13C NMR of DIPAC and DIPAB organic ferroelectrics.

The diisopropylammonium chloride (C6H16ClN, DIPAC) and diisopropylammonium bromide (C6H16BrN, DIPAB) molecular crystals are recently discovered ferroelectrics with sufficiently high spontaneous polarization and Curie temperature. We performed first studies of these crystals by 13C NMR. CP MAS spectra were collected within large temperature ranges covering the Curie points. The reconstructive phase transition from the initial orthorhombic P212121 structure of DIPAB to the monoclinic ferroelectric P21 structure leads to an abrupt alteration in the 13C spectrum. The 13C spectra for DIPAC and DIPAB in the ferroelectric P21 phase are quite similar with four lines at lower frequencies, which correspond to the CH3 groups, and two lines with close chemical shifts, which correspond to two CH groups. The transition into the paraphase leads to gradual reduction of the interline distances in the low-frequency quadruplet and in the doublet. The step-like changes in the interline frequency shifts at this transition indicating its first order. The analysis of the spectrum evolution in the paraphase shows that only a CH group lays in the reflection plane above the P21 → P21/m transition, while the second CH group only moves closer to the reflection plane upon further heating.

Dielectric properties of an organic ferroelectric of bromide diisopropylammonium embedded into the pores of nanosized Al2O3 films.

The study presents experimental results for investigating linear and nonlinear dielectric properties of nanocomposites based on bromide diisopropylammonium (C6H16NBr, DIPAB) and aluminum oxide films (Al2O3) with pore diameter of 330, 100 and 60 nm. It was indicated that the phase transition was blurred and shifted toward lower temperatures. This anomaly became more significant with decreasing pore size. The reduction of phase transition temperature in the nanocomposites, containing DIPAB, was consistent with theoretical models for the influence of size effects on the structural phase transition.

Phase transitions in K(1-x)Na(x)NO(3) embedded into molecular sieves.

Dielectric studies of molecular sieves MCM-41 filled with K(1-x)Na(x)NO(3) salts (x = 0, 0.05 and 0.10) were carried out and compared with results obtained for their bulk counterparts. The regular increase upon warming of the temperature of the reconstructive phase transition from phase II to phase I with decreasing pore sizes was observed for all x. A thermodynamic model for shifts of reconstructive phase transitions was suggested. Ferroelectric phase III was shown to occur upon cooling in bulk binary salts and for all x in confined geometry under the thermal conditions when phase III does not arise in bulk KNO(3). Ferroelectricity persisted below room temperature in the bulk binary salt with x = 0.10.