Bentonite has been considered as a buffer material in a deep geological repository for high-level radioactive waste (HLW). Bentonite may come into contacted with various chemical solutions during the long-term storage. In particular, solutions containing K+ can affect stability of bentonite (e.g., illitization). The bentonite can be gradually saturated with the inflow of groundwater, and the temperature can rise simultaneously due to the decay of HLW. This study aimed to evaluate the bentonite stability in contacted with very highly concentrated K+ solutions with different pHs at 150°C. Batch reaction tests using KJ-II bentonite were performed for 30–150 days in teflon-stainless steel reactors. De-ionized (DI) water (pH = 6.0) and 1 M KCl (pH = 6.0), and 1 M KOH (pH = 12.5) solutions were used as reaction solutions. After completing batch reaction tests, the reacted samples were analyzed using various analytical techniques. For DI water, chemical, mineralogical, and physicochemical properties of reacted samples were similar to those of unreacted samples. For 1 M KCl solutions, cation exchage for Ca by K and slight changes in mineralogical properties of reacted samples were observed, but there are no significant changes in the physicochemical properties. In contrast, for 1 M KOH solutions, changes in chemical, mineralogical, and physicochemical properties of reacted samples were observed. Results of X-ray diffraction (XRD) analysis indicated dissolution of montmorillonite and formation of zeolite minerals, which were confirmed by thermogravimetricdifferential thermal analysis (TGA-DTA) and fourier transform infrared (FTIR) analysis. These results suggest that highly concentrated K+ (1 M) solution combined with high pH (12.5) and high temperate (150°C) may affect bentonite alteration. These prelimiary experiments were intended to qualitatively evaluate the mechanism and influncing factors of the buffer material alteration under extreme experimental conditions, and it is revealed that the conditions do not reflect the actual repository environment.
FTIR (Fourier Transform Infrared) and Raman spectra of KJ-II bentonite provided by Clariant Korea were compared with those of MX-80 bentonite. The FTIR spectra were obtained using a Nicolet 5 FTIR spectrometer (Fisher Scientific) equipped with a diamond ATR (Attenuated Total Reflection) module. The spectra were collected for 64 scans with a resolution of 4 cm−1. Raman spectra were obtained using an optical microscope (Olympus, BX43) and a spectrometer (Andor, SR- 500). The laser beam was focused using an objective lens with a magnifying power of 50. The backscattered light from the sample was collected into an optical fiber with a core diameter of 0.4 mm. The Raman signals were recorded with CCDs (Andor, DV401A-BV for 532 nm laser wavelength and DV420A-OE for 638 and 785 nm laser wavelengths). Each pixel of CCD received the signal for 1 s and its 1000 times accumulated data were collected. The FTIR spectra of the two bentonite samples are very similar. The FTIR spectra of both bentonites showed absorption bands at 3623, 3399, 3231 cm−1 in the higher wavenumber region and at 1637, 1443, 1117, 997, 914, 887, 847, 797, 611, 515, 414 cm−1 in the lower wavenumber region. A sharp band at 3623 cm−1 and the strong band at 997 cm−1 correspond to the OH stretching of structural hydroxyl groups and the Si-O stretching vibration, respectively. In addition to these clear bands, several absorption bands observed in this experiment are well matched with the results reported in various literatures. Unlike the FTIR spectrum, it is not easy to observe the Raman bands of bentonite. The reason is that strong fluorescence interferes with the Raman spectrum. The two bentonite samples showed different fluorescence intensities. In the case of MX-80 bentonite, no clear Raman band was observed due to the influence of very strong fluorescence. KJ-II bentonite showed a relatively weak fluorescence intensity and Raman bands were partially visible at around 147, 260, 397, 709, and 1279 cm−1. In particular, the band at 1279 cm−1 is wide and sturdy. It was observed that the non-powder samples showed a better quality spectra. The Raman characteristics of KJ-II bentonite, which depend on the incident laser wavelength and the sample pretreatment, are discussed in detail.