The "specific sorption" of neptunium(V) on smectite, in other words, a strong sorption undesorbable by 1 M KCl, is studied with a combination of batch type sorption and desorption experiments over a pH range of 2 to 5. Six types of homoionic smectite (Li-, Na-, Κ-, Cs-, Mg-, and Ca-smectite) are used in this study. Distribution coefficients (K d ) of neptunium for smectite vary over a wide pH range; the maximum K d value of ~300 cm 3 · g _1 at around pH 2 for Li-and Na-smectite and the minimum value of ~2cm 3 · g"' for Cs-smectite. The specific sorption of neptunium depends on pH and on the affinity of the exchangeable cation for smectite; the lower the pH of solution or the affinity, the larger the specific sorption. The neptunium-smectite association varies with the elapse of contact time. Within the first day of the neptunium-smectite contact the neptunium sorbed on Nasmectite at low pH is desorbable by 1 M KCl solution, and on the passage of time most of the neptunium sorbed becomes undesorbable by KCl (the specific sorption). Hydronium ion in solution is sorbed on smectite at low pH and dissociates the exchangeable cation from smectite into solution, and the specific sorption of neptunium increases with increasing the exchangeable cation that is dissociated from smectite.

The microstructural changes of a simulated waste glass irradiated with doping of 238pu and 244Cm were observed by use of a preshadowed carbon replica technique in combination with scanning electron microscopy (SEM). The irradiated glass was annealed and its microstructural changes after annealing were observed by use of the sametechnique.In the glass irradiated at a dose of 2.75x1025 α-decays/m3, bubbles with a radius from 0.15μrm to 0.35μm were observed. The average bubble radius and the bubble density were 0.23μm and 1x1017 bubbles/m3, respectively. Using these observed values, the volume change of the glass resulting from the bubble formation was estimated to be + 0.51 %. This valuoof + 0.51 % was close to the volume change of the irradiated glass measured in our previous study, which suggests a large portion of the volume change by α-irradiation results from bubble formation. In the glass annealed after irradiation the average bubbleradius was observed to decrease with annealing time. The bubble radius as a function of annealing time was analyzed on the basis of the helium diffusion model with two chemicalprocesses, i.e. trapping at bubbles and re-solution from bubbles into glass matrix. The values of the diffusion coefficient of helium, the trapping parameter and the re-solution parameter, which had been obtained experimentally in our previous study on the helium release, were applied to the calculation. The calculated curve was in good agreement with the observed data.

A simulated nuclear waste glass was self-irradiated by doping with short-lived actinides of 238Pu and 244Cm. Changes in the hardness, the Young's modulus and the fracture toughness, as a function of irradiation dose, were measured by use of indentation techniques. The irradiated glass was annealed at temperatures from 573K to 723K for periods of up to 48hours, and the recovery of these changes were measured as a function of annealing temperature and time.It was observed that the hardness and the Young's modulus decreased, while the fracture toughness increased exponentially with the cumulative dose. The maximum values of the relative changes in the hardness, the Young's modulus and the fracture toughness were about −25%, −30% and +45%, respectively. The results of the annealing show that the hardness and the Young's modulus were almost recovered to the original values at temperatures above 673K within 10 hours, while the recovery of the fracture toughness was minimal in this region of temperature and time. The changes in the hardness and the Young's modulus can be well explained by the model, in which the changes is proportional to the volume fraction of damaged zones, F, and the recovery of F is first order. On the other hand, the changes in the fracture toughness cannot be explained by the model, which suggests that the mechanism of the change in the fracture toughness is different from that in the hardness and the Young's modulus.

Phase stability and effects of sintering atmosphere on the crystalline structure of Np-doped yttria-stabilized zirconia (YSZ) were evaluated in comparison with those same properties and conditions for Ce-doped YSZ. Different sintering atmospheres for Ce-doped YSZ led to differences in phase formation through reduction of the dopant from Ce 4؉ to Ce 3؉ . On the other hand, YSZ specimens containing up to 40 mol% Np formed only a fluorite-structure phase regardless of sintering atmosphere. Yttria-stabilized zirconia thus seems to accommodate Np within a wide range of concentrations and to have excellent phase stability under both oxidizing and reducing atmospheres.

A new type of flow-through test method using micro-reactor was developed and applied to measurement of the dissolution/alteration kinetics for a Japanese type of simulated HLW glass, P0798. In this test method, a face of coupon shaped glass specimen (30mm × 10mm × 4mm size) is in contact with a micro-channel (20mm length, 2mm width, 0.16mm depth) constructed on a PTFE (Teflon®) plate, and a solution is injected into the inlet of micro-channel at a constant rate. The injected solution, which flows through the micro-channel reacting with the glass to the outlet, is retrieved at certain intervals to be analyzed for determination of the glass dissolution/alteration rate. After the test, the glass specimen removed from the micro-reactor is subjected to surface analyses. This test method has major features as follows, 1) any controlled solution condition can be provided over the test duration, 2) a relatively high S/V ratio can be provided by use of micro-reactor in spite of using coupon shaped glass specimen, which results in precise and consistent analyses of both the solution and the reacted glass surface, 3) the test apparatus is simple with compact size and easy operation, which allows a flexible setup of test conditions. By use of this test method the dissolution/alteration rate for P0798 glass was measured as a function of pH, temperature, and time, and the results indicated that this test method is applicable and suitable for evaluation of the dissolution/alteration kinetics.