The isometric, pyrochlore structure type, A2B2O7, exhibits a wide variety of properties that find application in a large number of different technologies, from electrolytes in solid oxide fuel cells to actinide-bearing compositions that can be used as nuclear waste forms or inert matrix nuclear fuels. Swift xenon ions (1.43 GeV) have been used to systematically modify different compositions in the Gd2Zr2-xTixO7 binary at the nanoscale by radiation-induced phase transitions that include the crystalline-to-amorphous and order-disorder structural transformations. Synchrotron x-ray diffraction, Raman spectroscopy, and transmission electron microscopy provide a complete and consistent description of structural changes induced by the swift heavy ions and demonstrate that the response of pyrochlore depends strongly on chemical composition. The high and dense electronic energy deposition primarily results in amorphization of Ti-rich pyrochlore; whereas the formation of the fully disordered, defect-fluorite structure is the dominant process for Zr-rich pyrochlore.

Understanding the corrosion of spent nuclear fuel (SNF) and the subsequent mobilization of released radionuclides, particularly under oxidizing conditions, is one of the key issues in evaluating the long-term performance of a nuclear waste repository. However, the large amounts of iron in the metal waste package may create locally reducing conditions that would lower corrosion rates for the SNF, as well as reduce the solubility of some key radionuclides, e.g., Tc and Np. In order to investigate the interactions among SNF-waste package-fluids, four smallscale (∼1:40 by length) waste package mockups were constructed using metals similar to those proposed for use in waste packages at the proposed repository at Yucca Mountain. Each mockup experiment differed with respect to water input, exposure to the atmosphere, and temperature. Simulated Yucca Mountain process water (YMPW) was injected into three of the mockups at a rate of 200 μL per day for five days a week using a calibrated needle syringe. The YMPW was prepared by equilibrating 50 mg/L silica as sodium metasilicate with air, and adding enough HCl to lower the pH to 7.6 in contact with an excess of powdered calcite.

X-ray powder diffraction and scanning electron microscopy confirm that, where corrosion occurred, the dominant corrosion product in all cases was magnetite. In the high temperature (60°C) experiment, hematite and a fibrous, Fe-O-Cl phase were also identified. The Fe(II)/Fe(III) ratios measured in the corrosion products using a wet chemistry technique indicate extremely low oxygen fugacities (10-36 bar). Experiments are in progress in which 0.1g powdered UO2 was included in the mock-up in order to investigate the relative kinetics of Fe and U oxidation and to identify the U corrosion products formed under these conditions.

Systematic studies of a series of RE-titanate pyrochlore single crystals determined the formation enthalpies, ΔH0f-ox, and the critical amorphization temperature, Tc, the temperature above which the crystal can no longer be amorphized. A negative linear correlation was observed between ΔH0f-ox and Tc. In general as the cation radius ratio, RA/RB, decreases the formation enthalpy becomes less exothermic, i.e. the pyrochlore structure becomes less thermodynamically stable while the susceptibilty to ion beam-induced amorphization decreases. The opposite relation, i.e. a positive linear correlation between ΔH0f-ox and Tc was observed for a series of REPO4 single crystals with both the monazite and xenotime structures. Both relations can be understood in terms of pyrochlore and orthophosphate crystal chemistry, their formation of point defects, and the role of ion-irradiation induced phase transformations.

Electron and ion irradiation-induced nanostructures in an iron phosphate glass with a composition of 45 mol%Fe2O3-55 mol%P2O5 have been characterized by advanced electron microbeam techniques. Analysis by energy-filtered transmission electron microscopy indicated that Fe-rich and P-rich nanophases were formed when the glass was irradiated under a broad (with a diameter of 1.2μm) electron beam [give the dose range]. Phase separation developed with the increase in electron dose (from 1.0×1026e/m2 to 4.8×1026e/m2) as a result of the formation of an Fe-rich phase and pure P-phase. The formation of the Fe-rich and the P-phases are thought to be due to mainly ionization process. Under a low energy ion beam irradiation, Fe/FeO nanoparticles were formed, as confirmed by selected-area electron diffraction analysis. However, no nanoparticles were observed under a high-energy high-dose ion irradiation. The ion beam-irradiation results suggest that the formation of the Fe/FeO nanoparticles was due to preferential sputtering during ion irradiation and that the nanoparticles lie within the surface layers of the glass.

YSZ and MgAl2O4-YSZ composite are two promising materials as in the inert matrix nuclear fuel for the incineration of plutonium. In this study, 400 keV Cs ions were implanted to a fluence of 1×1017 ions/m2 in both materials in order to investigate the retention behavior of fission product at elevated temperature. The implantations were completed at room temperature for the YSZ and 973 K for MgAl2O4-YSZ, respectively. Subsequent annealing at 1273 K was performed after a room temperature implantation of YSZ. After annealing, a high density of gas bubbles formed with diameter from 3 to 40 nm from the surface to a depth of 150 nm in the YSZ matrix. The swelling due to bubbles formation was estimated to be 2.5%. In situ TEM was employed during high temperature ion implantation of the MgAl2O4-YSZ composite. A high density of small bubbles with 5 nm in diameter formed in the MgAl2O4 and YSZ grains after an ion dose of 1×1017 ions/cm2. There was no preferential precipitation along grain boundaries. Electron Paramagnetic resonance (EPR) spectroscopy was used to investigate the type of defects that formed in the YSZ matrix.

Pyrochlore is a complex oxide with general formula VIIIA2VIB2O6X (X – additional anion in specific position, usually O2-). It has a fluorite-derived structure (space group Fd3m) where one-eighth of oxygens are missing. Two different structural sites for cations exist, resulting in the cell parameter of pyrochlore is twice that of the fluorite lattice. Some pyrochlore-based actinide waste forms have been produced in the systems: CaO-CeO2-TiO2, CaO-UO2(ThO2)-ZrO2, CaO-UO2(ThO2)-Gd2O3-TiO2-ZrO2, and CaO-ThO2-SnO2. The oxide precursors were cold pressed at 200 – 400 MPa and sintered at 1500 – 1550 °C for 6-10 hours in air or at 1300 – 1350 °C for 5-50 hours in pure oxygen (Ce-doped batches only). The use of pure oxygen was used to try to put Ce in the tetravalent state required to form a pyrochlore.

The products were examined with XRD, SEM/EDS, and TEM. In the ceramics with bulk compositions: CaCeTi2O7, CaThZr2O7, (Ca0.5GdTh0.5)(TiZr)O7, (Ca0.5GdU0.5)(TiZr)O7, and CaThSn2O7, pyrochlore was the major phase, but fluorite-structured oxide was also present. In the samples with target compositions CaUZr2O7 and (Ca0.5GdU0.5)Zr2O7 pyrochlore was not identified, rather a fluorite-structured oxide appeared. Different occurrences of pyrochlore and defect fluorite in the ceramics produced are due to crystal chemical constraints.

Yttria stabilized zirconia (YSZ) is an important oxygen ion conducting solid electrolyte. YSZ is used in oxygen sensors, oxygen pumps, and fuel cells. Perovskite-type oxides of general formula ABO3 are also of fundamental significance due to their electrical and electro-optical properties. SrZrO3 is a promising material- for application as protonic conductor. in this paper, we present electron microscopy analysis of the formation of SrZrO3 nano-particles in the top surface of YSZ single crystal after ion implantation. These results demonstrate a unique process for obtaining mixed-conducting oxides in the surface layer of YSZ. in addition, it is important to study the behavior of strontium in YSZ because of the potential application of YSZ as an inert fuel matrix for “burning“ excess plutonium in nuclear reactors.

400 keV strontium ions have been implanted into YSZ at room temperature to a fluence of lxl021 ions/m2.

Cesium, iodine and strontium ions have been implanted into yttria-stabilized cubic zirconia (YSZ) to determine the effects of fission product incorporation in YSZ that is considered as an inert nuclear fuel matrix. The ion implantation was conducted at room temperature to 1 × 1021ions/m2 for each ion with ion energies ranging from 70 to 400 keV. The peak displacement damage level and the peak ion concentration in YSZ reached 205-330 dpa and 11-26 at%, respectively. The microstructure of the implanted YSZ was studied by in situ and cross-sectional transmission electron microscopy. In the iodine and strontium implanted samples, a damaged layer with a high density of defect clusters was observed, while in the cesium implanted specimen, the damaged layer is amorphous. Nanocrystalline precipitates were observed in the strontium implanted specimen after annealing at 1000°C. The results are discussedin terms of the ionic size, mobility and the solubility of the implanted species in YSZ.

A Gd-rich crystalline phase precipitated in a sodium gadolinium alumino-borosilicate glass during synthesis. The glass has a chemical composition of 45.4-31.1 wt% Gd2O3, 28.8-34.0 wt% SiO2, 10.8-14.0 wt% Na2O, 4.3-5.9 wt% Al2O3, and 10.8-14.9 wt% B2O3. Backscattered electron images revealed that the crystals are hexagonal, elongated, acicular, prismatic, skeletal or dendritic, tens of μm in size, some reaching 200 μm 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.

A calorimetric investigation of the enthalpies of formation of Gd2(Ti2-xZrx)O7, where 0≤ × ≤ 2 is underway. All samples exhibit pyrochlore (Fd3m) peaks in their XRD patterns. However, where x=2 significant local disorder is observed in the Raman spectra. Preliminary data for the enthalpies of formation from the oxides in kJ/mol are: x=0, ΔHf = -113.4±2.7; x=0.5, ΔHf = -94.0±3.0; x=1.0, ΔHf = -74.2±4.9; x=1.5, ΔHf = -64.5±2.0; x=2, ΔHf = -52.2±4.8. Two additional samples, Gd1.80Zr2.15O7.00 (pyrochlore) and Gd2.15Zr1.87O7.00 (fluorite), were also studied. Their enthalpies of formation from the oxides in kJ/mole are -50.9±3.3 and -46.4±3.4 respectively. Replacing Ti with Zr, i.e. when x=2, destabilizes the pyrochlore in enthalpy by approximately 60 kJ/mol. The ΔHmix for the Gd2(Ti2-xZrx)O7 solid-solution series is positive and can be described by a regular solution formalism with an estimated interaction parameter, ŝ = +20 kJ/mol. The results of this study suggest that the pyrochlore to fluorite transition enthalpy in Gd2Zr2O7 is small, of the order of the configurational entropy contribution due to cation disorder at the transition temperature, TΔSconf. ≍ 10 kJ/mol.

Numerous studies of pyrochlore group minerals have been completed over the previous 15 years, providing researchers in the field of nuclear waste disposal with a large body of data relevant to the behavior of these minerals in natural systems. The information obtained from studies of natural pyrochlore is applicable to the formulation of diverse waste form compositions and provides data for the assessment of the long-term behavior. Although resistant to dissolution, pyrochlore is subject to chemical alteration by ion exchange with hydrothermal fluids and low temperature ground water; however, Th and U are generally immobile and are retained in the structure. X-ray diffraction, TEM, EXAFS-XANES, and other techniques have been employed in studies of radiation damage. These studies reveal the classic sequence of damage microstructures with increasing dose and provide details about the structure of the amorphous state. Furthermore, the radiation damage studies are now complemented by data relating to the thermal histories of some of the host rocks.

The long-term radiation effects on materials in the near-field of a nuclear waste repository have been evaluated using accelerated laboratory experiments with energetic electron or ion beam irradiation. The materials studied include: zeolites, layered silicates (smectite clay and mica), as well as crystalline silicotitanate (CST) which is an important ion exchange material for the chemical separation of high-level liquid radioactive wastes.

In situ transmission electron microscopy (TEM) during irradiation by energetic electrons and ions has shown that all of the studied materials are susceptible to irradiation-induced amorphization. At room temperature, complete amorphization was observed after ionizing doses of 1010 ∼ 1012 Gy or displacement doses on the order of 0.1 dpa (equivalent to doses received in 400-1,000 years for a high-loading nuclear waste form). Amorphization may be preceded or accompanied by dehydration, layer spacing reduction and gas bubble formation. In the case of zeolites, CST and some layered silicates, radiation effects are significantly enhanced at higher temperatures. Our experiments have shown that amorphization or even partial amorphization will cause a dramatic reduction in ion exchange and sorption/desorption capacities for radionuclides, such as Cs and Sr. Because the near-field or chemical processing materials (e.g. zeolites or CST) will receive a substantial radiation dose after they have incorporated radionuclides, our results suggest that radiation effects may, in some cases, retard the release of sorbed or ion-exchanged radionuclides.

Various REE-Sr-(Pb)-crandallites, uraninite, and coffinite in the near-field of the 2 Ga old super-gene-altered Bangombé U-deposit and its natural fission reactor (RZB) have been examined. The crandallite minerals may have formed during syncriticality host-rock alteration, continous alteration of phosphates, episodic Pb-loss and/or supergene weathering. Coffinitization with P2O5 and SO4-substitution has occurred immediately below RZB and resulted in extensive loss of U (≤ 46%) and enrichment of Ce (≤ 190%) and Nd (≤ 780%). Additional loss of U during coffinitization also may have occurred due to dissolution. Current alteration under oxidizing conditions has resulted in partial dissolution of uraninite and coffinite and the formation of uranyl phases. Despite supergene alteration, the hydrogeochemistry (3.09 ppt U [235U/238U = 0.7012 to 0.7019%], 4.96 ppt Ce, and 1.92 ppt Nd) suggests a remarkable retardation of lanthanides and depleted uranium by REE-Sr-(Pb)-crandallites, uraninite, coffinite, and uranyl phases at RZB.

The solubilities of Hf and Gd in sodium alumino-borosilicate glasses based on the target compositions were examined and confirmed by electron microprobe analysis. The measured compositions of essentially crystal-free glasses are generally homogeneous and close to the target compositions. Therefore, the solubilities of Gd and Hf in sodium alumino-borosilicate glasses based on the target glass compositions are valid. However, for glasses containing precipitates (crystals grown from the melt) and undissolved HfO2 with overgrowths, the chemical compositions are often heterogeneous and may be significantly different from the target compositions. Precipitated crystalline phases include a rare earth silicate with the apatite sructure (NaGd9(Si5.25B)O26) in a gadolinium sodium alumino-borosilicate glass and a HfO2 phase in hafnium sodium alumino-borosilicate glasses.

Synthetic ZrSiO4, HfSiO4, and ThSiO4 single-crystal specimens were irradiated by 800 keV Kr+ ions, and the microstructural evolution was observed in-situ in a transmission electron microscope. All three compounds were found to become amorphous up to temperatures in excess of 600°C. Using a new model, the activation energies for annealing were found to be in the range of 3.1 to 3.6 eV for these compounds. At temperatures above 600°C, the orthosilicates were observed to decompose into the component oxides (e.g., tetragonal ZrO2 + amorphous SiO2 in the case of zircon). A single-crystal zircon specimen was also irradiated with a pulsed picosecond Nd:YAG laser operated at 355 nm, and the resulting microstructure was investigated by optical absorption, SEM, AFM, and TEM techniques.

The objective of this study was to simulate the aqueous corrosion of the nuclear waste glass over extended periods of time using vapor phase alteration by which reaction progress of glass corrosion is accelerated to form a characteristic suite of secondary alteration phases. In this study, extensive SEM/EDS, AEM, and HRTEM have been performed on the French SON68 waste glasses which were reacted in saturated water vapor at 200 °C for 908, 1013, and 1021 days, respectively. In order to study chemistry and microstructure of surface layers, TEM specimens were prepared in cross-section using the ultramicrotomy slicing technique. In this process, small chunks containing the surface layer and a thin layer of unaltered glass were broken off from the sample surface and each of these chunks was then embedded in resin to form a block. Finally, thin sections, approximately 50-90 nm thick, were microtomed from these blocks and were transferred to holey carbon coated copper grids.

Radiation damage in quartz has been of interest to the semiconductor industry, optical fiber industry, and nuclear industry. Cross-section transmission electron microscopy (TEM) is a powerful tool for investigating the irradiation effects since it provides a direct measurement of the ion and the damage distributions, and can also provide detailed microstructural information such as the presence of amorphous regions and the size, density and chemical nature of defect aggregates. The results reported below are from a systematic cross-section TEM study on 1.5 MeV Kr+ ion irradiated quartz.

3-mm discs of quartz (along 010 face) were prepared with 100 μm in thickness. One side for each discs was well polished using a 0.05 μm diamond paste. The well-polished side was irradiated at room temperature with 1.5 MeV Kr ions in the HVEM-Tandem Facility at Argonne National Laboratory. Following irradiation, cross-section TEM specimens were prepared using the so-called T-tool technique, a modified tripot technique

Zirconia containing actinides in solid solution, (Zr, An)Ox, where An = U, Pu, Am, Np, Cm is considered as a starting material for the synthesis of two durable crystalline host-phases for actinide immobilization: zircon (Zr, An)SiO4 and cubic zirconia (Zr,An)O2. The use of this starting material is necessary in order to provide for total actinide incorporation into the structures of the final phases, zircon and cubic zirconia, while avoiding the presence of unincorporated actinides. Difficulties arise when the chemically inert pure oxides, ZrO2 and AnOx are used as precursor materials. Melting techniques, which are commonly used to provide solid solution of inert oxides are not acceptable for ceramic preparation, particularly the synthesis of ceramic Pufuels. This paper presents a new approach utilizing plasma calcination. Solids containing both zirconium and actinides are calcined in a plasma. This allows the use of intermediate, stabilized actinide forms, for example, co-precipitated actinide-zirconium oxalates which have a low solubility level or a solid sol-gel precursor, such as (Zr, An)SiOx.

Calcination was completed using an induction plasma in an argon gas mredium. Two types of material were used: co-precipitated oxalates of Zr and Ce with 10 wt.% Ce and a solidified sol-gel (Zr, Ce)SiOx with 10 wt.% Ce. Weakly milled material with a particle size of 0.34 mm was dropped through the plasma at a speed of 40-60 grams per hour. The final product was examined by high resolution transmission electron microscopy (HRTEM). The calcined oxalate material consisted of aggregates of globular particles (tens to hundreds of nm) of monoclinic and tetragonal (Zr,Ce)O2. The calcined sol-gel consisted of globular particles (50 to 100s nm) of monoclinic and tetragonal (or pseudo-cubic) (Zr, Ce)O2 in an amorphous silica matrix. This paper discusses the application of plasma calcination to the immobilization of excess weapons Pu and other actinides. The plasma calcination of solid materials would be used for ceramic Pu-fuel fabrication, as well as for the final disposal in geological formations.

Zircon, ZrSiO4, is a prospective durable host material for the immobilization of excess weapons plutonium. Using cerium as a chemical analogue for plutonium, the experiments on the synthesis of Ce-doped zircon were conducted by sintering of sol-gel precursors in air and vacuum. The results showed that cerium substantially promotes zircon formation from sol-gel precursors and sintering in air is preferable for cerium incorporation in zircon structure. Based on measured lattice constants, solid solution compositions (Zr0.96Ce0.04)SiO4 and (Zr0.98Ce0.02)SiO4 were formed in samples sintered in air at 1400°C and 1600°C, respectively. The solubility limits of cerium and actinides in zircon and mechanism of zircon formation are discussed.