Double freezing of (NH(4))(2)SO(4)/H(2)O droplets below the eutectic point and the crystallization of (NH(4))(2)SO(4) to the ferroelectric phase.
This paper presents the differential scanning calorimetry (DSC) results obtained from measurements of single droplets of different subeutectic concentrations (<40 wt % (NH4)2SO4) and diameters of 1-1.5 mm. The measurements show that despite the fact that the freezing of the droplets takes place below the eutectic temperature of Te ≈ 254.5 K, a phase separation into ice and a residual freeze-concentrated solution occurs. The residual solution is formed by the expulsion of NH4+ and SO42- ions from the ice lattice during the nucleation and growth of ice and may possess the eutectic concentration of 40 wt % (NH4)2SO4. On further cooling, the residual solution freezes to the eutectic solid mixture of ice/(NH4)2SO4 at a temperature that is either above or below the ferroelectric "Curie" temperature of Tc ≈ 223 K. If the freezing of the residual solution takes place below the Tc, then (NH4)2SO4 crystallizes directly into the ferroelectric phase.
Bogdan
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Institute of Physical Chemistry, University of Innsbruck, Innrain 52a, A-6020 Innsbruck, Austria.
D000645:Ammonium Sulfate / Q000737:chemistry*; D002152:Calorimetry, Differential Scanning; D003460:Crystallization; D004574:Electromagnetic Fields; D005615:Freezing; D014867:Water / Q000737:chemistry*
D014867:Water; D000645:Ammonium Sulfate