the interface normal. X-ray reflectivity shows the adlayer to consist of a stack of five ionic layers, forming a single-unit-cell–thick crystalline PbFBr precursor film, which acts as a template for the subsequent quasiepitaxial 3D crystal growth. This growth behavior is assigned to the combined action of electrostatic and short-range chemical interactions.

  9. In situ study of maize starch gelatinization under ultra-high hydrostatic pressure using X-ray diffraction.

    PubMed

    Yang, Zhi; Gu, Qinfen; Hemar, Yacine

    2013-08-14

    The gelatinization of waxy (very low amylose) and high-amylose maize starches by ultra-high hydrostatic pressure (up to 6 GPa) was investigated in situ using synchrotron X-ray powder diffraction on samples held in a diamond anvil cell (DAC). The starch pastes, made by mixing starch and water in a 1:1 ratio, were pressurized and measured at room temperature. X-ray diffraction pattern showed that at 2.7 GPa waxy starch, which displayed A-type XRD pattern at atmospheric pressure, exhibited a faint B-type-like pattern. The B-type crystalline structures of high-amylose starch were not affected even when 1.5 GPa pressure was applied. However, both waxy and high-amylose maize starches can be fully gelatinized at 5.9 GPa and 5.1 GPa, respectively. In the case of waxy maize starch, upon release of pressure (to atmospheric pressure) crystalline structure appeared as a result of amylopectin aggregation. Copyright © 2013 Elsevier Ltd. All rights reserved.

  10. In situ and real-time monitoring of mechanochemical milling reactions using synchrotron X-ray diffraction.

    PubMed

    Halasz, Ivan; Kimber, Simon A J; Beldon, Patrick J; Belenguer, Ana M; Adams, Frank; Honkimäki, Veijo; Nightingale, Richard C; Dinnebier, Robert E; Friščić, Tomislav

    2013-09-01

    We describe the only currently available protocol for in situ, real-time monitoring of mechanochemical reactions and intermediates by X-ray powder diffraction. Although mechanochemical reactions (inducing transformations by mechanical forces such as grinding and milling) are normally performed in commercially available milling assemblies, such equipment does not permit direct reaction monitoring. We now describe the design and in-house modification of milling equipment that allows the reaction jars of the operating mill to be placed in the path of a high-energy (∼90 keV) synchrotron X-ray beam while the reaction is taking place. Resulting data are analyzed using conventional software, such as TOPAS. Reaction intermediates and products are identified using the Cambridge Structural Database or Inorganic Crystal Structure Database. Reactions are analyzed by fitting the time-resolved diffractograms using structureless Pawley refinement for crystalline phases that are not fully structurally characterized (such as porous frameworks with disordered guests), or the Rietveld method for solids with fully determined crystal structures (metal oxides, coordination polymers).

  11. Multiferroic CuCrO₂ under high pressure: In situ X-ray diffraction and Raman spectroscopic studies

    SciTech Connect

    Garg, Alka B. Mishra, A. K.; Pandey, K. K.; Sharma, Surinder M.

    2014-10-07

    The compression behavior of delafossite compound CuCrO₂ has been investigated by in situ x-ray diffraction (XRD) and Raman spectroscopic measurements up to 23.2 and 34 GPa, respectively. X-ray diffraction data show the stability of ambient rhombohedral structure up to ~23 GPa. Material shows large anisotropy in axial compression with c-axis compressibility, κ{sub c} = 1.26 × 10⁻³(1) GPa⁻¹ and a-axis compressibility, κ{sub a} = 8.90 × 10⁻³(6) GPa⁻¹. Our XRD data show an irreversible broadening of diffraction peaks. Pressure volume data when fitted to 3rd order Birch-Murnaghan equation of state give the value of bulk modulus, B₀ = 156.7(2.8) GPa with its pressure derivative, B₀{sup ’} as 5.3(0.5). All the observed vibrational modes in Raman measurements show hardening with pressure. Appearance of a new mode at ~24 GPa indicates the structural phase transition in the compound. Our XRD and Raman results indicate that CuCrO{sub 2} may be transforming to an ordered rocksalt type structure under compression.

  12. In-situ X-ray absorption spectroscopy analysis of capacity fade in nanoscale-LiCoO2

    NASA Astrophysics Data System (ADS)

    Patridge, Christopher J.; Love, Corey T.; Swider-Lyons, Karen E.; Twigg, Mark E.; Ramaker, David E.

    2013-07-01

    The local structure of nanoscale (∼10-40 nm) LiCoO2 is monitored during electrochemical cycling utilizing in-situ X-ray absorption spectroscopy (XAS). The high surface area of the LiCoO2 nanoparticles not only enhances capacity fade, but also provides a large signal from the particle surface relative to the bulk. Changes in the nanoscale LiCoO2 metal-oxide bond lengths, structural disorder, and chemical state are tracked during cycling by adapting the delta mu (Δμ) technique in complement with comprehensive extended X-ray absorption fine structure (EXAFS) modeling. For the first time, we use a Δμ EXAFS method, and by comparison of the difference EXAFS spectra, extrapolate significant coordination changes and reduction of cobalt species with cycling. This combined approach suggests Li-Co site exchange at the surface of the nanoscale LiCoO2 as a likely factor in the capacity fade and irreversible losses in practical, microscale LiCoO2.

  13. Quick extended x-ray absorption fine structure instrument with millisecond time scale, optimized for in situ applications

    SciTech Connect

    Khalid, S.; Caliebe, W.; Siddons, P.; So, I.; Clay, b.; Hanson, J.; Wang, Q.; Frenkel, A.; Marinkovicl, N.; Hould, N.; ginder-Vogel, M.; Landrot, G.L.; Sparks, D.L.; Ganjoo, A.

    2010-01-19

    In order to learn about in situ structural changes in materials at subseconds time scale, we have further refined the techniques of quick extended x-ray absorption fine structure (QEXAFS) and quick x-ray absorption near edge structure (XANES) spectroscopies at beamline X18B at the National Synchrotron Light Source. The channel cut Si (111) monochromator oscillation is driven through a tangential arm at 5 Hz, using a cam, dc motor, pulley, and belt system. The rubber belt between the motor and the cam damps the mechanical noise. EXAFS scan taken in 100 ms is comparable to standard data. The angle and the angular range of the monochromator can be changed to collect a full EXAFS or XANES spectrum in the energy range 4.7-40.0 KeV. The data are recorded in ascending and descending order of energy, on the fly, without any loss of beam time. The QEXAFS mechanical system is outside the vacuum system, and therefore changing the mode of operation from conventional to QEXAFS takes only a few minutes. This instrument allows the acquisition of time resolved data in a variety of systems relevant to electrochemical, photochemical, catalytic, materials, and environmental sciences.

  14. Quick extended x-ray absorption fine structure instrument with millisecond time scale, optimized for in situ applications.

    PubMed

    Khalid, S; Caliebe, W; Siddons, P; So, I; Clay, B; Lenhard, T; Hanson, J; Wang, Q; Frenkel, A I; Marinkovic, N; Hould, N; Ginder-Vogel, M; Landrot, G L; Sparks, D L; Ganjoo, A

    2010-01-01

    In order to learn about in situ structural changes in materials at subseconds time scale, we have further refined the techniques of quick extended x-ray absorption fine structure (QEXAFS) and quick x-ray absorption near edge structure (XANES) spectroscopies at beamline X18B at the National Synchrotron Light Source. The channel cut Si (111) monochromator oscillation is driven through a tangential arm at 5 Hz, using a cam, dc motor, pulley, and belt system. The rubber belt between the motor and the cam damps the mechanical noise. EXAFS scan taken in 100 ms is comparable to standard data. The angle and the angular range of the monochromator can be changed to collect a full EXAFS or XANES spectrum in the energy range 4.7-40.0 KeV. The data are recorded in ascending and descending order of energy, on the fly, without any loss of beam time. The QEXAFS mechanical system is outside the vacuum system, and therefore changing the mode of operation from conventional to QEXAFS takes only a few minutes. This instrument allows the acquisition of time resolved data in a variety of systems relevant to electrochemical, photochemical, catalytic, materials, and environmental sciences.

  15. In situ X-ray scattering evaluation of heat-induced ultrastructural changes in dental tissues and synthetic hydroxyapatite

    PubMed Central

    Sui, Tan; Sandholzer, Michael A.; Lunt, Alexander J. G.; Baimpas, Nikolaos; Smith, Andrew; Landini, Gabriel; Korsunsky, Alexander M.

    2014-01-01

    Human dental tissues consist of inorganic constituents (mainly crystallites of hydroxyapatite, HAp) and organic matrix. In addition, synthetic HAp powders are frequently used in medical and chemical applications. Insights into the ultrastructural alterations of skeletal hard tissues exposed to thermal treatment are crucial for the estimation of temperature of exposure in forensic and archaeological studies. However, at present, only limited data exist on the heat-induced structural alterations of human dental tissues. In this paper, advanced non-destructive small- and wide angle X-ray scattering (SAXS/WAXS) synchrotron techniques were used to investigate the in situ ultrastructural alterations in thermally treated human dental tissues and synthetic HAp powders. The crystallographic properties were probed by WAXS, whereas HAp grain size distribution changes were evaluated by SAXS. The results demonstrate the important role of the organic matrix that binds together the HAp crystallites in responding to heat exposure. This is highlighted by the difference in the thermal behaviour between human dental tissues and synthetic HAp powders. The X-ray analysis results are supported by thermogravimetric analysis. The results concerning the HAp crystalline architecture in natural and synthetic HAp powders provide a reliable basis for deducing the heating history for dental tissues in the forensic and archaeological context, and the foundation for further development and optimization of biomimetic material design. PMID:24718447

  16. Probing the isothermal (delta)->(alpha)' martensitic transformation in Pu-Ga with in situ x-ray diffraction

    SciTech Connect

    Jeffries, J R; Blobaum, K M; Schwartz, A J; Cynn, H; Yang, W; Evans, W J

    2010-03-11

    The time-temperature-transformation (TTT) curve for the {delta} {yields} {alpha}{prime} isothermal martensitic transformation in a Pu-1.9 at. % Ga alloy is peculiar because it is reported to have a double-C curve. Recent work suggests that an ambient temperature conditioning treatment enables the lower-C curve. However, the mechanisms responsible for the double-C are still not fully understood. When the {delta} {yields} {alpha}{prime} transformation is induced by pressure, an intermediate {gamma}{prime} phase is observed in some alloys. It has been suggested that transformation at upper-C temperatures may proceed via this intermediate phase, while lower-C transformation progresses directly from {delta} to {alpha}{prime}. To investigate the possibility of thermally induced transformation via the intermediate {gamma}{prime} phase, in situ x-ray diffraction at the Advanced Photon Source was performed. Using transmission x-ray diffraction, the {delta} {yields} {alpha}{prime} transformation was observed in samples as thin at 30 {micro}m as a function of time and temperature. The intermediate {gamma}{prime} phase was not observed at -120 C (upper-C curve) or -155 C (lower-C curve). Results indicate that the bulk of the {alpha}{prime} phase forms relatively rapidly at -120 C and -155 C.

  17. Observations on PVP-protected noble metallic nanoparticle deposits upon heating via in situ synchrotron radiation X-ray diffraction.

    PubMed

    Song, Jenn-Ming; Chiou, Guan-Di; Chen, Wei-Ting; Chen, Shih-Yun; Kao, Tzu-Hsuan; Chen, In-Gann; Lee, Hsin-Yi

    2011-03-21

    Through monitoring the evolution of the X-ray diffraction peaks, the phase transformation of PVP-protected Ag and Au nanoparticle deposits (NPDs) on electronic substrates of Cu and Ni upon heating in air was investigated via in situ synchrotron radiation X-ray diffraction. With an increasing temperature, the broad diffraction peak of nano-sized Ag and Au particles with the original average diameters of 4.2 nm and 9.6 nm, respectively, became sharp because of particle coarsening and coalescence. Complex phase transitions among Au, Cu, AuCu(3) and CuO(x) were observed, mainly due to the negative enthalpy of mixing between Au and Cu. The interactions between NPDs and the substrates affected the shift of diffraction peaks to lower angles, caused by thermal expansion and also the temperature for the oxide formation. Compared to Au, Ag NPDs did not form intermetallic compounds with Cu and the formation of copper oxides can also be retarded mainly due to the phase separation feature of the Ag-Cu system.

  18. Ultra-fast in-situ X-ray studies of evolving columnar dendrites in solidifying steel weld pools

    NASA Astrophysics Data System (ADS)

    Mirihanage, W. U.; Di Michiel, M.; Mathiesen, R. H.

    2015-06-01

    High-brilliance polychromatic synchrotron radiation has been used to conduct in-situ studies of the solidification microstructure evolution during simulated welding. The welding simulations were realized by rapidly fusing ∼ 5 mm spot in Fe-Cr-Ni steel. During the solid- liquid-solid phase transformations, a section of the weld pool was placed in an incident 50-150 keV polychromatic synchrotron X-ray beam, in a near-horizontal position at a very low inclination angle. Multiple high-resolution 2D detectors with very high frame rates were utilized to capture time resolved X-ray diffraction data from suitably oriented solid dendrites evolving in the weld pool. Comprehensive analysis of the diffraction data revealed individual and overall dendritic growth characteristics and relevant melt and solid flow dynamics during weld pool solidification, which was completed within 1.5 s. Columnar dendrite tip velocities were estimated from the experimental data and during early stages of solidification were exceeded 4 mm/s. The most remarkable observation revealed through the time-resolved reciprocal space observations are correlated to significant tilting of columnar type dendrites at their root during solidification, presumably caused by convective currents in the weld pool. When the columnar dendrite tilting are transformed to respective metric linear tilting velocities at the dendrite tip; tilting velocities are found to be in the same order of magnitude as the columnar tip growth velocities, suggesting a highly transient nature of growth conditions.

  19. In situ hard x-ray photoemission spectroscopy of barrier-height control at metal/PMN-PT interfaces

    NASA Astrophysics Data System (ADS)

    Kröger, E.; Petraru, A.; Quer, A.; Soni, R.; Kalläne, M.; Pertsev, N. A.; Kohlstedt, H.; Rossnagel, K.

    2016-06-01

    Metal-ferroelectric interfaces form the basis of novel electronic devices. A key effect determining the device functionality is the bias-dependent change of the electronic energy-level alignment at the interface. Here, hard x-ray photoelectron spectroscopy (HAXPES) is used to determine the energy-level alignment at two metal-ferroelectric interfaces—Au versus SrRuO3 on the relaxor ferroelectric Pb (Mg1 /3Nb2 /3 )0.72Ti0.28O3 (PMN-PT)—directly in situ as a function of electrical bias. The bias-dependent average shifts of the PMN-PT core levels are found to have two dominant contributions on the 0.1 -1-eV energy scale: one depending on the metal electrode and the remanent electric polarization and the other correlated with electric-field-induced strain. Element-specific deviations from the average shifts are smaller than 0.1 eV and appear to be related to predicted dynamical charge variations in PMN-PT. In addition, the efficiency of ferroelectric polarization switching is shown to be reduced near the coercive field under x-ray irradiation. The results establish HAXPES as a tool for the in operando investigation of metal-ferroelectric interfaces and suggest electric-field-induced modifications of the polarization distribution as a novel way to control the barrier height at such interfaces.

  20. Tuning of colossal dielectric constant in gold-polypyrrole composite nanotubes using in-situ x-ray diffraction techniques

    SciTech Connect

    Sarma, Abhisakh; Sanyal, Milan K.

    2014-09-15

    In-situ x-ray diffraction technique has been used to study the growth process of gold incorporated polypyrrole nanotubes that exhibit colossal dielectric constant due to existence of quasi-one-dimensional charge density wave state. These composite nanotubes were formed within nanopores of a polycarbonate membrane by flowing pyrrole monomer from one side and mixture of ferric chloride and chloroauric acid from other side in a sample cell that allows collection of x-ray data during the reaction. The size of the gold nanoparticle embedded in the walls of the nanotubes was found to be dependent on chloroauric acid concentration for nanowires having diameter more than 100 nm. For lower diameter nanotubes the nanoparticle size become independent of chloroauric acid concentration and depends on the diameter of nanotubes only. The result of this study also shows that for 50 nm gold-polypyrrole composite nanotubes obtained with 5.3 mM chloroauric acid gives colossal dielectric constant of about 10{sup 7}. This value remain almost constant over a frequency range from 1Hz to 10{sup 6} Hz even at 80 K temperature.

  1. In-situ X-ray observations of creep behavior during the olivine-spinel transformation in fayalite

    NASA Astrophysics Data System (ADS)

    Kubo, T.; Doi, N.; Imamura, M.; Kato, T.; Higo, Y.; Tange, Y.

    2016-12-01

    Most of constituent minerals in subducting slab cause high-pressure transformations in mantle transition zone, which largely affects rheology of the deep slab. Previous studies have suggested that the grain-size reduction due to non-equilibrium olivine-spinel transformation leads to weakening and shear instability in the slab, which may be responsible for the slab stagnation and deep earthquakes. However, there have been few experimental studies to examine the coupling process between transformation and deformation at high pressure quantitatively. Here we report preliminary results on in-situ X-ray observations of creep behaviors during the olivine-spinel transformation in fayalite (Fe2SiO4). High-pressure deformation experiments were conducted using Deformation-DIA apparatus in the beamline of BL04B1 at the synchrotron facility of SPring-8. Monochromatic X-ray (energy 50-60 keV) was used as the incident beam. We measured time-resolved two-dimensional X-ray diffraction patterns and X-ray radiography images to obtain stress-strain and transformation-time (strain) curves, simultaneously. After annealing polycrystalline fayalite at 3.5 GP and 1173 K for 2 hours, we observed the olivine-spinel transformation at 5-9 GPa and 873-1173 K with and without deformation (in uniaxial compression with constant strain rate of 4-5 x 10-5 s-1). Overpressures needed for the transformation increased with decreasing temperature from 1.5 GPa and 1173 K to 3.8 GPa at 973 K in the case of no deformation. When the sample was deformed, the overpressures decreased by 0.5-1 GPa compared to the case of no deformation, suggesting the enhancement of spinel nucleation. Transformation was not observed at 873 K even when the overpressure reached to 4 GPa with deformation. Stress in olivine, spinel, and the bulk sample (from stress marker arranged in tandem) were similar at the initial stage, and then spinel becomes dominant deformation phase at around 50% transformation. During the

  2. Hydraulic Properties of Fractured Rock Samples at In-Situ Conditions - Insights from Lab Experiments Using X-Ray Tomography

    NASA Astrophysics Data System (ADS)

    Nehler, Mathias; Stöckhert, Ferdinand; Duda, Mandy; Renner, Jörg; Bracke, Rolf

    2017-04-01

    The hydraulic properties of low-porosity rock formations are controlled by the geometry of open fractures, joints and faults. Aperture, surface roughness, accessible length, and thus, the volume available for fluids associated of such interfaces are strongly affected by their state of stress. Moreover, these properties may evolve with time in particular due to processes involving chemically active fluids. Understanding the physico-chemical interactions of rocks with fluids at reservoir conditions will help to predict the long-term reservoir development and to increase the efficiency of geothermal power plants. We designed an x-ray transparent flow-through cell. Confining pressure can be up to 50 MPa and pore fluid can currently be circulated through the sample with pressures of up to 25 MPa. All wetted parts are made of PEEK to avoid corrosion when using highly saline fluids. Laboratory experiments were performed to investigate hydraulic properties of fractured low-porosity samples under reservoir conditions while x-rays transmit the sample. The cell is placed inside a µCT scanner with a 225 kV multifocal x-ray tube for high resolution x-ray tomography. Samples measure 10 mm in diameter and 25 mm in length resulting in a voxel resolution of approximately 10 µm. Samples with single natural as well as artificial fractures were subjected to various confining pressures ranging from 2.5 MPa to 25 MPa. At each pressure level, effective permeability was determined from steady-state flow relying on Darcy's law. In addition, a full 3D image was recorded by the µCT scanner to gain information on the fracture aperture and geometry. Subvolumes (400x400x400 voxels) of the images were analyzed to reduce computational cost. The subvolumes were filtered in 3D with an edge preserving non-local means filter. Further quantification algorithms were implemented in Matlab. Segmentation into pore space and minerals was done automatically for all datasets by a peak finder algorithm

  3. Unraveling heme detoxification in the malaria parasite by in situ correlative X-ray fluorescence microscopy and soft X-ray tomography.

    PubMed

    Kapishnikov, Sergey; Grolimund, Daniel; Schneider, Gerd; Pereiro, Eva; McNally, James G; Als-Nielsen, Jens; Leiserowitz, Leslie

    2017-08-08

    A key drug target for malaria has been the detoxification pathway of the iron-containing molecule heme, which is the toxic byproduct of hemoglobin digestion. The cornerstone of heme detoxification is its sequestration into hemozoin crystals, but how this occurs remains uncertain. We report new results of in vivo rate of heme crystallization in the malaria parasite, based on a new technique to measure element-specific concentrations at defined locations in cell ultrastructure. Specifically, a high resolution correlative combination of cryo soft X-ray tomography has been developed to obtain 3D parasite ultrastructure with cryo X-ray fluorescence microscopy to measure heme concentrations. Our results are consistent with a model for crystallization via the heme detoxification protein. Our measurements also demonstrate the presence of considerable amounts of non-crystalline heme in the digestive vacuole, which we show is most likely contained in hemoglobin. These results suggest a tight coupling between hemoglobin digestion and heme crystallization, highlighting a new link in the crystallization pathway for drug development.

  4. In situ micro-Raman analysis and X-ray diffraction of nickel silicide thin films on silicon.

    PubMed

    Bhaskaran, M; Sriram, S; Perova, T S; Ermakov, V; Thorogood, G J; Short, K T; Holland, A S

    2009-01-01

    This article reports on the in situ analysis of nickel silicide (NiSi) thin films formed by thermal processing of nickel thin films deposited on silicon substrates. The in situ techniques employed for this study include micro-Raman spectroscopy (microRS) and X-ray diffraction (XRD); in both cases the variations for temperatures up to 350 degrees C has been studied. Nickel silicide thin films formed by vacuum annealing of nickel on silicon were used as a reference for these measurements. In situ analysis was carried out on nickel thin films on silicon, while the samples were heated from room temperature to 350 degrees C. Data was gathered at regular temperature intervals and other specific points of interest (such as 250 degrees C, where the reaction between nickel and silicon to form Ni(2)Si is expected). The transformations from the metallic state, through the intermediate reaction states, until the desired metal-silicon reaction product is attained, are discussed. The evolution of nickel silicide from the nickel film can be observed from both the microRS and XRD in situ studies. Variations in the evolution of silicide from metal for different silicon substrates are discussed, and these include (100) n-type, (100) p-type, and (110) p-type silicon substrates.

  5. In-situ characterization of highly reversible phase transformation by synchrotron X-ray Laue microdiffraction

    NASA Astrophysics Data System (ADS)

    Chen, Xian; Tamura, Nobumichi; MacDowell, Alastair; James, Richard D.

    2016-05-01

    The alloy Cu25Au30Zn45 undergoes a huge first-order phase transformation (6% strain) and shows a high reversibility under thermal cycling and an unusual martensitc microstructure in sharp contrast to its nearby compositions. This alloy was discovered by systematically tuning the composition so that its lattice parameters satisfy the cofactor conditions (i.e., the kinematic conditions of compatibility between phases). It was conjectured that satisfaction of these conditions is responsible for the enhanced reversibility as well as the observed unusual fluid-like microstructure during transformation, but so far, there has been no direct evidence confirming that these observed microstructures are those predicted by the cofactor conditions. To verify this hypothesis, we use synchrotron X-ray Laue microdiffraction to measure the orientations and structural parameters of variants and phases near the austenite/martensite interface. The areas consisting of both austenite and multi-variants of martensite are scanned by microLaue diffraction. The cofactor conditions have been examined from the kinematic relation of lattice vectors across the interface. The continuity condition of the interface is precisely verified from the correspondent lattice vectors between two phases.

  6. In-situ characterization of highly reversible phase transformation by synchrotron X-ray Laue microdiffraction

    SciTech Connect

    Chen, Xian; Tamura, Nobumichi; MacDowell, Alastair; James, Richard D.

    2016-05-23

    The alloy Cu{sub 25}Au{sub 30}Zn{sub 45} undergoes a huge first-order phase transformation (6% strain) and shows a high reversibility under thermal cycling and an unusual martensitc microstructure in sharp contrast to its nearby compositions. This alloy was discovered by systematically tuning the composition so that its lattice parameters satisfy the cofactor conditions (i.e., the kinematic conditions of compatibility between phases). It was conjectured that satisfaction of these conditions is responsible for the enhanced reversibility as well as the observed unusual fluid-like microstructure during transformation, but so far, there has been no direct evidence confirming that these observed microstructures are those predicted by the cofactor conditions. To verify this hypothesis, we use synchrotron X-ray Laue microdiffraction to measure the orientations and structural parameters of variants and phases near the austenite/martensite interface. The areas consisting of both austenite and multi-variants of martensite are scanned by microLaue diffraction. The cofactor conditions have been examined from the kinematic relation of lattice vectors across the interface. The continuity condition of the interface is precisely verified from the correspondent lattice vectors between two phases.

  7. In-situ characterization of highly reversible phase transformation by synchrotron X-ray Laue microdiffraction

    DOE PAGES

    Chen, Xian; Tamura, Nobumichi; MacDowell, Alastair; ...

    2016-05-23

    The alloy Cu 25 Au 30 Zn 45 undergoes a huge first-order phase transformation (6% strain) and shows a high reversibility under thermal cycling and an unusual martensitc microstructure in sharp contrast to its nearby compositions. We discovered this alloy by systematically tuning the composition so that its lattice parameters satisfy the cofactor conditions (i.e., the kinematic conditions of compatibility between phases). It was conjectured that satisfaction of these conditions is responsible for the enhanced reversibility as well as the observed unusual fluid-like microstructure during transformation, but so far, there has been no direct evidence confirming that these observed microstructuresmore » are those predicted by the cofactor conditions. In order to verify this hypothesis, we use synchrotron X-ray Laue microdiffraction to measure the orientations and structural parameters of variants and phases near the austenite/martensite interface. The areas consisting of both austenite and multi-variants of martensite are scanned by microLaue diffraction. The cofactor conditions have been examined from the kinematic relation of lattice vectors across the interface. The continuity condition of the interface is precisely verified from the correspondent lattice vectors between two phases.« less

  8. High-temperature, high-pressure hydrothermal synthesis, crystal structure, and solid-state NMR spectroscopy of Cs2(UO2)(Si2O6) and variable-temperature powder X-ray diffraction study of the hydrate phase Cs2(UO2)(Si2O6) x 0.5H2O.

    PubMed

    Chen, Chih-Shan; Chiang, Ray-Kuang; Kao, Hsien-Ming; Lii, Kwang-Hwa

    2005-05-30

    A new uranium(VI) silicate, Cs2(UO2)(Si2O6), has been synthesized by a high-temperature, high-pressure hydrothermal method and characterized by single-crystal X-ray diffraction and solid-state NMR spectroscopy. It crystallizes in the orthorhombic space group Ibca (No. 73) with a = 15.137(1) A, b = 15.295(1) A, c = 16.401(1) A, and Z = 16. Its structure consists of corrugated achter single chains of silicate tetrahedra extending along the c axis linked together via corner-sharing by UO6 tetragonal bipyramids to form a 3-D framework which delimits 8- and 6-ring channels. The Cs+ cations are located in the channels or at sites between channels. The 29Si and 133Cs MAS NMR spectra are consistent with the crystal structure as determined from X-ray diffraction, and the resonances in the spectra are assigned. Variable-temperature in situ powder X-ray diffraction study of the hydrate Cs2(UO2)(Si2O6) x 0.5H2O indicates that the framework structure is stable up to 800 degrees C and transforms to the structure of the title compound at 900 degrees C. A comparison of related uranyl silicate structures is made.

  9. Novel micro-reactor flow cell for investigation of model catalysts using in situ grazing-incidence X-ray scattering

    PubMed Central

    Kehres, Jan; Pedersen, Thomas; Masini, Federico; Andreasen, Jens Wenzel; Nielsen, Martin Meedom; Diaz, Ana; Nielsen, Jane Hvolbæk; Hansen, Ole

    2016-01-01

    The design, fabrication and performance of a novel and highly sensitive micro-reactor device for performing in situ grazing-incidence X-ray scattering experiments of model catalyst systems is presented. The design of the reaction chamber, etched in silicon on insulator (SIO), permits grazing-incidence small-angle X-ray scattering (GISAXS) in transmission through 10 µm-thick entrance and exit windows by using micro-focused beams. An additional thinning of the Pyrex glass reactor lid allows simultaneous acquisition of the grazing-incidence wide-angle X-ray scattering (GIWAXS). In situ experiments at synchrotron facilities are performed utilizing the micro-reactor and a designed transportable gas feed and analysis system. The feasibility of simultaneous in situ GISAXS/GIWAXS experiments in the novel micro-reactor flow cell was confirmed with CO oxidation over mass-selected Ru nanoparticles. PMID:26917133

  10. In situ X-ray powder diffraction study of Ho5Ge4

    SciTech Connect

    Singh, Niraj K; Mudryk, Ya; Pecharsky, V K; Gschneidner, K A

    2014-05-07

    In Ho5 Ge 4 the magnetostructural transition (MST) from high temperature paramagnetic Sm5 Ge 4-type (O-II type) orthorhombic structure to a new low temperature antiferromagnetic (AFM) monoclinic structure (Mβ-structure; the distortion occurs in the ac-plane) results in discontinuities of 400, 400, and 300 ppm along a, b, and c axes, respectively. During MST the unit cell volume exhibits discontinuity of 1000 ppm, and changes in both inter and intra slab bonds are less than 2%. In the AFM state the application of 35 kOe magnetic field leads to a partial reconstruction of the high temperature O-II structure, which is accompanied with a large magnetostriction. The strain energy associated with magnetostriction effects leads to an incomplete field driven MST in the magnetically ordered state.

  11. α-Synuclein insertion into supported lipid bilayers as seen by in situ X-ray reflectivity.

    PubMed

    Hähl, Hendrik; Möller, Isabelle; Kiesel, Irena; Campioni, Silvia; Riek, Roland; Verdes, Dorinel; Seeger, Stefan

    2015-03-18

    Large aggregates of misfolded α-synuclein inside neuronal cells are the hallmarks of Parkinson's disease. The protein's natural function and its supposed toxicity, however, are believed to be closely related to its interaction with cell and vesicle membranes. Upon this interaction, the protein folds into an α-helical structure and intercalates into the membrane. In this study, we focus on the changes in the lipid bilayer caused by this intrusion. In situ X-ray reflectivity was applied to determine the vertical density structure of the bilayer before and after exposure to α-synuclein. It was found that the α-synuclein insertion, wild type and E57K variant, caused a reduction in bilayer thickness. This effect may be one factor in the membrane pore formation ability of α-synuclein.

  12. Mechanisms Determining the Structure of Gold-Catalyzed GaAs Nanowires Studied by in Situ X-ray Diffraction

    DOE PAGES

    Takahasi, Masamitu; Kozu, Miwa; Sasaki, Takuo; ...

    2015-09-02

    The evolution of polytypism during GaAs nanowire growth was investigated with in situ X-ray diffraction. The growth of nanowires was found to start with the formation of zincblende structure, followed by the growth of wurtzite structure. The growth process was well reproduced by a simulation based on a layer-by-layer nucleation model. The good agreement between the measured and simulated results confirms that nucleation costs higher energy for the stackings changing the crystal structure than for those conserving the preceding structure. The transition in prevalent structure can be accounted for by the change of local growth conditions related to the shapemore » of triple phase line rather than by the change in supersaturation level, which quickly reaches steady state after starting growth.« less

  13. Mechanisms Determining the Structure of Gold-Catalyzed GaAs Nanowires Studied by in Situ X-ray Diffraction

    SciTech Connect

    Takahasi, Masamitu; Kozu, Miwa; Sasaki, Takuo; Hu, Wen

    2015-09-02

    The evolution of polytypism during GaAs nanowire growth was investigated with in situ X-ray diffraction. The growth of nanowires was found to start with the formation of zincblende structure, followed by the growth of wurtzite structure. The growth process was well reproduced by a simulation based on a layer-by-layer nucleation model. The good agreement between the measured and simulated results confirms that nucleation costs higher energy for the stackings changing the crystal structure than for those conserving the preceding structure. The transition in prevalent structure can be accounted for by the change of local growth conditions related to the shape of triple phase line rather than by the change in supersaturation level, which quickly reaches steady state after starting growth.

  14. Quantification of ion confinement and desolvation in nanoporous carbon supercapacitors with modelling and in situ X-ray scattering

    NASA Astrophysics Data System (ADS)

    Prehal, C.; Koczwara, C.; Jäckel, N.; Schreiber, A.; Burian, M.; Amenitsch, H.; Hartmann, M. A.; Presser, V.; Paris, O.

    2017-01-01

    A detailed understanding of confinement and desolvation of ions in electrically charged carbon nanopores is the key to enable advanced electrochemical energy storage and water treatment technologies. Here, we present the synergistic combination of experimental data from in situ small-angle X-ray scattering with Monte Carlo simulations of length-scale-dependent ion arrangement. In our approach, the simulations are based on the actual carbon nanopore structure and the global ion concentrations in the electrodes, both obtained from experiments. A combination of measured and simulated scattering data provides compelling evidence of partial desolvation of Cs+ and Cl‑ ions in water even in mixed micro-mesoporous carbons with average pore size well above 1 nm. A tight attachment of the aqueous solvation shell effectively prevents complete desolvation in carbons with subnanometre average pore size. The tendency of counter-ions to change their local environment towards high confinement with increasing voltage determines conclusively the performance of supercapacitor electrodes.

  15. Optical Properties of In Situ Eye Lenses Measured with X-Ray Talbot Interferometry: A Novel Measure of Growth Processes

    PubMed Central

    Hoshino, Masato; Uesugi, Kentaro; Yagi, Naoto; Mohri, Satoshi; Regini, Justyn; Pierscionek, Barbara

    2011-01-01

    The lens, a major optical component of the eye, has a gradient refractive index, which is required to provide sufficient refractive power and image quality. The refractive index variations across the lens are dependent on the distributions and concentrations of the varying protein classes. In this study, we present the first measurements of the refractive index in the in situ eye lens from five species using a specially constructed X-ray Talbot grating interferometer. The measurements have been conducted in two planes: the one containing the optic axis (the sagittal plane) and the plane orthogonal to this (the equatorial plane). The results show previously undetected discontinuities and fluctuations in the refractive index profile that vary in different species. These may be linked to growth processes and may be the first optical evidence of discrete developmental stages. PMID:21949870

  16. X-ray Energy Dispersive Spectrometry during in-situ Liquid Cell Studies using an Analytical Electron Microscope

    SciTech Connect

    Zaluzec, Nestor J.; Burke, M. Grace; Haigh, Sarah J.; Kulzick, Matthew

    2014-04-01

    The use of analytical spectroscopies during scanning/transmission electron microscope (S/TEM) investigations of micro- and nano-scale structures has become a routine technique in the arsenal of tools available to today's materials researchers. Essential to implementation and successful application of spectroscopy to characterization is the integration of numerous technologies, which include electron optics, specimen holders, and associated detectors. While this combination has been achieved in many instrument configurations, the integration of X-ray energy-dispersive spectroscopy and in situ liquid environmental cells in the S/TEM has to date been elusive. In this work we present the successful incorporation/modifications to a system that achieves this functionality for analytical electron microscopy.

  17. Monitoring the Phase Formation of Coevaporated Lead Halide Perovskite Thin Films by in Situ X-ray Diffraction.

    PubMed

    Pistor, Paul; Borchert, Juliane; Fränzel, Wolfgang; Csuk, René; Scheer, Roland

    2014-10-02

    Perovskite solar cells based on (CH3NH3)Pb(I,Cl)3 have recently demonstrated rapidly increasing cell efficiencies. Here, we show progress identifying phases present during the growth of (CH3NH3)Pb(I,Cl)3 perovskite thin films with the vacuum-based coevaporation approach using two sources under varying deposition conditions. With in situ X-ray diffraction, crystalline phases can be identified and monitored in real time. For different (CH3NH3)I-to-PbCl2 flux ratios, two distinct (CH3NH3)Pb(IxCl(1-x))3 phases with high (x > 0.95) and with lower (x < 0.5) iodine content as well as a broad miscibility gap in-between were found. During post deposition annealing we observe recrystallization and preferential orientation effects and finally the decomposition of the perovskite film to PbI2 at temperatures above 200 °C.

  18. Observation of localized heating phenomena during microwave heating of mixed powders using in situ x-ray diffraction technique

    SciTech Connect

    Sabelström, N. Hayashi, M.; Watanabe, T.; Nagata, K.

    2014-10-28

    In materials processing research using microwave heating, there have been several observations of various phenomena occurring known as microwave effects. One significant example of such a phenomenon is increased reaction kinetics. It is believed that there is a possibility that this might be caused by localized heating, were some reactants would attain a higher than apparent temperature. To examine whether such thermal gradients are indeed possible, mixed powders of two microwave non-absorbers, alumina and magnesia, were mixed with graphite, a known absorber, and heated in a microwave furnace. During microwave irradiation, the local temperatures of the respective sample constituents were measured using an in situ x-ray diffraction technique. In the case of the alumina and graphite sample, a temperature difference of around 100 °C could be observed.

  19. Crystallization in Fe- and Co-Based Amorphous Alloys Studied by In-Situ X-Ray Diffraction

    NASA Astrophysics Data System (ADS)

    Zhang, L. J.; Yu, P. F.; Cheng, H.; Zhang, M. D.; Liu, D. J.; Zhou, Z.; Jin, Q.; Liaw, P. K.; Li, G.; Liu, R. P.

    2016-12-01

    The amorphous alloys, Fe80Si20, Fe78Si9B13, and Fe4Co67Mo1.5Si16.5B11, were prepared by the spinning method in pure argon. The crystallization behaviors of the three amorphous alloys were researched by in-situ X-ray diffraction (XRD), and the crystallization activation energy was calculated, based on the results of differential scanning calorimetry. The crystallization mechanism of the Fe- and Co-based alloys was analyzed, based on the experimental data. The transformation kinetics was described in terms of Johnson-Mehl-Avrami kinetics, except that the Avrami exponent of the Fe78Si9B13 amorphous alloy annealed at 753 K (480 °C) was 4.12; the obtained values for the overall Avrami exponents of the other three amorphous alloys were below 1, as usually found for the Fe-Si amorphous alloys.

  20. Versatile plug flow catalytic cell for in situ transmission/fluorescence x-ray absorption fine structure measurements

    NASA Astrophysics Data System (ADS)

    Centomo, P.; Meneghini, C.; Zecca, M.

    2013-05-01

    A novel flow-through catalytic cell has been developed for in situ x-ray absorption spectroscopy (XAS) experiments on heterogeneous catalysts under working conditions and in the presence of a liquid and a gas phase. The apparatus allows to carry out XAS measurements in both the transmission and fluorescence modes, at moderate temperature (from RT to 50-80 °C) and low-medium gas pressure (up to 7-8 bars). The materials employed are compatible with several chemicals such as those involved in the direct synthesis of hydrogen peroxide (O2, H2, H2O2, methanol). The versatile design of the cell allows to fit it to different experimental setups in synchrotron radiation beamlines. It was used successfully for the first time to test nanostructured Pd catalysts during the direct synthesis of hydrogen peroxide (H2O2) in methanol solution from dihydrogen and dioxygen.

  1. Design of a miniature flow cell for in situ x-ray imaging of redox flow batteries

    NASA Astrophysics Data System (ADS)

    Jervis, Rhodri; Brown, Leon D.; Neville, Tobias P.; Millichamp, Jason; Finegan, Donal P.; Heenan, Thomas M. M.; Brett, Dan J. L.; Shearing, Paul R.

    2016-11-01

    Flow batteries represent a possible grid-scale energy storage solution, having many advantages such as scalability, separation of power and energy capabilities, and simple operation. However, they can suffer from degradation during operation and the characteristics of the felt electrodes are little understood in terms of wetting, compression and pressure drops. Presented here is the design of a miniature flow cell that allows the use of x-ray computed tomography (CT) to study carbon felt materials in situ and operando, in both lab-based and synchrotron CT. Through application of the bespoke cell it is possible to observe felt fibres, electrolyte and pore phases and therefore enables non-destructive characterisation of an array of microstructural parameters during the operation of flow batteries. Furthermore, we expect this design can be readily adapted to the study of other electrochemical systems.

  2. In-situ early stage electromigration study in Al line using synchrotron polychromatic X-ray microdiffraction

    SciTech Connect

    Chen, Kai; Tamura, Nobumichi; Tu, King-Ning

    2007-10-31

    Electromigration is a phenomenon that has attracted much attention in the semiconductor industry because of its deleterious effects on electronic devices (such as interconnects) as they become smaller and current density passing through them increases. However, the effect of the electric current on the microstructure of interconnect lines during the very early stage of electromigration is not well documented. In the present report, we used synchrotron radiation based polychromatic X-ray microdiffraction for the in-situ study of the electromigration induced plasticity effects on individual grains of an Al (Cu) interconnect test structure. Dislocation slips which are activated by the electric current stressing are analyzed by the shape change of the diffraction peaks. The study shows polygonization of the grains due to the rearrangement of geometrically necessary dislocations (GND) in the direction of the current. Consequences of these findings are discussed.

  3. In Situ Synchrotron X-ray Diffraction Measurement of the Strain Distribution in Si Die for the Embedded Substrates

    NASA Astrophysics Data System (ADS)

    Hsu, Hsueh Hsien; Chen, Hao; Ouyang, Yao Tsung; Chiu, Tz Cheng; Chang, Tao Chih; Lee, Hsin Yi; Ku, Chin Shun; Wu, Albert T.

    2015-10-01

    Three-dimensional packaging provides an acceptable solution for miniaturized integrated circuits. Because of the technological flexibility required for combining various modules to form a functional system, miniaturization can be achieved by using embedded techniques that could enhance the reliability of assembled systems. Because the mismatch of the thermal expansion coefficient among the materials has been an emerging issue when embedded components are subjected to thermal cycles, this study adopted the in situ synchrotron x-ray method to measure the strain distribution of a Si die in embedded substrates at various temperatures ranging from 25°C to 150°C. The out-of-plane strain of the Si die became less compressive when the temperature was increased. The numerical simulation of the finite elements software ANSYS also indicated the similar consequence of the strain behavior.

  4. Solvent exchange in a metal-organic framework single crystal monitored by dynamic in situ X-ray diffraction.

    PubMed

    Cox, Jordan M; Walton, Ian M; Bateman, Gage; Benson, Cassidy A; Mitchell, Travis; Sylvester, Eric; Chen, Yu Sheng; Benedict, Jason B

    2017-08-01

    Understanding the processes by which porous solid-state materials adsorb and release guest molecules would represent a significant step towards developing rational design principles for functional porous materials. To elucidate the process of liquid exchange in these materials, dynamic in situ X-ray diffraction techniques have been developed which utilize liquid-phase chemical stimuli. Using these time-resolved diffraction techniques, the ethanol solvation process in a flexible metal-organic framework [Co(AIP)(bpy)0.5(H2O)]·2H2O was examined. The measurements provide important insight into the nature of the chemical transformation in this system including the presence of a previously unreported neat ethanol solvate structure.

  5. An instrument for in situ coherent x-ray studies of metal-organic vapor phase epitaxy of III-nitrides

    DOE PAGES

    Ju, Guangxu; Highland, Matthew J.; Yanguas-Gil, Angel; ...

    2017-03-21

    Here, we describe an instrument that exploits the ongoing revolution in synchrotron sources, optics, and detectors to enable in situ studies of metal-organic vapor phase epitaxy (MOVPE) growth of III-nitride materials using coherent x-ray methods. The system includes high-resolution positioning of the sample and detector including full rotations, an x-ray transparent chamber wall for incident and diffracted beam access over a wide angular range, and minimal thermal sample motion, giving the sub-micron positional stability and reproducibility needed for coherent x-ray studies. The instrument enables surface x-ray photon correlation spectroscopy, microbeam diffraction, and coherent diffraction imaging of atomic-scale surface and filmmore » structure and dynamics during growth, to provide fundamental understanding of MOVPE processes.« less

  6. An instrument for in situ coherent x-ray studies of metal-organic vapor phase epitaxy of III-nitrides

    NASA Astrophysics Data System (ADS)

    Ju, Guangxu; Highland, Matthew J.; Yanguas-Gil, Angel; Thompson, Carol; Eastman, Jeffrey A.; Zhou, Hua; Brennan, Sean M.; Stephenson, G. Brian; Fuoss, Paul H.

    2017-03-01

    We describe an instrument that exploits the ongoing revolution in synchrotron sources, optics, and detectors to enable in situ studies of metal-organic vapor phase epitaxy (MOVPE) growth of III-nitride materials using coherent x-ray methods. The system includes high-resolution positioning of the sample and detector including full rotations, an x-ray transparent chamber wall for incident and diffracted beam access over a wide angular range, and minimal thermal sample motion, giving the sub-micron positional stability and reproducibility needed for coherent x-ray studies. The instrument enables surface x-ray photon correlation spectroscopy, microbeam diffraction, and coherent diffraction imaging of atomic-scale surface and film structure and dynamics during growth, to provide fundamental understanding of MOVPE processes.

  7. An instrument for in situ coherent x-ray studies of metal-organic vapor phase epitaxy of III-nitrides.

    PubMed

    Ju, Guangxu; Highland, Matthew J; Yanguas-Gil, Angel; Thompson, Carol; Eastman, Jeffrey A; Zhou, Hua; Brennan, Sean M; Stephenson, G Brian; Fuoss, Paul H

    2017-03-01

    We describe an instrument that exploits the ongoing revolution in synchrotron sources, optics, and detectors to enable in situ studies of metal-organic vapor phase epitaxy (MOVPE) growth of III-nitride materials using coherent x-ray methods. The system includes high-resolution positioning of the sample and detector including full rotations, an x-ray transparent chamber wall for incident and diffracted beam access over a wide angular range, and minimal thermal sample motion, giving the sub-micron positional stability and reproducibility needed for coherent x-ray studies. The instrument enables surface x-ray photon correlation spectroscopy, microbeam diffraction, and coherent diffraction imaging of atomic-scale surface and film structure and dynamics during growth, to provide fundamental understanding of MOVPE processes.

  8. Synchrotron micro-X-ray fluorescence analysis of natural diamonds: First steps in identification of mineral inclusions in situ

    SciTech Connect

    Sitepu, Husin; Kopylova, Maya G.; Quirt, David H.; Cutler, Jeffrey N.; Kotzer, Thomas G.

    2008-06-09

    Diamond inclusions are of particular research interest in mantle petrology and diamond exploration as they provide direct information about the chemical composition of upper and lower mantle and about the petrogenetic sources of diamonds in a given deposit. The objective of the present work is to develop semi-quantitative analytical tools for non-destructive in situ identification and characterization of mineral inclusions in diamonds using synchrotron micro-X-ray Fluorescence ({mu}SXRF) spectroscopy and micro-X-ray Absorption Near Edge Structure ({mu}XANES) spectroscopy at a focused spot size of 4 to 5 micrometers. The data were collected at the Pacific Northwest Consortium (PNC-CAT) 20-ID microprobe beamline at the Advanced Photon Source, located at the Argonne National Laboratory, and yielded the first high-resolution maps of Ti, Cr, Fe, Ni, Cu, and Zn for natural diamond grains, along with quantitative {mu}SXRF analysis of select chemical elements in exposed kimberlite indicator mineral grains. The distribution of diamond inclusions inside the natural diamond host, both visible and invisible using optical transmitted-light microscopy, can be mapped using synchrotron {mu}XRF analysis. Overall, the relative abundances of chemical elements determined by {mu}SXRF elemental analyses are broadly similar to their expected ratios in the mineral and therefore can be used to identify inclusions in diamonds in situ. Synchrotron {mu}XRF quantitative analysis provides accurate estimates of Cr contents of exposed polished minerals when calibrated using the concentration of Fe as a standard. Corresponding Cr K-edge {mu}XANES analyses on selected inclusions yield unique information regarding the formal oxidation state and local coordination of Cr.

  9. In-situ X-ray absorption spectroscopy analysis of capacity fade in nanoscale-LiCoO{sub 2}

    SciTech Connect

    Patridge, Christopher J.; Swider-Lyons, Karen E.; Twigg, Mark E.; Ramaker, David E.

    2013-07-15

    The local structure of nanoscale (∼10–40 nm) LiCoO{sub 2} is monitored during electrochemical cycling utilizing in-situ X-ray absorption spectroscopy (XAS). The high surface area of the LiCoO{sub 2} nanoparticles not only enhances capacity fade, but also provides a large signal from the particle surface relative to the bulk. Changes in the nanoscale LiCoO{sub 2} metal-oxide bond lengths, structural disorder, and chemical state are tracked during cycling by adapting the delta mu (Δμ) technique in complement with comprehensive extended X-ray absorption fine structure (EXAFS) modeling. For the first time, we use a Δμ EXAFS method, and by comparison of the difference EXAFS spectra, extrapolate significant coordination changes and reduction of cobalt species with cycling. This combined approach suggests Li–Co site exchange at the surface of the nanoscale LiCoO{sub 2} as a likely factor in the capacity fade and irreversible losses in practical, microscale LiCoO{sub 2}. - Graphical abstract: Electrochemical cycling of Li-ion batteries has strong impact on the structure and integrity of the cathode active material particularly near the surface/electrolyte interface. In developing a new method, we have used in-situ X-ray absorption spectroscopy during electrochemical cycling of nanoscale LiCoO{sub 2} to track changes during charge and discharge and between subsequent cycles. Using difference spectra, several small changes in Co-O bond length, Co-O and Co-Co coordination, and site exchange between Co and Li sites can be tracked. These methods show promise as a new technique to better understand processes which lead to capacity fade and loss in Li-ion batteries. - Highlights: • A new method is developed to understand capacity fade in Li-ion battery cathodes. • Structural changes are tracked during Li intercalation/deintercalation of LiCoO{sub 2}. • Surface structural changes are emphasized using nanoscale-LiCoO{sub 2} and difference spectra. • Full multiple

  10. Novel spectro-electrochemical cell for in situ/operando observation of common composite electrode with liquid electrolyte by X-ray absorption spectroscopy in the tender X-ray region

    PubMed Central

    Nakanishi, Koji; Kato, Daisuke; Arai, Hajime; Tanida, Hajime; Mori, Takuya; Orikasa, Yuki; Uchimoto, Yoshiharu; Ohta, Toshiaki; Ogumi, Zempachi

    2014-01-01

    A novel spectro-electochemical cell for X-ray absorption spectroscopy in the tender X-ray region (TX-XAS) was designed and fabricated to investigate the electrochemical behavior of common battery materials with liquid electrolytes under in situ/operando conditions. The cell has several unique features, such as high X-ray transmittance, high signal to noise ratio, and high vacuum tightness. These features enable us quick and reliable XAS measurements. Operando P K-edge XAS measurements of an olivine-type LiFePO4 composite positive electrode were carried out to clarify its phosphorus environment during the electrochemical charging process. Results of spectral analysis show that there is no significant change in the oxidation state of phosphorus and in the coordination of the phosphate anions in the charging process, but a closer look of the consecutive XAS spectra suggests the shrinkage of the PO4 cage during the charging process, and the structural changes in a biphasic manner. These results demonstrate the usefulness of the cell for in situ/operando TX-XAS observations of light elements in practical batteries. PMID:25173283

  11. Novel spectro-electrochemical cell for in situ/operando observation of common composite electrode with liquid electrolyte by X-ray absorption spectroscopy in the tender X-ray region.

    PubMed

    Nakanishi, Koji; Kato, Daisuke; Arai, Hajime; Tanida, Hajime; Mori, Takuya; Orikasa, Yuki; Uchimoto, Yoshiharu; Ohta, Toshiaki; Ogumi, Zempachi

    2014-08-01

    A novel spectro-electochemical cell for X-ray absorption spectroscopy in the tender X-ray region (TX-XAS) was designed and fabricated to investigate the electrochemical behavior of common battery materials with liquid electrolytes under in situ/operando conditions. The cell has several unique features, such as high X-ray transmittance, high signal to noise ratio, and high vacuum tightness. These features enable us quick and reliable XAS measurements. Operando P K-edge XAS measurements of an olivine-type LiFePO4 composite positive electrode were carried out to clarify its phosphorus environment during the electrochemical charging process. Results of spectral analysis show that there is no significant change in the oxidation state of phosphorus and in the coordination of the phosphate anions in the charging process, but a closer look of the consecutive XAS spectra suggests the shrinkage of the PO4 cage during the charging process, and the structural changes in a biphasic manner. These results demonstrate the usefulness of the cell for in situ/operando TX-XAS observations of light elements in practical batteries.

  12. Cu isotope fractionation during bornite dissolution: An in situ X-ray diffraction analysis

    SciTech Connect

    Wall, Andrew J.; Mathur, Ryan; Post, Jeffrey E.; Heaney, Peter J.

    2012-10-24

    Low-temperature ore deposits exhibit a large variation in {delta}{sup 65}Cu ({approx}12{per_thousand}), and this range has been attributed, in part, to isotope fractionation during weathering reactions of primary minerals such as chalcocite and chalcopyrite. Here, we examine the fractionation of Cu isotopes during dissolution of another important Cu ore mineral, bornite, using a novel approach that combines time-resolved X-ray diffraction (XRD) and isotope analysis of reaction products. During the initial stages of bornite oxidative dissolution by ferric sulfate (< 5 mol% of total Cu leached), dissolved Cu was enriched in isotopically heavy Cu ({sup 65}Cu) relative to the solid, with an average apparent isotope fractionation ({Delta}{sub aq - min} = {delta}{sup 65}Cu{sub aq} - {delta}{sup 65}Cu{sub min}{sup 0}) of 2.20 {+-} 0.25{per_thousand}. When > 20 mol% Cu was leached from the solid, the difference between the Cu isotope composition of the aqueous and mineral phases approached zero, with {Delta}{sub aq - min}{sup 0} values ranging from - 0.21 {+-} 0.61{per_thousand} to 0.92 {+-} 0.25{per_thousand}. XRD analysis allowed us to correlate changes in the atomic structure of bornite with the apparent isotope fractionation as the dissolution reaction progressed. These data revealed that the greatest degree of apparent fractionation is accompanied by a steep contraction in the unit-cell volume, which we identified as a transition from stoichiometric to non-stoichiometric bornite. We propose that the initially high {Delta}{sub aq - min} values result from isotopically heavy Cu ({sup 65}Cu) concentrating within Cu{sup 2+} during dissolution. The decrease in the apparent isotope fractionation as the reaction progresses occurs from the distillation of isotopically heavy Cu ({sup 65}Cu) during dissolution or kinetic isotope effects associated with the depletion of Cu from the surfaces of bornite particles.

  13. Silver transfer in proustite Ag{sub 3}AsS{sub 3} at high temperatures: Conductivity and single-crystal X-ray studies

    SciTech Connect

    Gagor, Anna Pawlowski, Antoni; Pietraszko, Adam

    2009-03-15

    Single crystals of proustite Ag{sub 3}AsS{sub 3} have been characterised by impedance spectroscopy and single-crystal X-ray diffraction in the temperature ranges of 295-543 and 295-695 K, respectively. An analysis of the one-particle potential of silver atoms shows that in the whole measuring temperature range defects in the silver substructure play a major role in the conduction mechanism. Furthermore, the silver transfer is equally probable within silver chains and spirals, as well as between chains and spirals. The trigonal R3c room temperature phase does not change until the decomposition of the crystal. The electric anomaly of the first-order character which appears near 502 K is related to an increase in the electronic component of the total conductivity resulting from Ag{sub 2}S deposition at the sample surface. - Joint probability density function map of silver atoms at T=695 K.

  14. Internally consistent elasticity measurements of mantle minerals at high-pressure and high-temperature by Brillouin spectroscopy and X-ray diffraction

    NASA Astrophysics Data System (ADS)

    Marquardt, H.; Kurnosov, A.; Boffa Ballaran, T.; Marquardt, K.; Frost, D. J.; Buchen, J.; Schulze, K.

    2015-12-01

    Elasticity is a material property that reflects the atomic structure and interatomic forces in crystalline materials. As a result, elastic properties are strongly affected by changes in pressure and temperature. In Earth Sciences, knowledge of the elastic behavior of geomaterials at pressure and temperature conditions of the Earth's interior is key to constrain our planet's inner structure and dynamics through forward modelling of seismic observables. Here, we will discuss internally consistent single-crystal elasticity measurements that combine the opportunities emerging from the recent development of combined Brillouin scattering (to derive acoustic wave velocities) and x-ray diffraction (XRD) systems (for structure and unit-cell parameter determination) with the advantages of sophisticated sample preparation using the focused ion beam (FIB) technique [1]. We will show results of experiments on mantle minerals that were performed using the combined Brillouin scattering and rotating anode XRD system at the Bayerisches Geoinstitut BGI. Multiple single-crystals, FIB-tailored in size and shape, were loaded in the single sample chambers of resistively-heated diamond-anvil cells (DAC). Such a multi-sample approach allows for internally consistent determinations of all independent elastic constants from low-symmetry crystals by Brillouin spectroscopy and x-ray diffraction measurements. Furthermore, the multi-sample approach facilitates direct quantification of the effects of chemical substitution on the structure and elasticity of high-symmetry crystals at non-ambient conditions. Our experimental approach eliminates uncertainties arising from the combination of data collected under (potentially) different conditions in several DAC runs, in different laboratories and/or from using different pressure-temperature sensors. We will also discuss the possibility to derive pressure independent from a secondary pressure scale. [1] H. Marquardt, K. Marquardt, Am. Mineral. 97, 299

  15. Novel High Temperature Materials for In-Situ Sensing Devices

    SciTech Connect

    Florian Solzbacher; Anil Virkar; Loren Rieth; Srinivasan Kannan; Xiaoxin Chen; Hannwelm Steinebach

    2009-12-31

    The overriding goal of this project was to develop gas sensor materials and systems compatible with operation at temperatures from 500 to 700 C. Gas sensors operating at these temperatures would be compatible with placement in fossil-energy exhaust streams close to the combustion chamber, and therefore have advantages for process regulation, and feedback for emissions controls. The three thrusts of our work included investigating thin film gas sensor materials based on metal oxide materials and electroceramic materials, and also development of microhotplate devices to support the gas sensing films. The metal oxide materials NiO, In{sub 2}O{sub 3}, and Ga{sub 2}O{sub 3} were investigated for their sensitivity to H{sub 2}, NO{sub x}, and CO{sub 2}, respectively, at high temperatures (T > 500 C), where the sensing properties of these materials have received little attention. New ground was broken in achieving excellent gas sensor responses (>10) for temperatures up to 600 C for NiO and In{sub 2}O{sub 3} materials. The gas sensitivity of these materials was decreasing as temperatures increased above 500 C, which indicates that achieving strong sensitivities with these materials at very high temperatures (T {ge} 650 C) will be a further challenge. The sensitivity, selectivity, stability, and reliability of these materials were investigated across a wide range of deposition conditions, temperatures, film thickness, as using surface active promoter materials. We also proposed to study the electroceramic materials BaZr{sub (1-x)}Y{sub x}O{sub (3-x/2)} and BaCe{sub (2-x)}Ca{sub x}S{sub (4-x/2)} for their ability to detect H{sub 2}O and H{sub 2}S, respectively. This report focuses on the properties and gas sensing characteristics of BaZr{sub (1-x)}Y{sub x}O{sub (3-x/2)} (Y-doped BaZrO{sub 3}), as significant difficulties were encounter in generating BaCe{sub (2-x)}Ca{sub x}S{sub (4-x/2)} sensors. Significant new results were achieved for Y-doped BaZrO{sub 3}, including

  16. In situ synchrotron X-ray powder diffraction for studying the role of induced structural defects on the thermoluminescence mechanism of nanocrystalline LiF.

    PubMed

    El Ashmawy, Mostafa; Amer, Hany; Abdellatief, Mahmoud

    2016-03-01

    The correlation between the thermoluminescence (TL) response of nanocrystalline LiF and its microstructure was studied. To investigate the detailed TL mechanism, the glow curves of nanocrystalline LiF samples produced by high-energy ball-milling were analyzed. The microstructure of the prepared samples was analyzed by synchrotron X-ray powder diffraction (XRPD) at room temperature. Then, the microstructure of a representative pulverized sample was investigated in detail by performing in situ XRPD in both isothermal and non-isothermal modes. In the present study, the dislocations produced by ball-milling alter the microstructure of the lattice where the relative concentration of the vacancies, responsible for the TL response, changes with milling time. An enhancement in the TL response was recorded for nanocrystalline LiF at high-temperature traps (after dislocations recovery starts >425 K). It is also found that vacancies are playing a major role in the dislocations recovery mechanism. Moreover, the interactions among vacancies-dislocations and/or dislocations-dislocations weaken the TL response.

  17. Temperature Dependence of the Structural Parameters in the Transformation of Aragonite to Calcite, as Determined from In Situ Synchrotron Powder X-ray-Diffratction Data

    SciTech Connect

    Antao, Sytle M.; Hassan, Ishmael

    2011-09-06

    The temperature dependency of the crystal structure and the polymorphic transition of CaCO{sub 3} from aragonite to calcite were studied using Rietveld structure refinement and high-temperature in situ synchrotron powder X-ray-diffraction data at ambient pressure, P. The orthorhombic metastable aragonite at room P, space group Pmcn, transforms to trigonal calcite, space group R{bar 3}c, at about T{sub c} = 468 C. This transformation occurs rapidly; it starts at about 420 C and is completed by 500 C, an 80 C interval that took about 10 minutes using a heating rate of 8 C/min. Structurally, from aragonite to calcite, the distribution of the Ca atom changes from approximately hexagonal to cubic close-packing. A 5.76% discontinuous increase in volume accompanies the reconstructive first-order transition. Besides the change in coordination of the Ca atom from nine to six from aragonite to calcite, the CO{sub 3} groups change by a 30{sup o} rotation across the transition.

  18. A multipurpose ultra-high vacuum-compatible chamber for in situ X-ray surface scattering studies over a wide range of temperature and pressure environment conditions

    NASA Astrophysics Data System (ADS)

    Ferrer, P.; Rubio-Zuazo, J.; Heyman, C.; Esteban-Betegón, F.; Castro, G. R.

    2013-03-01

    A low/high temperature (60-1000K) and pressure (10-10-3x103 mbar) "baby chamber", specially adapted to the grazing-incidence X-ray scattering station, has been designed, developed and installed at the Spanish CRG BM25 SpLine beamline at European Synchrotron Radiation Facility. The chamber has a cylindrical form with 100 mm of diameter, built on a 360° beryllium nipple of 150 mm height. The UHV equipment and a turbo pump are located on the upper part of the chamber to leave a wide solid angle for exploring reciprocal space. The chamber features 4 CF16 and 5 CF40 ports for electrical feed through and leak valves, ion gun, etc. The heat exchanger is a customized compact LN2 (or LHe) continuous flow cryostat. The sample is mounted on a Mo support on the heat exchanger, which has in the back side a BORALECTRIC® Heater Elements. Experiments of surfaces/interfaces/ multilayer materials, thin films or single crystals in a huge variety of environments can be performed, also in situ studies of growth or evolution of the samples. Data measurement can be collected with a punctual and a bi-dimensional detector, being possible to simultaneously use them.

  19. In situ and real-time characterization of metal-organic chemical vapor deposition growth by high resolution x-ray diffraction

    SciTech Connect

    Kharchenko, A.; Lischka, K.; Schmidegg, K.; Sitter, H.; Bethke, J.; Woitok, J.

    2005-03-01

    We present an x-ray diffractometer for the analysis of epitaxial layers during (in situ) metal-organic chemical vapor deposition (MOCVD). Our diffractometer has a conventional x-ray source, does not need a goniometer stage, and is not sensitive to precise adjustment of the samples before measurement. It allows us to perform measurements within a few seconds even from rotating and wobbling samples. The first results of laboratory tests performed with our x-ray diffraction system show that it is well suited for in situ and real-time monitoring of the MOCVD growth process. We were able to measure the growth rate of a cubic GaN layer and the intensity and peak position of Bragg reflections of the growing layer in less than 20 s only.

  20. An in situ X ray diffraction study of the kinetics of the Ni2SiO4 olivine-spinel transformation

    NASA Technical Reports Server (NTRS)

    Rubie, D. C.; Tsuchida, Y.; Yagi, T.; Utsumi, W.; Kikegawa, T.

    1990-01-01

    The kinetics of the olivine-spinel transformation in Ni2SiO4 were investigated in an in situ X-ray diffraction experiments in which synchrotron radiation was used as an X-ray source. The starting material was Ni2SO4 olivine which was hot-pressed in situ at 980 C and 2.5 GPa; during the transformation, X-ray diffraction patterns were collected at intervals of 30 or 120 sec. The kinetic data were analyzed using Cahn's (1956) model. The activation energy for growth at 3.6-3.7 GPa was estimated as 438 + or - 199 kJ/mol. It is shown that, in order to make significant extrapolations of the kinetic data to a geological scale, the dependence of the rates of both nucleation and growth on temperature and pressure must be evaluated separately.

  1. Mapping strain fields induced in Zr-based bulk metallic glasses during in-situ nanoindentation by X-ray nanodiffraction

    SciTech Connect

    Gamcová, J.; Bednarčík, J.; Franz, H.; Mohanty, G.; Wehrs, J.; Michler, J.; Michalik, Š.; Krywka, C.; Breguet, J. M.

    2016-01-18

    A pioneer in-situ synchrotron X-ray nanodiffraction approach for characterization and visualization of strain fields induced by nanoindentation in amorphous materials is introduced. In-situ nanoindentation experiments were performed in transmission mode using a monochromatic and highly focused sub-micron X-ray beam on 40 μm thick Zr-based bulk metallic glass under two loading conditions. Spatially resolved X-ray diffraction scans in the deformed volume of Zr-based bulk metallic glass covering an area of 40 × 40 μm{sup 2} beneath the pyramidal indenter revealed two-dimensional map of elastic strains. The largest value of compressive elastic strain calculated from diffraction data at 1 N load was −0.65%. The region of high elastic compressive strains (<−0.3%) is located beneath the indenter tip and has radius of 7 μm.

  2. Mapping strain fields induced in Zr-based bulk metallic glasses during in-situ nanoindentation by X-ray nanodiffraction

    NASA Astrophysics Data System (ADS)

    Gamcová, J.; Mohanty, G.; Michalik, Š.; Wehrs, J.; Bednarčík, J.; Krywka, C.; Breguet, J. M.; Michler, J.; Franz, H.

    2016-01-01

    A pioneer in-situ synchrotron X-ray nanodiffraction approach for characterization and visualization of strain fields induced by nanoindentation in amorphous materials is introduced. In-situ nanoindentation experiments were performed in transmission mode using a monochromatic and highly focused sub-micron X-ray beam on 40 μm thick Zr-based bulk metallic glass under two loading conditions. Spatially resolved X-ray diffraction scans in the deformed volume of Zr-based bulk metallic glass covering an area of 40 × 40 μm2 beneath the pyramidal indenter revealed two-dimensional map of elastic strains. The largest value of compressive elastic strain calculated from diffraction data at 1 N load was -0.65%. The region of high elastic compressive strains (<-0.3%) is located beneath the indenter tip and has radius of 7 μm.

  3. Fatigue History and in-situ Loading Studies of the overload Effect Using High Resolution X-ray Strain Profiling

    SciTech Connect

    Croft,M.; Jisrawi, N.; Zhong, Z.; Holtz, R.; Sadananda, K.; Skaritka, J.; Tsakalakos, T.

    2007-01-01

    High-energy synchrotron X-ray diffraction experiments are used to perform local crack plane strain profiling of 4140 steel compact tension specimens fatigued at constant amplitude, subjected to a single overload cycle, then fatigued some more at constant amplitude. X-ray strain profiling results on a series of samples employing in-situ load cycling are correlated with the crack growth rate (da/dN) providing insight into the da/dN retardation known as the 'overload effect'. Immediately after the overload, the strain under maximum load is greatly reduced but the range of strain, between zero and maximum load, remains unchanged compared to the pre-overload values. At the point of maximum retardation, it is the strain range that is greatly reduced while the maximum-load strain has begun to recover to the pre-overload value. For a sample that has recovered to approximately half of the original da/dN value following the overload, the strain at maximum load is fully recovered while the strain range, though partially recovered, is still substantially reduced. The dominance of the strain range in the overload effect is clearly indicated. Subject to some assumptions, strong quantitative support for a crack growth rate driving force of the suggested form [(K{sub max}){sup -p}({Delta}K){sup p}]{sup {gamma}} is found. A dramatic nonlinear load dependence in the spatial distribution of the strain at maximum retardation is also demonstrated: at low load the response is dominantly at the overload position; whereas at high loads it is dominantly at the crack tip position. This transfer of load response away from the crack tip to the overload position appears fundamental to the overload effect for high R-ratio fatigue as studied here.

  4. In situ x-ray absorption spectroscopy study of tin anode nanomaterials for lithium-ion batteries

    NASA Astrophysics Data System (ADS)

    Pelliccione, Christopher J.

    Tin is an attractive alternative to replace traditional carbon based anodes in lithium-ion batteries (LIBs) due to the nearly three-fold increase in theoretical capacity over carbon. However, metallic tin suffers from volumetric expansion of the crystal structure during initial lithium insertion that quickly degrades the material and reduces the performance of the battery. Various techniques have been previously investigated with the goal of suppressing this destructive expansion by incorporating oxygen or a lithium-inactive metal into the tin to provide structural support and mitigate volumetric expansion. These materials show increased capacity retention compared to metallic tin, but still suffer from capacity fading. The nature of these structural degradations must be fully understood to permit engineering of materials that avoid these destructive tendencies and can be considered as viable options for LIBs. In situ X-ray absorption spectroscopy (XAS) measurements were acquired on Sn, SnO2, Sn3O2(OH) 2, Cu6Sn5 and Ni3Sn4 nanoparticle anodes for LIBs. Accompanying the electrochemical characterization conducted on each material, the local atomic structure was modeled as a function of potential during the first charge and also as a function of charged/discharged states for several cycles. The extended X-ray absorption fine structure (EXAFS) theoretical modeling included the first unambiguous observation of Sn-Li coordination numbers and atomic distances in tin-based anode materials. From correlating the electrochemical performance to the EXAFS analysis, the long-term capacity retention of tin-based anodes is dependent on the structural deformations that occur during the first charge. The conversion of oxygen to amorphous Li2O, and the network that it forms, has a dramatic effect on the kinetics of the system and the stability of the local metallic tin structure.

  5. Compact Roll-to-Roll Coater for in Situ X-ray Diffraction Characterization of Organic Electronics Printing.

    PubMed

    Gu, Xiaodan; Reinspach, Julia; Worfolk, Brian J; Diao, Ying; Zhou, Yan; Yan, Hongping; Gu, Kevin; Mannsfeld, Stefan; Toney, Michael F; Bao, Zhenan

    2016-01-27

    We describe a compact roll-to-roll (R2R) coater that is capable of tracking the crystallization process of semiconducting polymers during solution printing using X-ray scattering at synchrotron beamlines. An improved understanding of the morphology evolution during the solution-processing of organic semiconductor materials during R2R coating processes is necessary to bridge the gap between "lab" and "fab". The instrument consists of a vacuum chuck to hold the flexible plastic substrate uniformly flat for grazing incidence X-ray scattering. The time resolution of the drying process that is achievable can be tuned by controlling two independent motor speeds, namely, the speed of the moving flexible substrate and the speed of the printer head moving in the opposite direction. With this novel design, we are able to achieve a wide range of drying time resolutions, from tens of milliseconds to seconds. This allows examination of the crystallization process over either fast or slow drying processes depending on coating conditions. Using regioregular poly(3-hexylthiophene-2,5-diyl) (P3HT) and phenyl-C61-butyric acid methyl ester (PCBM) inks based on two different solvents as a model system, we demonstrate the capability of our in situ R2R printing tool by observing two distinct crystallization processes for inks drying from the solvents with different boiling points (evaporation rates). We also observed delayed on-set point for the crystallization of P3HT polymer in the 1:1 P3HT/PCBM BHJ blend, and the inhibited crystallization of the P3HT during the late stage of the drying process.

  6. Induction of in situ DNA double-strand breaks and apoptosis by 200 MeV protons and 10 MV X-rays in human tumour cell lines.

    PubMed

    Gerelchuluun, Ariungerel; Hong, Zhengshan; Sun, Lue; Suzuki, Kenshi; Terunuma, Toshiyuki; Yasuoka, Kiyoshi; Sakae, Takeji; Moritake, Takashi; Tsuboi, Koji

    2011-01-01

    To clarify the properties of clinical high-energy protons by comparing with clinical high-energy X-rays. Human tumor cell lines, ONS76 and MOLT4, were irradiated with 200 MeV protons or 10 MV X-rays. In situ DNA double-strand breaks (DDSB) induction was evaluated by immunocytochemical staining of phosphorylated histone H2AX (γ-H2AX). Apoptosis was measured by flow-cytometry after staining with Annexin V. The relative biological effectiveness (RBE) was obtained by clonogenic survival assay. DDSB induction was significantly higher for protons than X-rays with average ratios of 1.28 (ONS76) and 1.59 (MOLT4) at 30 min after irradiation. However the differences became insignificant at 6 h. Also, apoptosis induction in MOLT4 cells was significantly higher for protons than X-rays with an average ratio of 2.13 at 12 h. However, the difference became insignificant at 20 h. RBE values of protons to X-rays at 10% survival were 1.06 ± 0.04 and 1.02 ± 0.15 for ONS76 and MOLT4, respectively. Cell inactivation may differ according to different timings and/or endpoints. Proton beams demonstrated higher cell inactivation than X-rays in the early phases. These data may facilitate the understanding of the biological properties of clinical proton beams.

  7. Evaluating the solid electrolyte interphase formed on silicon electrodes: A comparison of ex situ X-ray photoelectron spectroscopy and in situ neutron reflectometry

    SciTech Connect

    Doucet, Mathieu; Browning, Jim; Baldwin, J. K.; Winiarz, Jeffrey; Kaiser, Helmut; Taub, H.; Veith, Gabriel M.

    2016-04-15

    This work details the in situ characterization of the interface between a silicon electrode and an electrolyte using a linear fluorinated solvent molecule, 0.1 M lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) in deuterated dimethyl perfluoroglutarate (d6-PF5M2) (1.87 x 10-2 mS/cm-1). The solid electrolyte interphase (SEI) composition and thickness determined via in situ neutron reflectometry (NR) and ex situ X-ray photoelectron spectroscopy (XPS) were compared. The data show that SEI expansion and contraction (breathing) during electrochemical cycling was observed via both techniques; however, ex situ XPS suggests that the SEI thickness increases during Si lithiation and decreases during delithiation, while in situ NR suggests the opposite. The most likely cause of this discrepancy is the selective removal of SEI components (top 20 nm of the SEI) during the electrode rinse process, required to remove electrolyte residue prior to ex situ analysis, demonstrating the necessity of performing SEI characterizations in situ.

  8. Evaluating the solid electrolyte interphase formed on silicon electrodes: A comparison of ex situ X-ray photoelectron spectroscopy and in situ neutron reflectometry

    DOE PAGES

    Doucet, Mathieu; Browning, Jim; Baldwin, J. K.; ...

    2016-04-15

    This work details the in situ characterization of the interface between a silicon electrode and an electrolyte using a linear fluorinated solvent molecule, 0.1 M lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) in deuterated dimethyl perfluoroglutarate (d6-PF5M2) (1.87 x 10-2 mS/cm-1). The solid electrolyte interphase (SEI) composition and thickness determined via in situ neutron reflectometry (NR) and ex situ X-ray photoelectron spectroscopy (XPS) were compared. The data show that SEI expansion and contraction (breathing) during electrochemical cycling was observed via both techniques; however, ex situ XPS suggests that the SEI thickness increases during Si lithiation and decreases during delithiation, while in situ NR suggestsmore » the opposite. The most likely cause of this discrepancy is the selective removal of SEI components (top 20 nm of the SEI) during the electrode rinse process, required to remove electrolyte residue prior to ex situ analysis, demonstrating the necessity of performing SEI characterizations in situ.« less

  9. Evaluating the solid electrolyte interphase formed on silicon electrodes: a comparison of ex situ X-ray photoelectron spectroscopy and in situ neutron reflectometry.

    PubMed

    Fears, T M; Doucet, M; Browning, J F; Baldwin, J K S; Winiarz, J G; Kaiser, H; Taub, H; Sacci, R L; Veith, G M

    2016-05-18

    This work details the in situ characterization of the interface between a silicon electrode and an electrolyte using a linear fluorinated solvent molecule, 0.1 M lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) in deuterated dimethyl perfluoroglutarate (d6-PF5M2) (1.87 × 10(-2) mS cm(-1)). The solid electrolyte interphase (SEI) composition and thickness determined via in situ neutron reflectometry (NR) and ex situ X-ray photoelectron spectroscopy (XPS) were compared. The data show that SEI expansion and contraction (breathing) during electrochemical cycling were observed via both techniques; however, ex situ XPS suggests that the SEI thickness increases during Si lithiation and decreases during delithiation, while in situ NR suggests the opposite. The most likely cause of this discrepancy is the selective removal of SEI components (top 20 nm of the SEI) during the electrode rinse process, which is required to remove the electrolyte residue prior to ex situ analysis, demonstrating the necessity of performing SEI characterization in situ.

  10. In Situ Self Assembly of Nanocomposites: Competition of Chaotic Advection and Interfacial Effects as Observed by X-Ray Diffreaction

    PubMed Central

    Ratnaweera, Dilru R.; Mahesha, Chaitra; Zumbrunnen, David A.; Perahia, Dvora

    2015-01-01

    The effects of chaotic advection on the in situ assembly of a hierarchal nanocomposite of Poly Amide 6, (nylon 6 or PA6) and platelet shape nanoparticles (NPs) were studied. The assemblies were formed by chaotic advection, where melts of pristine PA6 and a mixture of PA6 with NPs were segregated into discrete layers and extruded into film in a continuous process. The process assembles the nanocomposite into alternating pristine-polymer and oriented NP/polymer layers. The structure of these hierarchal assemblies was probed by X-rays as a processing parameter, N, was varied. This parameter provides a measure of the extent of in situ structuring by chaotic advection. We found that all assemblies are semi-crystalline at room temperature. Increasing N impacts the ratio of α to γ crystalline forms. The effects of the chaotic advection vary with the concentration of the NPs. For nanocomposites with lower NP concentrations the amount of the γ crystalline form increased with N. However, at higher NP concentrations, interfacial effects of the NP play a significant role in determining the structure, where the NPs oriented along the melt flow direction and the polymer chains oriented perpendicular to the NP surfaces.

  11. Exploring 3D microstructural evolution in Li-Sulfur battery electrodes using in-situ X-ray tomography

    PubMed Central

    Yermukhambetova, Assiya; Tan, Chun; Daemi, Sohrab R.; Bakenov, Zhumabay; Darr, Jawwad A.; Brett, Daniel J. L.; Shearing, Paul R.

    2016-01-01

    Lithium sulfur (Li-S) batteries offer higher theoretical specific capacity, lower cost and enhanced safety compared to current Li-ion battery technology. However, the multiple reactions and phase changes in the sulfur conversion cathode result in highly complex phenomena that significantly impact cycling life. For the first time to the authors’ knowledge, a multi-scale 3D in-situ tomography approach is used to characterize morphological parameters and track microstructural evolution of the sulfur cathode across multiple charge cycles. Here we show the uneven distribution of the sulfur phase fraction within the electrode thickness as a function of charge cycles, suggesting significant mass transport limitations within thick-film sulfur cathodes. Furthermore, we report a shift towards larger particle sizes and a decrease in volume specific surface area with cycling, suggesting sulfur agglomeration. Finally, we demonstrate the nano-scopic length-scale required for the features of the carbon binder domain to become discernible, confirming the need for future work on in-situ nano-tomography. We anticipate that X-ray tomography will be a powerful tool for optimization of electrode structures for Li-S batteries. PMID:27748437

  12. In-situ Characterization of Water-Gas Shift Catalysts using Time-Resolved X-ray Diffraction

    SciTech Connect

    Rodriguez, J.; Hanson, J; Wen, W; Wang, X; Brito, J; Martnez-Arias, A; Fernandez-Garca, M

    2009-01-01

    Time-resolved X-ray diffraction (XRD) has emerged as a powerful technique for studying the behavior of heterogeneous catalysts (metal oxides, sulfides, carbides, phosphides, zeolites, etc.) in-situ during reaction conditions. The technique can identify the active phase of a heterogeneous catalyst and how its structure changes after interacting with the reactants and products (80 K < T < 1200 K; P < 50 atm). In this article, we review a series of recent works that use in-situ time-resolved XRD for studying the water-gas shift reaction (WGS, CO + H2O ? H2 + CO2) over several mixed-metal oxides: CuMoO4, NiMoO4, Ce1-xCuxO2-d and CuFe2O4. Under reaction conditions the oxides undergo partial reduction. Neutral Cu0 (i.e. no Cu1+ or Cu2+ cations) and Ni0 are the active species in the catalysts, but interactions with the oxide support are necessary in order to obtain high catalytic activity. These studies illustrate the important role played by O vacancies in the mechanism for the WGS. In the case of Ce1-xCuxO2-d, Rietveld refinement shows expansions/contractions in the oxide lattice which track steps within the WGS process: CO(gas) + O(oxi) ? CO2(gas) + O(vac); H2O(gas) + O(vac) ? O(oxi) + H2(gas).

  13. Exploring 3D microstructural evolution in Li-Sulfur battery electrodes using in-situ X-ray tomography

    NASA Astrophysics Data System (ADS)

    Yermukhambetova, Assiya; Tan, Chun; Daemi, Sohrab R.; Bakenov, Zhumabay; Darr, Jawwad A.; Brett, Daniel J. L.; Shearing, Paul R.

    2016-10-01

    Lithium sulfur (Li-S) batteries offer higher theoretical specific capacity, lower cost and enhanced safety compared to current Li-ion battery technology. However, the multiple reactions and phase changes in the sulfur conversion cathode result in highly complex phenomena that significantly impact cycling life. For the first time to the authors’ knowledge, a multi-scale 3D in-situ tomography approach is used to characterize morphological parameters and track microstructural evolution of the sulfur cathode across multiple charge cycles. Here we show the uneven distribution of the sulfur phase fraction within the electrode thickness as a function of charge cycles, suggesting significant mass transport limitations within thick-film sulfur cathodes. Furthermore, we report a shift towards larger particle sizes and a decrease in volume specific surface area with cycling, suggesting sulfur agglomeration. Finally, we demonstrate the nano-scopic length-scale required for the features of the carbon binder domain to become discernible, confirming the need for future work on in-situ nano-tomography. We anticipate that X-ray tomography will be a powerful tool for optimization of electrode structures for Li-S batteries.

  14. Monitoring simultaneously the growth of nanoparticles and aggregates by in situ ultra-small-angle x-ray scattering

    SciTech Connect

    Kammler, Hendrik K.; Beaucage, Gregory; Kohls, Douglas J.; Agashe, Nikhil; Ilavsky, Jan

    2005-03-01

    Ultra-small-angle x-ray scattering can provide information about primary particles and aggregates from a single scattering experiment. This technique is applied in situ to flame aerosol reactors for monitoring simultaneously the primary particle and aggregate growth dynamics of oxide nanoparticles in a flame. This was enabled through the use of a third generation synchrotron source (Advanced Photon Source, Argonne IL, USA) using specialized scattering instrumentation at the UNICAT facility which is capable of simultaneously measuring nanoscales to microscales (1 nm to 1 {mu}m). More specifically, the evolution of primary-particle diameter, mass-fractal dimension, geometric standard deviation, silica volume fraction, number concentration, radius of gyration of the aggregate, and number of primary particles per aggregate are measured along the flame axis for two different premixed flames. All these particle characteristics were derived from a single and nonintrusive measurement technique. Flame temperature profiles were measured in the presence of particles by in situ Fourier transform infrared spectroscopy and thermophoretic sampling was used to visualize particle growth with height above the burner as well as in the radial direction.

  15. In-situ synchrotron wide-angle X-ray diffraction as a rapid method for cocrystal/salt screening.

    PubMed

    Dong, Pin; Lin, Ling; Li, Yongcheng; Huang, Zhengwei; Lang, Tianqun; Wu, Chuanbin; Lu, Ming

    2015-12-30

    The purpose of this work was to explore in-situ synchrotron wide-angle X-ray diffraction (WAXD) as a rapid and accurate tool to screen and monitor the formation of cocrystal/salts during heating. The active pharmaceutical ingredients (caffeine, carbamazepine and lamotrigine) were respectively mixed with the coformer (saccharin), and then heated by the hot stage. Real-time process monitoring was performed using synchrotron WAXD to assess cocrystal formation and subsequently compared to differential scanning calorimetry (DSC) measurements. The effect of heating rates and cocrystal growth behavior were investigated. Synchrotron WAXD was fast and sensitive to detect cocrystal formation with the appearance of characteristic diffraction rings, even at the heating rate of 30°C/min, while DSC curves showed overlapped peaks. Unlike the indirect characterization of DSC on endo/exothermic peaks, synchrotron WAXD can directly and qualitatively determine cocrystal by diffraction peaks. The diffraction intensity-temperature curves and the corresponding first-derivative curves clearly exhibited the growth behavior of cocrystal upon heating, providing useful information to optimize the process temperature of hot melt extrusion to continuously manufacture cocrystal. The study suggests that in-situ synchrotron WAXD could provide a one-step process to screen cocrystal at high efficiency and reveal the details of cocrystal/salts growth behavior. Copyright © 2015 Elsevier B.V. All rights reserved.

  16. Strategies for in situ laser heating in the diamond anvil cell at an X-ray diffraction beamline

    PubMed Central

    Petitgirard, Sylvain; Salamat, Ashkan; Beck, Pierre; Weck, Gunnar; Bouvier, Pierre

    2014-01-01

    An overview of several innovations regarding in situ laser-heating techniques in the diamond anvil cell at the high-pressure beamline ID27 of the European Synchrotron Radiation Facility is presented. Pyrometry measurements have been adapted to allow simultaneous double-sided temperature measurements with the installation of two additional online laser systems: a CO2 and a pulsed Nd:YAG laser system. This reiteration of laser-heating advancements at ID27 is designed to pave the way for a new generation of state-of-the-art experiments that demand the need for synchrotron diffraction techniques. Experimental examples are provided for each major development. The capabilities of the double pyrometer have been tested with the Nd:YAG continuous-wave lasers but also in a time-resolved configuration using the nanosecond-pulsed Nd:YAG laser on a Fe sample up to 180 GPa and 2900 K. The combination of time-resolved X-ray diffraction with in situ CO2 laser heating is shown with the crystallization of a high-pressure phase of the naturally found pyrite mineral MnS2 (11 GPa, 1100–1650 K). PMID:24365921

  17. Quantitative determination of the oxidation state of iron in biotite using x-ray photoelectron spectroscopy: II. In situ analyses

    SciTech Connect

    Raeburn, S.P. |; Ilton, E.S.; Veblen, D.R.

    1997-11-01

    X-ray photoelectron spectroscopy (XPS) was used to determine Fe(III)/{Sigma}Fe in individual biotite crystals in thin sections of ten metapelites and one syenite. The in situ XPS analyses of Fe(III)/{Sigma}Fe in biotite crystals in the metapelites were compared with published Fe(III)/{Sigma}Fe values determined by Moessbauer spectroscopy (MS) for mineral separates from the same hand samples. The difference between Fe(III)/{Sigma}Fe by the two techniques was greatest for samples with the lowest Fe(III)/{Sigma}Fe (by MS). For eight metamorphic biotites with Fe(III)/{Sigma}Fe = 9-27% comparison of the two techniques yielded a linear correlation of r = 0.94 and a statistically acceptable fit of [Fe(III)/{Sigma}Fe]{sub xps} = [Fe(III)/{Sigma}Fe]{sub ms}. The difference between Fe(III)/{Sigma}Fe by the two techniques was greater for two samples with Fe(III)/{Sigma}Fe {le} 6% (by MS). For biotite in the syenite sample, Fe(III)/{Sigma}Fe determined by both in situ XPS and bulk wet chemistry/electron probe microanalysis were similar. This contribution demonstrates that XPS can be used to analyze bulk Fe(III)/{Sigma}Fe in minerals in thin sections when appropriate precautions taken to avoid oxidation of the near-surface during preparation of samples. 25 refs., 3 figs., 4 tabs.

  18. In situ X-ray Studies of Native and Mo-Seeded Surface Nanostructuring During Ion Bombardment of Si(100)

    SciTech Connect

    K, G.; Ludwig, Jr., K

    2009-01-01

    Native and Mo-seeded nanostructuring of the Si(100) surface during Ar+ ion bombardment is investigated by means of real-time grazing-incidence small-angle x-ray scattering and atomic force microscopy. During off-axis bombardment at room temperature, the native early-stage growth kinetics of nanoripples on the surface is found to be in reasonable overall agreement with theoretical predictions, particularly when an ion impact induced lateral mass redistribution term is included. For normal-incidence bombardment at room temperature, a native short wavelength smoothing of the amorphized Si surface is observed, suggesting that ion impact induced lateral mass redistribution dominates the Bradley-Harper instability. During 5% Mo-seeded normal-incidence bombardment at temperatures up to 450 C, nanodots form with heights decreasing as the substrate temperature increases. This trend is counter to that typically observed for the growth of large cone structures on metals and suggests that the primary effect of thermal energy here is in promoting surface smoothing, rather than increasing diffusion of seed atoms to form protective clusters. During seeded bombardment at 650 C the surface remains crystalline and surface corrugations exhibit dynamic scaling characteristic of surface diffusion-driven instabilities. This is the same behavior as is found in the absence of seeding and its presence suggests that at this concentration seeding does not play a large role during normal-incidence bombardment of the Si surface at high temperatures.

  19. Combined electrochemical and X-ray tomography study of the high temperature evolution of Nickel - Yttria Stabilized Zirconia solid oxide fuel cell anodes

    NASA Astrophysics Data System (ADS)

    Kennouche, David; Chen-Wiegart, Yu-chen Karen; Riscoe, Casey; Wang, Jun; Barnett, Scott A.

    2016-03-01

    Accelerated ageing of Ni-Yttria Stabilized Zirconia (YSZ) anode functional layers (AFLs) in solid oxide fuel cells (SOFCs) is carried out at 1000-1200 °C, the resulting morphological changes are investigated using transmission X-ray microscopy (TXM), and properties are characterized using electrochemical impedance spectroscopy (EIS). Prior to ageing, the as prepared NiO-YSZ AFLs are reduced to Ni-YSZ and then aged at 1100 °C for 100 h in order to eliminate early-stage morphological changes. Measured particle size and three phase boundary (TPB) density changes with ageing time and temperature are fit reasonably well using a power-law coarsening model. This model is also used in conjunction with an electrochemical model to predict changes in the anode charge-transfer polarization resistance. The models are used to make predictions of the structural and electrochemical performance evolution of these Ni-YSZ anodes, for cells operated long-term at normal (700-850 °C) operating temperatures. Additional experiments to verify the model predictions are suggested.

  20. Microstructural transformations and kinetics of high-temperature heterogeneous gasless reactions by high-speed x-ray phase-contrast imaging

    SciTech Connect

    Reeves, Robert V.; Son, Steven F.; White, Jeremiah D. E.; Mukasyan, Alexander S.; Dufresne, Eric M.; Fezzaa, Kamel; Varma, Arvind

    2009-12-01

    Heterogeneous gasless reactive systems, including high-energy density metal-nonmetal compositions, have seen increasing study due to their various applications. However, owing to their high reaction temperature, short reaction time, and small scale of heterogeneity, investigation of their reaction mechanisms and kinetics is very difficult. In this study, microstructural changes and the kinetics of product layer growth in the W-Si system was investigated using a high-speed x-ray phase-contrast imaging technique. Using the Advanced Photon Source of Argonne National Laboratory, this method allowed direct imaging of irreversible reactions in the W-Si reactive system at frame rates up to 36 000 frames per second with 4 {mu}s exposure and spatial resolution of 10 {mu}m. Details of the Si melt and reactions between W and Si, that are unable to be viewed with visible-light imaging, were revealed. These include processes such as the initiation of nucleated melting and other physical phenomena that provide insight into the mixing of reactants and subsequent reaction. Through the use of this imaging technique and future optimization in the imaging process, a model for accurately identifying kinetics of chemical reactions, both spatially and temporally, is also proposed.

  1. X-ray spectral measurement of high-temperature plasma parameters in porous targets irradiated with high-power laser pulses

    SciTech Connect

    Gavrilov, V V; Gol'tsov, A Yu; Koval'skii, N G; Koptyaev, S N; Magunov, A I; Pikuz, T A; Skobelev, I Yu; Faenov, A Ya

    2001-12-31

    The X-ray spectra of multiply charged ions were recorded from planar agar (C{sub 12}H{sub 18}O{sub 9}){sub n} based targets with an average density of 2 mg cm{sup -3} irradiated by high-power laser pulses ({lambda}=1.054 {mu}m, {tau}=2.5 ns, I {approx} 5 x10{sup 13} W cm{sup -2}). The spectra were recorded with a high spectral and spatial resolution employing spherically bent (focusing) crystals of mica and quartz. An analysis of the experimental data obtained by the irradiation of Al{sub 2}O{sub 3}-doped agar samples allowed us to determine the main parameters of the plasma produced inside the targets. The ion temperature of plasma in low-density porous targets was estimated for the first time to be 1.5 - 2 times higher than the electron temperature. (interaction of laser radiation with matter. laser plasma)

  2. High temperature structural study of Gd-doped ceria by synchrotron X-ray diffraction (673 K ≤ T ≤ 1073 K).

    PubMed

    Artini, Cristina; Pani, Marcella; Lausi, Andrea; Masini, Roberto; Costa, Giorgio A

    2014-10-06

    The crystallographic features of Gd-doped ceria were investigated at the operating temperature of solid oxides fuel cells, where these materials are used as solid electrolytes. (Ce(1-x)Gd(x))O(2-x/2) samples (x = 0.1, 0.3, 0.5, 0.7) were prepared by coprecipitation of mixed oxalates, treated at 1473 K in air, and analyzed by synchrotron X-ray diffraction in the temperature range 673 K ≤ T ≤ 1073 K at the Elettra synchrotron radiation facility located in Trieste, Italy. In the whole temperature span a boundary was found at x ∼ 0.2 between a CeO2-based solid solution (for x ≤ 0.2) and a structure where Gd2O3 microdomains grow within the CeO2 matrix, taking advantage of the similarity between Gd(3+) and Ce(4+) sizes; the existence of the boundary at x ∼ 0.2 was confirmed also by measurements of ionic conductivity performed by impedance spectroscopy. Similar to what observed at room temperature, the trend of the cell parameter shows the presence of a maximum; with increasing temperature, the composition corresponding to the maximum moves toward lower Gd content. This evidence can be explained by analyzing the behavior of the coefficient of thermal expansion as a function of composition.

  3. High temperature phase stability in Li0.12Na0.88NbO3: A combined powder X-ray and neutron diffraction study

    NASA Astrophysics Data System (ADS)

    Mishra, S. K.; Krishna, P. S. R.; Shinde, A. B.; Jayakrishnan, V. B.; Mittal, R.; Sastry, P. U.; Chaplot, S. L.

    2015-09-01

    The phase stabilities of ecofriendly piezoelectric material of lithium doped sodium niobate for composition Li0.12Na0.88NbO3 (LNN12) have been investigated by a combination of powder X-ray and neutron diffraction techniques in the temperature range of 300-1100 K. We observed interesting changes with appearance or disappearance of the super-lattice reflections in the powder diffraction patterns. Unambiguous experimental evidence is shown for coexistence of paraelectric and ferroelectric orthorhombic phases in the temperature range of 525 K to 675 K. We identified the correct crystal structure of LNN12 with temperature and correlated it with observed anomaly in the physical properties. Identification of crystal structure also helps in the mode assignments in Raman and infrared spectroscopies. We argued that application of chemical pressure as a result of Li substitution in NaNbO3 matrix favors the freezing of zone centre phonons in contrast to the freezing of zone boundary phonons in pure NaNbO3 with the variation of temperature.

  4. Characterization of beryllium deformation using in-situ x-ray diffraction

    SciTech Connect

    Magnuson, Eric Alan; Brown, Donald William; Clausen, Bjorn; Sisneros, Thomas A.; Park, Jun-Sang

    2015-08-24

    Beryllium’s unique mechanical properties are extremely important in a number of high performance applications. Consequently, accurate models for the mechanical behavior of beryllium are required. However, current models are not sufficiently microstructure aware to accurately predict the performance of beryllium under a range of processing and loading conditions. Previous experiments conducted using the SMARTS and HIPPO instruments at the Lujan Center(LANL), have studied the relationship between strain rate and texture development, but due to the limitations of neutron diffraction studies, it was not possible to measure the response of the material in real-time. In-situ diffraction experiments conducted at the Advanced Photon Source have allowed the real time measurement of the mechanical response of compressed beryllium. Samples of pre-strained beryllium were reloaded orthogonal to their original load path to show the reorientation of already twinned grains. Additionally, the in-situ experiments allowed the real time tracking of twin evolution in beryllium strained at high rates. The data gathered during these experiments will be used in the development and validation of a new, microstructure aware model of the constitutive behavior of beryllium.

  5. Application of in situ x-ray absorption and fluorescence measurements to analyze solutions in a simulated pit

    SciTech Connect

    Isaacs, H.S.; Davenport, A.J.; Cho, J.H.; Rivers, M.L.; Sutton, S.R.

    1991-12-31

    X-ray energy-dispersive spectroscopy has been used to study the compositions of metal ions in solutions developed during localized corrosion. An electrochemical cell was designed to simulate a corrosion pit, maintaining one-dimensional diffusion and fulfilling the requirements for x-ray fluorescence measurements. The working electrode consisted of a dissolving thin foil of Type 304 stainless steel sealed between Mylar sheets through which the x-ray beam passed. Concentration gradients within the artificial pit were quantitatively determined.

  6. Application of in situ x-ray absorption and fluorescence measurements to analyze solutions in a simulated pit

    SciTech Connect

    Isaacs, H.S.; Davenport, A.J.; Cho, J.H. ); Rivers, M.L.; Sutton, S.R. . Dept. of Geophysical Sciences)

    1991-01-01

    X-ray energy-dispersive spectroscopy has been used to study the compositions of metal ions in solutions developed during localized corrosion. An electrochemical cell was designed to simulate a corrosion pit, maintaining one-dimensional diffusion and fulfilling the requirements for x-ray fluorescence measurements. The working electrode consisted of a dissolving thin foil of Type 304 stainless steel sealed between Mylar sheets through which the x-ray beam passed. Concentration gradients within the artificial pit were quantitatively determined.

  7. X-ray Coherent Diffraction Imaging of Cellulose Fibrils in Situ

    SciTech Connect

    Lal, Jyotsana; Harder, Ross J.; Makowski, Lee

    2011-01-01

    Cellulose is the most abundant renewable source of organic molecules on earth[1]. As fossil fuel reserves become depleted, the use of cellulose as a feed stock for fuels and chemicals is being aggressively explored. Cellulose is a linear polymer of glucose that packs tightly into crystalline fibrils that make up a substantial proportion of plant cell walls. Extraction of the cellulose chains from these fibrils in a chemically benign process has proven to be a substantial challenge [2]. Monitoring the deconstruction of the fibrils in response to physical and chemical treatments would expedite the development of efficient processing methods. As a step towards achieving that goal, we here describe Bragg-coherent diffraction imaging (CDI) as an approach to producing images of cellulose fibrils in situ within vascular bundles from maize.

  8. Phthalic acid complexation and the dissolution of forsteritic glass studied via in situ FTIR and X-ray scattering

    NASA Astrophysics Data System (ADS)

    Morris, Peter M.; Wogelius, Roy A.

    2008-04-01

    Multiple Internal Reflection Fourier Transform Infra-Red (MIR-FTIR) spectroscopy was developed and used for in situ flow-through experiments designed to study the process of organic acid promoted silicate dissolution. In tandem with the FTIR analysis, ex situ X-ray scattering was used to perform detailed analyses of the changes in the surface structure and chemistry resulting from the dissolution process. Phthalic acid and forsteritic glass that had been Chemically Vapour Deposited (CVD) onto an internal reflection element were used as reactants, and the MIR-FTIR results showed that phthalic acid may promote dissolution by directly binding to exposed Mg metal ion centers on the solid surface. Integrated infrared absorption intensity as a function of time shows that phthalic acid attachment apparently follows a t1/2 dependence, indicating that attachment is a diffusive process. The diffusion coefficient of phthalic acid was estimated to be approximately 7 × 10 -6 cm 2 s -1 in the solution near the interface with the glass. Shifts in the infrared absorption structure of the phthalate complexed with the surface compared to the solute species indicate that phthalate forms a seven-membered ring chelate complex. This bidentate complex efficiently depletes Mg from the glass surface, such that after reaction as much as 95% of the Mg may be removed. Surface depletion in Mg causes adsorbate density to fall after an initial attachment stage for the organic ligand. In addition, the infrared analysis shows that silica in the near surface polymerizes after Mg removal, presumably to maintain charge balance. X-ray reflectivity shows that the dissolution rate of forsteritic glass at pH 4 based on Mg removal in such flow-through experiments was equal to 4 × 10 -12 mol cm -2 s -1 (geometric surface area normalized). Reflectivity also shows how the surface mass density decreases during reaction from 2.64 g cm -3 to 2.2 g cm -3, consistent with preferential loss of Mg from the

  9. An in situ sample environment reaction cell for spatially resolved x-ray absorption spectroscopy studies of powders and small structured reactors

    SciTech Connect

    Zhang, Chu; Gustafson, Johan; Merte, Lindsay R.; Evertsson, Jonas; Norén, Katarina; Carlson, Stefan; Svensson, Håkan; Carlsson, Per-Anders

    2015-03-15

    An easy-to-use sample environment reaction cell for X-ray based in situ studies of powders and small structured samples, e.g., powder, pellet, and monolith catalysts, is described. The design of the cell allows for flexible use of appropriate X-ray transparent windows, shielding the sample from ambient conditions, such that incident X-ray energies as low as 3 keV can be used. Thus, in situ X-ray absorption spectroscopy (XAS) measurements in either transmission or fluorescence mode are facilitated. Total gas flows up to about 500 ml{sub n}/min can be fed while the sample temperature is accurately controlled (at least) in the range of 25–500 °C. The gas feed is composed by a versatile gas-mixing system and the effluent gas flow composition is monitored with mass spectrometry (MS). These systems are described briefly. Results from simultaneous XAS/MS measurements during oxidation of carbon monoxide over a 4% Pt/Al{sub 2}O{sub 3} powder catalyst are used to illustrate the system performance in terms of transmission XAS. Also, 2.2% Pd/Al{sub 2}O{sub 3} and 2% Ag − Al{sub 2}O{sub 3} powder catalysts have been used to demonstrate X-ray absorption near-edge structure (XANES) spectroscopy in fluorescence mode. Further, a 2% Pt/Al{sub 2}O{sub 3} monolith catalyst was used ex situ for transmission XANES. The reaction cell opens for facile studies of structure-function relationships for model as well as realistic catalysts both in the form of powders, small pellets, and coated or extruded monoliths at near realistic conditions. The applicability of the cell for X-ray diffraction measurements is discussed.

  10. In situ phase separation following dehydration in bimetallic sulfates: a variable-temperature X-ray diffraction study.

    PubMed

    Swain, Diptikanta; Guru Row, Tayur N

    2009-08-03

    Phase separation resulting in a single-crystal-single-crystal transition accompanied by a polycrystalline phase following the dehydration of hydrated bimetallic sulfates [Na(2)Mn(1.167)(SO(4))(2)S(0.33)O(1.167) x 2 H(2)O and K(4)Cd(3)(SO(4))(5) x 3 H(2)O] has been investigated by in situ variable-temperature single-crystal X-ray diffraction. With two examples, we illustrate the possibility of generating structural frameworks following dehydration in bimetallic sulfates, which refer to the possible precursor phases at that temperature leading to the mineral formation. The room-temperature structure of Na(2)Mn(1.167)(SO(4))(2)S(0.33)O(1.167) x 2 H(2)O is trigonal, space group R3. On heating the crystal in situ on the diffractometer, the diffraction images display spherical spots and concentric rings suggesting phase separation, with the spherical spots getting indexed in a monoclinic space group, C2/c. The structure determination based on this data suggests the formation of Na(2)Mn(SO(4))(2). However, the diffraction images from concentric rings could not be indexed. In the second example, the room-temperature structure is determined to be K(4)Cd(3)(SO(4))(5) x 3 H(2)O, crystallizing in a monoclinic space group, P2(1)/n. On heating the crystal in situ, the diffraction images collected also have both spherical spots and diffuse rings. The spherical spots could be indexed to a cubic crystal system, space group P2(1)3, and the structure is K(2)Cd(2)(SO(4))(3). The possible mechanism for the phase transition in the dehydration regime resulting in this remarkable single-crystal to single-crystal transition with the appearance of a surrogate polycrystalline phase is proposed.

  11. In-situ Synchrotron X-ray Diffraction Analysis of the Setting Process of Brushite Cement: Reaction and Crystal Growth.

    PubMed

    Luo, Jun; Martinez-Casado, Francisco Javier; Balmes, Olivier; Yang, Jiaojiao; Persson, Cecilia; Engqvist, Håkan; Xia, Wei

    2017-09-26

    Brushite cements are fast self-setting materials that can be used as bone substitute materials. While tracing their fast setting process is a challenge, it is important for the understanding of the same, which in turn is important for the material's further development and use in the clinics. In this study, the setting rate, phase formation and crystal growth of brushite cements were quantitatively studied by in situ synchrotron powder X-ray diffraction (SXRD) on a time scale of seconds. The influence of reactant ratios and a retardant (citric acid) on the setting reaction were analyzed. To complement the in situ investigations, scanning electron microscopy (SEM) was carried out for ex situ morphological evolution of crystals. The initial reaction followed a four-step process including a fast nucleation induction period, nucleation, crystal growth, and completion of the setting. The brushite crystal size grew up to micro scale within 1 min and the brushite content increased linearly after the nucleation until all MCPM (monocalcium phosphate monohydrate; Ca(H2PO4)2ˑH2O) had dissolved within minutes, followed by a slow increase until the end of the monitoring. By adjusting the MCPM to β-TCP (β-tricalcium phosphate; β-Ca3(PO4)2) ratio in the starting powders, the brushite/monetite ratio in the cements could be modified. In the presence of citric acid, the formation of brushite nuclei was not significantly retarded, while the increase in brushite content and the growth of crystal size were effectively hindered. The amount of monetite also increased by adding citric acid. This is the first time that the brushite setting process has been characterized in the first seconds and minutes of the reaction by SXRD.

  12. In situ investigation of working battery electrodes using synchrotron x-ray diffraction

    SciTech Connect

    Jisrawi, N.M.; Thurston, T.R.; Yang, X.Q.

    1996-12-31

    The results of an in situ investigation of the structural changes that occur during the operation of working battery electrodes using synchrotron radiation are presented. Two types of electrodes were investigated: an AB{sub 2}-type Laves phase alloy anode with the composition Zr{sub x}Ti{sub 1-x}M{sub 2} and a proprietary cell based on a Li{sub x}Mn{sub 2}O{sub 4} spinel compound cathode made by Gould electronics. For the Laves phase alloy compositions with x=0.25 and 0.5 and M=V{sub 0.5}N{sub 1.1}Mn{sub 0.2}Fe{sub 0.2} were examined. Cells made from two different batches of Li{sub x}Mn{sub 2}O{sub 4} material were investigated. The relationships between battery performance and structural changes will be discussed. In the later case, we also discuss the role of over-discharging on the Li{sub x}Mn{sub 2}O{sub 4} structure and on battery operation.

  13. In-situ small-angle x-ray scattering study of nanoparticles in the plasma plume induced by pulsed laser irradiation of metallic targets

    SciTech Connect

    Lavisse, L.; Jouvard, J.-M.; Girault, M.; Potin, V.; Andrzejewski, H.; Marco de Lucas, M. C.; Bourgeois, S.; Le Garrec, J.-L.; Carles, S.; Mitchell, J. B. A.; Hallo, L.; Perez, J.; Decloux, J.

    2012-04-16

    Small angle x-ray scattering was used to probe in-situ the formation of nanoparticles in the plasma plume generated by pulsed laser irradiation of a titanium metal surface under atmospheric conditions. The size and morphology of the nanoparticles were characterized as function of laser irradiance. Two families of nanoparticles were identified with sizes on the order of 10 and 70 nm, respectively. These results were confirmed by ex-situ transmission electron microscopy experiments.

  14. Effect of hydration on the structure of solid-supported Niosomal membranes investigated by in situ energy dispersive X-ray diffraction

    NASA Astrophysics Data System (ADS)

    Caracciolo, Giulio; Pozzi, Daniela; Caminiti, Ruggero; Marianecci, Carlotta; Moglioni, Simone; Carafa, Maria; Amenitsch, Heinz

    2008-09-01

    The supramolecular structure of Niosomal vesicles (Niosomes) made of a binary mixture of polysorbate 20 (Tween 20) and Cholesterol in aqueous solution was investigated by means of synchrotron small angle X-ray scattering (SAXS). Solid-supported Niosomal membranes at full hydration exhibit the same structural properties, as determined by in situ energy dispersive X-ray diffraction (EDXD), than their counterpart in solution. Both Niosomes and solid-supported Niosomal membranes are made of highly swollen bilayers rich in Tween 20 coexisting with Cholesterol crystallites. EDXD patterns from oriented samples suggest that at least some Cholesterol crystals are aligned along the normal to the solid support.

  15. In situ X-ray diffraction measurement of the hydrogenation and dehydrogenation of aluminum and characterization of the recovered AlH3

    NASA Astrophysics Data System (ADS)

    Saitoh, H.; Sakurai, Y.; Machida, A.; Katayama, Y.; Aoki, K.

    2010-03-01

    Pristine aluminum was hydrogenated to form AlH3 at 8.9 GPa and 600 °C. The cyclic formation and decomposition of the hydride were measured by in situ synchrotron X-ray diffraction measurement. AlH3 synthesized under high pressure and temperature was recovered at ambient conditions. The recovered AlH3 was characterized by conventional powder X-ray diffraction measurement and Raman spectroscopy. The results of the characterization were consistent with that obtained for chemically prepared AlH3 and indicated that single phase α-AlH3 was obtained.

  16. Structural characterization of irreversibly adsorbed polymer layers at the polymer/solid interface - In-situ grazing incidence angle x-ray scattering studies

    NASA Astrophysics Data System (ADS)

    Jiang, Naisheng; Chen, Fen; Chen, Xiameng; Han, Zexi; Liang, Chen; Gin, Peter; Asada, Mitsunori; Endoh, Maya; Koga, Tad

    2012-02-01

    In recent years, great attention has been paid to irreversibly adsorbed polymer layers formed on solid substrates since they can modify various properties of polymeric materials confined at the nanometer scale. In this talk, by the combined use of in-situ grazing incidence small angle x-ray scattering and x-ray reflectivity techniques, we aim to characterize the detailed structures of the adsorbed layers composed of different homopolymers (polystyrene, polybutadiene, poly (ethylene oxide), and poly (methyl methacrylate)) prepared on silicon substrates. We will highlight the generality/differences in the structures, leading to a better understanding of the formation process of the adsorbed layers at the impenetrable solid interfaces.

  17. (De)lithiation mechanism of Li/SeS(x) (x = 0-7) batteries determined by in situ synchrotron X-ray diffraction and X-ray absorption spectroscopy.

    PubMed

    Cui, Yanjie; Abouimrane, Ali; Lu, Jun; Bolin, Trudy; Ren, Yang; Weng, Wei; Sun, Chengjun; Maroni, Victor A; Heald, Steve M; Amine, Khalil

    2013-05-29

    Electrical energy storage for transportation has gone beyond the limit of converntional lithium ion batteries currently. New material or new battery system development is an alternative approach to achieve the goal of new high-energy storage system with energy densities 5 times or more greater. A series of SeSx-carbon (x = 0-7) composite materials has been prepared and evaluated as the positive electrodes in secondary lithium cells with ether-based electrolyte. In situ synchrotron high-energy X-ray diffraction was utilized to investigate the crystalline phase transition during cell cycling. Complementary, in situ Se K-edge X-ray absorption near edge structure analysis was used to track the evolution of the Se valence state for both crystalline and noncrystalline phases, including amorphous and electrolyte-dissolved phases in the (de)lithiation process. On the basis of these results, a mechanism for the (de)lithiation process is proposed, where Se is reduced to the polyselenides, Li2Sen (n ≥ 4), Li2Se2, and Li2Se sequentially during the lithiation and Li2Se is oxidized to Se through Li2Sen (n ≥ 4) during the delithiation. In addition, X-ray photoelectron spectroscopy and electrochemical impedance spectroscopy demonstrated the reversibility of the Li/Se system in ether-based electrolyte and the presence of side products in the carbonate-based electrolytes. For Li/SeS2 and Li/SeS7 cells, Li2Se and Li2S are the discharged products with the presence of Se only as the crystalline phase in the end of charge.

  18. Electrochemical (de)lithiation of silver ferrite and composites: mechanistic insights from ex situ, in situ, and operando X-ray techniques

    DOE PAGES

    Durham, Jessica L.; Brady, Alexander B.; Cama, Christina A.; ...

    2017-08-02

    Here, the structure of pristine AgFeO2 and phase makeup of Ag0.2FeO1.6 (a one-pot composite comprised of nanocrystalline stoichiometric AgFeO2 and amorphous γ-Fe2O3 phases) was investigated using synchrotron x-ray diffraction. A new stacking-fault model was proposed for AgFeO2 powder synthesized using the co-precipitation method. The lithiation/de-lithiation mechanisms of silver ferrite, AgFeO2 and Ag0.2FeO1.6 were investigated using ex-situ, in-situ, and operando characterization techniques. An amorphous γ-Fe2O3 component in the Ag0.2FeO1.6 sample is quantified. Operando XRD of electrochemically reduced AgFeO2 and Ag0.2FeO1.6 composites demonstrated differences in the structural evolution of the nanocrystalline AgFeO2 component. As complimentary techniques to XRD, ex-situ x-ray Absorption Spectroscopymore » (XAS) provided insight into the short-range structure of the (de)lithiated nanocrystalline electrodes, and a novel in-situ high energy x-ray fluorescence nanoprobe (HXN) mapping measurement was applied to spatially resolve the progression of discharge. Based on the results, a redox mechanism is proposed where the full reduction of Ag+ to Ag0 and partial reduction of Fe3+ to Fe2+ occur on reduction to 1.0 V, resulting in a Li1+yFeIIIFeIIyO2 phase. The Li1+yFeIIIFeIIyO2 phase can then reversibly cycle between Fe3+ and Fe2+ oxidation states, permitting good capacity retention over 50 cycles. In the Ag0.2FeO1.6 composite, a substantial amorphous γ-Fe2O3 component is observed which discharges to rock salt LiFe2O3 and Fe0 metal phase in the 3.5 – 1.0 V voltage range (in parallel with the AgFeO2 mechanism), and reversibly reoxidizes to a nanocrystalline iron oxide phase.« less

  19. Investigations of the crystallization mechanism of CrSb and CrSb2 multilayered films using in-situ X-ray diffraction and in-situ X-ray reflectometry

    NASA Astrophysics Data System (ADS)

    Regus, Matthias; Kuhn, Gerhard; Mankovsky, Sergej; Ebert, Hubert; Bensch, Wolfgang

    2012-12-01

    Chromium and antimony multilayered films with variable elemental layer thickness were deposited on (1 0 0)-Si substrate cooled with liquid nitrogen. The stoichiometry of the films was adjusted to Cr:Sb=1:1 and 1:2. The thickness of Cr-Sb repeating units of these multifilms was varied between 11.4 and 102.5 Å. Satellite maxima in the X-ray reflectivity curves observed for films in the as-deposited state demonstrate an alternating stacking of the evaporated elements. The reactivity of the superlattice reactants was investigated with temperature dependent in-situ X-ray diffractometry and X-ray reflectometry. The crystallization temperature of CrSb depends on the double-layer thickness and is about 90 °C for a Cr:Sb ratio of 1:1 and double-layer thickness of 53.7 Å where nucleation and crystal formation occurs at the element interfaces, while for a thin double-layer thickness (11.4 Å) first interdiffusion of the elements occurs before crystallization starts, i.e., an amorphous intermediate is formed prior to crystallization of CrSb. A decomposition reaction into CrSb2 occurs at about 230 °C, and up to about 575 °C, CrSb, CrSb2 and amorphous Cr coexist. For the ratio Cr:Sb=1:2 and a thin double-layer thickness prior to crystallization of CrSb2 nano-sized crystallites with a composition near CrSb2 nucleate and grow. These crystallites are then successively transformed in long-range ordered crystals exhibiting a pronounced preferred orientation. For films with a thicker repeat unit first formation of CrSb is observed which then reacts with elemental Sb yielding crystalline CrSb2. An activation energy for interdiffusion of Cr and Sb of about 1.8 eV is estimated for a film with Cr:Sb=1:1 exhibiting a double-layer thickness of about 53.7 Å and an energy for crystal growth of about 1.1 eV. For the film with the thinner double-layer thickness of 11.4 Å a lower value of the activation energy for interdiffusion is obtained. For CrSb2 the energy for crystal growth is

  20. Investigations of the crystallization mechanism of CrSb and CrSb{sub 2} multilayered films using in-situ X-ray diffraction and in-situ X-ray reflectometry

    SciTech Connect

    Regus, Matthias; Kuhn, Gerhard; Mankovsky, Sergej; Ebert, Hubert; Bensch, Wolfgang

    2012-12-15

    Chromium and antimony multilayered films with variable elemental layer thickness were deposited on (1 0 0)-Si substrate cooled with liquid nitrogen. The stoichiometry of the films was adjusted to Cr:Sb=1:1 and 1:2. The thickness of Cr-Sb repeating units of these multifilms was varied between 11.4 and 102.5 A. Satellite maxima in the X-ray reflectivity curves observed for films in the as-deposited state demonstrate an alternating stacking of the evaporated elements. The reactivity of the superlattice reactants was investigated with temperature dependent in-situ X-ray diffractometry and X-ray reflectometry. The crystallization temperature of CrSb depends on the double-layer thickness and is about 90 Degree-Sign C for a Cr:Sb ratio of 1:1 and double-layer thickness of 53.7 A where nucleation and crystal formation occurs at the element interfaces, while for a thin double-layer thickness (11.4 A) first interdiffusion of the elements occurs before crystallization starts, i.e., an amorphous intermediate is formed prior to crystallization of CrSb. A decomposition reaction into CrSb{sub 2} occurs at about 230 Degree-Sign C, and up to about 575 Degree-Sign C, CrSb, CrSb{sub 2} and amorphous Cr coexist. For the ratio Cr:Sb=1:2 and a thin double-layer thickness prior to crystallization of CrSb{sub 2} nano-sized crystallites with a composition near CrSb{sub 2} nucleate and grow. These crystallites are then successively transformed in long-range ordered crystals exhibiting a pronounced preferred orientation. For films with a thicker repeat unit first formation of CrSb is observed which then reacts with elemental Sb yielding crystalline CrSb{sub 2}. An activation energy for interdiffusion of Cr and Sb of about 1.8 eV is estimated for a film with Cr:Sb=1:1 exhibiting a double-layer thickness of about 53.7 A and an energy for crystal growth of about 1.1 eV. For the film with the thinner double-layer thickness of 11.4 A a lower value of the activation energy for interdiffusion is

  1. Room temperature redox reaction by oxide ion migration at carbon/Gd-doped CeO2 heterointerface probed by an in situ hard x-ray photoemission and soft x-ray absorption spectroscopies

    PubMed Central

    Tsuchiya, Takashi; Miyoshi, Shogo; Yamashita, Yoshiyuki; Yoshikawa, Hideki; Terabe, Kazuya; Kobayashi, Keisuke; Yamaguchi, Shu

    2013-01-01

    In situ hard x-ray photoemission spectroscopy (HX-PES) and soft x-ray absorption spectroscopy (SX-XAS) have been employed to investigate a local redox reaction at the carbon/Gd-doped CeO2 (GDC) thin film heterointerface under applied dc bias. In HX-PES, Ce3d and O1s core levels show a parallel chemical shift as large as 3.2 eV, corresponding to the redox window where ionic conductivity is predominant. The window width is equal to the energy gap between donor and acceptor levels of the GDC electrolyte. The Ce M-edge SX-XAS spectra also show a considerable increase of Ce3+ satellite peak intensity, corresponding to electrochemical reduction by oxide ion migration. In addition to the reversible redox reaction, two distinct phenomena by the electrochemical transport of oxide ions are observed as an irreversible reduction of the entire oxide film by O2 evolution from the GDC film to the gas phase, as well as a vigorous precipitation of oxygen gas at the bottom electrode to lift off the GDC film. These in situ spectroscopic observations describe well the electrochemical polarization behavior of a metal/GDC/metal capacitor-like two-electrode cell at room temperature. PMID:27877594

  2. Solid state synthesis of layered sodium manganese oxide for sodium-ion battery by in-situ high energy X-ray diffraction and X-ray absorption near edge spectroscopy

    NASA Astrophysics Data System (ADS)

    Ma, Tianyuan; Xu, Gui-Liang; Zeng, Xiaoqiao; Li, Yan; Ren, Yang; Sun, Chengjun; Heald, Steve M.; Jorne, Jacob; Amine, Khalil; Chen, Zonghai

    2017-02-01

    In situ high energy X-ray diffraction (HEXRD) and in situ X-ray absorption near edge spectroscopy (XANES) were carried out to understand the solid state synthesis of NaxMnO2, with particular interest on the synthesis of P2 type Na2/3MnO2. It was found that there were multi intermediate phases formed before NaMnO2 appeared at about 600 °C. And the final product after cooling process is a combination of O‧3 NaMnO2 with P2 Na2/3MnO2. A P2 type Na2/3MnO2 was synthesized at reduced temperature (600 °C). The influence of Na2CO3 impurity on the electrochemical performance of P2 Na2/3MnO2 was thoroughly investigated in our work. It was found that the content of Na2CO3 can be reduced by optimizing Na2CO3/MnCO3 ratio during the solid state reaction or other post treatment such as washing with water. We expected our results could provide a good guide for future development of high performance cathode materials for sodium-ion batteries.

  3. In situ X-ray diffraction and the evolution of polarization during the growth of ferroelectric superlattices

    SciTech Connect

    Bein, Benjamin; Hsing, Hsiang-Chun; Callori, Sara J.; Sinsheimer, John; Chinta, Priya V.; Headrick, Randall L.; Dawber, Matthew

    2015-12-04

    In the epitaxially strained ferroelectric thin films and superlattices, the ferroelectric transition temperature can lie above the growth temperature. Ferroelectric polarization and domains should then evolve during the growth of a sample, and electrostatic boundary conditions may play an important role. In this work, ferroelectric domains, surface termination, average lattice parameter and bilayer thickness are simultaneously monitored using in situ synchrotron X-ray diffraction during the growth of BaTiO3/SrTiO3 superlattices on SrTiO3 substrates by off-axis radio frequency magnetron sputtering. The technique used allows for scan times substantially faster than the growth of a single layer of material. Effects of electric boundary conditions are investigated by growing the same superlattice alternatively on SrTiO3 substrates and 20 nm SrRuO3 thin films on SrTiO3 substrates. Our experiments provide important insights into the formation and evolution of ferroelectric domains when the sample is ferroelectric during the growth process.

  4. Aqueous Cu(II)-organic complexation studied in situ using soft X-ray and vibrational spectroscopies.

    PubMed

    Phillips, Courtney L; Regier, Tom Z; Peak, Derek

    2013-12-17

    In situ aqueous solutions containing copper-ligand mixtures were measured at the Cu L-edge using X-ray absorption near edge structure (XANES) and with attenuated total reflectance infrared (ATR-FTIR) spectroscopies. Copper complexation with environmentally relevant ligands such as EDTA, citrate, and malate provided a bridge between spectroscopic studies and general environmental behavior and will allow for future study of complex environmental samples. XANES results show that the lowest unoccupied molecular orbital (LUMO) energy is governed by the ligand field strength and is related to Lewis acid/base properties of the ligand functional groups. Complementary ATR-FTIR studies confirmed the importance of water molecules in the structure of these Cu-ligand complexes and provided in-depth structural analysis to support the XANES data. Copper-malate is shown to have a 5/6-O-ring structure, and Cu-ethylenediaminetetraacetate has pentadentate coordination. Cu L-edge XANES also revealed direct Cu-N coordination in these aqueous solutions with amide functional groups.

  5. Early stages of TiN thin film growth probed using in-situ soft X-ray absorption spectroscopy

    NASA Astrophysics Data System (ADS)

    Gupta, Rachana; Gupta, Mukul; Phase, D. M.

    2017-05-01

    In this work, we studied the growth behavior of TiN thin films prepared using a direct current magnetron sputtering (dcMS) process. First, we prepared a series of TiN thin films by varying the amount of reactive nitrogen gas flow (RN2) during sputtering. We find that such variation leads to a systematic increase in the number density of deposited film, confirming the formation of titanium mononitride (TiN) phase having orientation along (111) plane. We also observed that the deposition rate decreases significantly as RN2 increases. Recently, theoretical and experimental reports on TiN thin films suggested that the early stages of film growth can be different than those of thick films. In order to study the early stages of film growth we did in-situ N K-edge and Ti L-edge soft x-ray absorption (XAS) measurements. Our XAS measurements suggest that the hybridization of Ti and N orbitals is significantly different in the initial stages of film growth; characterized by a variation in the hybridization between unoccupied N 2p state with Ti 3d state. The origin of such behavior needs to investigated and could be due to a competitive grain growth taking along (001) and (111) direction in the early stages as suggested in theoretical calculations.

  6. In situ MEMS testing: correlation of high-resolution X-ray diffraction with mechanical experiments and finite element analysis.

    PubMed

    Schifferle, Andreas; Dommann, Alex; Neels, Antonia

    2017-01-01

    New methods are needed in microsystems technology for evaluating microelectromechanical systems (MEMS) because of their reduced size. The assessment and characterization of mechanical and structural relations of MEMS are essential to assure the long-term functioning of devices, and have a significant impact on design and fabrication. Within this study a concept for the investigation of mechanically loaded MEMS materials on an atomic level is introduced, combining high-resolution X-ray diffraction (HRXRD) measurements with finite element analysis (FEA) and mechanical testing. In situ HRXRD measurements were performed on tensile loaded single crystal silicon (SCSi) specimens by means of profile scans and reciprocal space mapping (RSM) on symmetrical (004) and (440) reflections. A comprehensive evaluation of the rather complex XRD patterns and features was enabled by the correlation of measured with simulated, 'theoretical' patterns. Latter were calculated by a specifically developed, simple and fast approach on the basis of continuum mechanical relations. Qualitative and quantitative analysis confirmed the admissibility and accuracy of the presented method. In this context [001] Poisson's ratio was determined providing an error of less than 1.5% with respect to analytical prediction. Consequently, the introduced procedure contributes to further going investigations of weak scattering being related to strain and defects in crystalline structures and therefore supports investigations on materials and devices failure mechanisms.

  7. In situ and real-time analysis of the growth and interaction of equiaxed grains by synchrotron X- ray radiography

    NASA Astrophysics Data System (ADS)

    Bogno, A.; Nguyen-Thi, H.; Billia, B.; Reinhart, G.; Mangelinck-Noël, N.; Bergeon, N.; Schenk, T.; Baruchel, J.

    2012-01-01

    The phenomena involved during equiaxed growth are dynamic, so that in situ and real-time investigation by X-ray imaging is compulsory to fully analyse the microstructure formation. The experiments on Al - 10 wt% Cu alloy of this paper are carried out at the European Synchrotron Radiation Facility (ESRF) in Grenoble (France). Equiaxed growth was achieved in nearly isothermal conditions and continuously monitored from the very early stages of solidification to an asymptotic state. First, measurements of dendrite arms velocity for a same grain showed slight differences in the early stages of the growth. This effect is attributed to a gravity-related "self - poisoning" of the grain. Then, the propagation of primary dendrite arms was analysed and two successive growth regimes were observed. First, due to the relative distance with neighbour grains, each grain could be considered as isolated (i.e. growing freely) and tip growth rate gradually increased. In a subsequent phase, tip growth rate slowly decreased towards zero, due to the proximity of neighbouring grains. Using an image analysis technique, we were able to measure the solute profiles in the liquid phase between interacting arms. These measurements confirmed that solutal impingement is responsible for stopping the grain growth.

  8. In situ x-ray scattering study of Ag island growth on Si(111)7 ×7

    NASA Astrophysics Data System (ADS)

    Chen, Yiyao; Gramlich, M. W.; Hayden, S. T.; Miceli, P. F.

    2016-07-01

    We report on the epitaxial relationship between Ag and the Si(111)7 ×7 substrate where the wetting layer and the emergence of islands was investigated using in situ x-ray scattering with a combination of grazing incidence diffraction, specular reflectivity, and crystal truncation rod measurements. The atomic-scale structure of the wetting layer evolves continuously with coverage until a transition where it ceases to change its structure concomitantly with the appearance of islands. The islands are observed to reside on the Si(111)7 ×7 and, although the minimum average island height is three atomic layers of face-centered-cubic Ag, the average island height depends on the coverage and temperature. The majority of the Ag islands are oriented along the symmetry-equivalent Si crystallographic axes and a minority population of islands are rotated by 15 .7∘ . A coincidence-site lattice model is used to show that kinetic considerations lead to the observed island orientations.

  9. Direct Observations of Rapid Diffusion of Cu in Au Thin Films using In-Situ X-ray Diffraction

    SciTech Connect

    Elmer, J W; Palmer, T A; Specht, E D

    2005-11-28

    In-situ x-ray diffraction was performed while annealing thin-film Au/Cu binary diffusion couples to directly observe diffusion at elevated temperatures. The temperature dependence of the interdiffusion coefficient was determined from isothermal measurements at 700 C, 800 C, and 900 C, where Cu and Au form a disordered continuous face centered cubic solid solution. Large differences in the lattice parameters of Au and Cu allowed the initial diffraction peaks to be easily identified, and later tracked as they merged into one diffraction peak with increased diffusion time. Initial diffusion kinetics were studied by measuring the time required for the Cu to diffuse through the Au thin film of known thickness. The activation energy for interdiffusion was measured to be 65.4 kJ/mole during this initial stage, which is approximately 0.4x that for bulk diffusion and 0.8x that for grain boundary diffusion. The low activation energy is attributed to the high density of columnar grain boundaries combined with other defects in the sputter deposited thin film coatings. As interdiffusion continues, the two layers homogenize with an activation energy of 111 kJ/mole during the latter stages of diffusion. This higher activation energy falls between the reported values for grain boundary and bulk diffusion, and may be related to grain growth occurring at these temperatures which accounts for the decreasing importance of grain boundaries on diffusion.

  10. Observation of in situ oxidation dynamics of vanadium thin film with ambient pressure X-ray photoemission spectroscopy

    NASA Astrophysics Data System (ADS)

    Kim, Geonhwa; Yoon, Joonseok; Yang, Hyukjun; Lim, Hojoon; Lee, Hyungcheol; Jeong, Changkil; Yun, Hyungjoong; Jeong, Beomgyun; Crumlin, Ethan; Lee, Jouhahn; Lee, Jaeyoung; Ju, Honglyoul; Mun, Bongjin Simon

    2016-11-01

    The evolution of oxidation/reduction states of vanadium oxide thin film was monitored in situ as a function of oxygen pressure and temperature via ambient pressure X-ray photoemission spectroscopy. Spectra analysis showed that VO2 can be grown at a relatively low temperature, T ˜ 523 K, and that V2O5 oxide develops rapidly at elevated oxygen pressure. Raman spectroscopy was applied to confirm the formation of VO2 oxide inside of the film. In addition, the temperature-dependent resistivity measurement on the grown thin film, e.g., 20 nm exhibited a desirable metal-insulator transition of VO2 with a resistivity change of ˜1.5 × 103 times at 349.3 K, displaying typical characteristics of thick VO2 film, e.g., 100 nm thick. Our results not only provide important spectroscopic information for the fabrication of vanadium oxides, but also show that high quality VO2 films can be formed at relatively low temperature, which is highly critical for engineering oxide film for heat-sensitive electronic devices.

  11. Measurement of Sn and In Solidification Undercooling and Lattice Expansion Using In Situ X-Ray Diffraction

    SciTech Connect

    Elmer, John W.; Specht, Eliot D.

    2010-12-15

    The solidification behavior of two low-melting-point metals, Sn and In, on three substrates has been examined using in situ x-ray diffraction. Undercoolings of up to 56.1°C were observed for Sn solidified on graphite, which is a non-wetting substrate, while lower undercoolings were observed for Sn on Au/Ni/Cu (17.3°C) and on Cu (10.5°C). Indium behaved quite differently, showing undercoolings of less than 4°C on all three substrates. The lattice expansion/contraction behavior of Sn, In, and intermetallic compounds (IMCs) that formed during the reaction of Sn with Au/Ni/Cu surfaces were also measured during heating and cooling. Results showed anisotropic and nonlinear expansion of both Sn and In, with a contraction, rather than expansion, of the basal planes of In during heating. The principal IMC that formed between Sn and the Au/Ni/Cu surface was characterized as Cu6Sn5, having an average expansion coefficient of 13.6 × 10₋6/°C, which is less than that of Sn or Cu.

  12. In situ X-ray diffraction and the evolution of polarization during the growth of ferroelectric superlattices

    PubMed Central

    Bein, Benjamin; Hsing, Hsiang-Chun; Callori, Sara J.; Sinsheimer, John; Chinta, Priya V.; Headrick, Randall L.; Dawber, Matthew

    2015-01-01

    In epitaxially strained ferroelectric thin films and superlattices, the ferroelectric transition temperature can lie above the growth temperature. Ferroelectric polarization and domains should then evolve during the growth of a sample, and electrostatic boundary conditions may play an important role. In this work, ferroelectric domains, surface termination, average lattice parameter and bilayer thickness are simultaneously monitored using in situ synchrotron X-ray diffraction during the growth of BaTiO3/SrTiO3 superlattices on SrTiO3 substrates by off-axis radio frequency magnetron sputtering. The technique used allows for scan times substantially faster than the growth of a single layer of material. Effects of electric boundary conditions are investigated by growing the same superlattice alternatively on SrTiO3 substrates and 20 nm SrRuO3 thin films on SrTiO3 substrates. These experiments provide important insights into the formation and evolution of ferroelectric domains when the sample is ferroelectric during the growth process. PMID:26634894

  13. In Situ X-ray Diffraction Studies of Metastable Phase Formation in Fe83B17 using Electrostatic Levitation

    NASA Astrophysics Data System (ADS)

    Quirinale, Dante G.; Rustan, Gustav E.; Kreyssig, Andreas; Goldman, Alan I.

    2015-03-01

    The Fe-B system has been broadly studied for its use in magnetic materials as well as its ready glass forming ability, yet the nature of the metastable structures commonly resulting from devitrification is not well understood. The solidification of eutectic Fe83B17 into both the metastable Fe23B6 and the stable Fe2B phases was probed in situ at Beamline 6-ID-D, Advanced Photon Source. Using a combination of high-energy x-ray diffraction and containerless processing via electrostatic levitation and laser heating, high-framerate structural information was obtained from the undercooled liquid through solidification and solid-solid phase transitions during cooling. The results of quantitative sequential Rietveld refinements will be presented and compared with observations in similar materials. This work was supported by the National Science Foundation under Grants No. DMR-1308099 and DMR-0817157. The work at Ames Laboratory was supported by the US DOE, Office of Basic Energy Sciences, Division of Materials Sciences and Engineering through Contract No. DE-AC02-07CH11358. This research used resources of the Advanced Photon Source, a US DOE Office of Science User Facility.

  14. Sound velocities of mantle and subducted slab lithologies: Constraints from combined in situ X-ray and ultrasonic measurements

    NASA Astrophysics Data System (ADS)

    Irifune, T.; Higo, Y.; Kono, Y.; Inoue, T.; Funakoshi, K.

    2007-12-01

    We have developed techniques to precisely measure the sound velocities of high-pressure phases at pressures to 22 GPa and temperatures to 1800K using a combination of synchrotron in situ X-ray and ultrasonic measurements with a Kawai-type multianvil apparatus. Using these techniques, we measured the sound velocities of ringwoodite and majorite in a pyrolite composition , as well as those of MORB in the garnetite facies (majorite + minor stishovite). We found quite strong non-linear decreases of Vp and Vs with temperature, particularly for Vs in majorite, under these P, T conditions of the mantle transition region (MTR). Our results suggest that pyrolite yields seismic velocities consistent with typical seismological models for the MTR, except for the bottom part of this region, whereas piclogite or basalt compositions may lead to velocities substantially lower than those seismologically derived. In contrast, harzburgite would better fit to the seismological models in the lower half of the mantle transition region, provided that the geotherm in this region is of adiabatic, which may be due to accumulation of main bodies of stagnant slabs (depleted peridotite or harzburgite) near the 660 km discontinuity.

  15. Automated scanning electron microscopy and x-ray microanalysis for in situ quantification of gadolinium deposits in skin.

    PubMed

    Thakral, Charu; Abraham, Jerrold L

    2007-10-01

    Gadolinium (Gd) has been identified as a possible causative agent of an emerging cutaneous and systemic fibrosing disorder, nephrogenic systemic fibrosis (NSF), which can cause serious disability and even death. To date, there are only two known associations with this disorder--renal insufficiency and Gd enhanced magnetic resonance imaging (MRI). We developed an automated quantitative scanning electron microscopy (SEM) and Energy dispersive x-ray spectroscopy (EDS) method for Gd in tissue of NSF patients. Freshly cut paraffin block surfaces examined using the variable pressure mode under standardized conditions and random search of the tissue area allow in situ detection and semiquantitative morphometric (volumetric) analysis of insoluble higher atomic number features using backscattered electron imaging. We detected Gd ranging from 1 to 2270 cps/mm2 in 57 cutaneous biopsies of NSF. Gd was associated with P, Ca, and usually Na in tissue deposits. Our method reproducibly determines the elemental composition, relative concentration, and spatial distribution of detected features within the tissue. However, we cannot detect features below our spatial resolution, nor concentrations below the detection limit of our SEM/EDS system. The findings confirm transmetallation and release of toxic Gd ions in NSF and allow dose-response analysis at the histologic level.

  16. Temperature Assisted in-Situ Small Angle X-ray Scattering Analysis of Ph-POSS/PC Polymer Nanocomposite

    PubMed Central

    Yadav, Ramdayal; Naebe, Minoo; Wang, Xungai; Kandasubramanian, Balasubramanian

    2016-01-01

    Inorganic/organic nanofillers have been extensively exploited to impart thermal stability to polymer nanocomposite via various strategies that can endure structural changes when exposed a wide range of thermal environment during their application. In this abstraction, we have utilized temperature assisted in-situ small angle X-ray scattering (SAXS) to examine the structural orientation distribution of inorganic/organic nanofiller octa phenyl substituted polyhedral oligomeric silsesquioxane (Ph-POSS) in Polycarbonate (PC) matrix from ambient temperature to 180 °C. A constant interval of 30 °C with the heating rate of 3 °C/min was utilized to guise the temperature below and above the glass transition temperature of PC followed by thermal gravimetric, HRTEM, FESEM and hydrophobic analysis at ambient temperature. The HRTEM images of Ph-POSS nano unit demonstrated hyperrectangular structure, while FESEM image of the developed nano composite rendered separated phase containing flocculated and overlapped stacking of POSS units in the PC matrix. The phase separation in polymer nanocomposite was further substantiated by thermodynamic interaction parameter (χ) and mixing energy (Emix) gleaned via Accelrys Materials studio. The SAXS spectra has demonstrated duplex peak at higher scattering vector region, postulated as a primary and secondary segregated POSS domain and followed by abundance of secondary peak with temperature augmentation. PMID:27436152

  17. Fluid adsorption in ordered mesoporous solids determined by in situ small-angle X-ray scattering.

    PubMed

    Findenegg, Gerhard H; Jähnert, Susanne; Müter, Dirk; Prass, Johannes; Paris, Oskar

    2010-07-14

    The adsorption of two organic fluids (n-pentane and perfluoropentane) in a periodic mesoporous silica material (SBA-15) is investigated by in situ small-angle X-ray scattering (SAXS) using synchrotron radiation. Structural changes are monitored as the ordered and disordered pores in the silica matrix are gradually filled with the fluids. The experiments yield integrated peak intensities from up to ten Bragg reflections from the 2D hexagonal pore lattice, and additionally diffuse scattering contributions arising from disordered (mostly intrawall) porosity. The analysis of the scattering data is based on a separation of these two contributions. Bragg scattering is described by adopting a form factor model for ordered pores of cylindrical symmetry which accounts for the filling of the microporous corona, the formation of a fluid film at the pore walls, and condensation of the fluid in the core. The filling fraction of the disordered intrawall pores is extracted from the diffuse scattering intensity and its dependence on the fluid pressure is analyzed on the basis of a three-phase model. The data analysis introduced here provides an important generalisation of a formalism presented recently (J. Phys. Chem. C, 2009, 13, 15201), which was applicable to contrast-matching fluids only. In this way, the adsorption behaviour of fluids into ordered and disordered pores in periodic mesoporous materials can be analyzed quantitatively irrespective of the fluid density.

  18. In situ proteolysis, crystallization and preliminary X-ray diffraction analysis of a VHH that binds listeria internalin B.

    PubMed

    Huh, Ian; Gene, Robert; Kumaran, Jyothi; MacKenzie, C Roger; Brooks, Cory L

    2014-11-01

    The variable region of camelid heavy-chain antibodies produces the smallest known antibody fragment with antigen-binding capability (a VHH). The VHH R303 binds internalin B (InlB), a virulence factor expressed by the pathogen Listeria monocytogenes. InlB is critical for initiation of Listeria infection, as it binds a receptor (c-Met) on epithelial cells, triggering the entry of bacteria into host cells. InlB is surface-exposed and is required for virulence, hence a VHH targeting InlB has potential applications for pathogen detection or therapeutic intervention. Here, the expression, purification, crystallization and X-ray diffraction of R303 are reported. Crystals of R303 were obtained following in situ proteolysis with trypsin. Gel filtration and SDS-PAGE revealed that trypsin removed the C-terminal tag region of R303, facilitating crystal formation. Crystals of R303 diffracted to 1.3 Å resolution and belonged to the monoclinic space group P2₁, with unit-cell parameters a=46.4, b=31.2, c=74.8 Å, β=93.8°. The crystals exhibited a Matthews coefficient of 1.95 Å3 Da(-1) with two molecules in the asymmetric unit.

  19. In-situ Surface X-ray Diffraction Study of Ruddlesden-Popper Series Thin Film Growth

    NASA Astrophysics Data System (ADS)

    Lee, June Hyuk; Chang, Seo Hyoung; Luo, Zhenlin; Tung, I.-Cheng; Malshe, Milind; Jellinek, Julius; Eastman, Jeff; Hong, Hawoong; Fong, Dillon; John, Freeland

    2013-03-01

    The layered Ruddlesden-Popper phases of An+1BnO3n+1, such as Sr2TiO4 and La2NiO4, have attracted much attention as potential materials for solid-oxide fuel cell cathodes and thermoelectrics. To understand the fundamentals of this class of layered oxide thin films, we studied the growth of (001)-oriented Sr2TiO4 and La2NiO4 on SrTiO3 substrates by using oxide molecular beam epitaxy with in-situ surface x-ray diffraction. For Sr2TiO4, the synthesis of the double SrO layer followed by TiO2 dynamically reconstructs back into the SrTiO3 phase, which demonstrates that during thin film deposition other pathways under growth conditions can give rise to new structural arrangements. In contrast with Sr2TiO4, the growth of La2NiO4 involves the stacking of polar LaO+ and NiO2-layers. This raises the question of how polarity mismatch at the interface with the SrTiO3 substrate will influence the growth process. A detail comparison of these two cases will be discussed. Work at the Advanced Photon Source, Argonne is supported by the U.S. Department of Energy, Office of Science, and Office of Basic Energy Sciences, under Contract No. DE-AC02-06CH11357.

  20. Time-Resolved In Situ X-ray Diffraction Reveals Metal-Dependent Metal-Organic Framework Formation.

    PubMed

    Wu, Yue; Henke, Sebastian; Kieslich, Gregor; Schwedler, Inke; Yang, Miaosen; Fraser, Duncan A X; O'Hare, Dermot

    2016-11-02

    Versatility in metal substitution is one of the key aspects of metal-organic framework (MOF) chemistry, allowing properties to be tuned in a rational way. As a result, it important to understand why MOF syntheses involving different metals arrive at or fail to produce the same topological outcome. Frequently, conditions are tuned by trial-and-error to make MOFs with different metal species. We ask: is it possible to adjust synthetic conditions in a systematic way in order to design routes to desired phases? We have used in situ X-ray powder diffraction to study the solvothermal formation of isostructural M2 (bdc)2 dabco (M=Zn, Co, Ni) pillared-paddlewheel MOFs in real time. The metal ion strongly influences both kinetics and intermediates observed, leading in some cases to multiphase reaction profiles of unprecedented complexity. The standard models used for MOF crystallization break down in these cases; we show that a simple kinetic model describes the data and provides important chemical insights on phase selection.