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Time and frequency domain dielectric spectroscopy for in-situ and ex-situ determination of amorphous fractions of isothermally cold-crystallized Polylactic acid

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Abstract

The three–phase structure of Polylactic acid (PLA), cold crystallized at two different crystallization temperatures (TC), is performed by complementary electrical characterization techniques in a wide frequency range. Initially amorphous samples are crystallized from the glassy state at 80 °C / 4 h and 130 °C / 2 h in two different Dielectric Spectroscopy setups i.e., a typical Dielectric Response setup (0.1 Hz-1 MHz) for TC = 80 °C, and an RF Impedance Analyzer (1 MHz to 1 GHz) for TC = 130 °C. The implementation of both setups allows for the crystallization monitoring by continuous acquisition of the dielectric α-relaxation spectra, since the corresponding dielectric loss maxima are located at around 104 Hz for TC = 80 °C, and 5 × 107 Hz for TC = 130 °C. X-ray Diffraction (XRD) and Differential Scanning Calorimetry (DSC) studies reveal the presence of only the α΄-crystal form of PLA at TC = 80 °C, transforming to the more stable α-form at elevated temperatures. Spherulite size and density is monitored by Polarizing Optical Microscopy (POM) and are strongly depended on the crystallization (cold/melt) process for samples crystallized at 130 °C. Determination of the different fractions (Crystalline, Mobile Amorphous and Rigid Amorphous) reveals that samples crystallized at 130 °C exhibit an extra amount of RAF, formed upon cooling below Tg, contrary to the case of samples crystallized at lower temperatures. Combined dielectric response studies over nine orders of magnitude (from 0.1 Hz to 1 GHz) are performed systematically, as a function of temperature, time and frequency and a complete analysis of all relaxation dynamics is presented. The implementation of high frequency dielectric response, along with other typically used techniques, is proven to be a powerful tool for the complete characterization of semicrystalline polymers.

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Acknowledgments

The authors wish to acknowledge access to the DSC apparatus of the Materials Science Department of the University of Patras.

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Authors and Affiliations

  1. Department of Physics, University of Patras, 26504, Patras, Greece

    Evangelia E. Zavvou, Panagiotis C. Tsaousis, Aimilia A. Barmpaki, Panagiota K. Karahaliou, Stavroula N. Georga & Christoforos A. Krontiras

  2. Department of Geology, University of Patras, 26504, Patras, Greece

    Ioannis Iliopoulos

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  1. Evangelia E. Zavvou
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Zavvou, E.E., Tsaousis, P.C., Barmpaki, A.A. et al. Time and frequency domain dielectric spectroscopy for in-situ and ex-situ determination of amorphous fractions of isothermally cold-crystallized Polylactic acid. J Polym Res 29, 284 (2022). https://doi.org/10.1007/s10965-022-03148-6

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