Measuring Thermal Crystallinity in PET
Vahid Shabafrooz1, Masoud Allahkarami1, 2, Sudheer Bandla2, and Jay C. Hanan1
1
Mechanical and Aerospace Engineering, Oklahoma State University, Tulsa, OK 74106
2
Research and Development, Niagara Bottling LLC, Ontario, CA 91761
Abstract
The mechanical properties of poly (ethylene
terephthalate) (PET) depend on the degree of crystallinity.
PET crystallizes from both thermal and strain-induced
process paths. Strain-induced crystallization occurs under
uniaxial or biaxial stretching, the latter is common in
stretch blow molding. Thermal crystallization takes place
when cooling from the melt or under sustained elevated
temperature which are both common during injection and
blow molding. The current work focuses on comparing
methods used to quantify the percent thermal crystallinity
in injection molded water bottle preforms. An injection
molded preform with a gradient of induced thermal
crystallinity was examined using Differential Scanning
Calorimetry (DSC), Micro X-ray Diffraction (µXRD), and
Raman Spectroscopy. Correlating these three techniques
for percent thermal crystallinity, helps with the
development of nondestructive crystallinity measurement
methods to aid with process optimization and part quality.
Introduction
Due to their unique properties, polymers are good
alternative materials to glass and metals for packing
applications [1]. Beverage packaging covers a wide range
of products such as carbonated beverages, isotonics, and
water [2]. Polyethylene terephthalate (PET) is a widely
used polymer in beverage packaging, for producing bottles
through injection stretch blow molding. PET is a semi-
crystalline polyester that exhibits an amorphous or semi-
crystalline microstructure based on processing history [3].
Over the years, several researchers have evaluated the
properties of PET from stretch-blow molded bottles.
Stretch crystallinity, formed due to the stretching of PET
chains, plays an important role in the performance of the
bottle [4]. Molecular orientation and the extent of
crystallinity have a great impact on the modulus of PET [5].
Along with others, Bandla et al. [6] showed that the percent
crystallinity of blow molded PET depend on the stretch
ratio.
PET bottles can have a complex shaped base and
multifaceted side geometries [7]. The quality of a stretch
blow molded bottle depends on several factors including
the quality and thermal history of the injection molded
preform. The current trend toward a more efficient
material usage in the plastic packaging industry is pushing
the limits on processing machinery. Producing a light
weight bottle with high quality is challenging and
necessitates innovation [8]. The thermal crystallization
behavior of PET influences the properties of PET during
bottle manufacturing. Crystallinity in PET can be
measured by different methods [9]. X-ray diffraction is a
commonly used technique for measuring crystallinity in
PET. It provides an advantage of obtaining additional
microstructural details such as crystal size and orientation
[10]. Raman Spectroscopy, which allows determining
crystallinity based on the polymer chain rotational
conformations, is another useful technique to study PET
crystallization [11]. It can be faster than XRD and more
easily examine a smaller spatial area.
With the objective of comparing different methods to
measure the thermal crystallinity in PET, in the present
work, X-ray Diffraction (XRD), Differential Scanning
Calorimetry (DSC), and Raman Spectroscopy were used.
Each of the abovementioned techniques measures
crystallinity based on different physics. Therefore,
correlating the measurements will help better understand
thermal crystallization in PET and aid with the
development of tools for quality and process optimization.
Materials
Commercially available PET of 0.8 dL/g intrinsic
viscosity (I.V.) was used in the current work. PET
preforms were injection molded on a 90 ton injection
molding machine manufactured by Husky Injection
molding systems. PET was dried for 4 hours at 170°C to
avoid degradation during processing due to the presence of
moisture. Preform samples used for the measurements
were collected after the injection process stabilized. The
preform was locally reheated above the glass transition
temperature using IR lamps, and air cooled to have thermal
crystallization. The crystallized preform was cut along its
length and samples for analysis were collected along the
gradient, as shown in Figure 1 (b) and (c).
Methods
DSC was performed using a Q-2000 TA instrument on
three different regions of the preform (along the amorphous
to crystalline gradient) to determine the thermal
crystallinity. DSC thermographs were obtained by heating
the samples from 25°C to 300°C at 10°C/min and held at
300°C for 5 minutes (first heating cycle), then cooled to
25°C at 10°C/min and held at 25°C for 5 minutes (first
cooling cycle), and finally reheated to 300°C at 10°C/min
(second heating cycle) under a nitrogen atmosphere.
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 XRD measurements were performed using a Bruker
D8 Discover micro-X-ray diffraction system equipped with
a 2D detector. CuKα radiation (λ = 1.54184 Å) was used.
Crystallinity and texture measurements were performed
using a 0.5 mm collimator. Samples were fixed on to a Si
single crystal (zero background substrate) for data
collection in the reflection orientation. The maximum
detector distance (300 mm) by this system was selected
since peaks were better distinguished, although their
intensity decreased. At 300 mm the detector
simultaneously covers the area of 20° in 2θ and 20° in ψ.
Multiple measurement points were selected on a straight
line from the crystalline to the amorphous regions, as
shown in Figure 1 (c). At each measurement point, three
frames were collected and merged to cover 12° to 58° of
the 2θ interval.
Figure 1. a) Schematic of the sample orientation with
respect to the Diffractometer geometry (the diffraction
vector is perpendicular to the cut surface, allowing
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
location on the gradient region obtained by optical
microscopy. A and B represent the crystalline and the
amorphous regions, respectively.
Raman Spectroscopy was carried out using a
Renishaw inVia confocal Raman microscope equipped
with 785 nm excitation laser. Measurements were
performed every 500 µm from crystalline to
amorphous regions of the PET preform. The intensity of
the 1096 cm-1 Raman peak was used for correlating with
respect to crystallinity [11].
Results
DSC Studies
The melt and the crystallization behavior of the PET
preform were investigated through DSC measurements on
three different regions. The glass transition (Tg) and
melting temperatures (Tm) were collected from the first
heating cycle (Figure 2a), and the crystallization
temperature (Tc) from the first cooling cycle (Figure 2b).
Figure 2. Thermal properties of PET preform collected
from crystalline, semi-crystalline, and amorphous
regions representing a) Tg and Tm, and b) Tc.
Heat of melting and heat of crystallization from the
first heating cycle were selected to determine the
crystallinity using the equation:
⎡ ΔH − ΔH cc ⎤
Xc = ⎢ m ⎥ ×100
⎣ ΔH c ⎦ (1)
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%
crystalline PET. As seen in Table 1, the crystallinity of the
preform is increasing from 9.60% to 25.92% by air cooling
the sample (Table 1).
XRD Measurements
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
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induced from injection molding. The triclinic crystal
structure was observed with four principle reflections from
the (010), (110), (100), and (105) planes (17.5°, 22.5°,
25.6°, and 42.6° 2θ for CuKα X-rays [10]. The percent
crystallinity was measured based on the ratio of the
crystalline fraction (Ac) to the total area (Aa + Ac) under the
diffracted curve, Equation 2 [6]. Percent crystallinity was
determined by rotating the sample to have orientation
independent measurements.
⎡ Ac ⎤
Xc = ⎢ ⎥ ×100
A
⎣ a + Ac⎦
(2)
The percent crystallinity data from DSC and XRD
measurements along the length were compared with the
intensity of the 1095 cm-1 Raman peak, as illustrated in
Figure 5. As seen in the crystalline region, Point A
(measurement location at 10) showed an average value of
25% crystallinity, from XRD, and 26%, from DSC, and
peak intensity variation of 180 for the 1095cm-1 peak from
Raman spectroscopy. Moving from measurement location
10 to 32, the percent crystallinity dropped to an average of
10 % obtained by XRD and DSC. Interestingly, the peak
intensity at 1095 cm-1 went to 89, showing a significant
decrease as compared to point A.

Figure 3. a) Typical 2D X-ray diffraction pattern from

the crystalline region, A, and amorphous region, B, b)
comparison of 1D diffraction pattern for amorphous
and crystalline samples.

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).

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 Table 1. Thermal properties of the PET preform in three different regions.

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

We acknowledge Dr. Andrew King at Renishaw Inc.

Figure 5. The percent crystallinity obtained by DSC,
XRD, and Raman Spectroscopy methods.
Discussion
The percent crystallinity measurements from X-ray
diffraction and Differential Scanning Calorimetry show
good correlation. Raman spectroscopy is also a useful
technique for measuring crystallinity in PET. However, the
technique is not self-sufficient and requires correlation
with other crystallinity measurement methods. Correlating
the percent crystallinity from XRD and DSC techniques for
different locations, with the respective Raman peak
intensity variations will help in developing a calibration to
the technique. While the prior work based on Raman
spectroscopy are mainly concentrated on stretch
crystallization, this work helps in improving the technique
application. The maximum thermal crystallinity measured
here is much lower compared to stretch crystallinity
measurements from the work by Bandla et al. [6].
Measuring crystallinity using DSC and XRD have
certain limitations in terms of sample preparation, analysis
time, accuracy and complexity with data analysis. While
XRD is a non-destructive technique, DSC is a destructive
technique. Further, X-ray analysis is relatively expensive
compared to the other two techniques discussed here.
Raman spectroscopy provides the advantage of having high
speed measurements. With the differences in thermal and
stretch crystallization kinetics and crystal formation, it is
necessary to develop separate calibrations for both types.
for his support and help with Raman Spectroscopy data
collection. This work was partially possible through
foundation grants to the Helmerich Research Center and
industry sponsorship.
References
1. J. Rowson, A. Yoxall, and J. H. Hart, “Modelling
Capping of 28 mm Beverage Closures Using Finite
Element Analysis,” Packaging Technology and
Science, vol. 21, pp. 287-296, 2008.
2. K. Pearson, "Market Statistics and Future Trends in
Global Packaging," World Packaging Organization,
2008.
3. J. P. Jog, “Crystallization of
polyethyleneterephthalate,” Journal of
Macromolecular Science, Part C: Polymer Reviews,
vol. 35, pp. 531-553, 1995.
4. S. A. Jabarin, “Strain-induced crystallization of poly
(ethylene terephthalate),” Polymer Engineering &
Science, vol. 32, pp. 1341-1349, 1992.
5. A. Viswanathan, D. R. Wiff, and W. W. Adams, “An
Investigation of Structure-Property Correlations in
Polyethylene Terephthalate Films,” No. AFML-TR-
75-207. AIR FORCE MATERIALS LAB WRIGHT-
PATTERSON AFB OH, 1976.
6. S. Bandla, M. Allahkarami, and J. C. Hanan, “Out-of-
plane orientation and crystallinity of biaxially
stretched polyethylene terephthalate,” Powder
Diffraction vol. 29, pp. 123-126, 2014.
7. J.C. Hanan, "Plastic container having sidewall ribs
with varying depth." United States patent, US
2013/0140264 A1.

SPE ANTEC™ Indianapolis 2016 / 1143

8. M. Allahkarami, R. U. Ahmed, S. Bandla, and J. C.
Hanan, “Thickness measurement methods aiding
lightweighting of PET bottles,” ANTEC 2014.
9. Z. Bashir, I. Al-Aloush, I. Al-Raqibah, and M.
Ibrahim, “Evaluation of three methods for the
measurement of crystallinity of PET resins, preforms,
and bottles,” Polymer Engineering & Science vol. 40,
pp. 2442-2455, 2000.
10. R. de P. Daubeny and C. W. Bunn, “The crystal
structure of polyethylene terephthalate,”
In Proceedings of the Royal Society of London A:
Mathematical, Physical and Engineering Sciences,
vol. 226, pp. 531-542. The Royal Society, 1954.
11. A. J. Melveger, “Laser-raman study of crystallinity
changes in poly (ethylene terephthalate),” Journal of
Polymer Science Part A-2: Polymer Physics vol. 10,
pp. 317-322, 1972.
12. C. Y. Liang and S. Krimm, “Infrared spectra of high
polymers: Part IX. Polyethylene terephthalate,”
Journal of Molecular Spectroscopy, vol. 3, pp. 554-
574, 1959.
13. T. R. Manley and D. A. Williams, “Structure of
terephthalate polymers I—Infra-red spectra and
molecular structure of poly (ethylene terephthalate),”
Polymer, vol. 10, pp. 339-384, 1969.

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