文摘
In order to clarify the polymorphism in the lithium sulfate family, LiRE<em>xem>(NH4)1 − <em>xem>SO4 (0.5 ≤ <em>xem> ≤ 4.0 mol%, nominal value; RE = Er3+, Yb3+ and Dy3+) crystals were grown from aqueous solution by slow evaporation between 298 and 313 K. The doping of the samples allowed us to obtain two polymorphic forms, α and β, of LiNH4SO4 (LAS). By means of X-ray diffraction (XRD) in single crystals, we determined the crystal structures of two new α-polytypes, which we have named α1- and α2-LAS. They present the same space group <em>Pem>21/<em>cem> and the following relation among their lattice parameters: <em>aem>2 = −<em>cem>1, <em>bem>2 = −<em>bem>1, <em>cem>2 = −2<em>aem>1 − <em>cem>1. In order to evaluate the stability of the new α-polytypes, we performed thermal analysis, X-ray diffraction and dielectric spectroscopy on single crystals and polycrystalline samples over the cyclic temperature range: 190 575 190 K. The results obtained by all the techniques used in this study demonstrate that α-polytypes are stable across a wide range of temperatures and they show an irreversible phase transition to the paraelectric β-phase above 500 K. In addition, a comparative study of α- and β-polytypes shows that both polymorphic structures have a common axis, with a possible intergrowth that facilitates their coexistence and promotes the reconstructive α β transition. This intergrowth was related to small anomalies detected between 240 and 260 K, in crystals with an α-habit.