Radiation tolerant ceramics for nuclear waste immobilization: Structure and stability of cesium containing hollandite of the form (Ba,Cs)1.33(Zn,Ti)8O16 and (Ba,Cs)1.33(Ga,Ti)8O16

Grote, Rob; Hong, Tao; Shuller-Nickles, Lindsay; Amoroso, Jake W.; Tang, Ming; Brinkman, Kyle S.

doi:10.1016/j.jnucmat.2019.03.005

Cited by 21 publications

(4 citation statements)

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“…At a fixed tunnel occupancy of 67%, a range of compositions of the Ba–Cs–Ga–Ti–O hollandite system with varying Ba/Cs and Ga/Ti contents were observed tetragonal [48], while Cs-free Ba–Zn–Ti–O was monoclinic converting to tetragonal upon the introduction of Cs for Ba [50]. At a fixed stoichiometry of octahedral cations, Ba 1.15− x Cs 2 x Cr 2.3 Ti 5.7 O 16 transformed from tetragonal symmetry to monoclinic, with the monoclinic nature increasing with Cs substitution [43], which contrasts the findings in other recent works [47,48,50,52]. In Ba x Cs y Zn 2 x − y Ti 8–2 x − y O 16 (0 ≤ x ≤ 1.333 and y = 1.333 − x ) hollandites, Ba-end member Ba 1.333 Zn 1.333 Ti 6.667 O 16 possessed monoclinic symmetry, but the addition of Cs ( y > 0) stabilised the I4/m tetragonal structure [50].…”

Section: Hollandites As Nuclear Waste Formsmentioning

confidence: 79%

“…Understanding how the inherent compositional inhomogeneity of octahedral cations and the resultant cation order–disorder affect the overall response to foreign chemical or electrochemical attacks is critical to the stability of these materials in service as a waste form. A recent study [52] offers a closer insight with regard to hollandites’ structure–durability–irradiation resistance relationship. Higher Cs loading in the tunnel imparted resistance to Cs leaching and radiation damage.…”

Section: Hollandites As Nuclear Waste Formsmentioning

confidence: 99%

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Hollandites’ crystal chemistry, properties, and processing: a review

Tumurugoti

Betal

Sundaram

2020

International Materials Reviews

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This review provides a broad overview of the structural characteristics, compositional flexibility, and structure-property relationships of hollandite materials. Hollandites have a general formula A x B 8 O 16 , x ≤ 2, with 'A' cations located in one-dimensional tunnels formed by a framework of 'B'-O octahedra. With numerous possibilities for chemical and structural modifications, hollandite family provides many opportunities to manipulate its properties for specific applications. First, we review the chemistry, structure-property relationship, and processing techniques for various applications. The primary focus is on the cumulative effects of Aand B-cation interaction, and the resultant parameters including unit cell symmetry, cation order-disorder, electronic and/or magnetic coupling, that dictate the material's applicability. Then, selected applications, such as crystalline hosts for radioactive caesium disposal, electrode material for Li-ion batteries, and ferromagnetic materials, are outlined from a structure-property relationship perspective. Finally, processing strategies in correlation with structural evolution and applications are briefly addressed.

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Section: Hollandites As Nuclear Waste Formsmentioning

confidence: 79%

Section: Hollandites As Nuclear Waste Formsmentioning

confidence: 99%

Hollandites’ crystal chemistry, properties, and processing: a review

Tumurugoti

Betal

Sundaram

2020

International Materials Reviews

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“…Complete amorphization at 0.041 dpa indicates a low resistance to radiation damage for the Na x MAn 6 F 30 structure type. For comparison, radiation damage studies on potential waste form structures reported previously by others in the CHWM research group include a double phosphate Rb 3 Nd(PO 4 ) 2 with single crystal amorphization dose at 0.22 dpa, a nanocrystalline phase at 0.52 dpa, and a hollandite crystal Cs 1.33 Zn 0.67 Ti 7.33 O 16 at 0.538 dpa . Other radiation damage studies found in the literature reported by other groups include the pyrochlore Ca 1.25 U 0.76 Zr 0.2 Ti 1.89 O 7 with an amorphization dose of 0.24 dpa and a brannerite structure UTi 2 O 6 at 0.15 dpa .…”

Section: Resultsmentioning

confidence: 97%

Developing Waste Forms for Transuranic Elements: Quaternary Neptunium Fluorides of the Type Na_xMNp₆F₃₀ (M = Ti, V, Cr, Mn, Fe, Co, Ni, Al, Ga)

et al. 2022

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A series of quaternary Np(IV) fluorides was synthesized using a mild hydrothermal synthesis approach. The compositions are all of the type Na x MNp6F30, where M = Ti(III), V(III), Cr(III), Mn(II), Fe(III), Co(II), Ni(II), Al(III), and Ga(III) and x = 4 for divalent metals, x = 3 for trivalent metals. The compounds all crystallize in the P-3c1 space group and are isotypic with actinide analogues Na x MAn6F30 (An = Ce, U, Th, Pu). Structure data from the neptunium crystals were combined with data from the other actinide analogues to establish the tetravalent, nine-coordinated ionic radii of neptunium (1.030(2) Å), plutonium (1.014(1) Å), and cerium (1.012(2) Å). Radiation damage studies were also carried out on a surrogate material, the cerium analogue Na3AlCe6F30, which indicates that the structure type has low resistance to amorphization. Density functional theory calculations were carried out to compute the band gaps and enthalpies of formation variations among the isotypic cerium and actinide structures to compare the stability of the structures.

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“…Similarly, sodalite-structured materials can incorporate iodide in the β-cage site of the crystal structure [ 23 , 24 ]. Hollandite and pollucite waste forms have been developed to incorporate Cs + in its large channel site and 12-coordinated crystallographic sites, respectively [ 25 , 26 , 27 , 28 , 29 , 30 , 31 , 32 , 33 , 34 ]. In addition, other crystalline ceramic waste forms such as perovskite, pyrochlore, murataite, monazite, and crichtonite have been developed for the incorporation of various radionuclides, including Cs, Sr, rare earth, and actinides [ 11 , 35 ].…”

Section: Introductionmentioning

confidence: 99%

Computational Materials Design for Ceramic Nuclear Waste Forms Using Machine Learning, First-Principles Calculations, and Kinetics Rate Theory

2023

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Ceramic waste forms are designed to immobilize radionuclides for permanent disposal in geological repositories. One of the principal criteria for the effective incorporation of waste elements is their compatibility with the host material. In terms of performance under environmental conditions, the resistance of the waste forms to degradation over long periods of time is a critical concern when they are exposed to natural environments. Due to their unique crystallographic features and behavior in nature environment as exemplified by their natural analogues, ceramic waste forms are capable of incorporating problematic nuclear waste elements while showing promising chemical durability in aqueous environments. Recent studies of apatite- and hollandite-structured waste forms demonstrated an approach that can predict the compositions of ceramic waste forms and their long-term dissolution rate by a combination of computational techniques including machine learning, first-principles thermodynamics calculations, and modeling using kinetic rate equations based on critical laboratory experiments. By integrating the predictions of elemental incorporation and degradation kinetics in a holistic framework, the approach could be promising for the design of advanced ceramic waste forms with optimized incorporation capacity and environmental degradation performance. Such an approach could provide a path for accelerated ceramic waste form development and performance prediction for problematic nuclear waste elements.

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Radiation tolerant ceramics for nuclear waste immobilization: Structure and stability of cesium containing hollandite of the form (Ba,Cs)1.33(Zn,Ti)8O16 and (Ba,Cs)1.33(Ga,Ti)8O16

Cited by 21 publications

References 36 publications

Hollandites’ crystal chemistry, properties, and processing: a review

Hollandites’ crystal chemistry, properties, and processing: a review

Developing Waste Forms for Transuranic Elements: Quaternary Neptunium Fluorides of the Type Na_xMNp₆F₃₀ (M = Ti, V, Cr, Mn, Fe, Co, Ni, Al, Ga)

Computational Materials Design for Ceramic Nuclear Waste Forms Using Machine Learning, First-Principles Calculations, and Kinetics Rate Theory

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Radiation tolerant ceramics for nuclear waste immobilization: Structure and stability of cesium containing hollandite of the form (Ba,Cs)1.33(Zn,Ti)8O16 and (Ba,Cs)1.33(Ga,Ti)8O16

Cited by 21 publications

References 36 publications

Hollandites’ crystal chemistry, properties, and processing: a review

Hollandites’ crystal chemistry, properties, and processing: a review

Developing Waste Forms for Transuranic Elements: Quaternary Neptunium Fluorides of the Type NaxMNp6F30 (M = Ti, V, Cr, Mn, Fe, Co, Ni, Al, Ga)

Computational Materials Design for Ceramic Nuclear Waste Forms Using Machine Learning, First-Principles Calculations, and Kinetics Rate Theory

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Developing Waste Forms for Transuranic Elements: Quaternary Neptunium Fluorides of the Type Na_xMNp₆F₃₀ (M = Ti, V, Cr, Mn, Fe, Co, Ni, Al, Ga)