Deliquescence of NaCl–NaNO(3), KNO(3)–NaNO(3), and NaCl–KNO(3 )salt mixtures from 90 to 120°C

We conducted reversed deliquescence experiments in saturated NaCl–NaNO(3)–H(2)O, KNO(3)–NaNO(3)–H(2)O, and NaCl–KNO(3)–H(2)O systems from 90 to 120°C as a function of relative humidity and solution composition. NaCl, NaNO(3), and KNO(3 )represent members of dust salt assemblages that are likely to deliquesce and form concentrated brines on high-level radioactive waste package surfaces in a repository environment at Yucca Mountain, NV. Discrepancy between model prediction and experiment can be as high as 8% for relative humidity and 50% for dissolved ion concentration. The discrepancy is attributed primarily to the use of 25°C models for Cl–NO(3 )and K–NO(3 )ion interactions in the current Yucca Mountain Project high-temperature Pitzer model to describe the nonideal behavior of these highly concentrated solutions

Hidden polymorphs drive vitrification in B2O3

Understanding the conditions that favour crystallization or vitrification of liquids has been a long-standing scientific problem(1-3). Another connected, and not yet well understood question is the relationship between the glassy and the various possible crystalline forms a system may adopt(4,5). In this context, B2O3 represents a puzzling case. It is one of the best glass-forming systems despite an apparent lack of low-pressure polymorphism. Furthermore, the system vitrifies in a glassy form abnormally different from the only known crystalline phase at ambient pressure(6). Last but not least, it never crystallizes from the melt unless pressure is applied, an intriguing behaviour known as the crystallization anomaly(7-9). Here, by means of ab initio calculations, we discover the existence of previously unknown B2O3 crystalline polymorphs with structural properties similar to the glass and formation energies comparable to the known ambient crystal. The energy degeneracy of the crystals, which is high at ambient pressure and suppressed under pressure, provides a framework to understand the system's ability to vitrify and the origin of the crystallization anomaly. This work reconciles the behaviour of B2O3 with that from other glassy systems and reaffirms the role played by polymorphism in a system's ability to vitrify(10,11). Some of the predicted crystals are cage-like materials entirely made of three-fold rings, opening new perspectives for the synthesis of boron-based nanoporous materials