The formation of uranium minerals is still continuing in Chernobyl Unit No. 4. Yellow products of alteration that stain the surface of Chernobyl “lava” have been examined by SEM and X-ray diffraction methods. Secondary minerals of uranium identified are: UO4·4H2O studtite; UO3·2H2O epiianthinite; UO2·CO3 rutherfordine; also, Na4(UO2)(CO3)3 was identified together with the sodium carbonate phases Na3H(CO3)2·2H2O and Na2CO3·H2O. These minerals formed due to the interaction between fuel-containing masses or “lava”, water and air. The matrices of the “lava” do not contain significant amounts of sodium. The source of sodium may be water that has penetrated into the “Sarcophagus”. All identified secondary minerals of uranium are highly unstable, and their continued formation can seriously endanger the radiological situation of the 4th Unit.
Various types of Chernobyl fuel containing masses named black “lava”, brown “lava”, porous “ceramic” and “hot” particles that formed during first days of the accident at the Chernobyl Nuclear Power Plant 4th Unit were studied by methods of optical and electron microscopy, microprobe and x-ray diffraction. Data about their chemical, phase and radionuclide composition are summarized. The products of interaction between fuel, zircaloy and concrete, produced under experiments in laboratory were examined for comparison with samples of Chernobyl “lava” and “hot” particles. The behavior of nuclear fuel in first days of the Chernobyl accident was a three-stage process. The first stage occurred before the moment of the Chernobyl explosion and was exceptionally short-lasting, perhaps, less than a few seconds. It was characterized by reaching a high temperature, ≥2600 °C, in the epicenter of accident and formation of a Zr-U-O melt in a local part of the core, which is estimated to be not more than 30% of whole core volume. The second stage lasted for about 6 days since the explosion, during which there was interaction between uranium products of the destroyed reactor: UOx, UOx with Zr, Zr-U-O, with the environment and silicate structural materials of the 4th Unit. The third stage, after 6 days involved the process of final formation of the radioactive silicate melt or Chernobyl “lava” at one of the sections of the destroyed 4th Unit. During this stage the melt's lamination occurred, followed by a break-through of the “lava” reservoir on the 11 th day of the accident and penetration of the “lava” into space under the reactor.
The use of garnet/perovskite-based ceramic, with formula type (Y, Gd,..) 3(AI, Ga,..) 5O12 12/(Y, Gd,..)(A1, Ga,..)O3, was tested for immobilizing plutonium residue wastes. Pu residue wastes originate from nuclear weapons production and can contain more than 50% of impurities including such elements as Am, Al, Mg, Ga, Fe, K, La, Na, Mo, Nd, Si, Ta, Ce, Ba, B, W, Zn, Zr, C and Cl. While for some of these residues, direct conversion to typical glass or ceramic forms may be difficult, ceramic forms based on durable actinide host-phases are preferred for Pu, Am and other actinides immobilization. Garnet/perovskite crystalline host-phases are chemically and mechanically durable and desirable for the incorporation of Pu and most of the impurity elements in the Pu residue wastes in the lattices of host-phases in the form of solid solutions. Experiments on the synthesis of garnet/perovskite ceramic samples were carried out using melting in air at temperatures from 1300°C (for samples doped with 10 wt.% Pu residue waste simulant) to 2000°C (for samples doped with 10 wt.% Ce or U). Samples were studied by XRD, SEM and cathodoluminescence techniques. It was found that the garnet phase can incorporate upto 6 wt.% Ce and up to 4.0-5.5 wt.% U, which is correlated with the increase of Ga content and decrease of Al content in the melt. In one of the features of the melt, the perovskite phase formation substitutes for the formation of garnet. The capacity of the perovskite lattice to accommodate Ce and U is higher than the capacity of garnet, reaching about 8 and 7 wt.%, respectively. It was shown that cathodoluminescence can be effectively used to determine the valence state of Ce and U, an important step to optimize the starting precursor preparation. Incase of U4+ in the melt, the charge-compensating elements (Sn2+, Ca2+...) are needed to successfully incorporate U in the garnet lattice.
Zircon, ZrSiO4, as well as its Hf-analogue hafnon, HfSiO4, have been proposed for use as durable Pu host phases for the immobilization of weapons grade Pu and other actinides. Four samples of Pu-doped ceramics based on the zircon and hafnon structures were synthesized through sintering in air using precursors containing 5-6 and 10 wt% 239Pu. Synthesized ceramic samples were studied by X-ray powder diffraction (XRD), scanning electron microscopy (SEM), microprobe method, MCC-1 leach test at 25 and 90°C. Inclusions of separated a PuO2phase in the matrix of zircon-based ceramic and presumably, (Pu,Hf)O2 phase in the hafnon-based ceramic were observed for samples obtained from precursors doped with 10 wt% Pu. No separated Pu-phases in significant amounts were identified in the matrices of both ceramics obtained from the precursors doped with 5-6 wt% Pu. It was found that normalized Pu mass losses (without correction on ceramic porosity) for samples doped with 10 wt% Pu which contain separated inclusions of PuO2 or (Pu,Hf)O2 after 14/28 days were approximately (in g/m2) - for zircon: 0.2/0.2 - at 90°C and 0.03/0.04 - at 25°C and for hafnon: 0.02/0.04 - at 90°C and 0.01/0.01 - at 25°C. The losses of Pu from samples doped with 5-6 wt% are 1-2 order of magnitude less. It was suggested that optimal amount of Pu which could be incorporated by zircon and hafnon lattices does not exceed 7 wt%. An important additional conclusion is that Pu- doped ceramic based on zircon or hafnon can be successfully fabricated excluding hot pressing method.
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.
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