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A new variety of matrices based on synthetic phases whose structure is close to that of murataite (a natural mineral) is proposed for immobilization of nuclear wastes. Murataite is Na, Ca, REE, Zn, and Nb titanate with a structure derived from the fluorite lattice. This very rare mineral was found in alkali pegmatites from Colorado in the United States and the Baikal region in Russia. The synthetic murataite-like phases contain manganese instead of zinc, as well as actinides and zirconium instead of sodium, calcium, and niobium. Varieties with threefold, as in the mineral, and five-, seven-, and eightfold repetition of the lattice relative to the fluorite cell have been established. Correspondingly, the structural varieties M3, M5, M7, and M8 are recognized among the synthetic murataites. A decrease in the contents of actinides, rare earth elements, and zirconium occurs in the series M7-M5-M8-M3, along with enrichment in Ti, Al, Fe, and Ga. Murataite-based ceramics are characterized by high chemical and radiation stability. The rate of U, Th, and Pu leaching with water at 90 ° C in static and dynamic tests is 10 -6 -10 -5 g/m 2 per day. These values are lower than the leaching rate of other actinide confinement matrices, for example, zirconolite-or pyrochlore-based. Murataite is close to other titanates in its radiation resistance. At 25 ° C, amorphization of its lattice is provided by a radiation dose of 2 × 10 18 α decays/g, or 0.2 displacements/atom. Murataite-based matrices are synthesized within a few hours by cold compacting combined with sintering at 1300 ° C or by melting at 1500-1600 ° C and subsequent crystallization. The melting technology, including induction smelters with a cold crucible, makes it possible to produce samples with zonal murataite grains. The inner zone of such grains is composed of structural variety M5 or M7; the intermediate zone, of M8; and the outer zone, of M3. The contents of actinides, zirconium, and rare earth elements reach a maximum in the inner zone and drop to a minimum in the outer zone, while the amounts of nonradioactive elements-Ti, Al, Fe, and Ga-vary conversely. The U, Th, and Pu contents in the inner and outer zones differ by three to five times. Such a distribution precludes removal of actinides by interaction of the matrix with solution after its underground disposal. Individual actinides (Np, Pu, Am); the actinide-zirconiumrare earth fraction of high-level radioactive wastes (HLW); Am-Ga residues of weapons plutonium reprocessing with its conversion into U-Pu mixed oxide (MOX) fuel; and other sorts of HLW enriched in actinides, REE, and products of corrosion (Mn, Fe, Al, Zr) can be incorporated into a murataite-based matrix. As much as 350 kg of HLW components can be included in 1 t of such a ceramic. An actinide matrix that is composed of titanates with a pyrochlore structure is its nearest analogue. The advantage of murataite in comparison with pyrochlore consists in its universal character; i.e., a murataite-based matrix can be used for utilization of a wider ...

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Synthetic analogues of murataite, a very rare mineral-a complex oxide of REE, actinide, Ti, Fe, and other elements,-are of great interest as confinement matrices of radioactive wastes. They are produced by sintering (1200-1300°C) and melting (1500-1600°C) with subsequent crystallization of the melt. Four structural varieties of murataite distinguished by unit cell parameters have been established by TEM study. All these varieties are derivatives of the fluorite structure designated as murataite 3C, 5C, 7C, and 8C depend ing on repetition factor of a parameter of the fluorite subcell. The structural features of the synthetic murataite varieties are analyzed in this paper based on data obtained from high resolution electron micros copy, microdiffraction, and X ray refinement. The hypothesis of a modular structure of the members of poly somatic pyrochlore-murataite series has been confirmed. At the same time, the structural modules are zero dimensional rather than two dimensional as had previously been suggested. The combinations of zero dimensional modules in 3D space create the entire structural diversity of the polysomatic series.

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Amongst fission products formed in atomic reactors, 99 Tc is the most hazardous for the environment because of its long half-life (213000 yr), high content in spent nuclear fuel (SNF) (0.8-1.0 kg per ton of SNF), low sorption ability, and high mobility under aerobic conditions. The bulk of 99 Tc (~200 t) is incorporated into SNF. In the course of SNF reprocessing, this radioisotope is released as a separate fraction or along with actinides. More than 60 t of highly concentrated 99 Tc have been accumulated to date. It is evident that isolation of 99 Tc from the environment is a matter of great urgency. The immobilization of technetium in a highly stable and poorly soluble matrix is a necessary element in settling this problem. Ceramics composed of titanates with pyrochlore, perovskite, and rutile structures are proposed as matrices able to retain technetium along with actinides. The high chemical stability of these compounds has been corroborated by experiments. The difficulties in production of such matrices are related to the fugacity of Tc and the necessity of converting it into Tc(IV). To overcome this obstacle, self-propagating high-temperature synthesis (SHS), characterized by reductive conditions and a high reaction rate, is proposed. The charge for matrix synthesis consists of reducing agents (metallic powders with a strong affinity to oxygen, e.g., Ti and Zr), oxidants (MoO 3 , Fe 2 O 3 , CuO), and additives (TiO 2 , ZrO 2 , Y 2 O 3 , CaO, etc.), which taken together with other elements form target phases. Instead of Tc, Mo, close in chemical properties, is used in matrix synthesis as a simulator. Samples of Mo-bearing matrices have been synthesized with SHS; their phase compositions and Mo distribution therein are characterized. It has been shown that up to 40 wt % Mo can be incorporated into the synthesized matrices in the form of metal or structural admixtures in titanates. The titanate-zirconate pyrochlore-based matrices are the most appropriate for the joint immobilization of actinides, REEs, and 99 Tc.