Na2La4(NH2)14·NH3, a lanthanum-rich intermediate in the ammonothermal synthesis of LaN and the effect of ammonia loss on the crystal structure

Single crystals of Na2La4(NH2)14·NH3 were obtained from supercritical ammonia under ammonobasic conditions at a temperature of 573 K and 120 MPa pressure. It represents a lanthanum-rich intermediate in the ammonothermal synthesis of LaN. Upon aging, the title compound loses the crystal ammonia, resulting in pale crystals of Na2La4(NH2)14, the original space group P212121 being retained in a very similar unit cell. However, the crystal structure reacts to subtle changes in the composition as well as to the modified coordination of particularly the sodium cations interconnecting lanthanum amide layers within a third dimension. Results of Raman spectroscopic studies are reported. The observations of thermal analysis measurements indicating the formation of lanthanum nitride, in combination with the observed retrograde solubility in liquid ammonia, contribute to the knowledge of the ammonothermal crystal growth of lanthanum nitride.

GaPO4 Single Crystals: Growth Condition by Hydrothermal Refluxing Method

Bulk GaPO4 is an advanced piezoelectric material operating under high temperatures according to the α-β phase transition at 970 °C. This work presents the technological development of a hydrothermal refluxing method first applied for GaPO4 single crystal growth. Crystals of 10–20 g were grown in mixtures of aqueous solutions of low- and high-vapor-pressure acids (H3PO4/HCl) at 180–240 °C (10–20 bars). The principal feature of the refluxing method is a spatial separation of crystal growth and nutrient dissolution zones. This leads to a constant mass transportation of the dissolved nutrient, even for materials with retrograde solubility. Mass transport is carried out by dissolution of GaPO4 nutrient in a dropping flow of condensed low-vapor-pressure solvent. This method allows an exact saturation at temperature of equilibrium and avoids spontaneous crystallization as well loss of seeds. Grown crystals have a moderate OH− content and reasonable structural uniformity. Moreover, the hydrothermal refluxing method allows a fine defining of GaPO4 concentration in aqueous solutions of H3PO4, H2SO4, HCl and their mixtures at set T–P parameters (T < 250 °C, p = 10–30 bars). The proposed method is relatively simple to use, highly reproducible for crystal growth of GaPO4 and probably could applied to other compounds with retrograde solubility.

Forming sulfate- and REE-rich fluids in the presence of quartz

The presence of sulfate-rich fluids in natural magmatic hydrothermal systems and some carbonatite-related rare earth element (REE) deposits is paradoxical, because sulfate salts are known for their retrograde solubility, implying that they should be insoluble in high-temperature geofluids. Here, we show that the presence of quartz can significantly change the dissolution behavior of Na2SO4, leading to the formation of extremely sulfate-rich fluids (at least 42.8 wt% Na2SO4) at temperatures &gt;∼330 °C. The elevated Na2SO4 solubility results from prograde dissolution of immiscible sulfate melt, the water-saturated solidus of which decreases from ≥∼450 °C in the binary Na2SO4-H2O system to ∼270 °C in the presence of silica. This implies that sulfate-rich fluids should be common in quartz-saturated crustal environments. Furthermore, we found that the sulfate-rich fluid is a highly effective medium for Nd mobilization. Thermodynamic modeling predicts that sulfate ions are more effective in complexing REE(III) than chloride ions. This reinforces the idea that REEs can be transported as sulfate complexes in sulfate-rich fluids, providing an alternative to the current REE transport paradigm, wherein chloride complexing accounts for REE solubility in ore fluids.