Diffusion of Corrosion Products of Iron in Compacted Bentonite.

1992 ◽  
Vol 294 ◽  
Author(s):  
K. Idemitsu ◽  
H. Furuya ◽  
Y. Inagaki

ABSTRACTCarbon steel is one of the candidate overpack materials for high-level waste disposal. The corrosion rate of carbon steel is reduced by the presence of buffer materials such as bentonite and seems to be affected by the diffusion of corrosive materials and corrosion products through the buffer material.The apparent diffusivities of corrosion product of iron were measured in some bentonite specimens in contact with carbon steel. The apparent diffusivities of iron were also measured without carbon steel for comparison. The apparent diffusivities of corrosion product were on the order of 10−12 m2/s and showed a tendency to decrease with increasing density of the bentonite specimen. There was no significant effect of silica sand on the apparent diffusivities. The apparent diffusivities of iron in the system without carbon steel were in the range of 10−14 m2/s and showed a tendency to increase with increasing silica sand content. The difference of the diffusivities between corrosion product and iron without carbon steel seems to be due to the difference of diffusing species. The color of the corrosion product was dark-green during contact with bentonite specimens and became red on exposure to air in a few minutes. Gas bubbles were also observed in the corrosion product. This suggests hydrogen generation during corrosion of the carbon steel. Thus the diffusing species seems to be in a reduced state, probably ferrous ion. On the other hand, the diffusing species of iron without carbon steel was probably a ferric hydroxide complex that was negatively charged. This suggests that ferrous ion could diffuse in the surface water adsorbed on bentonite, while ferric complex was excluded.

2004 ◽  
Vol 824 ◽  
Author(s):  
Kazuya Idemitsu ◽  
Xiaobin Xia ◽  
Yoshiro Kikuchi ◽  
Yaohiro Inagaki ◽  
Tatsumi Arima

AbstractCarbon steel is one of the candidate overpack materials for high-level waste disposal and is expected to assure complete containment of vitrified waste glass during an initial period of 1000 years in Japan. The lifetime of the carbon steel overpack will depend on its corrosion rate. The corrosion rate of carbon steel is reduced by the presence of buffer material such as bentonite. Buffer material will delay the supply of corrosive materials and discharge of corrosion products through it. Carbon steeloverpack will be corroded by consuming oxygen introduced by repository construction after closure of repository and then will keep the reducing environment in the vicinity of repository. Therefore, it is important to study the migration of iron corrosion products through the buffer material because it may affect the corrosion rate of overpack, migration of redox-sensitive radionuclides, and the properties of the buffer material. Electromigration experiments have been carried out with source of iron ions supplied byanode corrosion of iron coupon in compacted bentonite. The carbon steel coupon was connected as the working electrode to the potentiostat and was held at a constant applied potential between - 200 to 1000 mV vs. Ag/AgCl electrode for 48 hours. Corrosion currents were 0.5 to 2mA initially and depended on the supplied electrical potential, then decreased to approximately 0.1 mA in a few hours. The final corrosion current was independent of supplied electrical potential. It is expected that iron ion could migrate as ferrous ion through interlayer of montmorillonite replacing exchangeable sodium ions in the interlayer. The rate-determining process of this experimental configuration could be infiltration rate of ferrousioninto bentonite. Infiltration rate of ferrous ion into bentonite was increasing with dry density of bentonite.


2008 ◽  
Vol 1107 ◽  
Author(s):  
Kazuya Idemitsu ◽  
Syeda Afsarun Nessa ◽  
Shigeru Yamazaki ◽  
Hirotomo Ikeuchi ◽  
Yaohiro Inagaki ◽  
...  

AbstractCarbon steel overpack is corroded by consuming oxygen introduced by repository construction after closure of the repository and then maintains the reducing environment in the vicinity of the repository. The migration of iron corrosion products through the buffer material will affect the migration of redox-sensitive radionuclides. Therefore, it is important to study the migration of iron corrosion products through the buffer material because it may affect the corrosion rate of overpack, and migration of redox-sensitive radionuclides. Electromigration experiments have been conducted with the source of iron ions supplied by anode corrosion of the iron coupon in compacted bentonite. The carbon steel coupon was connected as the working electrode to the potentiostat and was held at a constant supplied potential between - 650 to +300 mV vs. Ag/AgCl electrode for up to 168 hours. The amount of iron penetrated into a bentonite specimen was in good agreement with the calculated value from the corrosion current under the assumption that iron is dissolved as ferrous ions. A model using dispersion and electromigration could explain the measured iron profiles in the bentonite specimens. The fitted value of electromigration velocity depended on the potential supplied. On the other hand the fitted value of the dispersion coefficient did not depend on the potential supplied but a constant. This constant dispersion coefficient could be due to the much larger diffusion coefficient of ferrous ion in bentonite compared with the effect of mechanical dispersion. The experimental configurations used in this study are applicable to the examination of the migration behaviour of cations with the source of iron ions under a reducing condition controlled with a potentiostat.


1997 ◽  
Vol 506 ◽  
Author(s):  
K. Idemitsu ◽  
Y Tachi ◽  
H. Furuya ◽  
Y. Inagaki ◽  
T. Arima

ABSTRACTIn high-level waste repositories, a carbon steel overpack will be corroded by consuming oxygen trapped in the repository after closure. Iron corrosion products are expected to interfere with migration of radionuclides by filling the pore in bentonite and sorbing radionuclides. In this study the apparent diffusion coefficients of cesium and strontium were measured in compacted Na-bentonites (Kunigel VI® and Kunipia F®, JAPAN) contacted with carbon steel and its corrosion products under reducing conditions or without carbon steel under oxidizing conditions for comparison. The apparent diffusion coefficients of cesium with and without corrosion product were 2.2 to 13 × 10−12 m2/s. The apparent diffusion coefficients of strontium with and without corrosion product were 3.1 to 25 × 10−12 m2/s. There were significant effects of dry density (0.8 to 2.0 g/cm3) and montmorillonite contents (50% for Kunigel V1 or 100% for Kunipia F). The presence of corrosion product decreased the apparent diffusion coefficients of Cs in both bentonites and that of Sr in Kunigel V1, especially at low dry density. This may be due to corrosion product filling the pore in the bentonite, decreasing the free pore size and density for diffusion.


2002 ◽  
Vol 713 ◽  
Author(s):  
Kazuya Idemitsu ◽  
Seiji Yano ◽  
Xia Xiaobin ◽  
Yaohiro Inagaki ◽  
Tatsumi Arima ◽  
...  

ABSTRACTCarbon steel is one of the candidate overpack materials for high-level waste disposal and is expected to assure complete containment of vitrified waste glass during an initial period of 1000 years in Japan. The lifetime of the carbon steel overpack will depend on its corrosion rate. The corrosion rate of carbon steel is reduced by the presence of buffer material such as bentonite. Buffer material will delay the supply of corrosive materials and discharge of corrosion products through it. Carbon steel overpack will be corroded by consuming oxygen introduced by repository construction after closure of repository and then will keep the reducing environment in the vicinity of repository. The reducing condition will be expected to retard the migration of redox-sensitive radionuclides by lowering their solubilities. Therefore, the diffusion of corrosion products of iron in buffer material is important to discuss the corrosion rate of overpack, migration of redox-sensitive radionuclides and properties of buffer material. The purpose of this paper is to study diffusion behavior of a corrosion product of iron in compacted bentonites under a reducing condition with a carbon steel. The diffusion mechanism of iron in the compacted bentonites were discussed by estimation of iron species in the bentonite pore water. There were two diffusion paths of iron in the compacted bentonites used in this study; the fast path has low capacity of iron, ca. 1wt%, and large apparent diffusion coefficient, ca. 10−12 m2/s and the slow path has high capacity of iron, ca. 10wt%, and small apparent diffusion coefficient, ca. 10−14 m2/s.


1993 ◽  
Vol 333 ◽  
Author(s):  
K. Idemitsu ◽  
H. Furuya ◽  
Y. Tachi ◽  
Y. Inagaki

ABSTRACTIn a high-level waste repository, a carbon steel overpack will be corroded by consuming oxygen trapped in the repository after closure. This will create a reducing environment in the vicinity of repository. Reducing conditions are expected to retard the migration of redox-sensitive radionuclides such as uranium.The apparent diffusivities of uranium were measured in compacted bentonite (Kunigel VI®, Japan) in contact with carbon steel under reducing conditions or without carbon steel under oxidizing conditions for comparison. The apparent diffusivities of uranium were 3.5 × 10-14 to 1.1 × 10-13 m2/s under reducing conditions and 9.0 × 10-13 to 1.4 × 10-12 m2/s under oxidizing conditions. There was no significant effect of dry density (1.6 to 1.8 g/cm3) and silica sand (0 or 40%) on the apparent diffusivities.Since the bentonite pore water would be buffered at a pH between 8 and 9, uranium in the bentonite pore water would probably exist as a neutral hydroxide complex under reducing conditions and as an anioníc carbonate or hydroxide complex under oxidizing conditions. The anion exclusion theory cannot explain the difference of diffusivities between the two conditions. The uranium concentrations in bentonite under oxidizing conditions were one order of magnitude higher than those under the reducing conditions. The uranium concentration in the bentonite pore water under the reducing condition is estimated to be two orders of magnitude lower than that under the oxidizing conditions under the assumption of diffusion in porous media.


2002 ◽  
Vol 757 ◽  
Author(s):  
Kazuya Idemitsu ◽  
Seiji Yano ◽  
Xiaobin Xia ◽  
Yoshiro Kikuchi ◽  
Yaohiro Inagaki ◽  
...  

ABSTRACTCarbon steel is one of the candidate overpack materials for high-level waste disposal and is expected to assure complete containment of vitrified waste glass during an initial period of 1000 years in Japan. The lifetime of the carbon steel overpack will depend on its corrosion rate. The corrosion rate of carbon steel is reduced by the presence of buffer material such as bentonite. Buffer material will delay the supply of corrosive materials and discharge of corrosion products through it. Carbon steel overpack will be corroded by consuming oxygen introduced by repository construction after closure of repository and then will keep the reducing environment in the vicinity of repository. The reducing condition will be expected to retard the migration of redox-sensitive radionuclides by lowering their solubilities. Therefore, the diffusion of corrosion products of iron in buffer material is important to discuss the corrosion rate of overpack, properties of buffer material and migration of redox-sensitive radionuclides. Electromigration experiments have been carried out with source of iron ions supplied by anode corrosion of iron coupon. Iron ions migrated as fast as 2mm in 2 or 3 hours under electrical field of 100V/m to the direction of cathode. Because the iron ions displaced exchangeable sodium ions in bentonite at a ratio of 1 to 2 during the electromigration, migrating iron ion could be ferrous ion.


2006 ◽  
Vol 985 ◽  
Author(s):  
Kazuya Idemitsu ◽  
Yosuke Yamasaki ◽  
Syeda Afsarun Nessa ◽  
Yaohiro Inagaki ◽  
Tatsumi Arima ◽  
...  

AbstractCarbon steel is one of the candidate overpack materials for high-level waste disposal and is expected to assure complete containment of vitrified waste glass during an initial period of 1000 years in Japan. Carbon steel overpack will be corroded by consuming oxygen introduced by repository construction after closure of repository and then will keep the reducing environment in the vicinity of repository. The migration of iron corrosion products through the buffer material will affect migration of redox-sensitive radionuclides. Therefore the authors have carried out electromigration experiments with source of iron ions supplied by anode corrosion of iron coupons attached to compacted bentonite. Authors tried to use plutonium in this experimental configuration to obtain the knowledge of migration behavior of actinides. Authors also used cesium as reference. The concentrations of iron and sodium showed nearly complementary distributions. It is expected that iron ion could migrate as ferrous ion through the interlayer of montmorillonite replacing exchangeable sodium ions in the interlayer. Concentration profiles of plutonium in bentonite grew as time supplying electric potential as long as 168 h. Plutonium migrated from the iron anode toward cathode as deeper than 1 mm of the interior of bentonite even in 48 h, though plutonium could not diffuse 1 mm for 2 years. On the other hand, profiles of cesium seemed to be controlled by ordinary diffusion because of large diffusion coefficient of cesium in bentonite as large as 10$^{-12}$ m$^{2}$/s. Drift of the cesium profile by electric potential gradient could be observed clearly after 240 h at individual experiment for cesium. Apparent dispersion coefficients of plutonium were calculated from the profiles and were as large as 10$^{-13}$ m$^{2}$/s. Since plutonium migration was accelerated by electric potential, plutonium chemical species would have positive charge and were estimated as PuOH$^{2+}$ or PuCl$^{2+}$ by the thermodynamic calculation. Thus this experiment can provide a diffusion field for cations under a reducing condition with ferrous ions in water-saturated bentonite.


2020 ◽  
Vol 8 (2) ◽  
pp. 159-168
Author(s):  
Ismi Nurhayati ◽  
◽  
Pulung Karo Karo ◽  
Syafriadi Syafriadi ◽  
◽  
...  

Research has been conducted on the effectiveness of maja fruit skin extract as an inhibitor of carbon steel AISI 1020 in a corrosive medium NaCl 3% with variations in immersion time. The samples carbon steel AISI 1020 were immersed in corrosive medium NaCl 3% without being given and given the inhibitor of maja skin extract with a concentration of 0.8% for 5, 15, 25, 35, and 45 days. Calculation of reduction in corrosion rate is carried out by the method of weight loss. The results showed that the addition of the maja fruit skin extract inhibitor was effective in reducing the corrosion rate of the sample with the greatest efficiency at 35 days immersion, which was equal to 72.35%. The results of XRD characterization show that the phase formed is pure Fe and Fe3O4 phase which is a corrosion product is immersed without inhibitor. The results of SEM characterization showed that the microstructure of the surface of the sample after immersion was there were cracks, holes, and lumps which indicated that the sample had been corroded. The results of EDS characterization show that in the soaked sample there were corrosion products in the form of FeO compounds whose magnitude increased every time immersion.


1995 ◽  
Vol 412 ◽  
Author(s):  
Kazuya Idemitsu ◽  
Y. Tachi ◽  
H. Furuya ◽  
Y. Inagaki ◽  
T. Arima

AbstractIn high-level waste repository, a carbon steel overpack will be corroded after closure. This will create a reducing environment in the vicinity of the repository. Reducing conditions are expected to retard the migration of redox-sensitive radionuclides such as uranium.The apparent diffusion coefficients of uranium were measured in compacted bentonites (Kunigel VI® and Kunipia F®, JAPAN) in contact with carbon steel and its corrosion products under reducing conditions or without carbon steel under oxidizing conditions for comparison. The apparent diffusion coefficients measured were 10-12 to 10-14 m2/s under oxidizing conditions and 10-13 to 10-14 m2/s under reducing conditions. There were significant effects of redox conditions, dry density (0.8 to 2.0 g/cm3) and montmorillonite contents (60% for Kunigel VI or 100% for Kunipia F) on the apparent diffusion coefficients. The sorption of uranium on corrosion products of iron was smaller than that on montmorillonite. Montmorillonite density could be a good index to explain density dependence of the diffusion coefficients under the reducing conditions. Uranium would diffuse in free pore water with diffusion coefficients greater than 10-13 m2/s in low density bentonites under both redox conditions because the diffusion coefficients depended on sorption coefficients. Since diffusion coefficients were independent of sorption coefficients in high density bentonites where free pore water is scarce, surface diffusion might occur with coefficients were of about 10-13 m2/s.


1996 ◽  
Vol 465 ◽  
Author(s):  
Yuji Kuroda ◽  
K. Idemitsu ◽  
H. Furuya ◽  
Y. Inagaki ◽  
T. Arima

ABSTRACTIn the vicinity of a high-level waste repository, corrosion of carbon steel overpacks will create a reducing environment. Reducing conditions are expected to retard the migration of redox-sensitive radionuclides such as technetium.The apparent diffusion coefficients of technetium were measured in compacted bentonites (Kunigel VI® and Kunipia F®, JAPAN) in contact with carbon steel and its corrosion products under reducing conditions or without carbon steel under oxidizing conditions for comparison. The apparent diffusion coefficients measured were 10-12 to 10-13 m2/s under oxidizing conditions and 10-12 to 10-13 m2/s under reducing conditions. There were significant effects of redox condition, dry density (0.2 to 2.3 g / cm3) and montmorillonite content (50% for Kunigel VI or 100% for Kunipia F) on the apparent diffusion coefficients. Montmorillonite density could be a good index to explain density dependence of the diffusion coefficients under both reducing and oxidizing conditions.


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