The Interaction Between Nuclear Waste Glasses and Clay-II

1989 ◽  
Vol 176 ◽  
Author(s):  
P. Van Iseghem ◽  
K. Berghman ◽  
W. Timmermans

ABSTRACTThe interaction between simulated HLW glasses and clay has been investigated, as part of a larger programme to evaluate the performance of vitrified HLW in repository conditions. Experimental conditions were carefully chosen to simulate repository conditions as close as possible. The glass corrosion seems to be controlled by a diffusion process, but there are indications of a (small) final corrosion rate. The leaching of 134Cs, 90Sr, 239Pu and 241Am is characterized by extremely small mobile concentrations leached (for 239pu and 241Am, below detection limit). The presence of a gamma irradiation field does not increase the glass dissolution. The production of radiolythic hydrogen is strongly reduced by the presence of clay.

2021 ◽  
Vol 5 (1) ◽  
Author(s):  
Clare L. Thorpe ◽  
James J. Neeway ◽  
Carolyn I. Pearce ◽  
Russell J. Hand ◽  
Adam J. Fisher ◽  
...  

AbstractStandard methods to assess the durability of vitrified radioactive waste were first developed in the 1980’s and, over the last 40 years, have evolved to yield a range of responses depending on experimental conditions and glass composition. Mechanistic understanding of glass dissolution has progressed in parallel, enhancing our interpretation of the data acquired. With the implementation of subsurface disposal for vitrified radioactive waste drawing closer, it is timely to review the available standard methodologies and reflect upon their relative advantages, limitations, and how the data obtained can be interpreted to support the post-closure safety case for radioactive waste disposal.


2015 ◽  
Vol 1744 ◽  
pp. 153-161 ◽  
Author(s):  
Michael I. Ojovan ◽  
William E. Lee

ABSTRACTThe pH-dependence of glass corrosion rates has a well-known U-shaped form with minima for near-neutral solutions. This paper analyses the change of U-shaped form with time and reveals that the pH dependence evolves even for solutions that have pH not affected by glass corrosion mathematically corresponding to a zero surface to volume ratio. The U(t) dependence is due to changes of concentration profiles of elements in the near-surface layers of glasses in contact with water and is most evident within the initial stages of glass corrosion at relatively low temperatures. Numerical examples are given for the nuclear waste borosilicate glass K-26 which is experimentally characterised by an effective diffusion coefficient of caesium DCs = 4.5 10-12 cm2/day and by a rate of glass hydrolysis in non-saturated groundwater as high as rh = 100 nm/year The changes of U-shaped form need to be accounted when assessing the performance of glasses in contact with water solutions.


1990 ◽  
Vol 212 ◽  
Author(s):  
Enzo Curti ◽  
P. A. Smith

ABSTRACTExperimental evidence indicates that glass corrosion rates decrease proportionally with the increase of silicic acid concentration in the solution contacting the glass surface. A minimum corrosion rate (Rsat) is reached when the solution becomes saturated with respect to an unidentified amorphous siliceous compound. In a repository where the vitrified waste form is surrounded by compacted bentonite, the silica dissolved from the glass will diffuse into the pore solution and concentration gradients will be established throughout the backfill material. The silicic acid concentration at the glass-bentonite interface, and thus the glass corrosion rate, will then be diffusion controlled. Moreover, experimental work suggests that significant sorption of silica by clay minerals in bentonite may accelerate glass corrosion.A model describing glass corrosion coupled with diffusive transport and sorption of silica in bentonite has been developed and incorporated in a FORTRAN computer code (GLADIS). The model assumes: (a) a linear isotherm for the sorption of silica (KD), (b) time and space invariant pH, temperature and ionic strength, (c) proportionality between the quantity of silica precipitated and the amount of glass dissolved and (d) cylindrical geometry. Preliminary calculations with a particular parameter set at 90°C, assuming no silica sorption on the bentonite, indicate for an unfractured glass block that a stationary state is rapidly reached in which the silica concentration at the glass-bentonite interface is lower than the saturation concentration. This implies that the glass corrodes at a more rapid rate than Rsat (RsS ∼ 8 Rsat) If moderate silica sorption is assumed (KD = 0.5 m3 kg−1), the attainment of stationary conditions is delayed by the removal of silicic acid from solution, and the average corrosion rate is further increased by a factor ∼ 2.


1993 ◽  
Vol 333 ◽  
Author(s):  
W.L. Ebert ◽  
J.J. Mazer

ABSTRACTA literature survey has been performed to assess the effects of the temperature, glass surface area/leachate volume ratio, leachant composition, leachant flow rate, and glass composition (actual radioactive vs. simulated glass) used in laboratory tests on the measured glass reaction rate. The effects of these parameters must be accounted for in mechanistic models used to project glass durability over long times. Test parameters can also be used to highlight particular processes in laboratory tests. Waste glass corrosion results as water diffusion, ion exchange, and hydrolysis reactions occur simultaneously to devitrify the glass and release soluble glass components into solution. The rates of these processes are interrelated by the effects of the solution chemistry and glass alteration phases on each process, and the dominant (fastest) process may change as the reaction progresses. Transport of components from the release sites into solution may also affect the observed corrosion rate. The reaction temperature will affect the rate of each process, while other parameters will affect the solution chemistry and the particular processes that are observed during the test. The early stages of corrosion will be observed under test conditions which maintain dilute leachates and the later stages will be observed under conditions that generate more concentrated leachate solutions. Typically, water diffusion and ion exchange reactions dominate the observed glass corrosion in dilute solutions, while hydrolysis reactions are dominant in more concentrated solutions. Which process controls the long-term glass corrosion is not fully understood, and the long-term corrosion rate may be either transport- or reaction-limited.


2012 ◽  
Vol 535-537 ◽  
pp. 1337-1340 ◽  
Author(s):  
Chi Yang ◽  
Nai Lin Ren

A new chemiluminescence system was built by using gadolinium as sensitizer, and the analysis capabilities of this system was tested as below. The method is based on chemluminescence of Ce (IV)-SO32- sensitized by Gd3+-OFLX. The effects of some critical experimental conditions were discussed and the optimum conditions for chemluminescence emission were investigated. The linear relationship between the relative chemiluminescence intensity and the concentration of OFLX is in the range of 2×10-9 g/mL~5×10-7 g/mL with a detection limit of 1.0×10-9g/mL .The relative standard deviation is 2.8% (n=11) for a level of 5.0×10-7 g/mL. The method has been applied to the analysis of OFLX in tablets with satisfactory results.


1994 ◽  
Vol 353 ◽  
Author(s):  
Masaki Tsukamoto ◽  
T. Ohe ◽  
T. Fujita ◽  
R. HesbÖl ◽  
H-P. Hermansson

AbstractDiffusion experiments of radionuclides in compacted sodium bentonite with a dry density of 1.0 g/cm3 were performed in nitrogen gas atmosphere at 90 °C for 208 d and 375 d. The corrosion experiments of crushed radioactive glass, JSS-A, carried out simultaneously to provide the source of the radionuclides for the diffusion experiments. The normalized elemental mass losses of cesium isotopes and 238Pu were lower than those of boron (ca. 10 g/m2) probably because of the difference of sorption and/or precipitation. The apparent diffusion coefficients of 238Pu, 234U and 125Sb were determined to be 2x 10-14 m2/s, 5x 10-12 m2/s and 2x 10-12 m2/s, respectively. The distribution coefficient of Pu estimated from the diffusion data was of the same order as that from batch sorption experiments. The glass corrosion and the plutonium diffusion were described by the geochemical codes PHREEQE, STRAG4 and GESPER. The calculation results well fitted the observed data.


1990 ◽  
Vol 196 ◽  
Author(s):  
Yan Ma ◽  
Terence G. Langdon

ABSTRACTIt is well known that cavities are nucleated and grow during the superplastic deformation of many materials. The various theories for cavity growth are examined with special emphasis on the role of growth by diffusion. It is demonstrated that the normal model for the diffusion growth of cavities is inadequate for superplastic materials when the grain boundary lengths are very small. By developing a new model for the growth of an isolated cavity to sizes exceeding the grain size, it is shown that the diffusion process may play a major role in cavity growth under a range of experimental conditions.


MRS Advances ◽  
2017 ◽  
Vol 3 (20) ◽  
pp. 1085-1091 ◽  
Author(s):  
Konstantin V. Martynov ◽  
Elena V. Zakharova ◽  
Sergey V. Stefanovsky ◽  
Boris F. Myasoedov

ABSTRACTSlow cooling of phosphate melt at liquid nuclear waste solidification yields glass-crystalline material. Partial crystallization during melt solidification results in elemental partitioning among crystalline phase and glass: Al, Cr, Fe are concentrated in the crystalline phosphate phase while Ca, Ni, La, U enter predominantly in the residual glass. Glass dissolution rate and leach rate of La and U as rare earth and actinide surrogates depends strongly on the glass composition, for example reduction of Al2O3 content in the glass to ∼10-12 wt.% increases leachability by three orders of magnitude as compared to the glass with specified composition (∼18-22 wt.% Al2O3).


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