Difference in expansion and dehydration behaviors between NH- and K-montmorillonite

Kawakita, Ryohei; Saito, Akito*; Sakuma, Hiroshi*; Anraku, Sohtaro; Kikuchi, Ryosuke*; Otake, Tsubasa*; Sato, Tsutomu*

Applied Clay Science, 231, p.106722_1 - 106722_7, 2023/01

https://doi.org/10.1016/j.clay.2022.106722

Texture analysis of water-hydrated montmorillonite clay by coarse-grained molecular dynamics simulation

Kimoto, Kazushi*; Kawamura, Katsuyuki*; Makino, Hitoshi

Journal of Computer Chemistry, Japan, 19(2), p.46 - 49, 2020/00

https://doi.org/10.2477/jccj.2020-0006

This study proposes a 2D coarse-grained molecular dynamics (CGMD) method for the compaction simulation of montmorillonite clay. In the CGMD method, a unit structure of a water-hydrated clay molecule is coarse-grained into a particle. Thus, the deformable molecules are modeled as a set of linearly connected coarse-grained particles. As the inter-particle forces, the intra-molecular bonding and inter-molecular van der Waals forces are considered. For simplicity, the intra-molecular bonding is modeled as a linear harmonic oscillator, while the Lenard-Jones potential is used to define the van der Waals force field. With this model, the mechanical compaction of moistured montmorillonite is numerically simulated to find that 4-6 considerably deformed molecules are layered as a result of the compaction. It is alsofound that the simulated XRD pattern agrees to the experiment in terms of the peak angle.

Sorption behavior of thorium onto montmorillonite and illite

Iida, Yoshihisa; Barr, L.; Yamaguchi, Tetsuji; Hemmi, Ko

Genshiryoku Bakkuendo Kenkyu (CD-ROM), 23(1), p.3 - 8, 2016/06

http://doi.org/10.3327/jnuce.23.1_3

Thorium (Th)-229 is one of the important radionuclides for the performance assessment calculations for high-level radioactive waste repositories. The sorption behavior of Th onto montmorillonite and illite were investigated by batch sorption experiments. Experiments were carried out under variable pH and carbonate concentrations. The sorbability of montmorillonite was higher than that of illite. Distribution coefficients, (m kg), decreased with increased carbonate concentrations and showed the minimal value at around pH 10. The sorption behaviors of Th were analyzed by the non-electrostatic surface complex model with PHREEQC computer program. The model calculations were able to explain the experimental results reasonably well. The decreases of was likely due to the stabilization of aqueous species by hydroxo-carbonate complexations in the solutions.

Direct observation of Cm(III)-fulvate species on fulvic acid-montmorillonite hybrid by laser-induced fluorescence spectroscopy

Takahashi, Yoshio*; Kimura, Takaumi; Minai, Yoshitaka*

Geochimica et Cosmochimica Acta, 66(1), p.1 - 12, 2002/01

https://doi.org/10.1016/S0016-7037(01)00748-7

no abstracts in English

Experimental investigations of the effect of alkali fluids on montmorillonite, albite and quartz

JNC TN8400 2001-008, 36 Pages, 2001/03

JNC-TN8400-2001-008.pdf:2.92MB

Research on geologic disposal of high-level radioactive waste(HLW) has been underway in many countries. Bentonite exhibiting a low permeability, high swelling property and high sorption capacity for many radioelements is proposed as a buffer material in many countlies. Recently, cementitious materials are considered as candidate matelials for the geologic disposal of high-level radioactive waste. As the pH and the Ca, Na, K contents of hyperalkaline pore water from the cementitious materials are high, this hyperalkaline pore water would alter the buffer material. The main aim of this study is to investigate the effect of alkaline pore water into the bentonite. Used materials are montmorillonite, albite and quartz composing bentonite. These minerals mixed in a constant ratio (1:1wt%) made to react to distilled water and the alkali solutions (pH11-13). These studies have been conducted at temperatures of 50 - 150C and run times of 10 - 200 day. XRD(X-ray powder diffraction) and SEM (Scanning Electron Microscopy) analyses were applied to studying the structure and quantitative data of each sample. From the result of this study, the main formed mineral of this experiment was analcime, which showed the tendency with a large amount of generation at a higher pH and temperature. Quantitative data of this study was conducted by X-ray powder diffraction method. THe order of the amount of the second analcime in each experiment is shown in the following. Montmorillonite and albite mixing test Montmorillonite test Montmorillonite and quartz mixing test Activation energies (E) using the quantitative data of each test are shown in the following. (1)Montmorillonite test : 54.9kJ/mol (2)Montmorillonite and albite mixing test : 51.9kJ/mol (3)Montmorillonite and quartz mixing test : 59.6kJ/mol

Raman spectroscopic measurements of porewater in bentonite

Suzuki, Satoru; ; *

JNC TN8400 2000-020, 25 Pages, 2000/04

JNC-TN8400-2000-020.pdf:0.94MB

Nature of porewater in bentonite plays important roles on the mass transport in the compacted bentonite used as a physical and chemical buffer material of the multi-barrier system in the high level radioactive waste manegement Higher activation energies of diffusion in the compacted bentonite than those in the aqueous solution is due probably to change in molecular structure of water in the porewater. The Raman spectroscopy was applied to studying the structure of porewater in bentonite at room temperature. Bentonite (Kunipia F, 98-99wt% of Na-smectite) was mixed with ion-exchanged water by water content of 75, 80, 90, 95 and 98wt% of water or with 0.5M NaCl aqueous solution by 75 and 80wt% of NaCl solution. Intensity maxima of the spectra of ion exchanged water, NaCl solution and their porewater were observed near 3200 to 3250, 3400, 3630cm. These bands can be attributed to water molecules forming stronger hydrogen bond in this manner. Ratio of intensity, 3250cm/3400cm, increased from 0.97 to 1.1 with a decrease in water content of 100wt% (water) to 75wt%. On the other hand, intensity ratio of 3400cm/3250cm of NaCl aqueous solution, 80wt%and 75wt% were 0.92, 1.2 and 1.3, respectively. Since the Raman scattering near 3250cm was attributed to water molecule forming the strongest hydrogen bonding in the three bands, those changes in intensity ratio suggests an increase in number of water molecule forming strong hydrogen bond in porewater of the bentonite. The constrained porewater possibly results in the high activation energy of diffusion in the compacted bentonite.

The Study on degradation of engineered barrier in radioactive waste repositories effect of nitrate and leaching solutions

Iriya, Keishiro*; *; Fujita, Hideki*; Kubo, Hiroshi*

JNC TJ8400 2000-034, 212 Pages, 2000/02

JNC-TJ8400-2000-034.pdf:7.91MB

Cementious materials and highly compacted bentnite are expectable candidates as materials of TRU waste repositories. It was pointed out that Bentonite might be changed to Zeolite and surrounding rock might be altered by high alkalinity water flow, since cement hydrate leached to pore water of cement and it was changed to alkaline. Transportation of radio-nuclides might be accelerated by organic materials, such as super plasticizer, and nitlate which is contained in nuclear wastes. It was concluded by previous studies that rock and bentonite is stable in alkaline water which pH is less than 10.5. The new type of low alkalinity cement with high silica fume and fly ash content which could keep pH below 11.0 was developed and its performance has been assessed. However since Zeolitation and ilitation were reported upon deterioration of bentonite bated in certain condition, it should be assessed by long term experiment. Since Capacity of keeping integrity of bentonite hasn't been directly checked by experiments upon the developed new type of low alkalinity cement it should be done. Although amount of leaching organic was quantitatively and experimentally assessed at an early age, effect of changing of amount and shape hasn't assessed in leaching of radio nuclides. Although it is pointed out that deterioration of cementitious materials isn't accelerated by condensed nitrate solution at early period after closure, it is considered that it might be accelerated corresponding to chemical composition in case of decrement of concentration of nitrate. In this study, deterioration of materials will be assessed in detail in order to feed back the results to assessment of transportation of radio nuclides. Long term deterioration of bentonite by leaching water of cement will be experimentally assessed, and deteriorating test of bentonite will be carried out by leaching water of low alkalinity cement. Amount of organic and component of it will be measured. Furthermore ...

Study on migration behavior of radionuclides in engineered clay barrier (II)

*; *; *

JNC TJ8400 2000-018, 79 Pages, 2000/02

JNC-TJ8400-2000-018.pdf:2.09MB

As a basic research for geological disposal of high-level radioactive wastes, diffusion behavior of radionuclides and corrosion behavior of overpack materials in clay buffer materials (bentonite) were studied. In the study on the diffusion behavior of radionuclides, basal spacing and water content were determined for water saturated, compacted Na-montmorillonite that is major clay mineral of bentonite. The apparent diffusion coefficients of Na, Sr, Cs and Cl ions and their activation energies were also determined at different dry densities of montmorillonite. For all kinds of ions, the activation energies were found to increase as the dry density increased. These findings suggest that the diffusion mechanism of ions in compacted montmorillonite changed with increasing dry density. As a reasonable explanation for the changes in the activation energy, we proposed a multiprocess diffusion model, in which predominant diffusion process is considered to change from pore water diffusion to interlayer diffusion via surface diffusion when the dry density increases. The Na-montmorillonite is expected to alter by the ion exchange with Ca ions, which could be introduced from groundwater and/or cementitious materials in a repository. The apparent diffusion coefficients of Na and Cs ions and their activation energies were studied for Na/Ca montmorillonite mixtures in order to know the effect of this kind of alteration on the diffusion behavior of ions. It was found that the alteration of montmorillonite affected diffusion coefficients and the activation energies for both kinds of cations. These effects cannot be explained only by the pore water diffusion. The multiprocess diffusion model proposed in this study is suggested as the most reasonable explanation for the effects. The oxidation behavior of pyrite in bentonite during drying process was studied for understanding corrosion behavior of overpack materials in bentonite. There ...

None

Tanaka, Hiroshi*

JNC TJ1400 99-042, 17 Pages, 1999/02

JNC-TJ1400-99-042.pdf:0.4MB

no abstracts in English

Speciation of europium(III) sorbed on a montmorillonite surface in the presence of polycarboxylic acid by laser-induced fluorescence spectroscopy

Takahashi, Yoshio*; Kimura, Takaumi; Kato, Yoshiharu; Minai, Yoshitaka*

Environmental Science & Technology, 33(22), p.4016 - 4021, 1999/00

https://doi.org/10.1021/es990037n

no abstracts in English