scholarly journals Interaction of Corroding Iron with Eight Bentonites in the Alternative Buffer Materials Field Experiment (ABM2)

Minerals ◽  
2021 ◽  
Vol 11 (8) ◽  
pp. 907
Author(s):  
Paul Wersin ◽  
Jebril Hadi ◽  
Andreas Jenni ◽  
Daniel Svensson ◽  
Jean-Marc Grenèche ◽  
...  
Keyword(s):  
Redox Reactions ◽  
Hard Rock ◽  
High Spatial Resolution ◽  
X Ray Diffraction ◽  
X Ray ◽  
Rock Laboratory ◽  
Reducing Conditions ◽  
Buffer Material ◽  
High Level ◽  
Redox Evolution

Bentonite, a common smectite-rich buffer material, is in direct contact with corroding steel in many high-level radioactive waste repository designs. The interaction of iron with the smectite-rich clay may affect its swelling and sealing properties by processes such as alteration, redox reactions and cementation. The chemical interactions were investigated by analysing the Fe/clay interfaces of eight bentonite blocks which had been exposed to temperatures up to 130 °C for five years in the ABM2 borehole at the Äspö Hard Rock Laboratory managed by the Swedish Nuclear Fuel and Waste Management Co (SKB). Eleven interface samples were characterised by high spatial resolution methods, including scanning electron microscopy coupled with energy dispersive X-ray spectroscopy and μ-Raman spectroscopy as well as by “bulk” methods X-ray diffraction, X-ray fluorescence and 57Fe Mössbauer spectrometry. Corrosion induced an iron front of 5–20 mm into the bentonite, except for the high-Fe bentonite where no Fe increase was detected. This Fe front consisted mainly of ferric (oxyhydr)oxides in addition to the structural Fe in the smectite fraction which had been partially reduced by the interaction process. Fe(II) was also found to extend further into the clay, but its nature could not be identified. The consistent behaviour is explained by the redox evolution, which shifts from oxidising to reducing conditions during the experiment. No indication of smectite alteration was found.

Micro Diffraction Imaging of Bulk Polycrystalline Materials

2006 ◽  
Vol 524-525 ◽  
pp. 273-278
Author(s):  
Thomas Wroblewski ◽  
A. Bjeoumikhov ◽  
Bernd Hasse
Keyword(s):  
High Spatial Resolution ◽  
Polycrystalline Materials ◽  
X Rays ◽  
X Ray Diffraction ◽  
Short Sample ◽  
X Ray ◽  
Detector Distance ◽  
Transmission Geometry ◽  
Diffraction Imaging ◽  
Position Sensitive

X-ray diffraction imaging applies an array of parallel capillaries in front of a position sensitive detector. Conventional micro channel plates of a few millimetre thickness have successfully been used as collimator arrays but require short sample to detector distances to achieve high spatial resolution. Furthermore, their limited absorption restricts their applications to low energy X-rays of around 10 keV. Progress in the fabrication of long polycapillaries allows an increase in the sample to detector distance without decreasing resolution and the use of high X-ray energies enables bulk investigations in transmission geometry.

scholarly journals Shape Tuning of Magnetite Nanoparticles Obtained by Hydrothermal Synthesis: Effect of Temperature

2019 ◽  
Vol 2019 ◽  
pp. 1-15 ◽  
Author(s):  
Nayely Torres-Gómez ◽  
Osvaldo Nava ◽  
Liliana Argueta-Figueroa ◽  
René García-Contreras ◽  
Armando Baeza-Barrera ◽  
...  
Keyword(s):  
Electron Microscopy ◽  
Nanoparticle Synthesis ◽  
Effect Of Temperature ◽  
X Ray Diffraction ◽  
X Ray ◽  
Transmission Electron ◽  
Pure Phase ◽  
High Level ◽  
Shape Tuning ◽  
Magnetite Phase

In this work, we present a simple and efficient method for pure phase magnetite (Fe3O4) nanoparticle synthesis. The phase structure, particle shape, and size of the samples were characterized by Raman spectroscopy (Rm), X-ray diffraction (XRD), scanning electron microscopy (SEM), energy-dispersive X-ray (EDS), and transmission electron microscopy (TEM). The morphology tuning was controlled by the temperature of the reaction; the nanoparticles were synthesized via the hydrothermal method at 120°C, 140°C, and 160°C, respectively. The Rm and XRD spectra showed that all the nanoparticles were Fe3O4 in a pure magnetite phase. The obtained nanoparticles exhibited a high level of crystallinity with uniform morphology at each temperature, as can be observed through TEM and SEM. These magnetic nanoparticles exhibited good saturation magnetization and the resulting shapes were quasi-spheres, octahedrons, and cubes. The samples showed striking magnetic properties, which were examined by a vibrating sample magnetometer (VSM). It has been possible to obtain a good morphological control of nanostructured magnetite in a simple, economical, and scalable method by adjusting the temperature, without the modification of any other synthesis parameter.

Alkin-Komplexe des Rheniums in hohen Oxidationsstufen / Alkyne Complexes of Rhenium in High Oxidation States

1990 ◽  
Vol 45 (6) ◽  
pp. 876-886 ◽  
Author(s):  
Wolfgang A. Herrmann ◽  
Josef K. Felixberger ◽  
Josef G. Kuchler ◽  
Eberhardt Herdtweck
Keyword(s):  
Diffraction Study ◽  
Scale Up ◽  
Oxidation States ◽  
X Ray Diffraction ◽  
X Ray ◽  
Reducing Conditions ◽  
Molar Amount ◽  
High Oxidation ◽  
Alkyne Complexes ◽  
Type 3

The class of π-alkyne complexes of metals in medium and high oxidation states has been extended by the type CH3ReO2(RC≡CR′) (3a—i). Exchange of alkyne for oxo ligands under reducing conditions has been employed as a new general synthesis. Compounds 3 are thus obtained by reaction of methyltrioxorhenium(VII) (1) with the alkynes 2a—i in the presence of a ca. 1.1-fold molar amount of polymer-bound triphenylphosphane as reducing agent (desoxygenation). The structural characterization was carried out for the example of the tolan complex 3 e by virtue of a single-crystal X-ray diffraction study at —80 °C, according to which the description of compounds 3 as “rhenacyclopropenes” seems justified. Evidence from NMR investigations of 3 a and 3 c shows that no fast rotation of the respective alkyne ligand around the axis to the metal atom occurs on the NMR time scale up to at least 105 °C. A minimal rotation barrier of approximately 20 kcal/mol is thus to be estimated. Reaction of type 3 compounds (R = R′ = CH3, b; R = R′ = C2H5, c) with polymer-bound triphenylphosphane under more drastic conditions (boiling toluene) for two days effects further reduction, with the dinuclear, diamagnetic rhenium(IV) complexes 4b and 4c, resp., being formed. Sterically demanding alkynes (e.g., R = R′ = Si(CH3)3, C6H5) seem to prevent this type of reaction. According to an X-ray diffraction study, 4b has an equilateral Re2O-triangular core geometry, with the ligands O, CH3, and butyne(2) arranged in such a way that C2-symmetry results. The alkyne complexes reported here are the first ones of tetra- and pentavalent rhenium.

Zirconolite transformation under reducing conditions

1998 ◽  
Vol 13 (11) ◽  
pp. 3181-3190 ◽  
Author(s):  
B. D. Begg ◽  
E. R. Vance ◽  
B. A. Hunter ◽  
J. V. Hanna
Keyword(s):  
Perovskite Phase ◽  
Charge Compensation ◽  
Fluorite Structure ◽  
Second Phase ◽  
X Ray Diffraction ◽  
Nmr Studies ◽  
Paramagnetic Resonance ◽  
X Ray ◽  
Reducing Conditions ◽  
Quadrupole Resonance

The structural behavior of zirconolite (CaZrTi2O7) under reducing conditions at high temperature has been studied, mainly by scanning electron microscopy (SEM) and x-ray diffraction (XRD), but also with x-ray absorption spectroscopy, thermogravimetry, and electron paramagnetic resonance. The partial reduction of Ti4+ to Ti3+, associated with a reducing atmosphere heat treatment, led to the initial formation of perovskite (CaTiO3) as a second phase. As the concentration of Ti3+ in the zirconolite increased, so did the amount of perovskite until the zirconolite was totally transformed into a fluorite structured phase. Analysis of the reduced zirconolites showed them to be consistently deficient in Ca and enriched in Zr, in proportion to the concentration of Ti3+. To determine how electroneutrality was preserved in these reduced zirconolites, a series of zirconolites were prepared in air using In3+ and Ga3+ as models for Ti3+. These samples were then investigated by neutron and x-ray diffraction, SEM, solid state nuclear magnetic resonance (NMR), and nuclear quadrupole resonance (NQR). 71Ga MAS NMR studies of the Ga substituted zirconolite exhibited a narrow resonance at ˜13 ppm which was attributed to six-coordinate Ga incorporated in a trace perovskite phase. Broadline 71Ga NMR and 69/71Ga NQR were required to characterize the Ga incorporated in the zirconolite. The resultant quadrupolar parameters of CQ = 30.0 ± 0.05 MHz and η = 1.0 ± 0.03 indicate that the Ga site is in a highly distorted environment which would suggest that it is located on the five-coordinate Ti site within the zirconolite lattice. These results were complemented by Rietveld refinement of the neutron diffraction data from the In-doped zirconolite sample, which was optimal when all the In was located on the five-coordinate Ti site with the excess Zr located on the Ca site. It would therefore appear that charge compensation for the presence of Ti3+ in zirconolite is effected via the substitution of an appropriate amount of Zr on the Ca site. The Ti3+-stabilized fluorite structure was readily oxidized back to a single phase zirconolite upon heating in air.

Effect of Synthesis Conditions and Actinide Contents on Phase Composition of Actinide Bearing Ceramics

2003 ◽  
Vol 807 ◽  
Author(s):  
A. G. Ptashkin ◽  
S. V. Stefanovsky ◽  
S. V. Yudintsev ◽  
S. A. Perevalov
Keyword(s):  
Electron Microscopy ◽  
Solid Solution ◽  
Phase Composition ◽  
Fluorite Structure ◽  
X Ray Diffraction ◽  
X Ray ◽  
Synthesis Conditions ◽  
Reducing Conditions ◽  
Dispersive System ◽  
Scanning Electron

ABSTRACTPu-bearing zirconolite and pyrochlore based ceramics were prepared by melting under oxidizing and reducing conditions at 1550 °C. 239Pu content in the samples ranged between ∼10 and ∼50 wt.%. Phase composition of the ceramics and Pu partitioning were studied using X-ray diffraction (XRD) and scanning electron microscopy with energy dispersive system (SEM/EDS). Major phases in the samples were found to be the target zirconolite and pyrochlore as well as a cubic fluorite structure oxide. Normally the Pu content in the Pu host phases was 10–12 wt.%. This corresponds to the Pu content recommended for matrices for immobilization of excess weapons plutonium. At higher Pu content (up to 50 wt.%) additional phases, such as a PuO2-based cubic fluorite-structured solid solution, perovskite, and rutile were found.

Uranium Redox States in Borosilicate Compositions

2004 ◽  
Vol 824 ◽  
Author(s):  
A.S. Aloy ◽  
A.V. Trofimenko ◽  
O.A. Iskhakova ◽  
L.J. Jardine
Keyword(s):  
Solid State ◽  
Borosilicate Glasses ◽  
X Ray Diffraction ◽  
X Ray ◽  
Synthesis Conditions ◽  
Redox States ◽  
Nuclear Gamma Resonance ◽  
Reducing Conditions ◽  
Optical Spectrophotometry

AbstractThe results of the studies of uranium valent states in the borosilicate glasses incorporating the components of uranium-containing sludge of Mining and Chemical Combine (MCC, Zheleznogorsks.) is presented in this work. The glasses were made under oxidative and reducing conditions.The optical spectrophotometry, nuclear gamma-resonance (NGR) and X-ray diffraction (XRD) showed that glasses produced under oxidative conditions are characterized by the presence of only U(6+), while U(4+) in the reducing conditions is present along with U(6+). The ratio U(6+)/to U(4+) varies in depending on the synthesis conditions.The glass samples synthesized under oxidative conditions were researched at initial solid state. The others synthesized under reducing conditions was dissolved preliminary without distort of uranium valency.The effect of U(4+)/U(6+) ratio on the uranium leach rates from the glasses has been studied at 90° using MCC-1 test.

Effect of Li, Fe, and B Addition on the Crystallization Behavior of Sodium Aluminosilicate Glasses as Analogues for Hanford High Level Waste Glasses

MRS Advances ◽  
2016 ◽  
Vol 2 (10) ◽  
pp. 549-555 ◽  
Author(s):  
José Marcial ◽  
Mostafa Ahmadzadeh ◽  
John S. McCloy
Keyword(s):  
Function Analysis ◽  
High Level Waste ◽  
X Ray Diffraction ◽  
X Ray ◽  
High Sodium ◽  
Chemical Ordering ◽  
Sodium Aluminosilicate ◽  
Aluminosilicate Glasses ◽  
Heat Treated ◽  
High Level

ABSTRACTCrystallization of aluminosilicates during the conversion of Hanford high-level waste (HLW) to glass is a function of the composition of the glass-forming melt. In high-sodium, high-aluminum waste streams, the crystallization of nepheline (NaAlSiO4) removes chemically durable glass-formers from the melt, leaving behind a residual melt that is enriched in less durable components, such as sodium and boron. We seek to further understand the effect of lithium, boron, and iron addition on the crystallization of model silicate glasses as analogues for the complex waste glass. Boron and iron behave as glass intermediates which allow for crystallization when present in low additions but frustrate crystallization in high additions. In this work, we seek to compare the average structures of quenched and heat treated glasses through Raman spectroscopy, X-ray diffraction, vibrating sample magnetometry, and X-ray pair distribution function analysis. The endmembers of this study are feldspathoid-like (LiAlSiO4, NaAlSiO4, NaBSiO4, and NaFeSiO4), pyroxene-like (LiAlSi2O6, NaAlSi2O6, NaBSi2O6, and NaFeSi2O6), and feldspar-like (LiAlSi3O8, NaAlSi3O8, NaBSi3O8, and NaFeSi3O8). Such a comparison will provide further insight on the complex relationship between the average chemical ordering and topology of glass on crystallization.

Inorganic matrices for immobilization of Tc-99

2009 ◽  
Vol 1193 ◽  
Author(s):  
Yulia I. Korneyko ◽  
Vladimir M. Garbuzov ◽  
Olga V. Schmidta ◽  
Boris E. Burakov
Keyword(s):  
Metallic Phase ◽  
Inert Atmosphere ◽  
X Ray Diffraction ◽  
X Ray ◽  
Synthesis Conditions ◽  
Mn Oxide ◽  
Ceramic Synthesis ◽  
Reducing Conditions ◽  
Metallic Inclusions ◽  
Inorganic Matrices

AbstractImmobilization of long-lived 99Tc requires development of chemically resistant inorganic matrices. Samples of ceramics based on crystalline Fe-Mn- and Zr-Mn-oxide compounds were synthesized at 1150°C in air, reducing or inert atmosphere from precursors doped with 5-12 wt.% Tc. All the samples obtained were studied using optical and scanning electron microscopy (SEM); powder X-ray diffraction (XRD) and microprobe analysis (EMPA). Content of Tc varied from 0.5-0.8 to 3-6 wt.% in oxide host phases and from 54 to 93 wt.% in metallic inclusions. It was demonstrated that synthesis of oxide host-phases under oxidizing or reducing conditions was not optimal due to partial Tc volatilization or metallic phase formation, respectively. The use of inert atmosphere for ceramic synthesis supports Tc incorporation into crystalline structure of stable host-phases. Development of optimal methods of precursor preparation and synthesis conditions of Tc-doped ceramic are being discussed.

Cold Crucible Vitrification of U-bearing SRS SB4 HLW Surrogate

2010 ◽  
Vol 1265 ◽  
Author(s):  
Sergey Stefanovsky ◽  
Alexander Ptashkin ◽  
Oleg Knyazev ◽  
Olga Stefanovsky ◽  
James C Marra
Keyword(s):  
High Level Waste ◽  
Cold Crucible ◽  
Savannah River ◽  
X Ray Diffraction ◽  
Alumina Crucible ◽  
X Ray ◽  
Xrd Study ◽  
Processing Facility ◽  
High Level ◽  
River Site

AbstractSavannah River Site Defense Waste Processing Facility (DWPF) Sludge Batch 4 (SB4) high level waste (HLW) simulant at 55 wt % waste loading was produced in the demountable cold crucible and cooled to room temperature in the cold crucible. Appreciable losses of Cs, S and Cl took place during the melting. A second glass sample was subjected to canister centerline cooling (CCC) regime in an alumina crucible in a resistive furnace. X-ray diffraction (XRD) study showed that the glass blocks were composed of vitreous and spinel structure phases. No separate U-bearing phases were found.

scholarly journals Effect of Oxidation Rate and Fe(II) State on Microbial Nitrate-Dependent Fe(III) Mineral Formation

2005 ◽  
Vol 71 (11) ◽  
pp. 7172-7177 ◽  
Author(s):  
John M. Senko ◽  
Thomas A. Dewers ◽  
Lee R. Krumholz
Keyword(s):  
Oxidation Rate ◽  
Sequence Similarity ◽  
Klebsiella Oxytoca ◽  
Xrd Analysis ◽  
X Ray Diffraction ◽  
16S Rrna Sequence ◽  
X Ray ◽  
Oxidation Rates ◽  
Reducing Conditions

ABSTRACT A nitrate-dependent Fe(II)-oxidizing bacterium was isolated and used to evaluate whether Fe(II) chemical form or oxidation rate had an effect on the mineralogy of biogenic Fe(III) (hydr)oxides resulting from nitrate-dependent Fe(II) oxidation. The isolate (designated FW33AN) had 99% 16S rRNA sequence similarity to Klebsiella oxytoca. FW33AN produced Fe(III) (hydr)oxides by oxidation of soluble Fe(II) [Fe(II)sol] or FeS under nitrate-reducing conditions. Based on X-ray diffraction (XRD) analysis, Fe(III) (hydr)oxide produced by oxidation of FeS was shown to be amorphous, while oxidation of Fe(II)sol yielded goethite. The rate of Fe(II) oxidation was then manipulated by incubating various cell concentrations of FW33AN with Fe(II)sol and nitrate. Characterization of products revealed that as Fe(II) oxidation rates slowed, a stronger goethite signal was observed by XRD and a larger proportion of Fe(III) was in the crystalline fraction. Since the mineralogy of Fe(III) (hydr)oxides may control the extent of subsequent Fe(III) reduction, the variables we identify here may have an effect on the biogeochemical cycling of Fe in anoxic ecosystems.

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