Technetium has been identified as an element of interest for the safety assessment of a deep geological repository for used nuclear fuel. In this study, the sorption of Tc(IV) onto MX-80 bentonite, illite, and shale in ionic strength (I) 0.1–6 mol·kgw−1 (m) Na-Ca-Cl solutions at pHm = 4–9 and limestone at pHm = 5–9 was studied. Tc(IV) sorption on MX-80 increased with pHm from 4 to 6, reached the maximum at pHm = 6–7, and then gradually decreased with pHm from 7 to 9. Tc(IV) sorption on illite gradually increased with pHm from 4 to 7, and then decreased as pHm increased. The sorption properties of Tc(IV) on shale were quite similar to those on illite. Tc(IV) sorption on limestone slightly increased with pHm from 5 to 6 and then seemed to be constant at pHm = 6–9. Tc(IV) sorption on all four solids was independent of ionic strength (0.1–6 m). The 2 site protolysis non-electrostatic surface complexation and cation exchange model successfully simulated the sorption of Tc(IV) onto MX-80 and illite and the optimized values of surface complexation constants were estimated.

Technetium-99 is identified as an element of interest for the safety assessment of a deep geological repository for used nuclear fuel. The sorption behavior of Tc(IV) onto MX-80 and granite in Ca-Na-Cl solutions of varying ionic strength (0.05–1 mol·kgw−1 (m)) and across a pHm range of 4–9 was studied in this paper. Sorption of Tc(IV) was found to be independent of ionic strength in the range of 0.05 to 1 m for both MX-80 and granite. Sorption of Tc(IV) on MX-80 increased with pHm from 4 to 7 and then decreased with pHm from 8 to 9. Sorption of Tc(IV) on granite gradually increased with pHm from 4 to 8 and then became almost constant or slightly decreased with pHm from 8 to 9. A 2 site protolysis non-electrostatic surface complexation and cation exchange sorption model successfully simulated sorption of Tc(IV) on MX-80 and granite. Optimized values of surface complexation constants (log K0) are proposed.

The sorption of Eu on MX-80 bentonite in Na–Ca–Cl solutions is investigated at a molal proton concentration (pHm) range of 3 to 10 and an ionic strength (I) range of 0.1 to 6 m (mol·kgw−1). The sorption equilibrium of Eu on MX-80 is achieved within 14 to 21 d at I = 0.1 and 6 m. The sorption distribution coefficient (Kd) values of Eu for MX-80 increase as pHm increases from 3 to 6 for all I values, and they are independent of pHm between 8 and 10 at I ≥ 0.5 m. Meanwhile, at I = 0.1 m, the Kd value at pHm = 10 is slightly lower than those at pHm = 8 and 9. The Kd values are not affected by the I values between 0.5 m and 6 m, whereas the Kd value at I = 0.1 m is greater than those at I ≥ 0.5 m, except at pHm = 10. A two-site protolysis nonelectrostatic surface complexation and cation exchange sorption model is applied to the Eu sorption data for I ≤ 4 m, and the equilibrium constants of the sorption reactions are estimated.

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.

The pH dependence of sorption distribution coefficient (Kd) of Np(IV) on MX-80 in Ca-Na-Cl type solution with the ionic strength of 0.3 M, which was similar to one of the reference groundwaters in crystalline rock, was experimentally investigated under the reducing conditions. The overall trend of Kd on MX-80 was independent of pH at 5 ≤ pH ≤ 10 but increased as pH increased at pH ≤ 5. The 2-site protolysis non-electrostatic surface complexation and cation exchange model was applied to the experimentally measured pH dependence of Kd and the optimized surface complexation constants of Np(IV) sorption on MX-80 were estimated. The values of surface complexation constants in this work agreed relatively well with those in the Na-Ca-Cl solution previously evaluated, suggesting that compared to Na+, the competition of Ca2+ with Np(IV) for surface complexation on MX-80 was not much strong in Ca-Na-Cl solution. The sorption model well predicted the pH dependence of Kd values but slightly overestimated the sorption at the low pH region.

과냉각액체구역(δTx=Tx-Tg)을 갖는 Fe80P10C6B4 조성에 천이금속(Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Co, Ni, Pd, Pt및 Cu)를 첨가하여 이들 원소가 유리화온도(Tg), 결정화온도(Tx) 및 과냉액체구역 (δTx)에 미치는 영향에 ?여 조사하였다. Fe80P10C6B4 합금의 δTx 값은 27K였으나 이 합금에 Hf, Ta 및 Mo을 각각 4at%첨가하면 그 값이 40k 이상으로 증가하였다. 이같은 δTx 값의 증가는 유리화온도(Tg의 상승보다 결정화온도(Tx)의 상승폭이 크기 때문이다. Tg 및 Tx는 외각전자밀도(e/a)가 약 7.38에서 7.05로 감소할수록 상승하였다. e/a의 감소는 천이금속과 다른 구성원소(반금속)사이의 상호결합상태를 의미한다. 즉 Tg 및 Tx의 상승은 강한 상호결합력에 기인하는 것으로 사료된다.