Oxygen Barrier Properties of Crystallized and Talc-Filled

Poly(ethylene terephthalate)

D. J. SEKELIK,1 E. V. STEPANOV,1 S. NAZARENKO,1 D. SCHIRALDI,2 A. HILTNER,1 E. BAER,1

1
Department of Macromolecular Science and Center for Applied Polymer Research, Case Western Reserve University,
10900 Euclid Avenue, Cleveland, Ohio 44106-7202

2
Hoechst Corporation, Spartanburg, South Carolina 29304

Received 14 July 1998; revised 13 November 1998; accepted 16 November 1998

ABSTRACT: The improvement in oxygen barrier properties of poly(ethylene terephtha-

late) (PET) by incorporation of an impermeable phase such as crystallinity or talc
platelets was examined. Crystallinity was induced by crystallization from the glassy
state (cold crystallization). Microlayering was used to create talc-filled structures with
controlled layer architecture. The reduction of permeability in crystallized and talc-
filled PET was well described by Nielsen’s model. Changes in permeability of crystalline
PET could not be ascribed to the filler effect of crystallites only. Our data on solubility,
obtained on the basis of measurements of the oxygen transport coefficients, confirmed
a previous finding that the amorphous phase density of PET decreases upon crystalli-
zation. The data were amenable to interpretation by free volume theory. Talc-filled
materials processed by different methods showed the same permeability; however,
much better mechanical properties were achieved by microlayering. © 1999 John Wiley &
Sons, Inc. J Polym Sci B: Polym Phys 37: 847– 857, 1999
Keywords: poly(ethylene terephthalate); barrier; oxygen permeability; microlayer
coextrusion

INTRODUCTION may be regarded as impermeable relative to the

It is well known that molecular orientation and
crystallinity improve the barrier properties of
polymers.1–3 Qualitatively, this is understood in
terms of free volume concepts because sorption
and diffusion processes depend upon the avail-
ability of unoccupied volume in the polymer. In
the lamellar crystals of a semicrystalline polymer
and the extended chain structure of oriented poly-
mers, chain packing is usually much more effi-
cient than in the amorphous, isotropic state. The
efficiency of chain packing in the crystalline
phase reduces the free volume available for trans-
port to such an extent that the crystalline phase
Correspondence to: A. Hiltner
Journal of Polymer Science: Part B: Polymer Physics, Vol. 37, 847– 857 (1999)
© 1999 John Wiley & Sons, Inc. CCC 0887-6266/99/080847-11
amorphous phase.
Alternatively, high aspect ratio flakes or plate-
lets have been used to improve gas barrier prop-
erties.4 Typical polymer processing operations
used in packaging lead to preferred orientation
with the platelets aligned parallel to the surfaces.
It is imagined that the aligned, overlapping plate-
let particles greatly increase the diffusion dis-
tance by creating a tortuous path for the diffusing
species. Platelet-type fillers, which are most use-
ful in thin barrier films, are aluminum flake,
mica, and talc; other types of platelets tend to be
either too large in particle size or to have too low
an aspect ratio to be useful.
Among the high-barrier polymers, PET is used
because of its low cost, good mechanical proper-
ties, and high resistance to oxygen. However,
there is a continuous practical need to improve
847
848 SEKELIK ET AL.
PET oxygen barrier. Both crystallization and ad-
dition of a platelet filler are approaches to barrier
enhancement that rely upon introduction of an
impermeable phase. However, the mechanisms of
barrier enhancement may not be completely anal-
ogous. This article compares the two approaches
as applied to poly(ethylene terephthalate) (PET).
Crystallinity was induced by crystallization from
the glassy state (cold crystallization). Microlayer-
ing was used to create talc-filled structures with
controlled layer architecture.5
EXPERIMENTAL
Poly(ethylene terephthalate) (PET) and its copol-
ymer with 2.6 mol % isophthalate (PET-I/2.6)
were supplied as pellets by the Hoechst Corpora-
tion, Spartanburg, SC. The pellets were dried in
vacuo at 120°C for 24 h prior to processing. Dried
pellets were placed in the 6 3 60 cavity of a 300
mm-thick metal spacer and sandwiched between
two 8 3 80 steel platens covered with Teflon-
coated aluminum foil. The platens were placed in
a press and heated at 265°C for 5 min with no
pressure. The pressure was increased to 20,000
psi and then released; this cycle was repeated
three times to ensure that the plaques would be
free of air bubbles. Finally, the platens were held
at 20,000 psi for 5 min and quenched in cold
water.
A density gradient column was constructed
from a solution of calcium nitrate/water in accor-
dance with ASTM-D 1505 Method B. The column
was calibrated with glass floats of known densi-
ties. Small pieces (;25 mm2) from each plaque
were placed in the column and allowed to equili-
brate for 15 min before a measurement was
taken.
The amount of crystallinity was determined
from both density and DSC measurements. A
Rheometric Scientific Differential Scanning Calo-
rimeter (DSC) was calibrated with tin, indium,
and sapphire standards. Heating and cooling
scans were recorded at 10°C/min over the temper-
ature range of 30 to 300°C with a 3-min hold
between heating and cooling scans.
To determine conditions for cold crystalliza-
tion, small portions of the quenched plaques were
wrapped in aluminum foil and isothermally cold
crystallized for 10 min in a press at temperatures
of 84, 95, 105, 118, 131, 151, and 171°C. Figure 1
shows the dependence of density of individual
specimens on the cold crystallization temperature
Figure 1. Effect of isothermal cold crystallization
temperature (Tcc) on the density of PET and PET-I/2.6.
Tcc for PET and PET-I/2.6. Subsequently, barrier
specimens of amorphous PET were wrapped in
aluminum foil and cold crystallized for 10 min in
a press at temperatures of 100, 104, 116, and
170°C. Barrier specimens of amorphous PET-I/2.6
were cold crystallized in a similar manner at tem-
peratures of 87, 100, 112, 116, and 171°C. The
densities of these samples, also shown in Figure
1, tended to be higher than those for the small
samples that were crystallized at the same Tcc.
However, both sets of experiments showed that a
higher temperature was required to cold crystal-
lize PET-I/2.6.
Talc-filled PET-I/2.6 was also studied. The talc
was Supra talc (Lot S01167), the talc platelets
had an aspect ratio of 1-20 and a thickness of
about 1–3 mm. Pellets of PET-I/2.6 with 19 vol %
(32 wt %) talc were used to extrude 30 and 60-wide
sheets of 64-layer microlayers using the micro-
layer coextrusion system described previously.5,6
The extrusion temperature was 265°C; the 30-
wide sheets were cooled in a 60°C water bath,
and the 60-wide sheets were cooled on a 60°C
chill roll. The resulting sheets were 10 –20 mil
thick. Three types of microlayer architecture
were prepared. In type U-U (unfilled-unfilled)
systems, all layers contained PET-I/2.6. In type
U-F (unfilled-filled) systems, PET-I/2.6 layers
alternated with 19 vol % talc-filled PET-I/2.6
layers to give an overall talc content of about 9
vol %. In type F-F systems, all 64 layers con-
tained 19 vol % talc-filled PET-I/2.6.
Single layer controls of various talc content
were extruded from dry blends of PET-I/2.6 and
19 vol % talc-filled PET-I/2.6 pellets. For this pur-
 OXYGEN BARRIER PROPERTIES OF PET 849

pose, one extruder of the microlayer coextrusion

system was used with no die elements. Pellets of
various talc content were prepared by melt blend-
ing PET-I/2.6 with talc in a Haake twin screw
extruder. These were used to compression mold
300 mm-thick plaques.
Talc content was determined with a Perkin–
Elmer Thermogravimetric Analyzer (TGA7).
Specimens were heated in air at 10°C/min over
the temperature range of 30 to 800°C. The organic
content was burned off and the inorganic content
that remained at 800°C was taken as the wt %
talc content. A talc density of 2.7 g/cm3 was used
to convert wt % to vol %. Layer structure and
particle orientation for talc-filled materials were
evaluated with a JEOL 840A Scanning Electron
Microscope (SEM). Specimens were notched with
a razor blade transverse to the extrusion direction
and fractured in liquid nitrogen. Mechanical
properties of the talc-filled materials were evalu-
ated in uniaxial tension on an Instron 1123. Mi-
crotensile dog bones were cut from the sheets
using a die in accordance with ASTM-D 1708 and
tested in the extrusion direction at a strain rate of
1%/min.
Oxygen flux J(t) at 25°C, 0% relative humidity,
and 1 atm pressure was measured with a MOCON
OXTRANt 2/20, which uses the continuous-flow cell
method that is approved by ASTM (Designation: D
3985-81) and is generally adopted for measure-
ments of oxygen permeation through polymers. A
mixture of 98% N2 with 2% H2 was the carrier gas
and 100% oxygen was used as the test gas. Perme-
ability of Mylar sheet supplied by MOCON was
used as the control for the instrument. Prior to
testing, specimens were conditioned in nitrogen in-
side the unit for a minimum of 24 h to remove traces
of atmospheric oxygen. Conditioning was especially
important for measuring the nonsteady-state oxy-
gen flux from which the diffusion coefficient D was
determined. The conditioning was continued until a
steady baseline was obtained where the oxygen flux
changed by less than 1% for a 30-min cycle. Subse-
quently, oxygen was introduced to the test cell. The
test ended when the flux reached a steady state
where the oxygen flux changed by less than 1%
during a 30-min test cycle.
The 30-wide extruded sheets were smaller than
the 50 cm2 test cell and, therefore, were masked
to aluminum foil. A 5 3 3.2 cm window was cut
out of the foil and the foil surface around the
window was treated with a water-based phospho-
ric acid surface cleaner followed by an ammonia
water surface cleaner. The specimen was placed
Figure 2. Experimental oxygen flux data and the fit
to Fick’s law for amorphous, 25 vol % crystallinity, and
19 vol % talc-filled PET-I/2.6.
over the window and bonded to the foil using
epoxy. After the epoxy was cured for 24 h at
ambient temperature, the masked sample was
placed in the test cell to begin conditioning.
The average thickness l of each specimen was
determined after the barrier measurement was
completed. For full-sized specimens, a 3 3 30
square was cut from the tested area. For masked
specimens, a 1 3 10 square was cut from the
tested area. Each square was weighed and the
area was determined with a ruler. The average
thickness was calculated as l 5 W/Ar, where W
was the sample weight, A was the sample area,
and r was the density.
RESULTS AND DISCUSSION
Oxygen Permeability
Figure 2 shows typical experimental J(t) curves
describing the oxygen flux through films of amor-
phous, talc-filled, and cold crystallized PET-I/2.6.
Careful conditioning and the appropriate choice
of specimen thickness resulted in excellent reso-
lution of the various features of the time depen-
dence. The initial increase in oxygen flux reflected
nonsteady-state diffusion, i.e., the process of pen-
etration of oxygen into the material. This part of
the curve was determined mainly by the diffusion
coefficient D. As the permeant concentration in
the specimen reached a constant distribution, the
flux leveled out and approached the steady state
value J. This value, normalized by the film thick-
850 SEKELIK ET AL.
ness l and the permeant gas pressure p, defined
the permeability coefficient P 5 J l/p. An imper-
meable phase, such as crystallinity or talc parti-
cles, had a strong effect on both the nonsteady-
state and steady-state parts of the oxygen flux
curve. The nonsteady-state region broadened
(slower diffusion) while the steady-state perme-
ability decreased with increasing content of the
impermeable phase.
The permeability coefficient of amorphous PET
(0.44 cc cm/m2/atm/day) was in good agreement
with the literature value (0.39).27 The latter was
obtained with the constant-volume technique
that does not use a carrier gas. The small differ-
ence between the two values cannot be ascribed to
the effect of carrier gas that would lead to lower
apparent permeability. Probably, the difference
reflects defferences in the PET materials used in
the two studies.
To obtain the diffusion coefficient and to accu-
rately determine the permeability coefficient, the
data were fit to the solution of Fick’s second law:
­c ­ 2c
5D 2
­t ­x
with boundary conditions for the oxygen concen-
tration c(x 5 0, t) 5 Sp; c(x 5 l, t) 5 0, where S is
the solubility coefficient and p is the gas pressure,
and initial condition c(x, t 5 0) 5 0:
O
Pp
` more. Such a low sensitivity of the diffusional flux
J~t! 5 @1 1 2 ~ 2 1!n exp~2Dp2 n2 t/l2 !#
l n51
The solubility is then obtained from the relation-
ship P 5 DS. The fitting curves are included with
the experimental points in Figure 2; from the
quality of the fit, it can be concluded that there is
no concentration dependence of the oxygen diffu-
sion coefficient in PET. The fit was equally good
for all the experiments in the study. The error in
determining the two fitting parameters, P/l and
D/l2, was estimated not to exceed 2%. Thus, the
main source of error in calculating P and D from
the experimental flux curves lay in the determi-
nation of film thickness l.
Because some thickness variation Dl was in-
herent to all the specimens, it was deemed impor-
tant to determine an acceptable range of Dl for
obtaining reliable values of P and D. Therefore,
the diffusional flux through a sheet with periodic
thickness variation was modeled. The thickness
Figure 3. Calculated effect of thickness uniformity
on reduced oxygen flux.
variation was considered to have the form l 5 l0
(1 1 d sin y/ll), where l0 was the average thick-
ness, d was the relative amplitude of the varia-
tion, y was the direction along the film surface,
and l was the corresponding period. If l .. l0,
the one-dimensional diffusion equation could be
used. In this case, the diffusional flux was calcu-
(1) lated from the solution, eq. (2), with l 5 l(y), and
then averaged over the period l. The results are
shown in Figure 3 for different values of dl but the
same average thickness l0. As seen, the curves
almost completely overlapped if dl # 0.1. The
effect of thickness variation became perceptible
only if dl $ 0.15, which corresponded to a mini-
mum to maximum thickness difference of 30% or
(2) to thickness variation meant that the accuracy of
P and D was determined mainly by the accuracy
of the average thickness measurement. For this
reason, special attention was paid to the average
thickness measurement as described in the Ex-
perimental section.
Effect of Crystallinity
Figure 4 shows changes in the permeability, dif-
fusion, and solubility coefficients with increasing
density. Compression-molded specimens were
used for these experiments, and density was var-
ied by cold crystallization at different tempera-
tures. Essentially identical results for PET and
PET-I/2.6 meant that any effect of comonomer in
PET-I/2.6 was small compared to the effect of
crystallization. The significant drop in permeabil-
ity with increased crystallinity is usually ex-
plained in terms of two factors.1,2 First, inclusion
of impermeable crystallites decreases the amount

Figure 4. Effect of density on the oxygen barrier
properties of PET and PET-I/2.6: (a) permeability coef-
ficient (P); (b) diffusion coefficient (D); and (c) solubility
coefficient (S).
of amorphous material through which the per-
meant can diffuse. Second, impermeable crystal-
lites increase the tortuosity of the transport path
(geometrical impedance). The former affects total
solubility of the permeant in the material, the
latter affects the diffusion coefficient. However, in
the present study of unoriented PET, the reduc-
tion in permeability was caused primarily by a
decrease in the diffusion coefficient [Fig. 4(b)].
The solubility coefficient [Fig. 4(c)] remained ap-
proximately constant in spite of the significant
increase in density. Thus, the specific solubility of
oxygen in the amorphous phase must have in-
creased. This suggests that a change occurred in
the amorphous phase as a result of crystalliza-
tion.
Correlation of the reduced oxygen transport
coefficients with morphological changes in the
material required an estimate of the volume frac-
tion of impermeable phase. It is well known that
the two-phase model with constant densities of
OXYGEN BARRIER PROPERTIES OF PET 851
crystal and amorphous phases fails to describe
PET.7–10 This characteristic is illustrated in Fig-
ure 5 with a comparison of crystallinity calculated
from DSC data, assuming a heat of fusion for the
perfect crystal of 30 cal/g,11 and crystallinity from
density using a simple two-phase model with con-
stant densities of crystalline and amorphous
phases, rc 5 1.515 g/cm3,10,12 and ra 5 1.335
g/cm3.13 An increase in the cold crystallization
temperature from 100 –120 to 170°C resulted in a
gradual increase of density, in contrast to the
DSC crystallinity which increased sharply to 35–
40% and remained almost independent of the cold
crystallization temperature. A similar discrep-
ancy was reported previously for both oriented
and isotropic PET.7–10,14 –16
On the other hand, the structural model of gas
permeability should consist of two phases only.
The permeability of crystals, no matter how de-
fective they are, is insignificant compared to the
permeability of the flexible amorphous phase.
One approach to calculating the fraction of imper-
meable phase that takes into account the compli-
cated nature of crystallized PET is to use a two-
phase model with variable densities of both crys-
talline and amorphous phases.10,17–19 Variations
in crystalline density are attributed to crystal
defects (which depend on crystallization temper-
ature);20 –22 variations in amorphous density
arise from conformational restrictions and
Figure 5. Comparison of the wt % crystallinity ob-
tained from density and DSC assuming a two-phase
model with constant densities of the crystalline and
amorphous phases, DHf 5 30 cal/g, rc 5 1.515 g/cm3
and ra 5 1.335 g/cm3.
852 SEKELIK ET AL.

changes in the ratio of amorphous gauche-to-

trans conformers as crystallization proceeds.23
Bornschlegl and Bonart19 obtained the crystal-
line phase density and the amorphous phase den-
sity independently from wide-angle X-ray and
small-angle X-ray measurements, respectively.
The crystalline phase density decreased with the
crystallization temperature from rc 5 1.515 g/cm3
for crystallization close to the melting point
(260°C) to rc 5 1.476 g/cm3 for crystallization at
200°C. However, this value did not change fur-
ther as the crystallization temperature decreased
to 120°C. The constancy of the crystal density
over so broad a range of crystallization tempera-
tures could be interpreted as indicating satura-
tion in the level of disordering. Therefore, the
value rc 5 1.476 g/cm3 can be considered as an
intrinsic characteristic of the defective crystalline
phase in PET obtained with any crystallization
temperature below 200°C. However, in this range
of crystallization temperatures, as the total den-
sity r increased from 1.335 g/cm3 (completely
amorphous) to 1.39 g/cm3, the density of the
amorphous phase decreased to 1.31 g/cm3. Figure 6. The solubility of oxygen in PET and PET-
Using rc 5 1.476 g/cm3 and interpolating the I/2.6 plotted vs. (a) amorphous phase density (ra); and
data ra 5 ra(r) presented in the literature (Fig. 13 (b) specific volume (va). Values of ra were obtain from
in ref. 19) to obtain ra, the values of the volume ref. 19. Extrapolation of the specific volume gave ra,max,
fraction crystallinity fc were calculated by the which represented the theoretical maximum amor-
equation: phous phase density of PET at ambient temperature.

r 5 r cf c 1 r a~ r !~1 2 f c! (3)
The values of fc obtained from eq. (3) were con-
siderably higher than those estimated by the sim-
ple model with constant phase densities. For ex-
ample, the volume fraction of crystallinity
reached 50% for a specimen of density 1.39 g/cm3,
whereas the simple model gave the value of 35%
(Fig. 5).
The decrease of the amorphous density with
increasing crystallinity was totally consistent
with the behavior of the solubility coefficient [Fig.
4(c)]. Figure 6(a) shows the dependence of the
specific solubility coefficient of the PET amor-
phous phase, defined as Sa 5 S/(1 2 f c), on
amorphous density ra. As seen, this quantity
gradually decreased with increasing amorphous
density. This result permits a straightforward in-
terpretation in terms of free volume theo-
ries.2,24 –26 It is well known that the thermal ex-
pansion coefficient k undergoes a jump Dk upon
cooling below the glass transition temperature Tg.
Hence, the specific volume in the glassy state is
higher than that in the supercooled liquid at the
same temperature T by free volume v 5 Dk (Tg
2 T). This quantity is usually ascribed to packing
defects frozen in by the restricted segmental mo-
tion below the Tg and can be considered as micro-
cavities where sorption of the gas molecules is
considerably facilitated. This concept underlies
the dual sorption model that distinguishes per-
meant molecules absorbed in the microcavities, or
“holes,” and those dissolved in the polymer ma-
trix.1,24,27 For oxygen in PET, it was shown that
the contribution of the dissolution mechanism is
small, and that the permeant molecules are
mainly sorbed in holes.27 In this case, sorption is
the process of filling the holes, and the solubility
coefficient should be proportional to the amount
of free volume.
The increase of the specific volume of the amor-
phous phase, va 5 1/ra, with crystallinity [Fig.
6(b)] indicated the appearance of additional free
volume. Accordingly, solubility also increased. If
this interpretation is correct, a linear extrapola-
tion back to zero solubility should give the specific

volume of amorphous PET with no holes. The
linear regression of the data in Figure 6(b) gives
the density of this material as ra,max 5 1.38
6 0.01 g/cm3. By definition, this density should
correspond to the specific volume of the super-
cooled liquid extrapolated to ambient tempera-
ture, the temperature used in the experiments:
v l 5 v a~0! 2 D k ~T g 2 T! (4)
where va(0) 5 0.749 cm3/g is the specific volume of
glassy PET with zero crystallinity at ambient
temperature, Tg 5 70°C, and, for Dk, the range
3.6 –5.2 cm3/g/k has been reported.28 The result
from eq. (4) is rl 5 1/vl 5 1.37–1.38 g/cm3, which
is in excellent agreement with the value of ra,max.
The additional free volume produced by crys-
tallization should also cause the diffusion coeffi-
cient in the amorphous phase to increase.2,24 –26
This effect was not seen because of the dramatic
increase of geometrical impedance provided by
the impermeable crystalline phase, which re-
sulted in the decrease in both the diffusion and
permeability coefficients [Fig. 4(a) and (b)]. As-
suming the filler effect to be the major one, it is
feasible to correlate the decrease in permeability
with morphological features of the crystalline
phase. Although permeability of the complex hi-
erarchical structure of the crystalline phase is
difficult to model accurately,1,2,29 the simple
Nielsen approximation that operates with only a
few parameters is useful.25,30 This model leads to
the following estimation of the permeability coef-
ficient P in a system filled with randomly dis-
persed particles of an aspect ratio a:
12f
P 5 P0 (5)
1 1 af /2
where f is the volume fraction of filler, and P0 is
the permeability of the unfilled material. For a
5 1, eq. (5) coincides with Maxwell’s solution for
impermeable spheres, which is well justified in
the case of small filler loading.2,31 Figure 7 shows
the values of the permeability coefficient plotted
vs. volume fraction of crystallinity fc. The latter
was converted from density in accordance with
eq. (3). As seen, the data are well described by eq.
(5), with an aspect ratio of about unity.
Effect of an Inorganic Filler
Filling PET with an inorganic particulate of high
aspect ratio made it possible to significantly in-
OXYGEN BARRIER PROPERTIES OF PET 853
Figure 7. Effect of crystalline volume fraction (fc) on
the permeability coefficient (P); the curves were ob-
tained from eq. (5) with the indicated aspect ratio (a) of
the impermeable phase.
crease the oxygen barrier with rather small load-
ing. To study the effect of talc particle orientation,
microlayered, extruded, and compression-molded
materials with different talc content were com-
pared. The arrangement of filler particles in these
materials is seen in scanning electron micro-
graphs of cryogenically fractured cross-sections
(Fig. 8). The best orientation was achieved by
microlayer coextrusion. Figure 8(a) and (b) shows
parallel particle alignment in microlayers with 64
filled layers (F-F) and microlayers with 64 alter-
nating unfilled and filled layers (U-F) with ap-
proximately the same talc content in the filled
layers. The filled material extruded as a single
layer also showed good particle orientation, with
fluctuations within a 20° angle of the extrusion
direction [Fig. 8(c)]. The poorest particle orienta-
tion was obtained by compression molding [Fig.
8(d)]. However, even in this case, the orientation
could not be considered as random; some prefer-
ential arrangement in the plane of the sheet can
be seen. Particles of high aspect ratio can be ro-
tated and aligned even by the moderate shear
forces that arise as the melt spreads out in the
press. The PET phase in both the extruded and
compression-molded materials was almost com-
pletely amorphous: DSC and density measure-
ments with talc content determined by TGA
showed the volume fraction of crystallinity not to
exceed 3%.
Figure 9 shows the permeability, diffusion and
solubility coefficients of the talc-filled materials
with different volume content of talc ft. Talc load-
854 SEKELIK ET AL.

Figure 8. Scanning electron micrographs comparing talc particle orientation: (a) FF

microlayer with 14 vol % talc; (b) UF microlayer with 10 vol % talc; (c) extruded single
layer with 18 vol % talc; and (d) compression molded sheet with 19 vol % talc.

ing of about 20% by volume increased the oxygen
barrier by a factor of 3. The reduction in perme-
ability [Fig. 9(a)] was mainly caused by a signifi-
cant drop in the diffusion coefficient [Fig. 9(b)].
Solubility decreased proportionally to the fraction
of PET [dashed line in Fig. 9(c)], so the specific
solubility of PET was not changed by filling with
talc. The points corresponding to zero loading rep-
resent the appropriate PET-I/2.6 control, i.e., U-U
microlayer, extruded single layer or compression
molded sheet.
Surprisingly, the effect of talc particle orienta-
tion was not systematically pronounced. Al-
though compression molded sheets with ft of
about 10% showed slightly higher permeability
and diffusion coefficients than the extruded
sheets, the difference vanished with increasing
talc content. It is possible that increased loading
improved the particle orientation in compression
molding due to particle–particle interactions in
the hydrodynamic flow. Nevertheless, a difference
in the particle orientation of compression-molded
and extruded sheets was noticeable even at the
highest loading used in the experiments (Fig. 8).
The small or negligible effect of particle orien-
tation is hard to understand on the basis of cur-
rent theoretical approaches to diffusion in filled
media.2,32 Even the most advanced treatments
assume either perfect orientation or close packing
of fillers and employ solutions for diffusion
through a hole, slot, or channel, or consider geo-
metrical impedance of a single particle and ne-
glect their mutual diffusional backscattering. A
rigorous solution of the diffusion problem in an
environment of multiple randomly located parti-
cles needs to be developed. This is especially im-
portant for the case of intermediate filler loading,
which includes the range used in the present ex-
periments.
Figure 10 shows the permeability coefficient of
talc-filled materials plotted vs. volume fraction of
an impermeable phase ft9, which consists of talc
particles and sometimes a small amount of crys-
tallinity. Because talc is well known as a nucle-
 OXYGEN BARRIER PROPERTIES OF PET 855

Figure 10. Effect of talc (ft9) on the permeability

coefficient (P); the curves were obtained from eq. (5)
with the indicated aspect ratio (a) of the impermeable
phase.

the values for the unfilled single layer and the

U-U microlayer. The fit of eq. (5) to the data is
presented by curves in Figure 10. As seen, the fit
results in realistic values of the effective aspect
ratio, consistent with the value of 20 estimated by
visual analysis of talc particles.
Figure 9. Effect of talc volume fraction (ft) on the Figure 11 compares the dependence of the per-
oxygen barrier properties of PET-I/2.6: (a) permeability meability coefficient on the amount of imperme-
coefficient (P); (b) diffusion coefficient (D); and (c) sol- able phase for crystalline and talc-filled materi-
ubility coefficient (S). The dashed line in (c) extrapo- als. Because both sets of data extrapolate to the
lates to zero solubility at ft 5 1. same value for permeability for amorphous PET,
it appears that possible orientation of the polymer
ating agent,33 talc-filled PET samples often con-
tained a small amount of crystallinity probably in
the form of epitaxial crystallization on the talc
surface. In this case, the crystals slightly in-
creased the effective size of the filler without
causing any significant change to the amorphous
phase. Therefore crystallinity was considered as
part of a unified impermeable phase with the
same effective aspect ratio as the talc particles.
This made it possible to apply the Nielsen model
to the total impermeable phase. To include the
data for the alternating U-F microlayer in the
analysis, the permeability of talc-filled layers Pt
was extracted from the measured permeability P
by the equation:

1 1 1
5 1 (6)
P 2P 0 2P t Figure 11. Comparison of the effect of crystallinity
(fc) and talc (ft9) on the permeability coefficient; the
where P0 5 0.42 cc cm/m2/atm/day is the perme- curves were obtained from eq. (5) with the indicated
ability of extruded PET, obtained as an average of aspect ratio (a) of the impermeable phase.
856 SEKELIK ET AL.
Figure 12. Effect of processing on the stress–strain
behavior of talc-filled PET-I/2.6.
due to microlayering did not affect the data. For
the same volume content of impermeable phase,
talc produced more than twice the reduction in
permeability as crystallinity.
Mechanical Properties of Filled Materials
Figure 12 shows typical stress–strain curves for
compression-molded, extruded single-layer, and
microlayered talc-filled PET. The compression-
molded sample with 9 vol % talc showed brittle
behavior, and fractured at about 2% strain [Fig.
12(a)]. In contrast, the extruded single-layer sam-
ple with 10 vol % talc was ductile with formation
of a stable neck that propagated some distance
along the gauge section before fracturing at 30%
strain [Fig. 12(b)]. The microlayered U-F sample
with 9 vol % talc also showed ductile behavior,
and fractured at an even higher strain of 73%
[Fig. 12(c)].
The increased fracture strain of microlayered
materials is attributed to two factors. For a filled
polymer with poor particle adhesion, the ductility
is determined by the area of load-bearing matrix
in the cross-section when particles debond from
the matrix.34 Strain hardening of the matrix lig-
aments helps sustain the high local stresses dur-
ing drawing. Nevertheless, ductility is lost when
the area of matrix in the cross-section drops below
a critical value. In this respect, debonded parti-
cles oriented along the load direction produce a
smaller reduction in the load-bearing area than
unoriented particles. Thus, the increased ductil-
ity achieved by microlayering resulted from a
higher degree of particle alignment. In this con-
figuration, the area of load-bearing PET in the
cross-section was higher than if the particles were
less oriented.
A further increase in fracture strain of U-F
microlayered materials was achieved by alternat-
ing high modulus talc-filled layers and ductile
PET layers. The unfilled PET layers inhibited
propagation of cracks that originated in the talc-
filled layers. Compared to compression molding,
microlayering made it possible to achieve the im-
proved oxygen barrier properties of talc-filled
PET with less sacrifice in mechanical properties.
CONCLUSIONS
The oxygen barrier of isotropic PET can be signif-
icantly improved by incorporating impermeable
phases such as crystallinity or talc platelet parti-
cles. However, changes in permeability of crystal-
line PET cannot be ascribed to the filler effect of
crystallites only. Our data on solubility, obtained
on the basis of measurements of the oxygen trans-
port coefficients, confirm a previous finding that
the amorphous phase density of PET decreases
upon crystallization. The data are amenable to
interpretation by free volume theory. The reduc-
tion of permeability in crystallized and talc-filled
PET is well described by Nielsen’s model. Talc-
filled materials processed by different methods
showed the same permeability; however, much
better mechanical properties were achieved by
microlayering.
This research was generously supported by the Hoechst
Corporation.
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