Long-term Corrosion of Zircaloy-4 and Zircaloy-2 by Continuous Hydrogen Measurement under Repository Condition

2013 ◽  
Vol 1518 ◽  
pp. 173-178 ◽  
Author(s):  
Tomofumi Sakuragi ◽  
Hideaki Miyakawa ◽  
Tsutomu Nishimura ◽  
Tsuyoshi Tateishi

ABSTRACTCorrosion behavior is a key issue for the waste disposal of irradiated metals, such as hulls and endpieces, and is considered to be a leaching source of radionuclides including C-14. However, little information about Zircaloy corrosion in anticorrosive conditions has been provided.In the present study, long-term corrosion tests of Zircaloy-4 and Zircaloy-2 were performed in assumed disposal conditions (dilute NaOH solution, pH 12.5, 303 K) by using the gas flow system for 1500 days. The corrosion rate, which was determined by measuring gaseous hydrogen and the hydrogen absorbed in Zircaloy, decreased with immersion time and was lower than the value of 2×10−2 μm/y used in performance assessment (1500-day values: 5.84×10−3 and 5.66×10−3 μm/y for Zircaloy-4, 1000-day values: 8.81×10−3 μm/y for Zircaloy-2). The difference in corrosion behavior between Zircaloy 4 and Zircaloy-2 was negligible. The average values of the hydrogen absorption ratios for Zircaloy-4 and Zircaloy-2 during corrosion were 91% and 94%, respectively.The hydrogen generation kinetics of both gas evolution and absorption into metal can be shown by a parabolic curve. This result indicates that the diffusion process controls the Zircaloy corrosion in the early corrosion stage of the present study, and that the thickness of the oxide film in this stage is limited to approximately 25 nm and may therefore be in the form of dense tetragonal zirconia.

2012 ◽  
Vol 1475 ◽  
Author(s):  
Tomofumi SAKURAGI ◽  
Hideaki MIYAKAWA ◽  
Tsutomu NISHIMURA ◽  
Tsuyoshi TATEISHI

ABSTRACTCorrosion tests of Zircaloy-4 were performed in a dilute NaOH solution (pH =12.5) at 303 K for 90 days using the gas flow system (oxygen; < 1 ppb) and a batch method (oxygen; < 0.1 ppm). The corrosion rate was determined by measuring gaseous hydrogen and the hydrogen absorbed into Zircaloy-4 assuming the following reaction:where x represents the Zircaloy-4 hydrogen absorption ratio. The initial hydrogen content in the Zircaloy-4 specimen was controlled to be below 10 ppm. The corrosion rate decreased with time (90-day values: 2.46×10-3 and 2.37×10-3 μm/y for the gas flow method and 6.72×10-2 μm/y for the batch test). The Zircaloy-4 hydrogen absorption ratio during corrosion was over 90%. The large amount of hydrogen absorbed in Zircaloy-4 will play an important role in the long-term safety for the disposal of irradiated Zircaloy materials.


1996 ◽  
Vol 465 ◽  
Author(s):  
L. Nuñez ◽  
W. L. Ebert ◽  
S. F. Wolf ◽  
J. K. Bates

ABSTRACTWe are characterizing the corrosion behavior of the radioactive glass that was made with sludge from Tank 51 at the Defense Waste Processing Facility (DWPF) and a nonradioactive glass having the same composition, except for the absence of radionuclides. Static dissolution tests are being conducted in a tuff groundwater solution at glass surface area/solution volume ratios (S/V) of 2000 and 20,000 m−1. These tests are being conducted to assess the relationship between the behavior of this glass in a 7-day Product Consistency Test and in long-term tests, to assess the effects of radionuclides on the glass corrosion behavior, and to measure the disposition of radionuclides that are released as the radioactive glass corrodes. The radioactive glass reacts slower than the nonradioactive glass through the longest test durations completed to date, which are 140 days for tests at 2000 m−1 and about 400 days for tests at 20,000 m−1. This is probably because radiolysis results in lower solution pH values being maintained in tests with the radioactive glass. Rate-affecting alteration phases that had formed within one year in tests with other glasses having compositions similar to the Tank 51 glass have not yet formed in tests with either glass.


2012 ◽  
Vol 1475 ◽  
Author(s):  
An Mariën ◽  
Elie Valcke ◽  
Nele Bleyen ◽  
Steven Smets

ABSTRACTThe behavior of Eurobitum bituminized radioactive waste under geological disposal conditions is studied in water uptake tests at the Belgian Nuclear Research Centre SCK•CEN to assess the feasibility of geological disposal for the long-term management of this waste. The hydro-mechanical behavior of this waste is affected by the continuous evolution of the rheological properties of bitumen due to radio-oxidation (i.e. ageing).The effect of the bitumen ageing degree on the kinetics of the water uptake, swelling and NaNO3 leaching is investigated in water uptake tests with ∼30 years old radioactive samples and inactive samples that were artificially aged. The first results of swelling and NaNO3 leaching of (i) radioactive samples that have been hydrated for more than 2 years at a constant total stress of 2.2 MPa, and (ii) a thermally aged sample that has been hydrated for ∼1.5 years under nearly zero effective stress conditions, revealed lower swelling and higher leach rates for these samples compared to non-aged samples. The effect of ageing on the osmotic efficiency of bitumen as a semi-permeable membrane is less pronounced when swelling of the samples is limited, and changes in time, probably because of the formation of low porosity layers, which seems to mask the difference in bitumen membrane efficiency of aged and non-aged bituminized waste.


1977 ◽  
Vol 16 (01) ◽  
pp. 30-35 ◽  
Author(s):  
N. Agha ◽  
R. B. R. Persson

SummaryGelchromatography column scanning has been used to study the fractions of 99mTc-pertechnetate, 99mTcchelate and reduced hydrolyzed 99mTc in preparations of 99mTc-EDTA(Sn) and 99mTc-DTPA(Sn). The labelling yield of 99mTc-EDTA(Sn) chelate was as high as 90—95% when 100 μmol EDTA · H4 and 0.5 (Amol SnCl2 was incubated with 10 ml 99mTceluate for 30—60 min at room temperature. The study of the influence of the pH-value on the fraction of 99mTc-EDTA shows that pH 2.8—2.9 gave the best labelling yield. In a comparative study of the labelling kinetics of 99mTc-EDTA(Sn) and 99mTc- DTPA(Sn) at different temperatures (7, 22 and 37°C), no significant influence on the reduction step was found. The rate constant for complex formation, however, increased more rapidly with increased temperature for 99mTc-DTPA(Sn). At room temperature only a few minutes was required to achieve a high labelling yield with 99mTc-DTPA(Sn) whereas about 60 min was required for 99mTc-EDTA(Sn). Comparative biokinetic studies in rabbits showed that the maximum activity in kidneys is achieved after 12 min with 99mTc-EDTA(Sn) but already after 6 min with 99mTc-DTPA(Sn). The long-term disappearance of 99mTc-DTPA(Sn) from the kidneys is about five times faster than that for 99mTc-EDTA(Sn).


2014 ◽  
Vol 3 ◽  
pp. 183-195
Author(s):  
Elena Macevičiūtė

The article deals with the requirements and needs for long-term digital preservation in different areas of scholarly work. The concept of long-term digital preservation is introduced by comparing it to digitization and archiving concepts and defined with the emphasis on dynamic activity within a certain time line. The structure of digital preservation is presented with regard to the elements of the activity as understood in Activity Theory. The life-cycle of digitization processes forms the basis of the main processing of preserved data in preservation archival system.The author draws on the differences between humanities and social sciences on one hand and natural and technological science on the other. The empirical data characterizing the needs for digital preservation within different areas of scholarship are presented and show the difference in approaches to long-term digital preservation, as well as differences in selecting the items and implementing the projects of digital preservation. Institutions and organizations can also develop different understanding of preservation requirements for digital documents and other objects.The final part of the paper is devoted to some general problems pertaining to the longterm digital preservation with the emphasis of the responsibility for the whole process of safe-guarding the cultural and scholarly heritage for the re-use of the posterior generations. It is suggested that the longevity of the libraries in comparison with much shorter life-span of private companies strengthens the claim of memory institutions to playing the central role in the long-term digital preservation.


2019 ◽  
Author(s):  
Chem Int

The kinetics of oxidation of methyl orange by vanadium(V) {V(V)} has been investigated in the pH range 2.3-3.79. In this pH range V(V) exists both in the form of decavanadates and VO2+. The kinetic results are distinctly different from the results obtained for the same reaction in highly acidic solution (pH &lt; 1) where V(V) exists only in the form of VO2+. The reaction obeys first order kinetics with respect to methyl orange but the rate has very little dependence on total vanadium concentration. The reaction is accelerated by H+ ion but the dependence of rate on [H+] is less than that corresponding to first order dependence. The equilibrium between decavanadates and VO2+ explains the different kinetic pattern observed in this pH range. The reaction is markedly accelerated by Triton X-100 micelles. The rate-[surfactant] profile shows a limiting behavior indicative of a unimolecular pathway in the micellar pseudophase.


2007 ◽  
Vol 2 (1) ◽  
Author(s):  
M. Hochedlinger ◽  
W. Sprung ◽  
H. Kainz ◽  
K. König

The simulation of combined sewer overflow volumes and loads is important for the assessment of the overflow and overflow load to the receiving water to predict the hydraulic or the pollution impact. Hydrodynamic models are very data-intensive and time-consuming for long-term quality modelling. Hence, for long-term modelling, hydrological models are used to predict the storm flow in a fast way. However, in most cases, a constant rain intensity is used as load for the simulation, but in practice even for small catchments rain occurs in rain cells, which are not constant over the whole catchment area. This paper presents the results of quality modelling considering moving storms depending on the rain cell velocity and its moving direction. Additionally, tipping bucket gauge failures and different corrections are also taken into account. The results evidence the importance of these considerations for precipitation due the effects on overflow load and show the difference up to 28% of corrected and uncorrected data and of moving rain cells instead of constant raining intensities.


1980 ◽  
Vol 45 (3) ◽  
pp. 697-702 ◽  
Author(s):  
Vlastimil Vyskočil ◽  
Miroslav Zdražil

Kinetics of isomerisation of cyclohexene to methylcyclopentene proceeding as parallel reaction to hydrogenation of cyclohexene to cyclohexane on cobalt-molybdenum catalysts of different composition has been measured. The surface acidity of these catalysts was estimated from the difference in the adsorption of toluene and heptane which was measured by chromatographic method. In a series of catalysts containing molybdenum the acidity parallels isomerisation activity. Cobalt on alumina catalysts and alumina itself have greater acidity but exhibit lower isomerisation activity compared to the catalysts containing molybdenum.


2014 ◽  
Vol 18 (9) ◽  
pp. 3763-3775 ◽  
Author(s):  
K. Meusburger ◽  
G. Leitinger ◽  
L. Mabit ◽  
M. H. Mueller ◽  
A. Walter ◽  
...  

Abstract. Snow processes might be one important driver of soil erosion in Alpine grasslands and thus the unknown variable when erosion modelling is attempted. The aim of this study is to assess the importance of snow gliding as a soil erosion agent for four different land use/land cover types in a subalpine area in Switzerland. We used three different approaches to estimate soil erosion rates: sediment yield measurements in snow glide depositions, the fallout radionuclide 137Cs and modelling with the Revised Universal Soil Loss Equation (RUSLE). RUSLE permits the evaluation of soil loss by water erosion, the 137Cs method integrates soil loss due to all erosion agents involved, and the measurement of snow glide deposition sediment yield can be directly related to snow-glide-induced erosion. Further, cumulative snow glide distance was measured for the sites in the winter of 2009/2010 and modelled for the surrounding area and long-term average winter precipitation (1959–2010) with the spatial snow glide model (SSGM). Measured snow glide distance confirmed the presence of snow gliding and ranged from 2 to 189 cm, with lower values on the north-facing slopes. We observed a reduction of snow glide distance with increasing surface roughness of the vegetation, which is an important information with respect to conservation planning and expected and ongoing land use changes in the Alps. Snow glide erosion estimated from the snow glide depositions was highly variable with values ranging from 0.03 to 22.9 t ha−1 yr−1 in the winter of 2012/2013. For sites affected by snow glide deposition, a mean erosion rate of 8.4 t ha−1 yr−1 was found. The difference in long-term erosion rates determined with RUSLE and 137Cs confirms the constant influence of snow-glide-induced erosion, since a large difference (lower proportion of water erosion compared to total net erosion) was observed for sites with high snow glide rates and vice versa. Moreover, the difference between RUSLE and 137Cs erosion rates was related to the measured snow glide distance (R2 = 0.64; p < 0.005) and to the snow deposition sediment yields (R2 = 0.39; p = 0.13). The SSGM reproduced the relative difference of the measured snow glide values under different land uses and land cover types. The resulting map highlighted the relevance of snow gliding for large parts of the investigated area. Based on these results, we conclude that snow gliding appears to be a crucial and non-negligible process impacting soil erosion patterns and magnitude in subalpine areas with similar topographic and climatic conditions.


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