Design of Crystal Growth Dimensionality in Synthetic Wax: The Kinetics of Nonisothermal Crystallization Processes.

The demand for the development of multifunctional materials in emerging technologies has stimulated intensive research on the control of crystallization processes in numerous scientific and engineering fields. In this article, we examine the kinetics of nonisothermal melt crystallization in synthetic wax using differential scanning calorimetry (DSC) supported by polarized optical microscopy (POM) to describe crystallization modes in a multicomponent molecular system. We detected the macroscopic growth of three crystal phases and the formation of two crystal phases as a transformation from a disordered crystal mesophase into an ordered crystal. To characterize individual crystal phase formation, we examine the activation energy evaluated by isoconversional analysis and utilize the Ozawa and Mo methods to determine the kinetic details of the crystal growth from the isotropic phase. Our investigation reveals the possibility of the design of crystal growth dimensionality as three-dimensional spherulitic-like, two-dimensional rodlike, and one-dimensional needle-shaped crystal forms of shorter n-alkanes by controlling the solidification pathway of long-chain n-alkanes and the interplay of the thermodynamic and kinetic mechanisms of crystallization.

Molecular dynamics and kinetics of isothermal cold crystallization with tunable dimensionality in a molecular glass former, 5'-(2,3-difluorophenyl)-2'-ethoxy-4-pentyloxy-2,3-difluorotolane.

This paper characterizes the molecular mobility that triggers the cold crystallization abilities in 5'-(2,3-difluorophenyl)-2'-ethoxy-4-pentyloxy-2,3-difluorotolane (short name DFP25DFT) material by broadband dielectric spectroscopy (BDS). We analyze the properties of identified molecular motions by referring to the Vogel-Fulcher-Tammann (VFT) model for the structural α-process associated with molecular rotation in isotropic liquid and the Eyring and Starkweather approach for the thermally activated processes, ß-process related to intramolecular movement in liquid and glassy state and emerging during cold crystallization α'-process ascribed to confined movements of molecules located adjacent to crystalline surfaces. To characterize the material, we employ single-crystal X-ray diffraction, differential scanning calorimetry (DSC), adiabatic calorimetry, and polarizing optical microscopy (POM), while we utilize molecular mechanics simulations (MM2) to explore molecular flexibility. Our study focuses on inter- and intramolecular interactions that determine the cold-crystallization tendency. We demonstrate that the solidification path is controlled by the fragility of the system, the dipole-dipole attraction, and the intramolecular dynamics. The study of cold crystallization kinetics under isothermal conditions reveals the complexity of the process: the formation of two crystalline phases, Cr2 and Cr3, proceeding in different modes. This feature discloses the possibility of switching the crystal growth between three- and two-dimensional in the cold-crystallization process driven by different mechanisms.

Designing the disorder: the kinetics of nonisothermal crystallization of the orientationally disordered crystalline phase in a nematic mesogen.

This article presents the molecular dynamics and solidification behavior of a 2,3-difluoro-4-propylphenyl 2,3-difluoro-4-(4-pentylcyclohexyl)benzoate nematic liquid crystal (5C4FPB3) observed by broadband dielectric spectroscopy (BDS) and differential scanning calorimetry (DSC). Polarized optical microscopy (POM) is also performed to confirm the phase transition temperatures. Our investigation reveals rare crystallization of the orientationally disordered crystal (ODIC) phase from the nematic phase and a glass transition of the crystal at cooling rates higher than 1 K min-1. The deconvolution of the dielectric spectra with derivative techniques is necessary because of the complex molecular dynamics in the crystalline phase. The BDS method enables us to capture the relaxation processes reflecting pre-crystallization molecular movements. The kinetics of nonisothermal crystallization is studied using the Ozawa, Mo, and isoconversional methods. The present studies suggest that the dominant factor of the crystal growth mechanism depends on the cooling rate. Two types of crystallization mechanisms are identified at cooling rates lower and higher than 5 K min-1. We design a diagram with crystallization and glass transition borders against the cooling rates. Estimations show that crystallization of the present compound can be bypassed at cooling rates higher than 78 kK min-1, at which a glass transition of the nematic phase occurs. We show various scenarios of the molecular order and the crystallization mechanism designed based on the process rate.

Relaxation dynamics and crystallization study of glass-forming chiral-nematic liquid crystal S,S-2,7-bis(4-pentylphenyl)-9,9-dimethylbutyl 9H-fluorene (5P-Am*FLAm*-P5).

The chiral nematic S,S-2,7-bis(4-pentylphenyl)-9,9-dimethylbutyl9H-fluorene (5P-Am*FLAm*-P5) liquid crystal shows a complex phase diagram strongly dependent on thermal treatment as identified by Polarizing Optical Microscopy (POM) and differential scanning calorimeter (DSC). The molecular dynamics in various thermodynamics states was studied by means of broadband dielectric spectroscopy (BDS). The vitrification of a chiral nematic phase (N*) is manifested by a Vogel-Fulcher-Tammann (VFT)-type temperature dependence of structural relaxation time ([Formula: see text]). Three dielectric relaxation processes exhibiting Arrhenius-like thermal activation were found in conformationally disordered (condis) Cr1 and Cr2 structures. The isothermal cold crystallization process of Cr2 occurs in the metastable N* phase; however, in the non-isothermal experiments, the Cr2 phase is formed in the isotropic phase obtained on heating the metastable N* phase. The findings for the isothermal process were compared with those regarding non-isothermal crystallization.

Interplay between Crystallization and Glass Transition in Nematic Liquid Crystal 2,7-Bis(4-pentylphenyl)-9,9-diethyl-9 H-fluorene.

This article presents the crystallization behavior and molecular dynamics of the supercooled nematic state of the newly synthesized liquid crystal 2,7-bis(4-pentylphenyl)-9,9-diethyl-9 H-fluorene (5P-EtFLEt-P5) studied by means of broadband dielectric spectroscopy (BDS). 5P-EtFLEt-P5 is a fragile glass-forming system with a high fragility parameter ( mf ≈ 121). The study compares the isothermal melt- and cold-crystallization processes at several selected temperatures Tc in the vicinity of the glass-transition temperature Tg (1.07 Tg ≤ T ≤ 1.17 Tg). Our findings reveal that at low temperatures, the crystallization of the Cr1 phase from the nematic melt state occurs more quickly than the cold crystallization. The dimensionality of the growing crystallites ( n) was found to be slightly higher for the cold- than for the melt-crystallization process, varying from n ∼ 5 to n ∼ 3 with increasing temperature. Our experimental results are discussed in terms of dynamic and thermodynamic properties of the material. The study also uses polarized optical microscopy to investigate the isothermal secondary cold crystallization (the formation of Cr2 from Cr1 upon heating), which is inaccessible by BDS measurements because of its very fast crystallization rates.

Isothermal high-pressure studies of 4-cyano-3-fluorophenyl 4-butylbenzoate dynamics near room temperature.

For 4-cyano-3-fluorophenyl 4-butylbenzoate, a glass former giving glass of nematic phase at ambient pressure and after rapid pressurizing, isothermal studies of complex dielectric permittivity vs pressure were performed near room temperature. In the previous isobaric experiment, on cooling the nematic phase two super-Arrhenius α relaxations, ascribed to the reorientations of molecules around short axes (main process) and precession of long molecular axes, and ß relaxation related to intramolecular motions were found. In the present isothermal experiments nematic-smectic phase transition was induced by increasing pressure. Linear pressure dependence of the logarithm of the dielectric relaxation time gives activation volume of about 70 cm(3)/mole for liquid crystalline phases and 50 cm(3)/mole for the isotropic phase. The time-temperature-pressure superposition principle for the α-relaxation process was found to be valid (i.e., a single master curve can be obtained by superpositioning dielectric loss curves measured at various temperatures and pressures).