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Measuring Thermal Crystallinity in PET: Spe Antec Indianapolis 2016
Measuring Thermal Crystallinity in PET: Spe Antec Indianapolis 2016
Figure 1. a) Schematic of the sample orientation with Heat of melting and heat of crystallization from the
respect to the Diffractometer geometry (the diffraction first heating cycle were selected to determine the
vector is perpendicular to the cut surface, allowing crystallinity using the equation:
measurement out of plane texture and crystallinity), b)
Sectioned PET preform having gradient of crystallinity
along the length axis, and c) photo of the measurement ⎡ ΔH − ΔH cc ⎤
location on the gradient region obtained by optical Xc = ⎢ m ⎥ ×100
microscopy. A and B represent the crystalline and the ⎣ ΔH c ⎦ (1)
amorphous regions, respectively.
Where ΔH m is the heat of melting, ΔH cc is the heat of cold
crystallization, and ΔH c is the heat of melting for 100%
Raman Spectroscopy was carried out using a
Renishaw inVia confocal Raman microscope equipped crystalline PET. As seen in Table 1, the crystallinity of the
with 785 nm excitation laser. Measurements were preform is increasing from 9.60% to 25.92% by air cooling
performed every 500 µm from crystalline to the sample (Table 1).
amorphous regions of the PET preform. The intensity of
the 1096 cm-1 Raman peak was used for correlating with XRD Measurements
respect to crystallinity [11]. The concentrated partial diffraction ring observed in
two-dimensional frames, showed strong orientation of the
PET crystallites (Figure 3). This can be due to orientation
Raman Spectroscopy
High-temperature annealing can have an impact on the
Raman spectrum of PET [11]. According to several
spectroscopic studies [12-13], significant changes take
place in the terephthalate segment of PET during the
amorphous to crystalline transition. Figure 4 shows the
intensity of the 1095 cm-1 peak, derived from curve fitting Figure 4. a) Peak intensity at 1095 cm-1, b) 3D plot of 23
indicating variation in the polymer structure. As seen in measurement points from region A to B.
the figure, variation of peak intensity can be informative
for measuring crystallinity (Figure 4).
Sample Region Tg (°C) TC (°C) Heat of Cold Crystallization Tm (°C) Heat of Melting %
∆H$$ (J/g) ∆H% (J/g) Crystallinity
Amorphous 80.91 166.11 23.54 246.62 36.99 9.60
Semi-crystalline 80.11 168 14.11 246.94 36.69 16.12
Crystalline 81.54 166.89 0.0 246.82 36.32 25.92
Conclusion
Three methods for crystallinity measurement: X-ray
diffraction, DSC, and Raman spectroscopy were employed
to characterize crystallization in PET. A significant range
of crystallinity was measured: 25% to 2% by XRD and
26% to 9% by DSC. Using the measurements from XRD
and DSC techniques, percent crystallinity and peak
intensity for the 1095 cm-1 Raman peak were correlated.
Acknowledgments