Ba3−xSrxTb3−xCexO9 (x = 1 and 1.5) ceramics (BSTC) with a relative density of 93% and a grain size distribution of 0.2–3 µm were prepared by the mixed-oxides reaction route. The crystalline structures, microstructures, valence states, and electrical properties of two ceramics were analyzed using X-ray powder diffraction (XRPD), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), electron paramagnetic resonance (EPR), and electrical measurements. Rietveld analyses of XRPD patterns show that BSTC1 is indexed as a trigonal structure with the space group R-3c, and BSTC3/2 is indexed as an orthorhombic perovskite structure with the space group Pmcn. The EPR, XPS, and electrical conductivity results confirm that Ce and Tb ions in BSTC exist as Ce4+ and mixed-valence states of Tb4+/Tb3+, respectively. At room temperature, the two BSTC ceramics exhibit a similar semiconducting behavior. The relationships between electrical conductivity and temperature/frequency are provided. The defect chemistry is discussed.

A suite of perovskite phases with the compositions NaTixNb1-xO3-0.5x, 0 ≤ x ≤ 0.2, has been synthesized for the first time using the sol-gel method. Rietveld analysis of powder XRD data reveals that with increasing Ti content, the orthorhombic perovskite structure becomes more cubic-like, as evidenced by the smaller differences among its three cell parameters. Enthalpies of formation of the synthesized phases from the constituent oxides and from the elements have been determined by drop solution calorimetry into molten 3Na2O·4MoO3 solvent at 974 K. As Ti4+ substitutes for Nb5+, the formation enthalpies become less exothermic in a nearly linear manner. This behavior suggests that the Ti→Nb substitution destabilizes the perovskite structure, presumably because of the concomitant occurrence of O2- vacancies, which compensate the charge imbalance between Ti4+ and Nb5+ in the structure.

IE-911 is a bound form of cystalline silicotitanate (CST) that was extensively tested for removing 137Cs from the Savannah River Site (SRS) tank wastes. In some simulant tests, column plugging incidents were observed, which led to thorough investigations to determine the causes and to develop protocols to avoid future plugging incidents. A related problem was the apparent decrease in Cs scavenging capability in some long-term tests. Our studies revealed that the interaction of IE-911 with the highly basic, high ionic strength, SRS average salt simulant could result in precipitation of; 1) poorly crystalline Nb-oxide, or 2) aluminosilicate zeolitic phases. The source for the Nb-oxide precipitate was determined to be a minor impurity phase that is a byproduct of CST manufacturing. The mechanisms of dissolution and re-precipitation of this phase in column pretreatment solution were investigated, and a protocol to rid IE-911 of this impurity was devised. The source material for the aluminosilicate zeolite precipitate was determined to be predominantly from the waste solution rather than the IE-911. Solubility experiments coupled with a thermodynamic analysis provided a protocol to predict when aluminosilicate precipitation will and will not occur. Finally, it was also established that aluminosilicate precipitation on the surfaces of the IE-911 granules could also account for an apparent decrease in equilibrium Kd and decrease in kinetics of Cs sorption.

Oxides of lanthanide dissolution in a Na2O-Al2O3-B2O3-SiO2 glass using Gd as a probe was studied in detail using Raman, fluorescence, and phonon sideband (PSB) spectroscopic techniques. A mechanism of Gd cation dissolution, via partitioning, in the borate-rich and silicate-rich environments was confirmed by examining characteristics of the Raman band evolution, fluorescence emission and lifetime, and PSBs. The study concluded that i) Gd(III) cations in the borate-rich environment resembles Gd-metaborate local structure, i.e., 1BO4:1Gd:2BO3, ii) Gd cations partitioning in the borate-rich environment at low Gd2O3 concentration, [Gd2O3] -1/3[B2O3] < 0, and iii) excess Gd(III) cations, [Gd2O3]–1/3[B2O3], in the silicate-rich environment at high Gd2O3 concentration, [Gd2O3]–1/3[B2O3]>0.

Silicotitanate ion exchangers are potential materials for the removal of radioactive Cs and Sr from tank wastes. In this paper the viability of direct thermal conversion of Cs-loaded silicotitanates to an acceptable high level waste form has been examined. Results show that in aqueous solutions, the Cs leach rates of crystalline silicotitanates (heat treated at 800°C) are 0.04, 0.18, 0.4 g/m2day for Cs loadings of 1, 5, and 20 wt%, respectively. Heating the Cs-loaded (up to 20 wt %) silicotitanates at or above 900 °C for 1 hour further reduces the Cs leach rates to approximately zero (beyond the lppm detection limits). Moreover, Cs volatilization was found to be < 0.8 wt% at temperatures as high as 1000 °C. These results suggest that thermally converted silicotitanate ion exchangers exhibit excellent chemical durability (comparable to or better than borosilicate glass) and thus, have great potential as an alternative waste form.

Aluminosilicates are one of the major class of species controlling the volume of radioactive high-level waste that will be produced from future remediation at Hanford site. Here we present studies of the phases and structures of aluminosilicates as a function of sludge composition using X-ray powder diffraction, solid state 27Al and 29Si NMR, and Raman spectroscopy. The results show that the content of NaNO3 in solution has significant effects on the nature of the insoluble aluminosilicate phases produced. It was found that regardless of the initial Si:Al ratio, nitrate cancrinite was the main phase formed in the solution with pH of 13.5 and 5 MNaNO3. However, at lower NaNO3 concentration with initial Si:Al ratios of 1.1, 2.2, and 11.0 in the solutions, a range of aluminosilicate zeolites was produced with Si: Al ratios of 1.1, 1.3, and 1.5, respectively. Lowering the solution pH appears to promote the formation of amorphous aluminosilicates. The results presented here are important for the prediction of the solubility and dissolution rate of Al in tank wastes.