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ISSN : 1738-1894(Print)
ISSN : 2288-5471(Online)
Journal of Nuclear Fuel Cycle and Waste Technology Vol.18 No.4 pp.509-516
DOI : https://doi.org/10.7733/jnfcwt.2020.18.4.509

Investigating the Leaching Rate of TiTe3O8 Towards a Potential Ceramic Solid Waste Form

Hye Ran Noh1,2,ͳ, Dong Woo Lee1,ͳ, Kyungwon Suh1, Jeongmook Lee1, Tae-Hyeong Kim1, Sang-Eun Bae1,2, Jong-Yun Kim1,2*, Sang Ho Lim1,2*
1Korea Atomic Energy Research Institute, 111, Daedeok-daero 989beon-gil, Yuseong-gu, Daejeon, Republic of Korea
2University of Science and Technology, 217, Gajeong-ro, Yuseong-gu, Daejeon, Republic of Korea
T

These authors contributed equally to this work and are co-first authors


Corresponding Author. Jong-Yun Kim, Korea Atomic Energy Research Institute, E-mail: kjy@kaeri.re.kr, Tel: +82-42-868-4736

Sang Ho Lim, Korea Atomic Energy Research Institute, E-mail: slim@kaeri.re.kr, Tel: +82-42-868-2105
November 6, 2020 ; November 20, 2020 ; December 14, 2020

Abstract


An important property of glass and ceramic solid waste forms is processability. Tellurite materials with low melting temperatures and high halite solubilities have potential as solid waste forms. Crystalline TiTe3O8 was synthesized through a solid-state reaction between stoichiometric amounts of TiO2 and TeO2 powder. The resultant TiTe3O8 crystal had a three-dimensional (3D) structure consisting of TiO6 octahedra and asymmetric TeO4 seesaw moiety groups. The melting temperature of the TiTe3O8 powder was 820℃, and the constituent TeO2 began to evaporate selectively from TiTe3O8 above around 840℃. The leaching rate, as determined using the modified American Society of Testing and Materials static leach test method, of Ti in the TiTe3O8 crystal was less than the order of 10-4 g·m-2·d-1 at 90℃ for durations of 14 d over a pH range of 2-12. The chemical durability of the TiTe3O8 crystal, even under highly acidic and alkaline conditions, was comparable to that of other well-known Ti-based solid waste forms.



초록


    National Research Foundation of Korea(NRF)
    NRF-2017M2A8A5014754

    1. Introduction

    The isolation of radioactive waste from the environment has been a critical concern for public health and safety. Since the first research on a new concept for vitreous or crystalline materials for the immobilization of radioactive waste was conducted in the 1950s, various glass waste forms have been studied for high-level radioactive wastes [1-3]. Amorphous borosilicate glass has been selected as a solid waste form in the past because, due to the unstructured molecular arrangement of glass, it can incorporate a wide range of chemical elements (. 20-30 elements). Other necessary properties such as waste loading, chemical durability, and processability for amorphous borosilicate glass are all reasonably acceptable for radioactive waste immobilization applications [4]. Thus, borosilicate glass has been used as a reference solid waste form for comparison of the performance characteristics. However, borosilicate glass is thermodynamically unstable and less resistant to leaching and weathering [5] than more stable crystalline ceramic waste forms currently in use. Various titanate-based (zirconolite, hollandite, perovskite, etc.), alumina-based (magnetoplumbite, nepheline, etc.), and silicate-based (pollucite, etc.) ceramic waste forms are advantageous over glass waste form equivalents [6,7]. These minerals exhibit various crystalline structures, such as fluorite, ABO3, and ABO4. A-site cations and B-site cations can be exchanged with fission product elements such as Cs, Rb, Sr, Ba, Th, and Pu [7-11].

    Processing temperature and chemical durability are noteworthy properties when screening for a potential solid waste form. Processing temperature is an important property in terms of cost-effectiveness and secondary off-gas treatment for volatile radionuclides [6], while chemical durability is one of the most important performance characteristics of solid waste. There are several standard leach test protocols developed by the International Atomic Energy Agency (IAEA), the International Organization for Standardization (ISO), the American Society of Testing and Materials (ASTM), and American Nuclear Society (ANS). However, there is no single standard leach test method that can evaluate the performance of chemical durability under various field conditions of disposal facilities.

    In this study, a chemical durability test was conducted based on the protocol described by ASTM C1220-17 [12] with some minor modifications of the experimental conditions. We identified the Ti4+-Te4+-oxide system for the immobilization of radioactive waste. TiTe3O8 is a potential Ti4+-Te4+-oxide because we anticipate that the replacement of cations in the crystal framework at the Ti4+ site with dopant cations can produce stable Ti1-xMxTe3O8 (M = Er3+, Ce4+, and Sn4+) compounds [13-15]. In addition, a high quality solid solution between stoichiometric amounts of TiO2 and TeO2 is expected to be easily prepared through a simple solid-state reaction at 600-700℃.

    2. Experimental

    2.1 Solid-state synthesis of TiTe3O8

    A polycrystalline sample of TiTe3O8 was prepared by the solid-state reaction of TiO2 and TeO2 powder. TiO2 (Showa, 99.0%) and TeO2 (Aldrich, 99.0%) were used as purchased without further purification. Stoichiometric amounts of TiO2 and TeO2 were thoroughly ground together in an agate mortar and pestle. After grinding, the reaction mixtures were pressed into pellets and transferred to an alumina crucible. The samples placed in the alumina crucible were heated to 650℃ at a rate of 5℃·min-1, held at this temperature for 18 h for sintering, and cooled to room temperature at a rate of 5℃·min-1.

    2.2 Material characterization

    Powder X-ray diffraction (XRD) analyses were conducted to examine the purity of the polycrystalline TiTe3O8 phase with a Bruker D8-Advance diffractometer using Cu Kα radiation at an operating voltage of 40 kV and a current of 40 mA. The powder samples, which were prepared by grinding the pellet samples, were mounted on the sample holder, and measured in the 2θ range of 10-80° with a step size of 0.02° and a step time of 0.1 s. To investigate the thermal effects, the powder samples were heated at a rate of 10℃·min-1 up to the three different target temperatures of 300, 600, and 900℃. Each target temperature was maintained for 10 min and subsequently cooled to room temperature to measure the powder XRD patterns. The weight loss and melting temperature of the TiTe3O8 powder samples were measured by thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC), respectively, using a SCINCO STA N-1500 TGA/DSC analyzer at a heating rate of 5℃·min-1 to 1,000℃ under a flow of argon gas.

    After the leaching experiments, scanning electron microscopy (SEM) analyses were conducted on the pelletized samples using a JEOL JSM-6610LV scanning electron microscope to investigate any harmful effects on the crystalline structures and surface morphologies. XRD analysis was also performed for the pelletized samples after leaching under the same operating conditions as those for the powder samples.

    2.3 Chemical durability test

    The static leaching test method described by ASTM C1220-17 using deionized water was used to test the chemical durability of pelletized TiTe3O8 samples. High-purity deionized water is one of the most frequently employed aqueous solvents for leaching, as the appropriate pH and salt compositions of the aqueous leaching solution can be manipulated to simulate the specific groundwater conditions at the disposal sites. The 15-mm-diameter and 1.4-mm-thick pellets were immersed in 10 mL of deionized water. The acidity of the leaching solution spanned from an acidic solution (0.01 M HCl, pH = 2) to an alkaline solution (0.01 M NaOH, pH = 12). A 17 mL Teflon-lined, stainless steel autoclave containing the leaching solution and the pelletized sample was placed in a convection oven at 90℃ for 7 and 14 d. After 14 d, the concentration of the released Ti was measured by inductively coupled plasma-mass spectrometry (ICP-MS) using a iCAP TQ ICP-MS (Thermo Fisher Scientific) with the limit of detection (LOD) of 0.005 mg·L-1.

    3. Results and discussion

    3.1 Crystalline Structures

    The incorporation of radionuclides into the crystalline framework of ceramic waste forms is key to the immobilization of radioactive wastes. Fundamental information on crystalline structures is helpful for understanding waste form stability and incongruent dissolution. The reported values of crystallographic information, bond distances, and bond angles for crystalline TiTe3O8 are given in Tables 1-3 [16]. Fig. 1 shows that the powder X-ray diffraction pattern for TiTe3O8 powder prepared through solidstate sintering matched the polycrystalline TiTe3O8 (PDF#: 01-070-2439 in Fig. 1). No other impurities such as TiO2 and TeO2 phases were found in the sintered powders. As previous studies have shown [17], the crystal structure of TiTe3O8 showed the centrosymmetric cubic space group, Iɑ-3 (No. 206). It reveals 3D frameworks consisting of TiO6 octahedra and TeO4 polyhedra (see Fig. 2). The unique Ti4+ cation is connected to six oxygen atoms in an octahedral coordination environment. The asymmetric unit indicated the presence of unique Te4+ cations, showing an unsymmetrical coordination moiety resulting from the stereoactive lone pairs. The three distorted TeO4 polyhedra share their corners through one O atom and form Te3O8 trimers. The Ti4+ cations in the center of the oxide octahedron are shared by two Te3O8 trimers in an asymmetric coordination environment. Each Te3O8 trimer is further connected by a TiO6 octahedron along the [100] direction, thereby resulting in the formation of a 3D framework.

    3.2 Thermal properties

    TGA data showed that no significant weight loss of the synthesized TiTe3O8 powders was observed until the temperature reached the melting point of TiTe3O8, as shown in Fig. 3(a). The weight loss started at approximately 840℃, where the decomposition of TiTe3O8 took place. At 1,000℃, almost 30% of the total weight was evaporated from the TiTe3O8 powder. In the DSC analysis, an endothermic peak was observed at 820℃, which indicates the melting of TiTe3O8. To investigate the chemical behavior introduced by the TeO2 volatilization on the TiTe3O8 melt, XRD patterns measured at room temperature were compared after heat treatments at different temperatures up to the volatilization temperature. Fig. 3(b) reveals that polycrystalline TiTe3O8 maintains crystallinity up to 600℃. However, it is evident from the XRD pattern of the sample heat-treated at 900℃ that an amorphous residue was formed after the selective evaporation of TeO2 from the TiTe3O8 melt. Small XRD peaks also appeared, corresponding to the polycrystalline TiO2 phase (PDF#: 21- 1276) as well as polycrystalline TeO2.

    3.3 Chemical durability

    Crystalline samples of pelletized TiTe3O8 were subjected to a static leach test. The leaching rate of TiTe3O8 was calculated using Eq. (2) from the normalized mass loss in Eq. (1) [12, 19].

    N L T i = C T i × V S × f T i
    (1)

    L R T i = N L T i t
    (2)

    where NLTi is the normalized mass loss of Ti (g·m-2), LRTi is the leaching rate of Ti (g·m-2·d-1), CTi is the concentration of elemental Ti in the leaching solution (g·L-1), V is the volume of the leaching solution (L), fTi is the mass fraction of element Ti in the sample, S is the surface area of the sample (m2), and t is the soaking time (d). All Ti concentrations in the leaching solutions of the 0.01 M HCl aqueous solution, pure deionized water, and 0.01 M NaOH aqueous solution were below the limit of detection (LOD). Based on the LOD values, LRTi under various leaching conditions in this study was less than the order of 10-4 g·m-2·d-1. The leaching rates of other titanate- based solid waste forms are shown in Table 4. The chemical durability of TiTe3O8 is comparable to that of known titanate-based solid waste forms, and is more stable than borosilicate glass, while the melting temperatures of titanate-based materials are higher than those of TiTe3O8. Because the high processing temperature can cause volatilization of radionuclides in waste, a low temperature process is advantageous in field practices.

    The leaching rate of pelletized TiTe3O8 was low. Therefore, no changes were expected in the surface and crystal structure. The XRD results in Fig. 4 confirm that the crystal structures of TiTe3O8 remained unchanged after 7 and 14 d of leaching with highly acidic and alkaline aqueous solutions, as well as pure deionized water. SEM images also demonstrated that notable surface cracks or damages were not observed after leaching.

    4. Conclusions

    Pure crystalline TiTe3O8 powder was synthesized through the solid-state sintering reaction of stoichiometric amounts of TiO2 and TeO2 powder. The two most important and fundamental properties required for the nuclear waste immobilization, thermal stability, and chemical durability of TiTe3O8 were tested to examine the potential as a promising solid waste form. Although the TiTe3O8 melt became unstable at around 840℃, a thermally stable TiO2 residue was formed after the volatilization of TeO2 from TiTe3O8. The low melting temperature of the TiTe3O8 is advantageous in terms of cost, processability, and stability of wastes. The leaching rates of Ti in pelletized TiTe3O8 crystals were comparable to the well-known solid waste forms even under severe acidic and basic conditions. Further studies are required to investigate other important performance characteristics such as the loading capacity of fission products, mechanical strength, and radiation resistance.

    Acknowledgements

    This work was supported by the Nuclear Research and Development Program through the National Research Foundation of Korea (NRF-2017M2A8A5014754) funded by the Ministry of Science and ICT, Republic of Korea.

    Figures

    JNFCWT-18-4-509_F1.gif

    Powder X-ray diffraction patterns of the solid-state synthesized TiTe3O8 powders (black line), and the reference structure of pure TiTe3O8 (red line, PDF#: 01-070-2439).

    JNFCWT-18-4-509_F2.gif

    Ball-and-stick representation of 3D structure of TiTe3O8 in ab-plane, TiO6 octahedron and Te3O8 trimers by corner sharing of TeO4 seesaw groups. The purple octahedrons represent TiO6, the blue balls Te atoms, and the red balls O atoms.

    JNFCWT-18-4-509_F3.gif

    Thermal behavior of TiTe3O8 powders. (a) Thermogravimetric analysis (black line), differential scanning calorimetry analysis (red line) data, and (b) X-ray diffraction patterns of TiTe3O8 powder treated at different temperatures for 10 min.

    JNFCWT-18-4-509_F4.gif

    XRD patterns of TiTe3O8 after leaching in (a) 0.01 M HCl aqueous solution, (b) pure deionized water, and (c) 0.01 M NaOH aqueous solution over t = 7 d (red line), 14 d (blue line), and XRD pattern of the sample before leaching (black line) as a reference.

    Tables

    Crystallographic data of TiTe3O8 [16]

    Atomic positions, site occupancies, and equivalent isotropic displacement parameters for TiTe3O8 [16]

    Selected interatomic bond lengths and bond angles for TiTe3O8 [16]

    Leaching rate of constituent Ti and Si element in various waste forms

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