title: Phase transformations undergone by Triton X-100 probed by differential scanning calorimetry and dielectric relaxation spectroscopy.
abstract: The phase transformations of the surfactant Triton X-100 were investigated by differential scanning calorimetry (DSC), polarized optical microscopy (POM), and dielectric relaxation spectroscopy (DRS). In particular, crystallization was induced at different cooling rates comprised between 13 and 0.5 K min(-1). Vitrification was detected by both DSC and DRS techniques with a glass transition temperature of ∼212 K (measured on heating by DSC) allowing classifying Triton X-100 as a glass former. A fully amorphous material was obtained by cooling at a rate ≥10 K min(-1), while crystallization was observed for lower cooling rates. The temperature of the onset of melt-crystallization was found to be dependent on the cooling scan rate, being higher the lower was the scan rate. In subsequent heating scans, the material undergoes cold-crystallization except if cooled previously at a rate ≤1 K min(-1). None of the different thermal histories led to a 100% crystalline material because always the jump typical of the glass transformation in both heat flux (DSC) and real permittivity (DRS) is observed. It was also observed that the extent/morphology of the crystalline phase depends on the degree of undercooling, with higher spherulites developing for lower undercooling degree (24 K ≤ T(m) - T(cr) ≤ 44 K) in melt-crystallization and a grain-like morphology emerging for T(m) - T(cr) ≈ 57 K either in melt- or cold-crystallization. The isothermal cold- and melt-crystallizations were monitored near above the calorimetric glass transition temperature by POM (221 K) and real-time DRS (T(cr) = 219, 220, and 221 K) to evaluate the phase transformation from an amorphous to a semicrystalline material. By DRS, the α-relaxation associated with the dynamic glass transition was followed, with the observation that it depletes upon both type of crystallizations with no significant changes either in shape or in location. Kinetic parameters were obtained from the time evolution of the normalized permittivity according to a modified Avrami model taking in account the induction time. The reason the isothermal crystallization occurs to a great extent in the vicinity of the glass transition was rationalized as the simultaneous effect of (i) a high dynamic fragile behavior and (ii) the occurrence of catastrophic nucleation/crystal growth probably enabled by a preordering tendency of the surfactant molecules. This is compatible with the estimated low Avrami exponent (1.12 ≤ n ≤ 1.6), suggesting that relative short length scale motions govern the crystal growth in Triton X-100 coherent with the observation of a grainy crystallization by POM.
authors.affiliation: REQUIMTE/CQFB, Departamento de Química, Faculdade de Ciências e Tecnologia, Universidade Nova de Lisboa, Caparica, Portugal.
authors.forename: Esther G
authors.initials: EG
authors.lastname: Merino
authors.forename: Carla
authors.initials: C
authors.lastname: Rodrigues
authors.forename: M Teresa
authors.initials: MT
authors.lastname: Viciosa
authors.forename: Carlos
authors.initials: C
authors.lastname: Melo
authors.forename: João
authors.initials: J
authors.lastname: Sotomayor
authors.forename: Madalena
authors.initials: M
authors.lastname: Dionísio
authors.forename: Natália T
authors.initials: NT
authors.lastname: Correia
mesh_terms: D002152:Calorimetry, Differential Scanning; D003460:Crystallization; D058266:Dielectric Spectroscopy; D007700:Kinetics; D008689:Methacrylates / Q000737:chemistry; D017830:Octoxynol / Q000737:chemistry*; D044367:Phase Transition; D044366:Transition Temperature
chemical_list: D008689:Methacrylates; C004919:ethylene dimethacrylate; D017830:Octoxynol