TY - JOUR
T1 - Crystallization kinetics of phosphonium ionic liquids: effect of cation alkyl chain length and thermal history
AU - Yao, B.
AU - Alvarez, V. Morales
AU - Paluch, M.
AU - Fedor, G.
AU - McLaughlin, S.
AU - McGrogan, A.
AU - Swadźba-Kwaśny, M.
AU - Wojnarowska, Z.
PY - 2024/7/11
Y1 - 2024/7/11
N2 - The effects of alkyl chain length on the crystallization kinetics and ion mobility of tetraalkylphosphonium, [P666,n][TFSI], (n = 2, 6, 8, and 12) ionic liquids were studied by differential scanning calorimetry (DSC) and broadband dielectric spectroscopy (BDS) over a wide temperature range. The liquid–glass transition temperature (Tg) and ion dynamics examined over a broad T range were almost insensitive to structural modifications of the phosphonium cation. In contrast, the crystallization kinetics were strongly affected by the length of the fourth alkyl chain. Furthermore, the thermal history of the sample (cold vs melt crystallization) significantly impacted the crystallization rate. It has been found that the nature of crystallization phenomena is the same across the homologous series, while the kinetic aspect differs. Finally, electric conductivity in supercooled liquid and crystalline solid phases was measured for all samples, revealing significant ionic conductivity, largely independent of the cation structure.
AB - The effects of alkyl chain length on the crystallization kinetics and ion mobility of tetraalkylphosphonium, [P666,n][TFSI], (n = 2, 6, 8, and 12) ionic liquids were studied by differential scanning calorimetry (DSC) and broadband dielectric spectroscopy (BDS) over a wide temperature range. The liquid–glass transition temperature (Tg) and ion dynamics examined over a broad T range were almost insensitive to structural modifications of the phosphonium cation. In contrast, the crystallization kinetics were strongly affected by the length of the fourth alkyl chain. Furthermore, the thermal history of the sample (cold vs melt crystallization) significantly impacted the crystallization rate. It has been found that the nature of crystallization phenomena is the same across the homologous series, while the kinetic aspect differs. Finally, electric conductivity in supercooled liquid and crystalline solid phases was measured for all samples, revealing significant ionic conductivity, largely independent of the cation structure.
U2 - 10.1021/acs.jpcb.4c01720
DO - 10.1021/acs.jpcb.4c01720
M3 - Article
SN - 1520-6106
VL - 128
SP - 6610
EP - 6621
JO - The Journal of Physical Chemistry B
JF - The Journal of Physical Chemistry B
IS - 27
ER -