G.R. Lumpkin

Physical and chemical characteristics of baddeleyite (monoclinic zirconia) in natural environments: an overview and case study

This report provides an overview of the natural occurrence, physical characteristics, and chemical composition of the mineral baddeleyite, ideally ZrO 2 . A survey of the literature shows that baddeleyite is widespread in nature as a trace mineral, but has a rather limited composition of 87-99 wt% ZrO 2 with most of the remainder comprised of FeO, TiO 2 and HfO 2 . Natural baddeleyite is invariably monoclinic due to the low concentrations of large cations such as Ca and Y. Although the concentrations of Th and U are low (generally <1500 ppm U and <100 ppm Th), the cumulative alpha-decay dose reaches 0.1-1. x × 10 16 mg -1 for samples with ages of 1-2 × 10 9 yr. The available data also suggest that baddeleyite is highly durable in aqueous fluids. For nuclear waste form applications, both the radiation damage effects and durability of baddeleyite need to be examined in further detail. A case study of baddeleyite from the Jacupiranga carbonatite complex of southern Brazil provides some additional information on the crystal chemistry, durability and radiation damage effects of the mineral. This work shows that baddeleyite can incorporate up to 4. 1 wt% Nb 2 O 5 and 1.2 wt% Ta 2 O 5 . Incorporation of Nb 5+ and Ta 5+ is partially compensated by the incorporation of up to 0.4 wt% MgO and 0.3 wt% FeO in a charge balanced substitution of the form 3Zr↔2(Nb, Ta) + (Mg, Fe). Similar substitution mechanisms may enable the incorporation of Np 5+ in the ZrO 2 phases of fuel and waste matrices. The mineral is highly resistant to hydrothermal alteration which affected associated uranpyrochlore crystals. Many of the baddeleyite crystals are partially enclosed within the uranpyrochlore grains which contain 19-26 wt% UO 2 and 0.3-3.5 wt% ThO 2 . These baddeleyite crystals received maximum alpha-particle doses of 3-4.5 × 10 16 mg -1 within 10 μm of the uranpyrochlore grain boundary, but the intense irradiation has not affected either the structural integrity or the aqueous durability of the mineral.

The durability of synroc

Abstract Polished specimens of well characterised Synroc (a polyphase titanate ceramic designed to immobilise high-level nuclear waste) containing 10 wt% simulated (PW-4b-D) waste were subjected to MCC-2 type dissolution tests at 150°C in doubly deionised water (surface area to volume ratio0.01 ± 0.0005 mm −1 ) for periods of up to 532 d. Scanning electron microscopy (SEM) of the polished surfaces and transverse sections confirmed that Synroc is highly durable and suffers little corrosion even after 532 d in doubly deionised water at 150°C (corrosion of the least resistant major phase, perovskite, was

Dissolution of synthetic brannerite in acidic and alkaline fluids

Abstract The dissolution of synthetic brannerite in aqueous media at 40 and 90 °C under atmospheric redox conditions has been studied. At 40 °C, the presence of phthalate as a buffer component in the pH range of 2–6 has little effect on uranium release from brannerite. Bicarbonate increases uranium release and enhances the dissolution of brannerite. Compared to UO 2 , brannerite is more resistant to dissolution in bicarbonate solutions. In under-saturated conditions at 90 °C, the dissolution of brannerite is incongruent (preferential release of uranium) at pH 2 and nearly congruent at pH 11. TEM examinations reveal a polymorph of TiO 2 (pH 2 specimen) and a fibrous Ti-rich material (pH 11 specimen) as secondary phases. XPS analyses indicate the existence of U(V) and U(VI) species on the surfaces of specimens both before and after leaching, and U(VI) was the dominant component on the specimen leached in the pH 11 solution.

Gadolinium Borosilicate Glass-Bonded Gd-Silicate Apatite: A Glass-Ceramic Nuclear Waste Form for Actinides

A Gd-rich crystalline phase precipitated in a sodium gadolinium alumino-borosilicate glass during synthesis. The glass has a chemical composition of 45.39-31.13 wt% Gd2O3, 28.80-34.04 wt% SiO2, 10.75-14.02 wt% Na2O, 4.30-5.89 wt% Al2O3, and 10.75-14.91 wt% B2O3. Backscattered electron images revealed that the crystals are hexagonal, elongated, acicular, prismatic, skeletal or dendritic, tens of mm in size, some reaching 200 mm in length. Electron microprobe analysis confirmed that the crystals are chemically homogeneous and have a formula of NaGd9(SiO4)6O2 with minor B substitution for Si. The X-ray diffraction pattern of this phase is similar to that of lithium gadolinium silicate apatite. Thus, this hexagonal phase is a rare earth silicate with the apatite structure. We suggest that this Gd-silicate apatite in a Gd-borosilicate glass is a potential glass-ceramic nuclear waste form for actinide disposition. Am, Cm and other actinides can easily occupy the Gd-sites. The potential advantages of this glass-ceramic waste form include: (1) both the glass and apatite can be used to immobilize actinides, (2) silicate apatite is thermodynamically more stable than the glass, (3) borosilicate glass-bonded Gd-silicate apatite is easily fabricated, and (4) the Gd is an effective neutron absorber.

Immobilization of sodium and potassium in Synroc

Substitution of K for Na in certain nuclear fuel reprocessing cycles may allow an increase of waste loading in Synroc, because K can be incorporated in the barium hollandite phase more easily than Na. The use of rare-earth additions to stabilize Na in the perovskite phase may also have merit.

Durabilities of Pyrochlore-Rich Titanate Ceramics Designed for Immobilization of Surplus Plutonium

The chemical durabilities of two Pu-doped pyrochlore samples were studied by Single-Pass-Flow-Through (SPFT) tests at 70°C. The dissolution of pyrochlore is incongruent with preferential releases of Ca and Gd over Ti, close to stoichiometric releases of U and Ti, and lower releases of Hf and Pu than Ti. Altered pyrochlore and polymorphs of TiO 2 (brookite and probably anatase) have been identified on the surface of the leached sample and the principal secondary phase is an unknown polymorph of TiO 2 containing Hf and varying amounts of Gd and Pu. These surface alteration phases are consistent with reported studies of natural samples. The releases of U, Gd, Ca and Ti into solution follow linear kinetics, whereas the releases of Pu and Hf exhibit non-linear behavior. The presence of ∼5% PuO 2 and trace amounts of glass does not appear to have an effect on the overall durability of the material. Further, the low Pu release rate and the similar kinetics for Pu and Hf releases limit the possibility of nuclear criticality under repository conditions. Overall, this study provides useful information on the lower bounds of durabilities of the materials.

Density and structural effects in the radiation tolerance of TiO2 polymorphs

The radiation response of TiO₂ has been studied using molecular dynamics. The simulations are motivated by experimental observations that the three low-pressure polymorphs, rutile, brookite and anatase, exhibit vastly different tolerances to amorphization under ion-beam irradiation. To understand the role of structure we perform large numbers of simulations using the small thermal spike method. We quantify to high statistical accuracy the number of defects created as a function of temperature and structure type, and reproduce all the main trends observed experimentally. To evaluate a hypothesis that volumetric strain relative to the amorphous phase is an important driving force for defect recovery, we perform spike simulations in which the crystalline density is varied over a wide range. Remarkably, the large differences between the polymorphs disappear once the density difference is taken into account. This finding demonstrates that density is an important factor which controls radiation tolerance in TiO₂.

The replacement of titanium by zirconium in ceramics for plutonium immobilization

Zirconates and titanates, based on the nominal baseline composition developed for the Plutonium Immobilization Project, have been prepared with and without process impurities. The titanates form pyrochlore as the major phase and the zirconates form a defect-fluorite. Very little, if any, of each impurity is accommodated in the defect-fluorite with powellite, kimzeyite, a spinel and a silicate glass appearing as extra phases in this ceramic. In the titanate ceramics the pyrochlore incorporates more impurities, with the remainder forming zirconolite and a small amount of silicate glass. At extreme levels of impurities, traces of magnetoplumbite, perovskite and loveringite were found. The defect-fluorite zirconate phase is more radiation damage resistant than the titanate pyrochlore, though the secondary phases in the zirconate will reduce the radiation damage resistance of zirconate monoliths. To produce a dense product the oxide-route zirconate required sintering temperatures of about 1550 C, 200 C higher than that required for the titanate. Silicate impurities reduce the sintering temperatures appreciably.

Atomic scale modelling of hexagonal structured metallic fission product alloys

Noble metal particles in the Mo-Pd-Rh-Ru-Tc system have been simulated on the atomic scale using density functional theory techniques for the first time. The composition and behaviour of the epsilon phases are consistent with high-entropy alloys (or multi-principal component alloys)—making the epsilon phase the only hexagonally close packed high-entropy alloy currently described. Configurational entropy effects were considered to predict the stability of the alloys with increasing temperatures. The variation of Mo content was modelled to understand the change in alloy structure and behaviour with fuel burnup (Mo molar content decreases in these alloys as burnup increases). The predicted structures compare extremely well with experimentally ascertained values. Vacancy formation energies and the behaviour of extrinsic defects (including iodine and xenon) in the epsilon phase were also investigated to further understand the impact that the metallic precipitates have on fuel performance.

Zirconoiate corrosion in dilute acidic and basic fluids at 180-700° C and 50 MPa

Corrosion of zirconolite in a closed system at elevated temperature and pressure for various fluid compositions has been investigated by several analytical techniques. Together with previous studies, the results indicate a weak corrosion below 250 C at 50 MPa. Above 400 C, secondary TiO{sub 2} phases crystallize in acidic and neutral fluids on the corroded surfaces and in near-surface pores. At 550 C and above, zirconolite starts to be replaced by perovskite and calzirtite in basic fluids. Results indicate that zirconolite is reasonably durable in acidic, neutral and basic fluids up to 500 C and 50 MPa which corresponds to deep borehole conditions.