Abstract
Understanding molten salt chemistry is essential in ongoing research of the molten salt nuclear reactor (MSR). In this context, detailed understanding of the mechanisms underlying selective oxidation of metal species, such as Cr, is required to guide the design of effective corrosion mitigation strategies in molten salts. An important starting point for such mechanistic understanding is knowledge of the solvation structure and its role in controlling metal speciation. In this work, we use ab initio molecular dynamics simulations to study the short-range (on the scale of the nearest-neighbor bond lengths) and medium-range (over length scales of several neighbor spacings) structure in three different fluoride melts with and without Cr addition; namely, 2KF-NaF, 2LiF-BeF2, and 3LiF-AlF3. We find that Cr0,Cr2+,Cr3+ can each be coordinated by different numbers of F-, with the variance in coordination number decreasing as oxidation state increases, and that these coordination geometries are largely independent of solvent. The manner by which Cr changes the medium-range structure, however, is found to be solvent-dependent. While 2KF-NaF melts show short and medium range order that is highly dynamic, 2LiF-BeF2 and 3LiF-AlF3 are characterized by molecular associates that are relatively long-lived that organize into oligomer structures on larger length scales. Rather than being solvated by F- ions alone, we find that Cr can incorporate into and be solvated within this oligomer structure. Fluoroacidity, alone, may therefore prove too simple a metric for assessing the corrosivity of molten fluorides. As our work suggests, the ability of Cr to solvate must be understood in the context of the short- and medium-range structure of the solvent.
Highlights
Molten halide salt mixtures have been studied extensively for a variety of nuclear engineering applications including use in the pyroprocessing of nuclear waste [1] and as a potential coolant and/or fuel carrier in nuclear reactors [2,3,4]
The results introduce the key features of the solvent structures in the salt mixtures, and provide base-line structural characteristics that are used to analyze Cr solvation, as well as the changes that this solute induce in the solvent structure
The data from the present work in this Table are obtained from the radial distribution function (RDF) shown in Fig. 1, which presents data for the other salt solvents discussed in the subsection
Summary
Molten halide salt mixtures have been studied extensively for a variety of nuclear engineering applications including use in the pyroprocessing of nuclear waste [1] and as a potential coolant and/or fuel carrier in nuclear reactors [2,3,4]. Investigation of molten fluorides for nuclear reactor technology began in the 1950s and 1960s with the Aircraft Reactor Experiment (ARE) [5] and the subsequent Molten Salt Reactor Experiment (MSRE) [6]. Of particular interest is the solvation of chromium in molten fluorides, which is present as an alloying element in structural materials used in MSRs and fluoride salt-cooled high-temperature reactors (FHRs). Compared to other common elements in these materials (such as Fe, Ni, or Mo), Cr more readily oxidizes to a fluoride and dissolves in the salt melt [8]. Despite the practical relevance of Cr solvation in molten salts, fundamental understanding of its speciation in these solvents remains incomplete
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