Preparation of Y2Ti2O7 pyrochlore glass-ceramics as potential waste forms for actinides: the effects of processing conditions

Glass-Y2Ti2O7 pyrochlore was fabricated by sintering the mixture of glass precursor powder and (YTi)-composite which was prepared by a soft chemistry route. X-ray diffraction and Raman spectroscopy confirmed that the phase pure pyrochlore was crystallized in-situ in amorphous glass matrix at 1200 °C with dwelling time over 1 h. Pyrochlore was formed in glass matrix with cooling rate ∼0.1–40 °C/min, and independent of addition of alkali/alkaline earth fluorides. Glass matrix was able to accommodate/dissolve small amounts of impurities and the mean pyrochlore particle size was between 1 and 2 μm in glass observed by scanning electron microscopy. © 2017 Elsevier B.V

Single and mixed phase TiO2 powders prepared by excess hydrolysis of titanium alkoxide

To investigate the excess hydrolysis of titanium alkoxides, TiO2 powders were fabricated from titanium tetraisopropoxide using 6 : 1 and 100 : 1 H2O/Ti (r) ratios. The powders were dried and fired at a range of temperatures ((800uC). Hydroxylation and organic content in powders were characterised using attenuated total reflectance Fourier transform infrared spectroscopy (FTIR), laser Raman microspectroscopy and elemental microanalysis; surface area and pore size distribution were evaluated using N2 gas adsorption; phase composition was analysed using Xray diffraction (XRD) and laser Raman microspectroscopy; and crystallite size was evaluated by XRD, TEM and SEM. Results showed near complete hydrolysis in a predominantly aqueous medium (r=100), resulting in precipitated crystalline powders exhibiting brookite and anatase,which begin to transform to rutile below 500uC. The powders precipitated in a predominantly organic medium (r=6) underwent partial hydrolysis, were highly porous and exhibited an amorphous structure, with the crystallisation of anatase occurring at 300C and the transformation to rutile beginning at 500–600C

Aqueous chemical synthesis of Ln2Sn2O7 pyrochlore-structured ceramics

Pyrochlore-structured lanthanide stannate ceramic (Ln2Sn2O7) has been synthesized via a new complex precipitation method. A suite of characterization techniques, including FTIR, Raman, X-ray, and electron diffraction as well as nitrogen sorption were employed to investigate the structural evolution of the synthesized and calcined powder. Raman, XRD, and selected area electron diffraction results confirm the presence of the pyrochlore structure after calcination of the powder above 1200°C. TEM imaging shows fine crystallites gradually increased in size from approximately 100 nm to about 500 nm with higher calcination temperatures. Grain growth and powder densification upon increasing the calcination temperature was confirmed by nitrogen sorption results. This aqueous synthetic method provides a simple pathway for the preparation of homogeneous lanthanide stannate ceramics. © 2013, The American Ceramic Society

Raman spectroscopic study of natural and synthetic brannerite

Raman spectra of a well-characterized natural brannerite and some synthetic brannerite samples have been collected and analysed. For the first time, all 12 theoretical Raman polyhedraof CeTi2O6 with brannerite structure have been positively identified by using quantum chemical calculations based on density functional theory (DFT) and assigned to the spectra. For synthetic samples with Y or Ca substitution on the U site and Fe substitution on the Ti site, Y–O, Fe–O and U–O vibrational modes are tentatively assigned. The U–O bond lengths for the uranyl (UO2)2+ groups, have been calculated by using the measured wavenumbers of ν1 (UO2)2+ symmetric stretching vibrations and compared with the published U–O bond lengths of a natural brannerite. © 2013 Elsevier B.V

Beneficial effect of iron oxide/hydroxide minerals on sulfuric acid baking and leaching of monazite

The sulfuric acid bake/leach process is an established industrial process for the extraction of rare earths from hard-rock monazite ores/concentrates. The chemical reactions in the monazite acid bake can be strongly influenced by the gangue mineralogy of the ore/concentrate. In this work, the beneficial effect of three iron oxide/hydroxide minerals, namely hematite, goethite and magnetite, added to high grade monazite concentrate in the acid bake (temperature range of 200–800°) and leach process was investigated to understand the role of iron gangue. Baked solids and leach residues were characterised by elemental analyses, XRD, SEM-EDS and FT-IR. It was found that the addition of iron minerals to the monazite acid bake had a significant impact on bake chemistry, acting to significantly increase the leaching of both the rare earth elements and thorium, compared to monazite alone, mainly for temperatures above 300 °C. The increased dissolution of rare earth elements and thorium was attributed to the formation of an amorphous and insoluble iron sulfate-polyphosphate type phase in preference to insoluble rare earth and thorium containing polyphosphates identified during acid baking of monazite alone. After baking at 650 °C, the iron sulfate-polyphosphate type phase was altered to a more soluble form, leading to an increase in dissolution of iron, phosphorus and thorium. Acid baking at 800 °C led to the formation of FePO4, Fe2O3, CePO4 (monazite) and in some cases CeO2, causing a decrease in leaching of rare earths and thorium, and either an increase or a decrease in leaching of iron and phosphorus depending on the formation of FePO4 versus Fe2O3

One-step approach for synthesis of nanosized Cu-doped zeolite A crystals using the Cu–EDTA-complex.

Copper-doped nanosized zeolite A crystals were synthesized by an in situ templating approach using [Cu(EDTA)]2−-complex. The structural properties of the copper containing zeolite crystals were characterized by a suite of different techniques including SEM–EDX, ESR, mid-IR and Far-IR, Raman, in situ XRD and non-ambient neutron powder diffraction. The SEM investigations on the morphology show spheroidal zeolite A crystals with average size ∼200 nm. The asymmetric ESR spectrum shows that the Cu2+ ion is in a tetragonal-distorted octahedral crystal field. FT-IR and Raman spectroscopies provide information on coordination environment of the copper ion. The band due to stretching vibration of C–N bond, where N is coordinated to the copper ion (C–N–Cu), was observed at 1109 cm−1 in the mid-infrared region. The Raman band due to the Cu–O bond is present at 630 cm−1 indicating the coordination of the Cu2+-cation to COO−-group of the EDTA-ion. The XRD data shows an enlarged d-spacing between the adjacent zeolite lattice planes due to the presence of the [Cu(EDTA)]2−-complex in comparison to template-free LTA zeolite structure. LeBail fitting approach on temperature-dependent in situ X-ray and neutron diffraction profiles have demonstrated the expansion of the zeolite cell during the thermal treatment followed by subsequent contraction with the decomposition of the organic template. © 2014, Elsevie

Oxidation of polyethylene implanted with low energy magnesium ions

The oxidation of polyethylene implanted with low energy, i.e. 25–50 keV, Mg ions to fluences from 5 × 1012–5 × 1016 ions/cm2 was studied. Rutherford back-scattering spectroscopy showed all implanted samples gained oxygen but the distribution did not match that of the implanted Mg. An increase in carbon content was also observed for the near-surface region. Depth profiles of hydrogen were obtained via elastic recoil detection analysis, showing that hydrogen was lost throughout and beyond the range of the Mg ions, producing unsaturated and chemically active sites available for oxidation. Fourier-transform infrared spectroscopy revealed the formation of carbon–oxygen bonding such as carbonyl groups, but showed no evidence of oxidised magnesium. Raman spectroscopy showed disordered and graphitic carbon bonding configurations were created by the irradiation, but no evidence of oxidised magnesium. The implantation of films to high fluence produced a carbonized surface-layer that made the irradiated polymer more resistant to oxidation. © 2013, Elsevier B.V

A study of TiO2 binder-free paste prepared for low temperature dye-sensitized solar cells

A binder-free titania paste was prepared by chemical modification of an acidic TiO2 sol with ammonia. By varying the ammonia concentration, the viscosity of the acidic TiO2 suspension increased, thereby allowing uniform films to be cast. The photoelectrochemical performance of TiO2 electrodes, cast as single layers, was dependent on the thermal treatment cycle. Fourier transform infrared spectroscopy was used to characterize the extent of residual organics and found that acetates from the TiO2 precursor preparation were retained within the electrode structure after thermal treatment at 150 °C. Electrodes of nominal thickness 4 lm produced an energy conversion efficiency as high as 5.4% using this simple thermal treatment. © 2012, Materials Research Society