Polymer crystallization dynamics investigated by synchronous scanning spectrum.

There is a cosine function between the reflected light intensity of a solid surface and its refractive index. And the mean squared fluctuation of refractive index is related to fluctuation of density and concentration. So some internal structures changes of materials can be reflected by changes in reflected light. Based on this theory, the synchronous scanning spectrum (SSS) technique was successfully applied to monitor melting and nonisothermal melt-crystallization of poly(ε-caprolactone) (PCL) film on a copper substrate. SSS can be implemented on a spectrofluorimeter by simultaneously scanning the excitation and emission monochromators (i. e, Δλ = λex-λem = 0 nm). In SSS of PCL films, two dominant peaks correlated to the light source spectrum of the spectrofluorimeter (at 467 and 473 nm) were used to characterize the macromolecular structure evolution during the melting and nonisothermal melt-crystallization processes. Detailed thermodynamic and crystallization kinetics parameters obtained by SSS method. The Avrami exponent n obtained by SSS method is in the range of 2.8-3.2 with an average of 3.13, illustrating a heterogeneous nucleation process followed by a three-dimensional spherulitic crystal growth mechanism. The crystallization activation energy is -158.2 kJ · mol(-1). These results are in agreement with values determined from differential scanning calorimetry (DSC) method. It indicates that SSS technique is a simple, effective in situ method for measuring the dynamic melting and crystallization process of polymers. Moreover, the SSS method is a universal spectroscopic technique based on a spectrofluorimeter for monitoring both luminescent and non-luminous solid polymers.

Evolution of density fluctuation to a lamellar crystal in a poly(trimethylene terephthalate) film revealed by the resonance light scattering technique.

The dynamic process of cold crystallization of amorphous poly(trimethylene terephthalate) (PTT) was investigated with resonance light scattering (RLS). By using an enhanced scattering peak at 329 nm, which was in close proximity to the absorption band of PTT film, density fluctuation due to gradual transition from amorphous to crystalline with increasing temperature was monitored. Accordingly, molecular chains movement and structure evolution in PTT during cold crystallization, in particular, the information about each phase of crystallization, including induction, nucleation, nucleus growth and secondary crystallization, were thoroughly revealed. The experimental results indicated that the kinetics parameters measured by the RLS method were in good agreement with those obtained by differential scanning calorimetry (DSC) and fluorescence spectroscopy. In addition, the RLS method can tell more details of the movement and variation in fine structures than DSC and fluorescence techniques as a result of its significantly enhanced scattering signals, like the orientation fluctuations of rigid segments in the course of glass transition and crystallization induction.

Kinetics of phase separation in polymer blends revealed by resonance light scattering spectroscopy.

In this work, kinetics of phase separation in the blends of polystyrene (PS) and poly(vinyl methyl ether) (PVME) was investigated by a simple and sensitive method, i.e., resonance light scattering (RLS) spectroscopy. Owing to the aggregation of chromophores (phenyl rings) in the systems when phase separation occurred, RLS intensities were drastically enhanced and hence acted as a characteristic indicator. At the early stage of phase separation, two different RLS behaviors corresponding to spinodal decomposition (SD) and nucleation and growth (NG) were observed. The Cahn-Hilliard (C-H) linearization theory was found not applicable for kinetics analysis of the scattering data at lambda < 346 nm due to RLS effect near the absorption band. Based on a decomposition reaction model, the apparent activation energy of SD phase separation was estimated by the Arrhenius equation. In view of its simplicity and sensitivity of measurement, affordability and availability of instrument, and wide application range of polymer blends, RLS proved to be an effective means for characterization of microstructural variation in polymer blends.

Quantitative description of aggregation and dissociation of polystyrene chains in cyclohexane solutions by resonance light scattering technique.

The resonance light scattering (RLS) technique based on a conventional fluorescence spectrophotometer was used to quantitatively describe the aggregation and dissociation of polystyrene (PS) in cyclohexane solution during cyclic heating and cooling. Transitions in conformation of PS molecules and aggregation of PS chains in the course of phase separation were revealed. The results indicated that PS chains changed from random coils to collapsed globules and then aggregated when temperature decreased. In contrast, when the system is heated, the chain aggregates were initially swelled and followed by gradual dissociation. Subsequently, the conformation of PS chains returned to the original state. Kinetics of phase separation of the PS solution was analyzed, which allowed estimation of the apparent activation energy.