F. De Candia

Thermally induced crystallization in glassy syndiotactic polystyrene

The thermal crystallization of glassy amorphous syndiotactic polystyrene has been studied using infrared, x-ray, and thermal analysis. The kinetics of the process is very rapid and the obtained crystalline phase is characterized by chains in zig-zag planar conformation. The use of the infrared analysis is indeed based on the presence of a skeleton band related to the zig-zag planar sequences. However infrared and x-ray data disagree in the evaluation of crystallinity, and a structural model has been proposed to account this experimental evidence. In particular the presence of a phase of intermediate order between amorphous and crystalline has been suggested. This mesomorphic phase is characterized by conformational order, and probably by crystalline order at very short range, both not sufficient to give rise to discrete x-ray diffraction patterns.

Solvent-induced crystallization of syndiotactic polystyrene in different liquids : sorption and diffusion phenomena

Abstract Transport properties of different liquids inducing crystallization in syndiotactic polystyrene (sPS) were investigated at 25°C. The weight uptake kinetics in the different liquids imply Fickian behaviour, with the exclusion of n-hexane and cyclohexane for which the weight uptake starts after an induction time. The equilibrium concentration of the different liquids in sPS is a function of the solubility parameter and shows a maximum with respect to chloroform, indicating a maximum in the polymer-solvent interaction. The swollen samples are birefringent but appear substantially amorphous on the basis of the X-ray diffractograms. After drying a well developed crystalline order appears, and the diffractograms indicate the presence of solvated structures, characterized by chains in helical conformation.

Drawing and dynamic-mechanical behavior of syndiotactic polystyrene an introduction

The drawing behavior of syndiotactic polystyrene was analyzed at different temperatures. Amorphous films were used and, depending on drawing temperature, strain-induced or thermal-induced cold crystallization was observed. This phenomenon, when present, greatly affects the drawing behavior. The dynamic-mechanical behavior of drawn samples was analyzed, and the obtained results indicate that the glass transition is affected by drawing, and that the effect depends drastically on the drawing temperature. Particularly interesting is the dynamic behavior at high temperature where the elastic modulus is weakly affected by temperature also near the melting point.

Polymorphism of syndiotactic polystyrene. Morphology of the solvent-induced crystalline forms

The morphology of the delta and gamma forms of syndiotactic polystyrene (sPS) was investigated using scanning electron microscopy. The crystalline forms, delta and gamma, characterized by the chains in helical conformation, were obtained by solvent-induced crystallization from the amorphous glassy polymer. Dichloromethane and acetone were used to obtain the delta and the gamma form, respectively. The last form was obtained by thermal treatments of the delta form, too. The surface of the solvent-crystallized samples shows a texture characterized by oriented elements and cavities, whereas the internal part is microspherulitic in the case of the delta form and is more complex in the gamma form. At variance, the gamma form obtained by annealing the delta form shows a much more regular microspherulitic texture.

Solvent crystallized syndiotactic polystyrene. Thermal and dynamic-mechanical behavior

The syndiotactic polystyrene can crystallize in different forms, depending on thermal and solvent treatments. The influence of the polymorphism on the dynamic-mechanical behavior has been analyzed. Thermogravimetric and calorimetric analysis were also carried out. The effects of phase transitions and solvent release on the relaxation phenomena were observed, and the correlations between structure and dynamic behavior allow to better understand some aspects of the polymorphism phenomena.

Phase organization of solvent-crystallized syndiotactic polystyrene films

Abstract Sorption and diffusion of dichloromethane vapor in the helical forms—that is, δ and γ—of syndiotactic polystyrene were investigated. The thermal transition from the δ to the γ form occurs through an intermediate mesomorphic form, also characterized by chains in helical conformation but lacking true crystalline order. The mesomorphic phase was found impermeable to the vapor at low activity, becoming permeable at higher activities. The presence of a mesomorphic phase, along with the crystalline and the amorphous forms, was suggested in the crystallized samples, too, and its fraction increases greatly going from the δ to the γ form.

Annealing of the delta form of syndiotactic polystyrene

Abstract The effects of thermal treatments on the phase organization in some polymorphic forms of syndiotactic polystyrene have been investigated. In particular the thermal stability of the delta form was studied using x-ray diffraction and infrared spectroscopy as analytical techniques. The obtained results show that this form, characterized by chains in helix conformation, is affected by non-equilibrium phenomena. Moreover, the transition from the delta to the gamma form occurs through an intermediate form which maintains the helix chain conformation but partially loses the crystalline order.

Mechanical properties and molecular mobility in oriented polyolefines

The static modulus of elasticity (E) and the correlation time of rotation (τc) of 2,-2,6,6-tetramethylpiperidine-1-oxyl are studied as a function of the temperature (210<T <350°K) for oriented films of isotactic polypropylene and polyethylene of high and low density.E andτc change both upon heating and polymer orientation; this result indicates that sample properties are influenced by the microstructure of the amorphous phase where probes are localized.

Transport properties of mesomorphic syndiotactic polystyrene

Amorphous syndiotactic polystyrene (sPS) films were annealed at 110° and 115°C for 24 h. The annealing at the higher temperature produced the mesomorphic form of sPS, characterized by conformational order, as shown both by the presence of the zigzag band in the infrared spectrum and by the presence of characteristic peaks in the x-ray diffractogram. The crystalline form was not formed at the investigated temperatures. Differential scanning calorimetry of the mesomorphic sample shows that the transformation of the mesophase into the crystalline phase occurs during the heating run. The transport properties of dichloromethane show that the mesophase is impermeable to the vapors at low activity and becomes permeable at higher activities. At low activity it is therefore possible to derive the fraction of impermeable phase, which corresponds to the fraction of mesophase. This fraction was about 50%.

Thermal behaviour and transport properties of liquid crystalline polymers : phase organization in a thermotropic polyester

Abstract The thermal behaviour and transport properties of a thermotropic semiflexible polyester have been analysed. The system is polymorphic and the transport properties indicate, rather surprisingly, that the Sorption coefficient increases on improving the structural organization of the polymer. A structural model has been suggested, based on the hypothesis that the non-crystalline nematic system is characterized by the fine interpenetration of impermeable nematic domains and less ordered permeable domains.