Morphology of Poly(ethylene

terephthalate) Blends:
An Analysis under Real
Processing Conditions by
Rheology and Microscopy
İLHAN ÖZEN
Erciyes University, Faculty of Engineering, Textile Engineering Department, Melikgazi, Kayseri, Turkey

YUSUF ZİYA MENCELOǦLU

Sabanci University, Faculty of Engineering and Natural Sciences, Materials Science and Engineering,
Tuzla, Istanbul, Turkey
Received: February 19, 2009
Accepted: August 19, 2009

ABSTRACT: The present work describes the formation of co-continuous

phase morphologies in uncompatibilized and compatibilized poly(ethylene
terephthalate) (PET)–poly(m-xylene adipamide) (MXD6) and PET–
poly(ethylene-co-vinyl alcohol) (EVOH) melt-extruded blends. Phase continuity
has been determined by using the Jordhamo relationship. Viscosity values, which
are essential for the calculation of the phase continuity, have been obtained by
capillary rheometry. Thermal behavior of the blends has been analyzed by
employing differential scanning calorimetry and phase continuity has been
investigated for the noncompatibilized and the compatibilized blends by
scanning electron microscopy. PET–MXD6 blends [92.35:7.65 (v/v) and 84.5:15.5

Correspondence to: İlhan Özen; e-mail: iozen@erciyes.edu.tr.

Contract grant sponsor: TÜBİTAK (The Scientific and
Technical Research Council of Turkey).
Contract grant number: 106 M505.

Advances in Polymer Technology, Vol. 28, No. 3, 173–184 (2009)


C 2009 Wiley Periodicals, Inc.
MORPHOLOGY OF POLY(ETHYLENE TEREPHTHALATE) BLENDS

(v/v)] and PET–EVOH blends [73.63:26.37 (v/v)] exhibit droplet-in-matrix phase

morphology, whereas uncompatibilized PET–MXD6 [75.8:24.2 (v/v)] blend has a
combination of rod-like, droplet–matrix structure, and quasi-interpenetrating
network structure.  C 2009 Wiley Periodicals, Inc. Adv Polym Techn 28: 173–184,

2009; Published online in Wiley InterScience (www.interscience.wiley.com). DOI

10.1002/adv.20156

KEY WORDS: Blending, Capillary rheometer, Co-continuous morphology,

Polyesters, Rheology

low concentrations. As a consequence of these stud-

Introduction ies, much interest has been generated in polymer
blends with a co-continuous morphology5−10,22−30
because of a number of promising applications31−36

T he versatile nature of polymer blends has made

them an object of research for many years.
One of the application fields of polymer blends is
food packaging where poly(ethylene terephthalate)
(PET) blends with improved barrier properties have
been of great importance. Poly(m-xylene adipamide)
(MXD6) or poly(ethylene-co-vinyl alcohol) (EVOH)
has been used as the supporting polymer in high
gas barrier applications. In polymer blending sys-
tems, morphology control, which is closely related
to the rheological properties of the blend compo-
nents, is of prime importance since the final proper-
ties including barrier properties of polymer blends
will depend, to a large extent, on the morphology
of the dispersed phase, such as its size and shape.1
However, controlling the microstructure in blends
of immiscible polymers is very difficult because of
(i) the complex flow and temperature fields devel-
oped during melt processing, (ii) process of droplet
elongation, breakdown, and coalescence, and (iii)
the viscoelastic nature of the phases.2 When melt
blending immiscible polymers, two major categories
of morphologies are possible: a droplet and a co-
continuous morphology. The droplet morphology,
which is the most common morphology, is defined
as the dispersion of the minor component into the
other component in the form of spherical droplets.3
On the other hand, co-continuity is a special case of
blend morphology in which each polymer is fully
interconnected through a continuous pathway.4 Co-
continuous phase morphologies are mainly formed
in the vicinity of the point of phase inversion, that
is, in the vicinity of a 50:50 volume-based viscos-
ity ratio of the two blend components.5−18 However,
Omonov et al.19−21 have most recently succeeded in
having a co-continuous morphology, especially at
including barrier properties.37
In most studies,5−10,22−30 blends prepared with
different blend ratios have been deformed with a
rotational rheometer without damaging the micro-
structure and the resulting morphological changes
have been correlated with the rheological properties
of the blend components and the flow conditions.
Relationship between rheological properties and mi-
crostructure of the blends was first established by
Paul and Barlow [7] and Jordhamo et al. [22] and was
later generalized by Miles and Zurek [29], which is
known as the Jordhamo equation. This relationship,
which is useful for many blend systems, has been
employed in the related studies.22−30 However, the
most important issue in terms of industrial applica-
tions is controlling and manipulating the morphol-
ogy during real processing conditions. Considering
this issue, morphology development in classical pro-
cessing equipment such as internal mixers or ex-
truders has received particular attention in the last
decades.38−41 Attempts have mainly concentrated on
the effects of the following factors on the morphol-
ogy development and properties of the blend: the
type and content of compatibilizer,42,43 processing
conditions,44−46 melt shear viscosity ratio of the dis-
persed phase to the continuous phase,47,48 etc.
In studies related to PET–MXD649−53 and PET–
EVOH54−58 blends, the amount of the dispersed
phase has been tried to keep as low as possible
(5–25 wt %) because of economical reasons and re-
lated processing difficulty. Hence, the related studies
have focused on the compatibilization of the blends
and thus size reduction of the dispersed phase par-
ticles with a spherical shape instead of obtaining
a co-continuous morphology. The purpose of this
study was to reveal the possible co-continuous phase

174 Advances in Polymer Technology DOI 10.1002/adv

 MORPHOLOGY OF POLY(ETHYLENE TEREPHTHALATE) BLENDS
structure created by the minor component in PET–
MXD6 and PET–EVOH blends during real process-
ing conditions. In this study, capillary rheometer was
chosen intentionally since rheological data obtained
by capillary rheometer simulate the real processing
conditions.
Experimental
MATERIALS
Matrix polymer and compatibilizer were pro-
vided by Artenius UK (Cleveland, England) in
the form of extruded pellets. Matrix polymer
was Melinar B60® (CSD Grade PET, IV:0.82
dL/g; Artenius UK). Disperse phases were
poly(m-xylene adipamide) (Nylon-MXD6 Grade
6007; Mitsubishi Gas Chemical Europe GmbH,
Dusseldorf, Germany), with a molecular weight of
25.000 g/mole, and EVAL™ SP-434 (EVOH with
32 mole % ethylene content; EVAL Europe N.V.,
Antwerp, Belgium). A PET copolymer consisting of 5
wt % sodium sulfonated isophthalate (PET-co-5SIPA;
Artenius UK) was used as the compatibilizer for
PET–MXD6 blends. The SIPA content used for the
PET–MXD6 blends was 0.45 wt %. Polymers were
dried before use. The drying conditions for both rhe-
ological measurements and extrusion process were
as follows: PET at 175◦ C for 6 h, and MXD6 and
EVOH at 85◦ C for 14 h in an air-circulating oven.
PET-co-5SIPA was dried at 175◦ C for 14 h in vacuo.
BLEND PREPARATION
Preparation of the PET–MXD6 and PET–EVOH
blends with and without the compatibilizer was per-
formed with a co-rotating intermeshing twin-screw
extruder (Leistritz Micro 27 LG 44D, Ø = 27 mm)
with a length-to-diameter (L/D) ratio of 44. The
screw profile is made up of conveying and knead-
ing elements, which also uses opposite pitch to en-
sure melting, mixing, shearing, and a good disper-
sion of the components. A processing temperature of
270◦ C was chosen according to the rheological mea-
surements. The extrusion process was carried out
with a screw rotation speed of 100 rpm (throughput:
4.5 kg/h) and 200 rpm (throughput: 9 kg/h). The
extrudates were cooled in water and pelletized.
Advances in Polymer Technology DOI 10.1002/adv
Characterization
RHEOLOGICAL ANALYSIS
Melt shear viscosity measurements of the neat
materials were carried out at constant shear rate test
with a Rosand RH-10 twin-bore, high-pressure cap-
illary rheometer. Testing temperatures were 260◦ C,
265◦ C, 270◦ C, 275◦ C, and 280◦ C. The range of shear
rate was between 100 and 5000 s−1 . Polymers were
dried before measurements as mentioned above.
The capillary rheometer used has two pres-
sure transducers locating on the left hand barrel
(10,000 psi) and on the right hand barrel (1500 psi).
The capillary die used was 0.5 mm in diameter and
8 mm in length with a L/D ratio of 16 and an entrance
angle of 180◦ , which was fitted into the left-hand bar-
rel. In addition, the orifice die (pin hole with negligi-
ble L/D ratio) has dimensions of 0.5 mm (diameter
of the die) × 0.25 mm (shear length) × 180◦ (entry
angle), which was fitted into the right-hand barrel.
For reliability of the results, tests were performed
according to the practical working range from 5%
to 95% of the pressure transducers. With the help
of twin-bore system on the rheometer, simultaneous
measurement of full pressure drop along the capil-
lary die and entrance pressure drop on the orifice die
is possible, which enables direct calculation of cor-
rected shear stress (Bagley’s correction). In the mean-
time, correction of the shear rate (Rabinowitch’s
correction) can be made automatically, which takes
into consideration the non-Newtonian behavior of
polymers.59,60
FT-IR ANALYSIS
The molecular interactions between PET-co-5SIPA
and MXD6 in the compatibilized blends were char-
acterized by Fourier transform infrared (FT-IR)
spectroscopy. Spectra were measured on a Bruker
Equinox 55 FT-IR spectrometer. Each spectrum was
the result of an accumulation of 32 scans at a resolu-
tion of 4 cm−1 . All spectrograms were normalized to
the characteristic polyester band, which is observed
at 1710 cm−1 .
MORPHOLOGICAL ANALYSIS
A Leo G34-Supra 35VP scanning electron micro-
scope was used for studying the microstructure of
the blends. To this end, the samples were cryogeni-
cally fractured and coated with the help of a carbon
175
MORPHOLOGY OF POLY(ETHYLENE TEREPHTHALATE) BLENDS
evaporator prior to scanning electron microscopic
(SEM) analysis.
THERMAL ANALYSIS
Differential scanning calorimetric (DSC) analyses
were performed to study the thermal properties of
the virgin materials and the blends. A Netsch DSC
204 thermal analyzer equipped with Proteus Ana-
lyzer software was utilized. Temperature calibration
was performed with indium and zinc. Calibration of
the heat of fusion was performed with the heat of
fusion of indium and zinc. Heating scans were per-
formed under dry nitrogen conditions at a heating
rate of 5◦ K/min, covering the range from 20◦ C to
300◦ C.
The Rheological Model
Viscosity data were collected versus shear rate
with the help of a capillary rheometer and these
data were used for co-continuity predictions at shear
rates present during extrusion. Such estimates of the
compositional location of the co-continuous region
in extruded blends are commonly made from vis-
cosity data using a variety of relationships. The most
common empirical relationship used to describe co-
continuity is the Jordhamo equation22 :
ηA ∼ ϕA
=
ηB ϕB
In this equation, η represents the viscosity (Pa·s) and
ϕ the volume fraction of the components of the bi-
nary blend. On the basis of the viscosity data, it
is possible to calculate the point of phase inver-
sion, that is, co-continuity for the noncompatibilized
blends, and to compare it with the experimental
results.
Results and Discussion
The lowest amount of the dispersed phase possi-
ble was chosen since low amount of the dispersed
phase provides cost-effective operations. Besides,
two approaches were examined:
1. Depending upon processing conditions, degra-
dation may take place during processing of
176
PET and MXD6 because of their polar and
highly hygroscopic characteristics, resulting in
molecular weight reduction, which is directly
related to shear viscosity. Hence, shear viscos-
ity values of the processed neat PET and MXD6
were determined and these values were also
considered for establishing the co-continuity
point of the PET–MXD6 blends.
2. As mentioned above, the Jordhamo equation
works well for the uncompatibilized blends.
In this study, we also checked whether com-
patibilizer incorporation has any influence on
the phase co-continuity. To this end, the PET–
MXD6 blends were compatibilized with a com-
patibilizer (i.e., PET-co-5SIPA).
RHEOLOGICAL ANALYSIS
To determine the co-continuity point for the two
systems studied in this work (i.e., PET–MXD6 and
PET–EVOH blends), rheological behavior of the neat
materials was studied. Figures 1–3 show the plots of
shear viscosity versus shear rate for the neat ma-
terials of PET, MXD6, and EVOH at different tem-
peratures, respectively. To be able to simulate the
real processing conditions, a common parameter in
extruders and rheometers should be found. Shear
rate applied during processing in extruders and gen-
erated during working on capillary rheometers is
the common parameter that is employed for the de-
termination of the phase co-continuity. Mohamed
et al.61 and Wu62 have shown that the average shear
rate generated in twin-screw extruders varies be-
tween 53 and 100 s−1 depending upon screw de-
sign and screw speed. Assuming that the shear rate
FIGURE 1. Plots of shear viscosity versus shear rate for
virgin PET at different temperatures.
Advances in Polymer Technology DOI 10.1002/adv
 MORPHOLOGY OF POLY(ETHYLENE TEREPHTHALATE) BLENDS

FIGURE 2. Plots of shear viscosity versus shear rate for FIGURE 3. Plots of shear viscosity versus shear rate for
virgin MXD6 at different temperatures. virgin EVOH at different temperatures.

generated in the extruder is 100 s−1 , the related calcu-
lations were made with the rheological data obtained
with this shear rate value. The shear viscosity values
at 100 s−1 are tabulated for PET and MXD6 in Table I
and for PET and EVOH in Table II. Volume frac-
tions necessary for the observation of co-continuity
point are also shown in the related tables by employ-
ing the Jordhamo equation. Processing temperature
was 270◦ C for all blends. According to the rheologi-
cal data of the neat PET and the neat MXD6, viscosity
ratio of PET to MXD6 is 12.08. The amount of PET
calculated was 92.35 vol % and that of MXD6 7.65
vol % for PET–MXD6 blends when using the Jord-
hamo relationship. Volume fractions for the PET–
EVOH blends are as follows: PET 73.63 vol % and
EVOH 26.37 vol %.

TABLE I
Shear Viscosity and Volume Fraction Values for PET–MXD6 Blends at Different Temperatures
Shear Viscosity Volume Fraction
at 100 s−1 (Pa·s) (vol %)
Temperature Viscosity Ratio,
(◦ C) PET MXD6 PET–MXD6 PET MXD6

260 1121 120 9.34 90.33 9.67

265 532 75 7.09 87.64 12.36
270 483 40 12.08 92.35 7.65
275 492 42 11.71 92.13 7.87
280 324 32 10.13 91.01 8.99

Bold characters show the processing temperature and the related volume fractions chosen for processing.

TABLE II
Shear Viscosity and Volume Fraction Values for PET–EVOH Blends at Different Temperatures
Shear Viscosity Volume Fraction
at 100 s−1 (Pa·s) (vol %)
Temperature Viscosity Ratio,
(◦ C) PET MXD6 PET–MXD6 PET MXD6

260 1121 300 2.8 73.7 26.3

265 532 252 2.11 67.86 32.14
270 483 173 2.79 73.63 26.37
275 492 197 2.50 71.41 28.59
280 324 158 2.05 67.22 32.78

Bold characters show the processing temperature and the related volume fractions chosen for processing.

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MORPHOLOGY OF POLY(ETHYLENE TEREPHTHALATE) BLENDS

TABLE III
Shear Viscosity and Volume Fraction Values for PET–MXD6 Blends Calculated from Shear Viscosity Values of the
Materials Extruded at Different Screw Speeds
Shear Viscosity Volume Fraction
at 100 s−1 (Pa·s) (vol %)
Screw Viscosity Ratio,
Speed PET MXD6 PET–MXD6 PET MXD6

100 219,33 70 3.13 75.8 24.2

200 207,99 38 5.47 84.5 15.5

Considering the degradation and the related vis-
cosity reduction during processing, the neat mate-
rials were processed at previously determined tem-
perature of 270◦ C by applying two screw speeds (i.e.,
100 and 200 rpm, respectively). Rheological analyses
were carried out at 270◦ C. Related viscosity profiles
of PET and MXD6 are shown in Figs. 4 and 5, respec-
tively. Volume fractions for the PET–MXD6 blends
were 75.8:24.2 (v/v) for 100 rpm screw speed and
84.5:15.5 (v/v) for 200 rpm screw speed (Table III).
SPECTROSCOPIC ANALYSIS
The interactions between the sodium sulfonate
group of the copolymer and MXD6 were character-
ized by FT-IR spectroscopy. Only the PET–MXD6
blends containing 7.65 vol % MXD6 were measured.
Figure 6 shows the IR spectra of the neat materi-
als and the blends with/without the compatibilizer.
The characteristic carbonyl (C O) stretching band
was observed at 1710 cm−1 when only PET and
PET-co-5SIPA were considered. Also, the neat MXD6
has two carbonyl stretching vibrations (amide I and
amide II) at 1630 and 1530 cm−1 , respectively. After
the incorporation of the PET-co-5SIPA, another peak
at 1340 cm−1 was observed, which corresponds to
C N stretching band (i.e., amide III), indicating

FIGURE 4. Plots of shear viscosity versus shear rate for

virgin and extruded PET at 270◦ C.

FIGURE 6. Normalized FT-IR spectra of the neat

materials and the extruded blends. C, PET-co-5SIPA; PM
100, PET–MXD6 [92.35:7.65 (v/v)]; PMC 100,
FIGURE 5. Plots of shear viscosity versus shear rate for PET–MXD6–PET-co-5SIPA [92.35:7.65 (v/v), SIPA
virgin and extruded MXD6 at 270◦ C. content: 0.45 wt %].

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 MORPHOLOGY OF POLY(ETHYLENE TEREPHTHALATE) BLENDS

an interaction involving the carbonyl group of the
polyamide.
Through FT-IR spectroscopic analysis, an interac-
tion between the amide linkage of MXD6 and the
sulfonate group of the PET-co-5SIPA and its coun-
terion has been observed. The employment of PET-
co-5SIPA as the compatibilizer for immiscible PET–
MXD6 blend creates sites for specific interactions
between the blend components and reduces domain
sizes.
MORPHOLOGY
PET–MXD6 Blends
The morphology of the PET blends with 7.65 vol %
MXD6 is shown in Fig. 7. Spherical polyamide par-
ticles were dispersed in a continuous PET matrix
phase. The uncompatibilized blends revealed a mor-
phology with MXD6 particle size of 0.4 to 0.6 μm
[Fig. 7a (screw speed: 100 rpm) and 7c (screw speed:
200 rpm)]. Incorporation of PET-co-5SIPA reduces
the particle size to 0.1 to 0.3 μm [Fig. 7b; screw speed:
100 rpm] and to 0.1 to 0.2 μm [Fig. 7d; screw speed:
200 rpm]. The PET–MXD6 blend [75.8:24.2 (v/v),
screw speed: 100 rpm] without containing the com-
patibilizer shows a combination of rod-like, droplet–
matrix structure, and quasi-interpenetrating net-
work structure that disappears, however, after the
addition of the compatibilizer (Figs. 8a and 8b).
The same blend containing the compatibilizer shows
distinctive spherical MXD6 domains (0.5–1.2 μm),
which are rather coarse (Fig. 8b). Addition of PET-
co-5SIPA obviously disrupts the above-mentioned
structure. The PET–MXD6 blend [84.5:15.5 (v/v),
screw speed: 200 rpm] without the compatibilizer
has particle sizes of 0.4 to 0.7 μm (Fig. 8c) and the
addition of the compatibilizer decreases the particle
sizes of MXD6 phase to 0.2 to 0.6 μm (Fig. 8d).
PET–EVOH Blends
PET–EVOH blends show the same structure, that
is, spherical EVOH inclusions in the PET matrix
phase. The PET–EVOH blend processed at a screw
speed of 100 rpm has EVOH particle sizes of 0.5

FIGURE 7. Scanning electron micrographs of the extruded PET–MXD6 [92.35:7.65 (v/v)] blends with/without using the
compatibilizer. Abbreviations: (a) PET–MXD6 without a compatibilizer (screw speed: 100 rpm, throughput: 4.5 kg/h);
(b) PET–MXD6 with 0.45 wt % SIPA content (screw speed: 100 rpm, throughput: 4.5 kg/h); (c) PET–MXD6 without a
compatibilizer (screw speed: 200 rpm, throughput: 9 kg/h); and (d) PET–MXD6 with 0.45 wt % SIPA content (screw
speed: 200 rpm, throughput: 9 kg/h). The volume fractions of PET and MXD6 were calculated according to the shear
viscosity values of the virgin materials.

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MORPHOLOGY OF POLY(ETHYLENE TEREPHTHALATE) BLENDS

FIGURE 8. Scanning electron micrographs of the extruded PET–MXD6 blends with/without using a compatibilizer.
Abbreviations: (a) PET–MXD6 without a compatibilizer [75.8:24.2 (v/v), screw speed: 100 rpm, throughput: 4.5 kg/h];
(b) PET–MXD6 [75.8:24.2 (v/v)] with 0.45 wt % SIPA content (screw speed: 100 rpm, throughput: 4.5 kg/h); (c)
PET–MXD6 without a compatibilizer [84.5:15.5 (v/v), screw speed: 200 rpm, throughput: 9 kg/h]; and (d) PET–MXD6
[84.5:15.5 (v/v) with 0.45 wt % SIPA content (screw speed: 200 rpm, throughput: 9 kg/h). The volume fractions of PET
and MXD6 were calculated according to the shear viscosity values of the materials after extrusion.

to 1.6 μm (Fig. 9a). Also, the blend processed at a Thermal Behavior

screw speed of 200 rpm has the same particle sizes
Not only the chemistry and morphology but also
(i.e., 0.5–1.6 μm; Fig. 9b). Screw speed apparently
the crystallinity changes taking place during pro-
does not have any influence on the particle size
cessing by the incorporation of additives play an
distribution.

FIGURE 9. Scanning electron micrographs of the extruded PET–EVOH [73.63:26.27 (v/v)] blends without using a
compatibilizer. Abbreviations: (a) PET–EVOH (screw speed: 100 rpm, throughput: 4.5 kg/h); (b) PET–EVOH (screw
speed: 200 rpm, throughput: 9 kg//h). The volume fractions of PET and EVOH were calculated according to the shear
viscosity values of the virgin materials.

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 MORPHOLOGY OF POLY(ETHYLENE TEREPHTHALATE) BLENDS

enormous role in determining the oxygen barrier TABLE IV

properties. Barrier properties of PET and its blends Cold Crystallization Temperatures (Tcc ) of the Ex-
will decrease if its crystallinity reduces after process- truded Neat Materials, PET–MXD6, and PET–EVOH
ing since barrier properties are directly related to the Blends
degree of crystallinity. The importance of thermal be- Sample Figure No. Tcc (◦ C)
havior in PET blends for improved barrier properties
is understood by considering the cold crystallization PET 100 10 118
since a reduction in cold crystallization temperature PET 200 10 122
would be an indication of increased crystallinity. In MXD6 100 10 96 and 109
MXD6 200 10 93 and 104
this regard, only cold crystallization behavior was
EVOH 100 12 N/A
taken into account in this study. EVOH 200 12 N/A
PET-co-5SIPA 100 10 N/A
PET-co-5SIPA 200 10 N/A
PET–MXD6 Blends
PM 100 10 120
First heating scans of the extruded neat materi- PMC 100 10 121
als and those of the PET–MXD6 [92.35:7.65 (v/v)] PM 200 10 122
blends are shown in Fig. 10. The results are summa- PMC 200 10 120
rized in Table IV. Cold crystallization temperature PM 100E 11 113 and 122
PMC 100E 11 119
(Tcc ) varies between 118◦ C (screw speed: 100 rpm)
PM 200E 11 117
and 122◦ C (screw speed: 200 rpm) for the extruded
PMC 200E 11 117
neat PET. Also, the neat MXD6 shows Tcc peaks at PE 100 12 119
96◦ C (screw speed: 100 rpm) and 93◦ C (screw speed: PE 200 12 119
200 rpm) and shoulder peaks at 109◦ C (screw speed:
Abbreviations: PM 100, extruded PET–MXD6 [92.35:7.65 (v/v)]
without a compatibilizer (screw speed: 100 rpm); PMC 100, ex-
truded PET–MXD6 [92.35:7.65 (v/v)] with 0.45 wt % SIPA con-
tent (screw speed: 100 rpm); PM 200, extruded PET–MXD6
[92.35:7.65 (v/v)] without a compatibilizer (screw speed: 200 rpm);
PMC 200, extruded PET–MXD6 [92.35:7.65 (v/v)] with 0.45 wt %
SIPA content (screw speed: 200 rpm); PM 100E, extruded PET–
MXD6 [75.8:24.2 (v/v)] without a compatibilizer (screw speed:
100 rpm); PMC 100E, extruded PET–MXD6 [75.8:24.2 (v/v)]
with 0.45 wt % SIPA content (screw speed: 100 rpm); PM
200E, extruded PET–MXD6 [84.5:15.5 (v/v)] without a compat-
ibilizer (screw speed: 200 rpm); PMC 200E, extruded PET–MXD6
[84.5:15.5 (v/v)] with 0.45 wt % SIPA content (screw speed:
200 rpm); PE 100, extruded PET–EVOH [73.63:26.27 (v/v), screw
speed: 100 rpm]; PE 200, extruded PET–EVOH [73.63:26.27 (v/v),
screw speed: 200 rpm].

FIGURE 10. Differential scanning calorimetric
thermograms of the extruded neat materials and
extruded PET–MXD6 [92.35:7.65 (v/v)] blends
with/without a compatibilizer (heating rate: 5◦ K/min, first
heating scan). Abbreviations: PM 100, extruded
PET–MXD6 without a compatibilizer (screw speed:
100 rpm, throughput: 4.5 kg/h); PMC 100, extruded
PET–MXD6 with 0.45 wt % SIPA content (screw speed:
100 rpm, throughput: 4.5 kg/h); PM 200, extruded
PET–MXD6 without a compatibilizer (screw speed:
200 rpm, throughput: 9 kg/h); and PMC 200, extruded
PET–MXD6 with 0.45 wt % SIPA content (screw speed:
200 rpm, throughput: 9 kg/h). The volume fractions of
PET and MXD6 were calculated according to the shear
viscosity values of the virgin materials.
100 rpm) and 104◦ C (screw speed: 200 rpm). The
material extruded with a screw speed of 200 rpm
goes through the water bath two times faster than
the material processed with 100-rpm screw speed,
which causes a faster quenching resulting in little
difference in Tcc values.
Cold crystallization temperatures of the blends
with/without the compatibilizer processed with two
different screw speeds (i.e., 100 and 200 rpm) remain
almost constant varying between 120◦ C and 122◦ C
both for the uncompatibilized blend and for the com-
patibilized blend (Fig. 10, Table IV, PM 100, PMC 100,
PM 200, PMC 200). As is often the case when a sec-
ond phase is added to PET,50,63−66 MXD6 domains

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MORPHOLOGY OF POLY(ETHYLENE TEREPHTHALATE) BLENDS
nucleate the cold crystallization of PET and shift Tcc
of PET to a lower temperature. Nonetheless, Tcc val-
ues remain constant in the blends containing 7.65
vol % MXD6.
Considering the shear viscosity values of the ex-
truded neat materials, different volume fractions
were determined for the co-continuity point. MXD6
content was 24.2 vol % for a screw speed of 100 rpm
and 15.5 vol % for a screw speed of 200 rpm. Because
of this difference in volume fractions, thermal be-
havior of these blends should also be studied. DSC
thermograms of the neat materials processed with
two different screw speeds are shown in Fig. 11 once
again for comparison purposes. The PET–MXD6
blend [75.8:24.2 (v/v), screw speed: 100 rpm] con-
taining no compatibilizer shows a Tcc peak at 113◦ C
and a shoulder peak at 122◦ C (Fig. 11, Table IV,
PM 100E). The compatibilized PET–MXD6 blend
FIGURE 11. Differential scanning calorimetric
thermograms of the extruded neat materials and
extruded PET–MXD6 blends with/without a compatibilizer
(heating rate: 5◦ K/min, first heating scan). Abbreviations:
PET 100, extruded PET (screw speed: 100 rpm,
throughput: 4.5 kg/h); MXD6 100, extruded MXD6 (screw
speed: 100 rpm, throughput: 4.5 kg/h); PM 100E,
extruded PET–MXD6 75.8:24.2 (v/v) without a
compatibilizer (screw speed: 100 rpm, throughput:
4.5 kg/h); PMC 100E, extruded PET–MXD6 75.8:24.2
(v/v) with 0.45 wt % SIPA content (screw speed: 100 rpm,
throughput: 4.5 kg/h); PET 200, extruded PET (screw
speed: 200 rpm, throughput: 9 kg/h); MXD6 200,
extruded MXD6 (screw speed: 200 rpm, throughput:
9 kg/h); PM 200E, extruded PET–MXD6 84.5:15.5 (v/v)
without a compatibilizer (screw speed: 200 rpm,
throughput: 9 kg/h); and PMC 200E, extruded
PET–MXD6 84.5:15.5 (v/v) with 0.45 wt % SIPA content
(screw speed: 200 rpm, throughput: 9 kg/h). The volume
fractions of PET and MXD6 were calculated according to
the shear viscosity values of the materials after extrusion.
182
[75.8:24.2 (v/v), screw speed: 100 rpm] has only one
Tcc peak at 119◦ C (Fig. 11, PMC 100E). The nucleation
effect of the MXD6 phase has been observed in the
uncompatibilized blend by decreasing the Tcc of the
neat PET. Nonetheless, the addition of PET-co-5SIPA
as the compatibilizer eliminates the nucleation ef-
fect of MXD6. Besides, the incorporation of PET-co-
5SIPA into the blend leads to diminished melting
endotherm of the MXD6 phase.
The thermal behaviors of the PET–MXD6
[84.5:15.5 (v/v)] blends prepared with a rotation
speed of 200 rpm are as follows: Tcc value reduces
from 122◦ C to 117◦ C both for the uncompatibilized
blend (Fig. 11, Table IV, PM 200E) and for the com-
patibilized blend (Fig. 11, PMC 200E), which point
out the nucleation effect of MXD6. Apparently, the
incorporation of PET-co-5SIPA has no influence on
the nucleation effect of MXD6.
PET–EVOH Blends
The PET–EVOH blends processed at screw speeds
of 100 and 200 rpm show the same Tcc as that of the
neat PET (i.e., 119◦ C, Fig. 12, Table IV, PE 100, PE
200). According to thermal analyses, EVOH does not
nucleate the cold crystallization of PET, as in the case
of the PET–MXD6 [92.35:7.65 (v/v)] blends.
FIGURE 12. Differential scanning calorimetric
thermograms of the extruded neat materials and
extruded PET–EVOH [73.63:26.37 (v/v)] blends
with/without a compatibilizer (heating rate: 5◦ K/min, first
heating scan). Abbreviations: PE 100, extruded
PET–EVOH (screw speed: 100 rpm, throughput:
4.5 kg/h); PE 200, extruded PET–EVOH (screw speed:
200 rpm, throughput: 9 kg/h). The volume fractions of
PET and EVOH were calculated according to the shear
viscosity values of the virgin materials.
Advances in Polymer Technology DOI 10.1002/adv
 MORPHOLOGY OF POLY(ETHYLENE TEREPHTHALATE) BLENDS
Conclusion
The ultimate aim of this study was to have
a co-continuous morphology in which the dis-
persed phase forms a three-dimensional interpen-
etrating network. Pursuing this goal, rheological
data obtained with the capillary rheometer were
employed representing the real processing condi-
tions and thus being more meaningful. Conclusions
that can be drawn from this study are as follows:
Apparently, the Jordhamo equation fails when con-
sidered the uncompatibilized/compatibilized PET–
MXD6 [92.35:7.65 (v/v) and 84.5:14.5 (v/v)] blends,
compatibilized PET–MXD6 [75.8:24.2 (v/v)] blend,
and PET–EVOH [73.63:26.37 (v/v)] blends. Hav-
ing a quasi co-continuous morphology in the PET–
MXD6 [75.8:24.2 (v/v)] blend without containing the
compatibilizer and having a conventional droplet–
matrix phase structure in the PET–MXD6 [92.35:7.65
(v/v) and 84.5:14.5 (v/v)] blends clearly indicate the
importance of material characteristics, processing
conditions, additives, and moieties of the blend com-
ponents used for establishing the co-continuity. Even
studies related to co-continuous morphology using
data obtained with a rotational rheometer show the
lack of sensitivity of the Jordhamo equation since
it contains only shear viscosity of the blend com-
ponents. Nonetheless, the interfacial tension of the
blend components, melt processing conditions, and
viscoelastic nature of the phases are also of great
importance for polymer blends and they all have
to be involved when making calculations for de-
termining the co-continuity point.9,67−69 It should
also be noted that using the viscosity data of the
extruded neat blend components, that is, PET and
MXD6, for the calculation of the co-continuity point
for a screw speed of 100 rpm has been shown to
approximate to this concept. On the other hand, the
Jordhamo relationship did not fit for the PET–EVOH
blends.
The Jordhamo equation seems to work partly
well, especially in uncompatibilized PET–MXD6
blends. However, it contains obstacles such as non-
applicability to all kinds of polymer pairs and con-
sidering just the viscosity data for calculating the
co-continuity point. Besides, there is a region for the
co-continuity in polymer blends instead of a single
point. All these facts point out that the Jordhamo
relationship should not be considered as a prefer-
able and reliable tool for determination of the co-
continuity in polymer blends.
Advances in Polymer Technology DOI 10.1002/adv
Acknowledgment
The authors thank Artenius Adana for material
supply.
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