Development of brannerite glass‐ceramics for the immobilization of actinide‐rich radioactive wastes

Brannerite‐based glass‐ceramics have been developed as potential waste forms for the immobilization of actinide‐rich radioactive wastes. For the first time, the formation of brannerite phases in glass has been demonstrated using uranium (U) and plutonium (Pu) with additions of gadolinium and hafnium as neutron absorbers. Both XRD and SEM‐EDS confirm that brannerite is the dominating phase with compositions close to Y_0.5U_0.5Ti₂O₆, Gd_0.2Pu_0.3U_0.5Ti₂O₆, and Gd_0.1Hf_0.1Pu_0.2U_0.6Ti₂O₆ internally crystallized in the glass. TEM SAED and Raman spectroscopy reveal the typical structure and vibration modes for brannerite. In addition, the presence of U⁵⁺ species as designed in the formulations has been confirmed by diffuse reflectance spectroscopy. More importantly, the U and Pu were partitioned exclusively in the ceramic phases with no detectable actinide in the glass.     

Phase evolution from Ln2Ti2O7 (Ln=Y and Gd) pyrochlores to brannerites in glass with uranium incorporation

Ln₂Ti₂O₇ (Ln=Y and Gd) pyrochlore glass‐ceramics have been fabricated successfully via internal crystallization. Subsequently, the phase evolution from Ln₂Ti₂O₇ pyrochlores to Ln_0.5U_0.5Ti₂O₆ brannerites in glass with uranium (U) substitutions on the Ln‐site of Ln₂Ti₂O₇ has been investigated using X‐ray diffraction, scanning electron microscope‐electron dispersive spectroscopy, transmission electron microscopy, Raman and diffuse reflectance spectroscopy. Combined characterization by XRD, SEM‐EDS and TEM SAED confirms the structures and phase evolution while Raman spectroscopy reveals characteristic vibration modes for both pyrochlore and brannerite. In addition, DRS of the U⁵⁺ ion has been used to probe the phase evolution, with the corresponding f‐f transition band of ²F_7/2 energy level significantly shifting to longer wavenumbers due to the local coordination environment changing from eightfold coordination in pyrochlore to sixfold coordination in brannerite.     

Uranium brannerite with Tb(III)/Dy(III) ions: Phase formation,structures, and crystallizations in glass

Uranium brannerite phases with terbium(III) or dysprosium(III) ions have been investigated. The precursors with molar ratio of 0.5:0.5:2 (Ln: U: Ti with Ln = Tb or Dy) were prepared and calcined at 750°C in argon. Sintering the pelletized samples in argon at 1200°C led to the formation of pyrochlore phases with TiO₂ rutile and U-rich oxides while sintering in air led to the formation of brannerite phases with the nominal composition close to Ln_0.5U_0.5Ti₂O₆ together with trace amounts of TiO₂ rutile and LnUO₄. Incorporating an excess of TiO₂ (20 wt%) and sintering at higher temperature (1300°C) resulted in no obvious change to the phase equilibrium. As designed, pentavalent uranium has been proven to be dominant in these brannerite phases with diffuse reflectance spectroscopy. The relationships between the cell parameters and the ionic radii of the A-site cations have been explored and rationalized from the structure point of view for a range of titanate brannerite phases (ATi₂O₆). In addition, the crystallization of Ln_0.5U_0.5Ti₂O₆ brannerite in glass has been achieved via heat treatment at 1200°C and confirmed with X-ray diffraction, scanning electron microscopy-energy dispersive spectroscopy and transmission electron microscopy–selected area electron diffraction.     

The charge state of titanium ions in Pd‐doped Ti:CMAS glass and glass‐ceramics

We have investigated the role of charge state of Ti in the electronic properties and structure of electrically conductive CMAS‐TiO₂‐Pd glass and glass‐ceramics by X‐ray photoelectron spectroscopy, electron paramagnetic resonance, positron annihilation lifetime spectroscopy, and fluorescence spectroscopy. These studies suggest the concentration of Ti³⁺ ions was, at most, ~0.1 wt% in glass‐ceramics devitrified in the reducing atmosphere of forming gas; no other glass or glass‐ceramic samples exhibited measurable levels of Ti³⁺. The observed fluorescence at liquid nitrogen temperature in parent glasses and glass‐ceramics obtained in air is explained by UV‐induced charge‐transfer processes involving Ti⁴⁺ ions and oxygen surroundings. The X‐ray photoelectron spectroscopy data are correlated with rutile, anorthite, diopside, and titanite crystalline phases identified in Pd‐free and Pd‐doped Ti:CMAS glass‐ceramics earlier.     

Photocatalytic Oxidation of Isopropanol in Aqueous Solution Using Perovskite‐Structured La2Ti2O7

This study is focused on the application of a highly‐doped layered perovskite, La₂Ti₂O₇, as the photocatalyst for the photocatalytic decomposition of isopropanol (IPA). The La₂Ti₂O₇ powder prepared by solid state reaction was characterized by X‐ray diffraction (XRD), scanning electron microscopy (SEM), UV‐Vis diffuse reflectance spectrophotometry (UV‐DRS), X‐ray photoelectron spectroscopy (XPS), and zeta potential. The temporal behavior of the photocatalytic decomposition of IPA in aqueous solution by the UV/La₂Ti₂O₇, with a photoreactor operated in a recirculation mode, was studied under various conditions including solution pH, light intensity, and La₂Ti₂O₇ loading. The decomposition of IPA in aqueous solution by La₂Ti₂O₇ photocatalytic processes was found to be technically feasible. A kinetic equation was developed for modeling the photocatalytic decomposition of IPA by the UV/La₂Ti₂O₇ photocatalytic processes.     

Pyrochlore glass-ceramics fabricated via both sintering and hot isostatic pressing for minor actinide immobilization

Pyrochlore glass-ceramics (GCs) have been investigated with samples fabricated via both sintering and hot isostatic pressing (HIPing) of a mixed oxide precursor. It has been demonstrated that sintering at 1200°C in air is necessary to obtain well-crystallized pyrochlore crystals in a sodium aluminoborosilicate glass through a one-step controlled cooling. The crystallization, structure, and microstructure of Eu₂Ti₂O₇ pyrochlore as the major phases in residual glass were confirmed with X-ray diffraction (XRD), scanning electron microscopy-energy dispersive spectroscopy, transmission electron microscopy, and Raman spectroscopy. The structures of major Eu₂Ti₂O₇ pyrochlore and minor [Eu_4.67O(SiO₄)₃] apatite in both sintered and HIPed samples were refined using synchrotron XRD data. While the processing atmosphere did not appear to affect the cell parameter of the main pyrochlore phase, very small volume expansion (~0.3%) was observed for the minor apatite phase in the HIPed sample. In addition, static leaching of the HIPed sample confirmed that pyrochlore GCs are chemically durable. Overall, pyrochlore GCs prepared via both sintering and HIPing with the Eu partitioning factor of ~23 between ceramics and the residual glass are suitable waste forms for minor actinides with processing chemicals.     

Conversion of Alumina to Aluminum Nitride Using Polymeric Carbon Nitride as a Nitridation Reagent

Polymeric carbon nitride, which was synthesized by polymerization of dicyandiamide at 500°C, was used as a nitridation reagent in the conversion of δ‐alumina (δ‐Al₂O₃) to aluminum nitride (AlN). The products obtained at various reaction temperatures were characterized by powder X‐ray diffraction, ²⁷Al magic‐angle spinning nuclear magnetic resonance (MAS NMR) spectroscopy, Raman spectroscopy, and X‐ray photoelectron spectroscopy (XPS). δ‐Al₂O₃ began to convert to AlN at 900°C, which is the lowest temperature reported for the formation of AlN from Al₂O₃, and completely converted to AlN at 1400°C. The occurrence of reaction intermediates during nitridation was confirmed by ²⁷Al MAS NMR and XPS. The change in Raman spectra with reaction temperatures indicated that lattice defects in AlN were reduced by calcining at higher reaction temperatures.     

Structural dependence of crystallization in glasses along the nepheline (NaAlSiO4) ‐ eucryptite (LiAlSiO4) join

Lithium and sodium aluminosilicates are important glass‐forming systems for commercial glass‐ceramics, as well as being important model systems for ion transport in battery studies. In addition, uncontrolled crystallization of LiAlSiO₄ (eucryptite) in high‐Li₂O compositions, analogous to the more well‐known problem of NaAlSiO₄ (nepheline) crystallization, can cause concerns for long‐term chemical durability in nuclear waste glasses. To study the relationships between glass structure and crystallization, nine glasses were synthesized in the Li_xNa_1‐xAlSiO₄ series, from x = 0 to x = 1. Raman spectra, nuclear magnetic resonance (NMR) spectroscopy (Li‐7, Na‐23, Al‐27, Si‐29), and X‐ray diffraction were used to study the quenched and heat‐treated glasses. It was found that different LiAlSiO₄ and NaAlSiO₄ crystal phases crystallize from the glass depending on the Li/Na ratio. Raman and NMR spectra of quenched glasses suggest similar structures regardless of alkali substitution. Li‐7 and Na‐23 NMR spectra of the glass‐ceramics near the endmember compositions show evidence of several differentiable sites distinct from known Li_xNa_1‐xAlSiO₄ crystalline phases, suggesting that these measurements can reveal subtle chemical environment differences in mixed‐alkali systems, similar to what has been observed for zeolites.     

Impact of Stoichiometry on Structural and Optical Properties of Sputter Deposited Multicomponent Tellurite Glass Films

Multicomponent TeO₂–Bi₂O₃–ZnO (TBZ) glass thin films were prepared using RF magnetron sputtering under different oxygen flow rates. The influences of oxygen flow rate on the structural and optical properties of the resulting thin films were investigated. We observed that thin films sputtered in an oxygen‐rich environment are optically transparent while those sputtered in an oxygen‐deficient environment exhibit broadband absorption. The structural origin of the optical property variation was studied using X‐ray diffraction, X‐ray photoelectron spectroscopy, Raman Spectroscopy, and transmission electron microscopy which revealed that the presence of under‐coordinated Te leads to the observed optical absorption in oxygen‐deficient films.     

The Nanocrystalline SnO2–TiO2 System—Part I: Structural Features

The phases present and their crystal structure and microstructure in the nanocrystalline SnO₂–TiO₂ system were studied in the compositional range Sn_1?xTi_xO₂ (0.0 ≤ x ≤ 0.9). There is an apparent increase in the solubility limits in the solid solution compared to bulk crystalline SnO₂–TiO₂. No two phase region was observed with increasing TiO₂ content. Electron energy loss spectroscopy, infrared spectroscopy (FTIR), and X‐ray diffraction (XRD) of the nanopowders showed that the apparent increase in solubility is related to the systematic Ti⁴⁺ segregation on the particle surface (surface excess) at the SnO₂‐rich side, avoiding the nucleation of a second phase even at high Ti⁴⁺ contents. Is this finding in accord with Raman spectra, which suggest localized Ti‐rich sites in the absence of a second crystalline phase. Ti⁴⁺ surface excess is also lead to a modification of the surface hydroxyls and a decrease in the crystallite size of the nanoparticles (with a concomitant increase in surface area), with expected implications to catalytic and sensorial properties of these nanoparticles.     

Magnetic Properties of Iron Phosphate Glass and Glass‐Ceramics

Magnetic properties of crystallized iron phosphate glasses and relationship between structural and magnetic properties modifications that occur during crystallization have been investigated. Iron phosphate glass exhibits the spin‐glass (SG) behavior and represents a prototype of solid with disordered spatially distributed magnetic moments. Glass of the composition 43Fe₂O₃–57P₂O₅ (wt%) was heat‐treated in air at 893, 923, and 1073 K for 24 h. The samples were studied using X‐ray diffraction, Raman spectroscopy, and dc magnetic measurements. The magnetic measurements show dominant antiferromagnetic (AF) interactions for all samples. The starting glass exhibits SG behavior, whereas magnetic behavior of samples heat‐treated at 893 and 923 K, which contain Fe₃(P₂O₇)₂ crystalline phase embedded in glass matrix, is ascribed to a mixture of superparamagnetism and SG behavior. In the sample heat‐treated at 1073 K, several peaks in the magnetization curves were observed which correspond to the various crystalline phases present in the sample: Fe₃(P₂O₇)₂, Fe₄(P₂O₇)₃ and Fe(PO₃)₃. Hysteresis loops show paramagnetic behavior at 300 K. Small curvature is present at low temperature (5 K) that can be ascribed to the AF ordering in the samples.     

Correlation Between Photoluminescence and Structural Defects in Ca1+xCu3−xTi4O12 Systems

Ca_1+xCu_{3 ? x}Ti₄O₁₂ powders were synthesized by a conventional solid‐state reaction. X‐ray diffraction (XRD) was performed to verify the formation of cubic CaCu₃Ti₄O₁₂ (CCTO) and orthorhombic CaTiO₃ (CTO) phases at long range. Rietveld refinements indicate that excess Ca atoms added to the Ca_{1 ? x}Cu_{3 ? x}Ti₄O₁₂ (x  =  1.0) composition segregated in a CaTiO₃ secondary phase suggesting that solubility limit of Ca atoms in the CaCu₃Ti₄O₁₂ lattice was reached for this system. The FE‐SEM images show that the Ca_1+xCu_{3 ? x}Ti₄O₁₂ (0  <  x  <  3) powders are composed of several agglomerated particles with irregular morphology. X‐ray absorption near‐edge structure spectroscopy (XANES) spectra indicated [TiO₅V_o^z]‐[TiO₆] complex clusters in the CaCu₃Ti₄O₁₂ structure which can be associated with oxygen vacancies (V_o^z  =  V_o^x, V_o^?, and V_o^??) whereas in the CaTiO₃ powder, this analysis indicated [TiO₆]–[TiO₆] complex clusters in the structure. Ultraviolet‐visible (UV–vis) spectra and photoluminescence (PL) measurements for the analyzed systems revealed structural defects such as oxygen vacancies, distortions, and/or strains in CaCu₃Ti₄O₁₂ and CaTiO₃ lattices, respectively.     

Defect mechanisms in BaTiO3‐BiMO3 ceramics

Often, addition of BiMO₃ to BaTiO₃ (BT) leads to improvement in resistivity with a simultaneous shift to n‐type conduction from p‐type for BT. In considering one specific BiMO₃ composition, that is, Bi(Zn_1/2Ti_1/2)O₃ (BZT), several prospective candidates for the origin of this n‐type behavior in BT‐BZT were studied—loss of volatile cations, oxygen vacancies, bismuth present in multiple valence states and precipitation of secondary phases. Combined x‐ray and neutron diffraction, prompt gamma neutron activation analysis and electron energy loss spectroscopy suggested much higher oxygen vacancy concentration in BT‐BZT ceramics (>4%) as compared to BT alone. X‐ray photoelectron spectroscopy and x‐ray absorption spectroscopy did not suggest the presence of bismuth in multiple valence states. At the same time, using transmission electron microscopy, some minor secondary phases were observed, whose compositions were such that they could result in effective donor doping in BT‐BZT ceramics. Using experimentally determined thermodynamic parameters for BT and slopes of Kröger‐Vink plots, it has been suggested that an ionic compensation mechanism is prevalent in these ceramics instead of electronic compensation. These ionic defects have an effect of shifting the conductivity minimum in the Kröger‐Vink plots to higher oxygen partial pressure values in BT‐BZT ceramics as compared to BT, resulting in a significantly higher resistivity values in air atmosphere and n‐type behavior. This provides an important tool to tailor transport properties and defects in BT‐BiMO₃ ceramics, to make them better suited for dielectric or other applications.     

Preparation of cerium titanate brannerite by solution combustion,and phase transformation during heat treatment

An aqueous solution route was employed to prepare cerium titanate oxide brannerite. Thermal analysis, X-ray diffraction, Raman spectroscopy, transmission and scanning electron spectroscopy, were used to investigate the brannerite structure formation and bulk properties. Mixed metal oxides (TiO₂, CeO₂ and brannerite CeTi₂O₆) were formed upon calcination at 800 °C for 12 h. The amount of brannerite phase decreased to form the constituent oxides with increasing calcination temperature and only pure TiO₂ and CeO₂ were present after 1200 °C calcination. The brannerite CeTi₂O₆ phase reformed at 1300 °C, and its relative amount was increased with dwell time. After 48 h calcination at 1300 °C, brannerite with only minor metal oxide impurities (<1%) was observed. The sample melted at 1400 °C which led to the collapse of brannerite back to its constituent oxides. Further, the phase formation was influenced by pelletization of the powders, which may be explained by a molar volume increase during brannerite formation. Attempts to confirm this hypothesis using Pu brannerite were inconclusive.     

Effects of Tm3+ Additions on the Crystallization of LaF3 Nanocrystals in Oxyfluoride Glasses: Optical Characterization and Up‐Conversion

The influence of the addition of 1 mol% Tm₂O₃ on the nanocrystallization of LaF₃ in a glass of composition 55SiO₂–20Al₂O₃–15Na₂O–10LaF₃ (mol%) has been studied. Tm₂O₃ affects the phase separation in the glass and delays the onset of crystallization with respect to the undoped glass. Additionally, the maximum LaF₃ crystal size is slightly greater than that in the undoped glass–ceramics. The microstructural and compositional changes in the glass matrix have been studied using several techniques, including viscosity, dilatometry, X‐ray and neutron diffraction (XRD, ND), quantitative Rietveld refinement, transmission electron microscopy (TEM), differential scanning calorimetry (DSC), and Raman spectroscopy. Photoluminescence measurements indicate that the Tm³⁺ ions are distributed between the glassy matrix and LaF₃ crystals. Eu₂O₃ has been used as structure probe and part of the Eu³⁺ ions are reduced to Eu²⁺ when incorporated in the LaF₃ nano‐crystals. Up‐conversion spectra under IR‐excitation show a higher intensity of the blue emission in the Tm‐doped glass–ceramic compared with that in the glass.     

Effect of Temperature on Structural and Optical Properties of Boehmite Nanostructure

The nanocrystalline boehmite, γ‐AlOOH, was synthesized by the hydrothermal method using AlCl₃·6H₂O and urea as precursors, and the effect of different annealing temperatures resulting in different phases of alumina (Al₂O₃) was obtained. The effects of different temperature on the phase and micrographs of the prepared γ‐AlOOH nanostructures were investigated. The obtained products were characterized by X‐ray powder diffraction (XRD), transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FTIR), and Raman spectroscopy techniques. The XRD results show that with the increasing temperature, the transformation of boehmite into well‐crystallized α‐Al₂O₃ and the morphology from nanoplatelets with spindle‐like edges to vermicular structure take place. The crystallite size and lattice parameters were calculated by Rietveld refinement. The convincing evidence for the crystal phase of the as‐prepared and annealed samples was provided by FTIR spectra. The Raman spectra unveil the change in vibrational modes of the phase transition alumina.     

Rapid Synthesis of Mesoporous,Nano‐Sized MgCr2O4 and Its Catalytic Properties

Monophasic MgCr₂O₄ has been synthesized by calcining the gel formed by the addition of epoxide to an ethanolic solution containing MgCl₂·6H₂O and CrCl₃·6H₂O. The sample has been characterized by a variety of analytical techniques including powder X‐ray diffraction (PXRD), FT‐IR, Raman, UV–Visible spectroscopy, transmission electron microscopy, and magnetic measurements at room temperature. Calcining the xerogel at 500°C and 700°C for 2 h yielded MgCr₂O₄ (yield of almost 61% by weight). BET surface area of 33.95 m²/g with an average pore diameter of 28.45 nm was obtained for the sample after calcination at 700°C. Square facets of the cubic spinel structure were observed in TEM images with an average crystallite diameter of 18 nm. HR‐TEM experiments and SAED measurements confirmed the spinel structure and negated the presence of other phases. The presence of MO₄ tetrahedral and MO₆ octahedral units in MgCr₂O₄ has also been evidenced from FTIR and Raman spectra. The sample showed paramagnetic behavior at room temperature with μ_eff of 3.54 B.M suggesting the presence of Cr in III oxidation state. Its use as an efficient catalyst for the oxidative degradation of Xylenol Orange (XO) and the photo degradation of Rhodamine‐6G (Rh‐6G) dyes have been demonstrated as these dye molecules are environmental pollutants.     

Three‐dimensional mapping of crystalline ceramic waste form materials

This work demonstrates the use of synchrotron‐based, transmission X‐ray microscopy (TXM) and scanning electron microscopy to image the 3‐D morphologies and spatial distributions of Ga‐doped phases within model, single‐ and two‐phase waste form material systems. Gallium doping levels consistent with those commonly used for nuclear waste immobilization (e.g., Ba_1.04Cs_0.24Ga_2.32Ti_5.68O₁₆) could be readily imaged. The analysis suggests that a minority phase with different stoichiometry/composition from the primary hollandite phase can be formed by the solid‐state ceramic processing route with varying morphology (globular vs. cylindrical) as a function of Cs content. The results presented in this work represent a crucial step in developing the tools necessary to gain an improved understanding of the microstructural and chemical properties of waste form materials that influence their resistance to aqueous corrosion. This understanding will aid in the future design of higher durability waste form materials.     

Enhanced Thermostability,Thermo‐Optics,and Thermomechanical Properties of Barium Gallo‐Germanium Oxyfluoride Glasses and Glass‐Ceramics

Serial substitutions of BaF₂ for BaO in BaO–Ga₂O₃–GeO₂ glasses were performed, and the effects of the substitutions on the glass properties were investigated. The glass transition temperature, density, refractive index, thermo‐optics coefficient, and figure of merit for thermal shock decreased with the replacement of oxygen by fluorine. On the other hand, the glass‐forming ability increased. Fluorine substitution removed the absorption band of hydroxyl near 2.9 μm. Raman scattering spectroscopy was used to characterize the fluorogermanate glasses. The crystallization process of the glass‐ceramics under different heat‐treatment conditions was also investigated using differential scanning calorimetry, X‐ray diffraction, scanning electron microscopy, and atomic force microscopy. The thermal and mechanical properties were improved by controlling the crystal size of the near‐ and middle‐infrared transparent glass‐ceramics.