1989
DOI: 10.1515/zna-1989-0113
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Structural Phase Transitions in Solid tert-Butylammonium Nitrate as Studied by Differential Thermal Analysis and 1H-NMR

Abstract: Seven solid phases including three metastable phases of (CH

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Cited by 5 publications
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“…Molecular plastic crystals such as succinonitrile have been studied for decades, 3,4 while organic ionic plastic crystals are a more recent discovery. 6,8 Both of these types of material display one or more solid-solid phase transitions before melting; these are associated with the onset of rotational or translational motions of the molecules/ions and thus a progressive transformation from an ordered crystalline phase to an increasingly disordered structure. Hence, a small entropy of fusion, DS f , is an indication of plasticity, as it reveals that the material in its highest temperature solid (plastic) phase is entropically close to the liquid phase.…”
Section: Introductionmentioning
confidence: 99%
See 1 more Smart Citation
“…Molecular plastic crystals such as succinonitrile have been studied for decades, 3,4 while organic ionic plastic crystals are a more recent discovery. 6,8 Both of these types of material display one or more solid-solid phase transitions before melting; these are associated with the onset of rotational or translational motions of the molecules/ions and thus a progressive transformation from an ordered crystalline phase to an increasingly disordered structure. Hence, a small entropy of fusion, DS f , is an indication of plasticity, as it reveals that the material in its highest temperature solid (plastic) phase is entropically close to the liquid phase.…”
Section: Introductionmentioning
confidence: 99%
“…In OIPCs one of the ionic species may exhibit little disorder (negligible translational or rotational motion), while the other species is the origin of the plasticity, and hence significant entropy can remain, to be released on melting. 9 Since the first report of organic ionic plastic crystals in the late 1980s/90s, [5][6][7][8]10,11 research has focussed both on application of these materials in devices and also on fundamental understanding of the materials themselves: for example, how the nature of the cations and anions influences the thermal and physical behaviour of the salts, 5,7,9 or the mechanism of conduction through the different matrices. 12 Conduction in these materials is believed to be enabled by the presence of (i) defects or vacancies in the crystal structure; (ii) rotational and/ or translational disorder of the cation or anion, 13 which may be less hindered in the vicinity of the defects; and/or (iii) conformational disorder of the ions.…”
Section: Introductionmentioning
confidence: 99%
“…In the present study, 1 4 by three times repeated crystallization from D 2 0 (99.8 D%). Because of the hygroscopicity of the purified crystals, they were handled in a dry bag and dried under a vacuum (ca.…”
Section: Introductionmentioning
confidence: 88%
“…In previous papers we have studied (CH 3 ) 3 CNH 3 -N0 3 [1] and (CH 3 ) 3 CNH 3 C10 4 [2] by NMR and thermal measurements. The nitrate was found to have seven solid phases (including three metastable phases) between 80 K and the melting point (418 K).…”
Section: Introductionmentioning
confidence: 99%
“…Ferroelectric (ionic) molecular crystals, in particular those of globular molecules, can also host orientationally disordered mesophases. ,, These phases can be highly ductile, or “plastic”, which can arise from reduced intermolecular interactions, and increased symmetry yielding many facile slip planes . This subgroup of molecular crystals is called plastic crystals, and the materials can be molded and fused, in contrast to the rigidity and brittleness observed for most molecular crystals and inorganic ceramics …”
Section: Introductionmentioning
confidence: 99%