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

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structure created by the minor component in PET–


MXD6 and PET–EVOH blends during real process- Characterization
ing conditions. In this study, capillary rheometer was
chosen intentionally since rheological data obtained RHEOLOGICAL ANALYSIS
by capillary rheometer simulate the real processing
conditions. 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
Experimental dried before measurements as mentioned above.
The capillary rheometer used has two pres-
MATERIALS sure transducers locating on the left hand barrel
(10,000 psi) and on the right hand barrel (1500 psi).
Matrix polymer and compatibilizer were pro- The capillary die used was 0.5 mm in diameter and
vided by Artenius UK (Cleveland, England) in 8 mm in length with a L/D ratio of 16 and an entrance
the form of extruded pellets. Matrix polymer angle of 180◦ , which was fitted into the left-hand bar-
was Melinar B60® (CSD Grade PET, IV:0.82 rel. In addition, the orifice die (pin hole with negligi-
dL/g; Artenius UK). Disperse phases were ble L/D ratio) has dimensions of 0.5 mm (diameter
poly(m-xylene adipamide) (Nylon-MXD6 Grade of the die) × 0.25 mm (shear length) × 180◦ (entry
6007; Mitsubishi Gas Chemical Europe GmbH, angle), which was fitted into the right-hand barrel.
Dusseldorf, Germany), with a molecular weight of For reliability of the results, tests were performed
25.000 g/mole, and EVAL™ SP-434 (EVOH with according to the practical working range from 5%
32 mole % ethylene content; EVAL Europe N.V., to 95% of the pressure transducers. With the help
Antwerp, Belgium). A PET copolymer consisting of 5 of twin-bore system on the rheometer, simultaneous
wt % sodium sulfonated isophthalate (PET-co-5SIPA; measurement of full pressure drop along the capil-
Artenius UK) was used as the compatibilizer for lary die and entrance pressure drop on the orifice die
PET–MXD6 blends. The SIPA content used for the is possible, which enables direct calculation of cor-
PET–MXD6 blends was 0.45 wt %. Polymers were rected shear stress (Bagley’s correction). In the mean-
dried before use. The drying conditions for both rhe- time, correction of the shear rate (Rabinowitch’s
ological measurements and extrusion process were correction) can be made automatically, which takes
as follows: PET at 175◦ C for 6 h, and MXD6 and into consideration the non-Newtonian behavior of
EVOH at 85◦ C for 14 h in an air-circulating oven. polymers.59,60
PET-co-5SIPA was dried at 175◦ C for 14 h in vacuo.
FT-IR ANALYSIS
The molecular interactions between PET-co-5SIPA
BLEND PREPARATION and MXD6 in the compatibilized blends were char-
Preparation of the PET–MXD6 and PET–EVOH acterized by Fourier transform infrared (FT-IR)
blends with and without the compatibilizer was per- spectroscopy. Spectra were measured on a Bruker
formed with a co-rotating intermeshing twin-screw Equinox 55 FT-IR spectrometer. Each spectrum was
extruder (Leistritz Micro 27 LG 44D, Ø = 27 mm) the result of an accumulation of 32 scans at a resolu-
with a length-to-diameter (L/D) ratio of 44. The tion of 4 cm−1 . All spectrograms were normalized to
screw profile is made up of conveying and knead- the characteristic polyester band, which is observed
ing elements, which also uses opposite pitch to en- at 1710 cm−1 .
sure melting, mixing, shearing, and a good disper-
sion of the components. A processing temperature of
MORPHOLOGICAL ANALYSIS
270◦ C was chosen according to the rheological mea-
surements. The extrusion process was carried out A Leo G34-Supra 35VP scanning electron micro-
with a screw rotation speed of 100 rpm (throughput: scope was used for studying the microstructure of
4.5 kg/h) and 200 rpm (throughput: 9 kg/h). The the blends. To this end, the samples were cryogeni-
extrudates were cooled in water and pelletized. cally fractured and coated with the help of a carbon

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evaporator prior to scanning electron microscopic PET and MXD6 because of their polar and
(SEM) analysis. highly hygroscopic characteristics, resulting in
molecular weight reduction, which is directly
THERMAL ANALYSIS related to shear viscosity. Hence, shear viscos-
ity values of the processed neat PET and MXD6
Differential scanning calorimetric (DSC) analyses were determined and these values were also
were performed to study the thermal properties of considered for establishing the co-continuity
the virgin materials and the blends. A Netsch DSC point of the PET–MXD6 blends.
204 thermal analyzer equipped with Proteus Ana-
2. As mentioned above, the Jordhamo equation
lyzer software was utilized. Temperature calibration
works well for the uncompatibilized blends.
was performed with indium and zinc. Calibration of
In this study, we also checked whether com-
the heat of fusion was performed with the heat of
patibilizer incorporation has any influence on
fusion of indium and zinc. Heating scans were per-
the phase co-continuity. To this end, the PET–
formed under dry nitrogen conditions at a heating
MXD6 blends were compatibilized with a com-
rate of 5◦ K/min, covering the range from 20◦ C to
patibilizer (i.e., PET-co-5SIPA).
300◦ C.

RHEOLOGICAL ANALYSIS
The Rheological Model To determine the co-continuity point for the two
systems studied in this work (i.e., PET–MXD6 and
Viscosity data were collected versus shear rate PET–EVOH blends), rheological behavior of the neat
with the help of a capillary rheometer and these materials was studied. Figures 1–3 show the plots of
data were used for co-continuity predictions at shear shear viscosity versus shear rate for the neat ma-
rates present during extrusion. Such estimates of the terials of PET, MXD6, and EVOH at different tem-
compositional location of the co-continuous region peratures, respectively. To be able to simulate the
in extruded blends are commonly made from vis- real processing conditions, a common parameter in
cosity data using a variety of relationships. The most extruders and rheometers should be found. Shear
common empirical relationship used to describe co- rate applied during processing in extruders and gen-
continuity is the Jordhamo equation22 : erated during working on capillary rheometers is
the common parameter that is employed for the de-
ηA ∼ ϕA termination of the phase co-continuity. Mohamed
=
ηB ϕB et al.61 and Wu62 have shown that the average shear
rate generated in twin-screw extruders varies be-
In this equation, η represents the viscosity (Pa·s) and tween 53 and 100 s−1 depending upon screw de-
ϕ the volume fraction of the components of the bi- sign and screw speed. Assuming that the shear rate
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- FIGURE 1. Plots of shear viscosity versus shear rate for
dation may take place during processing of virgin PET at different temperatures.

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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- was 270◦ C for all blends. According to the rheologi-
lations were made with the rheological data obtained cal data of the neat PET and the neat MXD6, viscosity
with this shear rate value. The shear viscosity values ratio of PET to MXD6 is 12.08. The amount of PET
at 100 s−1 are tabulated for PET and MXD6 in Table I calculated was 92.35 vol % and that of MXD6 7.65
and for PET and EVOH in Table II. Volume frac- vol % for PET–MXD6 blends when using the Jord-
tions necessary for the observation of co-continuity hamo relationship. Volume fractions for the PET–
point are also shown in the related tables by employ- EVOH blends are as follows: PET 73.63 vol % and
ing the Jordhamo equation. Processing temperature 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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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- tively. Volume fractions for the PET–MXD6 blends
cosity reduction during processing, the neat mate- were 75.8:24.2 (v/v) for 100 rpm screw speed and
rials were processed at previously determined tem- 84.5:15.5 (v/v) for 200 rpm screw speed (Table III).
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 SPECTROSCOPIC ANALYSIS
of PET and MXD6 are shown in Figs. 4 and 5, respec- 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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an interaction involving the carbonyl group of the 100 rpm] and to 0.1 to 0.2 μm [Fig. 7d; screw speed:
polyamide. 200 rpm]. The PET–MXD6 blend [75.8:24.2 (v/v),
Through FT-IR spectroscopic analysis, an interac- screw speed: 100 rpm] without containing the com-
tion between the amide linkage of MXD6 and the patibilizer shows a combination of rod-like, droplet–
sulfonate group of the PET-co-5SIPA and its coun- matrix structure, and quasi-interpenetrating net-
terion has been observed. The employment of PET- work structure that disappears, however, after the
co-5SIPA as the compatibilizer for immiscible PET– addition of the compatibilizer (Figs. 8a and 8b).
MXD6 blend creates sites for specific interactions The same blend containing the compatibilizer shows
between the blend components and reduces domain distinctive spherical MXD6 domains (0.5–1.2 μm),
sizes. 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),
MORPHOLOGY screw speed: 200 rpm] without the compatibilizer
has particle sizes of 0.4 to 0.7 μm (Fig. 8c) and the
PET–MXD6 Blends addition of the compatibilizer decreases the particle
The morphology of the PET blends with 7.65 vol % sizes of MXD6 phase to 0.2 to 0.6 μm (Fig. 8d).
MXD6 is shown in Fig. 7. Spherical polyamide par-
ticles were dispersed in a continuous PET matrix
PET–EVOH Blends
phase. The uncompatibilized blends revealed a mor-
phology with MXD6 particle size of 0.4 to 0.6 μm PET–EVOH blends show the same structure, that
[Fig. 7a (screw speed: 100 rpm) and 7c (screw speed: is, spherical EVOH inclusions in the PET matrix
200 rpm)]. Incorporation of PET-co-5SIPA reduces phase. The PET–EVOH blend processed at a screw
the particle size to 0.1 to 0.3 μm [Fig. 7b; screw speed: 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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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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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 100 rpm) and 104◦ C (screw speed: 200 rpm). The
thermograms of the extruded neat materials and material extruded with a screw speed of 200 rpm
extruded PET–MXD6 [92.35:7.65 (v/v)] blends goes through the water bath two times faster than
with/without a compatibilizer (heating rate: 5◦ K/min, first the material processed with 100-rpm screw speed,
heating scan). Abbreviations: PM 100, extruded which causes a faster quenching resulting in little
PET–MXD6 without a compatibilizer (screw speed: difference in Tcc values.
100 rpm, throughput: 4.5 kg/h); PMC 100, extruded Cold crystallization temperatures of the blends
PET–MXD6 with 0.45 wt % SIPA content (screw speed:
with/without the compatibilizer processed with two
100 rpm, throughput: 4.5 kg/h); PM 200, extruded
PET–MXD6 without a compatibilizer (screw speed:
different screw speeds (i.e., 100 and 200 rpm) remain
200 rpm, throughput: 9 kg/h); and PMC 200, extruded almost constant varying between 120◦ C and 122◦ C
PET–MXD6 with 0.45 wt % SIPA content (screw speed: both for the uncompatibilized blend and for the com-
200 rpm, throughput: 9 kg/h). The volume fractions of patibilized blend (Fig. 10, Table IV, PM 100, PMC 100,
PET and MXD6 were calculated according to the shear PM 200, PMC 200). As is often the case when a sec-
viscosity values of the virgin materials. ond phase is added to PET,50,63−66 MXD6 domains

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nucleate the cold crystallization of PET and shift Tcc [75.8:24.2 (v/v), screw speed: 100 rpm] has only one
of PET to a lower temperature. Nonetheless, Tcc val- Tcc peak at 119◦ C (Fig. 11, PMC 100E). The nucleation
ues remain constant in the blends containing 7.65 effect of the MXD6 phase has been observed in the
vol % MXD6. uncompatibilized blend by decreasing the Tcc of the
Considering the shear viscosity values of the ex- neat PET. Nonetheless, the addition of PET-co-5SIPA
truded neat materials, different volume fractions as the compatibilizer eliminates the nucleation ef-
were determined for the co-continuity point. MXD6 fect of MXD6. Besides, the incorporation of PET-co-
content was 24.2 vol % for a screw speed of 100 rpm 5SIPA into the blend leads to diminished melting
and 15.5 vol % for a screw speed of 200 rpm. Because endotherm of the MXD6 phase.
of this difference in volume fractions, thermal be- The thermal behaviors of the PET–MXD6
havior of these blends should also be studied. DSC [84.5:15.5 (v/v)] blends prepared with a rotation
thermograms of the neat materials processed with speed of 200 rpm are as follows: Tcc value reduces
two different screw speeds are shown in Fig. 11 once from 122◦ C to 117◦ C both for the uncompatibilized
again for comparison purposes. The PET–MXD6 blend (Fig. 11, Table IV, PM 200E) and for the com-
blend [75.8:24.2 (v/v), screw speed: 100 rpm] con- patibilized blend (Fig. 11, PMC 200E), which point
taining no compatibilizer shows a Tcc peak at 113◦ C out the nucleation effect of MXD6. Apparently, the
and a shoulder peak at 122◦ C (Fig. 11, Table IV, incorporation of PET-co-5SIPA has no influence on
PM 100E). The compatibilized PET–MXD6 blend 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 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 FIGURE 12. Differential scanning calorimetric
speed: 200 rpm, throughput: 9 kg/h); MXD6 200, thermograms of the extruded neat materials and
extruded MXD6 (screw speed: 200 rpm, throughput: extruded PET–EVOH [73.63:26.37 (v/v)] blends
9 kg/h); PM 200E, extruded PET–MXD6 84.5:15.5 (v/v) with/without a compatibilizer (heating rate: 5◦ K/min, first
without a compatibilizer (screw speed: 200 rpm, heating scan). Abbreviations: PE 100, extruded
throughput: 9 kg/h); and PMC 200E, extruded PET–EVOH (screw speed: 100 rpm, throughput:
PET–MXD6 84.5:15.5 (v/v) with 0.45 wt % SIPA content 4.5 kg/h); PE 200, extruded PET–EVOH (screw speed:
(screw speed: 200 rpm, throughput: 9 kg/h). The volume 200 rpm, throughput: 9 kg/h). The volume fractions of
fractions of PET and MXD6 were calculated according to PET and EVOH were calculated according to the shear
the shear viscosity values of the materials after extrusion. viscosity values of the virgin materials.

182 Advances in Polymer Technology DOI 10.1002/adv


MORPHOLOGY OF POLY(ETHYLENE TEREPHTHALATE) BLENDS

Conclusion Acknowledgment

The ultimate aim of this study was to have The authors thank Artenius Adana for material
a co-continuous morphology in which the dis- supply.
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 References
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184 Advances in Polymer Technology DOI 10.1002/adv